CN101108983B - Gasoline hydrodesulfurization method - Google Patents
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Abstract
A method using the gasoline hydrogenation to desulfurize is provided, which is carried out in a catalytic distillation column. The catalytic distillation column is divided into a rectification process section, a fractionation section, a stripping reaction section and a stripping section from top from bottom. The preheated raw materials are led into the fractionation section and the hydrogen is led into the bottom of the stripping section; the lighter components fractionated from the fractionation section enter into the section and conduct hydrodesulfurization reaction with the hydrogen under the contact with hydrodesulfurization catalyst A; the discharge on the tower top gains the liquid after cooling and separating; one part of the discharge returns to the rectification process section as the overhead reflux and the other part works as the desulfurized products 1; the heavier components fractionated enter the stripping reaction section and conduct hydrodesulfurization reaction with the hydrogen under the contact with hydrodesulfurization catalyst B and is discharged from the reboiler on the tower bottom after the a stripping section further separates the H2S to work as the desulfurized products 2. The method provided by the invention can obviously improve the rate of the desulfurization of gasoline and have low loss of the octane number of the gasoline.
Description
Technical field
The present invention relates to a kind of method of petroleum hydrocarbon hydrogenating desulfurization.More particularly, be a kind of particularly sulphur impurity in the catalytically cracked gasoline of gasoline that removes, reduce the method for gasoline octane rating loss simultaneously to greatest extent.
Background technology
Along with rapid development of automobile industry, vehicle exhaust is more and more serious to the pollution of environment, produces low-sulfur, low alkene, hangs down the target that the aromatic hydrocarbons vehicle fuel has become the common pursuit of people.The new vehicle fuel standard of the numerous and confused formulation in various countries, world fuel oil standard II class, III class gasoline standard require sulfur in gasoline content should be lower than 200ppm and 30ppm respectively.At present, the sulphur content 90～99% of gasoline product is from catalytically cracked gasoline; Therefore, reducing sulfur content of catalytic cracking gasoline is the key point that reduces the finished product content of sulfur in gasoline.
Sulfide in the gasoline mainly is divided into thio-alcohol, thioether class and thiophene-based, and wherein thiophene-type sulfide accounts for more than 70% of catalytic gasoline total sulfur.Mercaptan can remove by sophisticated soda finishing technology, and thiophene-type sulfide then needs to make thiophene sulphur compound and hydrogen reaction by hydrofining technology, and sulphur atom is converted into H
2S removes, and in order to reach higher desulfurization degree, must adopt harsh operational condition, but with the corresponding increase of raising alkene saturation exponent of desulfurization degree, the loss of octane number of gasoline products is very serious.Be devoted to both at home and abroad at present to develop catalytic gasoline selective hydrogenation technology, in desulfurization, reduce the gasoline octane rating loss as far as possible.
Olefin(e) centent height in the light fractions of FCC naphtha and sulfide content is low, sulfide content height in the last running, olefin(e) centent is lower simultaneously, therefore that a lot of gasoline selective hydrogen addition technologies normally cut into cat naphtha is light, weigh two cuts or light, in, weigh three cuts, and the characteristics of different cuts are handled respectively.
Patent CN1465668A discloses a kind of gasoline desulfating method, this method cuts into the weight cut with catalytic gasoline, lighting end is through the soda finishing mercaptan removal, last running enters fixed-bed reactor and flows to current downflow through selective hydrogenation catalyst (RSDS-1) bed after hydrogen mixing preheating, carry out hydrodesulfurization reaction.But in fixed-bed reactor, all materials all must be by whole beds, particularly C
6, C
7Alkene also must be unfavorable for improving the selectivity of hydrodesulfurization reaction by high temperature reaction zone.
US5779883 discloses a kind of catalytic distillation method of hydrocarbon-fraction hydrogenating desulfurization, this method is under refinery distillation, temperature raises at the bottom of from cat head to tower successively in the distillation Tata, the higher lighting end of olefin(e) centent is vertically to the cat head enrichment in the gasoline stocks, it is reacted in the lower catalytic distillation tower upper part of temperature, the higher last running of sulphur content is reacted in catalytic distillation tower lower part that temperature is higher vertically to the enrichment of tower still.This method can improve the selectivity of hydrodesulfurization reaction, and it is saturated to reduce alkene.
