CN101440302B - Method for lowering benzene content in gasoline and catalyst thereof - Google Patents
Method for lowering benzene content in gasoline and catalyst thereof Download PDFInfo
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- CN101440302B CN101440302B CN2008102315602A CN200810231560A CN101440302B CN 101440302 B CN101440302 B CN 101440302B CN 2008102315602 A CN2008102315602 A CN 2008102315602A CN 200810231560 A CN200810231560 A CN 200810231560A CN 101440302 B CN101440302 B CN 101440302B
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Abstract
本发明介绍了一种降低汽油中苯含量并提高催化裂化过程液态烃收率的方法以及该方法的催化剂，特征在于在催化裂化装置设置催化反应系统，将干气、汽油馏分等引入反应系统，在催化剂的作用下，干气中的烯烃与汽油馏分等的苯发生反应转化为大分子，苯转化为烷基苯。催化剂由15～95％的活性组分和5～85％的粘结剂及载体组成，活性组分由改性ZSM-5分子筛和改性Y型分子筛组成。本发明方法在不影响现有催化裂化装置操作状态的情况下，大幅降低干气产率，降低汽油的苯含量，提高目标产品的产率和质量；在提高丙烯产率的情况下，干气产率降低，液态烃产率提高或不降低；基本不增加催化裂化单元能耗；过程比较简单，经济效益好。The invention introduces a method for reducing the benzene content in gasoline and increasing the yield of liquid hydrocarbons in the catalytic cracking process and a catalyst for the method, which is characterized in that a catalytic reaction system is installed in the catalytic cracking unit, and dry gas, gasoline fractions, etc. are introduced into the reaction system, Under the action of the catalyst, the olefins in the dry gas react with benzene such as gasoline fractions to convert them into macromolecules, and benzene is converted into alkylbenzenes. The catalyst is composed of 15-95% active component and 5-85% binder and carrier, and the active component is composed of modified ZSM-5 molecular sieve and modified Y-type molecular sieve. The method of the present invention can greatly reduce the dry gas yield, reduce the benzene content of gasoline, and improve the yield and quality of the target product without affecting the operating state of the existing catalytic cracking unit; in the case of increasing the propylene yield, the dry gas The production rate is reduced, and the liquid hydrocarbon production rate is increased or not decreased; the energy consumption of the catalytic cracking unit is basically not increased; the process is relatively simple and the economic benefit is good.
Description
Technical field
The present invention relates to the method that a kind of catalytic cracking petroleum hydrocarbons prepares industrial chemicals and oil fuel, particularly a kind ofly reduce Determination of Benzene In Gasoline and improve the method for catalytic cracking process liquid hydrocarbon yield and catalyzer and the method for making thereof of the method.
Background technology
Catalytic cracking process is one of important oil secondary processing technique, pass through catalytic cracking process, heavier petroleum fractions can be converted into dry gas, liquefied petroleum gas (LPG), gasoline, diesel oil, coke etc., wherein liquefied petroleum gas (LPG), gasoline, diesel oil are the major objective products of catalytic cracking process, and dry gas, coke then are the association products of catalytic cracking process.In general, can satisfy under the thermally equilibrated condition of catalytic cracking process, the productive rate of coke is more few better; And with regard to dry gas, it is the target that realizes that the catalytic cracking process Optimizing operation is pursued always that pursuit catalytic cracking process dry gas yied minimizes.In recent years, along with market is increasing to the demand of propylene product, catalytic cracking process becomes again the significant process that obtains propylene product, but when increasing the catalytic cracking process productivity of propylene, dry gas yied also increases thereupon.Catalytically cracked gasoline, catalytic reforming gasoline are the main components of China's motor spirit, and along with the upgrading of China's motor spirit standard, the benzene content requirement in the gasoline is not more than 1.0% (v); And in fact the benzene content of catalytically cracked gasoline, catalytic reforming gasoline is often greater than 1.0% (v), and this just causes the motor spirit benzene content situation not up to standard of a part of enterprise production.In general, although the benzene content in the catalytically cracked gasoline catalytic reforming surpasses the benzene content of motor spirit regulation, but the benzene content in the catalytically cracked gasoline often is no more than 10.0% (v), this just makes and must remove benzene unnecessary in catalytically cracked gasoline, the catalytic reforming, has become the thing of a difficulty.
