CN100406416C - Method of preparing ethylene and propylene and catalyst used in said method - Google Patents
Method of preparing ethylene and propylene and catalyst used in said method Download PDFInfo
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- CN100406416C CN100406416C CNB2006100180601A CN200610018060A CN100406416C CN 100406416 C CN100406416 C CN 100406416C CN B2006100180601 A CNB2006100180601 A CN B2006100180601A CN 200610018060 A CN200610018060 A CN 200610018060A CN 100406416 C CN100406416 C CN 100406416C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The present invention discloses a method for preparing ethylene and propylene, and a catalyst used in the method. The method comprises the following steps: hydrocarbon raw materials react with a catalyst which is from a regenerator in a first reactor; after ethylene and propylene are separated from reaction products, a reaction happens in a second reactor; a catalyst of carbon deposition is separated from reaction products in the second reactor; through separation, an ethylene product and a propylene product are obtained. The catalyst used in the method comprises active components which account for 15 to 95 wt% of the total weight of the catalyst, binding agents which account for 5 to 85 wt% of the total weight of the catalyst, and carriers, wherein the active components of the catalyst comprise modified ZSM-5 molecular sieves and modified Y type molecular sieves. When the catalyst and the method are used, the high yield rate of ethylene and propylene can be obtained.
Description
Technical field
The invention belongs to the field that the petroleum hydrocarbon catalytic pyrolysis prepares industrial chemicals, particularly a kind of catalyzer of producing the method for ethene and propylene and being used for this method.
Background technology
Ethene and propylene all are important petrochemical complex basic materials, and the existing manufacturing technique method has: lighter hydrocarbons tube furnace preparing ethylene by steam cracking and propylene, its productivity of propylene are generally about 60% of ethene; By catalytic cracking or Deep Catalytic Cracking process, can obtain a certain amount of propylene and a spot of ethene.Along with continually developing of propylene Application Areas, market is increasing to the demand of propylene, the situation that existing production of propylene can not satisfy market demands occurred.Catalytic cracking or Deep Catalytic Cracking process are to serve as that main holding concurrently produced the technology of ethene to produce propylene, and more valuable is that this technology has adaptability to raw material widely, has product modulation ability flexibly, therefore receives much concern, and has emerged in large numbers many patented technologies.
CN1438296A three sections new riser catalytic cracking novel procesies, it mainly is to core one catalytic cracking riser reactor of oil-refining chemical process and the change of reaction-regeneration system technical process, also relates to the process of producing low-carbon alkenes such as gasoline, diesel oil, liquefied gas, propylene, ethene with various mink cell focuses.This technology can be at different production purposes, adopt the syllogic riser reactor, and make catalyzer in entire reaction course, constitute the three paths of independent recycle system, thereby different logistics are adopted suitable separately reaction conditions and catalyzer, the product that effectively improves catalytic cracking process distributes, improve the quality of products, realize that at catalytic cracking process the oil-refining chemical technology is integrated.Adopt three sections riser catalytic cracking systems, reactive system is too complicated, and all there is adverse factors in the normal running and the plant investment of system.
It is the method for raw material production alkene with the long residuum that USP5879535 discloses a kind of two-stage reactor structure that adopts.First step reactor carries out the heat cracking reaction of short residence time(SRT) (less than 2 seconds) for moving horizontally fluidized-bed, and temperature of reaction is 500～600 ℃.Second stage reactor (riser reactor) is that raw material is the heat cracking reaction that carries out short contacting time (less than 1 second) under 700～1100 ℃ of conditions in temperature of reaction with first step reaction product, and adopts chilling technique can obtain the olefins yield of 20～50wt% at second stage reaction zone.The reaction process of this technology belongs to the heat cracking reaction process basically, and temperature of reaction is very high, and methane production is very high in the product.Therefore, there is severe reaction conditions in this technology, the high shortcoming of non-purpose product methane production.
