CN102050691A - Method for preparing low carbon olefin by use of coupling between methanol and C4 hydrocarbon - Google Patents
Method for preparing low carbon olefin by use of coupling between methanol and C4 hydrocarbon Download PDFInfo
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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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
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- 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
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- Y02P30/40—Ethylene production
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Abstract
The invention relates to a method for preparing low carbon olefin by use of coupling between methanol and C4 hydrocarbon. The method comprises allowing methanol and C4 hydrocarbon to react as coupling raw materials in a reactor with phosphorus-modified ZSM molecular sieve as a catalyst to generate low carbon olefin. The method selects efficient molecular sieve catalyst to prepare low carbon olefin through catalytic cracking and coupling process; and can realize effective catalytic cracking of coupling raw materials at low temperature, so as to reduce energy consumption of low carbon olefin production. Compared with the report in the prior art, the inventive method greatly increases the yield of low carbon olefin, particularly propylene, and sufficiently utilizes the easily-accessible C4 hydrocarbon raw material. The inventive method can be used for industrial production of low carbon olefin through catalytic cracking.
Description
Technical field
The present invention relates to the technology of preparing of low-carbon alkene, relating in particular to a kind of employing phosphorus modified ZSM-5 molecular sieve is catalyzer, utilizes methyl alcohol coupling C4 hydrocarbon to prepare the method for low-carbon alkene, belongs to the petrochemical technology field.
Background technology
Low-carbon alkene such as ethene, propylene is a basic raw material important in the petrochemical industry.Along with the development of chemical industry and manufacturing technology, countries in the world present the trend that significantly rises year by year to the demand of low-carbon alkene, and are very urgent to the demand of propylene especially in recent years, and the production of development ethene, propylene receives publicity all the time.
In the technology of preparing of low-carbon alkene such as ethene, propylene, be the technology of widespread use by petroleum path (petroleum hydrocarbon catalyzed conversion).
In recent years, a lot of prior aries have been reported the method for petroleum hydrocarbon preparing low carbon alkene by catalytic conversion.For example, a kind of modified ZSM-5/ZSM-11 cocrystallization molecular sieve catalyst of using has been proposed with C among the Chinese patent CN1233603C (patent No. ZL03158799.2)
4-C
6Olefin cracking is the method for propylene/ethylene.The method of modifying of catalyzer is the performance with basic metal, alkaline-earth metal or rare earth metal allotment molecular sieve, or at 500-800 ℃ of steam-treated certain hour, deviates from non-framework aluminum.According to this patented technology disclosed method, at temperature 500-650 ℃, weight space velocity 1-50hr
-1, under the pressure 0.1-8atm reaction conditions, the selectivity of low-carbon alkene is more than 60%, yield is 40-55%, wherein propene yield is about 37%.
Be to improve purpose product selectivity of light olefin, Chinese patent CN1235845C (patent No. ZL200310108177.5) discloses phosphorus modified ZSM-5 type zeolite has been used for the method that catalyzed carbon C4 and above olefin cracking thereof prepare low-carbon alkene.In this method, at 530 ℃, weight space velocity 10 hours
-1Condition under, the selectivity of purpose product propylene reaches 54.7%, propene yield reaches 35.6%.
Chinese patent CN1274645C has proposed the method for a kind of C4 and above olefin catalytic cracking to produce propylene.This technology is by adopting little crystal grain, the high silica alumina ratio ZSM type molecular sieve catalyzer as scission reaction, the weakness of short, less stable of the catalyst regeneration cycle in the conventional art of preferably resolving.At 500 ℃, under 10 hours-1 the condition of weight space velocity, the initial stage yield of purpose product propylene has reached 37.9%.
