CN103420754A - Method for propylene preparation through methanol conversion - Google Patents
Method for propylene preparation through methanol conversion Download PDFInfo
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- CN103420754A CN103420754A CN2012101503070A CN201210150307A CN103420754A CN 103420754 A CN103420754 A CN 103420754A CN 2012101503070 A CN2012101503070 A CN 2012101503070A CN 201210150307 A CN201210150307 A CN 201210150307A CN 103420754 A CN103420754 A CN 103420754A
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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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Abstract
The present invention relates to a method for propylene preparation through methanol conversion, wherein problems of poor catalyst stability and not high propylene selectivity in the prior art are mainly solved with the present invention. The technical scheme comprises that: a methanol aqueous solution is adopted as a raw material, a ZSM-5 molecular sieve with a shape index of 3-100 is adopted as a catalyst at a reaction temperature of 400-600 DEG C under reaction pressure of 0.01-5 MPa at a methanol weight space velocity of 0.5-15 h<-1> according to a mass ratio of water to methanol of 0.2-5:1. With the technical scheme, the problems in the prior art are well solved, and the method can be used for industrial production of propylene preparation through methanol conversion.
Description
Technical field
The present invention relates to a kind of method of preparing propylene by methanol transformation.
Background technology
Propylene is the important foundation raw material of petrochemical industry, is subject to the driving of polypropylene and derivative demand rapid growth thereof, and the demand of a few years from now on propylene will be with speed increment faster, so propylene is considered to have the product of very big market potentiality.At present, the production method of propylene all be take oil as raw material both at home and abroad, and the China's oil resource extremely lacks, and prospective oil and output far can not meet the needs of national economy fast development, and imbalance between supply and demand is very severe.By methyl alcohol, be that catalytic material preparing low-carbon olefins (MTO) and methanol conversion preparing propone (MTP) technology are the novel procesies that is hopeful to replace petroleum path most, the key of MTP technology is the development of high performance catalyst, the HZSM-5 molecular sieve reaches adjustable silica alumina ratio on a large scale because of its suitable aperture, thereby become the first-selection of MTP catalyzer, under the effect of catalyzer, the methyl alcohol generation dme that at first dewaters, then the equilibrium mixture of methyl alcohol and dme continues to be converted into that to take ethene and propylene be main low-carbon alkene, the low-carbon alkene generated is by polycondensation, cyclisation, dehydrogenation, the reaction such as alkylation and hydrogen transference further generates alkane, aromatic hydrocarbons and higher olefins.Therefore, improving the diffusion of catalyzer, thereby make the product rapid diffusion reduce side reaction, thereby the selectivity of catalyst stability and product propylene is improved, is the key of MTP catalyst preparation.
Be used for the HZSM-5 molecular sieve of MTP reaction due to its unique pore passage structure and good catalytic performance, and be used widely in numerous catalyzed reactions.But there is diffusional limitation in this micro porous molecular sieve to larger molecule, to relating in macromolecular absorption, catalytic applications, there is certain limitation.1992, the researchist of Mobil company synthesized M41S series mesoporous silicon hydrochlorate and aluminate molecular sieve first, and the duct size is 1.5～10 nanometers.Synthesizing of these order mesoporous materials, greatly widened the pore diameter range of original micro porous molecular sieve.But, due to the hole wall of mesopore molecular sieve in unformed state, therefore, the hydrothermal stability of mesopore molecular sieve and acidly compare low with the micro-pore zeolite of crystalline structure, this has limited it and has directly used as catalyzer, usually using it as carrier or after further modifying, just can directly use.(the B.T.Holland such as Holland, L.Abrams, A. Stein. J. Am. Chem. Soc, 1999,121,4308 ~ 4309) with closelypacked polystyrene spheres, be the solid template, add wherein He Lv source, silicon source, crystallization forms after zeolite structured the method for removing the solid template and has obtained ZSM-5 zeolite with multilevel pore canals under certain condition, but this method need to solve the vitreous state temperature problem of polystyrene spheres, caused the loaded down with trivial details of building-up process, and also had no idea at present to address this problem.Find out thus, the structure of molecular sieve and pattern have a great impact its diffusion tool, so improve structure and the pattern of micropore ZSM-5 molecular sieve, are the directions of investigators' effort always.