It is that raw material carries out catalytic cracking reaction selectivity production C at two-stage reactor that USP6106697 discloses with wax oil or residual oil
2～C
4Alkene.In first step reaction zone, be that raw material carries out popular response and generates the gas oil fraction product on macroporous catalyst (mean pore size is greater than 0.7nm) with wax oil or residual oil.Second reaction zone is a raw material with the first reaction zone gas oil fraction product, and in temperature of reaction: 500～650 ℃, agent-oil ratio are 4～10: 1, hydrocarbon partial pressure is that intermediate pore molecular sieve catalyst under 70～280kPa condition (mean pore size is less than 0.7nm) contact is carried out catalyzed reaction and generated small-numerator olefin.The reaction process of this technology adopts two kinds of independent catalyzer, two cover reaction-regeneration systems.Therefore, this technology exists complex technical process, energy to be difficult to optimize shortcomings such as utilization.
In the prior art, FCC adopts two reactor or duo-lift tube reactor that two purposes are arranged, and the one, modification of gasoline while reducing olefin can increase production a small amount of propylene; Another kind is maximum light olefin productive rate scheme, and by adopting two kinds of different catalyzer or ZSM～5 being realized as auxiliary agent adding system, owing to there is imperfect reaction to take place as crossing cracking, isomerization, aromizing and hydrogen transference, the selectivity of light olefin is lower.Therefore, need a kind of light olefin productive rate height of exploitation and the good Technology of selectivity.
Summary of the invention
It is lower and a kind of hydrocarbon raw material that propose is produced the method for ethene, propylene through catalytic cracking to the objective of the invention is productive rate at ethene and propylene in the existing catalytic cracking process, the inventive method is by adopting new catalyst formulation and processing method, be raw material with the heavy hydrocarbon and non-purpose product carried out the freshening operation, can obtain higher ethene and productivity of propylene.
The present invention produces the method for ethene and propylene, and its concrete steps are:
(1) hydrocarbon raw material with enter first reactor from the catalyzer of revivifier, in temperature of reaction is 480～680 ℃, and reaction pressure is 0.03～0.30MPa, is preferably 0.06～0.10MPa, the weight ratio of water vapor and hydrocarbon raw material is 0.01～1.00, is preferably 0.05～0.50; Reaction times is 0.1～3s, is preferably 0.5～2s; The weight ratio of catalyzer and hydrocarbon raw material is 2～20, be preferably under 6～15 the condition and react, the reaction product of first reactor is separated in settling vessel with the catalyzer of carbon deposit, carbon deposited catalyst enters revivifier regeneration behind stripping, reaction product to first reactor is separated, and isolated ethene and propylene go out device, C as product
1～350 ℃ light hydrocarbon fraction enters step (2), returns first reactor greater than 350 ℃ of last running.
(2) C
1～350 ℃ of light hydrocarbon fractions enter second reactor with catalyzer from revivifier, are 530～730 ℃ in temperature of reaction, and reaction pressure is 0.03～0.20MPa, is preferably 0.03～0.10Mpa, water vapor and C
1The weight ratio of～350 ℃ of light hydrocarbon fractions is 0.01～1.00, is preferably 0.05～0.50; Reaction times is 0.5～10s, is preferably 1～5s; Catalyzer and C
1The weight ratio of～350 ℃ of light hydrocarbon fractions is 2～20, be preferably under 4～12 the condition and react, the reaction product of second reactor is separated with the catalyzer of carbon deposit, carbon deposited catalyst all enters revivifier behind stripping, perhaps a part enters revivifier, and another part enters first reactor; The second reactor reaction product is separated, and isolated ethene and propylene go out device, C as product
1 +Cut returns second reactor, and the carbon deposited catalyst of second reactor and first reactor is regenerated in same revivifier.
First reactor is the same with the used catalyzer of second reactor among the present invention, it is made up of the active ingredient that accounts for total catalyst weight 15～95 weight % and the binding agent and the carrier that account for total catalyst weight 5～85 weight %, and the catalyst activity component is made up of modified zsm-5 zeolite and Modified Zeolite Y.Weight ratio between modified zsm-5 zeolite and the Modified Zeolite Y is 2.5～8: 1.
