CN102040448A - Method for preparing propylene by catalyzing methanol/dimethyl ether with composite molecular sieve with core-shell structure - Google Patents
Method for preparing propylene by catalyzing methanol/dimethyl ether with composite molecular sieve with core-shell structure Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical industry, in particular to a method for preparing propylene by catalyzing methanol/dimethyl ether with a composite molecular sieve with a core-shell structure. In the invention, a composite molecular sieve catalyst consisting of an HZSM-5 molecular sieve and a mesoporous molecular sieve is adopted, methanol or/and dimethyl ether is/are used as raw material gas, water vapor and/or nitrogen are/is used as diluent gas to carry out a contact reaction to prepare propylene. The composite molecular sieve with the core-shell structure has the advantages that good propylene selectivity can be obtained, and better activity stability can be realized.
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, be specifically related to the method for core-shell structure compound molecular sieve catalysis methanol/dme system propylene.
Background technology
Propylene is one of petroleum chemicals of consumption maximum in the world, and keeps the annual growth of 5-6%.The traditional production method of propylene is by steam reforming technology and oil catalytic pyrolysis, but along with the shortage of petroleum resources, the propylene supply and demand is nervous year by year.Breach at market supply, whole world petro-chemical corporation exploitation multiple technologies are attempted the vacancy of the demand of filling up, and wherein methyl alcohol alkene is combined to propylene (MTP) technology and can utilizes abundant coal and natural gas source, perhaps other approach clean, environmental protection obtain material benzenemethanol, therefore are subjected to domestic and international common concern.
Since the eighties in 20th century, U.S. Mobil oil company etc. has just carried out the research of methyl alcohol synthesizing low-carbon alkene.The MTO technology of developing jointly with American UOP company and Norway Norsk Hydro company is a series of technology of representative, as US 6534692, US 4079095, US 5191141, US 5714662, US 5744680 etc., adopt the SAPO-34 molecular sieve catalyst, ethylene selectivity is higher, but productivity of propylene is lower, P/E than (propylene and ethene mass ratio) between 1.5-0.6.And German Lurgi company uses the MTP technology of Si-Al molecular sieve catalyzer (EP 0448000) exploitation of German Sud Chemie Cd of company and Zn modification, adopts three sections circulating reactions, has reached propylene selectivity preferably by the engineering approach.And in recent years, the Chinese patent application relevant with catalyst for producing propylene with methanol is a lot of, as CN200710037239.6, CN200710037240.9, CN200710039073.1, CN200710202215.1 etc., these patents mainly all are to introduce other element or adopt acid or steam-treated that the HZSM-5 catalyzer is carried out modification by methods such as dipping, ion-exchanges, be used for the preparing propylene from methanol reaction, the propylene selectivity remains further to be improved, influenced by the micropore catalyst structure, easily the carbon distribution inactivation.
The nucleocapsid structure molecular sieve is the class novel molecular sieve material that new development is in recent years got up.This type of material mainly is to adopt specific molecule sieve synthetic technology, does not use binding agent, by different synthetic methods different structure, different tart molecular sieve is combined.Having the intercommunication duct between molecular sieve, have chemical b `, is a kind of novel material of performance complement, can suitably strengthen the synergy between the different properties molecular sieve, improves the efficient and the quality product of catalyzer.And the introducing of multistage pore canal under the prerequisite that keeps acidic zeolite and hydrothermal stability, can make catalyzer have good shape selectivity energy and mass transfer ability.According to the mechanism of preparing propylene from methanol (MTP) reaction, utilize nucleocapsid structure molecular sieve structure characteristics, can obtain good propylene selectivity and superior activity stability.Use HZSM-5 and mesopore molecular sieve nucleocapsid composite structure molecular sieve catalyst to carry out not appearing in the newspapers as yet of preparing propylene from methanol reaction.
Summary of the invention
The object of the present invention is to provide a kind of method with core-shell structure compound molecular sieve catalysis methanol/dme system propylene.
