CN1317543A - Catalytic thermocracking process of hydrocarbons for higher output of ethylene and prpylene - Google Patents
Catalytic thermocracking process of hydrocarbons for higher output of ethylene and prpylene Download PDFInfo
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Abstract
A catalytic thermocracking process of heavy petroleum hydrocarbon for higher output of ethylene and propylene includes preheating heavy petroleum hydrocarbon, and catalytic thermoracking reaction of said heavy petroleum hydrocarbon with catalyst containing ZSM-5 molecular sieve at 650-750 deg.C and 0.15-0.4 MPa for 0.2-5 seconds under the existance of high-temp steam. The wt. ratio of raw oil, catalyst and steam is 1:(15-40):(0.3-1). It features that said ZSM-5 molecular sieve contains AG or Cu.
Description
The present invention relates to the catalytic thermocracking process of petroleum hydrocarbon, more particularly, relate to carry out the method for the catalytic pyrolysis of petroleum hydrocarbon with voluminous ethene with the catalyzer of the ZSM-5 molecular sieve that contains metallic components.
The traditional method of producing ethene from petroleum hydrocarbon is the heat of steam cracking process, and suitable raw material is light petroleum hydrocarbons such as ethane, propane, butane, Sweet natural gas, petroleum naphtha or solar oil.Along with crude oil becomes heavy day by day, the source of light petroleum hydrocarbon is restricted, so people come diversion to the technology of producing ethene from heavy petroleum hydrocarbon.For example adopt the heavy petroleum hydrocarbon pyrolysis method of inert solids such as quartz sand, coke, adopt basic metal or alkaline earth metal oxide catalyzer as the heavy petroleum hydrocarbon pyrolysis method of thermal barrier etc. as thermal barrier.The temperature of reaction of these methods all surpasses 800 ℃.
In recent years, some patent has been introduced the use solid acid catalyst under certain reaction type formula and operational condition, produces the method for low-carbon alkene from heavy petroleum hydrocarbon.For example DD 152356A uses the amorphous silicon Al catalysts, and reactor is fixed bed or moving-bed, and when being raw material with the vacuum gas oil, 700 ℃ of temperature of reaction, water vapour is 4.7 o'clock with the stock oil ratio, and ethylene yield is 13.5 heavy %, and productivity of propylene is 6.3 heavy %; In JP 60-222428, then used the catalyzer as active ingredient, with C with ZSM-5
5～C
25Paraffinic hydrocarbon is a raw material, is that 600～750 ℃, feed weight air speed are that the summation of ethene, propylene, butylene productive rate reaches about 30 heavy % under 20～300 o'clock-1 the condition in temperature of reaction; Disclosed among the CN 1069106A and a kind of heavy hydrocarbon has been transformed in fluidized-bed or plug flow reactor, produce ethene and the method for product propylene and butylene of holding concurrently, its principal reaction condition is: 650～900 ℃ of temperature, pressure 0.13～0.28MPa, agent-oil ratio 5～35,0.1～3 second duration of contact, the product yield of ethene reaches 17～27%, and ethene～butylene overall yield reaches 30～40%.Used the five-ring high silica zeolite catalyst that contains clay molecular sieve with layer structure and/or contain rare earth among the CN1083092A, at 680～780 ℃, 1.5～4.0 * 10
5Under the condition of Pa, 0.1～3 second reaction times, water-oil ratio 0.2～2.0, agent-oil ratio 5～40 the heavy hydrocarbon cracking can be obtained the ethylene yield of 23 heavy % and ethene～butylene overall yield of 50 heavy %.