The used modifying element of modified ZSM-5 is (i) phosphorus, (ii) chromium or molybdenum and (iii) at least a rare earth metal, and in oxide dry basis, modifying element accounts for the 0.1-10 weight % of molecular sieve gross weight after the modification, preferred 1-5 weight %.Wherein phosphorus accounts for 0.05～6.9% of molecular sieve gross weight after the modification, and chromium or molybdenum account for 0.01～2.2% of molecular sieve gross weight after the modification, and rare earth metal accounts for 0.04～4.1% of molecular sieve gross weight after the modification, all in oxide dry basis.The used modifying element of Modified Zeolite Y is (i) titanium or zirconium and (ii) at least a rare earth metal, wherein modifying element accounts for the 0.1-15 weight % of molecular sieve gross weight after the modification, preferred 1-10 weight %, the weight ratio between the above-mentioned two class modifying elements is 1～2.5, all in oxide dry basis.
Binding agent of the present invention can be selected from silicon sol, aluminium colloidal sol or its mixture; Carrier can be selected from kaolin, amorphous silicon aluminium, precipitated silica, aluminum oxide or its mixture etc.
The present invention adopts ordinary method modified zsm-5 zeolite and Y zeolite.The used modifying element of modified molecular screen can derive from water-soluble cpds, as: the nitrate of metal, chlorate, vitriol, oxalate, Citrate trianion, tartrate, malate or lactic acid salt etc.
Preparation of catalysts method of the present invention is modified zsm-5 zeolite and the Modified Zeolite Y after modification is handled, mix in proportion with binding agent and carrier, add deionized water and carry out homogenization treatment, the catalyst slurry for preparing is carried out mist projection granulating, carry out calcination process afterwards, promptly get catalyzer required for the present invention.
The charging C of second reactor of the present invention
4～350 ℃ of light hydrocarbon fractions can be parallel feedings, also it can be fractionated into each component along the second reactor different sites sectional feeding.This charging also can be from outside this device, as C
4Alkene, catalytic cracking naphtha fraction, delayed coking naphtha fraction, tube furnace steam cracking naphtha fraction, thermal naphtha cut or 200～350 ℃ of light hydrocarbon fractions etc.
The hydrocarbon raw material of first reactor described in the present invention is a boiling point greater than 350 ℃ hydro carbons, be selected from long residuum, VGO, vacuum residuum, crude oil and the heavy oil fraction that obtains by secondary processing in any or its mixture.C of the present invention
1 +Cut refers to C
1Cut and C
1Above cut.
The present invention carries out modification and the ZSM-5 molecular sieve is carried out modification by the main active component Y zeolite to catalyzer, make catalyzer of the present invention compared with prior art, both had the ability of cracking macromole hydrocarbon preferably, the selectivity that possesses higher ethene, propylene and aromatic hydrocarbon product again, therefore use the selectivity height of catalyzer of the present invention to low-molecular olefine, olefinicity is greater than 80% (olefinicity of splitting gas refers to the ratio of olefins yield and total splitting gas productive rate in the splitting gas) in the splitting gas; Secondly, the present invention is owing to adopt two relatively independent heavy oil, light oil reactor, therefore can be at the characteristics of heavy oil and light oil and according to demand to the purpose product, adopt suitable process conditions and technical process respectively, as required can free modulation propylene and the ratio of ethene, thus ethene and the propylene product higher obtained than prior art selectivity.
Embodiment
Below by specific embodiment, the present invention is further detailed, but embodiment does not limit claim scope of the present invention.
Agent-oil ratio described in the embodiment of the invention table during corresponding to reactor 1, refers to the weight ratio of catalyzer and hydrocarbon raw material, during corresponding to reactor 2, refers to catalyzer and C
4The weight ratio of～350 ℃ of light hydrocarbon fraction chargings; Described water-oil ratio during corresponding to reactor 1, refers to the weight ratio of water vapor and hydrocarbon raw material, during corresponding to reactor 2, refers to water vapor and C
4The weight ratio of～350 ℃ of light hydrocarbon fraction chargings.
