CN101417911A - Method for preparing light olefins from methanol using hydrocarbons as part material - Google Patents
Method for preparing light olefins from methanol using hydrocarbons as part material Download PDFInfo
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- CN101417911A CN101417911A CNA2007101764065A CN200710176406A CN101417911A CN 101417911 A CN101417911 A CN 101417911A CN A2007101764065 A CNA2007101764065 A CN A2007101764065A CN 200710176406 A CN200710176406 A CN 200710176406A CN 101417911 A CN101417911 A CN 101417911A
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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 invention relates to a preparation method of ethylene and propylene, in particular to a method for preparing light olefins in which ethylene and propylene are the primary products and methanol, carbon 4 and the hydrocarbons above carbon 4 are taken as raw material. In the process cracking ethylene and/or dimethyl ether to prepare the light olefins such as ethylene and propylene, part of from carbon 4 to carbon 18 alkane and olefin are added as feedings, and the scission reaction of hydrocarbon which absorbs heat is used for reducing the lot quantity of heat of reaction released from the cracking process of ethylene and/or dimethyl ether, thereby inhibiting the heat effect of the MTO reaction, raising the stability of the reaction system, allowing the operation easier, prolonging the service of catalytic agent, saving energy and reducing cost.
Description
Technical field
The present invention relates to the preparation method of low-carbon alkene, being specifically related to methyl alcohol and carbon four and above hydro carbons is that feedstock production is the method for the low-carbon alkene of primary product with ethene, propylene.
Background technology
Low-carbon alkene such as ethene, propylene is most important basic Organic Chemicals, and is along with the develop rapidly of chemical industry, more and more big to the demand of low-carbon alkene.In present industrial production, the production of the low-carbon alkene petroleum resources that place one's entire reliance upon basically, and the minimizing day by day of petroleum resources in the world wide makes with coal or Sweet natural gas to be that raw material is produced low-carbon alkene technology via methyl alcohol or dme and more and more received concern both domestic and external.
U.S. Mobil oil company passed through to improve processing condition in 1984, preparing gasoline by methanol technology (MTG) was used for the production of low-carbon alkene.Nineteen ninety-five, UOP (UOP) and Norway Norsk Hydro company are in the 4th the international conversion of natural gas meeting in South Africa, announced the MTO technology of its joint development first, be that natural gas via is further produced the technology of low-carbon alkenes such as ethene, propylene by methyl alcohol, and claim this technology can realize producing per year 500,000 tons of ethene.
Process of preparing low carbon olefinic hydrocarbon with methanol is a strong exothermal reaction, because of the reaction very exothermic causes the catalyst carbon deposit deactivation rate very fast.Therefore, the MTO technology is generally all used fluidized-bed reactor, to realize the cyclic regeneration of catalyzer.And because the problem of reaction heat adds a large amount of water as thinner or thermal barrier in the raw material of being everlasting when actually operating.A large amount of water gasifies in technological process, condensation, has greatly increased the energy consumption in the technological process, and has reduced the space-time yield of target product.
Many patents aspect converting methanol to prepare low carbon olefin, for example US5714662A1, US5191141A1, US5744680A1, US6534692, US6166282A etc., catalyst system therefor is all based on the SAPO-34 molecular sieve, adopt fluidized-bed reactor, with water content is that 20% methyl alcohol is raw material, and ethylene selectivity is higher in the low-carbon alkene.The operating temperature range of reactive system is 350 ℃～525 ℃, and by the regulation and control of processing condition, ethylene/propene can be 1.5～0.64 variations in the low-carbon alkene.When stable operation, the weight percentage of ethene, propylene, carbon tetraene is respectively in the hydrocarbon product: 40%, 38%, 11%.
It is the method for raw material production low-carbon alkene with methyl alcohol that European patent EP 0448000 has been introduced a kind of, this method adopts fixed-bed reactor, the weight ratio of water and methyl alcohol is 0.1～1.5 in the raw material, catalyst system therefor is the Si-Al molecular sieve of Zn, Cd modification, for reducing the reaction heat of reactive system, raw material is earlier by pre-reactor dehydration, and what enter main reactor is the mixture of methyl alcohol, dme and water.The reactive system temperature range is 280 ℃～570 ℃, and system pressure 10kPa～90kPa generates ethene, propylene in the low-carbon alkene, and the weight percentage of carbon tetraene in the generation hydrocarbon product is no less than 5%, 35%, 30% respectively.
