CN102040447A - New method for preparing propylene from methanol - Google Patents
New method for preparing propylene from methanol Download PDFInfo
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- CN102040447A CN102040447A CN2010105667757A CN201010566775A CN102040447A CN 102040447 A CN102040447 A CN 102040447A CN 2010105667757 A CN2010105667757 A CN 2010105667757A CN 201010566775 A CN201010566775 A CN 201010566775A CN 102040447 A CN102040447 A CN 102040447A
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- propylene
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- methanol
- catalyzer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention belongs to the technical field of chemical industry, and in particular relates to a method for preparing propylene from methanol serving as a raw material. The invention mainly solves the problem that the P/E ratio in a product (namely the mass ratio of propylene to ethylene) is low in the prior art. Zeolite containing melt flow index (MFI) micropores and wormhole-like mesopores simultaneously is adopted to serve as a catalyst, the reaction temperature is controlled to be between 300 and 600 DEG C, the pressure is controlled to be 0-1.0MPa, the liquid hourly space velocity is 0.1-10h<-1>, steam serves as diluent gas, and the propylene is prepared in a fixed bed reactor. The method has the advantages that: high activity is kept and the P/E ratio in the obtained product is greatly improved.
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, being specifically related to a kind of is the method for feedstock production propylene by methyl alcohol.
Background technology
Propylene is a class important chemical material, and is very big to the demand of propylene in the global range, and is the trend of cumulative year after year.Traditional production of propylene is mainly finished by steam cracking and catalytic cracking, but in these methods propylene all be as ethene byproduct produce, and depend on petroleum resources strongly.Along with the worsening shortages of petroleum resources, utilize non-oil approach to obtain methyl alcohol, be subjected to common concern both domestic and external by the method for methanol production propylene.
In U.S. Pat 4440871, U.S. Union Carbide Corp has developed a series of phosphorus aluminic acid molecular sieves, and wherein SAPO-34 shows in the methanol conversion olefine reaction well, but product is based on ethene, the amount of propylene less relatively (US5817906).
Mobil company finds also can realize methyl alcohol step-down carbon olefin on the ZSM-5 zeolite in the process of research methyl alcohol change gasoline.It is a technology of overlapping complete preparing propylene from methanol of catalyzer that LURGI has developed subsequently with the ZSM-5 zeolite of Cd and Zn modification, propylene surpasses ethene in the product that this technology obtains becomes main component, but the ratio of propylene/ethylene (being the P/E ratio) is still lower.Improve the propylene selectivity, improve P/E ratio in the product, reducing the by product generation is the key problem of new process development.
Summary of the invention
The purpose of this invention is to provide in a kind of product P/E than high, what by product was few prepares the novel method of propylene by methyl alcohol.
Method proposed by the invention is a raw material with methyl alcohol, and adopting the zeolitic material contain MFI micropore canals and worm meso-porous duct simultaneously is catalyzer, is carrier gas with the water vapor, is propylene with methanol conversion in fixed-bed reactor.
1) catalyst system therefor is the HZSM-5 zeolite that contains worm meso-porous duct among the present invention, and the Si/Al ratio is 50 – 500.Preferred Si/Al ratio is 100 – 300.
2) be reflected in the fixed-bed reactor and carry out, temperature of reaction can be 300-600
oC.Preferable reaction temperature is 400-550
oC.
Pressure is 0-1.0 MPa when 3) reacting, and liquid hourly space velocity is 0.1-10 h
-1Preferred reaction pressure is 0.1-0.5 MPa, and preferred liquid hourly space velocity is 0.25-2 h
-1
Among the present invention, pure water mol ratio is 1:1-1:6.
Among the present invention, be the organo-silicon ester that adds long-chain in the solution of synthetic ZSM-5 zeolite precursor body in order to the method for preparing catalyzer, its molecular formula is as follows:
[(CH
3O)
3SiC
3H
6N(CH
3)
2C
n H
2
n+1
]X (X=Cl,?Br;?
n=12,?14,?16,?18) ，
The add-on of organo-silicon ester is 0.02-0.4 mol/ mol Si.
