CN101165024B - Method for increasing selectivity and yield of propylene - Google Patents

Method for increasing selectivity and yield of propylene Download PDF

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CN101165024B
CN101165024B CN2006101173501A CN200610117350A CN101165024B CN 101165024 B CN101165024 B CN 101165024B CN 2006101173501 A CN2006101173501 A CN 2006101173501A CN 200610117350 A CN200610117350 A CN 200610117350A CN 101165024 B CN101165024 B CN 101165024B
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propylene
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CN101165024A (en
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刘俊涛
钟思青
朱志焱
李蕾
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/40Ethylene production

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Abstract

The present invention relates to one kind of propylene producing process with high selectivity and high yield. The production process includes the following steps: 1. reaction of oxygen compound material in the first reaction region through contacting with catalyst I to produce effluent I containing ethylene, propylene and butylene; and separating the effluent I to obtain ethylene, propylene, butylene-1, butylene-2 and other C4 and C4+ hydrocarbons; 2. reaction of butylene-1 in the second reaction region through contacting with catalyst II to produce effluent II containing butylene-2; and 3. reaction of ethylene and butylene-2 from the step 1 and effluent II from the step 2 in the third reaction region through contacting with catalyst III to produce effluent III containing propylene; and 4. reaction of C4 and C4+ hydrocarbons in the fourth reaction region through contacting with catalyst IV to produce effluent IV containing ethylene and propylene. The production process may be appliedin industrial production.

Description

Improve the method for propylene selectivity and yield
Technical field
The present invention relates to a kind of method that improves propylene selectivity and yield, particularly react compound butylenes double-bond isomerization about methyl alcohol or dimethyl ether catalysis, butylene and ethene transposition and olefins by catalytic cracking technology improve the method for propylene selectivity yield.
Background technology
Petrochemical complex is a mainstay industry important in the national economy, for industry, agricultural, departments such as traffic and national defence provide a large amount of industrial chemicals, is one of related and branch of industry that drive property is stronger in the national economy.Propylene and ethene then are to constitute modern petrochemical complex of paramount importance two big basic materials.
Propylene is mainly used in produces polypropylene, isopropyl benzene, oxo-alcohols, vinyl cyanide, propylene oxide, vinylformic acid, Virahol etc., and wherein polypropylene accounts for the over half of world's propylene demand.At present, 67% propylene is produced the byproduct of ethene from steam cracking in the world, and 30% produces the byproduct of vapour, diesel oil from refinery catalytic cracking (FCC), and a small amount of (about 3%) is obtained by dehydrogenating propane and ethene-butylene metathesis reaction.Estimate that following propylene demand growth speed is faster than supply.
Higher in view of the growth rate of demand of propylene, and traditional production model presents the pressure of " supply falls short of demand ", and therefore replenishing the propylene demand need be by means of other various propylene enhancing technology.
All the time; coal or Sweet natural gas preparing synthetic gas, synthesising gas systeming carbinol and alkene isolation technique have had the mass-producing mature experience; but the process by methanol to olefins is breakpoint and the difficult point of synthetic gas to this industrial chain of alkene, and this solution of key technology can be for providing a new raw material route by non-oil resource production basic organic ethene, propylene.Especially in the last few years, it is high that the demand of ethene and propylene continues, and under the deficient day by day situation of petroleum resources.How to hew out a non-oil resource and produce the Coal Chemical Industry variation route of propylene, for greatly alleviating China's oil situation in short supply, promote the great-leap-forward development of the heavy chemical industry of China and the structural adjustment of raw material route, have important strategic meaning and society, economic benefit.
Document CN1166478A, disclose a kind of method of being produced low-carbon alkenes such as ethene, propylene by methyl alcohol or dme, this method is catalyzer with the aluminium phosphate molecular sieve, adopts the ciculation fluidized formula processing method of upstriker dense bed, in 500~570 ℃ of preferred temperature of reaction, air speed 2~6 hours -1And under 0.01~0.05MPa condition, make methyl alcohol or dme cracking produce low-carbon alkenes such as ethene, propylene.There is the low technical disadvantages of purpose selectivity of product in this method.
