CN101165022A - Method for increasing yield of ethylene and propylene - Google Patents
Method for increasing yield of ethylene and propylene Download PDFInfo
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- CN101165022A CN101165022A CNA2006101173484A CN200610117348A CN101165022A CN 101165022 A CN101165022 A CN 101165022A CN A2006101173484 A CNA2006101173484 A CN A2006101173484A CN 200610117348 A CN200610117348 A CN 200610117348A CN 101165022 A CN101165022 A CN 101165022A
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The present invention relates to one kind of ethylene and 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 the effluent I containing ethylene, propylene and C4 and C4+ hydrocarbons, and separating to obtain the effluent II containing C4 and C4+ hydrocarbons, ethylene product and propylene product; and 2. reaction of the effluent II in the second reaction region through contacting with catalyst II to produce the effluent III containing ethylene, propylene and C4 and C4+ hydrocarbons, and separating the effluent III in a post step. The production process may be applied in industrial production.
Description
Technical field
The present invention relates to a kind of method that improves ethene and propene yield, particularly about adopting at least two reaction zones, the method for ethene and propene yield in realization raising methyl alcohol or the dimethyl ether catalysis reaction.
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.
Large derived product of ethene mainly contains polyethylene, oxyethane, ethylene glycol, polyvinyl chloride, vinylbenzene, vinyl acetate between to for plastic etc.The size of ethylene yield is to weigh the sign of a national petrochemical industry and even national economy development degree.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 ethene and propylene demand growth speed are faster than supply.
Higher in view of the growth rate of demand of ethene and propylene, and traditional production model presents the pressure of " supply falls short of demand ", so make-up ethylene and propylene demand need be by means of other various increasing output of ethylene propylene technology.
Oxygenatedchemicals is the promising feedstock candidate that is used to prepare alkene.Promising especially oxygen-containing compound material is alcohols such as methyl alcohol, dme, methyl ethyl ether, diethyl ether, dimethyl carbonate and methyl formate.These oxygenatedchemicalss are many can to comprise coal, recycled plastic, municipal wastes or any suitable organic materials production by fermentation or by Sweet natural gas deutero-synthetic gas, petroleum liquid, carbonaceous material.Because the source is varied, oxygenatedchemicals will become the source of finance that is used for olefin production.
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 ethene, 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 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%.
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 this method exists ethene and the low technical disadvantages of propene yield.
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 ethylene, propylene yield in the technical literature in the past, and a kind of new raising ethene and the method for propene yield are provided.This method has purpose product ethene, 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 ethene and propene 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 carbon four above alkene, obtains carbon four and above hydro carbons effluent II, ethylene product and propylene product after separating; (b) at least a portion enters second reactor from the effluent II of step (a) and contacts with catalyst I I, generates the effluent III that contains ethene, propylene and carbon four above hydrocarbon, and effluent III enters the separation of follow-up workshop section.
Catalyst I or catalyst I I all are selected from silicon phosphorus aluminium type or ZSM type molecular sieve in the technique scheme; Preferred version is selected from SAPO-34 molecular sieve or ZSM-5 molecular sieve.The oxygenatedchemicals preferred version is selected from least a in methyl alcohol or the dme.The temperature of reaction of first reaction zone is 200～580 ℃, and reaction pressure is 0.01～1.5MPa, and reaction velocity is 0.1～50 hour
-1The temperature of reaction of second reaction zone is 300～650 ℃, and reaction pressure is-0.09～1.0MPa, and reaction velocity is 0.1～100 hour
-1The temperature of reaction preferable range of first 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 preferable range of second reaction zone is 400～580 ℃, and the reaction pressure preferable range is-0.08～0.8MPa, and the reaction velocity preferable range is 0.2～50 hour
-1First reaction zone or second reaction zone all are selected from fixed bed, moving-bed, fluidized-bed, circulating fluidized bed or riser reactor.First reaction zone or the second reaction zone preferred version all are selected from fluidized-bed, circulating fluidized bed or riser reactor.
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 the resultant of oxygenatedchemicals catalyzed reaction obtained at least a portion carbon four and above hydro carbons by product and enter at least the second reaction zone and react after separating, generate ethene and propylene, reach the purpose that improves ethene and propene yield.
Adopt technical scheme of the present invention, adopt the SAPO-34 molecular sieve catalyst at first reactor, fast fluidized bed reactor, second reactor adopts the SAPO-34 molecular sieve catalyst, adopt riser reactor, the temperature of reaction of first reaction zone is 400～550 ℃, and reaction pressure is 0.02～1.0MPa, and reaction velocity is 0.5～30 hour
-1The reaction conditions temperature of reaction of second reactor is 400～580 ℃, and reaction pressure is-0.08～0.8MPa, and reaction velocity is 0.2～50 hour
-1Under the condition, ethene and propylene diene yield can reach more than 45%, have 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, and first reactor adopts fast fluidized bed reactor, is catalyzer with the SAPO-34 molecular sieve, and second reactor adopts fixed-bed reactor, is catalyzer with the ZSM-5 molecular sieve, and the first reactor reaction temperature is 460 ℃, and reaction velocity is 7 hours
-1, reaction pressure is 0.1MPa; The second reactor reaction temperature is 480 ℃, and reaction velocity is 8 hours
-1, reaction pressure is 0.11MPa.In the experiment, the first reactor reaction product is after separating, and all the other carbon four and above hydro carbons enter second reactor reaction, and the total reaction result is: methanol conversion 98%, yield of ethene 46.5%, propene yield 36.7%.