Embodiment 1～5 is a catalyst preparation example.
Embodiment 1
With phosphoric acid, chromium nitrate and lanthanum nitrate wiring solution-forming, again the ZSM-5 molecular sieve is immersed in this solution 2.0 hours, under 100 ℃ condition, dry then, under 550 ℃ condition, carry out roasting again, promptly get ZSM-5 molecular sieve after the modification, modifying element accounts for 2.3% of ZSM-5 molecular sieve gross weight after the modification.With modified material titanium tetrachloride and cerous nitrate wiring solution-forming, again Y zeolite is immersed in this solution 2.0 hours, under 100 ℃ condition, dry then, under 550 ℃ condition, carry out roasting again, promptly get Y zeolite after the modification, modifying element accounts for 13.1% of Y zeolite gross weight after the modification.Then the Y zeolite of the type ZSM 5 molecular sieve of 30% modification, 3% modification, 52% kaolin and surplus aluminium colloidal sol and deionized water are mixed, mist projection granulating places 550 ℃ roasting temperature more then, is catalyst A.
Embodiment 2
With ammonium phosphate, nitric acid molybdenum and cerous nitrate wiring solution-forming, again the ZSM-5 molecular sieve is immersed in this solution 1.0 hours, under 120 ℃ condition, dry then, under 550 ℃ condition, carry out roasting again, promptly get ZSM-5 molecular sieve after the modification, modifying element accounts for 3.2% of ZSM-5 molecular sieve gross weight after the modification.With modified material titanium tetrachloride and Lanthanum trichloride wiring solution-forming, again Y zeolite is immersed in this solution 2.0 hours, under 100 ℃ condition, dry then, under 550 ℃ condition, carry out roasting again, promptly get Y zeolite after the modification, modifying element accounts for 9.8% of Y zeolite gross weight after the modification.Then the Y zeolite of the type ZSM 5 molecular sieve of 50% modification, 2% modification, 9% kaolin, 9% amorphous silicon aluminium and surplus aluminium colloidal sol and deionized water are mixed, carry out mist projection granulating then, place 520 ℃ roasting temperature again, be catalyst B.
Embodiment 3
With phosphoric acid and molybdenum chloride and Lanthanum trichloride wiring solution-forming, again the ZSM-5 molecular sieve is immersed in this solution 3.0 hours, under 100 ℃ condition, dry then, under 550 ℃ condition, carry out roasting again, promptly get ZSM-5 molecular sieve after the modification, modifying element accounts for 5.5% of ZSM-5 molecular sieve gross weight after the modification.With modified material zirconium oxychloride and Cerium II Chloride wiring solution-forming, again Y zeolite is immersed in this solution 3.0 hours, under 100 ℃ condition, dry then, under 550 ℃ condition, carry out roasting again, promptly get Y zeolite after the modification, modifying element accounts for 6.3% of Y zeolite gross weight after the modification.Kaolin and deionized water with the Y zeolite of the type ZSM 5 molecular sieve of 15% modification, 5% modification, 20% amorphous aluminum silicide, 5% aluminum oxide and 25% mixes then, carry out mist projection granulating then, place 580 ℃ roasting temperature again, be catalyzer C.
Embodiment 4
With modified material ammonium phosphate and nitric acid molybdenum and lanthanum nitrate, cerous nitrate mixture wiring solution-forming, again the ZSM-5 molecular sieve is immersed in this solution 2.0 hours, under 100 ℃ condition, dry then, under 550 ℃ condition, carry out roasting again, promptly get ZSM-5 molecular sieve after the modification, modifying element accounts for 5.0% of ZSM-5 molecular sieve gross weight after the modification.With modified material zirconium nitrate and Lanthanum trichloride, Cerium II Chloride mixture wiring solution-forming, again Y zeolite is immersed in this solution 3.0 hours, under 100 ℃ condition, dry then, under 550 ℃ condition, carry out roasting again, promptly get Y zeolite after the modification, modifying element accounts for 6.0% of Y zeolite gross weight after the modification.Kaolin and deionized water with the Y zeolite of the type ZSM 5 molecular sieve of 15% modification, 5% modification, 20% amorphous aluminum silicide, 5% aluminum oxide and 25% mixes then, carry out mist projection granulating then, place 580 ℃ roasting temperature again, be catalyzer D.