The invention has the advantages that keeping the highly active while that P/E is than improving greatly in the resulting product.And byproduct reduces.
Embodiment
Embodiment 1
Dissolving 0.0209 g sodium aluminate in 135 ml waters, 1.1 g TPABr and 0.8 g NaOH.8.57 g TEOS are mixed with 1.19 g [3-(trimethoxy is silica-based) propyl group] octadecyl ammonium chloride, be added drop-wise in the above-mentioned solution, at room temperature stir 2 h, moving into has in the stainless steel autoclave of Teflon liner, 170
oC crystallization 2 days.Put into 100 after the filtering and washing
oThe baking oven inner drying of C spends the night, in air 550
oTemplate was removed in the C roasting in 6 hours.The zeolite of gained is in 80
oC adds 1 M ammonium nitrate solution (the 1g zeolite adds solution 10 ml) ion-exchange three times, and each 2 h are dried behind the suction filtration, in 450
oRoasting 5 h obtain catalyzer 1 under the C air atmosphere.
Embodiment 2
Dissolving 0.0134 g sodium aluminate in 135 ml waters, 1.1 g TPABr and 0.8 g NaOH.8.57 gTEOS are mixed with 1.745g [3-(trimethoxy is silica-based) propyl group] octadecyl ammonium chloride, be added drop-wise in the above-mentioned solution, at room temperature stir 2 h, moving into has in the stainless steel autoclave of Teflon liner, 170
oC crystallization 2 days.Put into 100 after the filtering and washing
oThe baking oven inner drying of C spends the night, in air 550
oTemplate was removed in the C roasting in 6 hours.The zeolite of gained is in 80
oC adds 1 M ammonium nitrate solution (the 1g zeolite adds solution 10 ml) ion-exchange three times, and each 2 h are dried behind the suction filtration, in 450
oRoasting 5 h obtain catalyzer 2 under the C air atmosphere.
Embodiment 3
With embodiment 1 and the 2 gained catalyzer internal diameter of packing into is 8 mm, highly is in the stainless steel fixed-bed reactor of 60 mm, catalyzer top and the bottom filling quartz sand, beds aspect ratio 10:1.With nitrogen catalyzer is heated to 520
oAbout C, activate 2 h, switch to water vapour then, in the 0.01MPa(gauge pressure) feed methyl alcohol down, the results are shown in Table 1.
Comparative Examples 1
With 33.5 g Na
2SiO
39H
2O, 0.0476 g NaAlO
2Be dissolved in the 56 g water after mixing with 6.4 g tetrapropyl amine bromides, under violent stirring, slowly drip and Na
2SiO
39H
2The H of O equimolar amount
2SO
4, drip NH then
3H
2O is until pH=8 ~ 9 of solution.Continue under the room temperature to stir 4 h, change in the reactor of Teflon bushing pipe sealing, 180 over to
oC crystallization 48 h.Product after filtration, after the washing, drying, 550
oRoasting was removed template in 5 hours under the C, obtained Na type ZSM-5 molecular sieve.The zeolite of gained is in 80
oC adds 1 M ammonium nitrate solution (the 1g zeolite adds solution 10 ml) ion-exchange three times, and each 2 h are dried behind the suction filtration, in 450
oRoasting 5 h obtain comparative catalyst 1 under the C air atmosphere, utilize embodiment 3 methods to carry out the methanol conversion reaction, the results are shown in Table 1.
