CN101347743A - Method for preparing catalyst for producing propylene transformed from methanol with high ratio of propylene/ethylene - Google Patents
Method for preparing catalyst for producing propylene transformed from methanol with high ratio of propylene/ethylene Download PDFInfo
- Publication number
- CN101347743A CN101347743A CNA200710043956XA CN200710043956A CN101347743A CN 101347743 A CN101347743 A CN 101347743A CN A200710043956X A CNA200710043956X A CN A200710043956XA CN 200710043956 A CN200710043956 A CN 200710043956A CN 101347743 A CN101347743 A CN 101347743A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- propylene
- acid
- catalyst
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Abstract
The invention relates to a preparation method of a catalyst for converting methanol with high P/E (propylene/ethylene) ratio to propylene, and the preparation method is mainly used for solving the problems of low yield of the target product propylene and low P/E weight ratio in the prior art. The preparation method firstly uses 0.1 to 5.0 mol/L of at least one alkaline solution which is selected from sodium hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate or sodium bicarbonate to process ZSM-5 molecular sieve raw powder for 1 to 48 hours under the condition of the temperature of 20 to 90 DEG C, then uses 0.1 to 8.5 mol/L of at least one acid solution which is selected from hydrochloric acid, nitric acid, sulfuric acid or acetic acid to process for 1 to 8 hours and further uses water vapor to process for 1 to 15 hours at the temperature of 400 to 700 DEG C and the water liquid phase weight space velocity of 0.1 to 10 hours <-1>, after that, the mixing, the shaping and the calcination with a binding agent, then at least one solution which is selected from oxalic acid, citric acid, phosphoric acid or tartaric acid with the concentration of 0.1 to 5 mol/L is used for the impregnation of a precursor of the ZSM-5 molecular sieve, and the catalyst of the modified ZSM-5 molecular sieve is obtained after the calcination; therefore, the technical proposal can better solve the problems and can be used in the industrial production of the catalyst for converting the methanol to the propylene.
Description
Technical field
The present invention relates to the preparation method of a kind of high propylene/ethylene than propylene catalyst from methanol conversion.
Background technology
Propylene is important Organic Chemicals, along with increasing rapidly of derivative demands such as polypropylene, to the also rising year by year of demand of propylene.Crude oil that traditional production of propylene technological requirement is a large amount of or liquefied petroleum gas are supplied with; the rising significantly and the following petroleum-based energy of whole world oil price face exhaustion, press for new energy substitution product of exploitation and new process to solve the energy crisis that following oil shortage causes.By methyl alcohol is that catalytic material is produced low-carbon alkene (MTO) and methanol conversion to produce propylene (MTP) technology be the novel process that is hopeful to replace petroleum path most.Methanol-to-olefins Study on Technology, exploitation, industrialization become the focus of international each major oil companies' technological development in recent years.Ripe to methanol conversion technology by natural gas, coal through synthesis gas, for good basis has been established in the development of methanol-to-olefins technology.
In United States Patent (USP) U.S.4440871, U.S. carbon compound company (UCC) has developed novel SAPO series molecular sieve (SAPO-n).Wherein SAPO-34 has represented the catalytic performance preferable to methanol-to-olefins.But the rich ethene that produces in this product, yield of ethene reaches 53.8%, and propylene is 29.1%, P/E lower than very (U.S.5817906).Recently, be reported in that the propylene selectivity reaches 45.4% in the methanol to olefins reaction, ethylene contents is still very high, and P/E is than less than 1.45 (US 6710218).SAPO series molecular sieve catalyst aperture is little, easily coking, and P/E is not suitable for MTP technology than low in the product component.
Mobil prepares in the gasoline process at research methyl alcohol and finds can realize the production of methyl alcohol to light alkene by the ZSM-5 molecular sieve catalyst being modified and being changed reaction condition.Germany Lurgi company develops the more complete MTP technology of a cover based on the ZSM-5 molecular sieve of Cd and Zn modification, adopts three sections circular responses, and the propylene selectivity reaches 71.2% (PEPReview 98-13).More than the methyl alcohol of Jie Shaoing produces that cyclopropene method exists all that purpose product propene yield is low, P/E is than problem such as low.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists the problem that propene yield is low, the P/E weight ratio is low in the preparing propylene by methanol transformation process, and a kind of preparation method of high P/E weight ratio propylene catalyst from methanol conversion newly is provided.The catalyst that uses the inventive method to make is used for the preparing propylene by methanol transformation reaction, has the advantage of higher propene yield and P/E weight ratio.