Embodiment 5
With embodiment 3, just modifying element accounts for 8.6% of ZSM-5 molecular sieve gross weight after the modification.Modifying element accounts for 3.6% of Y zeolite gross weight after the modification, and with type ZSM 5 molecular sieve, the Y zeolite of 15% modification, 10% amorphous aluminum silicide of 60% modification, all the other are kaolin, catalyzer F.
Embodiment 6～7 is the Comparative Examples catalyzer.
Embodiment 6
With embodiment 1, just the ZSM-5 molecular sieve does not contain chromium, titaniferous not in the Modified Zeolite Y, and catalyzer 1 as a comparison.
Embodiment 7
With embodiment 3, just the ZSM-5 molecular sieve does not contain molybdenum, does not contain zirconium in the Modified Zeolite Y, and catalyzer 2 as a comparison.
Embodiment 8～13rd, above catalyst performance test example.
Raw material oil properties used among the embodiment sees Table 1.Used mixed C among the embodiment
4Hydrocarbon is formed to contain 11.98% (mass percent) butane and 88.02% butylene (mass percent).Above-mentioned catalyzer all on the catalyst aging treatment unit, was handled 4 hours in 800 ℃, 100% water vapour before carrying out breaking test.
Table 1 raw material oil properties
Embodiment 8
Present embodiment explanation the inventive method is to the adaptability of raw material.Test is carried out on medium-sized tester, in the test with the mixed C that generates
4Hydrocarbon and gasoline fraction are introduced reactor 2 and are carried out cracking, and test conditions and test-results are listed in table 2.By table 2 as seen, adopt different catalysts and different material oil, all can obtain higher low-carbon alkene ethene, propylene.
Table 2 cracking product distributes
Embodiment 9
Present embodiment explanation the inventive method product with a kind of raw material under the differential responses condition distributes.Test is carried out on medium-sized tester, in the test with the mixed C that generates
4Hydrocarbon and gasoline fraction are introduced reactor 2 and are carried out cracking, and test conditions and test-results are listed in table 3.By table 3 as seen, long residuum can obtain the product of different distributions under the differential responses condition, therefore can obtain desired purpose product by changing reaction conditions according to demand.
Table 3 cracking product distributes
Embodiment 10
Present embodiment explanation the inventive method product with a kind of raw material under the differential responses condition distributes.Test is carried out on medium-sized tester, in the test with the C that generates
4～350 ℃ of cuts are introduced reactor 2 and are carried out cracking, and test conditions and test-results are listed in table 4.By table 4 as seen, vacuum gas oil can obtain the product of different distributions under differential responses condition and operational condition, therefore can obtain desired purpose product by changing reaction conditions and operational condition according to demand.
Table 4 cracking product distributes
Embodiment 11
Present embodiment explanation the inventive method is in same reaction conditions with a kind of raw material, and catalyst A and comparative catalyst's 1 product distributes.Test is carried out on medium-sized tester, in the test with the mixed C that generates
1Hydrocarbon and gasoline fraction are introduced reactor 2 and are carried out cracking, and test conditions and test-results are listed in table 5.By table 5 as seen, catalyst A is compared with comparative catalyst 1, and the selectivity of ethene, propylene obviously improves.