US5595654 discloses a kind of catalytic distillation method of gasoline hydrodesulfurizationmethod, catalytic gasoline is cut into the weight component in first catalytic distillation tower, making mercaptan in the lighting end and two alkene reactions generate heavier sulfide simultaneously flows out with the last running of tower still, thereby obtain the lighting end after the desulfurization, last running after the cutting is carried out hydrodesulfurization reaction in second catalytic distillation tower, remove most of sulfide of last running gasoline, the weight cut after the desulfurization is mixed obtaining the sweet gasoline product.
Compare with the conventional fixed bed process, catalytic distillation gasoline selective hydrodesulfurizationmodification technology has reduced the saturated of alkene in the gasoline products effectively.But full tower loads identical catalyzer and does not consider alkene and sulfide along the regularity of distribution that tower distributes, and is unfavorable for further improving the desulfurization degree of product and reduces the saturated of alkene.
Summary of the invention
The objective of the invention is on the basis of prior art, at the deficiencies in the prior art, provide a kind of hydrodesulfurizationprocess process that is fit to be rich in the gasoline of alkene, this method reduces the gasoline octane rating loss to greatest extent when removing sulphur impurity.
A kind of gasoline hydrodesulfurizationmethod method, this method is carried out in catalytic distillation tower, catalytic distillation tower is divided into the rectification process section from top to bottom, the fractionation section, carry and heat up in a steamer conversion zone and stripping section, introduce raw material after the preheating from the fractionation section, introduce hydrogen from the stripping section bottom, the fractionation section fractionates out than light constituent and heavy component, wherein enter the rectification process section than light constituent, with the contact of Hydrobon catalyst A under carry out hydrodesulfurization reaction with hydrogen, the cat head discharging is through cooling, obtain liquid after the separation, wherein a part is returned rectification process section top as trim the top of column, and another part is as desulfurization product 1; Heavy component enters downwards to carry heats up in a steamer conversion zone, with the contact of Hydrobon catalyst B under carry out hydrodesulfurization reaction with hydrogen, and further separate H through stripping section
2Discharge from tower bottom reboiler behind the S, as desulfurization product 2.
In the method provided by the invention, the raw material of introducing catalytic distillation tower can be full distillation gasoline, also can be the gasoline than last running after the fractionation.Preferably, can obtain: full distillation gasoline raw material is introduced preliminary fractionator, be cut into two cuts of weight by following steps than last running gasoline, in lighting end, substantially do not contain thiophene-type sulfide, lighting end obtains the very low desulfurization product of sulphur content 3 through the refining mercaptan that removes wherein of alkali cleaning; Catalytic distillation tower fractionation section is introduced in last running again.Wherein, the working pressure of described preliminary fractionator (absolute pressure) is 0.1～0.3Mpa, and tower top temperature is 60～75 ℃.
In the method provided by the invention, the temperature of reaction of described rectification process section is 200～290 ℃, preferred 260～280 ℃; Putting forward the temperature of reaction of heating up in a steamer conversion zone is 250～340 ℃, preferred 300～320 ℃; Distillation tower working pressure (absolute pressure) is 1～4.0MPa, preferred 1.5～2.6MPa, and feed hydrogen oil ratio volume ratio is 100～400Nm
3/ m
3, volume space velocity is 3～10h during feeding liquid
-1
In the method provided by the invention, described desulfurization product 1 can also further be introduced gas stripping column, carries the H that removes wherein through gas
2S obtains removing H
2The desulfurization product 4 of S.Obtain the gasoline products after the desulfurization after product 2,3 and 4 mixed.
In the method provided by the invention, hydrodesulfurization reaction is to carry out in catalytic distillation tower, described catalytic distillation tower is divided into rectification process section, fractionation section from top to bottom, carries and heat up in a steamer conversion zone and stripping section, and they account for the total bed height of catalytic distillation tower respectively: 50～60%:5～10%:20～30%:5～10%.
Said fractionation section accounts for 5～10% of total bed height, is mainly used in to be prefractionation is carried out in charging, prevents that olefin component lighter in the charging from heating up in a steamer the conversion zone high-temperature zone catalyst and contact with carrying, and olefin saturation takes place.The fractionation section can be loaded common distillation member, also can load selective hydrogenation catalyst.Under the hydrodesulfurization reaction condition, the easy rapid polymerization of the diolefine in the raw material generates macromolecular compound, and catalyst deactivation is caused in the duct of covering catalyst, reduces catalyst life.So it is active ingredient that the fractionation section is preferably loaded with one or more the mixture among Co, Mo, Ni and the W, is the selective hydrogenation catalyst of carrier with the porous alumina, make the diolefine selective hydrogenation generate monoolefine, to remove a spot of diolefine in the raw material.