Therefore, in the urgent need to a kind of technique, can when reducing the catalytic cracked dry gas productive rate, increasing the catalytic cracking liquid hydrocarbon productivity, reduce catalytic cracking, catalytic reforming Determination of Benzene In Gasoline.
Summary of the invention
Technical problem to be solved by this invention is that the benzene content of, catalytically cracked gasoline higher for existing catalytic cracking process process dry gas yied, catalytic reforming gasoline is often greater than 1.0% (v) of China's motor spirit regulation, and a kind of processing method that can realize reducing catalytically cracked gasoline, catalytic reforming Determination of Benzene In Gasoline when reducing the catalytic cracked dry gas productive rate, increasing the catalytic cracking liquid hydrocarbon productivity that proposes realizes the maximizing the benefits of the oil refining course of processing.
The technical problem that the present invention further solves provides a kind of Catalysts and its preparation method of above-mentioned processing method.
Reduction Determination of Benzene In Gasoline of the present invention also improves the method for catalytic cracking process liquid hydrocarbon yield, adopted following technical scheme: at the catalytic cracking unit productive unit catalytic reaction system is set, 65～90 ℃ of cuts of dry gas, catalytically cracked gasoline that catalytic cracking unit is produced and or 65～90 ℃ of cuts of catalytic reforming gasoline introduce reactive system, under the effect of catalyzer, alkene in the dry gas and catalytically cracked gasoline and or catalytic reforming gasoline in benzene react, conversion of olefines in the dry gas is that macromole enters liquid hydrocarbon, reduces the productive rate of dry gas; Benzene in the gasoline has reduced the benzene content in the gasoline because being converted into alkylbenzene; Reacted reaction product enters other operating unit and separates or process.For example, can separate in Separate System of Water-jet, the unreacted dry gas goes to dry gas stocking system or fuel gas pipe network system, and the liquid hydrocarbon of generation is sent into the liquid hydrocarbon system of catalytic cracking unit unit; Also can produce as required other products.
Method of the present invention, preferred technical scheme is: the temperature of reaction of catalytic reaction system is 200～410 ℃, reaction pressure 0.1～1.5MPa, air speed 0.1～1.5h
-1
Method of the present invention, preferred technical scheme is: the reaction pressure of catalytic reaction system is 0.3～0.70MPa, air speed is 0.2～0.6h
-1
The catalyzer of catalytic reaction system of the present invention is comprised of the active ingredient that accounts for total catalyst weight 15～95% and the binding agent and the carrier that account for total catalyst weight 5～85 % by weight, and its shape can be bar shaped or spherical catalyst; Active ingredient is comprised of the modified zsm-5 zeolite that accounts for total catalyst weight 15～95% and the Modified Zeolite Y that accounts for total catalyst weight 0～15%; The used modifying element of modified ZSM-5 be phosphorus be selected from zinc and or nickel and or rare earth metal in one or more metals, modifying element accounts for the 0.1-10% of molecular sieve weight after the modification, wherein preferred 1-5%; The used modifying element of Modified Zeolite Y is to be selected from one or more metals in titanium metal and the rare earth metal, and modifying element accounts for the 0.1-10% of molecular sieve weight after the modification, wherein preferred 1-5%; Binding agent can be selected from silicon sol, aluminium colloidal sol or its mixture, the optional order kaolin of carrier, amorphous silicon aluminium, precipitated silica, aluminum oxide or its mixture etc., perhaps binding agent and carrier are pseudo-boehmite and an amount of rare nitric acid and other mixture inorganic or aqueous solutions of organic acids, and these acid include, but are not limited to hydrochloric acid, phosphoric acid acetic acid, citric acid, oxalic acid etc.; The weight ratio of binding agent and carrier is 5～35.
