CN104399522A - Catalyst for production of low carbon olefin from methanol through iodination method, and preparation method thereof - Google Patents

Catalyst for production of low carbon olefin from methanol through iodination method, and preparation method thereof Download PDF

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Publication number
CN104399522A
CN104399522A CN201410558492.6A CN201410558492A CN104399522A CN 104399522 A CN104399522 A CN 104399522A CN 201410558492 A CN201410558492 A CN 201410558492A CN 104399522 A CN104399522 A CN 104399522A
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China
Prior art keywords
catalyst
methanol
zsm
low carbon
carbon olefin
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CN201410558492.6A
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Chinese (zh)
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刘飞
曹建新
李婷
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Guizhou University
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Guizhou University
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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
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Abstract

The present invention discloses a catalyst for production of a low carbon olefin from methanol through an iodination method, and a preparation method thereof. The preparation method comprises: carrying out mechanical mixing on SAPO-34 and a ZSM-5 molecular sieve according to a mass ratio of ZSM-5:SAPO-34 of 0.1-1.0, completely grinding, tableting, and crushing, wherein a Si/Al molar ratio in the ZSM-5molecular sieve is SiO2/Al2O3 of 45-360. The catalyst of the present invention is used for production of the low carbon olefin from methanol through the iodination method, and has the long service life.