The petroleum hydrocarbon catalytic pyrolysis reaction is a thermo-negative reaction process, be beneficial under the reaction conditions that improves ethene and propene yield, energy consumption of reaction makes production cost high, because limited supply of petroleum resources and price is high, causes the more continuous increase of production cost of low-carbon alkene.Therefore, countries in the world are devoted to study the technology of non-oil resource producing light olefins one after another in recent years, wherein, of greatest concern by preparing low carbon olefinic hydrocarbon with methanol (MTO) technology, explore by a large amount of research, the MTO technology is considered to be hopeful most to substitute the effective technique that petroleum path prepares low-carbon alkene.Result of study shows, with regard to the MTO catalyzer, current effective catalyst system is mainly aperture SAPO-34 molecular sieve, the SAPO-34 molecular sieve has elliposoidal cage and the three-dimensional open-framework that octatomic ring constitutes, orifice diameter is 0.43nm, its pore passage structure is sterically hindered to diffuseing to form of long chain hydrocarbon, only allows the hydrocarbon molecules of C1～C3 to free in and out the intracrystalline duct; In addition, the further reaction of ethene, propylene has been limited in the acid site of the medium tenacity that the SAPO-34 molecular sieve is had, and these a series of characteristics make this molecular sieve have good MTO catalytic performance.The relevant public technology report that can retrieve at present, also mostly be with the technical study of SAPO-34 molecular sieve as catalyzer, for example, Chinese patent application 200810043239.1,200810043238.7,200810043298.9, in 200810043972.3 grades, the related process that utilizes SAPO-34 molecular sieve catalytic methanol production low-carbon (LC)/light olefin is disclosed respectively.
Consider from the energy consumption that reduces the petroleum hydrocarbon catalytic pyrolysis, Chinese patent CN1206319C has then proposed the coupling of petroleum hydrocarbon and organic oxygen-containing compound is produced the technological line of low-carbon alkene, two reaction process (the petroleum hydrocarbon cracking process of heat absorption and the organic oxygen-containing compound of heat release transform the propylene process of producing) coupling with purpose product unanimity, the organic oxygen-containing compound liberated heat is utilized by converted in-situ, the endothermic effect of petroleum hydrocarbon cracking is weakened (becoming weak heat absorption) from strong heat absorption, and can improve the yield of low-carbon alkene, under the reaction conditions of report, ethene, the propylene total recovery can reach 40-50%.When the advantage of this patented technology is to reduce the scission reaction energy consumption, further improved the utilization ratio of petroleum hydrocarbon, and can regulate and control the coke content of catalyzer and the heat balance of reaction system by the ratio that changes two kinds of coupling raw materials.The catalyzer of this patent processing requirement is a solid acid catalyst, and temperature of reaction requires can see from embodiment at 500-720 ℃ that the petroleum hydrocarbon that this technology is suitable for is mainly heavy hydrocarbon, only reaches 23% and propene yield is the highest in the reaction product.
Also disclosing a kind of in the Chinese patent application 200710176406.5 is the method that the methyl alcohol of part material prepares low-carbon alkene with the hydro carbons, when methyl alcohol and/or dme are produced low-carbon alkenes such as ethene, propylene, add of alkane, the alkene common charging of part carbon four to carbon 18, utilize the hydrocarbon cracking of heat absorption to react the heat effect that suppresses the MTO reaction, thereby improve the stability of reactive system, the preferred catalyzer of this method remains the SAPO-34 molecular sieve.The method of putting down in writing in the CN1206319C, propene yield increases in the reaction product of this patent application scheme, but this technology is based on the improvement of MTO reaction, promptly, although having put down in writing the raw materials components mole ratio of first kind of raw material (methyl alcohol and/or dme) and second kind of raw material (hydro carbons) in the specification sheets can be 1: 0.5-10, but its preferred charge ratio is still based on methyl alcohol (in the raw material of embodiment, the ratio of methyl alcohol and hydro carbons was up to 10: 1), this also is the reason that this technology can recommend to adopt the SAPO-34 catalyzer.