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 high propylene/ethylene may further comprise the steps successively than the preparation method of propylene catalyst from methanol conversion:
A) with silica alumina ratio SiO
2/ Al
2O
3Be that 20～1000 ZSM-5 molecular sieve concentration is that at least a aqueous slkali that 0.1～5.0 mol is selected from NaOH, magnesium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate or the sodium acid carbonate was handled 1～48 hour under 20～90 ℃ of conditions of temperature, modified zeolite molecular sieve precursor I;
B) the modified zeolite molecular sieve precursor I concentration that step a) is obtained is that at least a acid solution that 0.1～8.5 mol is selected from hydrochloric acid, nitric acid, sulfuric acid or the acetate was handled 1～8 hour under 20～90 ℃ of conditions of temperature, gets modified zeolite molecular sieve presoma II;
C) the modified zeolite molecular sieve presoma II that step b) is obtained is 400～700 ℃ in temperature, and water vapour dividing potential drop in inert atmosphere is 0.01～0.1MPa, water liquid phase weight space velocity 0.1～10 hour
-1Steam treatment got modified zeolite molecular sieve presoma III in 1～15 hour under the condition;
D) the modified zeolite molecular sieve precursor III that step c) is obtained with account for modified zeolite molecular sieve catalyst weight 5～70% and be selected from SiO
2, clay or Al
2O
3In at least a adhesive mix, through extrusion, compressing tablet or spray ball, then temperature be 400～700 ℃ of roastings 1～15 hour modified zeolite molecular sieve precursor IV;
E) the modified zeolite molecular sieve presoma IV acid solutions that step d) is obtained is that 0.1～5 mol is selected from least a in oxalic acid, citric acid, phosphoric acid or the tartaric acid to be to flood 1～5 hour under 20～90 ℃ of conditions in temperature, to be that 400～700 ℃ of roastings made required modified zeolite molecular sieve catalyst in 1～15 hour in temperature then.
The binder dosage preferable range is 10～50% of a modified zeolite molecular sieve catalyst weight in the technique scheme; The silica alumina ratio SiO of ZSM-5 molecular sieve
2/ Al
2O
3Preferable range is 50～200; A) its alkali purification temp preferable range is 50～90 ℃ in the step, and the concentration preferable range of aqueous slkali is 0.1～3 mol, and aqueous slkali processing time preferable range is 10～36 hours; B) the acid solutions preferable range is 0.1～2 mol in the step; C) water liquid phase weight space velocity preferable range is 0.1～5 hour in the step
-1, steam treatment temperature preferable range is 550～700 ℃, steam treatment time preferable range is 3～10 hours; E) the acid solutions preferable range is 0.1～2 mol in the step.
Fixed bed reactors are adopted in the examination of catalyst among the present invention, are raw material with methyl alcohol, and water is diluent, and reaction pressure is 0.04MPa, methyl alcohol liquid phase weight space velocity 4 hours
-1Under 2: 1 conditions of water/methyl alcohol mol ratio raw material and diluent temperature be 350 ℃ down by aluminium oxide catalyst bed reaction of formation effluent I, reaction effluent I is to generate the effluent II contain propylene with ZSM-5 modified molecular screen haptoreaction under 500 ℃ of conditions in temperature, through separate propylene.
Studies show that the raising of the diffusion of propylene depends on the improvement in diffusion duct, increase as outlet diffusor, shorten the diffusion orifice throat length, the diffusion duct is blocked etc., therefore can adopt the way of alkali treatment to remove framework silicon selectively, make the molecular sieve surface produce a large amount of pits and the inner mutually diffusion that produces the way raising propylene of a large amount of cavitys of body, reduce the secondary response probability, improve the propylene selectivity.Because the ethene diffusion is better, pore passage structure improves the ethylene selectivity influence less.The molecular sieve silica alumina ratio descends after the alkali treatment, and acidic site density increases, and molecular sieve intensity, sour density distribute to product and has a significant impact, and the lower molecular sieve acid strength and the molecular sieve density of high dilution help the generation of low-carbon alkene.Can adopt water vapour to enter molecular sieve pore passage inside, generate Al (OH) with the framework aluminum reaction
x, realize dealuminzation, the simultaneous dehydroxylation of dealuminzation causes the molecular sieve total acid content to reduce, and acid strength reduces.The part non-framework aluminum that produces in the steam treatment process forms secondary pore on the molecular sieve surface, be unfavorable for the product diffusion, employing has the acid and the hexa-coordinate aluminium complexing that breaks away from skeleton of complexing characteristic, promotes that non-framework aluminum removes from molecular sieve, improves the selectivity of intermediate products such as propylene.The present invention is applied to above method of modifying on the preparing propylene by methanol transformation molecular sieve catalyst, makes the material benzenemethanol conversion ratio can reach 100%, and propene yield can reach 48.2%, and the P/E weight ratio can reach 10, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
The specific embodiment
[comparative example 1]
With silica alumina ratio SiO
2/ Al
2O
3Be that 110 ZSM-5 molecular screen primary powder is 90 ℃ in temperature, exchange is 5 hours in the 5 mol hydrochloric acid solutions.Is 550 ℃ of roastings 8 hours through washing, after dry in temperature, again with the adhesive SiO of weight percent meter 30%
2Mix, after extrusion temperature be 600 ℃ of roastings 8 hours Hydrogen ZSM-5 molecular sieve.
