US20090005593A1 - Catalyst for production of acrylic acid and process for production of acrylic acid using this catalyst - Google Patents
Catalyst for production of acrylic acid and process for production of acrylic acid using this catalyst Download PDFInfo
- Publication number
- US20090005593A1 US20090005593A1 US12/080,503 US8050308A US2009005593A1 US 20090005593 A1 US20090005593 A1 US 20090005593A1 US 8050308 A US8050308 A US 8050308A US 2009005593 A1 US2009005593 A1 US 2009005593A1
- Authority
- US
- United States
- Prior art keywords
- catalyst
- acrylic acid
- production
- dried material
- oxidation reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 514
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 151
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 75
- 230000008569 process Effects 0.000 title claims abstract description 40
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 153
- 229910052751 metal Inorganic materials 0.000 claims abstract description 78
- 239000010949 copper Substances 0.000 claims abstract description 75
- 239000002184 metal Substances 0.000 claims abstract description 69
- 230000003197 catalytic effect Effects 0.000 claims abstract description 66
- 229910052802 copper Inorganic materials 0.000 claims abstract description 58
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 58
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 49
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000010937 tungsten Substances 0.000 claims abstract description 49
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims description 271
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 82
- 239000007789 gas Substances 0.000 claims description 28
- 238000000465 moulding Methods 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 229910052750 molybdenum Inorganic materials 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 12
- 239000002344 surface layer Substances 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 description 84
- 230000000052 comparative effect Effects 0.000 description 53
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 35
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 32
- 239000002245 particle Substances 0.000 description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 27
- 239000007788 liquid Substances 0.000 description 24
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000001354 calcination Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000007858 starting material Substances 0.000 description 16
- 238000009826 distribution Methods 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 11
- 102000002322 Egg Proteins Human genes 0.000 description 10
- 108010000912 Egg Proteins Proteins 0.000 description 10
- 210000003278 egg shell Anatomy 0.000 description 10
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 230000010354 integration Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
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- 230000000694 effects Effects 0.000 description 7
- 230000002349 favourable effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 5
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- -1 organic acid salts Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
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- 230000001788 irregular Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 210000004940 nucleus Anatomy 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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- B01J35/30—
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- B01J35/40—
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/885—Molybdenum and copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
- B01J37/0223—Coating of particles by rotation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0228—Coating in several steps
Definitions
- the present invention relates to a catalyst for production of acrylic acid and a process for production of acrylic acid using this catalyst.
- catalysts for efficient production of acrylic acid by catalytic gas phase oxidation of acrolein As to catalysts for efficient production of acrylic acid by catalytic gas phase oxidation of acrolein (catalysts for production of acrylic acid), there is widely used a catalyst comprising molybdenum and vanadium as essential catalytic components, and various proposals have been made about its production processes.
- Examples of these production processes include: (a) a process in which a mixed liquid of starting materials is subjected to evaporation to dryness, and then, to the resultant dried material, there are added polyvinyl alcohol, a water-absorbent resin, and water, and then they are kneaded together and then extrusion-molded (e.g. refer to patent document 1 below); (b) a process in which a mixed liquid of starting materials is spray-dried and then calcined at 400° C., and then the resultant calcined material is supported onto a support with water as a binder by use of such as a rotary drum type supporting device (e.g.
- Patent Document 1 JP-A-096183/1993 (Kokai)
- an object of the present invention is to provide: a catalyst for production of acrylic acid which catalyst is so high active as to give a still higher selectivity of acrylic acid (which is the objective product) or a long-catalytic-life-time catalyst for production of acrylic acid which catalyst is so high active as to be able to give a high acrylic acid yield while suppressing the temperature rise of the oxidation reaction to a low one; and processes for production of acrylic acid using these catalysts.
- the present inventors diligently studied to solve the above problems. In its process, they have found out that the aforementioned problems can be solved all at once by arranging that tungsten and/or copper besides molybdenum and vanadium should be used as essential metal elements constituting the catalyst and further that a specific metal element should be maldistributed in the surface side and/or core side of the catalyst.
- the metal element is maldistributed like in the aforementioned first and second arrangements, then there can be obtained a selectivity of acrylic acid which selectivity is equal to or higher than prior ones while the temperature rise of the oxidation reaction is suppressed to a low one, so that, for a long time, the catalytic life time can be kept and a high acrylic acid yield can be given.
- the metal element is maldistributed like in the aforementioned third and fourth arrangements, then there can be obtained a still higher selectivity of acrylic acid. Then, they have completed the present invention by confirming these findings.
- a first catalyst according to the present invention for production of acrylic acid comprises an oxide and/or a composite oxide as an essential catalytic component, wherein the oxide and/or the composite oxide has a metal element composition shown by the following general formula (I):
- Mo molybdenum
- V vanadium
- W tungsten
- Cu copper
- O oxygen
- the catalyst being characterized in that: the tungsten is maldistributed in the surface side of the catalyst; and/or the copper is maldistributed in the core side of the catalyst.
- a second catalyst according to the present invention for production of acrylic acid comprises an oxide and/or a composite oxide as an essential catalytic component, wherein the oxide and/or the composite oxide has a metal element composition shown by the following general formula (1):
- Mo molybdenum
- V vanadium
- W tungsten
- Cu copper
- O oxygen
- a third catalyst according to the present invention for production of acrylic acid comprises an oxide and/or a composite oxide as an essential catalytic component, wherein the oxide and/or the composite oxide has a metal element composition shown by the following general formula (1):
- Mo molybdenum
- V vanadium
- W tungsten
- Cu copper
- O oxygen
- the catalyst being characterized in that: the copper is maldistributed in the surface side of the catalyst; and/or the tungsten is maldistributed in the core side of the catalyst.
- a fourth catalyst according to the present invention for production of acrylic acid comprises an oxide and/or a composite oxide as an essential catalytic component, wherein the oxide and/or the composite oxide has a metal element composition shown by the following general formula (I):
- Mo molybdenum
- V vanadium
- W tungsten
- Cu copper
- O oxygen
- processes according to the present invention for production of acrylic acid are characterized in that the above catalysts according to the present invention for production of acrylic acid (first, second, third, and fourth catalysts for production of acrylic acid) are used when acrylic acid is produced by catalytic gas phase oxidation of acrolein in the presence of molecular oxygen.
- the present invention can provide, in a long-time oxidation reaction of acrolein, a catalyst for production of acrylic acid which catalyst gives a still higher selectivity of acrylic acid (which is the objective product) or a long-catalytic-life-time catalyst for production of acrylic acid which catalyst is able to give a high acrylic acid yield while suppressing the temperature rise of the oxidation reaction to a low one.
- the first or second catalyst according to the present invention for production of acrylic acid is a long-catalytic-life-time catalyst which is able to give a high acrylic acid yield while suppressing the temperature rise of the oxidation reaction to a low one
- the third or fourth catalyst according to the present invention for production of acrylic acid is a catalyst which gives a still higher selectivity of acrylic acid which is the objective product.
- the present invention can provide processes for production of acrylic acid using these catalysts.
- any of the first, second, third, and fourth catalysts according to the present invention for production of acrylic acid (which may hereinafter be referred to generically as “catalyst according to the present invention”) is a catalyst comprising an oxide and/or a composite oxide as an essential catalytic component, wherein the oxide and/or the composite oxide has a metal element composition shown by the aforementioned general formula (I).
- first catalyst As to the first catalyst for production of acrylic acid (which may hereinafter be referred to as “first catalyst”), it is important that: the tungsten is maldistributed in the surface side of the aforementioned catalyst (which may hereinafter be referred to simply as “surface side”), and/or the copper is maldistributed in the core side of the aforementioned catalyst (which may hereinafter be referred to simply as “core side”).
- second catalyst As to the second catalyst for production of acrylic acid (which may hereinafter be referred to as “second catalyst”), it is important that the vanadium is maldistributed in the surface side of the aforementioned catalyst.
- the third catalyst for production of acrylic acid (which may hereinafter be referred to as “third catalyst”), it is important that: the copper is maldistributed in the surface side of the aforementioned catalyst, and/or the tungsten is maldistributed in the core side of the aforementioned catalyst.
- the fourth catalyst for production of acrylic acid (which may hereinafter be referred to as “fourth catalyst”), it is important that the vanadium is maldistributed in the core side of the aforementioned catalyst.
- the metal element is maldistributed like in the first and second catalysts, then there can be obtained a selectivity of acrylic acid which selectivity is equal to or higher than prior ones while the temperature rise of the oxidation reaction is suppressed to a low one, so that, for a long time, the catalytic life time can be kept and a high acrylic acid yield can be given.
- the metal element is maldistributed like in the third and fourth catalysts, then there can be obtained a still higher selectivity of acrylic acid (than those given by the aforementioned first and second catalysts).
- the above metal element composition may include an optional component (e.g. niobium, chromium, manganese, iron, cobalt, nickel, zinc, bismuth, tin, antimony) besides the metal elements shown in the general formula (1) (Mo, V, W, and Cu).
- a metal element maldistributed in the surface side i.e. tungsten in the case of the first catalyst, vanadium in the case of the second catalyst, and copper in the case of the third catalyst
- metal element ( ⁇ ) a metal element maldistributed in the core side
- metal element ( ⁇ ) a metal element maldistributed in the core side
- the form of the catalyst according to the present invention is not limited.
- it may be as follows:
- a catalyst obtained by molding e.g. extrusion molding of catalyst materials including the catalytic component, specifically, a catalyst which is a molding that comprises the catalytic component as an essential constitutional material without any support as a constitutional material (this catalyst may hereinafter be referred to as molded catalyst); or
- a catalyst obtained by supporting of catalyst materials including the catalytic component onto a support specifically, a catalyst which comprises both the catalytic component and a support as essential constitutional materials wherein the above catalytic component is supported on surfaces of the above support and/or inside it (this catalyst may hereinafter be referred to as supported catalyst).
- examples of the form of the supported catalyst cited as 2) above include:
- a catalyst such that: such as a porous and inside-supportable support is used as the support, and the catalytic component is supported at least inside the support (for example, only inside the support, or both inside the support and on its surfaces).
- examples of the form of the supported catalyst cited as 2-2) above include:
- 2-2-2 a catalyst such that the above two kinds of forms 2-1) and 2-2-1) are combined together, specifically, a combined type catalyst (catalyst of a type in combination of the uniform type and the eggshell type) such that the catalytic component is supported both inside the support and on its surfaces.
- a combined type catalyst catalyst of a type in combination of the uniform type and the eggshell type
- Examples of the shape of the catalyst according to the present invention include any shape of such as spheres (including, besides true spheres, other spheres such as flat spheres (such as formed by squashing spheres flat) (e.g. oval spheres) and substantial spheres), pillars (e.g. cylinders, oval cylinders, prisms), (regular) polyhedrons (e.g. dice), rings, and irregular shapes.
- spheres including, besides true spheres, other spheres such as flat spheres (such as formed by squashing spheres flat) (e.g. oval spheres) and substantial spheres), pillars (e.g. cylinders, oval cylinders, prisms), (regular) polyhedrons (e.g. dice), rings, and irregular shapes.
- the particle diameter (average outer diameter) of the catalyst according to the present invention is favorably in the range of 1 to 15 mm, more favorably 3 to 10 mm.
- the “average outer diameter” in the present invention is defined as referring to the average of lengths of the longest and shortest portions of the catalyst in particle diameter.
- the diameter and the average outer diameter are the same as each other.
- the average of the longest and shortest outer diameters is the average outer diameter.
- the thickness of the catalytic component supported on the support is not less than a definite value in any portion. Specifically, the above thickness is favorably not less than 30 ⁇ m, more favorably in the range of 60 ⁇ m to 5 mm, still more favorably 100 ⁇ m to 3 mm.
- the degree of the above maldistribution in the catalyst according to the present invention is as follows. As to the maldistribution of the metal element ( ⁇ ) in the surface side (maldistribution of tungsten in the case of the first catalyst, maldistribution of vanadium in the case of the second catalyst, or maldistribution of copper in the case of the third catalyst), it will do if the metal element (a) (tungsten (tungsten element) in the case of the first catalyst, vanadium (vanadium element) in the case of the second catalyst, copper (copper element) in the case of the third catalyst) contained in the catalytic component is maldistributed in the surface side in an amount larger than half the total content of the metal element ( ⁇ ).
- the metal element (a) tungsten (tungsten element) in the case of the first catalyst, vanadium (vanadium element) in the case of the second catalyst, copper (copper element) in the case of the third catalyst
- the maldistribution of the metal element ( ⁇ ) in the core side (maldistribution of copper in the case of the first catalyst, maldistribution of tungsten in the case of the third catalyst, or maldistribution of vanadium in the case of the fourth catalyst)
- the metal element ( ⁇ ) (copper (copper element) in the case of the first catalyst, tungsten (tungsten element) in the case of the third catalyst, vanadium (vanadium element) in the case of the fourth catalyst) contained in the catalytic component is maldistributed in the core side in an amount larger than half the total content of the metal element ( ⁇ ).
- the aforementioned problems can easily be solved by maldistributing the prescribed metal element in the surface side or core side in this way.
- the metal element ( ⁇ ) is maldistributed in the surface side is defined as meaning that the metal element ( ⁇ ) among the aforementioned various metal elements contained in the catalytic component is maldistributed in the surface side.
- the definition of the maldistribution in the surface side is similarly applicable to all regardless of the types of the aforementioned various forms of the catalyst (e.g. the eggshell type previously cited as 2-1), the uniform type previously cited as 2-2-1), the combined type previously cited as 2-2-2), and the molded type previously cited as 1)).
- the metal element ( ⁇ ) is maldistributed in the core side is defined as meaning that the metal element ( ⁇ ) among the aforementioned various metal elements contained in the catalytic component is maldistributed in the core side.
- it can be defined as follows in accordance with the types of the aforementioned forms of the catalyst.
- the metal element ( ⁇ ) is maldistributed in the core side is defined as meaning that, in the catalyst for production of acrylic acid, the above metal element ( ⁇ ) is maldistributed in a portion, contacting with the surfaces of the support, of the catalytic component supported on the support and/or in the neighborhood of this portion.
- the above metal element ( ⁇ ) is distributed mainly in the above contacting portion and/or mainly in the neighborhood of this contacting portion with a distribution range of some degree of broadness in the depth direction opposite to this contacting portion.
- the metal element ( ⁇ ) is maldistributed in the core side is defined as meaning that the above metal element ( ⁇ ) is maldistributed in a central portion of the catalyst for production of acrylic acid and/or in the neighborhood of this portion.
- the maldistribution of the prescribed metal elements (metal element ( ⁇ ) and metal element ( ⁇ )) (contained in the catalytic component) in the surface side and in the core side can be evaluated by measurement using an EPMA (Electron Probe Micro Analyzer) device in accordance with such methods and standards as shown in (i) to (iii) below.
- EPMA Electro Probe Micro Analyzer
- whether the metal element ( ⁇ ) is maldistributed in the surface side or not can be evaluated by (i) and (ii) below.
- the core-side maldistribution ratio of the metal element ( ⁇ ) can be evaluated by (i) and (iii) below.
- measurement conditions and evaluation methods are described in accordance with the types of the forms of the catalyst.
- the evaluation of the surface-side maldistribution ratio of the metal element ( ⁇ ) and the evaluation of the core-side maldistribution ratio of the metal element ( ⁇ ) shall be carried out by the below-mentioned methods.
- the prescribed metal element (metal element ( ⁇ ) or metal element ( ⁇ )) is individually examined analytically by the measurement using the EPMA device. Specifically, a section including the central portion of the catalyst is targeted and measured (linear-analytically measured) into the prescribed metal element (metal element ( ⁇ ) or metal element ( ⁇ )) continuously from a one-side outer surface to the opposite-side outer surface in the central-portion-through direction in the above section; Next, the following drawing figure (graph) is obtained in accordance with the types of the forms of the catalyst.
- the catalyst according to the present invention is the eggshell type catalyst previously cited as 2-1
- the surface-side maldistribution ratio Ma (%) as determined from the following formula (a):
- the above standard position is more favorably 3/5r 1 , still more favorably 2/3r 1 .
- the surface-side maldistribution ratio Mb (%) as determined from the following formula (b):
- the above standard position is more favorably 3/5r 2 , still more favorably 2/3r 2 .
- the core-side maldistribution ratio Mc (%) as determined from the following formula (c):
- Mc (%) ( N 31 /N 30 ) ⁇ 100 (c)
- the above standard position is more favorably 2/5r 1 , still more favorably 1/3r 1 .
- the core-side maldistribution ratio Md (%) as determined from the following formula (d):
- the above standard position is more favorably 2/5r 2 , still more favorably 1/3r 2 .
- favorable examples of the shape of the catalyst to be measured include shapes of such as spheres (particularly, such as true spheres and substantially true spheres), pillars (particularly, such as cylinders), and rings (particularly, such as rings whose sections are circular), and more favorable examples thereof include the shapes of spheres (particularly, such as true spheres and substantially true spheres).
- shapes of commonly known catalysts for production of acrylic acid could all be analyzed and evaluated.