Table 5 cracking product distributes
Embodiment 12
Present embodiment explanation the inventive method is in same reaction conditions with a kind of raw material, and catalyzer C and comparative catalyst's 2 product distributes.Test is carried out on medium-sized tester, in the test with the mixed C that generates
4Hydrocarbon and gasoline fraction are introduced reactor 2 and are carried out cracking, and test conditions and test-results are listed in table 6.By table 6 as seen, catalyzer C compares with comparative catalyst 2, and the selectivity of ethene, propylene obviously improves.
Table 6 cracking product distributes
Embodiment 13
Present embodiment explanation the inventive method product with a kind of raw material under the differential responses condition distributes.Test is carried out on medium-sized tester, in the test with the C that generates
4～350 ℃ of cuts are introduced reactor 2 and are carried out cracking, and test conditions and test-results are listed in table 7.By table 7 as seen, long residuum can obtain the product of different distributions under differential responses condition and operational condition, therefore can obtain desired purpose product by changing reaction conditions and operational condition according to demand.
Table 7 cracking product distributes
Claims (3)
1. a method of producing ethene and propylene is characterized in that this method comprises the steps:
(1) hydrocarbon raw material with enter first reactor from the catalyzer of revivifier, in temperature of reaction is 480～680 ℃, reaction pressure is 0.03～0.30MPa, the weight ratio of water vapor and hydrocarbon raw material is 0.01～1.00, reaction times is 0.1～3s, the weight ratio of catalyzer and hydrocarbon raw material is to react under 2～20 the condition, the reaction product of first reactor is separated in settling vessel with the catalyzer of carbon deposit, carbon deposited catalyst enters revivifier regeneration behind stripping, reaction product to first reactor is separated, and isolated ethene and propylene go out device as product, C
4～350 ℃ light hydrocarbon fraction enters step (2), returns first reactor greater than 350 ℃ of last running;
(2) C
4～350 ℃ of light hydrocarbon fractions enter second reactor with catalyzer from revivifier, are 530～730 ℃ in temperature of reaction, and reaction pressure is 0.03～0.20MPa, water vapor and C
4The weight ratio of～350 ℃ of light hydrocarbon fractions is 0.01～1.00, and the reaction times is 0.5～10s, catalyzer and C
4The weight ratio of～350 ℃ of light hydrocarbon fractions is to react under 2～20 the condition, the reaction product of second reactor is separated with the catalyzer of carbon deposit, carbon deposited catalyst all enters revivifier behind stripping, perhaps a part enters revivifier, another part enters first reactor, the second reactor reaction product is separated, and isolated ethene and propylene go out device, C as product
4 +Cut returns second reactor, and the carbon deposited catalyst of second reactor and first reactor is regenerated in same revivifier;
The hydrocarbon raw material of described first reactor is a boiling point greater than 350 ℃ hydro carbons, the used catalyzer of described first reactor and second reactor is made up of the active ingredient that accounts for total catalyst weight 15～95 weight % and the binding agent and the carrier that account for total catalyst weight 5～85 weight %, the catalyst activity component is made up of modified zsm-5 zeolite and Modified Zeolite Y, weight ratio between modified zsm-5 zeolite and the Modified Zeolite Y is 2.5～8: 1, the used modifying element of described modified ZSM-5 is (i) phosphorus, (ii) chromium or molybdenum and (iii) at least a rare earth metal, in oxide dry basis, modifying element accounts for the 0.1-10 weight % of molecular sieve gross weight after the modification, wherein phosphorus accounts for 0.05～6.9% of molecular sieve gross weight after the modification, chromium or molybdenum account for 0.01～2.2% of molecular sieve gross weight after the modification, rare earth metal accounts for 0.04～4.1% of molecular sieve gross weight after the modification, all in oxide dry basis; The used modifying element of Modified Zeolite Y is (i) titanium or zirconium and (ii) at least a rare earth metal, wherein modifying element accounts for the 0.1-15 weight % of molecular sieve gross weight after the modification, weight ratio between the above-mentioned two class modifying elements is 1～2.5, all in oxide dry basis.