The preferred catalyzer of catalytic reaction system of the present invention, the preparation method of its modified zsm-5 zeolite is: the modified material wiring solution-forming that will contain modifying element, again ZSM-5 molecular sieve is immersed in this solution 1.0～3.0 hours, then dry, bake out temperature preferably 100 ℃～130 ℃, carried out roasting 1～6 hour at 530 ℃～580 ℃ again; In the steeping process, modified material can be the difference wiring solution-forming, flood respectively, and also can be to be made into mixed solution, once finish dip treating.
The preferred catalyzer of catalytic reaction system of the present invention, the preparation method of its Modified Zeolite Y is, the modified material wiring solution-forming that will contain modifying element, again Y zeolite is immersed in this solution 0.80～3.5 hour, then dry, bake out temperature preferably 100 ℃～130 ℃, carried out roasting 1～6 hour at 530 ℃～580 ℃ again; In the steeping process, modified material can be the difference wiring solution-forming, flood respectively, and also can be to be made into mixed solution, once finish dip treating.
Above-mentioned modified zsm-5 zeolite and Modified Zeolite Y, its modified molecular screen element can derive from water-soluble cpds, as: the nitrate of metal, chlorate, vitriol or other water soluble salt, such as oxalate, Citrate trianion, tartrate, malate, lactic acid salt etc.; Phosphoric can come from phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate and other contain material of phosphate radical etc.
The preparation method of catalyzer of the present invention is with the modified zsm-5 zeolite after the modification and Modified Zeolite Y, mix in proportion with binding agent and carrier, after forming process, obtain bar shaped or spherical catalyzer, then dry, bake out temperature preferably 100 ℃～130 ℃, carried out roasting 1～6 hour at 530 ℃～580 ℃ again, be catalyzer required for the present invention.
The preparation method of catalyzer of the present invention also can adopt first commodity ZSM-5 molecular sieve, Y zeolite are mixed in proportion with binding agent and carrier, after forming process, obtain bar shaped or spherical catalyzer, carry out roasting, roasting was preferably carried out 1～6 hour at 530 ℃～580 ℃, after the roasting, carry phosphorus and carry metal by the preparation method of above-mentioned modified zsm-5 zeolite again, dry again, bake out temperature preferably 100 ℃～130 ℃, carried out roasting 1～6 hour at 530 ℃～580 ℃ again, be catalyzer required for the present invention.
By adopting above-mentioned technical scheme, beneficial effect of the present invention is:
(1) the inventive method can significantly reduce the productive rate of catalytic cracked dry gas in the situation that does not affect existing catalytic cracking unit operational stage, reduces the benzene content of catalytically cracked gasoline, catalytic reforming gasoline, improves productive rate and the quality of target product.
(2) adopt the inventive method, can be implemented in the situation that improves the catalytic cracking unit productivity of propylene, dry gas yied reduces, and liquid hydrocarbon productivity improves or do not reduce.
(3) process of realization the inventive method is fairly simple, and not needing increases or drop into more equipment, so economic benefit is fine.
(4) reaction process of the inventive method belongs to exothermic process, therefore in the process that realizes the inventive method, does not substantially increase the energy consumption of catalytic cracking unit.
Embodiment
Embodiment 1～5 is catalyst preparation example.
Embodiment 1
With phosphoric acid, zinc nitrate, lanthanum nitrate wiring solution-forming, phosphorous 3% in the solution, contain zinc 1.1%, contain lanthanum 1.8%, again ZSM-5 molecular sieve is immersed in this solution 2.0 hours, then under 100 ℃ condition, dry, under 550 ℃ condition, carry out again roasting 2 hours, namely get ZSM-5 molecular sieve after the modification.With titanous chloride, cerous nitrate wiring solution-forming, titaniferous 1.5% in the solution, contain cerium 3%, again Y zeolite is immersed in this solution 2.0 hours, then under 110 ℃ condition, dry, under 530 ℃ condition, carry out again roasting 5 hours, namely get Y zeolite after the modification.Then be that 9% diluted nitric acid aqueous solution mixes with the Modified Zeolite Y of modified ZSM-5 type molecular sieve, 3% titaniferous and the cerium of 67% phosphorous, zinc and lanthanum, 30% pseudo-boehmite and an amount of concentration, carry out kneading, be processed as bar shaped at forming machine, about 110 ℃, carried out drying 24 hours, place again 550 ℃ roasting temperature 4 hours, be catalyst A.