- the cylinder-shaped catalyst should be analyzed as to a cross section (circular section) crossing the center line of the cylinder at right angles; the sphere-shaped catalyst should be analyzed as to a section passing through the center of the sphere; and the ring-shaped catalyst should be analyzed as to a section as given by sectioning a thickness portion (which makes the ring) by a plane which crosses at right angles a plane made by the ring and passes through the center line of the ring.
- the particle diameter (average outer diameter) of the catalyst according to the present invention is favorably in the range of 1 to 15 mm, more favorably 3 to 10 mm. If the particle diameter is within the above range, then it follows that there are seen good correlations between the maldistributed state (specified by the analytic methods using the EPMA device) of the prescribed metal element and its effect.
- the thickness of the catalytic component supported on the support is not less than a definite value in any portion.
- the above thickness is favorably not less than 30 ⁇ m, more favorably in the range of 60 ⁇ m to 5 mm, still more favorably 100 ⁇ m to 3 mm.
- the catalyst according to the present invention for production of acrylic acid is generally obtained by a process comprising steps such as: a step in which a mixed liquid (being in a state of an aqueous solution or aqueous slurry) of starting materials of which the essential components include tungsten and/or copper as well as molybdenum and vanadium is dried to thus obtain a dried material; a step in which this dried material is molded with such as a liquid binder; and a step in which the resultant molding is calcined.
- the above starting materials for obtaining the oxide and/or the composite oxide are selected from among those which are commonly used for this type of catalysts, such as ammonium salts, nitrates, carbonates, chlorides, sulfates, hydroxides, organic acid salts, and oxides of the metal elements.
- the ammonium salts and the nitrates are favorably used.
- the mixed liquid of the starting materials will do if it is prepared by processes being commonly used for production of this type of catalysts. Accordingly, the starting materials are mixed in order into water to thus prepare an aqueous solution or aqueous slurry. However, in cases where at least two aqueous solutions or aqueous slurries have been prepared in accordance with the kinds of the starting materials, then it will do to mix these together in order.
- conditions of the above mixing e.g. mixing order, temperature, pressure, pH
- the mixed liquid of the starting materials, as obtained in the above way, is dried by various methods to thus form it into a dried material. Examples thereof include: a method in which the drying is carried out by heating; and a method in which the drying is carried out under reduced pressure.
- a powdery dried material may be obtained with such as spray driers and drum driers, or a blocky or flaky dried material may be obtained by heating under a gas flow with such as box type driers and tunnel type driers.
- the resultant dried material is processed, if necessary, by a pulverization step and/or classification step for obtaining a powder of an appropriate particle size and then fed to a subsequent molding step.
- the above particle size of the powder of the dried material is favorably not larger than 500 ⁇ m though not limited.
- a liquid binder can be used for molding the resultant dried material.
- the mixed liquid of the starting materials is used remaining a liquid without being dried, and this liquid is absorbed into a desired support or coated or attached onto this support, and then they are calcined. Therefore, as the mode of supporting the catalytic component onto the support, there can also be cited another mode in which the mixed liquid itself of the starting materials is supported besides the aforementioned mode in which the dried material is supported.
- binders which are commonly used for molding and supporting of this type of catalysts.
- water and besides, such as organic compounds (e.g. ethylene glycol, glycerol, propionic acid, maleic acid, benzyl alcohol, propyl alcohol, polyvinyl alcohol, phenol), nitric acid, ammonium nitrate, ammonium carbonate, and silica sol.
- organic compounds e.g. ethylene glycol, glycerol, propionic acid, maleic acid, benzyl alcohol, propyl alcohol, polyvinyl alcohol, phenol
- nitric acid e.g. ethylene glycol, glycerol, propionic acid, maleic acid, benzyl alcohol, propyl alcohol, polyvinyl alcohol, phenol
- nitric acid e.g. ethylene glycol, glycerol, propionic acid, maleic acid, benzyl alcohol, propyl alcohol, polyvinyl alcohol, phenol
- the amount of the above liquid binder being used (added) will do if it is set appropriately for such as: molding and supporting methods being adopted; and properties of the dried material powder.
- the catalyst according to the present invention it is possible to use various substances such as: molding assistants which can enhance the moldability; reinforcements for enhancing the strength of the catalyst; and pore-forming agents for formation of appropriate pores in the catalyst; wherein these various substances are commonly used for the purpose of these effects in the production of catalysts.
- these various substances include stearic acid, graphite, starch, cellulose, silica, alumina, glass fibers, silicon carbide, and silicon nitride. Those which do not exercise any bad influence on the catalytic performances (e.g. activity, selectivity of objective product) by cause of their addition are favorable.
- these various substances can be used, for example, in a way of being added to the above liquid binder and/or the mixed liquid of the starting materials to mix them together.
- these various substances if their addition amount is an excess, then there are cases where they greatly deteriorate the physical strength of the catalyst. Therefore, these various substances are added favorably in such an amount that the physical strength of the catalyst may not be deteriorated to such an extent that it becomes impossible to use the catalyst practically as an industrial catalyst.
- any inert support of a definite shape there can be used any inert support of a definite shape.
- Specific usable examples thereof include supports of definite shapes including such as alumina, silica, silica-alumina, titania, magnesia, steatite, and silicon carbide.
- the supporting ratio of the catalyst is determined appropriately with consideration given to such as: conditions of the oxidation reaction; and the activity and strength of the catalyst. However, it is favorably in the range of 10 to 70 mass %, more favorably 15 to 50 mass %.
- the supporting ratio is defined as a value determined by the calculation method as described in the below-mentioned detailed description of Examples of some preferred embodiments.
- molding methods adoptable in the molding step it will do to use hitherto publicly known methods and means.
- applicable molding methods include extrusion-molding methods (extrusion-molding machines), granulation methods (tumbling granulators, centrifugal flow coating devices), Marumerizer methods, tablet-molding methods, impregnation methods, evaporation-to-dryness methods, and spray methods. It is also possible that these methods are used in combination of appropriate selections.
- catalyst materials X and Y are separately prepared as the above at least two catalyst materials, and then thereto there can be applied such as the following processes 1) to 5): 1) a process in which the catalyst material X is tablet-molded, and then moldings obtained by this tablet-molding are used as nucleuses to further tablet-mold the catalyst material Y (nuclear tablet-molding method); 2) a process in which the catalyst material X is extrusion-molded, and then, as to moldings obtained by this extrusion-molding, the catalyst material Y is tablet-mold (nuclear tablet-molding method); 3) a process in which the catalyst material X is supported onto a support by the evaporation-to-dryness method, and then the catalyst material Y is supported thereonto by the evaporation-to-dryness method; 4) a process in which the catalyst material X is supported onto a support by the evaporation-to-dryness method, and
- heat treatment such as drying or calcination can be carried out between the molding or supporting treatments as carried out at least two times.
- the amount of the catalyst material being used during each of the molding or supporting treatments as carried out at least two times is not limited. This amount will do if it is set appropriately so that the aforementioned maldistribution of the prescribed catalytic component can be achieved (in other words, the catalyst according to the present invention can be obtained).
- the calcination temperature is favorably in the range of 350 to 450° C., more favorably 380 to 420° C., and the calcination time is favorably in the range of about 1 to about 10 hours.
- heat treatment may preliminarily be carried out at a temperature lower than the above calcination temperature.
- the process according to the present invention for production of acrylic acid is characterized in that the above catalyst according to the present invention for production of acrylic acid is used in a process in which acrylic acid is produced by catalytic gas phase oxidation of acrolein in the presence of molecular oxygen.
- acrolein is subjected to the catalytic gas phase oxidation generally in a state of a raw gas containing this acrolein.
- a mixed gas comprising acrolein, oxygen, and an inert gas can be used as a matter of course, and besides, an acrolein-containing mixed gas obtained by direct oxidation of propylene can also be used after air or oxygen and further water vapor and other gases have been added thereto if necessary.
- By-products (such as acrylic acid, acetic acid, carbon oxide, propane, or unreacted propylene) which are contained in the acrolein-containing mixed gas obtained by direct oxidation of propylene do no harm to the catalyst (being used in the present invention) for production of acrylic acid.
- the catalytic gas phase oxidation reaction in the present invention may be carried out by either of a one-pass process and a recycling process.
- reactors there can be used such as fixed-bed reactors, fluidized-bed reactors, and moving-bed reactors.
- a mixed gas comprising such as acrolein 1 to 15 volume % (favorably 4 to 12 volume %), oxygen 0.5 to 25 volume % (favorably 2 to 20 volume %), water vapor 0 to 30 volume % (favorably 0 to 25 volume %), and an inert gas (e.g. nitrogen) 20 to 80 volume % (favorably 50 to 70 volume %), is caused to contact and thereby react with the above catalyst according to the present invention for production of acrylic acid in the temperature range of 200 to 400° C.
- a mixed gas comprising such as acrolein 1 to 15 volume % (favorably 4 to 12 volume %), oxygen 0.5 to 25 volume % (favorably 2 to 20 volume %), water vapor 0 to 30 volume % (favorably 0 to 25 volume %), and an inert gas (e.g. nitrogen) 20 to 80 volume % (favorably 50 to 70 volume %), is caused to contact and thereby react with
- the present invention is more specifically illustrated by the following Examples of some preferred embodiments. However, the present invention is not limited to them in any way.
- the present invention is illustrated by supported catalysts (eggshell type catalysts) such that the catalytic component is supported only on surfaces of inert supports.
- the present invention is not limited to this type of catalysts or processes for production of acrylic acid using this type of catalysts.
- the unit “mass part(s)” may be referred to simply as “part(s)”
- the unit “liter(s)” may be referred to simply as “L”.
- Supporting ratio (mass %) [(mass of catalyst obtained ⁇ mass of support used)/mass of catalyst obtained] ⁇ 100
- Beam current 0.1 ⁇ A
- Step width (moving width) of X-ray beam 5 ⁇ m
- compositional ratio of the metal elements except oxygen in the dried material (A) having been obtained in the above way was as follows.
- Dried materials (B) to (G) were obtained in the same way as of the above process for preparation of the dried material (A) except that the amounts of the ammonium metavanadate, ammonium paratungstate, and copper nitrate trihydrate being used were changed.
- the compositional ratios of the metal elements except oxygen in these dried materials were as follows.
- a silica-alumina support of 5.0 mm in average diameter was put into a rotary dish of a dish type tumbling granulator. While the rotary dish was rotated at a revolution rate of 15 rpm in a state tilted at 30° to the horizontal plane, a 10 mass % aqueous ethylene glycol solution was sprayed to the support. After this spraying had been carried out for 10 minutes, first the dried material (A) was added and thereby supported onto the support. Subsequently, the dried material (B) was added and thereby supported onto the outside of the dried material (A), thus obtaining a supported structure.
- this supported structure was taken out and then calcined at 400° C. under an air atmosphere for 6 hours, thus obtaining a spherical catalyst (1-1).
- the dried materials (A) and (B) their amounts of addition into the tumbling granulator were adjusted so that their respective supporting ratios would be 10 mass % after the calcination.
- the resultant catalyst (1-1) was cut off into hemispheres along a plane passing through the center of the catalyst.
- a cut section of this hemispherical catalyst was analyzed with the EPMA device into tungsten and copper linearly from a one-side outer surface through the central portion to the opposite-side outer surface in the above section.
- the surface-side maldistribution ratio Ma (%) was determined from the aforementioned formula (a) with the standard position defined as 1/2r 1 .
- the core-side maldistribution ratio Mc (%) was determined from the aforementioned formula (c) with the standard position defined as 1/2r 1 .
- Their results are shown in Table 1.
- a stainless reaction tube of 25 mm in inner diameter and 800 mm in length as heated with a molten nitrate was packed with 100 mL of the catalyst (1-1). Then, a mixed gas of acrolein 4 volume %, oxygen 4 volume %, water vapor 30 volume %, and nitrogen 62 volume % was introduced into the reaction tube at a space velocity of 2,500 hr ⁇ 1 (STP) to thus carry out an oxidation reaction of acrolein continuously. During this, the reaction temperature was adjusted so that the conversion of acrolein might be maintained in the range of 98 to 99 mol %. The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of the oxidation reaction, are shown in Table 2.
- a silica-alumina support of 4.5 to 5.0 mm in diameter was put into a rotary dish of a dish type tumbling granulator. While the rotary dish was rotated at a revolution rate of 15 rpm in a state tilted at 30° to the horizontal plane, a 10 mass % aqueous ethylene glycol solution was sprayed to the support. After this spraying had been carried out for 10 minutes, the dried material (A) was added and thereby supported onto the support. The resultant supported structure was taken out and then calcined at 400° C. under an air atmosphere for 6 hours, thus obtaining a spherical catalyst (c1-1). Incidentally, as to the dried material (A), its amount of addition into the tumbling granulator was adjusted so that its supporting ratio would be 20 mass % after the calcination.
- the surface-side maldistribution ratio Ma (%) of the tungsten and the core-side maldistribution ratio Mc (%) of the copper were determined in the same way as of Example 1-1. Their results are shown in Table 1.
- a spherical catalyst (c1-2) was obtained in the same way as of the catalyst production process of Comparative Example 1-1 except that the dried material (A) was replaced with the dried material (B).
- the surface-side maldistribution ratio Ma (%) of the tungsten and the core-side maldistribution ratio Mc (%) of the copper were determined in the same way as of Example 1-1. Their results are shown in Table 1.
- a spherical catalyst (c1-3) was obtained in the same way as of the catalyst production process of Comparative Example 1-1 except that the dried material (A) was replaced with a mixed powder having been obtained by uniformly mixing the dried materials (A) and (B) in equal quantities together.
- the dried materials (A) and (B) their amounts of addition into the tumbling granulator were adjusted so that their respective supporting ratios would be 10 mass % after the calcination.
- the surface-side maldistribution ratio Ma (%) of the tungsten and the core-side maldistribution ratio Mc (%) of the copper were determined in the same way as of Example 1-1. Their results are shown in Table 1.
- a spherical catalyst (1-2) was obtained in the same way as of the catalyst production process of Example 1-1 except that the dried material (B) was replaced with the dried material (C).
- the surface-side maldistribution ratio Ma (%) of the tungsten and the core-side maldistribution ratio Mc (%) of the copper were determined in the same way as of Example 1-1. Their results are shown in Table 1.
- a spherical catalyst (c1-4) was obtained in the same way as of the catalyst production process of Comparative Example 1-1 except that the dried material (A) was replaced with the dried material (C).
- the surface-side maldistribution ratio Ma (%) of the tungsten and the core-side maldistribution ratio Mc (%) of the copper were determined in the same way as of Example 1-1. Their results are shown in Table 1.
- a spherical catalyst (r1-1) was obtained in the same way as of the catalyst production process of Example 1-1 except that the dried material (B) was replaced with the dried material (A), and that the dried material (A) was replaced with the dried material (C).
- the surface-side maldistribution ratio Ma (%) of the tungsten and the core-side maldistribution ratio Mc (%) of the copper were determined in the same way as of Example 1-1. Their results are shown in Table 1.
- Spherical catalysts (1-3), (1-4), and (1-5) were obtained in the same way as of the catalyst production process of Example 1-1 except that the dried material (B) was replaced with the dried materials (D), (E), and (F) respectively.
- Oxidation reactions were carried out in the same way as of Example 1-1 except that the catalyst (1-1) was replaced with the catalysts (1-3), (1-4), and (1-5) respectively.
- the reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of each oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of each oxidation reaction, are shown in Table 2.
- Spherical catalysts (1-6), (1-7), (1-8), and (1-9) were obtained in the same way as of the catalyst production process of Example 1-1 except that the dried material (A) was replaced with the dried material (B) or (C) respectively, and that the dried material (B) was replaced with the dried material (E) or (F) respectively (for the specific combinations of the dried materials used, refer to Table 1 or 2).
- Oxidation reactions were carried out in the same way as of Example 1-1 except that the catalyst (1-1) was replaced with the catalysts (1-6), (1-7), (1-8), and (1-9) respectively.
- the reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of each oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of each oxidation reaction, are shown in Table 2.
- a stainless reaction tube of 25 mm in inner diameter and 3,000 mm in length as heated with a molten nitrate was packed with 1,000 mL of the catalyst (1-2). Then, a mixed gas of acrolein 5 volume %, air 25 volume %, water vapor 30 volume %, and an inert gas (e.g. nitrogen) 40 volume % was introduced into the reaction tube at a space velocity of 1,600 hr (STP) to thus carry out an oxidation reaction.
- STP space velocity 1,600 hr
- a silica-alumina support of 5.0 mm in average diameter was put into a rotary dish of a dish type tumbling granulator. While the rotary dish was rotated at a revolution rate of 15 rpm in a state tilted at 30° to the horizontal plane, a 10 mass % aqueous ethylene glycol solution was sprayed to the support. After this spraying had been carried out for 10 minutes, first the dried material (A) was added and thereby supported onto the support. Subsequently, the dried material (G) was added and thereby supported onto the outside of the dried material (A), thus obtaining a supported structure.
- this supported structure was taken out and then calcined at 400° C. under an air atmosphere for 6 hours, thus obtaining a spherical catalyst (2-1).
- the dried materials (A) and (G) their amounts of addition into the tumbling granulator were adjusted so that their respective supporting ratios would be 10 mass % after the calcination.