Document CN1356299A discloses a kind of processing method and system thereof that produces low-carbon alkene by methyl alcohol or dme.This process using silicoaluminophosphamolecular molecular sieves (SAPO-34) is as catalyzer, utilize the ultrashort contact reactor of gas-solid cocurrent flow descending formula fluidized-bed, catalyzer contacts in the ultrashort contact reactor of gas-solid cocurrent flow descending formula fluidized-bed with raw material, the reactant flow direction is descending; Catalyzer and reaction product go out to enter the gas-solid quick disconnector that is arranged on this reactor lower part behind the reactor and carry out sharp separation; Isolated catalyzer enters charcoal regeneration in the revivifier, and catalyzer is cyclic regeneration in system, and reaction cycle is carried out.This technology dme or conversion of methanol are greater than 98%.But there is the low technical disadvantages of propylene selectivity equally in this method.
Summary of the invention
Technical problem to be solved by this invention is to have the low and low problem of selectivity of purpose product propene yield in the technical literature in the past, and a kind of new raising propylene selectivity and the method for yield are provided.This method has purpose product propene yield height, the advantage that selectivity is good.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method that improves propylene selectivity and yield, with the oxygenatedchemicals is raw material, may further comprise the steps successively: a) raw material contacts by the interior catalyst I of first reaction zone and reaction zone, generation contains the effluent I of ethene, propylene and butylene, obtains ethene, propylene, butene-1, butene-2 and other carbon four and above hydro carbons after separating; B) enter second reactor from the butene-1 of step (a) and contact, generate the effluent II that contains butene-2 with catalyst I I; C) enter the 3rd reaction zone and catalyst I II contact reacts from the ethene of step a) and butene-2 and from the effluent II of step b), generation contains the effluent III of propylene; D) other carbon four and above hydro carbons enter the 4th reaction zone and contact with catalyst I V, and reaction generates the effluent IV that contains ethene, propylene.
Be selected from silicon phosphorus aluminium type or ZSM type molecular sieve in catalyst I and catalyst I V in the technique scheme, catalyst I I is selected from the oxide catalyst of supported palladium, copper, nickel or magnesium, ZSM type molecular sieve; Catalyst I II is selected from the oxide catalyst of load Tungsten oxide 99.999, molybdenum oxide or rhenium oxide; Catalyst I and catalyst I V preferred version are selected from SAPO-34 molecular sieve or ZSM-5 molecular sieve; Catalyst I II preferred version is selected from the oxide catalyst of load Tungsten oxide 99.999; Catalyst I I preferred version is selected from the ZSM-5 molecular sieve.The oxygenatedchemicals preferred version is selected from least a in methyl alcohol or the dme.The temperature of reaction of the first and the 4th reaction zone is 300~650 ℃, and reaction pressure is 0.01~1.5MPa, and reaction velocity is 0.1~50 hour -1The temperature of reaction preferable range of the first and the 4th reaction zone is 400~550 ℃, and the reaction pressure preferable range is 0.02~1.0MPa, and the reaction velocity preferable range is 0.5~30 hour -1The temperature of reaction of second reactor is 40~450 ℃, and reaction pressure is 0.01~4.0MPa, and reaction velocity is 0.1~50 hour -1The temperature of reaction preferable range of second reactor is 60~400 ℃, and the reaction pressure preferable range is 0.1~2.0MPa, and the reaction velocity preferable range is 1~20 hour -1The temperature of reaction of the 3rd reaction zone is 200~550 ℃, and reaction pressure is 0.01~4.0MPa, and reaction velocity is 0.1~20 hour -1The temperature of reaction preferable range of the 3rd reaction zone is 250~500 ℃, and the reaction pressure preferable range is 0.1~3.0MPa, and the reaction velocity preferable range is 0.2~5 hour -1
When oxygenatedchemicals such as methyl alcohol or dimethyl ether catalysis reaction generate ethene and propylene, unavoidably to generate carbon four and above hydro carbons thereof, influence the selectivity and the yield of ethylene, propylene; The method that improves the ethylene, propylene yield or regulate the propylene and ethylene ratio is except that the selectivity of catalyst type, and the reasonable arrangement of Selection of technological conditions or technical process also is an effective means.Among the present invention with the resultant of oxygenatedchemicals catalyzed reaction after separating, with butene-1 at first isomerization become butene-2, separate butene-2 and the ethene that the butene-2 obtain and reaction obtain then and pass through metathesis reaction, realize that 1 molecule ethene and 1 molecule butene-2 generate 2 molecule propylene, reach the purpose that improves propene yield.In addition, consider in the resultant of oxygenatedchemicals catalyzed reaction and also have iso-butylene and carbon four above alkene, and this part alkene can further generate ethylene, propylene by catalytic cracking reaction equally, for this reason among the present invention, with a part of butylene and carbon four above alkene return the oxygenatedchemicals reactor or independent reactor carries out the purpose that catalyzed reaction realizes further increasing output of ethylene propylene.