The MTP relevant report has Chinese patent CN200710037239.6, CN200710037240.9, CN200710039073.1 etc.In addition, strange (Lurgi) company in German Shandong has also developed the catalyzer of Cd and Zn modification for process for preparing propylene from methanol.Have the ZSM-5 molecular sieve catalyzer for preparing propylene by methanol transformation reaction now, have that propene yield is low, catalyst activity poor stability and not high shortcoming of Propylene Selectivity.Reduce by product and generate, improve Propylene Selectivity, extending catalyst stability is the key of MTP catalyst development.
Summary of the invention
Technical problem to be solved by this invention is the poor catalyst stability of existing preparing propylene by methanol transformation reaction, the problem that Propylene Selectivity is not high, and a kind of method of new preparing propylene by methanol transformation is provided.When the method is reacted for preparing propylene by methanol transformation, have the advantages that catalyst stability is high, the product Propylene Selectivity is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of preparing propylene by methanol transformation, take methanol aqueous solution as raw material, and in temperature of reaction, be 400～600 ℃, reaction pressure is 0.01～5MPa, the methyl alcohol weight space velocity is 0.5～15 hour
-1, under the condition that the mass ratio of water and methyl alcohol is 0.2～5:1, raw material generates propylene by beds, and wherein catalyzer used, in parts by weight, comprises following component:
A) ZSM-5 that the type shape index of 30～80 parts is 3 ~ 100, the ratio that its medium-sized shape index definition is longest edge and bond length on the molecular sieve crystal three-dimensional;
B) binding agent of 20～70 parts.
In technique scheme, the temperature of reaction preferable range is 420～550 ℃, and the reaction pressure preferable range is 0.02～3MPa, and methyl alcohol weight space velocity preferable range is 0.8～10h
-1, water is 0.5～2:1 with the quality of methyl alcohol than preferable range.The consumption preferable range of parts by weight ZSM-5 molecular sieve of take is 40～75 parts, and the silica alumina ratio preferable range of ZSM-5 molecular sieve is SiO
2/ Al
2O
3Be 200～800.The type shape index preferable range of ZSM-5 molecular sieve is 10 ~ 60.The binding agent preferred version is selected from least one in silicon sol, aluminum oxide and aluminum phosphate.Adopt at least one element in P, La, Ce, Cu, Zn to be modified catalyzer, catalyzer is in parts by weight, and modifier content preferable range is 0.1 ~ 2 part.
Prepared according to following methods by the catalyzer used in the inventive method: a) with the tetrapropyl amine bromide, TPAOH, etamon chloride, in ammoniacal liquor, at least one is template, aluminum nitrate, Tai-Ace S 150, sodium aluminate or aluminum phosphate are the aluminium source, water glass, tetraethoxy or silicon sol are the silicon source, first raw material fully is hydrolyzed, transfer to again in stainless steel autoclave, in suitable salinity and basicity, under hydrothermal condition, control the direction of growth of molecular sieve crystal, 80～200 ℃ of crystallization 30～100 hours, by different proportioning raw materials, can obtain silica alumina ratio (SiO
2/ Al
2O
3) be 200～800, ZSM-5 molecular sieve that type shape index is 3 ~ 100, b) the former powder of ZSM-5 molecular sieve, binding agent and the water kneading and compacting that by type shape index, are 3 ~ 100, in 80～120 ℃ of dryings 5～10 hours, then 500～600 ℃ of lower roastings 4～8 hours, c) forming composition step b) obtained is exchanged with the ammonium salt aqueous solution of 5～10 % by weight under 80～90 ℃, after washing, drying, in 500～600 ℃ of lower roastings 4～8 hours, obtains required catalyzer, adopt equi-volume impregnating, the solid that step c) is obtained floods 1 ~ 24 hour by the soluble salt solution that contains P, La, Ce, Cu, at least one element of Zn, 80 ~ 100 ℃ of oven dry, then roasting 3 ~ 6 hours in 500 ~ 550 ℃ of retort furnaces, obtain the catalyzer of modification.