Description

For the Catalysts and its preparation method of iodo method preparing low carbon olefin hydrocarbon with methanol
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of catalyst for iodo method preparing low carbon olefin hydrocarbon with methanol, also relate to this preparation method for the catalyst of iodo method preparing low carbon olefin hydrocarbon with methanol simultaneously.
Background technology
Low-carbon alkene is important basic chemical raw materials, domestic and international market consumption growth space is huge, current most of ethylene yield in the world comes from naphtha steam cracking technology, and production of propylene is mainly produced the byproduct of ethene and oil plant catalytic cracking with steam cracking and obtains.Because world oil reserves are limited, traditional production low-carbon alkene method can not be met the need of market, and countries in the world all start the exploitation being devoted to Non oil-based route preparing ethylene and propylene class alkene.
Iodo method preparing low carbon olefinic hydrocarbon with methanol (IMTO) is that the low-carbon alkene developed in recent years produces variation route, the method with the mixed solution of methyl alcohol and hydroiodic acid for raw material, under the effect of ZSM-5 and modified zsm-5 zeolite dual catalyst, first there is nucleophilic substitution, generate iodomethane, then there is elimination reaction, slough hydrogen iodide and generate low-carbon alkene product.But there is the easy carbon distribution inactivation of reacting middle catalyst in the method, the problem that the life-span is short.
Summary of the invention
The object of the present invention is to provide a kind of catalyst for iodo method preparing low carbon olefin hydrocarbon with methanol of long service life.
Another object of the present invention is to the preparation method of the catalyst providing this for iodo method preparing low carbon olefin hydrocarbon with methanol.
For a catalyst for iodo method preparing low carbon olefin hydrocarbon with methanol, obtained by the raw material of following mass ratio: ZSM-5:SAPO-34=0.1-1.0.
The above-mentioned catalyst for iodo method preparing low carbon olefin hydrocarbon with methanol, wherein: the silica alumina ratio of ZSM-5 molecular sieve is SiO 2: Al 2o 3=45-360.
A kind of preparation method of the catalyst for iodo method preparing low carbon olefin hydrocarbon with methanol, comprise: SAPO-34 and ZSM-5 molecular sieve are carried out mechanical mixture, its mass ratio is ZSM-5:SAPO-34=0.1-1.0, compressing tablet after abundant grinding, pulverize and get final product, wherein: the silica alumina ratio of ZSM-5 molecular sieve is SiO 2: Al 2o 3=45-360.
The present invention compared with prior art, has obvious beneficial effect, as can be known from the above technical solutions: the present invention selects ZSM-5/SAPO-34 composite molecular screen as the catalyst of IMTO method, has effectively delayed catalyst carbon deposition coking time.Low-carbon alkene (ethene+propylene) is selective when reaching 85.4%, 1h catalyzer coke content is 13.7%, with be used alone compared with ZSM-5 molecular sieve catalyst (1h coke content is 27.8%), 1h catalyzer coke content reduces 14.1%, with be used alone compared with SAPO-34 molecular sieve catalyst (1h coke content is 21.5%), 1h catalyzer coke content reduces 7.8%, and it effectively extends catalyst service life as can be seen here.
Detailed description of the invention
embodiment 1-5
For a preparation method for the catalyst of iodo method preparing low carbon olefin hydrocarbon with methanol, comprising: be n (SiO by SAPO-34 and mass ratio 2): n (Al 2o 3the ZSM-5 molecular sieve of)=45-360 carries out mechanical mixture, and its mass ratio is that m (ZSM-5): m (SAPO-34)=0.1-1.0(is specifically in table 1), fully grind rear compressing tablet, pulverize and get final product.
application examples
By above-described embodiment gained catalyst application in iodide process methanol-to-olefins, adopt fixed bed reactors, by ground for ZSM-5/SAPO-34 composite molecular sieve catalyst 20-40 mesh sieve, be filled into reaction tube.Open temperature controller, reaction tube mean temperature is 250 DEG C, passes into nitrogen as carrier gas, and flow velocity is 40mlmin -1.Design temperature to be warmed up to, raw material enters reaction tube by feed pump, and pulp furnish is CH 3oH:HI:H 2o=1:1:1, Feed space velocities is 2.0h -1.After reaction certain hour, product is through gas-liquid separator separates, and hydroiodic acid condensation is recycled, and gas-phase product enters gas chromatograph and carries out on-line analysis.Mass ratio m (the ZSM-5)/m (SAPO-34) of ZSM-5/SAPO-34 composite molecular screen used and experimental result are shown in Table 1.
Table 1
Parameter m(ZSM-5)/m(SAPO-34) Selectivity of light olefin 1h carbon deposition quantity of catalyst
Embodiment 1 0.2 58.2% 12.1%
Embodiment 2 0.3 72.7% 12.9%
Embodiment 3 0.5 77.4% 14.5%
Embodiment 4 0.7 68.5% 15.9%
Embodiment 5 0.8 32.8% 17.1%
According to condition described in embodiment 3, just feed change proportioning, experimental result is shown in Table 2.
Table 2
Pulp furnish (CH 3OH:HI:H 2O） Selectivity of light olefin 1h carbon deposition quantity of catalyst
0.5:1:1 75.8% 14.8%
1:0.5:1 68.9% 13.6%
1:1:2 82.6% 13.9%
3:1:5 70.1% 13.5%
2:5:10 65.3% 15.5%
According to condition described in embodiment 2, pulp furnish is 1:1:2, and change Feed space velocities, experimental result is shown in Table 3.
Table 3
Feed space velocities (h -1） Selectivity of light olefin 1h carbon deposition quantity of catalyst
0.5 77.2% 7.3%
1.0 80.6% 11.4%
1.5 85.4% 13.7%
2.5 74.8% 17.5%
The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, anyly do not depart from technical solution of the present invention content, the any simple modification done above embodiment according to technical spirit of the present invention, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.

Claims (4)