Adopt technical scheme of the present invention, adopt the SAPO-34 molecular sieve catalyst at first reactor, fluidized-bed reactor, second reactor adopts magnesia catalyst, adopt fixed-bed reactor, the 3rd reactor adopts tungsten oxide catalyst, adopts fixed-bed reactor, and the 4th reactor adopts the ZSM-5 molecular sieve catalyst, adopt fixed-bed reactor, the first and the 4th reactor reaction temperature is 400~550 ℃, and reaction pressure is 0.02~1.0MPa, and reaction velocity is 0.2~30 hour -1The reaction conditions of second and third reactor is 200~500 ℃ of temperature of reaction, and reaction pressure is 0.1~3.5MPa, and reaction velocity is 0.2~5 hour -1Under the condition, propene yield can reach more than 46%, has obtained better technical effect.
The invention will be further elaborated below by embodiment, but should be by any way as restriction of the present invention.
Embodiment
[embodiment 1]
With methyl alcohol is raw material, first reactor adopts fluidized-bed reactor, with the SAPO-34 molecular sieve is catalyzer, and second reactor adopts fixed-bed reactor, is catalyzer with magnesium oxide, the 3rd reactor adopts fixed-bed reactor, with the Tungsten oxide 99.999 is catalyzer, and the 4th reactor adopts fixed-bed reactor, is catalyzer with the ZSM-5 molecular sieve, 460 ℃ of the first reactor reaction temperature, reaction velocity are 5 hours -1, reaction pressure is 0.3MPa; 300 ℃ of the second reactor reaction temperature, reaction velocity are 3 hours -1, reaction pressure is 0.3MPa; 310 ℃ of the 3rd reactor reaction temperature, reaction velocity are 1 hour -1, ethene and butylene mass ratio are 1.1: 1, reaction pressure is 3MPa.470 ℃ of the 4th reactor reaction temperature, reaction velocity 9 hours -1, pressure is 0.2MPa.In the experiment, the first reactor reaction product is after separating, butene-1 enters second reactor, its product and the butene-2 that separation obtains from the first reactor reaction product all enter the 3rd reactor reaction, all the other carbon four and above hydro carbons enter the 4th reactor reaction, the total reaction result is: methanol conversion 98.8%, propene yield 472%.
[embodiment 2]
With the dme is raw material, first reactor adopts fluidized-bed reactor, with the SAPO-34 molecular sieve is catalyzer, and second reactor adopts fixed-bed reactor, is catalyzer with magnesium oxide, the 3rd reactor adopts fixed-bed reactor, with the Tungsten oxide 99.999 is catalyzer, and the 4th reactor adopts fixed-bed reactor, is catalyzer with the ZSM-5 molecular sieve, the first reactor reaction temperature is 555 ℃, reaction velocity 45 hours -1, reaction pressure is 0.5MPa; 450 ℃ of the second reactor reaction temperature, reaction velocity are 022 hour -1, reaction pressure is 2.3MPa; 530 ℃ of the 3rd reactor reaction temperature, reaction velocity are 10 hours -1, ethene and butylene mass ratio are 1: 1, reaction pressure is 0.01MPa.The 4th reactor reaction temperature is 570 ℃, and reaction velocity is 20 hours -1, reaction pressure is 0.01MPa.In the experiment, the first reactor reaction product is after separating, butene-1 enters second reactor, its product and the butene-2 that separation obtains from the first reactor reaction product all enter the 3rd reactor reaction, all the other carbon four and above hydro carbons enter the 4th reactor reaction, the total reaction result is: dimethyl ether conversion rate 88.5%, propene yield 36.8%.