Said rectification process section accounts for 50～60% of total bed height, and olefin(e) centent height in the light constituent that the fractionation of fractionation section obtains, alkene mainly are C
7Following alkene, if hydrogenation is saturated, loss of octane number is very big; And content of sulphur compounds is lower, and sulfide mainly is lightweight thiophene such as thiophene, thiotolene and part ethylthiophene, and this part sulfide more easily removes.Therefore the temperature of rectification process section is lower, selects at a lower temperature that the desulphurizing activated catalyzer good, that the alkene saturation exponent is low of thiophene carries out hydrofining, can keep olefin component wherein in desulfurization as much as possible.Such catalyzer is to be carrier with unformed aluminum oxide or sial, contains that one or more are the catalyzer of active ingredient among Co, Mo, the Ni.Preferably contain 1～40% molybdenum and/or cobalt in metal oxide, specific surface is not less than 200m
2The catalyzer of/g.More preferably, contain 1～25% molybdenum and/or cobalt, also contain 1～7% auxiliary agent magnesium, 5～60% macropore and one or more the catalyzer in the mesopore zeolite in metal oxide.
Said carrying heated up in a steamer conversion zone and accounted for 20～30% of total bed height, the heavy component that the fractionation section fractionates out enters downwards to carry heats up in a steamer conversion zone, the sulfide content of this heavy component is very high, and macromolecular cpds such as the ethylthiophene that sulfide is mainly, propyl group thiophene, butyl thiophene and thionaphthene need harsh hydrodesulfurization reaction condition just can remove.This part heavy constituent olefin(e) centent is low simultaneously, mainly is C
8Above alkene, even hydrogenation is saturated, loss of octane number is less relatively.It is aromatic hydrocarbons that the heavy constituent octane value is mainly contributed, and aromaticity content wherein is very high.Therefore it is saturated few to carry when heating up in a steamer conversion zone requirement deep hydrodesulfurizationof aromatic hydrocarbons.Down active higher, the saturated few Hydrobon catalyst of aromatic hydrocarbons of profit reduction and reserving conversion zone filling comparatively high temps.Such catalyzer is to contain among Co, Mo, Ni, the W one or more for active ingredient, is the selective desulfurization catalyst of carrier with the activated alumina.Preferably in metal oxide, contain 10～30% W, 1.0～7.0% Ni and 0.01～1.0% Co, and 0.1～2% zinc is or/and magnesium, and the catalyzer of the activated alumina of surplus.This catalyzer has excellent hydrodesulfurization performance, and aromatic hydrogenation is seldom saturated simultaneously.
Said stripping section accounts for 5～10% of total bed height, and the effect that stripping section is set is to heat up in a steamer the reacted material of conversion zone and carry through further gas carrying, and removes H wherein
2S, discharging does not contain H at the bottom of the assurance tower
2S.
In the method provided by the invention, described catalyst shape is cloverleaf pattern, cylindrical, spherical, Raschig ring shape, flat annular, wheel shape or regular catalyst filler.When catalyzer was low particle size, the filling form of catalyzer was with the filling of catalyzer bale packing or catalyzer and random packing mixed packing, or is prepared into filling.Catalyzer is in rectification process section, fractionation section and to put forward the filling voidage of heating up in a steamer conversion zone be 50～80%, and preferred 60～75%.
In the method provided by the invention, described raw material is meant that the boiling range scope is 20～250 ℃ a gasoline fraction, is particularly suitable for handling the high catalytically cracked gasoline of olefin(e) centent.
The advantage of method provided by the invention is:
Method provided by the invention, compare with the method for catalytic distillation hydrogenation desulfurization, increase the fractionation section at catalytic distillation tower feed entrance point place, and the rectification process district is set and carries and heat up in a steamer reaction zone, contacting under comparatively high temps with high activity hydrogenation and desulphurization catalyst than heavy naphtha that olefin(e) centent is low, sulfide content is high reacted, the light gasoline fraction of olefin(e) centent height, sulfide content contacts reaction at a lower temperature with the high-selective and hydrogenating desulfurization catalyst, can significantly improve the gasoline desulfur rate, gasoline octane rating loss simultaneously is little; When handling C
6During the high full distillation gasoline of following olefin(e) centent, before catalytic distillation tower, increase preliminary fractionator, and adopt caustic washing method to remove mercaptan in the discharging of preliminary fractionator cat head, so the present invention can handle the gasoline fraction that different boiling ranges and alkene, sulfide are formed flexibly.