[embodiment 2]
With the dme is raw material, and first reactor adopts fast fluidized bed reactor, is catalyzer with the SAPO-34 molecular sieve, second reactor adopts riser reactor, with the SAPO-34 molecular sieve is catalyzer, and the first reactor reaction temperature is 560 ℃, reaction velocity 35 hours
-1, reaction pressure is 0.5MPa; The second 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 and butene-2 all enter second reactor reaction, all the other carbon four and above hydro carbons enter the 3rd reactor reaction, and in the experiment, the first reactor reaction product is after separating, all the other carbon four and above hydro carbons enter second reactor reaction, the total reaction result is: dimethyl ether conversion rate 89%, yield of ethene 35.2%, propene yield 30.3%.
[embodiment 3]
With the dme is raw material, water is thinner, the mass ratio of dme and water is 1: 2, first reactor adopts riser reactor, with the SAPO-34 molecular sieve is catalyzer, and second reactor adopts riser reactor, is catalyzer with the SAPO-34 molecular sieve, 510 ℃ of the first reactor reaction temperature, air speed 25 hours
-1, reaction pressure is 1.2MPa; 600 ℃ of the second reactor reaction temperature, reaction velocity 10 hours
-1, reaction pressure is 1.5MPa.In the experiment, the first reactor reaction product is after separating, and all the other carbon four and above hydro carbons enter second reactor reaction, and the total reaction result is: dimethyl ether conversion rate 95%, yield of ethene 44.2%, propene yield 33.1%.
[embodiment 4]
With dme and methyl alcohol is raw material, dme is 1: 1 with the methanol quality ratio, first reactor adopts riser reactor, with the SAPO-34 molecular sieve is catalyzer, second reactor adopts riser reactor, with the SAPO-34 molecular sieve is catalyzer, and the first reactor reaction temperature is 500 ℃, and reaction velocity is 4 hours
-1, reaction pressure is 0.1MPa; The second 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, and all the other carbon four and above hydro carbons enter second reactor reaction, and the total reaction result is: methyl alcohol and dme total conversion rate 100%, yield of ethene 47.1%, propene yield 40.1%.
[embodiment 5]
With the dme is raw material, and first reactor adopts fluidized-bed reactor, is catalyzer with the SAPO-34 molecular sieve, and second reactor adopts fixed-bed reactor, is catalyzer with the ZSM-5 molecular sieve, and the first reactor reaction temperature is 480 ℃, and reaction velocity is 2 hours
-1, reaction pressure is 0.02MPa; The second reactor reaction temperature is 530 ℃, and reaction velocity is 5 hours
-1, reaction pressure is-0.05MPa.In the experiment, the first reactor reaction product is after separating, and all the other carbon four and above hydro carbons enter second reactor reaction, and the total reaction result is: dimethyl ether conversion rate 100%, yield of ethene 46.1%, propene yield 41.7%.
[embodiment 6]
With the dme is raw material, and first reactor adopts fluidized-bed reactor, is catalyzer with the SAPO-11 molecular sieve, and second reactor adopts fluidized-bed reactor, is catalyzer with the SAPO-11 molecular sieve, and the first reactor reaction temperature is 530 ℃, and reaction velocity is 4 hours
-1, reaction pressure is 0.04MPa; The second reactor reaction temperature is 460 ℃, and reaction velocity is 1 hour
-1, reaction pressure is 0.08MPa.In the experiment, the first reactor reaction product is after separating, and all the other carbon four and above hydro carbons enter second reactor reaction, and the total reaction result is: dimethyl ether conversion rate 100%, yield of ethene 20.7%, propene yield 50.8%.
[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 4, just adopt the first independent reactor to react, reaction result is: methyl alcohol and dme total conversion rate 99%, propene yield 41%.
Claims (8)
1. a method that improves ethene and propene 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 carbon four above alkene, obtains carbon four and above hydro carbons effluent II, ethylene product and propylene product after separating;
B) at least a portion enters second reactor from the effluent II of step (a) and contacts with catalyst I I, generates the effluent III that contains ethene, propylene and carbon four above hydrocarbon, and effluent III enters the separation of follow-up workshop section.
2. according to the method for described raising ethene of claim 1 and propene yield, it is characterized in that catalyst I or catalyst I I all are selected from silicon phosphorus aluminium type or ZSM type molecular sieve.