U.S. Pat P4,579,997, USP4, the hydrocarbon pyrolysis catalyzer that 705,769 grades are developed is many to be active ingredient with the manganese oxide, with refractory materials (MgO, TiO
2Deng) be carrier, or contain the oxide compound of other alkaline-earth metal or rare earth metal, Sn, Sb, Cr, Si, Al etc., be raw material with the normal butane, with voluminous ethene.Patent USP3, then use in 767,567 any one oxide compound among CaO, BeO, the SrO (＞20wt%) and aluminum oxide be catalyzer, be that raw material obtains ethene with the petroleum naphtha, CaO-Al wherein
2O
3The type catalyzer is best.Use this quasi-metal oxides or its mixture as catalyzer, temperature of reaction requires very high, though can improve the productive rate and the selectivity of ethene, generates a large amount of dry gas, CO and CO in reaction process
2, recovery brings many difficulties to product.The catalyzer that application contains molecular sieve carries out the catalytic pyrolysis reaction, not only can obtain relatively large ethene, can also generate more propylene, butylene.German Patent DD248,516A is a catalyzer with the A type zeolite of calcium, magnesium or mn ion exchange.The Deep Catalytic Cracking process and the catalyzer of a series of low-carbon olefines high-outputs have been proposed in the patents such as CN1031834A, CN1085825A, CN1099788A, CN1117518A, generally all adopt the catalyst for cracking of the five-ring supersiliceous zeolite of phosphorous and rare earth in these patents, they are all with volume increase C
3 =～C
5 =Alkene is purpose, and its ethylene yield is not very high.
USP4, the synthesizing flokite catalyzer of using copper, silver or cobalt ion exchange in 172,816 carries out catalytic pyrolysis reaction, not mentioned employing ZSM-5 zeolite.USP4, disclose in 845,063 in zeolite in conjunction with on I B family metal Ag especially, can improve the hydrothermal stability of zeolite, but the not mentioned reaction that can be used for catalytic pyrolysis fecund ethene.
Disclose a kind of combination of molecular sieve that is used for voluminous ethene and propylene among CN1211469A and the CN1211470A, said composition is made up of the penta-basic cyclic molecular sieve of 85～95 heavy %, the phosphorus (in oxide compound) of 2～10 heavy %, (in oxide compound) a kind of alkaline-earth metal of 0.3～5 heavy % and/or (in oxide compound) a kind of transition metal of 0.3～5 heavy %.
A kind of catalytic thermocracking process of being produced ethene and propylene by heavy petroleum hydrocarbon is disclosed among the CN1218786A, be to make the heavy petroleum hydrocarbon of preheating in riser tube or downstriker transfer limes reactor, in the presence of high-temperature steam with contain clay molecular sieve with layer structure and/or contact through the catalyzer of phosphorus with the five-ring supersiliceous zeolite of aluminium or magnesium or calcium modification, be that 650～750 ℃, reaction pressure are 1.5～4 * 10 in temperature of reaction
5Handkerchief, reaction times are that the weight ratio of 0.2～5 second, catalyzer and stock oil is (15～40): 1, the weight ratio of water vapor and stock oil is (0.3～1): carry out the catalytic pyrolysis reaction under 1 the condition.
USP4,549, a kind of catalyst cracking method of petroleum hydrocarbon is disclosed in 956, wherein used a kind of interpolation catalyzer that contains zeolite component, the Ag that contains 0.05～5 weight % on the said zeolite component, what but this patent adopted is traditional catalytic cracking process, temperature of reaction is for being lower than 600 ℃, its objective is the octane value that improves gasoline component, wherein also not adopting this interpolation catalyzer to carry out the catalytic pyrolysis reaction (is generally more than 650 ℃, radical reaction mechanism) with the instruction of voluminous ethene, be not improved from its ethylene yield of embodiment yet, this is because traditional catalytic cracking is the carbonium ion reaction mechanism, even adopt the interpolation catalyzer that contains Ag can not reach the purpose of increasing output of ethylene under the catalytic cracking reaction temperature of routine.
The objective of the invention is to provide on the basis of existing technology the method for a kind of petroleum hydrocarbon catalytic pyrolysis fecund ethene and propylene, the catalyzer of the ZSM-5 type by adopting argentiferous or copper reaches the purpose of increasing output of ethylene and propylene.