[embodiment 1～5]
With silica alumina ratio SiO
2/ Al
2O
3Be that 40,70,110,300 ZSM-5 molecular sieve is that 0.1,0.6,1.0,2.0 mol NaOH or magnesium hydroxide or sodium carbonate aqueous slkali are to handle 12,24,36 hours under 40,60,80 ℃ of conditions in temperature with concentration successively, the dry back of washing is 550 ℃ of following roastings 8 hours in temperature, be that 0.1,1.0,5.0 mol hydrochloric acid or salpeter solution were handled 5 hours under 20,50,90 ℃ of conditions of temperature with concentration again, the dry back of washing is 550 ℃ in temperature, water liquid phase weight space velocity 0.2 hour
-1Steam treatment is 8 hours under the condition, again with percentage by weight 10,30,50%SiO
2Adhesive mixes, after extrusion, be 550 ℃ of roastings 8 hours in temperature, with molecular sieve concentration after the moulding is that 2.0 mol citric acids are to flood 5 hours under 90 ℃ of conditions in temperature, is that 550 ℃ of roastings made required modified zeolite molecular sieve catalyst in 8 hours in temperature then.
[embodiment 6～11]
With silica alumina ratio SiO
2/ Al
2O
3Be that 110 ZSM-5 molecular sieve concentration is that 0.6 mol sodium carbonate aqueous slkali is to handle 36 hours under 80 ℃ of conditions in temperature, the dry back of washing is 550 ℃ of following roastings 8 hours in temperature, be that 5.0 mol hydrochloric acid solutions were handled 5 hours under 90 ℃ of conditions of temperature with concentration again, the dry back of washing is 500,550,600,700 ℃ in temperature, water liquid phase weight space velocity 0.2,1.0,5.0 hours
-1Steam treatment is 2,8,12 hours under the condition, again with percentage by weight 30%SiO
2Adhesive mixes, after extrusion, be 550 ℃ of roastings 8 hours in temperature, with molecular sieve concentration after the moulding is that 0.1,2.0,5.0 mol citric acids, oxalic acid, maleic acid are to flood 5 hours under 40,70,90 ℃ of conditions in temperature, is that 550 ℃ of roastings made required modified zeolite molecular sieve catalyst in 8 hours in temperature then.
[embodiment 12]
The modified molecular sieve catalyst that comparative example and embodiment 1～11 and comparative example are made is used for the preparing propylene by methanol transformation reaction, with methyl alcohol is raw material, at the aluminium oxide catalyst bed temperature is 350 ℃, the modified zsm-5 zeolite bed temperature is 500 ℃, reaction pressure is 0.02MPa, methyl alcohol liquid phase weight space velocity 4 hours
-1, reaction raw materials successively passes through Al under 2: 1 conditions of water/methyl alcohol mol ratio
2O
3Beds and modified zsm-5 zeolite bed, reaction generates propylene.Reaction result is listed in table 1 and the table 2.