Embodiment 2
With ammonium phosphate, zinc acetate wiring solution-forming, solution is phosphorous 5.5%, contain zinc 2.8%, ZSM-5 molecular sieve is immersed in this solution 1.0 hours again, then dries under 120 ℃ condition, under 570 ℃ condition, carry out again roasting 2 hours, namely get ZSM-5 molecular sieve after the modification.It is 7% acetic acid,diluted aqueous solution with the modified ZSM-5 type molecular sieve of 70% phosphorous, zinc, 30% pseudo-boehmite and an amount of concentration, carry out kneading, be processed as bar shaped at forming machine, about 110 ℃, carried out drying 24 hours, place again 580 ℃ roasting temperature 1.5 hours, be catalyst B.
Embodiment 3
Just phosphoric acid, lanthanum nitrate wiring solution-forming, solution is phosphorous 3.5%, contain lanthanum 2.3%, ZSM-5 molecular sieve is immersed in this solution 3.0 hours again, then dries under 100 ℃ condition, under 550 ℃ condition, carry out again roasting 3 hours, namely get ZSM-5 molecular sieve after the modification.With titanium tetrachloride, cerous acetate wiring solution-forming, titaniferous 2.5% in the solution, contain cerium 2.3%, again Y zeolite is immersed in this solution 3.0 hours, then under 100 ℃ condition, dry, under 550 ℃ condition, carry out again roasting 4 hours, namely get Y zeolite after the modification.Then Y zeolite, 3% amorphous aluminum silicide, 27% pseudo-boehmite and an amount of concentration that 69.5% phosphorous and modified ZSM-5 type molecular sieve, 0.5% lanthanum is contained modified material titanium and cerium is that 6.5% diluted nitric acid aqueous solution mixes, carry out kneading, be processed as sphere at forming machine, drying is 24 hours about 110 ℃, place again 560 ℃ roasting temperature 3 hours, be catalyzer C.
Embodiment 4
Catalyzer D consist of: the Y zeolite of type ZSM 5 molecular sieve, 1% titaniferous and the lanthanum of 75% phosphorous and lanthanum, all the other are pseudo-boehmite.Other preparation conditions of catalyzer D are identical with catalyst A.
Embodiment 5
Catalyzer E consist of: the type ZSM 5 molecular sieve of 80% phosphorous and cerium, 20% pseudo-boehmite.Other preparation conditions of catalyzer E are identical with catalyst B.
Embodiment 6～10th, the invention process effect example.Wherein used catalytically cracked gasoline narrow fraction, the character of catalytic reforming gasoline narrow fraction see Table 1 among the embodiment, and test-results is listed in table 2.
Table 1 raw material properties
| Raw material | Catalytically cracked gasoline narrow fraction 1 | Catalytically cracked gasoline narrow fraction 2 | Catalytic reforming gasoline narrow fraction 3 | Catalytic reforming gasoline narrow fraction 4 |
| Density (20 ℃)/gcm -3 | 0.70 | 0.72 | 0.73 | 0.71 |
| The benzene volume content, % | 15 | 20 | 25 | 22 |
| Boiling range, ℃ | 65-90 | 65-90 | 65-90 | 65-90 |
Embodiment 6
The dry gas of the alkene weight content 19.5% of catalytic cracking device and catalytically cracked gasoline narrow fraction 1 are introduced the testing apparatus that 100 gram catalyst A are housed in the future, and the operational condition of reactor is 320 ℃ of temperature of reaction, reaction pressure 0.6Mpa, air speed 0.4h
-1Test-results is listed in table 2.By adopting as seen from Table 2 the inventive method, the dry gas reduced rate is 18.8%, and the liquid hydrocarbon increment rate is 18%, and the benzene volume content of the generation oil of catalytically cracked gasoline narrow fraction 1 is 0.9%.