Description of drawings
Accompanying drawing is the schematic flow sheet of hydrodesulfurizationprocess process provided by the invention,
Wherein: the I-preliminary fractionator; The II-catalytic distillation tower; The III-return tank; 1-preliminary fractionator feeding line; 2-fractionator overhead discharging pipeline; Discharging pipeline at the bottom of the 3-prefractionation Tata; Discharging pipeline behind the 4-mercaptan removal; The 5-hydrogen feed line; 6-catalytic distillation column overhead discharge nozzle line; 7-gas discharging pipeline; The 8-reflux pipeline; 9-backflow discharging pipeline; 10-takes off H
2Discharging pipeline behind the S; Discharging pipeline at the bottom of the 11-tower; The 12-reboiler; 13-bottom product pipeline; 11-rectification process section; 12-fractionation section; 13-carries and heats up in a steamer conversion zone; The 14-stripping section.
Embodiment
Below in conjunction with accompanying drawing method provided by the present invention further is illustrated, but not thereby limiting the invention.
Raw material is introduced preliminary fractionator I through pipeline 1, and the gasoline lighting end after fractionation is introduced alkali cleaning refining desulfurization alcohol device through pipeline 2, and the petroleum naphtha behind the mercaptan removal is drawn through pipeline 4; Gasoline last running after the preliminary fractionator fractionation is introduced the fractionation section at catalytic distillation tower II middle part through pipeline 3, hydrogen is introduced below 14 from stripping section by pipeline 5, fractionation section 12 filling selective hydrogenation catalyst C, gasoline last running is after diene is taken off in fractionation section 12 fractionation reaction, wherein, upwards enter rectification process section 11 than light constituent, with the contact of Hydrobon catalyst A under carry out hydrodesulfurization reaction with hydrogen, reacted logistics and unreacted H
2Draw through pipeline 6 from cat head, after the condensation cooling, enter return tank III again and be divided into gas-liquid two-phase, H
2And H
2Gas phases such as S part is discharged through pipeline 7, and the part in the liquid phase turns back to rectifying section conversion zone 11 tops through pipeline 8 as backflow, and another part liquid is drawn stripping tower through pipeline 9 and taken off H
2S discharges through pipeline 10 and takes off H
2Product behind the S; Heavy component after 12 fractionation of fractionation section, flow downward to enter to carry and heat up in a steamer conversion zone 13, with the contact of Hydrobon catalyst B under and hydrogen react, reacted liquid phase is drawn through distillation tower bottom pipeline 11, part liquid returns stripping section 14 bottoms after reboiler 12 heating, take off H in the lighting end of another part liquid product mercaptan removal in pipeline 13 and pipeline 4, the pipeline 10
2Return tank III liquid mixing behind the S obtains the sweet gasoline product.
The following examples will illustrate further to method provided by the invention, but not thereby limiting the invention.
The trade names of used Hydrobon catalyst are RGO-2, RSDS-1 and CH-18 in embodiment and the Comparative Examples, and these three kinds of catalyzer are produced by Sinopec Group's Chang Ling oil-refining chemical head factory catalyst plant.Catalyst property sees Table 1.
Comparative Examples
With the catalytically cracked gasoline is raw material, earlier in preliminary fractionator raw material is carried out fractionation, the separation column operational condition is: working pressure 0.2MPa (absolute pressure), 65 ℃ of cat head recovered temperatures, the gasoline last running of cutting back accounts for 66% of raw material gross weight, and the character of raw material and cutting back gasoline weight cut sees Table 2.
The catalytic distillation tower diameter is the high 4m of being of Φ 32mm, wherein, the high 30cm of stripping section, all the other filling selective hydrogenation catalyst RSDS-1 are totally 200 grams, and the catalytic distillation tower working pressure is 2.3MPa, the middle part charging, the above beds medial temperature of charging is 260 ℃, the following beds medial temperature of charging is 290 ℃, and inlet amount is 800 Grams Per Hours, and the charging hydrogen to oil volume ratio is 300Nm
3/ m
3, the discharging of catalytic distillation column overhead is 600 Grams Per Hours.Gasoline last running and mercaptan removal gasoline lighting end mixing prod character see Table 3 after the desulfurization.