Table 1 preparing propylene by methanol transformation reaction result
| Embodiment | 1 | 2 | 3 | 4 | 5 | Comparative example |
| Silica alumina ratio SiO 2/Al 2O 3 | 40 | 70 | 300 | 110 | 110 | 70 |
| The adhesive kind | SiO 2 | Al 2O 3 | Al 2O 3 | SiO 2 | Al 2O 3 | SiO 2 |
| Weight of binder percentage/% | 50 | 10 | 30 | 30 | 50 | 30 |
| The alkali treatment kind | NaOH | Sodium carbonate | NaOH | Sodium carbonate | Magnesium hydroxide | - |
| Alkali treatment concentration/mole rises -1 | 0.1 | 1.0 | 0.6 | 0.6 | 2.0 | - |
| Its alkali purification temp/℃ | 60 | 60 | 40 | 80 | 60 | - |
| Alkali treatment time/hour | 12 | 24 | 36 | 36 | 12 | - |
| Acid exchange kind | Hydrochloric acid | Hydrochloric acid | Hydrochloric acid | Nitric acid | Nitric acid | Hydrochloric acid |
| Acid exchange concentration/mole rises -1 | 0.1 | 1.0 | 5.0 | 1.0 | 0.1 | 5.0 |
| Acid exchange temperature/℃ | 90 | 50 | 20 | 90 | 50 | 90 |
| Acid swap time/hour | 2 | 5 | 8 | 8 | 5 | 5 |
| Methanol conversion/% | 99.8 | 99.7 | 95.2 | 100 | 78.9 | 100 |
| Propylene mass yield/% | 44.1 | 46.6 | 39.4 | 47.8 | 28.1 | 45.2 |
| The P/E weight ratio | 5.6 | 8.7 | 4.2 | 10.6 | 6.4 | 3.8 |
Table 2 preparing propylene by methanol transformation reaction result
| Embodiment | 6 | 7 | 8 | 9 | 10 | 11 |
| The steam treatment temperature/℃ | 500 | 550 | 600 | 700 | 550 | 600 |
| The water weight space velocity/hour -1 | 0.2 | 1.0 | 1.0 | 5.0 | 0.2 | 1.0 |
| Steam treatment time/hour | 2 | 8 | 12 | 8 | 8 | 2 |
| Pickling kind after the steam treatment | Citric acid | Oxalic acid | Citric acid | Oxalic acid | Maleic acid | Citric acid |
| Pickling concentration/mole rises after the steam treatment -1 | 0.1 | 2.0 | 5.0 | 5.0 | 2.0 | 0.1 |
| Pickling pickling temperature after the steam treatment/℃ | 40 | 70 | 90 | 90 | 70 | 40 |
| Methanol conversion/% | 99.5 | 100 | 100 | 78.3 | 100 | 99.3 |
| Propylene mass yield/% | 46.8 | 48.2 | 47.5 | 33.4 | 46.4 | 46.1 |
| The P/E weight ratio | 4.8 | 10.7 | 9.6 | 3.7 | 8.8 | 6.2 |
Claims (7)
1, a kind of high propylene/ethylene may further comprise the steps successively than the preparation method of propylene catalyst from methanol conversion:
A) with silica alumina ratio SiO
2/ Al
2O
3Be that 20～1000 ZSM-5 molecular sieve concentration is that at least a aqueous slkali that 0.1～5.0 mol is selected from NaOH, magnesium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate or the sodium acid carbonate was handled 1～48 hour under 20～90 ℃ of conditions of temperature, modified zeolite molecular sieve precursor I;
B) the modified zeolite molecular sieve precursor I concentration that step a) is obtained is that at least a acid solution that 0.1～8.5 mol is selected from hydrochloric acid, nitric acid, sulfuric acid or the acetate was handled 1～8 hour under 20～90 ℃ of conditions of temperature, gets modified zeolite molecular sieve presoma II;
C) the modified zeolite molecular sieve presoma II that step b) is obtained is 400～700 ℃ in temperature, and water vapour dividing potential drop in inert atmosphere is 0.01～0.1MPa, water liquid phase weight space velocity 0.1～10 hour
-1Steam treatment got modified zeolite molecular sieve presoma III in 1～15 hour under the condition;
D) the modified zeolite molecular sieve precursor III that step c) is obtained with account for modified zeolite molecular sieve catalyst weight 5～70% and be selected from SiO
2, clay or Al
2O
3In at least a adhesive mix, through extrusion, compressing tablet or spray ball, then temperature be 400～700 ℃ of roastings 1～15 hour modified zeolite molecular sieve precursor IV;
E) the modified zeolite molecular sieve presoma IV acid solutions that step d) is obtained is that 0.1～5 mol is selected from least a in oxalic acid, citric acid, phosphoric acid or the tartaric acid to be to flood 1～5 hour under 20～90 ℃ of conditions in temperature, to be that 400～700 ℃ of roastings made required modified zeolite molecular sieve catalyst in 1～15 hour in temperature then.