3. according to the method for described raising ethene of claim 2 and propene yield, it is characterized in that described catalyst I or catalyst I I all are selected from SAPO-34 molecular sieve or ZSM-5 molecular sieve.
4. according to the method for described raising ethene of claim 1 and propene yield, it is characterized in that oxygenatedchemicals is selected from least a in methyl alcohol or the dme.
5. according to the method for described raising ethene of claim 1 and propene yield, the temperature of reaction that it is characterized in that first reaction zone is 200～580 ℃, and reaction pressure is 0.01～1.5MPa, and reaction velocity is 0.1～50 hour
-1The temperature of reaction of second reaction zone is 300～650 ℃, and reaction pressure is-0.09～1.0MPa, and reaction velocity is 0.1～100 hour
-1
6. according to the method for described raising ethene of claim 5 and propene yield, the temperature of reaction that it is characterized in that first 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 reaction zone is 400～580 ℃, and reaction pressure is-0.08～0.8MPa, and reaction velocity is 0.2～50 hour
-1
7. according to the method for described raising ethene of claim 1 and propene yield, it is characterized in that first reaction zone or second reaction zone all are selected from fixed bed, moving-bed, fluidized-bed, circulating fluidized bed or riser reactor.
8. according to the method for described raising ethene of claim 7 and propene yield, it is characterized in that first reaction zone or second reaction zone all are selected from fluidized-bed, circulating fluidized bed or riser reactor.
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| CN2006101173484A CN101165022B (en) | 2006-10-20 | 2006-10-20 | Method for increasing yield of ethylene and propylene |
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| CN2006101173484A CN101165022B (en) | 2006-10-20 | 2006-10-20 | Method for increasing yield of ethylene and propylene |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891576A (en) * | 2010-07-12 | 2010-11-24 | 兆威兴业有限公司 | Process and device for preparing low-carbon olefin by methanol and/or dimethyl ether |
| CN102040439A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for removing O2, N2 and dimethyl ether from olefin streams |
| CN102344329A (en) * | 2011-08-03 | 2012-02-08 | 上海碧科清洁能源技术有限公司 | Method for preparing olefin by alcohol and/or ether |
| CN102464523A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for producing light olefins |
| CN102746889A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for producing ethene and propylene by catalytic cracking |
| CN102746888A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for producing ethene and propylene by fluidizing and catalytic cracking |
| CN103772109A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing propylene co-production ethylbenzene by methanol conversion |
| CN105441113A (en) * | 2014-08-20 | 2016-03-30 | 中国石油化工股份有限公司 | Catalytic cracking method of naphtha feedstock |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6455749B1 (en) * | 1997-10-03 | 2002-09-24 | Exxonmobil Chemical Patents, Inc. | Method for increasing light olefin yield by conversion of a heavy hydrocarbon fraction of a product to light olefins |
| US7414167B2 (en) * | 2005-01-14 | 2008-08-19 | Uop Llc | Conversion of oxygenate to propylene using moving bed technology and a separate heavy olefin interconversion step |
-
2006
- 2006-10-20 CN CN2006101173484A patent/CN101165022B/en active Active
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040439A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for removing O2, N2 and dimethyl ether from olefin streams |
| CN101891576A (en) * | 2010-07-12 | 2010-11-24 | 兆威兴业有限公司 | Process and device for preparing low-carbon olefin by methanol and/or dimethyl ether |
| CN102464523A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for producing light olefins |
| CN102746889B (en) * | 2011-04-20 | 2015-05-13 | 中国石油化工股份有限公司 | Method for producing ethene and propylene by catalytic cracking |
| CN102746889A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for producing ethene and propylene by catalytic cracking |
| CN102746888A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for producing ethene and propylene by fluidizing and catalytic cracking |
| CN102746888B (en) * | 2011-04-20 | 2014-12-10 | 中国石油化工股份有限公司 | Method for producing ethene and propylene by fluidizing and catalytic cracking |
| CN102344329B (en) * | 2011-08-03 | 2014-10-22 | 上海碧科清洁能源技术有限公司 | Method for preparing olefin by alcohol and/or ether |
| CN102344329A (en) * | 2011-08-03 | 2012-02-08 | 上海碧科清洁能源技术有限公司 | Method for preparing olefin by alcohol and/or ether |
| CN103772109A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing propylene co-production ethylbenzene by methanol conversion |
| CN103772109B (en) * | 2012-10-25 | 2016-09-07 | 中国石油化工股份有限公司 | The method of preparing propylene by methanol transformation coproduction ethylbenzene |
| CN105441113A (en) * | 2014-08-20 | 2016-03-30 | 中国石油化工股份有限公司 | Catalytic cracking method of naphtha feedstock |
| CN105441113B (en) * | 2014-08-20 | 2017-05-24 | 中国石油化工股份有限公司 | Catalytic cracking method of naphtha feedstock |
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| CN101165022B (en) | 2011-07-20 |
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