- the resultant catalyst (2-1) was cut off into hemispheres along a plane passing through the center of the catalyst.
- a cut section of this hemispherical catalyst was analyzed with the EPMA device into vanadium linearly from a one-side outer surface through the central portion to the opposite-side outer surface in the above section.
- the surface-side maldistribution ratio Ma (%) was determined from the aforementioned formula (a) with the standard position defined as 1/2r 1 . Its results are shown in Table 3.
- a stainless reaction tube of 25 mm in inner diameter and 800 mm in length as heated with a molten nitrate was packed with 100 mL of the catalyst (2-1). Then, a mixed gas of acrolein 4 volume %, oxygen 4 volume %, water vapor 30 volume %, and nitrogen 62 volume % was introduced into the reaction tube at a space velocity of 2,500 hr ⁇ 1 (STP) to thus carry out an oxidation reaction of acrolein continuously. During this, the reaction temperature was adjusted so that the conversion of acrolein might be maintained in the range of 98 to 99 mol %. The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of the oxidation reaction, are shown in Table 4.
- a silica-alumina support of 4.5 to 5.0 mm in diameter was put into a rotary dish of a dish type tumbling granulator. While the rotary dish was rotated at a revolution rate of 15 rpm in a state tilted at 30° to the horizontal plane, a 10 mass % aqueous ethylene glycol solution was sprayed to the support. After this spraying had been carried out for 10 minutes, the dried material (A) was added and thereby supported onto the support. The resultant supported structure was taken out and then calcined at 400° C. under an air atmosphere for 6 hours, thus obtaining a spherical catalyst (c2-1). Incidentally, as to the dried material (A), its amount of addition into the tumbling granulator was adjusted so that its supporting ratio would be 20 mass % after the calcination.
- a spherical catalyst (c2-2) was obtained in the same way as of the catalyst production process of Comparative Example 2-1 except that the dried material (A) was replaced with the dried material (G).
- a spherical catalyst (c2-3) was obtained in the same way as of the catalyst production process of Comparative Example 2-1 except that the dried material (A) was replaced with a mixed powder having been obtained by uniformly mixing the dried materials (A) and (G) in equal quantities together.
- the dried materials (A) and (G) their amounts of addition into the tumbling granulator were adjusted so that their respective supporting ratios would be 10 mass % after the calcination.
- Example 2-1 An oxidation reaction was carried out in the same way as of Example 2-1 except that the catalyst (2-1) was replaced with the catalyst (c2-3).
- the reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of the oxidation reaction, are shown in Table 4.
- a spherical catalyst (r2-1) was obtained in the same way as of the catalyst production process of Example 2-1 except that the dried material (A) was replaced with the dried material (G), and that the dried material (G) was replaced with the dried material (A).
- a stainless reaction tube of 25 mm in inner diameter and 3,000 mm in length as heated with a molten nitrate was packed with 1,000 mL of the catalyst (2-1). Then, a mixed gas of acrolein 5 volume %, air 25 volume %, water vapor 30 volume %, and an inert gas (e.g. nitrogen) 40 volume % was introduced into the reaction tube at a space velocity of 1,600 hr ⁇ 1 (STP) to thus carry out an oxidation reaction.
- STP space velocity 1,600 hr ⁇ 1
- a silica-alumina support of 5.0 mm in average diameter was put into a rotary dish of a dish type tumbling granulator. While the rotary dish was rotated at a revolution rate of 15 rpm in a state tilted at 30° to the horizontal plane, a 10 mass % aqueous ethylene glycol solution was sprayed to the support. After this spraying had been carried out for 10 minutes, first the dried material (B) was added and thereby supported onto the support. Subsequently, the dried material (A) was added and thereby supported onto the outside of the dried material (B), thus obtaining a supported structure.
- this supported structure was taken out and then calcined at 400° C. under an air atmosphere for 6 hours, thus obtaining a spherical catalyst (3-1).
- the dried materials (A) and (B) their amounts of addition into the tumbling granulator were adjusted so that their respective supporting ratios would be 10 mass % after the calcination.
- the resultant catalyst (3-1) was cut off into hemispheres along a plane passing through the center of the catalyst.
- a cut section of this hemispherical catalyst was analyzed with the EPMA device into copper and tungsten linearly from a one-side outer surface through the central portion to the opposite-side outer surface in the above section.
- the surface-side maldistribution ratio Ma (%) was determined from the aforementioned formula (a) with the standard position defined as 1/2r 1 .
- the core-side maldistribution ratio Mc (%) was determined from the aforementioned formula (c) with the standard position defined as 1/2r 1 .
- Their results are shown in Table 5.
- a stainless reaction tube of 25 mm in inner diameter and 800 mm in length as heated with a molten nitrate was packed with 100 mL of the catalyst (3-1). Then, a mixed gas of acrolein 4 volume %, oxygen 4 volume %, water vapor 30 volume %, and nitrogen 62 volume % was introduced into the reaction tube at a space velocity of 2,500 hr ⁇ 1 (STP) to thus carry out an oxidation reaction of acrolein continuously. During this, the reaction temperature was adjusted so that the conversion of acrolein might be maintained in the range of 98 to 99 mol %. The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction are shown in Table 6.
- a silica-alumina support of 4.5 to 5.0 mm in diameter was put into a rotary dish of a dish type tumbling granulator. While the rotary dish was rotated at a revolution rate of 15 rpm in a state tilted at 30° to the horizontal plane, a 10 mass % aqueous ethylene glycol solution was sprayed to the support. After this spraying had been carried out for 10 minutes, the dried material (A) was added and thereby supported onto the support. The resultant supported structure was taken out and then calcined at 400° C. under an air atmosphere for 6 hours, thus obtaining a spherical catalyst (c3-1). Incidentally, as to the dried material (A), its amount of addition into the tumbling granulator was adjusted so that its supporting ratio would be 20 mass % after the calcination.
- the surface-side maldistribution ratio Ma (%) of the copper and the core-side maldistribution ratio Mc (%) of the tungsten were determined in the same way as of Example 3-1. Their results are shown in Table 5.
- a spherical catalyst (c3-2) was obtained in the same way as of the catalyst production process of Comparative Example 3-1 except that the dried material (A) was replaced with the dried material (B).
- the surface-side maldistribution ratio Ma (%) of the copper and the core-side maldistribution ratio Mc (%) of the tungsten were determined in the same way as of Example 3-1. Their results are shown in Table 5.
- a spherical catalyst (c3-3) was obtained in the same way as of the catalyst production process of Comparative Example 3-1 except that the dried material (A) was replaced with a mixed powder having been obtained by uniformly mixing the dried materials (A) and (B) in equal quantities together.
- the dried materials (A) and (B) their amounts of addition into the tumbling granulator were adjusted so that their respective supporting ratios would be 10 mass % after the calcination.
- the surface-side maldistribution ratio Ma (%) of the copper and the core-side maldistribution ratio Mc (%) of the tungsten were determined in the same way as of Example 3-1. Their results are shown in Table 5.
- a spherical catalyst (3-2) was obtained in the same way as of the catalyst production process of Example 3-1 except that the dried material (B) was replaced with the dried material (C).
- the surface-side maldistribution ratio Ma (%) of the copper and the core-side maldistribution ratio Mc (%) of the tungsten were determined in the same way as of Example 3-1. Their results are shown in Table 5.
- a spherical catalyst (c3-4) was obtained in the same way as of the catalyst production process of Comparative Example 3-1 except that the dried material (A) was replaced with the dried material (C).
- the surface-side maldistribution ratio Ma (%) of the copper and the core-side maldistribution ratio Mc (%) of the tungsten were determined in the same way as of Example 3-1. Their results are shown in Table 5.
- a spherical catalyst (r3-1) was obtained in the same way as of the catalyst production process of Example 3-1 except that the dried material (B) was replaced with the dried material (A), and that the dried material (A) was replaced with the dried material (C).
- the surface-side maldistribution ratio Ma (%) of the copper and the core-side maldistribution ratio Mc (%) of the tungsten were determined in the same way as of Example 3-1. Their results are shown in Table 5.
- a spherical catalyst (r3-2) was obtained in the same way as of the catalyst production process of Example 3-1 except that the dried material (B) was replaced with the dried material (C), and that the dried material (A) was replaced with the dried material (F).
- the surface-side maldistribution ratio Ma (%) of the copper and the core-side maldistribution ratio Mc (%) of the tungsten were determined in the same way as of Example 3-1. Their results are shown in Table 5.
- Spherical catalysts (3-3) and (3-4) were obtained in the same way as of the catalyst production process of Example 3-1 except that the dried material (B) was replaced with the dried materials (E) and (F) respectively.
- Oxidation reactions were carried out in the same way as of Example 3-1 except that the catalyst (3-1) was replaced with the catalysts (3-3) and (3-4) respectively.
- the reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of each oxidation reaction are shown in Table 6.
- Spherical catalysts (3-5), (3-6), (3-7), and (3-8) were obtained in the same way as of the catalyst production process of Example 3-1 except that the dried material (B) was replaced with either of the dried materials (E) and (F) respectively, and that the dried material (A) was replaced with either of the dried materials (B) and (C) respectively (for the specific combinations of the dried materials used, refer to Tables 5 and 6).
- Oxidation reactions were carried out in the same way as of Example 3-1 except that the catalyst (3-1) was replaced with the catalysts (3-5), (3-6), (3-7), and (3-8) respectively.
- the reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of each oxidation reaction are shown in Table 6.
- a stainless reaction tube of 25 mm in inner diameter and 3,000 mm in length as heated with a molten nitrate was packed with 1,000 mL of the catalyst (3-2). Then, a mixed gas of acrolein 5 volume %, air 25 volume %, water vapor 30 volume %, and an inert gas (e.g. nitrogen) 40 volume % was introduced into the reaction tube at a space velocity of 1,600 hr ⁇ 1 (STP) to thus carry out an oxidation reaction.
- STP space velocity 1,600 hr ⁇ 1
- a silica-alumina support of 5.0 mm in average diameter was put into a rotary dish of a dish type tumbling granulator. While the rotary dish was rotated at a revolution rate of 15 rpm in a state tilted at 30° to the horizontal plane, a 10 mass % aqueous ethylene glycol solution was sprayed to the support. After this spraying had been carried out for 10 minutes, first the dried material (G) was added and thereby supported onto the support. Subsequently, the dried material (A) was added and thereby supported onto the outside of the dried material (G), thus obtaining a supported structure.
- this supported structure was taken out and then calcined at 400° C. under an air atmosphere for 6 hours, thus obtaining a spherical catalyst (4-1).
- the dried materials (A) and (G) their amounts of addition into the tumbling granulator were adjusted so that their respective supporting ratios would be 10 mass % after the calcination.
- the resultant catalyst (4-1) was cut off into hemispheres along a plane passing through the center of the catalyst.
- a cut section of this hemispherical catalyst was analyzed with the EPMA device into vanadium linearly from a one-side outer surface through the central portion to the opposite-side outer surface in the above section.
- Mc the core-side maldistribution ratio
- a stainless reaction tube of 25 mm in inner diameter and 800 mm in length as heated with a molten nitrate was packed with 100 mL of the catalyst (4-1). Then, a mixed gas of acrolein 4 volume %, oxygen 4 volume %, water vapor 30 volume %, and nitrogen 62 volume % was introduced into the reaction tube at a space velocity of 2,500 hr ⁇ 1 (STP) to thus carry out an oxidation reaction of acrolein continuously. During this, the reaction temperature was adjusted so that the conversion of acrolein might be maintained in the range of 98 to 99 mol %. The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction are shown in Table 8.
- a silica-alumina support of 4.5 to 5.0 mm in diameter was put into a rotary dish of a dish type tumbling granulator. While the rotary dish was rotated at a revolution rate of 15 rpm in a state tilted at 30° to the horizontal plane, a 10 mass % aqueous ethylene glycol solution was sprayed to the support. After this spraying had been carried out for 10 minutes, the dried material (A) was added and thereby supported onto the support. The resultant supported structure was taken out and then calcined at 400° C. under an air atmosphere for 6 hours, thus obtaining a spherical catalyst (c4-1). Incidentally, as to the dried material (A), its amount of addition into the tumbling granulator was adjusted so that its supporting ratio would be 20 mass % after the calcination.
- a spherical catalyst (c4-2) was obtained in the same way as of the catalyst production process of Comparative Example 4-1 except that the dried material (A) was replaced with the dried material (G).
- a spherical catalyst (c4-3) was obtained in the same way as of the catalyst production process of Comparative Example 4-1 except that the dried material (A) was replaced with a mixed powder having been obtained by uniformly mixing the dried materials (A) and (G) in equal quantities together.
- the dried materials (A) and (G) their amounts of addition into the tumbling granulator were adjusted so that their respective supporting ratios would be 10 mass % after the calcination.
- a spherical catalyst (r4-1) was obtained in the same way as of the catalyst production process of Example 4-1 except that the dried material (G) was replaced with the dried material (A), and that the dried material (A) was replaced with the dried material (G).
- a stainless reaction tube of 25 mm in inner diameter and 3,000 mm in length as heated with a molten nitrate was packed with 1,000 mL of the catalyst (4-1). Then, a mixed gas of acrolein 5 volume %, air 25 volume %, water vapor 30 volume %, and an inert gas (e.g. nitrogen) 40 volume % was introduced into the reaction tube at a space velocity of 1,600 hr ⁇ 1 (STP) to thus carry out an oxidation reaction.
- STP space velocity 1,600 hr ⁇ 1
- the catalyst according to the present invention is favorable as a catalyst for production of acrylic acid.
- the production process according to the present invention is favorable for production of acrylic acid.
Abstract
An object of the present invention is to provide: a catalyst for production of acrylic acid which catalyst is so high active as to give a still higher selectivity of acrylic acid (which is the objective product) or a long-catalytic-life-time catalyst for production of acrylic acid which catalyst is so high active as to be able to give a high acrylic acid yield while suppressing the temperature rise of the oxidation reaction to a low one; and processes for production of acrylic acid using these catalysts. As a means of achieving this object, a catalyst according to the present invention for production of acrylic acid comprises an oxide and/or a composite oxide as an essential catalytic component, wherein the oxide and/or the composite oxide has a metal element composition shown by general formula (1):
MoaVbWcCudOx (1)
- (wherein: when a=12, then 1≦b≦14, 0≦c≦12, 0≦d≦10, and 0<c+d; and x is a numerical value determined by oxidation states of the elements);
- with the catalyst being characterized in that any of the vanadium, tungsten, and copper is maldistributed in the surface side or core side of the catalyst.
Description
- A. Technical Field
- The present invention relates to a catalyst for production of acrylic acid and a process for production of acrylic acid using this catalyst.
- B. Background Art
- As to catalysts for efficient production of acrylic acid by catalytic gas phase oxidation of acrolein (catalysts for production of acrylic acid), there is widely used a catalyst comprising molybdenum and vanadium as essential catalytic components, and various proposals have been made about its production processes.
- Examples of these production processes include: (a) a process in which a mixed liquid of starting materials is subjected to evaporation to dryness, and then, to the resultant dried material, there are added polyvinyl alcohol, a water-absorbent resin, and water, and then they are kneaded together and then extrusion-molded (e.g. refer to patent document 1 below); (b) a process in which a mixed liquid of starting materials is spray-dried and then calcined at 400° C., and then the resultant calcined material is supported onto a support with water as a binder by use of such as a rotary drum type supporting device (e.g. refer to patent document 2 below); (c) a process in which a mixed liquid of starting materials is dried by any method of evaporation to dryness, spray drying, drum drying, and gas flow drying, and then, to the resultant dried material, there are added propyl alcohol and water to mix them together, and then the resultant mixture is extrusion-molded (e.g. refer to patent document 3 below); (d) a process in which a mixed liquid of starting materials is spray-dried and then calcined at 400° C., and then the resultant calcined material is supported onto a support with a liquid binder comprising water and an organic compound of higher than 100° C. in boiling point or sublimation temperature under normal pressure (e.g. refer to patent document 4 below); and (e) a process in which a mixed liquid of starting materials is dried and then calcined at 250-500° C., and then the resultant calcined material is supported onto a support with such as aqueous glycerol solution as a binder by use of a tumbling granulator (e.g. refer to patent documents 5 and 6 below).
- [Patent Document 1] JP-A-096183/1993 (Kokai)
- [Patent Document 2] JP-A-279030/1994 (Kokai)
- [Patent Document 3] JP-A-010621/1996 (Kokai)
- [Patent Document 4] JP-A-252464/1996 (Kokai)
- [Patent Document 5] JP-A-299797/1996 (Kokai)
- [Patent Document 6] JP-A-079408/2001 (Kokai)
- However, still none of the catalysts for production of acrylic acid which catalysts are obtained by the above prior production processes is sufficient in a point of the selectivity of acrylic acid which is the objective product. Furthermore, still none of these catalysts can be said to be sufficient also in a point that chemical and physical properties (e.g. properties such as specific surface area, pore volume, pore distribution, acidity/basicity, acid strength/basic strength) of the catalysts are stable for a long time and further that the catalysts enable the efficient production of acrylic acid. Therefore, there has been much room for their improvements.