Embodiment 7
The dry gas of the alkene weight content 23% of catalytic cracking device and catalytically cracked gasoline narrow fraction 2 are introduced the testing apparatus that 110 gram catalyst B are housed in the future, and the operational condition of reactor is 350 ℃ of temperature of reaction, reaction pressure 0.8Mpa, air speed 0.6h
-1Test-results is listed in table 2.By adopting as seen from Table 2 the inventive method, the dry gas reduced rate is 21%, and the liquid hydrocarbon increment rate is 20.8%, and the benzene volume content of the generation oil of catalytically cracked gasoline narrow fraction 2 is 0.86%.
Embodiment 8
The dry gas of the alkene weight content 30% of catalytic cracking device and catalytic reforming gasoline narrow fraction 3 are introduced the testing apparatus that 130 gram catalyzer C are housed in the future, and the operational condition of reactor is 380 ℃ of temperature of reaction, reaction pressure 0.5Mpa, air speed 0.8h
-1Test-results is listed in table 2.By adopting as seen from Table 2 the inventive method, the dry gas reduced rate is 28.5%, and the liquid hydrocarbon increment rate is 28.4%, and the benzene volume content of the generation oil of catalytic reforming gasoline narrow fraction 3 is 0.84%.
Embodiment 9
The dry gas of the alkene weight content 35% of catalytic cracking device and catalytic reforming gasoline narrow fraction 4 are introduced the testing apparatus that 110 gram catalyzer D are housed in the future, and the operational condition of reactor is 400 ℃ of temperature of reaction, reaction pressure 0.6Mpa, air speed 0.4h
-1Test-results is listed in table 2.By adopting as seen from Table 2 the inventive method, the dry gas reduced rate is 34.3%, and the liquid hydrocarbon increment rate is 34.2%, and the benzene volume content of the generation oil of catalytic reforming gasoline narrow fraction 4 is 0.99%.
Embodiment 10
The dry gas of the alkene weight content 12% of catalytic cracking device and catalytic reforming gasoline narrow fraction 3 are introduced the testing apparatus that 100 gram catalyzer E are housed in the future, and the operational condition of reactor is 360 ℃ of temperature of reaction, reaction pressure 0.6Mpa, air speed 0.4h
-1Test-results is listed in table 2.By adopting as seen from Table 2 the inventive method, the dry gas reduced rate is 11.6%, and the liquid hydrocarbon increment rate is 11.5%, and the benzene volume content of the generation oil of catalytic reforming gasoline narrow fraction 3 is 0.97%.
Table 2 embodiment 6-10 test-results
| Catalyzer | A | B | C | D | E |
| Enter the alkene weight content of the material of reactor, % | 19.5 | 23 | 30 | 35 | 12 |
| Catalysis drying gas | 800g | 900g | 1200g | 1000g | 980g |
| Catalytically cracked gasoline narrow fraction 1 | 600g | ||||
| Catalytically cracked gasoline narrow fraction 2 | 700g | ||||
| Catalytic reforming gasoline narrow fraction 3 | 890g | 500g | |||
| Catalytic reforming gasoline narrow fraction 4 | 750g |
| The material of outflow reactor | |||||
| Dry gas, weight | 649g | 711g | 858g | 657g | 866g |
| Liquid hydrocarbon, weight generates the benzene volume content of gasoline, % | 751g 0.9 | 889g 0.86 | 1232g 0.84 | 1093g 0.99 | 614g 0.97 |
| The dry gas reduced rate, % by weight | 18.8％ | 21％ | 28.5％ | 34.3％ | 11.6％ |
| The liquid hydrocarbon increment rate, % by weight | 18％ | 20.8％ | 28.4％ | 34.2％ | 11.5％ |
Claims (9)