The method of petroleum hydrocarbon catalytic pyrolysis provided by the present invention fecund ethene and propylene comprises that heavy petroleum hydrocarbon with preheating is in reactor, contacting with the catalyzer that contains the ZSM-5 molecular sieve in the presence of high-temperature steam, is that 650～750 ℃, reaction pressure are 1.5～4 * 10 in temperature of reaction
5Handkerchief, reaction times are that the weight ratio of 0.2～5 second, catalyzer and stock oil is (15～40): 1, the weight ratio of water vapor and stock oil is (0.3～1): carry out the catalytic pyrolysis reaction under 1 the condition, it is characterized in that said ZSM-5 molecular sieve is that benchmark contains 0.1～8% Ag or Cu with the weight of this molecular sieve, preferred Ag.
Said ZSM-5 molecular sieve is the disclosed molecular sieve with ZSM-5 basic structure in the prior art in the method provided by the present invention, its SiO
2/ Al
2O
3Mol ratio is 15～200, and can pass through the whole bag of tricks modification.
The catalyzer of the said ZSM-5 of containing molecular sieve can also further contain y-type zeolite, Beta zeolite or clay molecular sieve with layer structure isoreactivity component and inorganic oxide support material in the method provided by the invention; These active ingredients and solid support material determine that according to prior art the present invention has no particular limits it.
Said Ag or Cu can be by carrying out said ZSM-5 molecular sieve ion exchange reaction and combine with molecular sieve with containing the Ag ion or the Cu ionic aqueous solution in the method provided by the invention; Perhaps by the catalyzer of the said ZSM-5 of containing molecular sieve is carried out ion exchange reaction and combines with molecular sieve with containing the Ag ion or the Cu ionic aqueous solution.
Method provided by the present invention is characterized in that said ZSM-5 molecular sieve is that benchmark contains 0.3～6% Ag or Cu with the weight of this molecular sieve.
Said heavy crude hydrocarbon feed can be atmospheric gas oil, vacuum gas oil or its mixture in the method provided by the present invention, and residual oil or crude oil.
The method and the existing conventional catalyst cracking method USP4 of petroleum hydrocarbon catalytic pyrolysis fecund ethene provided by the present invention and propylene, 549,956 productive rates of comparing its ethene, propylene and butylene obviously increase; Compare with CN1211469A, CN1211470A, phosphorous, the alkaline-earth metal among the catalyzer of Ag of containing of the present invention or Cu and CN1211469A, the CN1211470A and/or the catalyzer of transition metal are compared, its ethylene yield is slightly high or quite, and that the productive rate of propylene, butylene exceeds is more.
The following examples only are used for illustrating that the present invention uses the ZSM-5 molecular sieve that contains Ag or Cu can access higher ethene and productivity of propylene during as the activity of such catalysts component under the temperature condition of catalytic pyrolysis, used other reaction conditions such as stock oil, temperature of reaction, reaction pressure, agent-oil ratio, water-oil ratio etc. are determined according to prior art among the present invention, do not need the present invention to be described with specific embodiment again.
The content of Ag and Cu is measured with x ray fluorescence spectrometry (XRF), and used instrument is Japanese 3271E type Xray fluorescence spectrometer of science.
Comparative Examples 1
The effect of catalytic thermocracking of bydrocarbon reaction of the present invention is carried out in the explanation of this Comparative Examples with conventional Hydrogen ZSM-5 molecular sieve.
(Chang Ling oil-refining chemical factory catalyst plant is produced to get the ZSM-5 molecular sieve, silica alumina ratio is 25.0) sample is with molecular sieve: ammonium nitrate: under the condition of deionized water=1: 1: 20 in 90 ℃ of exchanges 2 hours, filter, wash with 10 times of deionized waters to reaction solution, the gained filter cake obtains ammonium type ZSM-5 sample after 120 ℃ of oven dry, then in 550 ℃ of roastings 2 hours, obtain Hydrogen ZSM-5 sieve sample, its Na
2O content is less than 0.1 weight %.
With above-mentioned Hydrogen ZSM-5 sieve sample carry out compression molding and the sieve get 20～40 purpose particles, in the stainless steel reaction pipe of packing into, 800 ℃ of burin-in process of carrying out 4 hours 100% water vapour atmosphere.Molecular sieve after will wearing out then carries out the little anti-experiment of light oil, and gained the results are shown in table 1, the table 2.