1., for a catalyst for iodo method preparing low carbon olefin hydrocarbon with methanol, obtained by the raw material of following mass ratio: ZSM-5:SAPO-34=0.1-1.0.
2. as claimed in claim 1 for the catalyst of iodo method preparing low carbon olefin hydrocarbon with methanol, wherein: the silica alumina ratio of ZSM-5 molecular sieve is SiO 2: Al 2o 3=45-360.
3. the preparation method of a kind of catalyst for iodo method preparing low carbon olefin hydrocarbon with methanol as claimed in claim 1 or 2, comprise: SAPO-34 and ZSM-5 molecular sieve are carried out mechanical mixture, its mass ratio is ZSM-5:SAPO-34=0.1-1.0, fully grinds rear compressing tablet, pulverizes and get final product.
4. the preparation method of a kind of catalyst for iodo method preparing low carbon olefin hydrocarbon with methanol as claimed in claim 3, wherein: the silica alumina ratio of ZSM-5 molecular sieve is SiO 2: Al 2o 3=45-360.
CN201410558492.6A 2014-10-21 2014-10-21 Catalyst for production of low carbon olefin from methanol through iodination method, and preparation method thereof Pending CN104399522A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104923294A (en) * 2015-04-29 2015-09-23 天津众智科技有限公司 Composite molecular sieve for MTO (Methanol to Olefins) and preparation method therefor and application thereof
CN105688981A (en) * 2016-04-13 2016-06-22 贵州大学 Preparation method of modified SAPO-34 molecular sieve catalyst
CN105772063A (en) * 2016-04-13 2016-07-20 贵州大学 Modified ZSM-5 molecular sieve based catalyst and preparing method thereof
CN105772065A (en) * 2016-04-13 2016-07-20 贵州大学 Modified ZSM-5 molecular sieve based catalyst and preparing method thereof
CN105854931A (en) * 2016-04-13 2016-08-17 贵州大学 Preparation method of modified SAPO-34 molecular sieve catalyst
CN111454179A (en) * 2020-05-08 2020-07-28 河南金鹏化工有限公司 Device and continuous process for producing methyl isocyanate by using dimethyl sulfate

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CN101165018A (en) * 2006-10-20 2008-04-23 中国石油化工股份有限公司 Method for producing ethylene and propylene
CN101417911A (en) * 2007-10-26 2009-04-29 中国石油化工股份有限公司 Method for preparing light olefins from methanol using hydrocarbons as part material

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US20040105787A1 (en) * 1997-07-03 2004-06-03 Lattner James Richardson Process for converting oxygenates to olefins using molecular sieve catalysts comprising desirable carbonaceous deposits
CN101165018A (en) * 2006-10-20 2008-04-23 中国石油化工股份有限公司 Method for producing ethylene and propylene
CN101417911A (en) * 2007-10-26 2009-04-29 中国石油化工股份有限公司 Method for preparing light olefins from methanol using hydrocarbons as part material

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104923294A (en) * 2015-04-29 2015-09-23 天津众智科技有限公司 Composite molecular sieve for MTO (Methanol to Olefins) and preparation method therefor and application thereof
CN104923294B (en) * 2015-04-29 2020-04-10 天津众智科技有限公司 Composite molecular sieve for preparing olefin from methanol, preparation method and application
CN105688981A (en) * 2016-04-13 2016-06-22 贵州大学 Preparation method of modified SAPO-34 molecular sieve catalyst
CN105772063A (en) * 2016-04-13 2016-07-20 贵州大学 Modified ZSM-5 molecular sieve based catalyst and preparing method thereof
CN105772065A (en) * 2016-04-13 2016-07-20 贵州大学 Modified ZSM-5 molecular sieve based catalyst and preparing method thereof
CN105854931A (en) * 2016-04-13 2016-08-17 贵州大学 Preparation method of modified SAPO-34 molecular sieve catalyst
CN105772065B (en) * 2016-04-13 2018-01-30 贵州大学 A kind of molecular sieve catalyst of modified ZSM-5 5 and preparation method thereof
CN105772063B (en) * 2016-04-13 2018-01-30 贵州大学 A kind of molecular sieve catalyst of modified ZSM-5 5 and preparation method thereof
CN105854931B (en) * 2016-04-13 2018-01-30 贵州大学 A kind of preparation method of the molecular sieve catalysts of modified SAPO 34
CN105688981B (en) * 2016-04-13 2018-02-09 贵州大学 A kind of preparation method of the molecular sieve catalysts of modified SAPO 34
CN111454179A (en) * 2020-05-08 2020-07-28 河南金鹏化工有限公司 Device and continuous process for producing methyl isocyanate by using dimethyl sulfate
CN111454179B (en) * 2020-05-08 2023-10-20 河南金鹏化工有限公司 Device and continuous process for producing methyl isocyanate from dimethyl sulfate

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Application publication date: 20150311