The present invention proposes method, be with the composite molecular sieve catalyst of the nucleocapsid structure fixed-bed reactor constant temperature zone of packing into, with in methyl alcohol, the dme one or both is unstripped gas, with in water vapour, the nitrogen one or both is carrier gas, contact reacts, generation contains the propylene effluent, through separate propylene.
Core-shell structure compound molecular sieve of the present invention, its kernel are the HZSM-5 molecular sieve, and the sial atomic molar is than being 20:1-300:1, and particle diameter 50-1000 nm, its shell are mesopore molecular sieve (including but not limited to SBA-15, MCM-41), thickness 50-500 nm.The preparation process of core-shell structure compound molecular sieve is as follows: the HZSM-5 sieve particle of suitable particle diameter is scattered in the water, add an amount of mesoporous template direction agent CTAB or P123 according to required shell, use the potential of hydrogen of NaOH or HCl allotment solution, stir under the room temperature, drip silicon source (as TEOS) according to shell thickness, stir 2-3 h, filter then, wash, drying, 500 ℃--600 ℃ of roasting 5 h-7h obtain required composite molecular screen after the removal template.
The mol ratio of unstripped gas methyl alcohol of the present invention and carrier gas is 10:1-1:10, and the mol ratio of described unstripped gas dme and carrier gas is 5:1-1:20.
Method with core-shell structure compound molecular sieve catalysis methanol/dme system third of the present invention, wherein temperature of reaction is 380-500 ℃, and reaction pressure is 0.1-1.0 MPa, and liquid hourly space velocity is 0.1-10 h
-1
Adopt the core-shell structure compound molecular sieve catalyzer, methanol conversion reaches as high as 100%, and the propylene selectivity is near 55%, and P/E can reach 15 than (propylene and ethene mass ratio), and still has excellent activity after reacting 300 h.Compare with common ZSM-5 catalyzer, have propylene selectivity and P/E than advantage higher and that catalyst activity stable, the life-span is long.
Embodiment
Embodiment 1, the preparing propylene from methanol reaction:
Selecting for use with silica alumina ratio is that 140 HZSM-5 molecular sieve is that nuclear, SBA-15 molecular sieve are that the nucleocapsid structure molecular sieve of shell (HZSM-5 particle diameter 400 nm, SBA-15 shell thickness 200 nm) is a catalyzer, after process compression molding and granulation are the 40-60 order, the internal diameter of packing into is the fixed-bed reactor of 6mm, catalyzer top and the bottom filling quartz sand, with nitrogen catalyzer is heated to about 460 ℃, pre-treatment 5 h feed methyl alcohol and water vapor mixing raw material gas then, and liquid hourly space velocity is 2 h
-1, methyl alcohol and water vapour mol ratio are 1:3, reaction pressure 0.1 MPa.Methanol conversion 100%, the propylene selectivity reaches 54.1%, and the P/E ratio reaches 15.0.
Embodiment 2, the preparing propylene from methanol reaction:
Selecting for use with silica alumina ratio is that 140 HZSM-5 molecular sieve is that nuclear, SBA-15 molecular sieve are that the nucleocapsid structure molecular sieve of shell (HZSM-5 particle diameter 400 nm, SBA-15 shell thickness 200 nm) is a catalyzer, after process compression molding and granulation are the 40-60 order, the internal diameter of packing into is the fixed-bed reactor of 6mm, catalyzer top and the bottom filling quartz sand, with nitrogen catalyzer is heated to about 400 ℃, pre-treatment 5 h feed methyl alcohol and nitrogen mixing raw material gas then, and liquid hourly space velocity is 1 h
-1, methyl alcohol and nitrogen mol ratio are 5:1, reaction pressure 0.1 MPa.Transformation efficiency 97.6%, the propylene selectivity reaches 41.9%, and P/E is than 7.6.