2,, it is characterized in that adhesive consumption is 10～50% of a modified zeolite molecular sieve catalyst weight according to the preparation method of the described high propylene/ethylene of claim 1 than propylene catalyst from methanol conversion.
3, according to the preparation method of the described high propylene/ethylene of claim 1, it is characterized in that molecular sieve silica alumina ratio SiO than propylene catalyst from methanol conversion
2/ Al
2O
3Be 50～200.
4, according to the preparation method of the described high propylene/ethylene of claim 1 than propylene catalyst from methanol conversion, it is characterized in that a) its alkali purification temp is 50～90 ℃ in the step, the concentration of aqueous slkali is 0.1～3 mol, and the aqueous slkali processing time is 10～36 hours.
5, according to the preparation method of the described high propylene/ethylene of claim 1, it is characterized in that b than propylene catalyst from methanol conversion) concentration of acid solution is 0.1～2 mol in the step.
6, according to the preparation method of the described high propylene/ethylene of claim 1, it is characterized in that c than propylene catalyst from methanol conversion) water liquid phase weight space velocity 0.1～5 hour in the step
-1, the temperature of steam treatment is 550～700 ℃.
7, according to the preparation method of the described high propylene/ethylene of claim 1, it is characterized in that e than propylene catalyst from methanol conversion) acid solutions 0.1～2 mol in the step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710043956XA CN101347743B (en) | 2007-07-18 | 2007-07-18 | Method for preparing catalyst for producing propylene transformed from methanol with high ratio of propylene/ethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710043956XA CN101347743B (en) | 2007-07-18 | 2007-07-18 | Method for preparing catalyst for producing propylene transformed from methanol with high ratio of propylene/ethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101347743A true CN101347743A (en) | 2009-01-21 |
| CN101347743B CN101347743B (en) | 2010-11-10 |
Family
ID=40266806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710043956XA Active CN101347743B (en) | 2007-07-18 | 2007-07-18 | Method for preparing catalyst for producing propylene transformed from methanol with high ratio of propylene/ethylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101347743B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218336A (en) * | 2011-04-20 | 2011-10-19 | 西南化工研究设计院 | Method for preparing propylene catalyst by using carbinol |
| CN102746096A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for liquid phase transalkylation of polyethylbenzene and benzene |
| CN102746097A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for production of ethylbenzene through liquid phase transalkylation of polyethylbenzene and benzene |
| CN103055928A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing arene via direct methanol conversion and preparation method thereof |
| CN104307560A (en) * | 2014-10-20 | 2015-01-28 | 丁泳 | Catalyst for preparing propylene byproduct high-octane gasoline by taking methanol as raw material and preparation method of catalyst |
| CN104525250A (en) * | 2015-01-09 | 2015-04-22 | 中国科学院上海高等研究院 | SAPO-34 molecular sieve based catalyst of hierarchical pore structure and preparation and application thereof |
| CN104628011A (en) * | 2013-11-08 | 2015-05-20 | 中国石油天然气股份有限公司 | ZSM-5 modification treatment method |
| CN105175204A (en) * | 2014-12-03 | 2015-12-23 | 胡齐放 | Method for preparing p-xylene and propylene by utilizing alcohol-ether mixture |
| CN105566049A (en) * | 2014-10-13 | 2016-05-11 | 中国石油化工股份有限公司 | Method for liquid-phase transalkylation of polyethylated benzene and benzene |
| CN106466621A (en) * | 2015-08-20 | 2017-03-01 | 中国石油化工股份有限公司 | Catalyst of preparing propylene by methanol transformation and preparation method thereof |
| CN107921414A (en) * | 2015-07-13 | 2018-04-17 | Ifp 新能源公司 | For ethanol to be converted into the catalyst based on the tantalum being deposited on silica of butadiene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1116931C (en) * | 2000-02-24 | 2003-08-06 | 中国石油化工集团公司 | Method of raising the stability of catalyst for benzene and ethylene alkylation |
-
2007
- 2007-07-18 CN CN200710043956XA patent/CN101347743B/en active Active
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746096A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for liquid phase transalkylation of polyethylbenzene and benzene |