- Thus, an object of the present invention is to provide: a catalyst for production of acrylic acid which catalyst is so high active as to give a still higher selectivity of acrylic acid (which is the objective product) or a long-catalytic-life-time catalyst for production of acrylic acid which catalyst is so high active as to be able to give a high acrylic acid yield while suppressing the temperature rise of the oxidation reaction to a low one; and processes for production of acrylic acid using these catalysts.
- The present inventors diligently studied to solve the above problems. In its process, they have found out that the aforementioned problems can be solved all at once by arranging that tungsten and/or copper besides molybdenum and vanadium should be used as essential metal elements constituting the catalyst and further that a specific metal element should be maldistributed in the surface side and/or core side of the catalyst. In detail, they have found out that: first, if it is arranged that the tungsten should be maldistributed in the surface side of the catalyst and/or the copper should be maldistributed in the core side of the catalyst, then the activity of the catalyst is enhanced and the aforementioned properties of the catalyst are stabilized for a long time; secondly, if it is arranged that the vanadium should be maldistributed in the surface side of the catalyst, then the activity of the catalyst is enhanced and the aforementioned properties of the catalyst are stabilized for a long time; thirdly, if it is arranged that the copper should be maldistributed in the surface side of the catalyst and/or the tungsten should be maldistributed in the core side of the catalyst, then the selectivity of acrylic acid which is the objective product becomes still higher; and fourthly, if it is arranged that the vanadium should be maldistributed in the core side of the catalyst, then the selectivity of acrylic acid which is the objective product becomes still higher. That is to say, if the metal element is maldistributed like in the aforementioned first and second arrangements, then there can be obtained a selectivity of acrylic acid which selectivity is equal to or higher than prior ones while the temperature rise of the oxidation reaction is suppressed to a low one, so that, for a long time, the catalytic life time can be kept and a high acrylic acid yield can be given. On the other hand, if the metal element is maldistributed like in the aforementioned third and fourth arrangements, then there can be obtained a still higher selectivity of acrylic acid. Then, they have completed the present invention by confirming these findings.
- Accordingly, a first catalyst according to the present invention for production of acrylic acid comprises an oxide and/or a composite oxide as an essential catalytic component, wherein the oxide and/or the composite oxide has a metal element composition shown by the following general formula (I):
-
MoaVbWcCudOx (1) - (wherein: Mo is molybdenum; V is vanadium; W is tungsten; Cu is copper; and O is oxygen; and a, b, c, d, and x denote atomic ratios of Mo, V, W, Cu, and O respectively; when a=12, then 1≦b≦14, 0≦c≦12, 0≦d≦10, and 0<c+d; and x is a numerical value determined by oxidation states of the elements);
with the catalyst being characterized in that: the tungsten is maldistributed in the surface side of the catalyst; and/or the copper is maldistributed in the core side of the catalyst. - A second catalyst according to the present invention for production of acrylic acid comprises an oxide and/or a composite oxide as an essential catalytic component, wherein the oxide and/or the composite oxide has a metal element composition shown by the following general formula (1):
-
MoaVbWcCudOx (1) - (wherein: Mo is molybdenum; V is vanadium; W is tungsten; Cu is copper; and O is oxygen; and a, b, c, d, and x denote atomic ratios of Mo, V, W, Cu, and O respectively; when a=12, then 1≦b≦14, 0≦c≦12, 0≦d≦10, and 0<c+d; and x is a numerical value determined by oxidation states of the elements); with the catalyst being characterized in that the vanadium is maldistributed in the surface side of the catalyst.
- A third catalyst according to the present invention for production of acrylic acid comprises an oxide and/or a composite oxide as an essential catalytic component, wherein the oxide and/or the composite oxide has a metal element composition shown by the following general formula (1):
-
MoaVbWcCudOx (1) - (wherein: Mo is molybdenum; V is vanadium; W is tungsten; Cu is copper; and O is oxygen; and a, b, c, d, and x denote atomic ratios of Mo, V, W, Cu, and O respectively; when a=12, then 1≦b≦14, 0≦c≦12, 0≦d≦10, and 0<c+d; and x is a numerical value determined by oxidation states of the elements);
with the catalyst being characterized in that: the copper is maldistributed in the surface side of the catalyst; and/or the tungsten is maldistributed in the core side of the catalyst. - A fourth catalyst according to the present invention for production of acrylic acid comprises an oxide and/or a composite oxide as an essential catalytic component, wherein the oxide and/or the composite oxide has a metal element composition shown by the following general formula (I):
-
MoaVbWcCudOx (1) - (wherein: Mo is molybdenum; V is vanadium; W is tungsten; Cu is copper; and O is oxygen; and a, b, c, d, and x denote atomic ratios of Mo, V, W, Cu, and O respectively; when a=12, then 1≦b≦14, 0≦c≦12, 0≦d≦10, and 0<c+d; and x is a numerical value determined by oxidation states of the elements);
with the catalyst being characterized in that the vanadium is maldistributed in the core side of the catalyst. - In addition, processes according to the present invention for production of acrylic acid are characterized in that the above catalysts according to the present invention for production of acrylic acid (first, second, third, and fourth catalysts for production of acrylic acid) are used when acrylic acid is produced by catalytic gas phase oxidation of acrolein in the presence of molecular oxygen.
- The present invention can provide, in a long-time oxidation reaction of acrolein, a catalyst for production of acrylic acid which catalyst gives a still higher selectivity of acrylic acid (which is the objective product) or a long-catalytic-life-time catalyst for production of acrylic acid which catalyst is able to give a high acrylic acid yield while suppressing the temperature rise of the oxidation reaction to a low one. In detail, the first or second catalyst according to the present invention for production of acrylic acid is a long-catalytic-life-time catalyst which is able to give a high acrylic acid yield while suppressing the temperature rise of the oxidation reaction to a low one, and the third or fourth catalyst according to the present invention for production of acrylic acid is a catalyst which gives a still higher selectivity of acrylic acid which is the objective product. In addition, the present invention can provide processes for production of acrylic acid using these catalysts.
- These and other objects and advantages of the present invention will be more fully apparent from the following detailed disclosure.
- Hereinafter, detailed descriptions are given about the catalyst according to the present invention for production of acrylic acid and the process according to the present invention for production of acrylic acid using this catalyst. However, the scope of the present invention is not bound to these descriptions. And other than the following illustrations can also be carried out in the form of appropriate modifications of the following illustrations within the scope not departing from the spirit of the present invention.
- Any of the first, second, third, and fourth catalysts according to the present invention for production of acrylic acid (which may hereinafter be referred to generically as “catalyst according to the present invention”) is a catalyst comprising an oxide and/or a composite oxide as an essential catalytic component, wherein the oxide and/or the composite oxide has a metal element composition shown by the aforementioned general formula (I). On top of that, as is aforementioned, as to the first catalyst for production of acrylic acid (which may hereinafter be referred to as “first catalyst”), it is important that: the tungsten is maldistributed in the surface side of the aforementioned catalyst (which may hereinafter be referred to simply as “surface side”), and/or the copper is maldistributed in the core side of the aforementioned catalyst (which may hereinafter be referred to simply as “core side”). As to the second catalyst for production of acrylic acid (which may hereinafter be referred to as “second catalyst”), it is important that the vanadium is maldistributed in the surface side of the aforementioned catalyst. As to the third catalyst for production of acrylic acid (which may hereinafter be referred to as “third catalyst”), it is important that: the copper is maldistributed in the surface side of the aforementioned catalyst, and/or the tungsten is maldistributed in the core side of the aforementioned catalyst. As to the fourth catalyst for production of acrylic acid (which may hereinafter be referred to as “fourth catalyst”), it is important that the vanadium is maldistributed in the core side of the aforementioned catalyst. If the metal element is maldistributed like in the first and second catalysts, then there can be obtained a selectivity of acrylic acid which selectivity is equal to or higher than prior ones while the temperature rise of the oxidation reaction is suppressed to a low one, so that, for a long time, the catalytic life time can be kept and a high acrylic acid yield can be given. On the other hand, if the metal element is maldistributed like in the third and fourth catalysts, then there can be obtained a still higher selectivity of acrylic acid (than those given by the aforementioned first and second catalysts). In addition, in the present invention, the above metal element composition may include an optional component (e.g. niobium, chromium, manganese, iron, cobalt, nickel, zinc, bismuth, tin, antimony) besides the metal elements shown in the general formula (1) (Mo, V, W, and Cu).
- Hereinafter, as to the catalyst according to the present invention, a metal element maldistributed in the surface side (i.e. tungsten in the case of the first catalyst, vanadium in the case of the second catalyst, and copper in the case of the third catalyst) may be referred to as “metal element (α)”, and a metal element maldistributed in the core side (i.e. copper in the case of the first catalyst, tungsten in the case of the third catalyst, and vanadium in the case of the fourth catalyst) may be referred to as “metal element (β)”.
- The form of the catalyst according to the present invention is not limited. For example, it may be as follows:
- 1) a catalyst obtained by molding (e.g. extrusion molding) of catalyst materials including the catalytic component, specifically, a catalyst which is a molding that comprises the catalytic component as an essential constitutional material without any support as a constitutional material (this catalyst may hereinafter be referred to as molded catalyst); or
- 2) a catalyst obtained by supporting of catalyst materials including the catalytic component onto a support, specifically, a catalyst which comprises both the catalytic component and a support as essential constitutional materials wherein the above catalytic component is supported on surfaces of the above support and/or inside it (this catalyst may hereinafter be referred to as supported catalyst).
- Above all, examples of the form of the supported catalyst cited as 2) above include:
- 2-1) what is called eggshell type catalyst such that: the catalytic component is supported on surfaces of the support (surface-supported) (it will do that the catalytic component is supported substantially on surfaces of the support, and a part of the catalytic component may exist inside the support), and there is substantially seen a change of property in shape between the original support and the resultant catalyst (specifically, for example, the particle diameter, after the supporting of the catalytic component, is larger than that of the original support alone); and
- 2-2) a catalyst such that: such as a porous and inside-supportable support is used as the support, and the catalytic component is supported at least inside the support (for example, only inside the support, or both inside the support and on its surfaces).
- Furthermore, examples of the form of the supported catalyst cited as 2-2) above include:
- 2-2-1) what is called uniform type catalyst such that: the catalytic component is supported only inside the support (inside-supported) (it will do that the catalytic component is supported substantially only inside the support, and a part of the catalytic component may exist on surfaces of the support), and there is seen substantially no change of property in shape between the original support and the resultant catalyst (specifically, for example, the particle diameter, after the supporting of the catalytic component, is the same as that of the original support alone); and
- 2-2-2) a catalyst such that the above two kinds of forms 2-1) and 2-2-1) are combined together, specifically, a combined type catalyst (catalyst of a type in combination of the uniform type and the eggshell type) such that the catalytic component is supported both inside the support and on its surfaces.
- Examples of the shape of the catalyst according to the present invention include any shape of such as spheres (including, besides true spheres, other spheres such as flat spheres (such as formed by squashing spheres flat) (e.g. oval spheres) and substantial spheres), pillars (e.g. cylinders, oval cylinders, prisms), (regular) polyhedrons (e.g. dice), rings, and irregular shapes.
- Though not limited, the particle diameter (average outer diameter) of the catalyst according to the present invention is favorably in the range of 1 to 15 mm, more favorably 3 to 10 mm. Incidentally, the “average outer diameter” in the present invention is defined as referring to the average of lengths of the longest and shortest portions of the catalyst in particle diameter. For example, as to a truly spherical catalyst, the diameter and the average outer diameter are the same as each other. However, as to a non-truly-spherical catalyst, the average of the longest and shortest outer diameters is the average outer diameter.
- In addition, as to cases where the catalyst according to the present invention is the eggshell type catalyst previously cited as 2-1), it is favorable that the thickness of the catalytic component supported on the support is not less than a definite value in any portion. Specifically, the above thickness is favorably not less than 30 μm, more favorably in the range of 60 μm to 5 mm, still more favorably 100 μm to 3 mm.
- The degree of the above maldistribution in the catalyst according to the present invention is as follows. As to the maldistribution of the metal element (α) in the surface side (maldistribution of tungsten in the case of the first catalyst, maldistribution of vanadium in the case of the second catalyst, or maldistribution of copper in the case of the third catalyst), it will do if the metal element (a) (tungsten (tungsten element) in the case of the first catalyst, vanadium (vanadium element) in the case of the second catalyst, copper (copper element) in the case of the third catalyst) contained in the catalytic component is maldistributed in the surface side in an amount larger than half the total content of the metal element (α). On the other hand, as to the maldistribution of the metal element (β) in the core side (maldistribution of copper in the case of the first catalyst, maldistribution of tungsten in the case of the third catalyst, or maldistribution of vanadium in the case of the fourth catalyst), it will do if the metal element (β) (copper (copper element) in the case of the first catalyst, tungsten (tungsten element) in the case of the third catalyst, vanadium (vanadium element) in the case of the fourth catalyst) contained in the catalytic component is maldistributed in the core side in an amount larger than half the total content of the metal element (β). The aforementioned problems can easily be solved by maldistributing the prescribed metal element in the surface side or core side in this way.
- In the present invention, that the metal element (α) is maldistributed in the surface side is defined as meaning that the metal element (α) among the aforementioned various metal elements contained in the catalytic component is maldistributed in the surface side. In detail, it is defined as meaning that the above metal element (α) is maldistributed in a surface layer portion of the catalyst for production of acrylic acid and/or in the neighborhood of this portion. In more detail, it is defined as meaning that the above metal element (α) is distributed mainly in the above surface layer portion and/or mainly in the neighborhood of this surface layer portion with a distribution range of some degree of broadness in the deeper direction than this surface layer portion. Incidentally, the definition of the maldistribution in the surface side, as hereupon referred to, is similarly applicable to all regardless of the types of the aforementioned various forms of the catalyst (e.g. the eggshell type previously cited as 2-1), the uniform type previously cited as 2-2-1), the combined type previously cited as 2-2-2), and the molded type previously cited as 1)).
- In the present invention, that the metal element (β) is maldistributed in the core side is defined as meaning that the metal element (β) among the aforementioned various metal elements contained in the catalytic component is maldistributed in the core side. In detail, it can be defined as follows in accordance with the types of the aforementioned forms of the catalyst.
- That is to say, in cases where the catalyst according to the present invention is the eggshell type catalyst previously cited as 2-1), then that the metal element (β) is maldistributed in the core side is defined as meaning that, in the catalyst for production of acrylic acid, the above metal element (β) is maldistributed in a portion, contacting with the surfaces of the support, of the catalytic component supported on the support and/or in the neighborhood of this portion. In more detail, it is defined as meaning that the above metal element (β) is distributed mainly in the above contacting portion and/or mainly in the neighborhood of this contacting portion with a distribution range of some degree of broadness in the depth direction opposite to this contacting portion.
- On the other hand, in cases where the catalysts according to the present invention are the uniform type previously cited as 2-2-1), the combined type previously cited as 2-2-2), and the molded type previously cited as 1), then that the metal element (β) is maldistributed in the core side is defined as meaning that the above metal element (β) is maldistributed in a central portion of the catalyst for production of acrylic acid and/or in the neighborhood of this portion. In more detail, it is defined as meaning that the above metal element (β) is distributed mainly in the above central portion and/or mainly in the neighborhood of this central portion with a distribution range of some degree of broadness from this central portion up to its periphery.
- As to the catalysts according to the present invention, the maldistribution of the prescribed metal elements (metal element (α) and metal element (β)) (contained in the catalytic component) in the surface side and in the core side can be evaluated by measurement using an EPMA (Electron Probe Micro Analyzer) device in accordance with such methods and standards as shown in (i) to (iii) below. In detail, whether the metal element (α) is maldistributed in the surface side or not (the surface-side maldistribution ratio of the metal element (α)) can be evaluated by (i) and (ii) below. Whether the metal element (β) is maldistributed in the core side or not (the core-side maldistribution ratio of the metal element (β)) can be evaluated by (i) and (iii) below. In (i) to (iii) below, measurement conditions and evaluation methods are described in accordance with the types of the forms of the catalyst. Incidentally, also in the below-mentioned detailed description of Examples of some preferred embodiments, the evaluation of the surface-side maldistribution ratio of the metal element (α) and the evaluation of the core-side maldistribution ratio of the metal element (β) shall be carried out by the below-mentioned methods.
- (i) The prescribed metal element (metal element (α) or metal element (β)) is individually examined analytically by the measurement using the EPMA device. Specifically, a section including the central portion of the catalyst is targeted and measured (linear-analytically measured) into the prescribed metal element (metal element (α) or metal element (β)) continuously from a one-side outer surface to the opposite-side outer surface in the central-portion-through direction in the above section; Next, the following drawing figure (graph) is obtained in accordance with the types of the forms of the catalyst.
- That is to say, in cases where the catalyst according to the present invention is the eggshell type catalyst previously cited as 2-1), then the range of from the support surface to the above outer surface in the measurement position range of from the above central portion to the above outer surfaces is taken as the position range to be analyzed, and there is obtained a drawing figure (graph) which shows relations between the distance r1 (x-axis) of from the above support surface (x=0) to the above outer surface (x=r1) and the X-ray intensity I (y-axis) being measured correspondingly to the existence amount of the prescribed metal element.