China's oil-refining chemical process can a large amount of C of output
4Hydrocarbon makes full use of the industry of these C4 hydrocarbon source development propylene, has in essence different with above-mentioned petroleum path.If can utilize relatively inexpensive C
4Low-carbon alkene is produced in the hydrocarbon pyrolysis, and is obviously significant to improving the petrochemical enterprise benefit.Though the cracking of methyl alcohol coupling hydro carbons prepares low-carbon alkene a small amount of record has been arranged, also do not had special catalyzer to be in the news research and development methyl alcohol coupling C so far at methyl alcohol coupling C4 hydrocarbon
4The effective catalyst of the reaction process of hydrocarbon catalytic pyrolysis is to improving cheap C
4The chemical utilization rate of hydrocarbon and bulk product methyl alcohol has important practical significance, and is improving yield of light olefins, can reduce the energy consumption of reaction process when especially improving propene yield greatly, helps petrochemical industry, oil play is increased economic efficiency.
Summary of the invention
Technical problem underlying solved by the invention provides a kind of method of methyl alcohol coupling C4 olefin production low-carbon alkene, this method is passed through selection of catalysts, can less energy-consumption produce low-carbon alkene, and report than prior art, the yield of low-carbon alkene, especially propylene is obviously improved, and can make full use of the abundant C4 hydrocarbon feed in source.
For achieving the above object, the invention provides a kind of method of utilizing methyl alcohol coupling C4 hydrocarbon to prepare low-carbon alkene, this method comprises that utilization is catalyzer through the ZSM of phosphorus modification type molecular sieve, methyl alcohol and C4 hydrocarbon are reacted in reactor for the coupling raw material, generate the process of low-carbon alkene, wherein, in the ZSM type molecular sieve of described phosphorus modification, phosphoric is 2～4: 100 with the ratio of the quality of ZSM type molecular sieve.
The front is by the agency of, C4 hydrocarbon catalytic pyrolysis is consistent with the purpose product of methyl alcohol catalyzed reaction (MTO), it all is low-carbon alkene, MTO is an exothermal reaction process, C4 hydrocarbon catalytic cracking reaction is a thermo-negative reaction process, with two reaction process couplings, can utilize the inner MTO liberated heat of reaction to supply with the catalytic cracking reaction that needs heat absorption on the one hand, thereby reduce energy expenditure; On the other hand, preliminary study shows that the active intermediate that the MTO process produces has promoter action to the hydrocarbon catalytic cracking process.Therefore,, not only be beneficial to the heat balance of reaction process, be beneficial to also that further raising purpose product---low-carbon alkene is the yield of propylene especially the coupling of two reaction process.On comprising the prior art basis of front in being presented in, applicant's research thinks, explores more rationally, catalyzer efficiently, that is, the modified catalyst of determining to be fit to more this coupling reaction is extremely important link.
For the catalyzer of independent MTO and C4 hydrocarbon catalytic pyrolysis process, the reaction that catalyzer experienced in the catalyst system of methyl alcohol coupling C4 hydrocarbon reaction process is more complicated, requires in function and will take into account two kinds of raw materials in Catalyst Design to reach reaction characteristics separately.With regard to the MTO catalyzer, current generally acknowledged effective catalyst system is mainly aperture SAPO-34, and its principle has had explanation in background technology, but for coupling reaction, the small aperture of SAPO-34 is but not too suitable to the C4 in the coupling raw material; With regard to C4 hydrocarbon catalytic cracking catalyst, this type of catalyzer should have high reactivity and selectivity, should guarantee highlyer, prevent effectively that again the purpose product from deep reaction further taking place generate methane and product liquid, also should have high stability and intensity simultaneously than thermal cracking processes target product yield.The catalytic cracking catalyst type mainly contains molecular sieve, metal oxide and both compound system agent etc. at present, wherein, molecular sieve catalyst is ZSM series molecular sieve especially, because its unique pore structure, but the acidity of modulation and strong anti-carbon deposition ability and extremely pay attention to.So, take all factors into consideration coupling raw material and catalyzer characteristics, the ZSM catalyst system should be more suitable for than SAPO catalyst system, but consider the variation of reaction raw materials system, applicant's conclusion is, the modification modulation that should suit to ZSM type catalyzer just can make it further to be suitable for coupling reaction, thereby improves particularly propene yield of low-carbon alkene.Also be based on a large amount of research and explore, the present invention proposes phosphorus modified ZSM-5 type catalyzer is used for methyl alcohol coupling C
4The scheme of hydrocarbon preparing low-carbon olefin by catalytically cracking.