[embodiment 3]
With the dme is raw material, and water is thinner, and the mass ratio of dme and water is 1: 2, first reactor adopts fluidized-bed reactor, with the SAPO-34 molecular sieve is catalyzer, and second reactor adopts fixed-bed reactor, is catalyzer with the ZSM-5 molecular sieve, the 3rd reactor adopts fixed-bed reactor, with the Tungsten oxide 99.999 is catalyzer, and the 4th reactor adopts fixed-bed reactor, is catalyzer with the ZSM-5 molecular sieve, 620 ℃ of the first reactor reaction temperature, air speed 26 hours -1, reaction pressure is 1.2MPa; 340 ℃ of the second reactor reaction temperature, reaction velocity are 30 hours -1, reaction pressure is 1.0MPa; The 3rd reactor reaction temperature is 450 ℃, and reaction velocity is 5 hours -1, ethene and butylene mass ratio are 1: 1, reaction pressure is 0.2MPa.600 ℃ of the 4th reactor reaction temperature, reaction velocity 40 hours -1, reaction pressure is 1.5MPa.In the experiment, the first reactor reaction product is after separating, butene-1 enters second reactor, its product and the butene-2 that separation obtains from the first reactor reaction product all enter the 3rd reactor reaction, all the other carbon four and above hydro carbons enter the 4th reactor reaction, the total reaction result is: dimethyl ether conversion rate 96.8%, propene yield 42.3%.
[embodiment 4]
With dme and methyl alcohol is raw material, dme is 1: 1 with the methanol quality ratio, and first reactor adopts fluidized-bed reactor, is catalyzer with the SAPO-34 molecular sieve, second reactor adopts fixed-bed reactor, silicon oxide with supported palladium is a catalyzer, and the 3rd reactor adopts fixed-bed reactor, is catalyzer with the Tungsten oxide 99.999, the 4th reactor adopts fluidized-bed reactor, with the ZSM-5 molecular sieve is catalyzer, and the first reactor reaction temperature is 510 ℃, and reaction velocity is 5 hours -1, reaction pressure is 0.1MPa; 50 ℃ of the second reactor reaction temperature, reaction velocity are 15 hours -1, reaction pressure is 2.0MPa; The 3rd reactor reaction temperature is 400 ℃, and reaction velocity is 2 hours -1, ethene and butylene mass ratio are 1: 1, reaction pressure is 0.8MPa.The 4th reactor reaction temperature is 530 ℃, and reaction velocity is 15 hours -1, reaction pressure is 0.3MPa.In the experiment, the first reactor reaction product is after separating, butene-1 enters second reactor, its product and the butene-2 that separation obtains from the first reactor reaction product all enter the 3rd reactor reaction, all the other carbon four and above hydro carbons enter the 4th reactor reaction, the total reaction result is: methyl alcohol and dme total conversion rate 100%, propene yield 51.6%.
[embodiment 5]
With the dme is raw material, first reactor adopts fluidized-bed reactor, with the SAPO-34 molecular sieve is catalyzer, and second reactor adopts fixed-bed reactor, is catalyzer with the silicon oxide of nickel-loaded, the 3rd reactor adopts fixed-bed reactor, with the Tungsten oxide 99.999 is catalyzer, and the 4th reactor adopts riser reactor, is catalyzer with the ZSM-5 molecular sieve, the first reactor reaction temperature is 500 ℃, and reaction velocity is 2.5 hours -1, reaction pressure is 0.02MPa; 80 ℃ of the second reactor reaction temperature, reaction velocity are 5 hours -1, reaction pressure is 0.8MPa; The 3rd reactor reaction temperature is 300 ℃, and reaction velocity is 1 hour -1, ethene and butylene mass ratio are 1: 1, reaction pressure is 3.0MPa.The 4th reactor reaction temperature is 530 ℃, and reaction velocity is 5 hours -1, reaction pressure is 0.04MPa.In the experiment, the first reactor reaction product is after separating, butene-1 enters second reactor, its product and the butene-2 that separation obtains from the first reactor reaction product all enter the 3rd reactor reaction, all the other carbon four and above hydro carbons enter the 4th reactor reaction, the total reaction result is: dimethyl ether conversion rate 100%, propene yield 55.1%.
[embodiment 6]
With the dme is raw material, first reactor adopts fluidized-bed reactor, with the SAPO-11 molecular sieve is catalyzer, and second reactor adopts fixed-bed reactor, is catalyzer with the ZSM-5 molecular sieve, the 3rd reactor adopts fixed-bed reactor, with the molybdenum oxide is catalyzer, and the 4th reactor adopts fluidized-bed reactor, is catalyzer with the ZSM-35 molecular sieve, the first reactor reaction temperature is 520 ℃, and reaction velocity is 3 hours -1, reaction pressure is 0.04MPa; 320 ℃ of the second reactor reaction temperature, reaction velocity are 20 hours -1, reaction pressure is 1.5MPa; The 3rd reactor reaction temperature is 200 ℃, and reaction velocity is 0.5 hour -1, ethene and butylene mass ratio are 1: 1, reaction pressure is 1.0MPa.The 4th reactor reaction temperature is 460 ℃, and reaction velocity is 1 hour -1, reaction pressure is 0.06MPa.In the experiment, the first reactor reaction product is after separating, butene-1 enters second reactor, its product and the butene-2 that separation obtains from the first reactor reaction product all enter the 3rd reactor reaction, all the other carbon four and above hydro carbons enter the 4th reactor reaction, the total reaction result is: dimethyl ether conversion rate 99.5%, propene yield 48.2%.