The little anti-experiment of light oil is carried out with reference to RIPP standard method (seeing " petrochemical complex analytical procedure (RIPP test method), volumes such as Yang Cuiding, Science Press, nineteen ninety publication "), its main operational condition following (down together):
Stock oil: standard solar oil (216～337 ℃ of boiling ranges)
Temperature of reaction: 650 ℃ or 680 ℃
Catalyzer loading amount: 5.0g
Agent-oil ratio: 3.2
Air speed (l/h): 16
Embodiment 1
The present embodiment explanation uses the ZSM-5 molecular sieve that contains Ag to carry out the effect of catalytic thermocracking of bydrocarbon reaction.
Get Comparative Examples 1 described Hydrogen ZSM-5 sample 20g (dry basis), with contain 1.99 the gram AgNO
3, the 100g deionized water solution mix after, stirred 2 hours down in 90 ℃, filter, wash with 10 times of deionized waters to reaction solution, the gained filter cake is in 120 ℃ of oven dry, then 550 ℃ of roastings 2 hours, the gained molecular sieve is designated as AgZ1.Show that by XRF analysis this sample contains the Ag of 4.1 weight %.
With above-mentioned AgZ1 sample carry out compression molding and the sieve get 20～40 purpose particles, in the stainless steel reaction pipe of packing into, 800 ℃ of burin-in process of carrying out 4 hours 100% water vapour atmosphere.Molecular sieve after will wearing out then carries out the little anti-experiment of light oil, and gained the results are shown in table 1, the table 2.
Embodiment 2
Get Comparative Examples 1 described Hydrogen ZSM-5 sample 20g (dry basis), with contain 4.02 the gram AgNO
3, the 100g deionized water solution mix after, stirred 2 hours down in 90 ℃, filter, wash with 10 times of deionized waters to reaction solution, the gained filter cake is in 120 ℃ of oven dry, then 550 ℃ of roastings 2 hours, the gained molecular sieve is designated as AgZ2.Show that by XRF analysis this sample contains the Ag of 5.9 weight %.With sample carry out compression molding and the sieve get 20～40 purpose particles, in the stainless steel tube of packing into,, carry out the burin-in process of 4 hours 100% water vapour atmosphere at 800 ℃.Carry out the little anti-experiment of light oil then, gained the results are shown in table 1, the table 2.
Embodiment 3
Get Comparative Examples 1 described Hydrogen ZSM-5 sample 20g (dry basis), with contain 0.51 the gram AgNO
3, the 100g deionized water solution mix after, stirred 2 hours down in 90 ℃, filter, wash with 10 times of deionized waters to reaction solution, the gained filter cake is in 120 ℃ of oven dry, then 550 ℃ of roastings 2 hours, the gained molecular sieve is designated as AgZ3.Show that by XRF analysis this sample contains the Ag of 0.76 weight %.With sample carry out compression molding and the sieve get 20～40 purpose particles, in the stainless steel tube of packing into,, carry out the burin-in process of 4 hours 100% water vapour atmosphere at 800 ℃.Carry out the little anti-experiment of light oil then, gained the results are shown in table 1, the table 2.
Embodiment 4
Get Comparative Examples 1 described Hydrogen ZSM-5 sample 20g (dry basis), and contain 3.02 gram Cu (NO
3)
23H
2After the solution of O, 100g deionized water mixes, stirred 2 hours down in 90 ℃, filter, wash with 10 times of deionized waters to reaction solution, the gained filter cake is in 120 ℃ of oven dry, and then 550 ℃ of roastings 2 hours, the gained molecular sieve is designated as CuZ1.Show that by XRF analysis this sample contains the Cu of 1.8 weight %.With sample carry out compression molding and the sieve get 20～40 purpose particles, in the stainless steel reaction pipe of packing into, 800 ℃ of burin-in process of carrying out 4 hours 100% water vapour atmosphere.Molecular sieve after will wearing out then carries out the little anti-experiment of light oil, and gained the results are shown in table 1, the table 2.