Method according to methyl alcohol coupling C4 alkene provided by the invention, the ZSM type molecular sieve of the phosphorus modification of being adopted preferably includes the HZSM-5 molecular sieve of phosphorus modification, the HZSM-23 molecular sieve of phosphorus modification, the HSM-11 molecular sieve of phosphorus modification etc., is more preferably the HZSM-5 molecular sieve of phosphorus modification; And the preferred 15-80 of the silica alumina ratio of molecular sieve (with the molar ratio computing of silica/alumina), more preferably silica alumina ratio is 20～50.
Method of the present invention has also comprised introduces phosphoric to the modification of ZSM type molecular sieve in molecular sieve: solution containing phosphate and ZSM type molecular sieve are mixed, then with mixture drying, roasting, obtain modified molecular sieve catalyst, wherein introduce the phosphoric amount and be preferably 2～4% of ZSM type molecular sieve raw material quality.
For the benefit of molecular sieve is uniformly dispersed in solution containing phosphate, can utilize sonic oscillation to carry out abundant dispersed with stirring, can be 10-30 minute to time of solution containing phosphate and ZSM type molecular sieve mixture sonic oscillation, and ultrasonic power is 100-300W.Certainly, also can adopt other feasible method to realize molecular sieve fully being uniformly dispersed in solution containing phosphate.
The method according to this invention, in molecular sieve modified, to after the mixture drying of molecular sieve and solution containing phosphate at 450-650 ℃ of roasting 3-5 hour, obtain modified molecular sieve catalyst.
The ZSM type molecular sieve of the phosphorus modification that the present invention adopts is by suitable means phosphoric to be introduced product behind the molecular sieve, and used solution containing phosphate is preferably the phosphorated ammonium salt aqueous solution in the modifying process, for example ammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate etc.Generally use its Hydrogen product for selected ZSM type molecular sieve, that is, the HZSM molecular sieve can utilize the HZSM molecular sieve to implement the phosphorus modification, also can be that the ZSM molecular sieve is implemented earlier to implement hydrogen treatment again after the phosphorus modification, concrete operations can be adopted the ordinary method of catalyst field.
According to the method for utilizing methyl alcohol coupling C4 hydrocarbon to prepare low-carbon alkene provided by the invention, react that the mol ratio of methyl alcohol and C4 hydrocarbon is 0.5-5 in the used coupling raw material: 1, guaranteeing under the prerequisite of propene yield, for raising C4 hydrocarbon utilization ratio, be preferably 1-3: 1.
In the coupling raw material of the present invention, used methyl alcohol can be industrial methanol, and used C4 hydrocarbon then from the output C4 of refinery, can be one or more mixing raw materials in normal butane, Trimethylmethane, 1-butylene, 2-butylene, suitable-butylene and the anti--butylene.
Utilize methyl alcohol coupling C4 hydrocarbon to prepare the method for low-carbon alkene according to the present invention, preferably, the temperature of reaction of methyl alcohol coupling C4 hydrocarbon is 350～650 ℃, the controlled 0.01～0.20Mpa that is made as of reaction pressure, the mol ratio of methyl alcohol and C4 hydrocarbon is 0.5-5 in the coupling raw material: 1, be preferably 1～3: 1.
In a specific embodiments of the present invention, the method that described methyl alcohol coupling C4 hydrocarbon prepares low-carbon alkene can may further comprise the steps:
1) with content of phosphorus-containing ammonium salt, for example (NH
4)
2HPO
4(concentration 0.043mol/L～2.58mol/L) joins (this molecular sieve can be the hydrogen type molecular sieve that is hydrogenated processing in advance) in the powdery ZSM type molecular sieve to the aqueous solution that is made into, fully stirred 0.5-1.5 hour, and to mixture sonic oscillation 10-30 minute, preferred ZSM-5 molecular sieve of used ZSM type molecular sieve or HZSM-5 molecular sieve, silica alumina ratio is chosen as 15-180, especially the ZSM type molecular sieve of silica alumina ratio 20-100 can be, the product of being purchased or synthetic voluntarily can be used according to ordinary method;
2) mix products that step 1 is obtained is at 100-120 ℃ of following forced air drying 10-14 hour, then in 450-650 ℃, preferred 500-650 ℃, more preferably 500-600 ℃ roasting 3-5 hour, naturally cooling obtains powdered phosphorus modified ZSM-5 type molecular sieve catalyst;
3) above-mentioned phosphorus modified ZSM-5 type molecular sieve catalyst is added reactor, as the coupling methyl alcohol of raw material and C4 hydrocarbon according to 0.5-5: 1 mol ratio feeds reactor, at 350-650 ℃ of catalytic pyrolysis, reaction feeds diluent gas simultaneously, nitrogen commonly used, diluting gas flow can be 20-100ml/min, temperature of reaction is preferably 450-600 ℃, and can suitably pressurize, pressure is 0.01-0.20Mpa.