2. method according to claim 1, it is characterized in that: the reaction pressure of described first reactor is 0.06～0.10MPa, the weight ratio of water vapor and hydrocarbon raw material is 0.05～0.50, and the reaction times is 0.5～2s, and the weight ratio of catalyzer and hydrocarbon raw material is 6～15; The reaction pressure of second reactor is 0.03～0.10Mpa, water vapor and C
4The weight ratio of～350 ℃ of light hydrocarbon fractions is 0.05～0.50, and the reaction times is 1～5s, catalyzer and C
4The weight ratio of～350 ℃ of light hydrocarbon fractions is 4～12.
3. catalyzer that is used for the described method of claim 1, it is characterized in that: this catalyzer is made up of the active ingredient that accounts for total catalyst weight 15～95 weight % and the binding agent and the carrier that account for total catalyst weight 5～85 weight %, the catalyst activity component is made up of modified zsm-5 zeolite and Modified Zeolite Y, weight ratio between modified zsm-5 zeolite and the Modified Zeolite Y is 2.5～8: 1, the used modifying element of described modified ZSM-5 is (i) phosphorus, (ii) chromium or molybdenum and (iii) at least a rare earth metal, in oxide dry basis, modifying element accounts for the 0.1-10 weight % of molecular sieve gross weight after the modification, wherein phosphorus accounts for 0.05～6.9% of molecular sieve gross weight after the modification, chromium or molybdenum account for 0.01～2.2% of molecular sieve gross weight after the modification, rare earth metal accounts for 0.04～4.1% of molecular sieve gross weight after the modification, all in oxide dry basis; The used modifying element of Modified Zeolite Y is (i) titanium or zirconium and (ii) at least a rare earth metal, wherein modifying element accounts for the 0.1-15 weight % of molecular sieve gross weight after the modification, weight ratio between the above-mentioned two class modifying elements is 1～2.5, all in oxide dry basis.
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| CN102924209B (en) * | 2008-07-26 | 2016-06-08 | 中石化洛阳工程有限公司 | The conversion process of carbon four and more heavy constituent in a kind of preparing low-carbon olefin from oxygen-containing compounds by-product |
| CN102924210B (en) * | 2008-07-26 | 2015-06-03 | 中石化洛阳工程有限公司 | Conversion method of C4 and heavier components |
| CN101440302B (en) * | 2008-12-22 | 2013-02-13 | 洛阳瑞泽石化工程有限公司 | Method for lowering benzene content in gasoline and catalyst thereof |
| CN102268291B (en) * | 2010-06-02 | 2013-10-02 | 中国石油化工集团公司 | Catalytic cracking technology and device for reducing olefins in gasoline |
| CN113385223A (en) * | 2021-07-19 | 2021-09-14 | 郑州中科新兴产业技术研究院 | Catalyst for directly catalytically cracking crude oil to increase yield of low-carbon olefin and preparation method thereof |
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| CN1043520A (en) * | 1988-12-21 | 1990-07-04 | 中国石油化工总公司石油化工科学研究院 | A kind of catalyst for cracking of producing low-carbon alkene |
| CN1069513A (en) * | 1992-07-30 | 1993-03-03 | 中国石油化工总公司 | Catalyst for heavy oil catalytic cracking and preparation method thereof |
| WO1994021378A1 (en) * | 1993-03-17 | 1994-09-29 | Consejo Superior Investigaciones Cientificas | Process for the preparation of catalysts based on zeolites treated with phosphoric acid, useful for catalytic cracking units |
| CN1298923A (en) * | 2000-09-21 | 2001-06-13 | 中国石油化工集团公司 | Catalyst for catalytic cracking and its preparing process |
| CN1356378A (en) * | 2001-09-26 | 2002-07-03 | 中国石油化工集团公司 | Hydrocatalyst and its preparing process |
| WO2005042148A1 (en) * | 2003-10-22 | 2005-05-12 | Abb Lummus Global Inc. | Novel zeolite composite, method for making and catalytic application thereof |
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| CN1868983A (en) | 2006-11-29 |
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