At present, there is the problem that catalyst stability is not high, Propylene Selectivity is on the low side in the preparing propylene by methanol transformation reaction, this is mainly because ZSM-5 molecular sieve grain morphology used is single, diffusion is poor, when reaction intermediates or product molecule pass through, easily produce and be detained therein, the reactant molecule that makes to enter in duct is difficult for diffusing out and causes unwanted degree of depth side reaction, assemble gradually coking, stop up molecular sieve pore passage, thereby catalyst activity is reduced greatly, finally cause catalyst deactivation.We adopt the ZSM-5 molecular sieve with a typing shape index to solve this problem, and product is diffusion rapidly in molecular sieve pore passage, and macromole product coking degree obviously reduces, and catalyst stability obviously improves.The catalyzer of preparing propylene by methanol transformation of the present invention has effectively overcome poor catalyst stability and the low shortcoming of Propylene Selectivity in the prior art, by optimizing reaction conditions, catalyst stability surpasses 1300 hours, and Propylene Selectivity, more than 40%, has been obtained technique effect preferably.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Take the tetrapropyl amine bromide as template, and aluminum nitrate is the aluminium source, and silicon sol is the silicon source, at first by raw material SiO in molar ratio
2/ Al
2O
3=200; OH
-/ SiO
2=0.3; R/SiO
2=0.5; H
2O/SiO
2=40 ratio is mixed, and under room temperature, fully, the stainless steel cauldron of packing into, under hydrothermal condition, control the direction of growth of molecular sieve crystal in hydrolysis, and 100 ℃ of crystallization 60 hours, obtain silica alumina ratio SiO
2/ Al
2O
3The NaZSM-5 molecular sieve that be 200, type shape index is 50.
Take NaZSM-5 molecular sieve, the 25 gram silicon sol (SiO of the above-mentioned preparation of 40 gram
2Weight percentage 40%), add the water kneading, the mould extruded moulding that is 1.5 millimeters with diameter, dry, be placed in 80 ℃ of baking ovens 8 hours, in 600 ℃ of retort furnaces, roasting is 6 hours, remove template, in 90 ℃ of 5% ammonium nitrate solution, exchange is three times, roasting 4 hours in 550 ℃ of retort furnaces after oven dry, the HZSM-5 molecular sieve catalyst that to obtain silica alumina ratio 200, type shape index be 50.
[embodiment 2]
Take the tetrapropyl oxyammonia as template, and Tai-Ace S 150 is the aluminium source, and water glass is the silicon source, and raw material is SiO in molar ratio
2/ Al
2O
3=500; OH
-/ SiO
2=0.05; R/SiO
2=1.5; H
2O/SiO
2=10 ratio is mixed, and adopts method described in embodiment 1, and 80 ℃ of crystallization 100 hours, obtain silica alumina ratio SiO
2/ Al
2O
3The NaZSM-5 molecular sieve that be 500, type shape index is 3.
Take NaZSM-5 molecular sieve, the 38 gram silicon sol (SiO of the above-mentioned preparation of 30 gram
2Weight percentage 40%) and 15 gram aluminum oxide, add the water kneading, the mould extruded moulding that is 1.5 millimeters with diameter, dry, be placed in 100 ℃ of baking ovens 5 hours, in 600 ℃ of retort furnaces, roasting is 4 hours, remove template, in 85 ℃ of 10% ammonium chloride solution, exchange is three times, roasting 8 hours in 500 ℃ of retort furnaces after oven dry, the HZSM-5 molecular sieve catalyst that to obtain silica alumina ratio 500, type shape index be 3.
[embodiment 3]
Take etamon chloride as template, and sodium aluminate is the aluminium source, and tetraethoxy is the silicon source, and raw material is SiO in molar ratio
2/ Al
2O
3=800; OH
-/ SiO
2=1.5; R/SiO
2=0.02; H
2O/SiO
2=30 ratio is mixed, and adopts method described in embodiment 1, and 120 ℃ of crystallization 50 hours, obtain silica alumina ratio SiO
2/ Al
2O
3The NaZSM-5 molecular sieve that be 800, type shape index is 10.
Take the above-mentioned preparation of 10 gram NaZSM-5 molecular sieve, 32 gram silicon sol (SiO
2Weight percentage 40%) and 10 gram aluminum phosphates, add the water kneading, the mould extruded moulding that is 1.5 millimeters with diameter, dry, be placed in 120 ℃ of baking ovens 8 hours, in 500 ℃ of retort furnaces, roasting is 8 hours, remove template, in 80 ℃ of 10% ammonium nitrate solution, exchange is three times, roasting 4 hours in 600 ℃ of retort furnaces after oven dry, the HZSM-5 molecular sieve catalyst that to obtain silica alumina ratio 800, type shape index be 10.