In the above-mentioned specific embodiments, also can directly use the phosphorus modification of not hydrotreated ZSM molecular sieve elder generation, and then carry out ammonium switching implementation hydrogenation and become hydrogen type molecular sieve and be used for the catalysis coupling reaction.
Low-carbon alkene of the present invention is meant that carbonatoms is the alkene of 2-3, and promptly ethene and propylene are targets of the present invention and pursue high as far as possible propene yield.
To the be coupled evaluation of product and can add chromatogram on-line evaluation device for micro fixed-bed reactor of the present invention to the activity rating device of used molecular sieve catalyst.
The methyl alcohol coupling C4 hydrocarbon that utilizes of implementing the present invention's proposition prepares the method for low-carbon alkene, has the following advantages:
1, the present invention adopts phosphorus modified ZSM-5 type molecular sieve, compare with molecular sieve before the modification, the catalytic cracking to prepare lower carbon olefin yield is obviously improved, especially can obtain higher propene yield, under the reaction conditions of report, propene yield on the phosphorus modified catalyst reaches as high as 44.0%, than the raising on the unmodified catalyzer 26.5%.
2, the molecular sieve catalyst preparation method of the present invention's use is simple, easy to operate, cost is low, there be not harsh the requirement and restriction for coupling reaction system and reaction conditions and parameter, can under lower temperature, realize the effective catalytic pyrolysis of coupling raw material is beneficial to the suitability for industrialized production that catalytic pyrolysis prepares low-carbon alkene.
Embodiment
Below by specific embodiment implementation process of the present invention and beneficial effect are further elaborated,, but can not be interpreted as restriction the scope of the present invention so that the reader understands essence of the present invention better.
Embodiment 1
The silica alumina ratio that 20g is purchased is that 25 HZSM-5 molecular sieve places flask, at room temperature with glass stick while stirring with the (NH of 1.29mol/L
4)
2HPO
4Solution adds wherein, the phosphoric that control is added is 3% with the ratio of the quality of HZSM-5 molecular sieve, and continuously stirring 0.5 hour is then with 100W ultra-sonic oscillation instrument vibration 20min, again in air dry oven 120 ℃ dry 12 hours down, with being placed in the retort furnace 500 ℃ of roastings 5 hours.It is 40～80 purpose products that the powdered modified molecular sieve that makes grinds the screening granularity through compressing tablet, and as the catalytic cracking reaction catalyzer, the mass ratio of phosphoric of introducing in this catalyzer and raw material HZSM-5 molecular sieve is 3%.
The evaluating apparatus of catalyzer is the little inverse spectrum of a fixed bed on-line detecting system, reaction conditions is: the described phosphorus modified HZSM-5 of filling 0.3g molecular sieve catalyst in the fixed-bed reactor, temperature of reaction is respectively 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, reaction pressure is 0.1Mpa, N
2The carrier gas flow is 38ml/min.Reaction raw materials is industrial methanol, 1-butylene, and two material feeding mol ratios are: 1: 1, reaction result and primary product yield saw Table 1.(" BTX " represents benzene,toluene,xylene, " C in the table 1
2 =+ C
3 =" represent the total recovery of ethene and propylene, below all identical)
Table 1 scission reaction primary product yield distributes
Embodiment 2
Coupling primary industry methyl alcohol described in the embodiment 1, the raw materials components mole ratio of 1-butylene are changed into 3: 1, and other condition is all identical with embodiment 1, and reaction result that obtains and primary product yield see Table 2.