1. method that reduces benzene content in gasoline, it is characterized in that: at the catalytic cracking unit productive unit catalytic reaction system is set, 65～90 ℃ of cuts of dry gas, catalytically cracked gasoline that catalytic cracking unit is produced and or 65～90 ℃ of cuts of catalytic reforming gasoline introduce reactive system, under the effect of catalyzer, alkene in the dry gas and catalytically cracked gasoline and or catalytic reforming gasoline in benzene react, conversion of olefines in the dry gas is that macromole enters liquid hydrocarbon, and the benzene in the gasoline is converted into alkylbenzene; Reacted reaction product enters other operating unit and processes; Described catalyzer is comprised of the active ingredient that accounts for total catalyst weight 15～95% and the binding agent and the carrier that account for total catalyst weight 5～85 % by weight, and its shape is bar shaped or spherical catalyst; Active ingredient is comprised of the modified zsm-5 zeolite that accounts for total catalyst weight 15～95% and the Modified Zeolite Y that accounts for total catalyst weight 0～15%, the used modifying element of modified ZSM-5 be phosphorus be selected from zinc and or rare earth metal in one or more metals, modifying element accounts for the 0.1-10% of molecular sieve after the modification; The used modifying element of Modified Zeolite Y is to be selected from one or more metals in titanium metal and the rare earth metal, and modifying element accounts for the 0.1-10% of molecular sieve after the modification; Binding agent is selected from silicon sol, aluminium colloidal sol or its mixture, carrier is selected from kaolin, amorphous silicon aluminium, precipitated silica, aluminum oxide or its mixture, perhaps binding agent and carrier are pseudo-boehmite and an amount of rare nitric acid or other mixture inorganic or aqueous solutions of organic acids, and described organic or inorganic acid is hydrochloric acid, phosphoric acid, acetic acid, citric acid or oxalic acid; The weight ratio of binding agent and carrier is 5～35.
2. the method for reduction benzene content in gasoline according to claim 1, it is characterized in that: the temperature of reaction of catalytic reaction system is 200～410 ℃, reaction pressure 0.1～1.5MPa, air speed 0.1～1.5h
-1
3. the method for reduction benzene content in gasoline according to claim 2, it is characterized in that: the reaction pressure of catalytic reaction system is 0.3～0.70MPa, air speed is 0.2～0.6h
-1
4. catalyzer for reducing the method for benzene content in gasoline, described method is: at the catalytic cracking unit productive unit catalytic reaction system is set, 65～90 ℃ of cuts of dry gas, catalytically cracked gasoline that catalytic cracking unit is produced and or 65～90 ℃ of cuts of catalytic reforming gasoline introduce reactive system, under the effect of catalyzer, alkene in the dry gas and catalytically cracked gasoline and or catalytic reforming gasoline in benzene react, conversion of olefines in the dry gas is that macromole enters liquid hydrocarbon, and the benzene in the gasoline is converted into alkylbenzene; Reacted reaction product enters other operating unit and processes, and it is characterized in that: catalyzer is comprised of the active ingredient that accounts for total catalyst weight 15～95% and the binding agent and the carrier that account for total catalyst weight 5～85%, and its shape is bar shaped or sphere; Active ingredient is comprised of the modified zsm-5 zeolite that accounts for total catalyst weight 15～95% and the Modified Zeolite Y that accounts for total catalyst weight 0～15%, the used modifying element of modified ZSM-5 be phosphorus be selected from zinc and or rare earth metal in one or more metals, modifying element accounts for the 0.1-10% of molecular sieve after the modification; The used modifying element of Modified Zeolite Y is to be selected from one or more metals in titanium metal and the rare earth metal, and modifying element accounts for the 0.1-10% of molecular sieve after the modification; Binding agent is selected from silicon sol, aluminium colloidal sol or its mixture, carrier is selected from kaolin, amorphous silicon aluminium, precipitated silica, aluminum oxide or its mixture, perhaps binding agent and carrier are pseudo-boehmite and an amount of rare nitric acid or other mixture inorganic or aqueous solutions of organic acids, and described organic or inorganic acid is hydrochloric acid, phosphoric acid, acetic acid, citric acid or oxalic acid; The weight ratio of binding agent and carrier is 5～35.