Comparative Examples 2
According to the same procedure of the embodiment among the CN1211469A 4, obtain containing P
2O
55.0 weight %, the ZSM-5 molecular sieve of MgO1.4 weight % is designated as ZEP-4.With sample carry out compression molding and the sieve get 20～40 purpose particles, in the stainless steel reaction pipe of packing into, 800 ℃ of burin-in process of carrying out 4 hours 100% water vapour atmosphere.Molecular sieve after will wearing out then carries out the little anti-experiment of light oil, and gained the results are shown in table 1, the table 2.
Comparative Examples 3
According to the same procedure of the embodiment among the CN1211470A 6, obtain containing P
2O
54.9 weight %, MgO1.4 weight %, the ZSM-5 molecular sieve of CuO 0.91 weight % is designated as ZEP-15.With sample carry out compression molding and the sieve get 20～40 purpose particles, in the stainless steel reaction pipe of packing into, 800 ℃ of burin-in process of carrying out 4 hours 100% water vapour atmosphere.Molecular sieve after will wearing out then carries out the little anti-experiment of light oil, and gained the results are shown in table 1, the table 2.
Embodiment 5
Get LV-23 catalyzer 20.1g (dry basis, Lanzhou catalyst plant commerical prod, by super-stable Y molecular sieves, ZSM-5 molecular sieve, Al
2O
3Binding agent and kaolin support are formed), with its with contain 0.5 the gram AgNO
3, the 100g deionized water solution mix after, stirred 2 hours down in 90 ℃, filter, wash with 10 times of deionized waters to reaction solution, the gained filter cake is in 120 ℃ of oven dry, then 550 ℃ of roastings 2 hours, the gained catalyzer is designated as AgC.Show that by XRF analysis this catalyst sample contains the Ag of 0.49 weight %.With sample carry out compression molding and the sieve get 20～40 purpose particles, in the stainless steel tube of packing into,, carry out the burin-in process of 4 hours 100% water vapour atmosphere at 800 ℃.Carry out the little anti-experiment of light oil then, gained the results are shown in table 1, the table 2.
Comparative Examples 3
Get the LV-23 catalyzer (Lanzhou catalyst plant commerical prod, by super-stable Y molecular sieves, ZSM-5 molecular sieve, Al
2O
3Binding agent and kaolin support are formed), be designated as C, its compression molding and sieve are got 20～40 purpose particles, in the stainless steel tube of packing into,, carry out the burin-in process of 4 hours 100% water vapour atmosphere at 800 ℃.Carry out the little anti-experiment of light oil then, gained the results are shown in table 1, the table 2.
Activity when table 1,650 ℃ of reactions, productivity ratio are
| Catalyzer | HZSM-5 | ?ZEP-4 | ?ZEP-15 | ?AgZ1 | ?AgZ2 | ?AgZ3 | ?CuZ1 | ????C | AgC |
| Component | Productive rate weight % | Productive rate weight % | Productive rate weight % | Productive rate weight % | Productive rate weight % | Productive rate weight % | Productive rate weight % | Productive rate weight % | Productive rate weight % |
| Hydrogen | ????0.19 | ????0.35 | ????0.37 | ????0.57 | ????0.58 | ????0.55 | ????0.31 | ????0.50 | ????0.57 |
| Methane | ????2.28 | ????4.21 | ????3.63 | ????3.02 | ????3.01 | ????2.98 | ????2.41 | ????6.13 | ????6.16 |
| Ethane | ????1.91 | ????4.20 | ????3.63 | ????2.88 | ????2.90 | ????2.84 | ????2.22 | ????4.07 | ????4.24 |
| Ethene | ????8.50 | ????11.39 | ????11.32 | ????12.68 | ????12.91 | ????12.52 | ????11.17 | ????7.83 | ????8.93 |
| Propane | ????1.64 | ????6.05 | ????5.63 | ????4.21 | ????5.10 | ????3.72 | ????3.57 | ????1.74 | ????1.76 |