[embodiment 4]
Take etamon chloride and ammoniacal liquor as template, and aluminum phosphate is the aluminium source, and water glass is the silicon source, and raw material is SiO in molar ratio
2/ Al
2O
3=600; OH
-/ SiO
2=1.0; R/SiO
2=0.06; H
2O/SiO
2=50 ratio is mixed, and adopts method described in embodiment 1, and 200 ℃ of crystallization 30 hours, obtain silica alumina ratio SiO
2/ Al
2O
3The NaZSM-5 molecular sieve that be 600, type shape index is 100.
Take the above-mentioned preparation of 20 gram NaZSM-5 molecular sieve, 25 gram silicon sol (SiO
2Weight percentage 40%), add the water kneading, the mould extruded moulding that is 2.0 millimeters with diameter, dry, be placed in 90 ℃ of baking ovens 10 hours, in 550 ℃ of retort furnaces, roasting is 8 hours, remove template, in 80 ℃ of 5% ammonium nitrate solution, exchange is three times, roasting 8 hours in 550 ℃ of retort furnaces after oven dry, the HZSM-5 molecular sieve catalyst that to obtain silica alumina ratio 600, type shape index be 100.
[embodiment 5]
Take tetrapropyl oxyammonia and ammoniacal liquor as template, and sodium aluminate is the aluminium source, and silicon sol is the silicon source, and raw material is SiO in molar ratio
2/ Al
2O
3=300; OH
-/ SiO
2=0.08; R/SiO
2=0.5; H
2O/SiO
2=20 ratio is mixed, and adopts method described in embodiment 1, and 180 ℃ of crystallization 40 hours, obtain silica alumina ratio SiO
2/ Al
2O
3The NaZSM-5 molecular sieve that be 300, type shape index is 60.
Take the above-mentioned preparation of 30 gram NaZSM-5 molecular sieve, 28 gram silicon sol (SiO
2Weight percentage 40%) and 19 gram aluminum oxide, add the water kneading, the mould extruded moulding that is 2.0 millimeters with diameter, dry, be placed in 100 ℃ of baking ovens 10 hours, in 550 ℃ of retort furnaces, roasting is 6 hours, remove template, in 85 ℃ of 10% ammonium chloride solution, exchange is three times, roasting 8 hours in 500 ℃ of retort furnaces after oven dry, the HZSM-5 molecular sieve catalyst that to obtain silica alumina ratio 300, type shape index be 60.
[embodiment 6]
Take ammoniacal liquor as template, and aluminum nitrate is the aluminium source, and tetraethoxy is the silicon source, and raw material is SiO in molar ratio
2/ Al
2O
3=500; OH
-/ SiO
2=0.6; R/SiO
2=1.2; H
2O/SiO
2=30 ratio is mixed, and adopts method described in embodiment 1, and 150 ℃ of crystallization 40 hours, obtain silica alumina ratio SiO
2/ Al
2O
3The NaZSM-5 molecular sieve that be 500, type shape index is 20.
Take NaZSM-5 molecular sieve, the 20 gram silicon sol (SiO of the above-mentioned preparation of 20 gram
2Weight percentage 40%) and 14.8 gram aluminum phosphates, add the water kneading, the mould extruded moulding that is 1.5 millimeters with diameter, dry, be placed in 120 ℃ of baking ovens 8 hours, in 550 ℃ of retort furnaces, roasting is 8 hours, remove template, in 80 ℃ of 10% ammonium nitrate solution, exchange is three times, roasting 4 hours in 600 ℃ of retort furnaces after oven dry, the HZSM-5 molecular sieve catalyst that to obtain silica alumina ratio 500, type shape index be 20.
[embodiment 7]
Take tetrapropyl oxyammonia and etamon chloride as template, and aluminum nitrate aluminium is the aluminium source, and water glass is the silicon source, and raw material is SiO in molar ratio
2/ Al
2O
3=800; OH
-/ SiO
2=1.0; R/SiO
2=1.0; H
2O/SiO
2=50 ratio is mixed, and adopts method described in embodiment 1, and 100 ℃ of crystallization 60 hours, obtain silica alumina ratio SiO
2/ Al
2O
3The NaZSM-5 molecular sieve that be 800, type shape index is 80.