Embodiment 3, the preparing propylene from methanol reaction:
Selecting for use with silica alumina ratio is that 280 HZSM-5 molecular sieve is that nuclear, SBA-15 molecular sieve are that the nucleocapsid structure molecular sieve of shell (HZSM-5 particle diameter 800 nm, SBA-15 shell thickness 300 nm) is a catalyzer, after process compression molding and granulation are the 40-60 order, the internal diameter of packing into is the fixed-bed reactor of 6mm, catalyzer top and the bottom filling quartz sand, with nitrogen catalyzer is heated to about 460 ℃, pre-treatment 5 h feed methyl alcohol and water vapor mixing raw material gas then, and liquid hourly space velocity is 0.1 h
-1, methyl alcohol and water vapour mol ratio are 1:10, reaction pressure 0.1 MPa.Transformation efficiency 97.7%, the propylene selectivity reaches 48.0%, and P/E is than 14.2.
Embodiment 4, the preparing propylene from methanol reaction:
Selecting for use with silica alumina ratio is that 110 HZSM-5 molecular sieve is that nuclear, SBA-15 molecular sieve are that the nucleocapsid structure molecular sieve of shell (HZSM-5 particle diameter 80 nm, SBA-15 shell thickness 100 nm) is a catalyzer, after process compression molding and granulation are the 40-60 order, the internal diameter of packing into is the fixed-bed reactor of 6mm, catalyzer top and the bottom filling quartz sand, with nitrogen catalyzer is heated to about 500 ℃, pre-treatment 5 h feed methyl alcohol and water vapor mixing raw material gas then, and liquid hourly space velocity is 10 h
-1, methyl alcohol and water vapour mol ratio are 1:5, reaction pressure 0.8 MPa.Transformation efficiency 99.1%, the propylene selectivity reaches 51.6%, and P/E is than 14.8.
Embodiment 5, the preparing propylene from methanol reaction:
Selecting for use with silica alumina ratio is that 20 HZSM-5 molecular sieve is that nuclear, MCM-41 molecular sieve are that the nucleocapsid structure molecular sieve of shell (HZSM-5 particle diameter 1000 nm, MCM-41 shell thickness 500 nm) is a catalyzer, after process compression molding and granulation are the 40-60 order, the internal diameter of packing into is the fixed-bed reactor of 6mm, catalyzer top and the bottom filling quartz sand, with nitrogen catalyzer is heated to about 460 ℃, pre-treatment 5 h feed methyl alcohol and water vapor mixing raw material gas then, and liquid hourly space velocity is 4 h
-1, methyl alcohol and water vapour mol ratio are 1:3, reaction pressure 0.3 MPa.Transformation efficiency 97.1%, the propylene selectivity reaches 47.3%, and P/E is than 11.2.
Embodiment 6, the reaction of dme system propylene:
Selecting for use with silica alumina ratio is that 140 HZSM-5 molecular sieve is that nuclear, SBA-15 molecular sieve are that the nucleocapsid structure molecular sieve of shell (HZSM-5 particle diameter 400 nm, SBA-15 shell thickness 200 nm) is a catalyzer, after process compression molding and granulation are the 40-60 order, the internal diameter of packing into is the fixed-bed reactor of 6mm, catalyzer top and the bottom filling quartz sand, with nitrogen catalyzer is heated to about 460 ℃, pre-treatment 5 h feed dme and nitrogen mixing raw material gas then, and liquid hourly space velocity is 0.6 h
-1, dme and nitrogen mol ratio are 2:1, reaction pressure 0.1 MPa.Dimethyl ether conversion rate 99.3%, the propylene selectivity reaches 43.1%, and P/E is than 7.6.