Chinese patent CN1166478, CN1356299 are catalyzer with the SAPO-34 molecular sieve, with methyl alcohol or dme is the feedstock production low-carbon alkene, owing to emit a large amount of reaction heat in the reaction process, causes the catalyst carbon deposit inactivation serious, therefore all using fluidized-bed reactor, the weight space velocity of charging is 1h
-1～10h
-1, the internal circulating load of catalyzer is greater than 1kg/h, and use thinner in various degree is to reduce the reaction heat in the reaction process.
Produce in the catalytic cracking process of ethene and refinery at cracking petroleum hydrocarbon vapor, the above hydro carbons of C4 and C4 (based on C4 alkene) is main by product, and how effectively utilizing this part resource is the important topic that ethylene plant and refinery face jointly.If with the part charging of this part C4 and above hydro carbons as methanol-to-olefins, then can utilize this part hydrocarbon cracking to need the characteristics of a large amount of heats, effectively reduce the heat effect of reacting in the methanol-to-olefins process, help improving the stability of reactive system, make to be reflected at easier operation on the engineering; Simultaneously and since C4 and above hydro carbons at high temperature the cracked primary product also be based on low-carbon alkene, therefore, in preparing low carbon olefin hydrocarbon by methanol, add the yield that portion C 4 and above hydro carbons also help to improve target product.
Summary of the invention
The technical problem to be solved in the present invention is:
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of is that the methyl alcohol of part material prepares the low-carbon alkene method with the hydro carbons, produce in the process of low-carbon alkenes such as ethene, propylene at methyl alcohol and/or dme cracking, add part carbon four and carbon four above hydro carbons as common charging, utilize the hydrocarbon cracking that absorbs heat to react and reduce a large amount of reaction heat that discharged in methyl alcohol and/or the dme cracking process.
Technical scheme of the present invention is:
A kind of is that the methyl alcohol of part material prepares the low-carbon alkene method with the hydro carbons, comprising:
Use two kinds of raw materials, first kind of raw material is: at least a in methyl alcohol and the dme; Can be single methyl alcohol, also can be single dme, can also be the mixture of methyl alcohol and dme.
Second kind of raw material is at least a in following: carbon four to carbon octadecane hydrocarbon, carbon four to carbon octadecylene hydrocarbon; Can be a kind of above-mentioned alkane or a kind of above-mentioned alkene, also can be the mixture of above-mentioned alkane or the mixture of above-mentioned alkene, can also be the mixture of above-mentioned alkane and alkene, and alkene can be monoolefine, also can be polyene hydrocarbon.Contain olefin fraction more than five as various C-4-fractions, C5 fraction, the carbon of producing ethene, propylene unit or plant catalytic cracking unit from steam cracking, with and composition thereof.
The ratio of two kinds of raw materials is, described first kind of raw material be in moles of methanol, with the ratio of second kind of feed molar number is:
First kind of raw material: second kind of raw material=1:0.05～10
Wherein, in first kind of raw material per 1 mole of dme in 2 mole, of methanol;
Promptly the mole number of first kind of raw material is amounting to into the mole number of methyl alcohol, and the mole number of second kind of raw material is in the actual mole number of carbon four to carbon octadecane hydrocarbon, alkene.
Prepare at methyl alcohol under the effect of light olefins catalyst, above-mentioned two kinds of raw materials are reacted in reactor, generate low-carbon alkene.The low-carbon alkene that generates, main ethene, propylene also comprise some by products usually.
Inventive point of the present invention is carbon four and above hydro carbons are produced the part charging that low-carbon alkene reacts (MTO) as methyl alcohol and/or dme, because carbon four and above hydro carbons are under hot conditions, the cracked primary product also is low-carbon alkenes such as ethene, propylene on the MTO catalyzer, therefore, can be when not influencing or improving yield of light olefins, play the reduction reaction heat effect, improve the effect of reactive system stability, make to be reflected at easier operation on the engineering.
In the present invention,, the heat effect of reaction is effectively extenuated, help the catalyzer prolongation in work-ing life owing to add carbon four and above hydro carbons.Because carbon four and above hydro carbons are during as common charging, the heat effect of entire reaction significantly reduces, make the reaction bed temperature in the reaction process be tending towards even, in the time of independent methyl alcohol and/or dme can occurring and be reaction raw materials, the too high phenomenon of reaction occurrence positions temperature in the catalyzer micropore, so the coking deactivation speed of catalyzer slows down, catalyst life is longer than originally.