Take NaZSM-5 molecular sieve, the 30 gram silicon sol (SiO of the above-mentioned preparation of 40 gram
2Weight percentage 40%), add the water kneading, the mould extruded moulding that is 2.0 millimeters with diameter, dry, be placed in 90 ℃ of baking ovens 10 hours, in 550 ℃ of retort furnaces, roasting is 8 hours, remove template, in 80 ℃ of 5% ammonium nitrate solution, exchange is three times, roasting 8 hours in 550 ℃ of retort furnaces after oven dry, the HZSM-5 molecular sieve catalyst that to obtain silica alumina ratio 800, type shape index be 80.
[embodiment 8]
The catalyzer of embodiment 7 preparation is adopted to the solution incipient impregnation 24 hours of at least one element in P, La, Ce, Cu, Zn, 80 ~ 100 ℃ of oven dry, then roasting 3 ~ 6 hours in 500 ~ 550 ℃ of retort furnaces, obtain loaded catalyst.
[embodiment 9]
Adopt fixed-bed catalytic reactor, reactor is stainless steel tube, catalyzer to embodiment 7 preparations has carried out the evaluation of preparing propylene by methanol transformation reactive behavior, investigating processing condition used is: catalyzer fills 3 grams, service temperature is 500 ℃, working pressure is 0.02MPa, and the methyl alcohol weight space velocity is 1.0h
-1, water/methyl alcohol weight ratio is 2:1.Appraisal result is as shown in table 1.
Table 1
[embodiment 10～13]
The catalyzer according to embodiment 9 processing condition used prepared by embodiment 1 carries out the evaluation of preparing propylene by methanol transformation reactive behavior, just changes temperature of reaction, and appraisal result is listed in table 2.
[embodiment 14～17]
The catalyzer according to embodiment 9 processing condition used prepared by embodiment 2 carries out the evaluation of preparing propylene by methanol transformation reactive behavior, just changes reaction pressure, and appraisal result is listed in table 2.
[embodiment 18～21]
The catalyzer according to embodiment 9 processing condition used prepared by embodiment 3 carries out the evaluation of preparing propylene by methanol transformation reactive behavior, just changes the weight space velocity of methyl alcohol, and appraisal result is listed in table 2.
[embodiment 22～25]
The catalyzer according to embodiment 9 processing condition used prepared by embodiment 5 carries out the evaluation of preparing propylene by methanol transformation reactive behavior, just changes water/methyl alcohol weight ratio, and appraisal result is listed in table 2.
Table 2
[embodiment 26]
Processing condition according to embodiment 9 have been carried out the activity stability investigation of preparing propylene by methanol transformation reaction to the catalyzer of embodiment 8 preparations, the results are shown in table 3.
[embodiment 27]
Processing condition according to embodiment 9 have been carried out the activity stability investigation of preparing propylene by methanol transformation reaction to the catalyzer of embodiment 7 preparations, the results are shown in table 3.
[comparative example 1]
Take 40 gram silica alumina ratio (SiO
2/ Al
2O
3) be 800 spherical NaZSM-5 molecular sieve, 30 gram silicon sol (SiO
2Weight percentage 40%), add the water kneading, the mould extruded moulding that is 2.0 millimeters with diameter, dry, be placed in 90 ℃ of baking ovens 10 hours, in 550 ℃ of retort furnaces, roasting is 8 hours, remove template, in 80 ℃ of 5% ammonium nitrate solution, exchange is three times, roasting 8 hours in 550 ℃ of retort furnaces after oven dry, the HZSM-5 molecular sieve catalyst that to obtain silica alumina ratio be 800.
The activity stability that adopts the processing condition of embodiment 9 to carry out the preparing propylene by methanol transformation reaction above-mentioned catalyzer is investigated, and the results are shown in table 3.
[comparative example 2]
Take 40 gram silica alumina ratio (SiO
2/ Al
2O
3) be NaZSM-5 molecular sieve 800, that type shape index is 1,30 gram silicon sol (SiO
2Weight percentage 40%), add the water kneading, the mould extruded moulding that is 2.0 millimeters with diameter, dry, be placed in 90 ℃ of baking ovens 10 hours, in 550 ℃ of retort furnaces, roasting is 8 hours, remove template, in 80 ℃ of 5% ammonium nitrate solution, exchange is three times, roasting 8 hours in 550 ℃ of retort furnaces after oven dry, the HZSM-5 molecular sieve catalyst that obtain silica alumina ratio and be 800, type shape index is 1.
The activity stability that adopts the processing condition of embodiment 9 to carry out the preparing propylene by methanol transformation reaction above-mentioned catalyzer is investigated, and the results are shown in table 3.