Table 2 scission reaction primary product yield distributes
Embodiment 3
Change the coupling raw material described in the embodiment 1 into industrial methanol, mixed C
4Hydrocarbon, the raw materials components mole ratio of industrial methanol and hydrocarbon mixture are 1: 1, and temperature of reaction is respectively 350 ℃, 375 ℃, 400 ℃, 425 ℃, 450 ℃, 500 ℃, 525 ℃, 550 ℃, 575 ℃, 600 ℃, and all the other conditions are all identical with embodiment 1, mixed C
4The hydrocarbon composition parameter sees Table 3, and reaction result that obtains and primary product yield see Table 4.
Table 3 mixed C
4The mole of hydrocarbon is formed
Table 4 scission reaction primary product yield distributes
Embodiment 4
Change the coupling raw material described in the embodiment 1 into industrial methanol, mixed C
4Hydrocarbon, the raw materials components mole ratio of industrial methanol and hydrocarbon mixture are 3: 1, and temperature of reaction is respectively 350 ℃, 375 ℃, 400 ℃, 425 ℃, 450 ℃, 500 ℃, 525 ℃, 550 ℃, 575 ℃, 600 ℃, and all the other conditions are all identical with embodiment 1, mixed C
4The hydrocarbon composition parameter sees Table 3, and reaction result that obtains and primary product yield see Table 5.
Table 5 scission reaction primary product yield distributes
Comparative Examples 1
Investigate the catalytic cracking reaction activity that the silica alumina ratio that is purchased is 25 HZSM-5 molecular sieve according to the reaction raw materials of embodiment 1 and appreciation condition, appreciation condition is identical with embodiment 1 with step, is that molecular sieve is without (NH
4)
2HPO
4Solution-treated.Reaction result and primary product yield see Table 6.
Table 6 scission reaction primary product yield distributes
Comparative Examples 2
The silica alumina ratio that is purchased according to the reaction raw materials of embodiment 2 and appreciation condition examination is the catalytic cracking reaction activity of 25 HZSM-5 molecular sieve, and appreciation condition is identical with embodiment 2 with step, is that molecular sieve is without (NH
4)
2HPO
4Solution-treated.Reaction result and primary product yield see Table 7.
Table 7 scission reaction primary product yield distributes
Comparative Examples 3
The silica alumina ratio that is purchased according to the examination of the reaction raw materials of embodiment 3 is the catalytic cracking reaction activity of 25 HZSM-5 molecular sieve, and appreciation condition and step are identical with embodiment 3, are that molecular sieve is without (NH
4)
2HPO
4Solution-treated.Reaction result and primary product yield see Table 8.
Table 8 scission reaction primary product yield distributes
Comparative Examples 4
Be the catalytic cracking reaction activity of 25 HZSM-5 molecular sieve according to the commercial silica alumina ratio of the reaction raw materials of embodiment 4 examination, appreciation condition and step are identical with embodiment 4, are that molecular sieve is without (NH
4)
2HPO
4Solution-treated.Reaction result and primary product yield see Table 9
Table 9 scission reaction primary product yield distributes
Claims (9)
1. method of utilizing methyl alcohol coupling C4 hydrocarbon to prepare low-carbon alkene, this method comprises that utilization is catalyzer through the ZSM of phosphorus modification type molecular sieve, methyl alcohol and C4 hydrocarbon are reacted in reactor for the coupling raw material, generate the process of low-carbon alkene, wherein, in the ZSM type molecular sieve of described phosphorus modification, phosphoric is 2～4: 100 with the ratio of the quality of ZSM type molecular sieve.
2. the method for utilizing methyl alcohol coupling C4 hydrocarbon to prepare low-carbon alkene according to claim 1, wherein, the ZSM type molecular sieve of described phosphorus modification comprises the HZSM-5 of phosphorus modification, the HZSM-23 of phosphorus modification or the HZSM-11 molecular sieve of phosphorus modification, and the silica alumina ratio 15-80 of molecular sieve.