In the present invention, can use any catalyzer that can realize methyl alcohol and/or low-carbon alkenes such as dimethyl ether production ethene, propylene, or multiplely have a described function mixture of catalysts.Hybrid mode comprises that two or more catalyzer combines or the simple physics fusion by tackiness agent or auxiliary agent.The MTO catalyzer is a known technology, and used catalyzer but is not got rid of the use that other has function catalyzer of the present invention for being the catalyzer of main active ingredient with the SAPO-34 molecular sieve in the embodiment of the invention.
In the described reactor, reaction pressure is a normal pressure, and temperature of reaction is 300 ℃～600 ℃, and mass space velocity is 0.1h
-1～10h
-1
With before described catalyzer contacts, described second kind of raw material mixes with described first kind of raw material at described first kind of raw material.The charging form that is reactor can be selected different modes, as:
Described first kind of raw material adds described reactor with after described second kind of raw material directly mixes;
Also can described second kind of raw material be injected described first kind of material feeding at described reactor inlet place;
Described first kind of raw material is in the charging of reactor inlet place, with described second kind of raw material injecting reactor before the reactor catalyst bed.
Add diluent gas in the described reaction system, described diluent gas is to be selected from least a in following: nitrogen, helium, argon gas, hydrogen, methane, ethane, propane, butane, carbon monoxide, carbonic acid gas, water vapour.
In molar ratio, diluent gas: raw material=0～1:1
Above-mentioned raw materials calculates with the mole number sum of first kind of raw material and second kind of raw material.
Be that raw material can be with charging behind the inert gas dilution, also can be without diluent gas, diluent gas is not participated in reaction.When industrial application, described diluent gas can recycle.The separation of diluent gas and Recycle design can adopt the known technology of industrial routine.
The present invention is raw materials used for having added methyl alcohol and/or the dme parallel feeding of part carbon four to carbon 18 hydro carbons, owing to add carbon four to carbon 18 hydro carbons, the heat that methyl alcohol and/or dme cracking are discharged is compared during with independent charging and is effectively extenuated, and therefore can or reduce the consumption of the water of thermal barrier effect in reaction process.
Usually, described reactor is: at least a in fluidized-bed reactor, fixed-bed reactor and the moving-burden bed reactor.Promptly when using a reactor, can be fixed-bed reactor, fluidized-bed reactor or moving-burden bed reactor also; When using many reactors, can use identical reactor, also can use different reactors.
Because the present invention has prolonged the work-ing life of catalyzer, therefore reaction of the present invention can realize on the fluidized-bed reactor that MTO technology is used always, also can on fixed-bed reactor, carry out, also not get rid of simultaneously and use moving-bed etc. other can realize the reactor of process of the present invention.
When concrete operations, first kind of raw material can obtain with the methyl alcohol pre-reaction: earlier methyl alcohol is sent into pre-reactor, wherein the part methanol conversion becomes dme, and the product that will contain methyl alcohol and dme again adds described reactor as described first kind of raw material with described second kind of raw material.Also be that dme in the raw material is directly by methanol conversion.
Usually, to prepare light olefins catalyst be at least a in following to described methyl alcohol: have tart natural molecule sieve, have the tart synthesis of molecular sieve.Promptly can have a tart natural molecule sieve, or have a tart synthesis of molecular sieve with a kind of with a kind of, also can be with the mixture of above-mentioned molecular sieve.
Further preferred, described methyl alcohol prepares light olefins catalyst and is selected from least a in following: X type molecular sieve, Y zeolite, ZSM type molecular sieve, SAPO type molecular sieve, the molecular sieve modified product of X type, Y zeolite modified product, the molecular sieve modified product of ZSM type, the molecular sieve modified product of SAPO type.Promptly can be a kind of in X type molecular sieve or its modified product, Y zeolite or its modified product, ZSM type molecular sieve or its modified product, SAPO type molecular sieve or its modified product, also can be the mixture of multiple above-mentioned zeolite product.
Especially, to prepare light olefins catalyst be SAPO-34 type molecular sieve for described methyl alcohol.
It can be that independent a kind of catalyzer is by the tackiness agent moulding that described methyl alcohol prepares light olefins catalyst.Used tackiness agent is known routine techniques, and shaping of catalyst also is a known technology.