Embodiment 7, methyl alcohol/dme system propylene reaction:
Selecting for use with silica alumina ratio is that 140 HZSM-5 molecular sieve is that nuclear, MCM-41 molecular sieve are that the nucleocapsid structure molecular sieve of shell (HZSM-5 particle diameter 400 nm, MCM-41 shell thickness 100 nm) is a catalyzer, after process compression molding and granulation are the 40-60 order, the internal diameter of packing into is the fixed-bed reactor of 6mm, catalyzer top and the bottom filling quartz sand, with nitrogen catalyzer is heated to about 460 ℃, pre-treatment 5 h feed methyl alcohol, dme and water vapor mixing raw material gas then, and liquid hourly space velocity is 2 h
-1, methyl alcohol, dme and water vapour mol ratio are 1:1:1, reaction pressure 0.5 MPa.Methyl alcohol/dimethyl ether conversion rate 98.3%, the propylene selectivity reaches 46.5%, and P/E is than 13.1.
Embodiment 7, the catalyst life test
Adopt the method for embodiment 1 to react the investigation catalyst stability for a long time, behind 300 h, methanol conversion 93.3%, the propylene selectivity reaches 48.6%, and P/E still can keep very high catalytic activity and propylene selectivity than 15.2.
Claims (6)
1. method with core-shell structure compound molecular sieve catalysis methanol/dme system propylene, it is characterized in that concrete steps are as follows: with the composite molecular sieve catalyst of the nucleocapsid structure fixed-bed reactor constant temperature zone of packing into, with in methyl alcohol, the dme one or both is unstripped gas, with in water vapour, the nitrogen one or both is carrier gas, contact reacts, generation contains the propylene effluent, through separate propylene.
2. method according to claim 1 is characterized in that described core-shell structure compound molecular sieve, and its kernel is the HZSM-5 molecular sieve, and the sial atomic molar is than being 20:1-300:1, particle diameter 50-1000 nm; Its shell is a mesopore molecular sieve, thickness 50-500 nm.
3. method according to claim 2 is characterized in that described mesopore molecular sieve is SBA-15 or MCM-41.
4. method according to claim 1 and 2, the mol ratio that it is characterized in that described unstripped gas methyl alcohol and carrier gas is 10:1-1:10, the mol ratio of described unstripped gas dme and carrier gas is 5:1-1:20.
5. method according to claim 1 and 2 is characterized in that control reaction temperature is 380-500 ℃, and reaction pressure is 0.1-1.0 MPa, and liquid hourly space velocity is 0.1-10 h
-1
6. method according to claim 4 is characterized in that control reaction temperature is 380-500 ℃, and reaction pressure is 0.1-1.0 MPa, and liquid hourly space velocity is 0.1-10 h
-1
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104056652A (en) * | 2013-03-22 | 2014-09-24 | 中国石油化工股份有限公司 | Core-shell ZSM-5 molecular sieve microsphere catalyst |
| CN104056655A (en) * | 2013-03-22 | 2014-09-24 | 中国石油化工股份有限公司 | Core-shell microsphere catalyst |
| CN106040294A (en) * | 2016-06-16 | 2016-10-26 | 中国华能集团公司 | Preparation method of SBA-15/SAPO-34 core-shell structural molecular sieve for methanol-to-ethanol reaction |
| CN106111182A (en) * | 2016-06-16 | 2016-11-16 | 中国华能集团公司 | A kind of method using microwave heating method to prepare MCM 41/SAPO 34 nucleocapsid structure molecular sieve |
| CN106391106A (en) * | 2016-09-12 | 2017-02-15 | 中国华能集团公司 | Preparation method of metal-containing core-shell structure molecular sieve |
| CN107999123A (en) * | 2016-10-27 | 2018-05-08 | 中国科学院大连化学物理研究所 | Methanol or/and dimethyl ether produce higher olefins catalyst and preparation method and application |