- On the other hand, in cases where the catalysts according to the present invention are the uniform type previously cited as 2-2-1), the combined type previously cited as 2-2-2), and the molded type previously cited as 1), then the range of from the above central portion to the above outer surface is taken as the position range to be analyzed, and there is obtained a drawing figure (graph) which shows relations between the distance r2 (x-axis) of from the above central portion (x=0) to the above outer surface (x=r2) and the X-ray intensity I (y-axis) being measured correspondingly to the existence amount of the prescribed metal element.
- (ii) The method and standard for evaluation of the maldistribution in the surface side is defined in accordance with the types of the forms of the catalyst.
- That is to say, in the case of the eggshell type catalyst previously cited as 2-1), then, as to the metal element (α), the integration value N10 of the X-ray intensity I is determined throughout the entire position range, to be analyzed, of from the above support surface (x=0) to the above outer surface (x=r1), and the integration value of the X-ray intensity I in all positions (including the following standard position) on the outer surface side of a position (standard position) of 1/2r1 from the above support surface (x=0) toward the above outer surface (x=r1) is denoted by N11. Then, the surface-side maldistribution ratio Ma (%) as determined from the following formula (a):
-
Ma(%)=(N 11 /N 10)×100 (a) - is favorably more than 50%, more favorably not less than 55%, still more favorably not less than 60%. In addition, in this case, the above standard position is more favorably 3/5r1, still more favorably 2/3r1. In cases where the above evaluation standard is not satisfied, then there is a possibility that the aforementioned problems cannot easily be solved.
- On the other hand, in cases where the catalysts according to the present invention are the uniform type previously cited as 2-2-1), the combined type previously cited as 2-2-2), and the molded type previously cited as 1), then, as to the metal element (α), the integration value N20 of the X-ray intensity I is determined throughout the entire position range, to be analyzed, of from the above central portion (x=0) to the above outer surface (x=r2), and the integration value of the X-ray intensity I in all positions (including the following standard position) on the outer surface side of a position (standard position) of 1/2r2 from the above central portion (x=0) toward the above outer surface (x=r2) is denoted by N2. Then, the surface-side maldistribution ratio Mb (%) as determined from the following formula (b):
-
Mb(%)=(N 21 /N 20)×100 (b) - is favorably more than 50%, more favorably not less than 55%, still more favorably not less than 60%. In addition, in this case, the above standard position is more favorably 3/5r2, still more favorably 2/3r2. In cases where the above evaluation standard is not satisfied, then there is a possibility that the aforementioned problems cannot easily be solved.
- (iii) The method and standard for evaluation of the maldistribution in the core side is defined in accordance with the types of the forms of the catalyst.
- That is to say, in the case of the eggshell type catalyst previously cited as 2-1), then, as to the metal element (β), the integration value N30 of the X-ray intensity I is determined throughout the entire position range, to be analyzed, of from the above support surface (x=0) to the above outer surface (x=r1), and the integration value of the X-ray intensity I in all positions (including the following standard position) on the support surface side of a position (standard position) of 1/2r1 from the above support surface (x=0) toward the above outer surface (x=r1) is denoted by N31. Then, the core-side maldistribution ratio Mc (%) as determined from the following formula (c):
-
Mc(%)=(N 31 /N 30)×100 (c) - is favorably more than 50%, more favorably not less than 55%, still more favorably not less than 60%. In addition, in this case, the above standard position is more favorably 2/5r1, still more favorably 1/3r1. In cases where the above evaluation standard is not satisfied, then there is a possibility that the aforementioned problems cannot easily be solved.
- On the other hand, in cases where the catalysts according to the present invention are the uniform type previously cited as 2-2-1), the combined type previously cited as 2-2-2), and the molded type previously cited as 1), then, as to the metal element (β), the integration value N40 of the X-ray intensity I is determined throughout the entire position range, to be analyzed, of from the above central portion (x=0) to the above outer surface (x=r2), and the integration value of the X-ray intensity I in all positions (including the following standard position) on the central portion side of a position (standard position) of 1/2r2 from the above central portion (x=0) toward the above outer surface (x=r2) is denoted by N41. Then, the core-side maldistribution ratio Md (%) as determined from the following formula (d):
-
Md(%)=(N 41 /N 40)×100 (d) - is favorably more than 50%, more favorably not less than 55%, still more favorably not less than 60%. In addition, in this case, the above standard position is more favorably 2/5r2, still more favorably 1/3r2. In cases where the above evaluation standard is not satisfied, then there is a possibility that the aforementioned problems cannot easily be solved.
- In cases where various measurements and analyses about the catalyst according to the present invention are carried out with the EPMA device in the aforementioned ways, then favorable examples of the shape of the catalyst to be measured include shapes of such as spheres (particularly, such as true spheres and substantially true spheres), pillars (particularly, such as cylinders), and rings (particularly, such as rings whose sections are circular), and more favorable examples thereof include the shapes of spheres (particularly, such as true spheres and substantially true spheres). Incidentally, depending on the shape of the catalyst, there can possibly be cases where it is difficult to examine the distribution of the prescribed metal element in accordance with the method for analysis and evaluation using the EPMA device. However, usually, shapes of commonly known catalysts for production of acrylic acid could all be analyzed and evaluated. In addition, as to catalyst sections to be analyzed with the EPMA device, for example, it is recommended that: the cylinder-shaped catalyst should be analyzed as to a cross section (circular section) crossing the center line of the cylinder at right angles; the sphere-shaped catalyst should be analyzed as to a section passing through the center of the sphere; and the ring-shaped catalyst should be analyzed as to a section as given by sectioning a thickness portion (which makes the ring) by a plane which crosses at right angles a plane made by the ring and passes through the center line of the ring.
- In cases where the evaluations according to the methods and standards as shown in the aforementioned (i) to (iii) are carried out with the EPMA device, then the particle diameter (average outer diameter) of the catalyst according to the present invention is favorably in the range of 1 to 15 mm, more favorably 3 to 10 mm. If the particle diameter is within the above range, then it follows that there are seen good correlations between the maldistributed state (specified by the analytic methods using the EPMA device) of the prescribed metal element and its effect.
- In addition, as to cases where the catalyst according to the present invention is the eggshell type catalyst (previously cited as 2-1)) in cases where the same evaluations as the above are carried out, it is favorable that the thickness of the catalytic component supported on the support is not less than a definite value in any portion. Specifically, the above thickness is favorably not less than 30 μm, more favorably in the range of 60 μm to 5 mm, still more favorably 100 μm to 3 mm.
- The catalyst according to the present invention for production of acrylic acid is generally obtained by a process comprising steps such as: a step in which a mixed liquid (being in a state of an aqueous solution or aqueous slurry) of starting materials of which the essential components include tungsten and/or copper as well as molybdenum and vanadium is dried to thus obtain a dried material; a step in which this dried material is molded with such as a liquid binder; and a step in which the resultant molding is calcined.
- The above starting materials for obtaining the oxide and/or the composite oxide (wherein the oxide and/or the composite oxide includes, as essential metal elements, tungsten and/or copper as well as molybdenum and vanadium) are selected from among those which are commonly used for this type of catalysts, such as ammonium salts, nitrates, carbonates, chlorides, sulfates, hydroxides, organic acid salts, and oxides of the metal elements. However, the ammonium salts and the nitrates are favorably used.
- The mixed liquid of the starting materials will do if it is prepared by processes being commonly used for production of this type of catalysts. Accordingly, the starting materials are mixed in order into water to thus prepare an aqueous solution or aqueous slurry. However, in cases where at least two aqueous solutions or aqueous slurries have been prepared in accordance with the kinds of the starting materials, then it will do to mix these together in order. As to conditions of the above mixing (e.g. mixing order, temperature, pressure, pH), there is no especial limitation.
- The mixed liquid of the starting materials, as obtained in the above way, is dried by various methods to thus form it into a dried material. Examples thereof include: a method in which the drying is carried out by heating; and a method in which the drying is carried out under reduced pressure.
- As to the heating method for obtaining the dried material and as to the form of the dried material, for example, a powdery dried material may be obtained with such as spray driers and drum driers, or a blocky or flaky dried material may be obtained by heating under a gas flow with such as box type driers and tunnel type driers.
- The resultant dried material is processed, if necessary, by a pulverization step and/or classification step for obtaining a powder of an appropriate particle size and then fed to a subsequent molding step. Incidentally, the above particle size of the powder of the dried material is favorably not larger than 500 μm though not limited.
- In the molding step, such as a liquid binder can be used for molding the resultant dried material. Specifically, there can be adopted such as: a process in which the liquid binder is added to the resultant dried material to mix them together and then the resultant mixture is molded; and, in cases where the dried material is supported onto a desired support (the supported catalyst is obtained), a process in which the support is beforehand wetted with the liquid binder and then the dried material is added thereto to thus support it.
- Incidentally, in order to obtain the catalyst according to the present invention, there can also be adopted, besides the aforementioned general production processes, another process in which: the mixed liquid of the starting materials is used remaining a liquid without being dried, and this liquid is absorbed into a desired support or coated or attached onto this support, and then they are calcined. Therefore, as the mode of supporting the catalytic component onto the support, there can also be cited another mode in which the mixed liquid itself of the starting materials is supported besides the aforementioned mode in which the dried material is supported.
- Though not limited, as the above liquid binder, it is possible to use binders which are commonly used for molding and supporting of this type of catalysts. Specifically, it is possible to use water, and besides, such as organic compounds (e.g. ethylene glycol, glycerol, propionic acid, maleic acid, benzyl alcohol, propyl alcohol, polyvinyl alcohol, phenol), nitric acid, ammonium nitrate, ammonium carbonate, and silica sol. In addition, of these, only one kind may be used alone, or at least two kinds may be used in combinations with each other.
- Though not limited, the amount of the above liquid binder being used (added) will do if it is set appropriately for such as: molding and supporting methods being adopted; and properties of the dried material powder.
- In cases where the catalyst according to the present invention is obtained, then it is possible to use various substances such as: molding assistants which can enhance the moldability; reinforcements for enhancing the strength of the catalyst; and pore-forming agents for formation of appropriate pores in the catalyst; wherein these various substances are commonly used for the purpose of these effects in the production of catalysts. Examples of these various substances include stearic acid, graphite, starch, cellulose, silica, alumina, glass fibers, silicon carbide, and silicon nitride. Those which do not exercise any bad influence on the catalytic performances (e.g. activity, selectivity of objective product) by cause of their addition are favorable. These various substances can be used, for example, in a way of being added to the above liquid binder and/or the mixed liquid of the starting materials to mix them together. As to these various substances, if their addition amount is an excess, then there are cases where they greatly deteriorate the physical strength of the catalyst. Therefore, these various substances are added favorably in such an amount that the physical strength of the catalyst may not be deteriorated to such an extent that it becomes impossible to use the catalyst practically as an industrial catalyst.
- As the aforementioned support, there can be used any inert support of a definite shape. Specific usable examples thereof include supports of definite shapes including such as alumina, silica, silica-alumina, titania, magnesia, steatite, and silicon carbide.
- In the case of the supported catalyst, the supporting ratio of the catalyst is determined appropriately with consideration given to such as: conditions of the oxidation reaction; and the activity and strength of the catalyst. However, it is favorably in the range of 10 to 70 mass %, more favorably 15 to 50 mass %. The supporting ratio is defined as a value determined by the calculation method as described in the below-mentioned detailed description of Examples of some preferred embodiments.
- As molding methods adoptable in the molding step, it will do to use hitherto publicly known methods and means. Examples of applicable molding methods include extrusion-molding methods (extrusion-molding machines), granulation methods (tumbling granulators, centrifugal flow coating devices), Marumerizer methods, tablet-molding methods, impregnation methods, evaporation-to-dryness methods, and spray methods. It is also possible that these methods are used in combination of appropriate selections.
- As methods for appropriately adjusting and controlling the distribution amount and existence amount of the metal element (α) and/or metal element (β) (as a catalytic component) in the catalyst surface side or catalyst core side (catalyst center side) (methods for maldistributing the metal element (α) and/or metal element (β) in the catalyst surface side or catalyst core side (catalyst center side)) in the catalyst according to the present invention, for example, there can be adopted such as (A) a process in which: at least two catalyst materials (e.g. mixed liquids of catalytic components, and/or their dried materials) different in compositional amount about the metal element (α) and/or metal element (β) (as a catalytic component) are beforehand prepared, and then each of them is molded (inclusive of being supported) while the distribution amount of the metal element (α) and/or metal element (β) is controlled so as to make a difference between the catalyst surface side and the catalyst core side and be predetermined existence amounts therein.
- As to the above process (A), in detail, for example, catalyst materials X and Y are separately prepared as the above at least two catalyst materials, and then thereto there can be applied such as the following processes 1) to 5): 1) a process in which the catalyst material X is tablet-molded, and then moldings obtained by this tablet-molding are used as nucleuses to further tablet-mold the catalyst material Y (nuclear tablet-molding method); 2) a process in which the catalyst material X is extrusion-molded, and then, as to moldings obtained by this extrusion-molding, the catalyst material Y is tablet-mold (nuclear tablet-molding method); 3) a process in which the catalyst material X is supported onto a support by the evaporation-to-dryness method, and then the catalyst material Y is supported thereonto by the evaporation-to-dryness method; 4) a process in which the catalyst material X is supported onto a support by the evaporation-to-dryness method, and then the catalyst material Y is supported thereonto by the tumbling granulation method; and 5) a process in which the catalyst material X is supported onto a support by the evaporation-to-dryness method, and then the catalyst material Y is supported thereonto by the spray method. Incidentally, in the above processes 1) to 5), heat treatment such as drying or calcination can be carried out between the molding or supporting treatments as carried out at least two times. In addition, in the above processes 1) to 5), the amount of the catalyst material being used during each of the molding or supporting treatments as carried out at least two times is not limited. This amount will do if it is set appropriately so that the aforementioned maldistribution of the prescribed catalytic component can be achieved (in other words, the catalyst according to the present invention can be obtained).
- In cases where the calcination of the molding is carried out when the catalyst according to the present invention is obtained, then the calcination temperature is favorably in the range of 350 to 450° C., more favorably 380 to 420° C., and the calcination time is favorably in the range of about 1 to about 10 hours. Before the above calcination, heat treatment may preliminarily be carried out at a temperature lower than the above calcination temperature.
- The process according to the present invention for production of acrylic acid is characterized in that the above catalyst according to the present invention for production of acrylic acid is used in a process in which acrylic acid is produced by catalytic gas phase oxidation of acrolein in the presence of molecular oxygen. By using the catalyst according to the present invention, the aforementioned problems can be solved all at once and easily.
- As to the process in which acrylic acid is produced by catalytic gas phase oxidation of acrolein, there is no especial limitation except the point of using the catalyst according to the present invention as the catalyst. This process can be carried out by use of such devices, methods, and conditions as are commonly used.
- The above acrolein is subjected to the catalytic gas phase oxidation generally in a state of a raw gas containing this acrolein. As such a raw gas, a mixed gas comprising acrolein, oxygen, and an inert gas can be used as a matter of course, and besides, an acrolein-containing mixed gas obtained by direct oxidation of propylene can also be used after air or oxygen and further water vapor and other gases have been added thereto if necessary. By-products (such as acrylic acid, acetic acid, carbon oxide, propane, or unreacted propylene) which are contained in the acrolein-containing mixed gas obtained by direct oxidation of propylene do no harm to the catalyst (being used in the present invention) for production of acrylic acid.
- The catalytic gas phase oxidation reaction in the present invention may be carried out by either of a one-pass process and a recycling process. As reactors, there can be used such as fixed-bed reactors, fluidized-bed reactors, and moving-bed reactors.
- At the mention about conditions of the above reaction, it is possible to adopt conditions which are commonly used for the production of acrylic acid by the catalytic gas phase oxidation reaction. For example, it will do that a mixed gas, comprising such as acrolein 1 to 15 volume % (favorably 4 to 12 volume %), oxygen 0.5 to 25 volume % (favorably 2 to 20 volume %), water vapor 0 to 30 volume % (favorably 0 to 25 volume %), and an inert gas (e.g. nitrogen) 20 to 80 volume % (favorably 50 to 70 volume %), is caused to contact and thereby react with the above catalyst according to the present invention for production of acrylic acid in the temperature range of 200 to 400° C. (favorably 220 to 380° C.), under a pressure of 0.1 to 1 MPa, and at a space velocity of 300 to 10,000 hr−1 (STP) (favorably 500 to 5,000 hr−1 (STP)).
- Hereinafter, the present invention is more specifically illustrated by the following Examples of some preferred embodiments. However, the present invention is not limited to them in any way. In detail, the present invention is illustrated by supported catalysts (eggshell type catalysts) such that the catalytic component is supported only on surfaces of inert supports. However, the present invention is not limited to this type of catalysts or processes for production of acrylic acid using this type of catalysts. Incidentally, hereinafter, for convenience, the unit “mass part(s)” may be referred to simply as “part(s)”, and the unit “liter(s)” may be referred to simply as “L”.