Described methyl alcohol prepares light olefins catalyst: multiple catalyzer with different catalytic performances combines by tackiness agent becomes mixed catalyst or multiple catalyzer with different catalytic performances becomes mixed catalyst by the physics fusion.
According to general catalyzer common practise, described methyl alcohol prepares light olefins catalyst can add auxiliary agent in preparation process, and described auxiliary agent comprises at least a in various known binding agents, pore-forming material, dispersion agent, the lubricant.
At least a during described second kind of raw material is preferably following: carbon four to carbon ten alkane, carbon four to carbon ten alkene; At least a in further preferably following: carbon four to carbon six alkane, carbon four to C 6 olefin.
Described first kind of raw material be in moles of methanol, with the preferred proportion of second kind of feed molar number is:
First kind of raw material: second kind of raw material=1:0.1～2.
Further preferred proportion is first kind of raw material: second kind of raw material=1:0.1～0.5.
The invention has the beneficial effects as follows:
The present invention is by preparing to carbon octadecane hydrocarbon, alkene carbon four the common charging of low-carbon alkene as methyl alcohol and/or dme cracking, the hydrocarbon cracking reaction that a large amount of reaction heat of being discharged in methyl alcohol and/or the dme cracking process are absorbed heat absorbs, thereby the heat effect that has suppressed the MTO reaction, thereby reactive system stability, processing ease have been improved; Reaction bed temperature is tending towards evenly, and the coking deactivation speed of catalyzer will be slowed down, and catalyst life is prolonged; Reduce the consumption of thinner, conserve energy; Cost is descended.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Embodiment 1 Preparation of catalysts
The 30.15g aluminum isopropylate is mixed with 54.17g water, stir and to add 17.11g phosphoric acid down, continue to stir, add the 9.32g tetraethyl orthosilicate, add 36.19g content at last and be 30% tetraethyl ammonium hydroxide template, continue to stir and make into the homogeneous gel shape.Above-mentioned gelating soln is transferred to stainless steel crystallization device, airtight, left standstill crystallization 120 hours in 200 ℃ of constant temperature.After crystallization was finished, product was cooled off rapidly, and inclining mother liquor, the centrifugation throw out, and with the pure water washing for several times, be 8～9 until the pH of solution value, then the gained crystallisate was descended dry 3 hours at 115 ℃, 5 hours removed template methods of 550 ℃ of following roastings obtain the SAPO-34 molecular sieve.With the moulding of gained SAPO-34 molecular sieve direct compression, the particle of selecting particle diameter 0.84mm～2mm (10～20 order) is as the experiment catalyzer.
Embodiment 2
On the fixed-bed reactor of continuous flow, the catalyzer 3ml that filling embodiment 1 is prepared.Under normal pressure, blowing air, flow velocity 50ml/min in 500 ℃ of following calcined catalysts 2 hours, switches to N then
2Purged 0.5 hour.With N
2Be carrier gas, flow velocity 50ml/min, methyl alcohol and C 4 olefin are raw material, and mol ratio is methyl alcohol: C 4 olefin=1:0.167, mass space velocity are 3h
-1, temperature of reaction is 380 ℃.Table 1 is that the raw material of C 4 olefin is formed.Table 2 is the methanol to olefins reaction result of C 4 olefin during as the part charging.
Comparative Examples 1
Adopt catalyzer and the experiment condition identical with embodiment 2, raw material is a methyl alcohol, and temperature of reaction is 380 ℃, and experimental result sees Table 2.
Table 1 C 4 olefin weight percent is formed
| Form | 1-butylene | Suitable-2-butylene | Instead-2-butylene | Iso-butylene |
| Content, % | 22.3 | 43.1 | 19.8 | 14.8 |
Table 2 C 4 olefin is as common charging methanol to olefins reaction result
| Embodiment 2 | Comparative Examples 1 | |
| Charging | CH 3OH+C4 | CH 3OH |
| The outer temperature of reaction tubes, ℃ | 380 | 380 |
| The reaction bed temperature, ℃ | 384 | 388 |
| The one way activity cycle, h | 8 | 4 |
| Product is formed | wt％ | wt％ |
| Methyl alcohol+dme | 0 | 0 |
| C1+C2+C3 | 5.34 | 5.64 |
| C2＝ | 28.99 | 31.22 |
| C3＝ | 38.37 | 40.09 |
| C4 | 18.18 | 16.19 |
| C5+ | 6.90 | 4.35 |
| Aromatic hydrocarbons | 1.13 | 1.09 |
| COx | 1.09 | 1.41 |
Embodiment 3
Adopt catalyzer, raw material, the experiment condition identical with embodiment 2, the experimental result when temperature of reaction is respectively 350 ℃, 480 ℃ sees Table 3.