| CN110416525A (en) * | 2019-08-08 | 2019-11-05 | 上海华谊（集团）公司 | The composite material and preparation method of phosphoric acid manganese iron lithium with core-shell structure |
| CN110773226A (en) * | 2019-10-29 | 2020-02-11 | 中国华能集团有限公司 | Method for catalyzing fusel oil conversion by using core-shell structure molecular sieve catalyst |
| CN111420632A (en) * | 2020-03-30 | 2020-07-17 | 中国石油大学(北京) | Composite molecular sieve, desulfurization adsorbent, preparation method and application thereof |
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| JPS5916833A (en) * | 1983-03-16 | 1984-01-28 | Agency Of Ind Science & Technol | Preparation of lower olefin |
| CN101711992A (en) * | 2008-09-29 | 2010-05-26 | 宁夏大学 | Catalyst for selectively producing propene by methanol or dimethyl ether and preparation method thereof |
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2010
- 2010-12-01 CN CN201010566882XA patent/CN102040448B/en not_active Expired - Fee Related
Patent Citations (2)
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| JPS5916833A (en) * | 1983-03-16 | 1984-01-28 | Agency Of Ind Science & Technol | Preparation of lower olefin |
| CN101711992A (en) * | 2008-09-29 | 2010-05-26 | 宁夏大学 | Catalyst for selectively producing propene by methanol or dimethyl ether and preparation method thereof |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104056655A (en) * | 2013-03-22 | 2014-09-24 | 中国石油化工股份有限公司 | Core-shell microsphere catalyst |
| CN104056652B (en) * | 2013-03-22 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of hud typed ZSM-5 molecular sieve pellet catalyst |
| CN104056655B (en) * | 2013-03-22 | 2016-07-06 | 中国石油化工股份有限公司 | A kind of hud typed pellet catalyst |
| CN104056652A (en) * | 2013-03-22 | 2014-09-24 | 中国石油化工股份有限公司 | Core-shell ZSM-5 molecular sieve microsphere catalyst |
| CN106040294B (en) * | 2016-06-16 | 2018-11-09 | 中国华能集团公司 | A kind of preparation method of SBA-15/SAPO-34 nucleocapsid molecular sieves for methanol to propylene reaction |
| CN106040294A (en) * | 2016-06-16 | 2016-10-26 | 中国华能集团公司 | Preparation method of SBA-15/SAPO-34 core-shell structural molecular sieve for methanol-to-ethanol reaction |
| CN106111182A (en) * | 2016-06-16 | 2016-11-16 | 中国华能集团公司 | A kind of method using microwave heating method to prepare MCM 41/SAPO 34 nucleocapsid structure molecular sieve |
| CN106111182B (en) * | 2016-06-16 | 2018-11-30 | 中国华能集团公司 | A method of MCM-41/SAPO-34 core-shell structure molecular sieve is prepared using microwave heating method |
| CN106391106A (en) * | 2016-09-12 | 2017-02-15 | 中国华能集团公司 | Preparation method of metal-containing core-shell structure molecular sieve |
| CN106391106B (en) * | 2016-09-12 | 2018-11-30 | 中国华能集团公司 | A kind of preparation method of the core-shell structure molecular sieve containing metal |
| CN107999123A (en) * | 2016-10-27 | 2018-05-08 | 中国科学院大连化学物理研究所 | Methanol or/and dimethyl ether produce higher olefins catalyst and preparation method and application |
| CN110416525A (en) * | 2019-08-08 | 2019-11-05 | 上海华谊（集团）公司 | The composite material and preparation method of phosphoric acid manganese iron lithium with core-shell structure |
| CN110773226A (en) * | 2019-10-29 | 2020-02-11 | 中国华能集团有限公司 | Method for catalyzing fusel oil conversion by using core-shell structure molecular sieve catalyst |
| CN111420632A (en) * | 2020-03-30 | 2020-07-17 | 中国石油大学(北京) | Composite molecular sieve, desulfurization adsorbent, preparation method and application thereof |
| CN111420632B (en) * | 2020-03-30 | 2021-06-25 | 中国石油大学(北京) | Composite molecular sieve, desulfurization adsorbent, preparation method and application thereof |
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