- Details of various measurement and calculation methods in the below-mentioned Examples and Comparative Examples are shown below.
- <Method for Calculation of Supporting Ratio>:
-
Supporting ratio (mass %)=[(mass of catalyst obtained−mass of support used)/mass of catalyst obtained]×100 - <Conversion of Acrolein>:
-
Conversion (mol %) of acrolein=(mols of acrolein reacted/mols of acrolein supplied)×100 - <Yield of Acrylic Acid>:
-
Yield (mol %) of acrylic acid=(mols of acrylic acid formed/mols of acrolein supplied)×100 - <Selectivity of Acrylic Acid>:
-
Selectivity (mol %) of acrylic acid=(mols of acrylic acid formed/mols of acrolein reacted)×100 - <Sectional Linear Analysis with EPMA>:
- Analyzer: produced by Shimadzu Corporation, product name: EPMA-1610
- X-ray beam diameter: 1 μm
- Acceleration voltage: 15 kV
- Beam current: 0.1 μA
- Measurement time: 20 msec
- Data point: 1024×1024
- Step width (moving width) of X-ray beam: 5 μm
- While 20,000 parts of pure water was heat-mixed, 3,000 parts of ammonium molybdate, 663 parts of ammonium metavanadate, and 268 parts of ammonium paratungstate were dissolved thereinto. Separately, while 2,000 parts of pure water was heat-mixed, 1,026 parts of copper nitrate trihydrate was dissolved thereinto. The resultant two aqueous solutions were mixed together, and then 62 parts of antimony trioxide was further added thereto, thus obtaining a mixed liquid of starting materials. The resultant mixed liquid of starting materials was dried with a drum drier and then pulverized into the size of not larger than 500 μm, thus obtaining a dried material (A).
- The compositional ratio of the metal elements except oxygen in the dried material (A) having been obtained in the above way was as follows.
- Dried material (A): Mo12V4.0W0.7Cu3.0Sb0.3
- Dried materials (B) to (G) were obtained in the same way as of the above process for preparation of the dried material (A) except that the amounts of the ammonium metavanadate, ammonium paratungstate, and copper nitrate trihydrate being used were changed. The compositional ratios of the metal elements except oxygen in these dried materials were as follows.
- Dried material (B): Mo12V4.0W1.3Cu3.0Sb0.3
- Dried material (C): Mo12V4.0W0.7Cu2.0Sb0.3
- Dried material (D): Mo12V4.0W1.3Cu2.0Sb0.3
- Dried material (E): Mo12V3.5W1.3Cu2.0Sb0.3
- Dried material (F): Mo12V5.0W1.3Cu2.0Sb0.3
- Dried material (G): Mo12V5.0W0.7Cu3.0Sb0.3
- [First Catalyst]:
- A silica-alumina support of 5.0 mm in average diameter was put into a rotary dish of a dish type tumbling granulator. While the rotary dish was rotated at a revolution rate of 15 rpm in a state tilted at 30° to the horizontal plane, a 10 mass % aqueous ethylene glycol solution was sprayed to the support. After this spraying had been carried out for 10 minutes, first the dried material (A) was added and thereby supported onto the support. Subsequently, the dried material (B) was added and thereby supported onto the outside of the dried material (A), thus obtaining a supported structure.
- Next, this supported structure was taken out and then calcined at 400° C. under an air atmosphere for 6 hours, thus obtaining a spherical catalyst (1-1). Incidentally, as to the dried materials (A) and (B), their amounts of addition into the tumbling granulator were adjusted so that their respective supporting ratios would be 10 mass % after the calcination.
- The resultant catalyst (1-1) was cut off into hemispheres along a plane passing through the center of the catalyst. A cut section of this hemispherical catalyst was analyzed with the EPMA device into tungsten and copper linearly from a one-side outer surface through the central portion to the opposite-side outer surface in the above section. Based on the results of this analysis, as to the tungsten, the surface-side maldistribution ratio Ma (%) was determined from the aforementioned formula (a) with the standard position defined as 1/2r1. Along therewith, as to the copper, the core-side maldistribution ratio Mc (%) was determined from the aforementioned formula (c) with the standard position defined as 1/2r1. Their results are shown in Table 1.
- A stainless reaction tube of 25 mm in inner diameter and 800 mm in length as heated with a molten nitrate was packed with 100 mL of the catalyst (1-1). Then, a mixed gas of acrolein 4 volume %, oxygen 4 volume %, water vapor 30 volume %, and nitrogen 62 volume % was introduced into the reaction tube at a space velocity of 2,500 hr−1 (STP) to thus carry out an oxidation reaction of acrolein continuously. During this, the reaction temperature was adjusted so that the conversion of acrolein might be maintained in the range of 98 to 99 mol %. The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of the oxidation reaction, are shown in Table 2.
- A silica-alumina support of 4.5 to 5.0 mm in diameter was put into a rotary dish of a dish type tumbling granulator. While the rotary dish was rotated at a revolution rate of 15 rpm in a state tilted at 30° to the horizontal plane, a 10 mass % aqueous ethylene glycol solution was sprayed to the support. After this spraying had been carried out for 10 minutes, the dried material (A) was added and thereby supported onto the support. The resultant supported structure was taken out and then calcined at 400° C. under an air atmosphere for 6 hours, thus obtaining a spherical catalyst (c1-1). Incidentally, as to the dried material (A), its amount of addition into the tumbling granulator was adjusted so that its supporting ratio would be 20 mass % after the calcination.
- As to the resultant catalyst (c1-1), the surface-side maldistribution ratio Ma (%) of the tungsten and the core-side maldistribution ratio Mc (%) of the copper were determined in the same way as of Example 1-1. Their results are shown in Table 1.
- An oxidation reaction was carried out in the same way as of Example 1-1 except that the catalyst (1-1) was replaced with the catalyst (c1-1). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of the oxidation reaction, are shown in Table 2.
- A spherical catalyst (c1-2) was obtained in the same way as of the catalyst production process of Comparative Example 1-1 except that the dried material (A) was replaced with the dried material (B).
- As to the resultant catalyst (c1-2), the surface-side maldistribution ratio Ma (%) of the tungsten and the core-side maldistribution ratio Mc (%) of the copper were determined in the same way as of Example 1-1. Their results are shown in Table 1.
- An oxidation reaction was carried out in the same way as of Example 1-1 except that the catalyst (1-1) was replaced with the catalyst (c1-2). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of the oxidation reaction, are shown in Table 2.
- A spherical catalyst (c1-3) was obtained in the same way as of the catalyst production process of Comparative Example 1-1 except that the dried material (A) was replaced with a mixed powder having been obtained by uniformly mixing the dried materials (A) and (B) in equal quantities together. Incidentally, as to the dried materials (A) and (B), their amounts of addition into the tumbling granulator were adjusted so that their respective supporting ratios would be 10 mass % after the calcination.
- As to the resultant catalyst (c1-3), the surface-side maldistribution ratio Ma (%) of the tungsten and the core-side maldistribution ratio Mc (%) of the copper were determined in the same way as of Example 1-1. Their results are shown in Table 1.
- An oxidation reaction was carried out in the same way as of Example 1-1 except that the catalyst (1-1) was replaced with the catalyst (c1-3). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of the oxidation reaction, are shown in Table 2.
- A spherical catalyst (1-2) was obtained in the same way as of the catalyst production process of Example 1-1 except that the dried material (B) was replaced with the dried material (C).
- As to the resultant catalyst (1-2), the surface-side maldistribution ratio Ma (%) of the tungsten and the core-side maldistribution ratio Mc (%) of the copper were determined in the same way as of Example 1-1. Their results are shown in Table 1.
- An oxidation reaction was carried out in the same way as of Example 1-1 except that the catalyst (1-1) was replaced with the catalyst (1-2). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of the oxidation reaction, are shown in Table 2.
- A spherical catalyst (c1-4) was obtained in the same way as of the catalyst production process of Comparative Example 1-1 except that the dried material (A) was replaced with the dried material (C).
- As to the resultant catalyst (c1-4), the surface-side maldistribution ratio Ma (%) of the tungsten and the core-side maldistribution ratio Mc (%) of the copper were determined in the same way as of Example 1-1. Their results are shown in Table 1.
- An oxidation reaction was carried out in the same way as of Example 1-1 except that the catalyst (1-1) was replaced with the catalyst (c1-4). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of the oxidation reaction, are shown in Table 2.
- A spherical catalyst (r1-1) was obtained in the same way as of the catalyst production process of Example 1-1 except that the dried material (B) was replaced with the dried material (A), and that the dried material (A) was replaced with the dried material (C).
- As to the resultant catalyst (r1-1), the surface-side maldistribution ratio Ma (%) of the tungsten and the core-side maldistribution ratio Mc (%) of the copper were determined in the same way as of Example 1-1. Their results are shown in Table 1.
- An oxidation reaction was carried out in the same way as of Example 1-1 except that the catalyst (1-1) was replaced with the catalyst (r1-1). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of the oxidation reaction, are shown in Table 2.
- Spherical catalysts (1-3), (1-4), and (1-5) were obtained in the same way as of the catalyst production process of Example 1-1 except that the dried material (B) was replaced with the dried materials (D), (E), and (F) respectively.
- As to the resultant catalysts (1-3), (1-4), and (1-5), the surface-side maldistribution ratio Ma (%) of the tungsten and the core-side maldistribution ratio Mc (%) of the copper were determined in the same way as of Example 1-1. Their results are shown in Table 1.
- Oxidation reactions were carried out in the same way as of Example 1-1 except that the catalyst (1-1) was replaced with the catalysts (1-3), (1-4), and (1-5) respectively. The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of each oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of each oxidation reaction, are shown in Table 2.
- Spherical catalysts (1-6), (1-7), (1-8), and (1-9) were obtained in the same way as of the catalyst production process of Example 1-1 except that the dried material (A) was replaced with the dried material (B) or (C) respectively, and that the dried material (B) was replaced with the dried material (E) or (F) respectively (for the specific combinations of the dried materials used, refer to Table 1 or 2).
- As to the resultant catalysts (1-6), (1-7), (1-8), and (1-9), the surface-side maldistribution ratio Ma (%) of the tungsten and the core-side maldistribution ratio Mc (%) of the copper were determined in the same way as of Example 1-1. Their results are shown in Table 1.
- Oxidation reactions were carried out in the same way as of Example 1-1 except that the catalyst (1-1) was replaced with the catalysts (1-6), (1-7), (1-8), and (1-9) respectively. The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of each oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of each oxidation reaction, are shown in Table 2.
- A stainless reaction tube of 25 mm in inner diameter and 3,000 mm in length as heated with a molten nitrate was packed with 1,000 mL of the catalyst (1-2). Then, a mixed gas of acrolein 5 volume %, air 25 volume %, water vapor 30 volume %, and an inert gas (e.g. nitrogen) 40 volume % was introduced into the reaction tube at a space velocity of 1,600 hr (STP) to thus carry out an oxidation reaction. The results of the oxidation reaction at a passage of 100 hours from the start of the oxidation reaction were, at a reaction temperature of 260° C., as follows: conversion of acrolein 99.1 mol %, selectivity of acrylic acid=95.1 mol %, yield of acrylic acid=94.2 mol %.
-
TABLE 1 Maldistribution ratio (%) Surface-side Core-side Compositional distribution in catalyst particle maldistribution ratio maldistribution ratio Catalyst (inside of particle/outer surface of particle) (Ma) of W (Mc) of Cu Example 1-1 Catalyst (1-1) Dried material (A)/dried material (B) 64 50 Comparative Example 1-1 Catalyst (c1-1) Dried material (A) only 50 50 Comparative Example 1-2 Catalyst (c1-2) Dried material (B) only 50 50 Comparative Example 1-3 Catalyst (c1-3) Uniform mixture of dried materials (A) and (B) 50 50 Example 1-2 Catalyst (1-2) Dried material (A)/dried material (C) 50 62 Comparative Example 1-4 Catalyst (c1-4) Dried material (C) only 50 50 Referential Example 1-1 Catalyst (r1-1) Dried material (C)/dried material (A) 47 43 Example 1-3 Catalyst (1-3) Dried material (A)/dried material (D) 65 60 Example 1-4 Catalyst (1-4) Dried material (A)/dried material (E) 65 59 Example 1-5 Catalyst (1-5) Dried material (A)/dried material (F) 63 62 Example 1-6 Catalyst (1-6) Dried material (C)/dried material (E) 64 50 Example 1-7 Catalyst (1-7) Dried material (C)/dried material (F) 62 52 Example 1-8 Catalyst (1-8) Dried material (B)/dried material (E) 50 58 Example 1-9 Catalyst (1-9) Dried material (B)/dried material (F) 50 60 -
TABLE 2 At passage of 100 At passage of 2,000 hours from start of hours from start of oxidation reaction oxidation reaction Reaction Selectivity of Reaction Selectivity of Compositional distribution in catalyst particle temperature acrylic acid temperature acrylic acid Catalyst (inside of particle/outer surface of particle) (° C.) (mol %) (° C.) (mol %) Example 1-1 Catalyst (1-1) Dried material (A)/dried material (B) 271 94.0 303 92.9 Comparative Example 1-1 Catalyst (c1-1) Dried material (A) only 275 93.7 321 91.3 Comparative Example 1-2 Catalyst (c1-2) Dried material (B) only 270 93.4 308 91.1 Comparative Example 1-3 Catalyst (c1-3) Uniform mixture of dried materials (A) and (B) 273 93.5 310 91.8 Example 1-2 Catalyst (1-2) Dried material (A)/dried material (C) 272 94.1 304 93.0 Comparative Example 1-4 Catalyst (c1-4) Dried material (C) only 268 93.4 305 91.3 Referential Example 1-1 Catalyst (r1-1) Dried material (C)/dried material (A) 275 94.8 319 92.3 Example 1-3 Catalyst (1-3) Dried material (A)/dried material (D) 269 94.0 295 93.2 Example 1-4 Catalyst (1-4) Dried material (A)/dried material (E) 272 94.5 301 93.4 Example 1-5 Catalyst (1-5) Dried material (A)/dried material (F) 266 93.8 290 93.2 Example 1-6 Catalyst (1-6) Dried material (C)/dried material (E) 271 94.5 302 93.3 Example 1-7 Catalyst (1-7) Dried material (C)/dried material (F) 266 94.0 291 93.0 Example 1-8 Catalyst (1-8) Dried material (B)/dried material (E) 270 94.3 299 93.1 Example 1-9 Catalyst (1-9) Dried material (B)/dried material (F) 266 93.8 290 92.8 - [Second Catalyst]:
- A silica-alumina support of 5.0 mm in average diameter was put into a rotary dish of a dish type tumbling granulator. While the rotary dish was rotated at a revolution rate of 15 rpm in a state tilted at 30° to the horizontal plane, a 10 mass % aqueous ethylene glycol solution was sprayed to the support. After this spraying had been carried out for 10 minutes, first the dried material (A) was added and thereby supported onto the support. Subsequently, the dried material (G) was added and thereby supported onto the outside of the dried material (A), thus obtaining a supported structure.
- Next, this supported structure was taken out and then calcined at 400° C. under an air atmosphere for 6 hours, thus obtaining a spherical catalyst (2-1). Incidentally, as to the dried materials (A) and (G), their amounts of addition into the tumbling granulator were adjusted so that their respective supporting ratios would be 10 mass % after the calcination.
- The resultant catalyst (2-1) was cut off into hemispheres along a plane passing through the center of the catalyst. A cut section of this hemispherical catalyst was analyzed with the EPMA device into vanadium linearly from a one-side outer surface through the central portion to the opposite-side outer surface in the above section. Based on the results of this analysis, as to the vanadium, the surface-side maldistribution ratio Ma (%) was determined from the aforementioned formula (a) with the standard position defined as 1/2r1. Its results are shown in Table 3.
- A stainless reaction tube of 25 mm in inner diameter and 800 mm in length as heated with a molten nitrate was packed with 100 mL of the catalyst (2-1). Then, a mixed gas of acrolein 4 volume %, oxygen 4 volume %, water vapor 30 volume %, and nitrogen 62 volume % was introduced into the reaction tube at a space velocity of 2,500 hr−1 (STP) to thus carry out an oxidation reaction of acrolein continuously. During this, the reaction temperature was adjusted so that the conversion of acrolein might be maintained in the range of 98 to 99 mol %. The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of the oxidation reaction, are shown in Table 4.
- A silica-alumina support of 4.5 to 5.0 mm in diameter was put into a rotary dish of a dish type tumbling granulator. While the rotary dish was rotated at a revolution rate of 15 rpm in a state tilted at 30° to the horizontal plane, a 10 mass % aqueous ethylene glycol solution was sprayed to the support. After this spraying had been carried out for 10 minutes, the dried material (A) was added and thereby supported onto the support. The resultant supported structure was taken out and then calcined at 400° C. under an air atmosphere for 6 hours, thus obtaining a spherical catalyst (c2-1). Incidentally, as to the dried material (A), its amount of addition into the tumbling granulator was adjusted so that its supporting ratio would be 20 mass % after the calcination.
- As to the resultant catalyst (c2-1), the surface-side maldistribution ratio Ma (%) of the vanadium was determined in the same way as of Example 2-1. Its results are shown in Table 3.