Table 3 C 4 olefin is as common charging methanol to olefins reaction result
| Temperature, ℃ | 350 | 480 |
| Product is formed | wt％ | wt％ |
| Methyl alcohol+dme | 0 | 0 |
| C1+C2+C3 | 3.21 | 8.62 |
| C2＝ | 21.58 | 24.44 |
| C3＝ | 32.16 | 35.21 |
| C4 | 24.82 | 16.17 |
| The C5+ hydrocarbon | 16.93 | 5.36 |
| Aromatic hydrocarbons | 0.24 | 1.56 |
| COx | 1.06 | 8.64 |
Embodiment 4
Adopt catalyzer and the experiment condition identical with embodiment 2, raw materials used be methyl alcohol and the mixture of octene just, and mol ratio is methyl alcohol: octene=1:0.1 just, experimental result sees Table 4.
Embodiment 5
Adopt catalyzer and the experiment condition identical with embodiment 2, raw materials used be methyl alcohol and the mixture of laurylene just, and mol ratio is methyl alcohol: laurylene=1:0.067 just, experimental result sees Table 4.
Table 4 C8 alkene and C12 alkene are as common charging methanol to olefins reaction result
| Embodiment 4 | Implement 5 | |
| Charging | CH 3OH+C8＝ | CH 3OH+C12＝ |
| Product is formed | wt％ | wt％ |
| Methyl alcohol+dme | 0 | 0 |
| C1+C2+C3，％ | 6.22 | 6.54 |
| C2＝ | 20.56 | 18.87 |
| C3＝ | 33.46 | 31.72 |
| C4 | 22.63 | 21.66 |
| The C5+ hydrocarbon | 13.64 | 18.06 |
| Aromatic hydrocarbons | 2.13 | 2.01 |
| COx | 1.36 | 1.14 |
Embodiment 6
Adopt catalyzer and the raw material identical, with carrier gas N with embodiment 2
2Replace with water, the input speed of water is 4g/ml, and other reaction conditions is constant, and experimental result sees Table 5.
Table 5 C 4 olefin is as common charging methanol to olefins reaction result
| Product is formed | wt％ |
| Methyl alcohol+dme | 0 |
| C1+C2+C3 | 4.96 |
| C2＝ | 29.64 |
| C3＝ | 39.64 |
| C4 | 17.58 |
| C5+ | 6.32 |
| Aromatic hydrocarbons | 1.02 |
| COx | 0.84 |
Claims (10)
1 one kinds is that the methyl alcohol of part material prepares the low-carbon alkene method with the hydro carbons, it is characterized in that:
Use two kinds of raw materials, first kind of raw material is: at least a in methyl alcohol and the dme;
Second kind of raw material is at least a in following: carbon four to carbon octadecane hydrocarbon, carbon four to carbon octadecylene hydrocarbon;
Described first kind of raw material be in moles of methanol, with the ratio of second kind of feed molar number is:
First kind of raw material: second kind of raw material=1:0.05～10
Wherein, in first kind of raw material per 1 mole of dme in 2 mole, of methanol;
Prepare at methyl alcohol under the effect of light olefins catalyst, above-mentioned two kinds of raw materials are reacted in reactor, generate low-carbon alkene.
2 according to claim 1 be that the methyl alcohol of part material prepares the low-carbon alkene method with the hydro carbons, it is characterized in that:
In the described reactor, reaction pressure is a normal pressure, and temperature of reaction is 300 ℃～600 ℃, and mass space velocity is 0.1h
-1～10h
-1
With before described catalyzer contacts, described second kind of raw material mixes with described first kind of raw material at described first kind of raw material.
3 according to claim 1 be that the methyl alcohol of part material prepares the low-carbon alkene method with the hydro carbons, it is characterized in that:
Add diluent gas in the described reaction system, described diluent gas is to be selected from least a in following: nitrogen, helium, argon gas, hydrogen, methane, ethane, propane, butane, carbon monoxide, carbonic acid gas, water vapour;
In molar ratio, diluent gas: raw material=0～1:1
Above-mentioned raw materials calculates with the mole number sum of first kind of raw material and second kind of raw material.