| Propylene | ????15.99 | ????9.49 | ????9.30 | ????13.77 | ????12.66 | ????14.43 | ????13.27 | ????16.92 | ????16.62 |
| Butane | ????0.70 | ????1.16 | ????1.15 | ????1.62 | ????1.56 | ????1.69 | ????1.29 | ????0.85 | ????0.89 |
| Butylene | ????6.82 | ????2.31 | ????2.20 | ????4.09 | ????3.47 | ????4.55 | ????3.85 | ????7.90 | ????8.05 |
| C 2-4 = | ????31.31 | ????23.19 | ????22.82 | ????30.54 | ????29.04 | ????31.51 | ????28.29 | ????32.64 | ????33.61 |
| Reacted gas | ????38.04 | ????39.17 | ????37.22 | ????42.83 | ????42.20 | ????43.29 | ????38.09 | ????45.93 | ????47.23 |
| Gasoline | ????18.27 | ????19.28 | ????20.52 | ????17.07 | ????16.09 | ????17.88 | ????16.51 | ????18.98 | ????19.11 |
| Diesel oil | ????37.50 | ????35.73 | ????36.20 | ????32.64 | ????33.09 | ????31.53 | ????38.02 | ????29.03 | ????26.47 |
| Heavy oil | ????5.21 | ????4.97 | ????5.31 | ????4.03 | ????4.01 | ????4.13 | ????5.74 | ????2.24 | ????2.60 |
| Coke | ????0.98 | ????0.85 | ????0.75 | ????3.43 | ????4.61 | ????3.17 | ????1.65 | ????3.81 | ????4.60 |
| Active | ????57.55 | ????66.09 | ????62.78 | ????68.28 | ????67.17 | ????69.06 | ????58.72 | ????72.86 | ????74.03 |
Activity when table 2,680 ℃ of reactions, productivity ratio are
| Catalyzer | HZSM-5 | ?ZEP-4 | ?ZEP-15 | ?AgZ1 | ?AgZ2 | AgZ3 | ?CuZ1 | ????C | AgC |
| Component | Productive rate weight % | Productive rate weight % | Productive rate weight % | Productive rate weight % | Productive rate weight % | Productive rate weight % | Productive rate weight % | Productive rate weight % | Productive rate weight % |
| Hydrogen | 0.30 | ?0.37 | ?0.39 | ?0.72 | ?0.68 | ?0.70 | ?0.42 | ?0.54 | ?0.62 |
| Methane | 4.13 | ?4.53 | ?4.38 | ?4.58 | ?4.85 | ?4.40 | ?4.00 | ?6.69 | ?6.76 |
| Ethane | 2.98 | ?4.41 | ?3.88 | ?3.64 | ?3.89 | ?3.54 | ?3.08 | ?4.45 | ?4.65 |
| Ethene | 11.71 | ?13.07 | ?13.22 | ?16.29 | ?16.65 | ?15.62 | ?14.37 | ?10.91 | ?12.35 |
| Propane | 1.54 | ?6.36 | ?6.02 | ?3.65 | ?3.87 | ?3.41 | ?2.59 | ?1.90 | ?1.93 |
| Propylene | 18.77 | ?10.61 | ?10.59 | ?15.12 | ?14.76 | ?16.33 | ?16.42 | ?18.46 | ?18.44 |
| Butane | 0.55 | ?1.43 | ?1.46 | ?0.99 | ?1.10 | ?0.79 | ?0.96 | ?0.93 | ?0.98 |
| Butylene | 7.90 | ?2.73 | ?2.74 | ?3.97 | ?3.68 | ?4.57 | ?4.33 | ?8.62 | ?8.83 |
| ?C 2-4 = | 38.12 | ?26.41 | ?26.54 | ?35.25 | ?34.95 | ?36.51 | ?34.97 | ?37.99 | ?39.63 |
| Reacted gas | 47.88 | ?43.51 | ?42.66 | ?48.98 | ?49.47 | ?49.35 | ?46.17 | ?52.49 | ?54.57 |
| Gasoline | 19.16 | ?21.84 | ?22.67 | ?19.87 | ?17.95 | ?19.80 | ?16.77 | ?19.00 | ?19.96 |
| Diesel oil | 27.51 | ?28.19 | ?27.63 | ?23.61 | ?25.56 | ?22.11 | ?29.95 | ?21.03 | ?17.21 |
| Heavy oil | 3.57 | ?5.38 | ?6.02 | ?3.61 | ?2.67 | ?4.96 | ?4.15 | ?2.90 | ?3.03 |
| Coke | 1.88 | ?1.08 | ?1.02 | ?3.94 | ?4.35 | ?3.78 | ?2.95 | ?4.57 | ?5.22 |
| Active | 73.48 | ?70.24 | ?69.57 | ?78.40 | ?77.68 | ?76.97 | ?70.41 | ?80.60 | ?83.83 |
Claims (6)
1, the method for a kind of petroleum hydrocarbon catalytic pyrolysis fecund ethene and propylene, this method comprises that heavy petroleum hydrocarbon with preheating is in reactor, contacting with the catalyzer that contains the ZSM-5 molecular sieve in the presence of high-temperature steam, is that 650～750 ℃, reaction pressure are 1.5～4 * 10 in temperature of reaction
5Handkerchief, reaction times are that the weight ratio of 0.2～5 second, catalyzer and stock oil is (15～40): 1, the weight ratio of water vapor and stock oil is (0.3～1): carry out the catalytic pyrolysis reaction under 1 the condition, it is characterized in that said ZSM-5 molecular sieve is that benchmark contains 0.1～8% Ag or Cu with the weight of this molecular sieve.