Raw materials used, treatment capacity, reaction conditions are identical with Comparative Examples, and different is to increase a fractionation section at tower middle part opening for feed, and the fractionation section highly be 40cm, and the filling of fractionation section selects hydrogenation catalyst RGO-2 catalyzer 25 to restrain.Bottom stripping section high 30cm, carries and heats up in a steamer reaction zone and all load the RSDS-1 catalyzer rectification process district, and rectification process district height is 220cm, carries and heats up in a steamer reaction zone height 110cm.Product property sees Table 3 after the desulfurization.
Raw materials used, treatment capacity, reaction conditions, catalyst loading position are identical with embodiment 1, and different is rectification process section filling RSDS-1 catalyzer, carry heating up in a steamer conversion zone and loading high activity hydrogenation and desulphurization catalyst CH-18, and product property sees Table 2 after the desulfurization
Table 1
| Catalyzer | CH-18 | RGO-2 | RSDS-1 |
| WO 3，％ | ≮19.0 | / | / |
| MoO 3，％ | / | ≮5.0 | ≮8.0 |
| NiO，％ | ≮2.0 | ≮2.5 | / |
| CoO，％ | ≮0.04 | / | ≮2.5 |
| Specific surface, m 2/g | ≮130 | ≮170 | ≮250 |
| Pore volume, ml/g | ≮0.27 | ≮0.50 | ≮0.35 |
*Percentage ratio in the table is weight percentage.
Table 2
| ? | Raw material | The mercaptan removal lighting end | Last running |
| Density, g/cm3 | 0.7157 | 0.6035 | 0.774 |
| Olefin(e) centent, % | 34 | 41.4 | 30.2 |
| Aromaticity content, % | 17 | 0.9 | 26.6 |
| Sulphur content, ppm | 760 | 10 | 1150 |
| Mercaptans content, ppm | 63 | <3 | 28 |
| RON | 93.6 | ? | ? |
*Percentage ratio in the table is volumn concentration.
Table 3
| ? | | Embodiment | 1 | |
| Density, g/cm3 | 0.7142 | 0.7135 | 0.7130 | |
| Olefin(e) centent, % | 28.5 | 31.7 | 31.6 | |
| Aromaticity content, % | 16.9 | 17.0 | 16.9 | |
| Sulphur content, ppm | 61 | 55 | 25 | |
| Mercaptans content, ppm | <3 | <3 | <3 | |
| RON | 92.5 | 92.7 | 92.7 | |
| The gasoline desulfur rate, % | 92.0 | 92.8 | 96.7 | |
| ΔRON | 1.1 | 0.9 | 0.9 |
*Percentage ratio in the table is volumn concentration.
By table 3 as seen, method provided by the invention, catalytic distillation tower fractionation section filling selective hydrogenation catalyst RGO-2, rectification process section filling catalyst for selectively hydrodesulfurizing RSDS-1, carry and heat up in a steamer conversion zone filling high-activity hydrogenation catalyst CH-18 (embodiment 2), than Comparative Examples, the gasoline desulfur rate has increased by 4～5 percentage points, and gasoline octane rating loses 0.2 less; Catalytic distillation tower fractionation section filling selective hydrogenation catalyst RGO-2, rectification process section filling catalyst for selectively hydrodesulfurizing RSDS-1 carries and heats up in a steamer conversion zone and also load RSDS-1 (embodiment 1), than Comparative Examples, the gasoline desulfur rate has increased by 0.8 percentage point, and gasoline octane rating loses 0.2 less.
Claims (13)
1. gasoline hydrodesulfurizationmethod method, this method is carried out in catalytic distillation tower, it is characterized in that catalytic distillation tower is divided into the rectification process section from top to bottom, the fractionation section, carry and heat up in a steamer conversion zone and stripping section, introduce raw material after the preheating from the fractionation section, introduce hydrogen from the stripping section bottom, the fractionation section fractionates out than light constituent and heavy component, wherein enter the rectification process section than light constituent, with the contact of Hydrobon catalyst A under carry out hydrodesulfurization reaction with hydrogen, the cat head discharging is through cooling, obtain liquid after the separation, wherein a part is returned rectification process section top as trim the top of column, and another part is as desulfurization product 1; Heavy component enters downwards to carry heats up in a steamer conversion zone, with the contact of Hydrobon catalyst B under carry out hydrodesulfurization reaction with hydrogen, and further separate H through stripping section
2Discharge from tower bottom reboiler behind the S, as desulfurization product 2, the temperature of reaction of described rectification process section is 200～290 ℃, and putting forward the temperature of reaction of heating up in a steamer conversion zone is 250～340 ℃, the absolute working pressure of distillation tower is 1～4.0MPa, and feed hydrogen oil ratio volume ratio is 100～400Nm
3/ m
3, volume space velocity is 3～10h during feeding liquid
-1
2. according to the method for claim 1, it is characterized in that earlier described raw material being obtained lighting end and last running through the preliminary fractionator cutting earlier, catalytic distillation tower fractionation section is introduced in last running again, and the absolute working pressure of described preliminary fractionator is 0.1～0.3Mpa, and tower top temperature is 60～75 ℃.