- An oxidation reaction was carried out in the same way as of Example 2-1 except that the catalyst (2-1) was replaced with the catalyst (c2-1). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of the oxidation reaction, are shown in Table 4.
- A spherical catalyst (c2-2) was obtained in the same way as of the catalyst production process of Comparative Example 2-1 except that the dried material (A) was replaced with the dried material (G).
- As to the resultant catalyst (c2-2), the surface-side maldistribution ratio Ma (%) of the vanadium was determined in the same way as of Example 2-1. Its results are shown in Table 3.
- An oxidation reaction was carried out in the same way as of Example 2-1 except that the catalyst (2-1) was replaced with the catalyst (c2-2). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of the oxidation reaction, are shown in Table 4.
- A spherical catalyst (c2-3) was obtained in the same way as of the catalyst production process of Comparative Example 2-1 except that the dried material (A) was replaced with a mixed powder having been obtained by uniformly mixing the dried materials (A) and (G) in equal quantities together. Incidentally, as to the dried materials (A) and (G), their amounts of addition into the tumbling granulator were adjusted so that their respective supporting ratios would be 10 mass % after the calcination.
- As to the resultant catalyst (c2-3), the surface-side maldistribution ratio Ma (%) of the vanadium was determined in the same way as of Example 2-1. Its results are shown in Table 3.
- An oxidation reaction was carried out in the same way as of Example 2-1 except that the catalyst (2-1) was replaced with the catalyst (c2-3). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of the oxidation reaction, are shown in Table 4.
- A spherical catalyst (r2-1) was obtained in the same way as of the catalyst production process of Example 2-1 except that the dried material (A) was replaced with the dried material (G), and that the dried material (G) was replaced with the dried material (A).
- As to the resultant catalyst (r2-1), the surface-side maldistribution ratio Ma (%) of the vanadium was determined in the same way as of Example 2-1. Its results are shown in Table 3.
- An oxidation reaction was carried out in the same way as of Example 2-1 except that the catalyst (2-1) was replaced with the catalyst (r2-1). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction, and the reaction temperature and the selectivity of acrylic acid at a passage of 2,000 hours from the start of the oxidation reaction, are shown in Table 4.
- A stainless reaction tube of 25 mm in inner diameter and 3,000 mm in length as heated with a molten nitrate was packed with 1,000 mL of the catalyst (2-1). Then, a mixed gas of acrolein 5 volume %, air 25 volume %, water vapor 30 volume %, and an inert gas (e.g. nitrogen) 40 volume % was introduced into the reaction tube at a space velocity of 1,600 hr−1 (STP) to thus carry out an oxidation reaction. The results of the oxidation reaction at a passage of 100 hours from the start of the oxidation reaction were, at a reaction temperature of 262° C., as follows: conversion of acrolein=99.3 mol %, selectivity of acrylic acid=94.6 mol %, yield of acrylic acid=93.9 mol %.
-
TABLE 3 Maldistribution ratio (%) Compositional distribution in catalyst particle Surface-side maldistribution ratio Catalyst (inside of particle/outer surface of particle) (Ma) of V Example 2-1 Catalyst (2-1) Dried material (A)/dried material (G) 54 Comparative Example 2-1 Catalyst (c2-1) Dried material (A) only 50 Comparative Example 2-2 Catalyst (c2-2) Dried material (G) only 50 Comparative Example 2-3 Catalyst (c2-3) Uniform mixture of dried materials (A) and (G) 50 Referential Example 2-1 Catalyst (r2-1) Dried material (G)/dried material (A) 45 -
TABLE 4 At passage of 100 At passage of 2,000 hours from start of hours from start of oxidation reaction oxidation reaction Reaction Selectivity of Reaction Selectivity of Compositional distribution in catalyst particle temperature acrylic acid temperature acrylic acid Catalyst (inside of particle/outer surface of particle) (° C.) (mol %) (° C.) (mol %) Example 2-1 Catalyst (2-1) Dried material (A)/dried material (G) 271 93.7 303 92.6 Comparative Example 2-1 Catalyst (c2-1) Dried material (A) only 275 93.7 321 91.3 Comparative Example 2-2 Catalyst (c2-2) Dried material (G) only 268 92.9 302 90.7 Comparative Example 2-3 Catalyst (c2-3) Uniform mixture of dried materials (A) and (G) 272 93.2 311 90.9 Referential Example 2-1 Catalyst (r2-1) Dried material (G)/dried material (A) 273 94.4 314 91.8 - [Third Catalyst]:
- A silica-alumina support of 5.0 mm in average diameter was put into a rotary dish of a dish type tumbling granulator. While the rotary dish was rotated at a revolution rate of 15 rpm in a state tilted at 30° to the horizontal plane, a 10 mass % aqueous ethylene glycol solution was sprayed to the support. After this spraying had been carried out for 10 minutes, first the dried material (B) was added and thereby supported onto the support. Subsequently, the dried material (A) was added and thereby supported onto the outside of the dried material (B), thus obtaining a supported structure.
- Next, this supported structure was taken out and then calcined at 400° C. under an air atmosphere for 6 hours, thus obtaining a spherical catalyst (3-1). Incidentally, as to the dried materials (A) and (B), their amounts of addition into the tumbling granulator were adjusted so that their respective supporting ratios would be 10 mass % after the calcination.
- The resultant catalyst (3-1) was cut off into hemispheres along a plane passing through the center of the catalyst. A cut section of this hemispherical catalyst was analyzed with the EPMA device into copper and tungsten linearly from a one-side outer surface through the central portion to the opposite-side outer surface in the above section. Based on the results of this analysis, as to the copper, the surface-side maldistribution ratio Ma (%) was determined from the aforementioned formula (a) with the standard position defined as 1/2r1. Along therewith, as to the tungsten, the core-side maldistribution ratio Mc (%) was determined from the aforementioned formula (c) with the standard position defined as 1/2r1. Their results are shown in Table 5.
- A stainless reaction tube of 25 mm in inner diameter and 800 mm in length as heated with a molten nitrate was packed with 100 mL of the catalyst (3-1). Then, a mixed gas of acrolein 4 volume %, oxygen 4 volume %, water vapor 30 volume %, and nitrogen 62 volume % was introduced into the reaction tube at a space velocity of 2,500 hr−1 (STP) to thus carry out an oxidation reaction of acrolein continuously. During this, the reaction temperature was adjusted so that the conversion of acrolein might be maintained in the range of 98 to 99 mol %. The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction are shown in Table 6.
- A silica-alumina support of 4.5 to 5.0 mm in diameter was put into a rotary dish of a dish type tumbling granulator. While the rotary dish was rotated at a revolution rate of 15 rpm in a state tilted at 30° to the horizontal plane, a 10 mass % aqueous ethylene glycol solution was sprayed to the support. After this spraying had been carried out for 10 minutes, the dried material (A) was added and thereby supported onto the support. The resultant supported structure was taken out and then calcined at 400° C. under an air atmosphere for 6 hours, thus obtaining a spherical catalyst (c3-1). Incidentally, as to the dried material (A), its amount of addition into the tumbling granulator was adjusted so that its supporting ratio would be 20 mass % after the calcination.
- As to the resultant catalyst (c3-1), the surface-side maldistribution ratio Ma (%) of the copper and the core-side maldistribution ratio Mc (%) of the tungsten were determined in the same way as of Example 3-1. Their results are shown in Table 5.
- An oxidation reaction was carried out in the same way as of Example 3-1 except that the catalyst (3-1) was replaced with the catalyst (c3-1). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction are shown in Table 6.
- A spherical catalyst (c3-2) was obtained in the same way as of the catalyst production process of Comparative Example 3-1 except that the dried material (A) was replaced with the dried material (B).
- As to the resultant catalyst (c3-2), the surface-side maldistribution ratio Ma (%) of the copper and the core-side maldistribution ratio Mc (%) of the tungsten were determined in the same way as of Example 3-1. Their results are shown in Table 5.
- An oxidation reaction was carried out in the same way as of Example 3-1 except that the catalyst (3-1) was replaced with the catalyst (c3-2); The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction are shown in Table 6.
- A spherical catalyst (c3-3) was obtained in the same way as of the catalyst production process of Comparative Example 3-1 except that the dried material (A) was replaced with a mixed powder having been obtained by uniformly mixing the dried materials (A) and (B) in equal quantities together. Incidentally, as to the dried materials (A) and (B), their amounts of addition into the tumbling granulator were adjusted so that their respective supporting ratios would be 10 mass % after the calcination.
- As to the resultant catalyst (c3-3), the surface-side maldistribution ratio Ma (%) of the copper and the core-side maldistribution ratio Mc (%) of the tungsten were determined in the same way as of Example 3-1. Their results are shown in Table 5.
- An oxidation reaction was carried out in the same way as of Example 3-1 except that the catalyst (3-1) was replaced with the catalyst (c3-3). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction are shown in Table 6.
- A spherical catalyst (3-2) was obtained in the same way as of the catalyst production process of Example 3-1 except that the dried material (B) was replaced with the dried material (C).
- As to the resultant catalyst (3-2), the surface-side maldistribution ratio Ma (%) of the copper and the core-side maldistribution ratio Mc (%) of the tungsten were determined in the same way as of Example 3-1. Their results are shown in Table 5.
- An oxidation reaction was carried out in the same way as of Example 3-1 except that the catalyst (3-1) was replaced with the catalyst (3-2). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction are shown in Table 6.
- A spherical catalyst (c3-4) was obtained in the same way as of the catalyst production process of Comparative Example 3-1 except that the dried material (A) was replaced with the dried material (C).
- As to the resultant catalyst (c3-4), the surface-side maldistribution ratio Ma (%) of the copper and the core-side maldistribution ratio Mc (%) of the tungsten were determined in the same way as of Example 3-1. Their results are shown in Table 5.
- An oxidation reaction was carried out in the same way as of Example 3-1 except that the catalyst (3-1) was replaced with the catalyst (c3-4). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction are shown in Table 6.
- A spherical catalyst (r3-1) was obtained in the same way as of the catalyst production process of Example 3-1 except that the dried material (B) was replaced with the dried material (A), and that the dried material (A) was replaced with the dried material (C).
- As to the resultant catalyst (r3-1), the surface-side maldistribution ratio Ma (%) of the copper and the core-side maldistribution ratio Mc (%) of the tungsten were determined in the same way as of Example 3-1. Their results are shown in Table 5.
- An oxidation reaction was carried out in the same way as of Example 3-1 except that the catalyst (3-1) was replaced with the catalyst (r3-1). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction are shown in Table 6.
- A spherical catalyst (r3-2) was obtained in the same way as of the catalyst production process of Example 3-1 except that the dried material (B) was replaced with the dried material (C), and that the dried material (A) was replaced with the dried material (F).
- As to the resultant catalyst (r3-2), the surface-side maldistribution ratio Ma (%) of the copper and the core-side maldistribution ratio Mc (%) of the tungsten were determined in the same way as of Example 3-1. Their results are shown in Table 5.
- An oxidation reaction was carried out in the same way as of Example 3-1 except that the catalyst (3-1) was replaced with the catalyst (r3-2). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction are shown in Table 6.
- Spherical catalysts (3-3) and (3-4) were obtained in the same way as of the catalyst production process of Example 3-1 except that the dried material (B) was replaced with the dried materials (E) and (F) respectively.
- As to the resultant catalysts (3-3) and (3-4), the surface-side maldistribution ratio Ma (%) of the copper and the core-side maldistribution ratio Mc (%) of the tungsten were determined in the same way as of Example 3-1. Their results are shown in Table 5.
- Oxidation reactions were carried out in the same way as of Example 3-1 except that the catalyst (3-1) was replaced with the catalysts (3-3) and (3-4) respectively. The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of each oxidation reaction are shown in Table 6.
- Spherical catalysts (3-5), (3-6), (3-7), and (3-8) were obtained in the same way as of the catalyst production process of Example 3-1 except that the dried material (B) was replaced with either of the dried materials (E) and (F) respectively, and that the dried material (A) was replaced with either of the dried materials (B) and (C) respectively (for the specific combinations of the dried materials used, refer to Tables 5 and 6).
- As to the resultant catalysts (3-5), (3-6), (3-7), and (3-8), the surface-side maldistribution ratio Ma (%) of the copper and the core-side maldistribution ratio Mc (%) of the tungsten were determined in the same way as of Example 3-1. Their results are shown in Table 5.
- Oxidation reactions were carried out in the same way as of Example 3-1 except that the catalyst (3-1) was replaced with the catalysts (3-5), (3-6), (3-7), and (3-8) respectively. The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of each oxidation reaction are shown in Table 6.
- A stainless reaction tube of 25 mm in inner diameter and 3,000 mm in length as heated with a molten nitrate was packed with 1,000 mL of the catalyst (3-2). Then, a mixed gas of acrolein 5 volume %, air 25 volume %, water vapor 30 volume %, and an inert gas (e.g. nitrogen) 40 volume % was introduced into the reaction tube at a space velocity of 1,600 hr−1 (STP) to thus carry out an oxidation reaction. The results of the oxidation reaction at a passage of 100 hours from the start of the oxidation reaction were, at a reaction temperature of 264° C., as follows: conversion of acrolein=99.0 mol %, selectivity of acrylic acid=95.9 mol %, yield of acrylic acid 94.9 mol %.
-
TABLE 5 Maldistribution ratio (%) Surface-side Core-side Compositional distribution in catalyst particle maldistribution ratio maldistribution ratio Catalyst (inside of particle/outer surface of particle) (Ma) of Cu (Mc) of W Example 3-1 Catalyst (3-1) Dried material (B)/dried material (A) 50 64 Comparative Example 3-1 Catalyst (c3-1) Dried material (A) only 50 50 Comparative Example 3-2 Catalyst (c3-2) Dried material (B) only 50 50 Comparative Example 3-3 Catalyst (c3-3) Uniform mixture of dried materials (A) and (B) 50 50 Example 3-2 Catalyst (3-2) Dried material (C)/dried material (A) 60 50 Comparative Example 3-4 Catalyst (c3-4) Dried material (C) only 50 50 Referential Example 3-1 Catalyst (r3-1) Dried material (A)/dried material (C) 42 50 Referential Example 3-2 Catalyst (r3-2) Dried material (C)/dried material (F) 50 40 Example 3-3 Catalyst (3-3) Dried material (E)/dried material (A) 58 66 Example 3-4 Catalyst (3-4) Dried material (F)/dried material (A) 60 64 Example 3-5 Catalyst (3-5) Dried material (E)/dried material (C) 50 65 Example 3-6 Catalyst (3-6) Dried material (F)/dried material (C) 50 64 Example 3-7 Catalyst (3-7) Dried material (E)/dried material (B) 58 50 Example 3-8 Catalyst (3-8) Dried material (F)/dried material (B) 60 50 -
TABLE 6 At passage of 100 hours from start of oxidation reaction Reaction Selectivity of Compositional distribution in catalyst particle temperature acrylic acid Catalyst (inside of particle/outer surface of particle) (° C.) (mol %) Example 3-1 Catalyst (3-1) Dried material (B)/dried material (A) 274 94.8 Comparative Example 3-1 Catalyst (c3-1) Dried material (A) only 275 93.7 Comparative Example 3-2 Catalyst (c3-2) Dried material (B) only 270 93.4 Comparative Example 3-3 Catalyst (c3-3) Uniform mixture of dried materials (A) and (B) 273 93.5 Example 3-2 Catalyst (3-2) Dried material (C)/dried material (A) 275 94.8 Comparative Example 3-4 Catalyst (c3-4) Dried material (C) only 268 93.4 Referential Example 3-1 Catalyst (r3-1) Dried material (A)/dried material (C) 272 94.1 Referential Example 3-2 Catalyst (r3-2) Dried material (C)/dried material (F) 266 94.0 Example 3-3 Catalyst (3-3) Dried material (E)/dried material (A) 273 95.2 Example 3-4 Catalyst (3-4) Dried material (F)/dried material (A) 270 94.7 Example 3-5 Catalyst (3-5) Dried material (E)/dried material (C) 274 95.2 Example 3-6 Catalyst (3-6) Dried material (F)/dried material (C) 271 94.9 Example 3-7 Catalyst (3-7) Dried material (E)/dried material (B) 273 95.1 Example 3-8 Catalyst (3-8) Dried material (F)/dried material (B) 272 94.8 - [Fourth Catalyst]:
- A silica-alumina support of 5.0 mm in average diameter was put into a rotary dish of a dish type tumbling granulator. While the rotary dish was rotated at a revolution rate of 15 rpm in a state tilted at 30° to the horizontal plane, a 10 mass % aqueous ethylene glycol solution was sprayed to the support. After this spraying had been carried out for 10 minutes, first the dried material (G) was added and thereby supported onto the support. Subsequently, the dried material (A) was added and thereby supported onto the outside of the dried material (G), thus obtaining a supported structure.
- Next, this supported structure was taken out and then calcined at 400° C. under an air atmosphere for 6 hours, thus obtaining a spherical catalyst (4-1). Incidentally, as to the dried materials (A) and (G), their amounts of addition into the tumbling granulator were adjusted so that their respective supporting ratios would be 10 mass % after the calcination.