4 according to claim 1 be that the methyl alcohol of part material prepares the low-carbon alkene method with the hydro carbons, it is characterized in that:
Described reactor is: at least a in fluidized-bed reactor, fixed-bed reactor and the moving-burden bed reactor.
5 according to claim 1 be that the methyl alcohol of part material prepares the low-carbon alkene method with the hydro carbons, it is characterized in that:
Earlier methyl alcohol is sent into pre-reactor, wherein the part methanol conversion becomes dme, and the product that will contain methyl alcohol and dme again adds described reactor as described first kind of raw material with described second kind of raw material.
6 according to claim 1 be that the methyl alcohol of part material prepares the low-carbon alkene method with the hydro carbons, it is characterized in that:
It is at least a in following that described methyl alcohol prepares light olefins catalyst: have tart natural molecule sieve, have the tart synthesis of molecular sieve.
7 according to claim 6 be that the methyl alcohol of part material prepares the low-carbon alkene method with the hydro carbons, it is characterized in that:
Described methyl alcohol prepares light olefins catalyst and is selected from least a in following: X type molecular sieve, Y zeolite, ZSM type molecular sieve, SAPO type molecular sieve, the molecular sieve modified product of X type, Y zeolite modified product, the molecular sieve modified product of ZSM type, the molecular sieve modified product of SAPO type.Preferably: SAPO-34 type molecular sieve.
8 according to claim 6 be that the methyl alcohol of part material prepares the low-carbon alkene method with the hydro carbons, it is characterized in that:
Described methyl alcohol prepares light olefins catalyst and add auxiliary agent in preparation process, and described auxiliary agent comprises at least a in various known binding agents, pore-forming material, dispersion agent, the lubricant.
9 described according to one of claim 1 to 9 be that the methyl alcohol of part material prepares the low-carbon alkene method with the hydro carbons, it is characterized in that:
Described second kind of raw material is at least a in following: carbon four to carbon ten alkane, carbon four to carbon ten alkene.Preferably: carbon four to carbon six alkane, carbon four to C 6 olefin.
10 according to claim 1 be that the methyl alcohol of part material prepares the low-carbon alkene method with the hydro carbons, it is characterized in that:
First kind of raw material: second kind of raw material=1:0.1～2.
Preferably, first kind of raw material: second kind of raw material=1:0.1～0.5.
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| CN103130603A (en) * | 2011-11-30 | 2013-06-05 | 中国科学院大连化学物理研究所 | Method for preparing low-carbon alkene by promoting conversion of pentane |
| CN103130605A (en) * | 2011-11-30 | 2013-06-05 | 中国科学院大连化学物理研究所 | Method for preparing low-carbon olefin by promoting conversion of butane |
| CN104399522A (en) * | 2014-10-21 | 2015-03-11 | 贵州大学 | Catalyst for production of low carbon olefin from methanol through iodination method, and preparation method thereof |
| CN105439788A (en) * | 2015-12-10 | 2016-03-30 | 七台河宝泰隆煤化工股份有限公司 | Method for improving selectivity of olefins in methanol-to-olefin reaction process |
| CN106866329A (en) * | 2017-01-22 | 2017-06-20 | 江苏天诺新材料科技股份有限公司 | The preparation method of low-carbon alkene |
| CN114804993A (en) * | 2021-01-27 | 2022-07-29 | 国家能源投资集团有限责任公司 | Method for preparing olefin from methanol and method for preparing olefin from dimethyl ether |
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| CN102372539A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin |
| CN101928598A (en) * | 2010-09-28 | 2010-12-29 | 上海应用技术学院 | Method and system for producing gasoline and propylene by integrating heavy oil catalytic cracking with oxygen-containing compound conversion |
| CN102675020A (en) * | 2011-03-17 | 2012-09-19 | 江苏煤化工程研究设计院有限公司 | Process for preparing low-carbon olefin, aromatic hydrocarbon and functional alkane from multi-element carbon-containing raw material by using fixed bed reactor |
| CN102875297B (en) * | 2011-07-12 | 2015-09-09 | 中国石油化工股份有限公司 | The method of low-carbon alkene is prepared with methyl alcohol and petroleum naphtha |
| CN102875297A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin from methanol and naphtha |
| CN102875299A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Method for producing low-carbon olefins by using methanol and naphtha |
| CN102389833A (en) * | 2011-09-23 | 2012-03-28 | 辽阳华程化工有限公司 | Catalyst for preparing low-carbon olefin from light dydrocarbon and methanol mixtures |
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