3. the method for utilizing methyl alcohol coupling C4 hydrocarbon to prepare low-carbon alkene according to claim 1 and 2, wherein, this method also comprises the modification to ZSM type molecular sieve: solution containing phosphate and HZSM type molecular sieve are mixed, then with mixture drying, roasting, obtain the phosphorus modified molecular sieves catalyzer, wherein the phosphoric of Yin Ruing is 2～4: 100 with the ratio of the quality of HZSM-5 molecular sieve.
4. the method for utilizing methyl alcohol coupling C4 hydrocarbon to prepare low-carbon alkene according to claim 2 wherein, is implemented sonic oscillation to solution containing phosphate and ZSM type molecular sieve mixture and is mixed with further, and the time is 10-30 minute, and ultrasonic power is 100-300W.
5. the method for utilizing methyl alcohol coupling C4 hydrocarbon to prepare low-carbon alkene according to claim 3, wherein, to after the mixture drying of solution containing phosphate and HZSM type molecular sieve in 450-650 ℃ of roasting 3-5 hour, obtain described phosphorus modified molecular sieves catalyzer.
6. the method for utilizing methyl alcohol coupling C4 hydrocarbon to prepare low-carbon alkene according to claim 3, wherein, described solution containing phosphate is the phosphorated ammonium salt aqueous solution.
7. the method for utilizing methyl alcohol coupling C4 hydrocarbon to prepare low-carbon alkene according to claim 1, wherein, the mol ratio of methyl alcohol and C4 hydrocarbon is 0.5-5 in the coupling raw material: 1.
8. according to claim 1 or the 7 described methods of utilizing methyl alcohol coupling C4 hydrocarbon to prepare low-carbon alkene, wherein, in the coupling raw material, the C4 hydrocarbon is one or more mixing raw materials in normal butane, Trimethylmethane, 1-butylene, 2-butylene, suitable-butylene and the anti--butylene.
9. according to claim 1 or the 7 described methods of utilizing methyl alcohol coupling C4 hydrocarbon to prepare low-carbon alkene, wherein, the temperature of reaction of methyl alcohol coupling C4 hydrocarbon is 350～650 ℃, and reaction pressure is 0.01～0.20Mpa.
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Cited By (7)
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| CN102266793A (en) * | 2011-06-21 | 2011-12-07 | 西北大学 | Catalyst for producing propylene and producing method and application thereof |
| 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 |
| 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 |
| CN103755510A (en) * | 2014-01-03 | 2014-04-30 | 浙江大学 | Process for producing propylene by using alcohol-hydrocarbon co-refining technology |
| CN105289703A (en) * | 2015-11-30 | 2016-02-03 | 西北大学 | Catalyst for producing aromatic hydrocarbon by converting through coupling of methanol and C4-hydrocarbons and application of catalyst |
| CN108191593A (en) * | 2018-01-08 | 2018-06-22 | 中石化炼化工程（集团）股份有限公司 | A kind of olefin preparation method and device |
| CN116351458A (en) * | 2023-03-28 | 2023-06-30 | 中化泉州石化有限公司 | Preparation method of catalyst for preparing low-carbon olefin by co-cracking C4-C6 olefin coupling oxygen-containing compound |
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| CN102266793A (en) * | 2011-06-21 | 2011-12-07 | 西北大学 | Catalyst for producing propylene and producing method and application thereof |
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| 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 |
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| CN105289703A (en) * | 2015-11-30 | 2016-02-03 | 西北大学 | Catalyst for producing aromatic hydrocarbon by converting through coupling of methanol and C4-hydrocarbons and application of catalyst |
| CN108191593A (en) * | 2018-01-08 | 2018-06-22 | 中石化炼化工程（集团）股份有限公司 | A kind of olefin preparation method and device |
| CN116351458A (en) * | 2023-03-28 | 2023-06-30 | 中化泉州石化有限公司 | Preparation method of catalyst for preparing low-carbon olefin by co-cracking C4-C6 olefin coupling oxygen-containing compound |
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