- The resultant catalyst (4-1) was cut off into hemispheres along a plane passing through the center of the catalyst. A cut section of this hemispherical catalyst was analyzed with the EPMA device into vanadium linearly from a one-side outer surface through the central portion to the opposite-side outer surface in the above section. Based on the results of this analysis, as to the vanadium, the core-side maldistribution ratio Mc (%) was determined from the aforementioned formula (c) with the standard position defined as 1/2r1. Its results are shown in Table 7.
- A stainless reaction tube of 25 mm in inner diameter and 800 mm in length as heated with a molten nitrate was packed with 100 mL of the catalyst (4-1). Then, a mixed gas of acrolein 4 volume %, oxygen 4 volume %, water vapor 30 volume %, and nitrogen 62 volume % was introduced into the reaction tube at a space velocity of 2,500 hr−1 (STP) to thus carry out an oxidation reaction of acrolein continuously. During this, the reaction temperature was adjusted so that the conversion of acrolein might be maintained in the range of 98 to 99 mol %. The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction are shown in Table 8.
- A silica-alumina support of 4.5 to 5.0 mm in diameter was put into a rotary dish of a dish type tumbling granulator. While the rotary dish was rotated at a revolution rate of 15 rpm in a state tilted at 30° to the horizontal plane, a 10 mass % aqueous ethylene glycol solution was sprayed to the support. After this spraying had been carried out for 10 minutes, the dried material (A) was added and thereby supported onto the support. The resultant supported structure was taken out and then calcined at 400° C. under an air atmosphere for 6 hours, thus obtaining a spherical catalyst (c4-1). Incidentally, as to the dried material (A), its amount of addition into the tumbling granulator was adjusted so that its supporting ratio would be 20 mass % after the calcination.
- As to the resultant catalyst (c4-1), the core-side maldistribution ratio Mc (%) of the vanadium was determined in the same way as of Example 4-1. Its results are shown in Table 7.
- An oxidation reaction was carried out in the same way as of Example 4-1 except that the catalyst (4-1) was replaced with the catalyst (c4-1). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction are shown in Table 8.
- A spherical catalyst (c4-2) was obtained in the same way as of the catalyst production process of Comparative Example 4-1 except that the dried material (A) was replaced with the dried material (G).
- As to the resultant catalyst (c4-2), the core-side maldistribution ratio Mc (%) of the vanadium was determined in the same way as of Example 4-1. Its results are shown in Table 7.
- An oxidation reaction was carried out in the same way as of Example 4-1 except that the catalyst (4-1) was replaced with the catalyst (c4-2). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction are shown in Table 8.
- A spherical catalyst (c4-3) was obtained in the same way as of the catalyst production process of Comparative Example 4-1 except that the dried material (A) was replaced with a mixed powder having been obtained by uniformly mixing the dried materials (A) and (G) in equal quantities together. Incidentally, as to the dried materials (A) and (G), their amounts of addition into the tumbling granulator were adjusted so that their respective supporting ratios would be 10 mass % after the calcination.
- As to the resultant catalyst (c4-3), the core-side maldistribution ratio Mc (%) of the vanadium was determined in the same way as of Example 4-1. Its results are shown in Table 7.
- An oxidation reaction was carried out in the same way as of Example 4-1 except that the catalyst (4-1) was replaced with the catalyst (c4-3). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction are shown in Table 8.
- A spherical catalyst (r4-1) was obtained in the same way as of the catalyst production process of Example 4-1 except that the dried material (G) was replaced with the dried material (A), and that the dried material (A) was replaced with the dried material (G).
- As to the resultant catalyst (r4-1), the core-side maldistribution ratio Mc (%) of the vanadium was determined in the same way as of Example 4-1. Its results are shown in Table 7.
- An oxidation reaction was carried out in the same way as of Example 4-1 except that the catalyst (4-1) was replaced with the catalyst (r4-1). The reaction temperature and the selectivity of acrylic acid at a passage of 100 hours from the start of the oxidation reaction are shown in Table 8.
- A stainless reaction tube of 25 mm in inner diameter and 3,000 mm in length as heated with a molten nitrate was packed with 1,000 mL of the catalyst (4-1). Then, a mixed gas of acrolein 5 volume %, air 25 volume %, water vapor 30 volume %, and an inert gas (e.g. nitrogen) 40 volume % was introduced into the reaction tube at a space velocity of 1,600 hr−1 (STP) to thus carry out an oxidation reaction. The results of the oxidation reaction at a passage of 100 hours from the start of the oxidation reaction were, at a reaction temperature of 263° C., as follows: conversion of acrolein=98.8 mol %, selectivity of acrylic acid=96.0 mol %, yield of acrylic acid=94.8 mol %.
-
TABLE 7 Maldistribution ratio (%) Compositional distribution in catalyst particle Surface-side maldistribution ratio Catalyst (inside of particle/outer surface of particle) (Ma) of V Example 4-1 Catalyst (4-1) Dried material (G)/dried material (A) 55 Comparative Example 4-1 Catalyst (c4-1) Dried material (A) only 50 Comparative Example 4-2 Catalyst (c4-2) Dried material (G) only 50 Comparative Example 4-3 Catalyst (c4-3) Uniform mixture of dried materials (A) and (G) 50 Referential Example 4-1 Catalyst (r4-1) Dried material (A)/dried material (G) 46 -
TABLE 8 At passage of 100 hours from start of oxidation reaction Reaction Selectivity of Compositional distribution in catalyst particle temperature acrylic acid Catalyst (inside of particle/outer surface of particle) (° C.) (mol %) Example 4-1 Catalyst (4-1) Dried material (G)/dried material (A) 273 94.4 Comparative Example 4-1 Catalyst (c4-1) Dried material (A) only 275 93.7 Comparative Example 4-2 Catalyst (c4-2) Dried material (G) only 268 92.9 Comparative Example 4-3 Catalyst (c4-3) Uniform mixture of dried materials (A) and (G) 272 93.2 Referential Example 4-1 Catalyst (r4-1) Dried material (A)/dried material (G) 271 93.7 - The catalyst according to the present invention is favorable as a catalyst for production of acrylic acid.
- The production process according to the present invention is favorable for production of acrylic acid.
- Various details of the invention may be changed without departing from its spirit not its scope. Furthermore, the foregoing description of the preferred embodiments according to the present invention is provided for the purpose of illustration only, and not for the purpose of limiting the invention as defined by the appended claims and their equivalents.
Claims (16)
1. A catalyst for production of acrylic acid, which comprises an oxide and/or a composite oxide as an essential catalytic component, wherein the oxide and/or the composite oxide has a metal element composition shown by the following general formula (I):
MoaVbWcCudOx (1)
MoaVbWcCudOx (1)
(wherein: Mo is molybdenum; V is vanadium; W is tungsten; Cu is copper; and O is oxygen; and a, b, c, d, and x denote atomic ratios of Mo, V, W, Cu, and O respectively; when a=12, then 1≦b≦14, 0≦c≦12, 0≦d≦10, and 0<c+d; and x is a numerical value determined by oxidation states of the elements);
wherein: the tungsten is maldistributed in the surface side of the catalyst; and/or the copper is maldistributed in the core side of the catalyst.
2. (canceled)
3. A catalyst according to claim 1 for production of acrylic acid, which comprises both the catalytic component and a support as essential constitutional materials wherein the catalytic component is supported at least inside the support, or which is a molding that comprises the catalytic component as an essential constitutional material,
wherein: the surface side of the catalyst refers to a surface layer portion of the catalyst and/or the neighborhood of this portion; and the core side of the catalyst refers to a central portion of the catalyst and/or the neighborhood of this portion.
4. A catalyst for production of acrylic acid, which comprises an oxide and/or a composite oxide as an essential catalytic component, wherein the oxide and/or the composite oxide has a metal element composition shown by the following general formula (1):
MoaVbWcCudOx (1)
MoaVbWcCudOx (1)
(wherein: Mo is molybdenum; V is vanadium; W is tungsten; Cu is copper; and O is oxygen; and a, b, c, d, and x denote atomic ratios of Mo, V, W, Cu, and O respectively; when a=12, then 1≦b≦14, 0≦c≦12, 0≦d≦10, and 0<c+d; and x is a numerical value determined by oxidation states of the elements);
wherein: the vanadium is maldistributed in the surface side of the catalyst.
5. (canceled)
6. A catalyst according to claim 4 for production of acrylic acid, which comprises both the catalytic component and a support as essential constitutional materials wherein the catalytic component is supported at least inside the support, or which is a molding that comprises the catalytic component as an essential constitutional material,
wherein the surface side of the catalyst refers to a surface layer portion of the catalyst and/or the neighborhood of this portion.
7. A catalyst for production of acrylic acid, which comprises an oxide and/or a composite oxide as an essential catalytic component, wherein the oxide and/or the composite oxide has a metal element composition shown by the following general formula (I):
MoaVbWcCudOx (1)
MoaVbWcCudOx (1)
(wherein: Mo is molybdenum; V is vanadium; W is tungsten; Cu is copper; and O is oxygen; and a, b, c, d, and x denote atomic ratios of Mo, V, W, Cu, and O respectively; when a=12, then 1≦b≦14, 0≦c≦12, 0≦d≦10, and 0<c+d; and x is a numerical value determined by oxidation states of the elements);
wherein: the copper is maldistributed in the surface side of the catalyst; and/or the tungsten is maldistributed in the core side of the catalyst.
8. (canceled)
9. A catalyst according to claim 7 for production of acrylic acid, which comprises both the catalytic component and a support as essential constitutional materials wherein the catalytic component is supported at least inside the support, or which is a molding that comprises the catalytic component as an essential constitutional material,
wherein: the surface side of the catalyst refers to a surface layer portion of the catalyst and/or the neighborhood of this portion; and the core side of the catalyst refers to a central portion of the catalyst and/or the neighborhood of this portion.
10. A catalyst for production of acrylic acid, which comprises an oxide and/or a composite oxide as an essential catalytic component, wherein the oxide and/or the composite oxide has a metal element composition shown by the following general formula (I):
MoaVbWcCudOx (1)
MoaVbWcCudOx (1)
(wherein: Mo is molybdenum; V is vanadium; W is tungsten; Cu is copper; and O is oxygen; and a, b, c, d, and x denote atomic ratios of Mo, V, W, Cu, and O respectively; when a=12, then 1≦b≦14, 0≦c≦12, 0≦d≦10, and 0<c+d; and x is a numerical value determined by oxidation states of the elements);
wherein the vanadium is maldistributed in the core side of the catalyst.
11. (canceled)
12. A catalyst according to claim 10 for production of acrylic acid, which comprises both the catalytic component and a support as essential constitutional materials wherein the catalytic component is supported at least inside the support, or which is a molding that comprises the catalytic component as an essential constitutional material,
wherein the core side of the catalyst refers to a central portion of the catalyst and/or the neighborhood of this portion.
13. A process for production of acrylic acid, wherein the catalyst as recited in claim 1 for production of acrylic acid is used when acrylic acid is produced by catalytic gas phase oxidation of acrolein in the presence of molecular oxygen.
14. A process for production of acrylic acid, wherein the catalyst as recited in claim 4 for production of acrylic acid is used when acrylic acid is produced by catalytic gas phase oxidation of acrolein in the presence of molecular oxygen.
15. A process for production of acrylic acid, wherein the catalyst as recited in claim 7 for production of acrylic acid is used when acrylic acid is produced by catalytic gas phase oxidation of acrolein in the presence of molecular oxygen.
16. A process for production of acrylic acid, wherein the catalyst as recited in claim 10 for production of acrylic acid is used when acrylic acid is produced by catalytic gas phase oxidation of acrolein in the presence of molecular oxygen.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US12/080,503 US20090005593A1 (en) | 2004-03-25 | 2008-04-02 | Catalyst for production of acrylic acid and process for production of acrylic acid using this catalyst |
Applications Claiming Priority (10)
Application Number | Priority Date | Filing Date | Title |
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JP2004089948 | 2004-03-25 | ||
JP2004-089948 | 2004-03-25 | ||
JP2004145313 | 2004-05-14 | ||
JP2004-145313 | 2004-05-14 | ||
JP2004-164969 | 2004-06-02 | ||
JP2004164969 | 2004-06-02 | ||
JP2004167464 | 2004-06-04 | ||
JP2004-167464 | 2004-06-04 | ||
US11/078,680 US7378367B2 (en) | 2004-03-25 | 2005-03-11 | Catalyst for production of acrylic acid and process for production of acrylic acid using the catalyst |
US12/080,503 US20090005593A1 (en) | 2004-03-25 | 2008-04-02 | Catalyst for production of acrylic acid and process for production of acrylic acid using this catalyst |
Related Parent Applications (1)
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US11/078,680 Division US7378367B2 (en) | 2004-03-25 | 2005-03-11 | Catalyst for production of acrylic acid and process for production of acrylic acid using the catalyst |
Publications (1)
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US20090005593A1 true US20090005593A1 (en) | 2009-01-01 |
Family
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Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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US11/078,680 Active 2025-12-13 US7378367B2 (en) | 2004-03-25 | 2005-03-11 | Catalyst for production of acrylic acid and process for production of acrylic acid using the catalyst |
US12/080,503 Abandoned US20090005593A1 (en) | 2004-03-25 | 2008-04-02 | Catalyst for production of acrylic acid and process for production of acrylic acid using this catalyst |
Family Applications Before (1)
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US11/078,680 Active 2025-12-13 US7378367B2 (en) | 2004-03-25 | 2005-03-11 | Catalyst for production of acrylic acid and process for production of acrylic acid using the catalyst |
Country Status (3)
Country | Link |
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US (2) | US7378367B2 (en) |
EP (1) | EP1579910A3 (en) |
KR (1) | KR100770638B1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110034330A1 (en) * | 2008-04-09 | 2011-02-10 | Basf Se | Coated catalysts comprising a multimetal oxide comprising molybdenum, bismuth and iron |
US20110275856A1 (en) * | 2010-04-28 | 2011-11-10 | Basf Se | Eggshell catalyst consisting of a hollow cylindrical support body and a catalytically active oxide material applied to the outer surface of the support body |
WO2013167405A1 (en) * | 2012-05-10 | 2013-11-14 | Basf Se | Process for the heterogeneously catalysed gas-phase partial oxidation of (meth)acrolein to (meth)acrylic acid |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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KR100954045B1 (en) * | 2007-08-13 | 2010-04-20 | 주식회사 엘지화학 | Method for preparing improved catalyst for the production of acrylic acid |
TW200948474A (en) | 2008-04-09 | 2009-12-01 | Basf Se | Coated catalysts comprising a multimetal oxide comprising molybdenum |
MY159015A (en) | 2010-11-05 | 2016-11-30 | Asahi Kasei Chemicals Corp | Oxide catalyst, process for production of oxide catalyst, process for production of unsaturated acid, and process for production of unsaturated nitrile |
CN104437526B (en) * | 2013-09-24 | 2017-02-15 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid through acrolein oxidation and preparation method of catalyst |
US9751822B2 (en) | 2013-10-10 | 2017-09-05 | Nippon Kayaku Kabushiki Kaisha | Method for producing unsaturated carboxylic acid and supported catalyst |
JP6973618B2 (en) * | 2018-03-14 | 2021-12-01 | 三菱ケミカル株式会社 | A catalyst molded product and a method for producing an unsaturated aldehyde and an unsaturated carboxylic acid using the catalyst molded product. |
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JP3883755B2 (en) | 1999-09-17 | 2007-02-21 | 日本化薬株式会社 | Catalyst production method |
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- 2005-03-17 EP EP20050102100 patent/EP1579910A3/en not_active Ceased
- 2005-03-25 KR KR1020050024891A patent/KR100770638B1/en not_active IP Right Cessation
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US20110034330A1 (en) * | 2008-04-09 | 2011-02-10 | Basf Se | Coated catalysts comprising a multimetal oxide comprising molybdenum, bismuth and iron |
US20110275856A1 (en) * | 2010-04-28 | 2011-11-10 | Basf Se | Eggshell catalyst consisting of a hollow cylindrical support body and a catalytically active oxide material applied to the outer surface of the support body |
US9149799B2 (en) * | 2010-04-28 | 2015-10-06 | Basf Se | Eggshell catalyst consisting of a hollow cylindrical support body and a catalytically active oxide material applied to the outer surface of the support body |
WO2013167405A1 (en) * | 2012-05-10 | 2013-11-14 | Basf Se | Process for the heterogeneously catalysed gas-phase partial oxidation of (meth)acrolein to (meth)acrylic acid |
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US9181169B2 (en) | 2012-05-10 | 2015-11-10 | Basf Se | Process for heterogeneously catalyzed gas phase partial oxidation of (meth)acrolein to (meth)acrylic acid |
Also Published As
Publication number | Publication date |
---|---|
KR20060044752A (en) | 2006-05-16 |
EP1579910A2 (en) | 2005-09-28 |
KR100770638B1 (en) | 2007-10-29 |
EP1579910A3 (en) | 2006-06-07 |
US20050215818A1 (en) | 2005-09-29 |
US7378367B2 (en) | 2008-05-27 |
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