| CN102746097A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for production of ethylbenzene through liquid phase transalkylation of polyethylbenzene and benzene |
| CN102218336B (en) * | 2011-04-20 | 2012-11-21 | 西南化工研究设计院 | Method for preparing propylene catalyst by using carbinol |
| CN102218336A (en) * | 2011-04-20 | 2011-10-19 | 西南化工研究设计院 | Method for preparing propylene catalyst by using carbinol |
| CN103055928A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing arene via direct methanol conversion and preparation method thereof |
| CN104628011A (en) * | 2013-11-08 | 2015-05-20 | 中国石油天然气股份有限公司 | ZSM-5 modification treatment method |
| CN105566049A (en) * | 2014-10-13 | 2016-05-11 | 中国石油化工股份有限公司 | Method for liquid-phase transalkylation of polyethylated benzene and benzene |
| CN104307560A (en) * | 2014-10-20 | 2015-01-28 | 丁泳 | Catalyst for preparing propylene byproduct high-octane gasoline by taking methanol as raw material and preparation method of catalyst |
| CN105175204A (en) * | 2014-12-03 | 2015-12-23 | 胡齐放 | Method for preparing p-xylene and propylene by utilizing alcohol-ether mixture |
| CN104525250A (en) * | 2015-01-09 | 2015-04-22 | 中国科学院上海高等研究院 | SAPO-34 molecular sieve based catalyst of hierarchical pore structure and preparation and application thereof |
| CN107921414A (en) * | 2015-07-13 | 2018-04-17 | Ifp 新能源公司 | For ethanol to be converted into the catalyst based on the tantalum being deposited on silica of butadiene |
| CN107921414B (en) * | 2015-07-13 | 2021-08-10 | Ifp 新能源公司 | Catalyst for the conversion of ethanol to butadiene based on tantalum deposited on silica |
| CN106466621A (en) * | 2015-08-20 | 2017-03-01 | 中国石油化工股份有限公司 | Catalyst of preparing propylene by methanol transformation and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101347743B (en) | 2010-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101347743B (en) | Method for preparing catalyst for producing propylene transformed from methanol with high ratio of propylene/ethylene | |
| CN101172246B (en) | Process for preparation of propylene catalysts with methanol conversion | |
| CN101279283B (en) | Modified ZSM-5 molecular sieve catalyst for preparing propylene transformed from methanol and preparation thereof | |
| CN101172918B (en) | Method for producing propylene with methanol conversion | |
| CN102040448B (en) | Method for preparing propylene by catalyzing methanol/dimethyl ether with composite molecular sieve with core-shell structure | |
| CN101279282B (en) | ZSM-5 mesoporous molecular sieve catalyst for preparing propylene from methanol and preparation thereof | |
| CN101306381B (en) | ZSM-5 molecular sieve catalyst of propone prepared by methanol conversation and its preparation method | |
| CN109704900B (en) | Method for preparing olefin by synthesis gas one-step method | |
| CN106608777B (en) | The production method of propylene | |
| CN105174286B (en) | A kind of preparation method of the eutectic molecular sieves of AEI/CHA at high proportion | |
| Xin et al. | The influence of pore structures and Lewis acid sites on selective hydrogenolysis of guaiacol to benzene over Ru/TS-1 | |
| CN101570469B (en) | Method for continuously producing isobutyl alcohol through hydrogenation of methylacrolein | |
| CN101279280B (en) | Catalyst for preparing propylene transformed from methanol | |
| CN109701627B (en) | Composite catalyst containing spinel structure and application thereof in one-step preparation of olefin from synthesis gas | |
| CN100593434C (en) | Method for preparing propylene catalyst from methanol conversion | |
| CN101279281B (en) | High stability molecular sieve catalyst for preparing propylene transformed from methanol and preparation thereof | |
| CN102211036A (en) | Modified molecular sieve catalyst, and precursor and preparation method thereof | |
| CN101948120A (en) | SAPO-18 molecular sieve catalyst for producing low-carbon olefin and preparation method thereof | |
| CN106881146B (en) | A kind of preparation method for dry gas and benzene alkylation reaction F-ZSM-11 molecular sieve catalyst | |
| CN106890669A (en) | A kind of catalyst for producing methyl acetate, its preparation method and application | |
| CN111253204B (en) | Method for preparing ethylene by ethanol dehydration | |
| CN102060644B (en) | Method for preparing olefin by dehydration of methanol | |
| CN111253199B (en) | Method for preparing ethylene by ethanol dehydration | |
| CN112675904B (en) | Carbon-containing catalyst and application thereof in one-step method for producing low-carbon olefin by using synthesis gas | |
| Zheng | Conversion of 2, 3-butanediol over bifunctional catalysts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |