CN1074388C - Zeolite synthesizing method - Google Patents

Zeolite synthesizing method

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Publication number
CN1074388C
CN1074388C CN97111745A CN97111745A CN1074388C CN 1074388 C CN1074388 C CN 1074388C CN 97111745 A CN97111745 A CN 97111745A CN 97111745 A CN97111745 A CN 97111745A CN 1074388 C CN1074388 C CN 1074388C
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sio
zeolite
tea
accordance
fluorochemical
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CN97111745A
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CN1198404A (en
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祁晓岚
刘希尧
陈钢
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Beijing Research Institute of Beijing Yanshan Petrochemical Corp
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Beijing Research Institute of Beijing Yanshan Petrochemical Corp
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Abstract

The present invention relates to a synthesis method for beta-zeolite crystallization, which is characterized in that a compounded template agent formed by tetraethyl halide of ammonium, tetraethyl ammonium hydroxide and fluoride under the condition of alkalescence is adopted so as to make a silicon source, an aluminum source and crystal seed reaction crystallization generate the beta-zeolite crystallization. A reaction system is composed of the following molar ratios: SiO2 to Al2O3 is from 10 to 400; (TEA) 2O to SiO2 is from 0.03 to 0.5; Na2O to SiO2 is from 0.005 to 0.6; H2O to SiO2 is form 10 to 30; (NH4) 2O to SiO2 is from 0 to 1.0; TEA+ to F-is from 0.25 to 4. The present invention has the advantages of less organic template agent dosage, high zeolite yield and low cost.

Description

A kind of synthetic method of zeolite
The invention relates to the novel method that adopts the synthetic beta-zeolite molecular sieve of composite mould plate agent system.Technical field belongs to C01B 33/34 by International Classification of Patents.
The β zeolite synthesized (USP3308069) first by U.S. Mobil company in 1967, it is up to the present unique supersiliceous zeolite with three-dimensional staggered twelve-ring pore passage structure.Very big using value is arranged at aspects such as catalysis and absorption.In the described method of this patent, the consumption of template tetraethyl ammonium hydroxide is very big, so cost is higher.
Existing β zeolite synthesis technology, adopt expensive tetraethyl ammonium hydroxide (TEAOH) to make template (USP3308069 mostly, EP164939), in order to reduce synthetic cost, also have and adopt the lower slightly tetraethyl-ammonium halide of price to replace (EP164939, USP4847055), or replace with other organic amine, as dimethyl benzylamine one benzyl halide (EP159846), dibenzyl-1,4-azabicyclo [2,2,2] octane (EP159847), dibenzyl dimethylamine (USP4642226) and 4,4 ,-cyclopropyl two piperidines.Also there are some technology to use the TEAOH and second reagent to constitute compound system, as TEAOH--TEABr--trolamine (USP5164170), TEAOH--diethanolamine (USP5139759) etc.Caullet etc. introduce fluorion and synthesize the β zeolite in synthetic system, but it adopt diaza-1 in the USP5171556 technology, 4-dicyclo [2,2,2] octanes (DABCO) are structural agent, other adds methylamine, and synthetic in (PH＜9) of specific non-alkalescence medium, the system complexity.Above-mentioned these equal ends of existing technology overcome synthetic β zeolite because of a large amount of organic formwork agent cost of need problem of higher.Silicon ester or silica gel, soft silica etc. are generally adopted in the silicon source in the prior art, use silicon sol to do the also less of silicon source.
The present invention adopts tetraethylammonium cation and fluorochemical composite mould plate agent system, synthetic β zeolite in alkaline medium, and its purpose under the prerequisite that guarantees β zeolite quality, reduces production cost just.The present invention does the silicon source with the technical grade silicon sol, adopts composite mould plate agent.Owing to the adding of fluorochemical, can reduce the consumption of organic amine, and make comparisons with not adding fluorochemical, can enlarge the one-tenth phase region of β zeolite, productive rate also obviously increases.Thereby reduced cost.
The invention provides a kind of method of synthetic β zeolite, comprise that adding aluminium source, silicon source and weight in the basic solution that contains composite mould plate agent is the SiO that feeds intake 2The crystal seed of weight 0～5%, in 90～200 ℃ of reaction crystallization, washing after filtration,, drying, obtain the β zeolite product, it is characterized in that composite mould plate agent is that halogenide, tetraethyl ammonium hydroxide or its mixture and fluorochemical by tetraethyl ammonium constitutes, used material feeds intake according to following molar ratio range when synthetic β zeolite:
SiO 2/Al 2O 3 10--400
(TEA) 2O/SiO 2 0.03--0.5
Na 2O/SiO 2 0.005--0.6
H 2O/SiO 2 10--30
(NH 4) 2O/SiO 2 0--1.0
TEA +/ F -0.25--4 material proportion is the molar ratio range that reaches following preferably:
SiO 2/Al 2O 3=15～250
(TEA) 2O/SiO 2=0.04～0.35
Na 2O/SiO 2=0.04～0.4
H 2O/SiO 2=15～27
(NH 4) 2O/SiO 2=0～0.9
TEA +/F -=0.33～3.5
Fluorochemical of the present invention can be IA family fluorochemical, Neutral ammonium fluoride or its mixture; Mineral alkali of the present invention can be sodium hydroxide, potassium hydroxide or ammonium hydroxide; The preferred technical grade silicon sol in silicon of the present invention source; The preferred sodium aluminate in aluminium of the present invention source.
The crystallization temperature of synthetic β zeolite is 90-200 ℃, and more preferably 100-170 ℃, crystallization time is 4-15 days.
The preferred method of the synthetic β zeolite of the present invention is:
Under stirring fluorochemical is joined in the organic amine solution, add ammoniacal liquor after waiting to dissolve again, add sodium aluminate or its solution, silicon sol, crystal seed (also can not adding) successively, after continuously stirring 30-60 minute, change in the stainless steel cauldron, in 90-200 ℃ of following crystallization.PH value＞10 of reaction mixture.Crystallization finishes and carries out suction filtration, washing, and is dry under 140 ℃, obtains the β zeolite product, with X-ray diffraction its degree of crystallinity of technical Analysis and phase structure, analyzes its chemical constitution with chemical analysis method.
The method of calculation of yield are, gained β zeolite 500 ℃ of following roastings, is weighed after the cooling, after deducting institute and adding crystal seed weight, again divided by the sial (SiO that feeds intake 2And Al 2O 3) weight.
β zeolite with the method for the invention provides makes can become Hydrogen through roasting after also can exchanging with ammonium salt solution again through the roasting removed template method after pickling transformation is a Hydrogen.Can be by ion-exchange, dipping or other method with various metals or its compound, introduce wherein to make it to become the zeolite that contains different metal as element such as basic metal, alkaline-earth metal, rare earth element, Pt, Pd, Re, Sn, Ni, W, Co or its compound; The compound that also can introduce elements such as different compounds such as P, Ga, Ti, B makes it to become the zeolite with special purpose; Can also be by method dealuminzations such as pickling, chemical extractings to improve silica alumina ratio.Can be used as multiple catalyzer, catalyst adjuvant and sorbent material with present method synthetic β zeolite and modified version thereof.
Be recited in down according to embodiments of the invention.When adopting the TEABr+ fluorochemical to make template, can synthesize the β zeolite of Different Silicon aluminum ratio, see embodiment 1-example 5.
Embodiment 1 raw material is (A), silicon sol: contain SiO 2＞25%, industrial goods.
(B), sodium aluminate: contain Al 2O 3＞43%, contain Na 2O＞39%,
Industrial goods.
(C), tetraethylammonium bromide, commercially available product.
(D), Sodium Fluoride, commercially available product.
9.55g (C) and after 1.29g (D) is dissolved in the 25g deionized water, add 15ml25% ammoniacal liquor, stir to add successively by 1.78g (B) down and be dissolved in 20g solution that deionized water forms, 34.6g silicon sol and crystal seed 0.45g, continue to stir 60 minutes, change in the stainless steel cauldron, in 140 ℃ of following crystallization 9 days.BETA zeolite initial material mol ratio is: 1Al 2O 320SiO 23 (TEA) 2O4Na 2O13 (NH 4) 2O4F -595H 2O embodiment 2:
Raw material (A)-(D) is with embodiment 1
16g (C) and 1.6g (D) are dissolved in the 30g deionized water, stir to add successively by 1.67g (B) down to be dissolved in 20g deionized water gained solution, 53.7g (A) and 0.72g crystal seed, continue to stir 60 minutes, change in the stainless steel cauldron, in 140 ℃ of following crystallization 10 days.BETA zeolite initial material mol ratio is: 1Al 2O 333SiO 25 (TEA) 2O4Na 2O5F -709H 2The OXRD diffraction the results are shown in Table 1.
Table 1
2θ d() I/I 0
7.80 11.32 18
11.54 7.66 3
21.36 4.16 21
22.43 3.96 100
25.19 3.53 8
26.81 3.32 16
28.81 3.10 8
29.49 3.03 13
30.46 2.93 6
33.40 2.68 5
43.65 2.07 6
Embodiment 3
Raw material (A)-(D) all with embodiment 1 feeding quantity and reinforced order all with 2,160 ℃ of following crystallization of embodiment 4 days.BETA zeolite initial material mol ratio is: 1Al 2O 333SiO 25 (TEA) 2O5Na 2O6F -705H 2O embodiment 4
Raw material (A)-(D) is all with embodiment 1
After 16g (C) and 3.2g (D) are dissolved in the 35g deionized water, add 15ml25% ammoniacal liquor, stir to add successively by 0.55g (B) down and be dissolved in 10g solution that deionized water forms, 54.1g silicon sol and crystal seed 0.70g, continue to stir 60 minutes, change in the stainless steel cauldron, in 140 ℃ of following crystallization 12 days.BETA zeolite initial material mol ratio is: 1Al 2O 3101SiO 216 (TEA) 2O18Na 2O43 (NH 4) 2O32F -2268H 2O embodiment 5
After raw material (A)-(D) all is dissolved in the 40g deionized water with embodiment 125.5g (C) and 5.16g (D), add 25ml25% ammoniacal liquor, stir to add successively by 0.25g (B) down and be dissolved in 6g solution that deionized water forms, 46.7g silicon sol and crystal seed 0.45g, continue to stir 60 minutes, change in the stainless steel cauldron, in 140 ℃ of following crystallization 10 days.BETA zeolite initial material mol ratio is: 1Al 2O 3194SiO 2114 (TEA) 2O59Na 2O159 (NH 4) 2O114F -5200H 2O
Table 2
Embodiment 1 2 3 4 5
Silica alumina ratio feeds intake 20 33 33 101 194
The product silica alumina ratio 26 44 43 122 205
Relative crystallinity (%) 93 100 78 67 71
When adopting the TEAOH+ fluorochemical to make template, also can synthesize the BETA zeolite of Different Silicon aluminum ratio, see embodiment 6 and example 7.
Embodiment 6
Raw material (C) tetraethyl ammonium hydroxide, 23%, industrial goods
Raw material (A), (B), (D) are all with embodiment 1
46.5g add 1.5g (D) (C), stirring is dissolved in 20g deionized water gained solution, 53.6g (A) the following adding successively by 1.68g (B), continues to stir 60 minutes, changes in the stainless steel cauldron, in 140 ℃ of following crystallization 6 days, BETA zeolite initial material mol ratio was: 1Al 2O 333SiO 25 (TEA) 2O4Na 2O5F -753H 2O embodiment 7
Raw material (C) tetraethyl ammonium hydroxide, 23%, industrial goods
Raw material (A), (B), (D) are all with embodiment 1
32.3g add 1.0g (D) (C), stir and add 0.95g (B), 45.5g (A) down successively, continue to stir 60 minutes, change in the stainless steel cauldron, in 140 ℃ of following crystallization 6 days, BETA zeolite initial material mol ratio was: 1Al 2O 350SiO 26 (TEA) 2O6Na 2O6F -945H 2O
Table 3
Embodiment 6 7
Silica alumina ratio feeds intake 33 50
The product silica alumina ratio 32 48
Relative crystallinity (%) 96 97
Adopt composite mould plate agent system of the present invention can reduce consumption of template agent.For template be the TEABr+ fluorochemical the results are shown in embodiment 8-example 10, (TEA) 2O/SiO 2Reduce to 0.10 even 0.05 by 0.16.For template is the TEAOH+ fluorochemical, can obviously improve degree of crystallinity, sees embodiment 12 and example 7.Adopt composite mould plate agent system of the present invention, it is about 1/4 to 1/3 especially can to improve the zeolite yield, sees embodiment 8-example 11.
Embodiment 8 (Comparative Examples)
Raw material (A)～(C) is with embodiment 1
16g (C) is dissolved in the ammoniacal liquor that adds 15ml25% behind the 20g water, stir to add successively by 1.67g (B) and 0.9gNaOH down and be dissolved in 30g water gained solution, 53.7g (A) and 0.72g crystal seed, continue to stir 60 minutes, and changed in the stainless steel cauldron, in 140 ℃ of following crystallization 7 days.BETA zeolite initial material mol ratio is: 1Al 2O 333SiO 25 (TEA) 2O3Na 2O790H 2O embodiment 9
Raw material (A)-(D) is with embodiment 1
9.9g (C) and 1.96g (D) add 15ml25% ammoniacal liquor after being dissolved in the 20g deionized water, stir to add successively by 1.67g (B) down and be dissolved in 20g deionized water gained solution, 53.7g (A) and 0.70g crystal seed, continue to stir 60 minutes, and changed in the stainless steel cauldron, in 140 ℃ of following crystallization 10 days.BETA zeolite initial material mol ratio is: 1Al 2O 333SiO 23 (TEA) 2O5Na 2O3F -710H 2O embodiment 10
Raw material (A)-(D) is with embodiment 1
4.0g (C) and 1.24g (D) add 15ml25% ammoniacal liquor after being dissolved in the 20g deionized water, stir to add successively by 1.78g (B) down and be dissolved in 20g deionized water gained solution, 44.4g (A) and 0.58g crystal seed, continue to stir 60 minutes, and changed in the stainless steel cauldron, in 140 ℃ of following crystallization 12 days.BETA zeolite initial material mol ratio is: 1Al 2O 326SiO 21 (TEA) 2O3Na 2O4F610H 2O embodiment 11
Raw material (A)-(D) is with embodiment 1
Except that replacing the NaOH, with embodiment 8 with 1.6g (D).BETA zeolite initial material mol ratio is: 1Al 2O 333SiO 25 (TEA) 2O4Na 2O5F -790H 2O embodiment 12 (Comparative Examples)
Remove not add and fluoridize beyond the region of objective existence with embodiment 7
Table 4
Embodiment 8 9 10
Organic formwork agent TEABr
Content of fluoride (molar fraction) 0 0.009 0.006
Silica alumina ratio feeds intake 33 33 26
(TEA) 2O/SiO 2 0.16 0.10 0.05
Relative crystallinity (%) 100 75 66
Zeolite yield (%) 65.3 95.5 92.7
Table 5
Example 8 11 12 7
Organic formwork agent TEABr TEABr TEAOH TEAOH
Content of fluoride (molar fraction) 0 0.006 0 0.006
Silica alumina ratio feeds intake 33 33 50 50
(TEA) 2O/SiO 2 0.16 0.16 0.125 0.125
Relative crystallinity (%) 100 85 85 96
Zeolite yield (%) 65.3 98.0 69.5 74.5

Claims (7)

1. the method for a synthetic β zeolite comprises that adding aluminium source, silicon source and weight in the basic solution that contains composite mould plate agent is the SiO that feeds intake 2The crystal seed of weight 0～5%, in 90～200 ℃ of reaction crystallization, washing after filtration,, drying, obtain the β zeolite product, it is characterized in that composite mould plate agent is that halogenide, tetraethyl ammonium hydroxide or its mixture and fluorochemical by tetraethyl ammonium constitutes, used material feeds intake according to following molar ratio range when synthetic β zeolite:
SiO 2/Al 2O 3 10--400
(TEA) 2O/SiO 2 0.03--0.5
Na 2O/SiO 2 0.005--0.6
H 2O/SiO 2 10--30
(NH 4) 2O/SiO 2 0--1.0
TEA +/F - 0.25-4
2. in accordance with the method for claim 1, it is characterized in that fluorochemical is IA family fluorochemical, Neutral ammonium fluoride or its mixture.
3. in accordance with the method for claim 1, it is characterized in that the silicon source is a silicon sol.
4. in accordance with the method for claim 1, it is characterized in that the aluminium source is a sodium aluminate.
5. in accordance with the method for claim 1, it is characterized in that mineral alkali is sodium hydroxide, potassium hydroxide or ammonium hydroxide.
6. according to the described method of one of claim 1～5, the molar ratio range of the various compositions that feed intake when it is characterized in that synthesizing the β zeolite is:
SiO 2/Al 2O 3 15--250
(TEA) 2O/SiO 2 0.04--0.35
Na 2O/SiO 2 0.04-0.4
H 2O/SiO 2 15--27
(NH 4) 2O/SiO 2 0--0.9
TEA +/F - 0.33-3.5
7. in accordance with the method for claim 1, the crystallization temperature that it is characterized in that synthetic β zeolite is 100--170 ℃.
CN97111745A 1997-05-07 1997-05-07 Zeolite synthesizing method Expired - Lifetime CN1074388C (en)

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Publication number Priority date Publication date Assignee Title
CN101274764B (en) * 2007-03-30 2011-05-18 中国石油化工股份有限公司 Preparation for nanometer allitic beta-zeolite
CN106140286B (en) * 2015-03-27 2018-06-19 中国石油化工股份有限公司 The preparation method of carrier of hydrocracking catalyst
CN106140279B (en) * 2015-03-27 2018-10-12 中国石油化工股份有限公司 A kind of preparation method of diesel oil hydrogenation modification catalyst
CN106140281B (en) * 2015-03-27 2018-06-19 中国石油化工股份有限公司 A kind of preparation method of middle oil type hydrocracking catalyst
CN106140287B (en) * 2015-03-27 2018-06-19 中国石油化工股份有限公司 The preparation method of hydrocracking catalyst
CN106140251B (en) * 2015-03-27 2018-07-20 中国石油化工股份有限公司 Carrier of hydrocracking catalyst and preparation method thereof
CN106140249B (en) * 2015-03-27 2018-06-19 中国石油化工股份有限公司 A kind of preparation method of carrier of hydrocracking catalyst
FR3081342B1 (en) * 2018-05-24 2020-06-26 IFP Energies Nouvelles PROCESS FOR THE SYNTHESIS OF A COMPOSITE MATERIAL COMPOSED OF A MIXTURE OF ZEOLITHS OF STRUCTURAL TYPE AFX AND OF STRUCTURAL TYPE BEA IN THE PRESENCE OF AN ORGANIC NITROGEN STRUCTURANT

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4061724A (en) * 1975-09-22 1977-12-06 Union Carbide Corporation Crystalline silica
US4526879A (en) * 1978-11-13 1985-07-02 Mobil Oil Corporation Synthesis of zeolite ZSM-5
US5240892A (en) * 1987-09-02 1993-08-31 Mobil Oil Corporation Small crystal ZSM-5, as a catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4061724A (en) * 1975-09-22 1977-12-06 Union Carbide Corporation Crystalline silica
US4526879A (en) * 1978-11-13 1985-07-02 Mobil Oil Corporation Synthesis of zeolite ZSM-5
US5240892A (en) * 1987-09-02 1993-08-31 Mobil Oil Corporation Small crystal ZSM-5, as a catalyst

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