The reaction result of table 1 different catalysts
| Catalyzer | Embodiment 1 | Embodiment 1 | Embodiment 2 | Comparative Examples 1 |
| Temperature of reaction ( oC) | 460 | 420 | 500 | 460 |
| Alcohol water ratio | 1:5 | 1:5 | 1:2 | 1:5 |
| Liquid hourly space velocity (h -1) | 0.75 | 0.75 | 1.0 | 0.75 |
| Transformation efficiency (%) | 91.0 | 80.4 | 96.8 | 100 |
| Efficiency of pcr product (%) | ? | ? | ? | ? |
| C 1-3 | 0.6 | 0.5 | 1.2 | 2.6 |
| C 2 = | 2.6 | 1.9 | 4.2 | 11.0 |
| C 3 = | 41.4 | 38.3 | 44.6 | 42.1 |
| C 4 | 6.9 | 1.0 | 6.8 | 12.5 |
| C 4 = | 13.9 | 13.8 | 14.1 | 12.6 |
| C 5 | 13.5 | 9.5 | 15.4 | 7.9 |
| C 6 | 11.4 | 14.8 | 8.1 | 5.6 |
| Aromatic hydrocarbons | 0.7 | 0.6 | 2.4 | 5.7 |
| The P/E ratio | 15.9 | 20.2 | 10.6 | 3.8 |
Claims (5)
1. the method for a preparing propylene from methanol, it is characterized in that with methyl alcohol being raw material, is catalyzer with the zeolitic material that contains MFI micropore canals and worm meso-porous duct simultaneously, is carrier gas with the water vapor, in fixed-bed reactor be that propylene is main hydrocarbon mixture with methanol conversion, wherein:
1) Si/Al of described zeolitic material ratio is 50 – 500;
2) Fan Ying temperature is 300-600
oC;
Pressure is 0-1.0 MPa when 3) reacting, and liquid hourly space velocity is 0.1-10 h
-1
2. method according to claim 1 is characterized in that used catalyzer is the HZSM-5 zeolite that contains worm meso-porous duct, and the Si/Al ratio is 100 – 300.
3. method according to claim 1 and 2 is characterized in that described catalyzer is to add the organo-silicon ester of long-chain and prepare in the solution of synthetic ZSM-5 zeolite precursor body, and the molecular formula of this organo-silicon ester is as follows:
[(CH
3O)
3SiC
3H
6N (CH
3)
2C
n H
2
n+ 1
] X, X=Cl, or Br;
n=12,14,16, or 18,
The add-on of organo-silicon ester is 0.02-0.4 mol/ mol Si.
4. method according to claim 1 and 2 is characterized in that the temperature of reacting is 400-550
oC.
5. method according to claim 1 and 2 is characterized in that reaction pressure is 0.1-0.5 MPa, and liquid hourly space velocity is 0.25-2 h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105667757A CN102040447B (en) | 2010-12-01 | 2010-12-01 | New method for preparing propylene from methanol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105667757A CN102040447B (en) | 2010-12-01 | 2010-12-01 | New method for preparing propylene from methanol |
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| Publication Number | Publication Date |
|---|---|
| CN102040447A true CN102040447A (en) | 2011-05-04 |
| CN102040447B CN102040447B (en) | 2013-07-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145519A (en) * | 2011-09-29 | 2013-06-12 | 中国石油化工股份有限公司 | Method for preparing propylene by methanol conversion |
-
2010
- 2010-12-01 CN CN2010105667757A patent/CN102040447B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| CHANGSONG MEI: "Selective production of propylene from methanol: Mesoporosity development in high silica HZSM-5", 《JOURNAL OF CATALYSIS》 * |
| JEONGNAM KIM: "Effect of mesoporosity against the deactivation of MFI zeolite catalyst during the methanol-to-hydrocarbon conversion process", 《JOURNAL OF CATALYSIS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145519A (en) * | 2011-09-29 | 2013-06-12 | 中国石油化工股份有限公司 | Method for preparing propylene by methanol conversion |
| CN103145519B (en) * | 2011-09-29 | 2015-04-08 | 中国石油化工股份有限公司 | Method for preparing propylene by methanol conversion |
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| Publication number | Publication date |
|---|---|
| CN102040447B (en) | 2013-07-10 |
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