3. according to the method for claim 2, it is characterized in that described lighting end through the refining mercaptan that removes wherein of alkali cleaning, obtains desulfurization product 3.
4. according to the method for claim 1, it is characterized in that described desulfurization product 1 removes wherein hydrogen sulfide through gas stripping column.
5. according to the method for claim 1, it is characterized in that described catalytic distillation tower rectification process section, fractionation section, carry and heat up in a steamer conversion zone and stripping section and account for total bed height respectively: 50～60%, 5～10%, 20～30%, 5～10%.
6. according to the method for claim 1, it is characterized in that in fractionation section filling is active ingredient, is the catalyzer of carrier with the porous alumina with one or more the mixture among Co, Mo, Ni and the W.
7. according to the method for claim 1, it is characterized in that described catalyst A is to contain VI
BOr VIII family metal is active ingredient, is the catalyzer of carrier with unformed aluminum oxide or sial.
8. according to the method for claim 7, it is characterized in that the content of molybdenum in the described catalyst A and/or cobalt accounts for 1%～40% of catalyst weight in metal oxide, the specific surface of catalyzer is not less than 200m
2/ g.
9. according to the method for claim 8, it is characterized in that the content of molybdenum in the described catalyst A and/or cobalt accounts for 1～25% of catalyst weight in metal oxide, also contain 1～7% auxiliary agent magnesium, 5～60% macropore and in the mesopore zeolite one or more.
10. according to the method for claim 1, it is characterized in that described catalyst B is to contain among Co, Ni, Mo, the W one or more to be active ingredient, be the selective desulfurization catalyst of carrier with the activated alumina.
11., it is characterized in that containing in the described catalyst B 10～30% W, 1.0～7.0% the Ni, 0.01～1.0% Co and 0.1～2% auxiliary agent zinc and/or the magnesium that account for catalyst weight in metal oxide according to the method for claim 10.
12. according to the method for claim 1, it is characterized in that the temperature of reaction of described rectification process section is 260～280 ℃, putting forward the temperature of reaction of heating up in a steamer conversion zone is 300～320 ℃.
13. according to the method for claim 1, it is characterized in that described rectification process section, fractionation section and putting forward the filling voidage of heating up in a steamer conversion zone is 50～80%.
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| CN102879522B (en) * | 2011-07-11 | 2016-01-13 | 中国石油化工股份有限公司 | Measure the method for organic sulfur in hydrodesulfurization reaction product |
| CN102876374B (en) * | 2011-07-11 | 2015-04-01 | 中国石油化工股份有限公司 | Inferior diesel oil hydrodesulfurization method |
| CN103074104B (en) * | 2011-10-26 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of gasoline hydrodesulfurizationmethod method |
| CN103773494B (en) * | 2013-12-24 | 2016-01-20 | 天津市昊永化工工程有限公司 | The production technique of hydrogen circulation differential catalytic distillation desulfurization and equipment |
| CN111909726B (en) * | 2020-07-15 | 2023-01-17 | 凯瑞环保科技股份有限公司 | Process for thioalkylation of thiophenes |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5779833A (en) * | 1995-08-04 | 1998-07-14 | Case Western Reserve University | Method for constructing three dimensional bodies from laminations |
| CN1356377A (en) * | 2000-12-01 | 2002-07-03 | 中国石化集团齐鲁石油化工公司 | Catalyst for selectively hydrodesulfurizing gasoline and its preparing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5779833A (en) * | 1995-08-04 | 1998-07-14 | Case Western Reserve University | Method for constructing three dimensional bodies from laminations |
| CN1356377A (en) * | 2000-12-01 | 2002-07-03 | 中国石化集团齐鲁石油化工公司 | Catalyst for selectively hydrodesulfurizing gasoline and its preparing process |
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