[embodiment 7]
With methyl alcohol and ethanol is raw material, wherein methyl alcohol and ethanol mass ratio are 1: 1, and first reactor adopts fluidized-bed reactor, is catalyzer with the SAPO-43 molecular sieve, second reactor adopts fixed-bed reactor, silicon oxide with load copper is a catalyzer, and the 3rd reactor adopts fixed-bed reactor, is catalyzer with the molybdenum oxide, the 4th reactor adopts fluidized-bed reactor, with the ZSM-23 molecular sieve is catalyzer, and the first reactor reaction temperature is 560 ℃, and reaction velocity is 6 hours -1, reaction pressure is 0.2MPa; 150 ℃ of the second reactor reaction temperature, reaction velocity are 2 hours -1, reaction pressure is 0.5MPa; The 3rd reactor reaction temperature is 260 ℃, and reaction velocity is 1 hour -1, ethene and butylene mass ratio are 2: 1, reaction pressure is 1.0MPa.The 4th reactor reaction temperature is 580 ℃, and reaction velocity is 1.5 hours -1, reaction pressure is 0.6MPa.In the experiment, the first reactor reaction product is after separating, butene-1 enters second reactor, its product and the butene-2 that separation obtains from the first reactor reaction product all enter the 3rd reactor reaction, all the other carbon four and above hydro carbons enter the 4th reactor reaction, the total reaction result is: methanol conversion 98%, ethanol conversion are 100%, propene yield 35.7%.
[embodiment 8]
With methyl alcohol and propyl alcohol is raw material, wherein methyl alcohol and propyl alcohol mass ratio are 1: 4, and first reactor adopts fluidized-bed reactor, is catalyzer with the SAPO-34 molecular sieve, second reactor adopts fixed-bed reactor, with magnesium oxide is catalyzer, and the 3rd reactor adopts fixed-bed reactor, is catalyzer with the Tungsten oxide 99.999, the 4th reactor adopts fluidized-bed reactor, with the SAPO-34 molecular sieve is catalyzer, and the first reactor reaction temperature is 520 ℃, and reaction velocity is 5 hours -1, reaction pressure is 0.2MPa; 410 ℃ of the second reactor reaction temperature, reaction velocity are 0.5 hour -1, reaction pressure is 3.0MPa; The 3rd reactor reaction temperature is 300 ℃, and reaction velocity is 3 hours -1, ethene and butylene mass ratio are 1.2: 1, reaction pressure is 2.5MPa.The 4th reactor reaction temperature is 530 ℃, reaction velocity 5 hours -1, reaction pressure is 0.02MPa.In the experiment, the first reactor reaction product is after separating, butene-1 enters second reactor, its product and the butene-2 that separation obtains from the first reactor reaction product all enter the 3rd reactor reaction, all the other carbon four and above hydro carbons enter the 4th reactor reaction, the total reaction result is: methanol conversion 100%, propyl alcohol transformation efficiency are 100%, propene yield 61.3%.
[embodiment 9]
With methyl alcohol and butanols is raw material, wherein methyl alcohol and butanols mass ratio are 1: 5, and first reactor adopts fluidized-bed reactor, is catalyzer with the ZSM-5 molecular sieve, second reactor adopts fixed-bed reactor, with magnesium oxide is catalyzer, and the 3rd reactor adopts fixed-bed reactor, is catalyzer with the Tungsten oxide 99.999, the 4th reactor adopts fluidized-bed reactor, with the SAPO-34 molecular sieve is catalyzer, and the first reactor reaction temperature is 570 ℃, and reaction velocity is 12 hours -1, reaction pressure is 1.0MPa; 310 ℃ of the second reactor reaction temperature, reaction velocity are 1 hour -1, reaction pressure is 0.2MPa; The 3rd reactor reaction temperature is 310 ℃, and reaction velocity is 1 hour -1, ethene and butylene mass ratio are 1: 1, reaction pressure is 2.8MPa.The 4th reactor reaction temperature is 580 ℃, and reaction velocity is 12 hours -1, reaction pressure is 0.1MPa.In the experiment, the first reactor reaction product is after separating, butene-1 enters second reactor, its product and the butene-2 that separation obtains from the first reactor reaction product all enter the 3rd reactor reaction, all the other carbon four and above hydro carbons enter the 4th reactor reaction, the total reaction result is: methanol conversion 99.2%, butanols transformation efficiency are 100%, propene yield 54.8%.
[comparative example 1]
With reference to each step and the reaction conditions of embodiment 1, just adopt the first independent reactor to react, reaction result is: methanol conversion 97%, propene yield 35%.
[comparative example 2]
With reference to each step and the reaction conditions of embodiment 1, just do not adopt second reactor to react, reaction result is: methanol conversion 98%, propene yield 45.1%.
[comparative example 3]
With reference to each step and the reaction conditions of embodiment 1, just do not adopt the 4th reactor to react, reaction result is: methanol conversion 98%, propene yield 40.1%.
[comparative example 4]
With reference to each step and the reaction conditions of embodiment 1, just do not adopt the 3rd reactor to react, reaction result is: methanol conversion 98%, propene yield 40.9%.

Claims (6)

1. a method that improves propylene selectivity and yield is a raw material with the oxygenatedchemicals, may further comprise the steps successively:
A) raw material contacts by the interior catalyst I of first reaction zone and reaction zone, generates the effluent I that contains ethene, propylene and butylene, obtains ethene, propylene, butene-1, butene-2 and other carbon four and above hydro carbons after separating;
B) enter second reactor from the butene-1 of step a) and contact, generate the effluent II that contains butene-2 with catalyst I I;
C) enter the 3rd reaction zone and catalyst I II contact reacts from the ethene of step a) and butene-2 and from the effluent II of step b), generation contains the effluent III of propylene;
D) other carbon four and above hydro carbons enter the 4th reaction zone and contact with catalyst I V, and reaction generates the effluent IV that contains ethene, propylene.
2. according to the method for claim 1 described raising propylene selectivity and yield, it is characterized in that catalyst I and catalyst I V are selected from silicon phosphorus aluminium type or ZSM type molecular sieve; Catalyst I I is selected from the oxide catalyst of supported palladium, copper, nickel or magnesium, ZSM type molecular sieve; Catalyst I II is selected from the oxide catalyst of load Tungsten oxide 99.999, molybdenum oxide or rhenium oxide.
3. according to the method for claim 2 described raising propylene selectivity and yield, it is characterized in that described catalyst I and catalyst I V are selected from SAPO-34 molecular sieve and ZSM-5 molecular sieve; Catalyst I II is selected from the oxide catalyst of load Tungsten oxide 99.999; Catalyst I I is selected from the ZSM-5 molecular sieve.
4. according to the method for claim 1 described raising propylene selectivity and yield, it is characterized in that oxygenatedchemicals is selected from least a in methyl alcohol or the dme.
5. according to the method for claim 1 described raising propylene selectivity and yield, the temperature of reaction that it is characterized in that the first and the 4th reaction zone is 300~650 ℃, and reaction pressure is 0.01~1.5MPa, and reaction velocity is 0.1~50 hour -1The temperature of reaction of second reactor is 40~450 ℃, and reaction pressure is 0.01~4.0MPa, and reaction velocity is 0.1~50 hour -1The temperature of reaction of the 3rd reaction zone is 200~550 ℃, and reaction pressure is 0.01~4.0MPa, and reaction velocity is 0.1~20 hour -1
6. according to the method for claim 5 described raising propylene selectivity and yield, the temperature of reaction that it is characterized in that the first and the 4th reaction zone is 400~550 ℃, and reaction pressure is 0.02~1.0MPa, and reaction velocity is 0.5~30 hour -1The temperature of reaction of second reactor is 60~400 ℃, and reaction pressure is 0.1~2.0MPa, and reaction velocity is 1~20 hour -1The temperature of reaction of the 3rd reaction zone is 250~500 ℃, and reaction pressure is 0.1~3.0MPa, and reaction velocity is 0.2~5 hour -1
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CN102190539B (en) * 2010-03-03 2013-10-16 中国石油化工股份有限公司 Method for increasing propylene yield
CN114426442A (en) * 2020-10-15 2022-05-03 中国石油化工股份有限公司 Method for preparing low-carbon olefin by using oxygen-containing compound

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