5. the catalyzer of described method for reducing benzene content in gasoline according to claim 4, it is characterized in that: the modifying element of described modified zsm-5 zeolite accounts for the 1-5% of molecular sieve after the modification, and the modifying element of Modified Zeolite Y accounts for the 1-5% of molecular sieve after the modification.
6. the catalyzer of described method for reducing benzene content in gasoline according to claim 4, it is characterized in that: the preparation method of described modified zsm-5 zeolite is, the modified material wiring solution-forming that will contain modifying element, again ZSM-5 molecular sieve is immersed in this solution 1.0～3.0 hours, modified material difference wiring solution-forming floods respectively in the steeping process; Or be made into mixed solution, once finish dip treating; Then dry, carried out roasting 1～6 hour at 530 ℃～580 ℃ again.
7. the catalyzer of described method for reducing benzene content in gasoline according to claim 4, it is characterized in that: the preparation method of described Modified Zeolite Y is, the modified material wiring solution-forming that will contain modifying element, again Y zeolite is immersed in this solution 0.80～3.5 hour, in the steeping process, modified material is wiring solution-forming respectively, floods respectively; Perhaps be made into mixed solution, once finish dip treating; Then dry, carried out roasting 1～6 hour at 530 ℃～580 ℃ again.
8. the catalyzer of described method for reducing benzene content in gasoline according to claim 4, it is characterized in that: modified zsm-5 zeolite and Modified Zeolite Y, its modified molecular screen element derives from water-soluble cpds, and water-soluble cpds is nitrate, chlorate, vitriol, oxalate, Citrate trianion, tartrate, malate, the lactic acid salt of metal; Phosphoric comes from phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate.
9. the method for preparing catalyst of the described method for reducing benzene content in gasoline of a claim 4, it is characterized in that: with the modified zsm-5 zeolite after the modification and Modified Zeolite Y, mix in proportion with binding agent and carrier, after forming process, obtain bar shaped or spherical catalyzer, then dry, carry out roasting at 530 ℃～580 ℃ again and got final product in 1～6 hour.
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| CN103131465A (en) * | 2011-11-28 | 2013-06-05 | 上海河图工程股份有限公司 | Method for reducing benzene content in gasoline |
| CN103816936B (en) * | 2014-02-27 | 2015-09-09 | 赵连堂 | Aluminium phosphate molecular sieve of a kind of modification and preparation method thereof |
| CN115722261B (en) * | 2021-08-31 | 2024-05-24 | 中国石油化工股份有限公司 | Phosphorus-containing catalyst for reducing benzene content and sulfur content in gasoline, preparation method and application thereof |
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| US4827069A (en) * | 1988-02-19 | 1989-05-02 | Mobil Oil Corporation | Upgrading light olefin fuel gas and catalytic reformate in a turbulent fluidized bed catalyst reactor |
| CN1335358A (en) * | 2000-07-26 | 2002-02-13 | 中国科学院大连化学物理研究所 | Benzene-beairng gasoline and olefine reaction process to produce benzene-free gasoline |
| CN1651141A (en) * | 2004-12-01 | 2005-08-10 | 中国石油化工集团公司 | A kind of aromatization catalyst and its preparation method and application |
| CN1868983A (en) * | 2006-07-03 | 2006-11-29 | 中国石油化工集团公司 | Method of preparing ethylene and propylene and catalyst used in said method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4827069A (en) * | 1988-02-19 | 1989-05-02 | Mobil Oil Corporation | Upgrading light olefin fuel gas and catalytic reformate in a turbulent fluidized bed catalyst reactor |
| CN1335358A (en) * | 2000-07-26 | 2002-02-13 | 中国科学院大连化学物理研究所 | Benzene-beairng gasoline and olefine reaction process to produce benzene-free gasoline |
| CN1651141A (en) * | 2004-12-01 | 2005-08-10 | 中国石油化工集团公司 | A kind of aromatization catalyst and its preparation method and application |
| CN1868983A (en) * | 2006-07-03 | 2006-11-29 | 中国石油化工集团公司 | Method of preparing ethylene and propylene and catalyst used in said method |
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