2, according to the process of claim 1 wherein said its SiO of ZSM-5 molecular sieve
2/ Al
2O
3Mol ratio is 15～200.
3, according to the process of claim 1 wherein that the catalyzer of the said ZSM-5 of containing molecular sieve also further contains active ingredient and the inorganic oxide support material that is selected from y-type zeolite, Beta zeolite or clay molecular sieve with layer structure.
4, according to the process of claim 1 wherein that said Ag or Cu are by said ZSM-5 molecular sieve is carried out ion exchange reaction and combines with molecular sieve with containing the Ag ion or the Cu ionic aqueous solution; Perhaps by the catalyzer of the said ZSM-5 of containing molecular sieve is carried out ion exchange reaction and combines with molecular sieve with containing the Ag ion or the Cu ionic aqueous solution.
5,, it is characterized in that said ZSM-5 molecular sieve is that benchmark contains 0.3～6% Ag with the weight of this molecular sieve according to the method for claim 1.
6, according to the process of claim 1 wherein that said heavy crude hydrocarbon feed is atmospheric gas oil, vacuum gas oil or its mixture, or residual oil or crude oil.
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| CN1323136C (en) * | 2004-07-14 | 2007-06-27 | 中国石油化工股份有限公司 | Process for conversion of hydrocarbon oil |
| CN100392047C (en) * | 2005-06-09 | 2008-06-04 | 中国科学院大连化学物理研究所 | Method for preparing olefin by catalytic oxidation of petroleum hydrocarbon |
| US7615143B2 (en) | 2004-07-30 | 2009-11-10 | Exxonmobil Chemical Patents Inc. | Hydrothermally stable catalyst and its use in catalytic cracking |
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| US7923399B2 (en) | 2004-03-31 | 2011-04-12 | China Petroleum & Chemical Corporation | Zeolite-containing hydrocarbon-converting catalyst, the preparation process thereof, and a process for converting hydrocarbon oils with the catalyst |
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| WO2011050505A1 (en) * | 2009-10-30 | 2011-05-05 | 中国石油天然气股份有限公司 | Double-component modified molecular sieve with improved hydrothermal stability and production method thereof |
| US9895686B2 (en) | 2009-10-30 | 2018-02-20 | Petrochina Company Limited | Double-component modified molecular sieve with improved hydrothermal stability and production method thereof |
| CN102103134B (en) * | 2009-12-18 | 2012-03-21 | 中国科学院大连化学物理研究所 | Method and device for evaluating coupling effect of methanol-coupling alkanes catalytic conversion reaction |
| CN109663613A (en) * | 2017-10-17 | 2019-04-23 | 中国石油大学(北京) | A kind of metal-modified ZSM-5 molecular sieve catalyst and its preparation and application |
| CN109663613B (en) * | 2017-10-17 | 2021-07-16 | 中国石油大学(北京) | Metal modified ZSM-5 molecular sieve catalyst, and preparation and application thereof |
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