Table 3
| ? | The molecular sieve silica alumina ratio | Type shape index | Propylene Selectivity (%) | Catalyst stability (h) |
| Embodiment 26 | 800 | 60 | 41.3 | 1350 |
| Embodiment 27 | 500 | 20 | 40.5 | 1200 |
| Comparative example 1 | 800 | / | 40.8 | 800 |
| Comparative example 2 | 500 | / | 38.6 | 750 |
Claims (8)
1. the method for a preparing propylene by methanol transformation, take methanol aqueous solution as raw material, in temperature of reaction, is 400～600 ℃, and reaction pressure is 0.01～5MPa, and the methyl alcohol weight space velocity is 0.5～15 hour
-1, under the condition that the mass ratio of water and methyl alcohol is 0.2～5:1, raw material generates propylene by beds, and wherein catalyzer used, in parts by weight, comprises following component:
A) ZSM-5 that the type shape index of 30～80 parts is 3 ~ 100, the ratio that its medium-sized shape index definition is longest edge and bond length on the molecular sieve crystal three-dimensional;
B) binding agent of 20～70 parts.
2. the method for preparing propylene by methanol transformation according to claim 1, is characterized in that temperature of reaction is 420～550 ℃, and reaction pressure is 0.02～3MPa, and the methyl alcohol weight space velocity is 0.8～10 hour
-1, the mass ratio of water and methyl alcohol is 0.5～2:1.
3. the method for preparing propylene by methanol transformation according to claim 1, is characterized in that take that the consumption of catalyst weight umber ZSM-5 molecular sieve is 40～75 parts.
4. the method for preparing propylene by methanol transformation according to claim 1, is characterized in that the type shape index of ZSM-5 molecular sieve is 3 ~ 80.
5. the method for preparing propylene by methanol transformation according to claim 1, is characterized in that the silica alumina ratio SiO of ZSM-5 molecular sieve
2/ Al
2O
3Be 200～800.
6. the method for preparing propylene by methanol transformation according to claim 4, is characterized in that the type shape index of ZSM-5 molecular sieve is 10 ~ 60.
7. the method for preparing propylene by methanol transformation according to claim 1, is characterized in that binding agent is selected from least one in silicon sol, aluminum oxide and aluminum phosphate.
8. the method for preparing propylene by methanol transformation according to claim 1, is characterized in that in catalyzer also containing at least one element in P, La, Ce, Cu, Zn, and in the catalyst weight umber, its content is 0.1 ~ 5 part.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104107708A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Catalyst for preparing propylene and aromatic hydrocarbons by converting methanol, and preparation method and use thereof |
| CN106608803A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Method for preparing propylene through methanol conversion |
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| CN101239875A (en) * | 2007-02-07 | 2008-08-13 | 中国石油化工股份有限公司 | Method for preparing propylene from methanol |
| CN101279283A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Modified ZSM-5 molecular sieve catalyst for preparing propylene transformed from methanol and preparation thereof |
| CN101462070A (en) * | 2007-12-17 | 2009-06-24 | 亚申科技研发中心（上海）有限公司 | Modified ZSM-5 type molecular sieve catalyst and preparation method thereof |
| US20110098519A1 (en) * | 2007-08-13 | 2011-04-28 | Kanaparthi Ramesh | Modified catalyst composition for conversion of alcohol to alkene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101239875A (en) * | 2007-02-07 | 2008-08-13 | 中国石油化工股份有限公司 | Method for preparing propylene from methanol |
| CN101279283A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Modified ZSM-5 molecular sieve catalyst for preparing propylene transformed from methanol and preparation thereof |
| US20110098519A1 (en) * | 2007-08-13 | 2011-04-28 | Kanaparthi Ramesh | Modified catalyst composition for conversion of alcohol to alkene |
| CN101462070A (en) * | 2007-12-17 | 2009-06-24 | 亚申科技研发中心（上海）有限公司 | Modified ZSM-5 type molecular sieve catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104107708A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Catalyst for preparing propylene and aromatic hydrocarbons by converting methanol, and preparation method and use thereof |
| CN104107708B (en) * | 2013-04-16 | 2017-06-20 | 中国石油化工股份有限公司 | Preparing propylene by methanol transformation and arenes catalytic agent and its production and use |
| CN106608803A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Method for preparing propylene through methanol conversion |
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Application publication date: 20131204 |