CN101433858A - HZSM-5 molecular sieve catalyst for producing propylene from methanol/dimethyl ether, preparation method and application - Google Patents
HZSM-5 molecular sieve catalyst for producing propylene from methanol/dimethyl ether, preparation method and application Download PDFInfo
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- CN101433858A CN101433858A CNA2008102072598A CN200810207259A CN101433858A CN 101433858 A CN101433858 A CN 101433858A CN A2008102072598 A CNA2008102072598 A CN A2008102072598A CN 200810207259 A CN200810207259 A CN 200810207259A CN 101433858 A CN101433858 A CN 101433858A
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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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- 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 chemistry and chemical engineering, and in particular relates to a catalyst for preparing an HZSM-5 molecular sieve of propylene by using methanol/ dimethyl ether, a preparation method and application. The catalyst adopts an impregnation method, the HZSM-5 catalyst is modified by a tungsten element, and weight percentage of W is 0.005 to 10 percent. The reaction temperature is controlled at between 300 and 600 DEG C, the pressure is 0 to 1.0MPa, the liquid hourly space velocity is 0.1 to 10 h<-1>, the methanol or the dimethyl ether is used as raw material gas, water vapor or nitrogen gas is used as diluent gas, and the gases are subjected to methanol-alkene reaction. The catalyst has the advantages that high propylene and ethylene ratio can be obtained when the catalyst keeps high activity.
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, be specifically related to a kind of HZSM-5 molecular sieve catalyst, preparation method and application that is used for methyl alcohol/dimethyl ether system propylene.
Background technology
Propylene (propene) is as the important source material of modern chemical industry industry, by a large amount of multiple polypropylene plastics of preparation, acrylonitrile, propylene oxide and other commercial chemicals used.The traditional production method of propylene is by steam reforming technology and oil catalytic pyrolysis.Propylene all produces as the byproduct of ethene without exception, and depends on petroleum resources strongly.Along with the propylene consumption increases exhaustion with petroleum resources day by day, utilize abundant coal and natural gas resource, perhaps other approach clean, environmental protection make methyl alcohol, prepare propylene through methyl alcohol and are subjected to domestic and international common concern.
In United States Patent (USP) U.S.4440871, U.S. carbon compound company (UCC) has developed serial novel molecular sieve SAPO-n, utilizes this molecular sieve to obtain higher yield of ethene as the catalyst of methanol to olefins reaction, but P/E ratio very low (U.S.5817906).Similar report by methanol-to-olefins (MTO) technology has United States Patent (USP) U.S.6534692B1, U.S.2002/0147376A1 and U.S.4079095.But obtain propylene by methanol-to-olefins technology and have the higher and unfavorable problem of propylene selectivity of ethylene selectivity.
Preparing propylene from methanol (MTP) relevant report has Chinese patent CN200710037239.6, CN200710037240.9, CN200710039073.1, CN200710202215.1.In addition, strange (Lurgi) company in German Shandong catalyst of also having developed Cd and Zn modification is used for preparing propylene from methanol technology.There is not report to relate to the element modified HZSM-5 catalyst of W so far as yet.
At present preparing propylene from methanol (MTP, it is more that Methanol-to-Propene) still there is accessory substance in technology, has the higher and unfavorable problem of propylene selectivity of ethylene selectivity to a certain extent, P/E ratio is not high.Improve the propylene selectivity, improve P/E ratio in the product, reducing the accessory substance generation is the key problem of catalyst development.
Summary of the invention
The purpose of this invention is to provide a kind of HZSM-5 molecular sieve catalyst, preparation method and application that is used for methyl alcohol/dimethyl ether system propylene.
The HZSM-5 molecular sieve catalyst that is used for methyl alcohol/dimethyl ether system propylene that the present invention proposes, described catalyst is the HZSM-5 molecular sieve of modifying with the W element, wherein the shared mass percent of W element is 0.005-10%, the W element adopts the soluble-salt of W, and the sial atomic molar of described HZSM-5 molecular sieve is than being 10:1-300:1.
Among the present invention, the mass percent of W element is 0.01-8% in the described catalyst.
The preparation method of the HZSM-5 molecular sieve catalyst that is used for methyl alcohol/dimethyl ether system propylene that the present invention proposes, concrete steps are as follows:
With the soluble-salt of W behind dilute with water under the 10-70 ℃ of temperature, gained solution is poured in the container that the HZSM-5 molecular sieve is housed, the HZSM-5 quality is that 0.005-10% calculates according to the shared mass percent of W element, dipping 2-36h, filter the back and dry 2-5h down at 90-120 ℃, at 400-600 ℃ of following roasting 3-10h, moulding promptly gets required product then.
Among the present invention, the soluble-salt of described W is nitrate or the ammonium salt of W.
The application of HZSM-5 molecular sieve catalyst in methyl alcohol/dimethyl ether system propylene that the present invention proposes, concrete steps are as follows: with the described catalyst fixed bed reactors constant temperature zone of packing into, the beds ratio of height to diameter is 5:1-10:1, with in methyl alcohol, the dimethyl ether one or both is unstripped gas, in steam, the nitrogen one or both are carrier gas, the control reaction temperature is 300-600 ℃, and reaction pressure is 0-1.0MPa, and liquid hourly space velocity (LHSV) is 0.1-10h
-1
Among the present invention, the mol ratio of described unstripped gas methyl alcohol and carrier gas is 10:1-1:10.
Among the present invention, the mol ratio of described unstripped gas dimethyl ether and carrier gas is 5:1-1:20.
It is catalyst Precursors that the present invention adopts the HZSM-5 molecular sieve, and preparation technology is simple, and methanol conversion reaches as high as 100%, the propylene selectivity is greater than 55%, P/E (propylene and ethene mass ratio) reaches as high as 15, and ethene, propylene, butylene total amount can reach 80%, and arenes selectivity is lower than 2%.This catalyst is compared with unmodified ZSM-5 catalyst, has the high advantage of propylene selectivity.
The specific embodiment
The invention is further illustrated by the following examples, but do not limit content of the present invention.
Embodiment 1, Preparation of catalysts:
Selecting silica alumina ratio for use is that 100 HZSM-5 molecular sieve is put into beaker as base catalyst, is presoma with the ammonium tungstate, is 3% W (in element) by the dipping method load percentage of improving quality.Maceration extract at room temperature leaves standstill 24h, 120 ℃ of following oven dry 5h, then in air atmosphere in 500 ℃ of roasting 4h, be the 40-60 order through compression molding and granulation after, promptly get catalyst for producing propylene with methanol.
Embodiment 2, Preparation of catalysts:
Selecting silica alumina ratio for use is that 170 HZSM-5 molecular sieve is put into beaker as base catalyst, is presoma with the ammonium tungstate, is 1% W (in element) by the dipping method load percentage of improving quality.Maceration extract at room temperature leaves standstill 15h, 100 ℃ of following oven dry 2h, then in air atmosphere in 500 ℃ of roasting 5h, be the 40-60 order through compression molding and granulation after, promptly get catalyst for producing propylene with methanol.
Embodiment 3, Preparation of catalysts:
Selecting silica alumina ratio for use is that 220 HZSM-5 molecular sieve is as base catalyst, take the method for embodiment 1, the load W (in element) of percentage 1.5% that improves quality on the HZSM-5 molecular sieve, 10h is placed in the dipping back under room temperature, dry 5h down for 90 ℃, then in air atmosphere in 520 ℃ of roasting 3h, be the 40-60 order through compression molding and granulation after, promptly get catalyst for producing propylene with methanol.
Embodiment 4, the preparing propylene from methanol reaction:
The catalyst that embodiment 1 the is made internal diameter of packing into is 8mm, highly is the stainless steel fixed bed reactors of 60mm, catalyst top and the bottom filling quartz sand, and the beds ratio of height to diameter is 5:1.With nitrogen catalyst is heated to about 500 ℃, keeps the 5h preliminary treatment, switch to steam then, and feed methyl alcohol under normal pressure, liquid hourly space velocity (LHSV) is 2h
-1, methyl alcohol and steam mol ratio are 1:5.Conversion ratio 100%, the propylene selectivity reaches 37.01%, and the P/E ratio reaches 7.2.Other data see Table-1.
Embodiment 5, the preparing propylene from methanol reaction:
The catalyst that embodiment 2 the is made internal diameter of packing into is 8mm, highly is the stainless steel fixed bed reactors of 60mm, catalyst top and the bottom filling quartz sand, and the beds ratio of height to diameter is 8:1.With nitrogen catalyst is heated to about 430 ℃, keeps the 2h preliminary treatment, switch to steam then, and feed methyl alcohol down at 0.02MPa (gauge pressure), liquid hourly space velocity (LHSV) is 0.9h
-1, methyl alcohol and steam mol ratio are 1:6.Conversion ratio 100%, the propylene selectivity reaches 55.37%, and the P/E ratio reaches 15.18.Other data see Table-1.
Embodiment 6, the preparing propylene from methanol reaction:
The catalyst that embodiment 3 the is made internal diameter of packing into is 8mm, highly is the stainless steel fixed bed reactors of 60mm, catalyst top and the bottom filling quartz sand, and the beds ratio of height to diameter is 10:1.With nitrogen catalyst is heated to about 520 ℃, keeps the 2h preliminary treatment, switch to steam then, feed methyl alcohol down at 0.01MPa (gauge pressure), liquid hourly space velocity (LHSV) is 0.9h
-1, methyl alcohol and steam mol ratio are 1:5.Conversion ratio 100%, the propylene selectivity reaches 57.23%, and the P/E ratio reaches 9.62.Other data see Table-1.
Embodiment 7: the reaction of dimethyl ether system propylene:
The catalyst that embodiment 2 the is made internal diameter of packing into is 8mm, highly is the stainless steel fixed bed reactors of 60mm, catalyst top and the bottom filling quartz sand, and the beds ratio of height to diameter is 10:1.With nitrogen catalyst is heated to about 430 ℃, keeps the 2h preliminary treatment, switch to steam then, feed dimethyl ether under normal pressure, liquid hourly space velocity (LHSV) is 0.6h
-1, dimethyl ether and steam mol ratio are 1:10.Conversion ratio 99.35%, the propylene selectivity reaches 37.38%, and the P/E ratio reaches 7.66.Other data see Table-1.
The reactivity worth of table-1 catalyst for producing propylene with methanol
Claims (7)
1, a kind of HZSM-5 molecular sieve catalyst that is used for methyl alcohol/dimethyl ether system propylene, it is characterized in that described catalyst is the HZSM-5 molecular sieve of modifying with the W element, wherein the shared mass percent of W element is 0.005-10%, the W element adopts the soluble-salt of W, and the sial atomic molar of described HZSM-5 molecular sieve is than being 10:1-300:1.
2, the HZSM-5 molecular sieve catalyst that is used for methyl alcohol/dimethyl ether system propylene according to claim 1, the mass percent that it is characterized in that W element in the described catalyst is 0.01-8%.
3, the HZSM-5 molecular sieve catalyst that is used for methyl alcohol/dimethyl ether system propylene according to claim 1, the soluble-salt that it is characterized in that described W is nitrate or the ammonium salt of W.
4, a kind of preparation method who is used for the HZSM-5 molecular sieve catalyst of methyl alcohol/dimethyl ether system propylene according to claim 1 is characterized in that concrete steps are as follows:
With the soluble-salt of W behind dilute with water under the 10-70 ℃ of temperature, gained solution is poured in the container that the HZSM-5 molecular sieve is housed, the HZSM-5 quality is that 0.005-10% calculates according to the shared mass percent of W element, dipping 2-36h, filter the back and dry 2-5h down at 90-120 ℃, at 400-600 ℃ of following roasting 3-10h, moulding promptly gets required product then.
5, the preparation method who is used for the HZSM-5 molecular sieve catalyst of methyl alcohol/dimethyl ether system propylene according to claim 1, the soluble-salt that it is characterized in that described W is nitrate or the ammonium salt of W.
6, the application of a kind of HZSM-5 molecular sieve catalyst as claimed in claim 1 in methyl alcohol/dimethyl ether system propylene, it is characterized in that concrete steps are as follows: with the described catalyst fixed bed reactors constant temperature zone of packing into, the beds ratio of height to diameter is 5:1-10:1, with in methyl alcohol, the dimethyl ether one or both is unstripped gas, in steam, the nitrogen one or both are carrier gas, the control reaction temperature is 300-600 ℃, and reaction pressure is 0-1.0MPa, and liquid hourly space velocity (LHSV) is 0.1-10h
-1
7, the application of HZSM-5 molecular sieve catalyst according to claim 1 in methyl alcohol/dimethyl ether system propylene, the mol ratio that it is characterized in that described unstripped gas methyl alcohol and carrier gas is 10:1-1:10, and the mol ratio of described unstripped gas dimethyl ether and carrier gas is 5:1-1:20.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531823A (en) * | 2010-12-23 | 2012-07-04 | 中国科学院金属研究所 | Propylene preparation method with high propylene production rate by using methanol |
| CN105289712A (en) * | 2015-11-30 | 2016-02-03 | 西北大学 | Catalyst for producing propylene by converting through coupling of methanol and C4-hydrocarbons and application of catalyst |
| US9675971B2 (en) | 2014-10-22 | 2017-06-13 | King Fahd University Of Petroleum And Minerals | Honeycomb monolith structure loaded with nanozeolites for enhanced propylene selectivity in methanol conversion |
| CN113509956A (en) * | 2020-04-09 | 2021-10-19 | 大唐国际化工技术研究院有限公司 | Molecular sieve catalyst, preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2007240813B2 (en) * | 2006-04-21 | 2011-03-17 | Exxonmobil Chemical Patents Inc. | Production of aromatics from methane |
| CN101306381B (en) * | 2007-05-16 | 2011-09-21 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve catalyst of propone prepared by methanol conversation and its preparation method |
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2008
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531823A (en) * | 2010-12-23 | 2012-07-04 | 中国科学院金属研究所 | Propylene preparation method with high propylene production rate by using methanol |
| CN102531823B (en) * | 2010-12-23 | 2014-10-22 | 中国科学院金属研究所 | Propylene preparation method with high propylene production rate by using methanol |
| US9675971B2 (en) | 2014-10-22 | 2017-06-13 | King Fahd University Of Petroleum And Minerals | Honeycomb monolith structure loaded with nanozeolites for enhanced propylene selectivity in methanol conversion |
| US9738570B1 (en) | 2014-10-22 | 2017-08-22 | King Fahd University Of Petroleum And Minerals | Method for methanol conversion to propylene over a monolithic catalyst system |
| US9845271B2 (en) | 2014-10-22 | 2017-12-19 | King Fahd University Of Petroleum And Minerals | Method for forming light olefins from methanol |
| CN105289712A (en) * | 2015-11-30 | 2016-02-03 | 西北大学 | Catalyst for producing propylene by converting through coupling of methanol and C4-hydrocarbons and application of catalyst |
| CN105289712B (en) * | 2015-11-30 | 2018-02-16 | 西北大学 | The catalyst preparing propylene transformed for coupling between methanol C_4 hydrocarbon and its application |
| CN113509956A (en) * | 2020-04-09 | 2021-10-19 | 大唐国际化工技术研究院有限公司 | Molecular sieve catalyst, preparation method and application thereof |
| CN113509956B (en) * | 2020-04-09 | 2023-08-22 | 大唐国际化工技术研究院有限公司 | Molecular sieve catalyst, preparation method and application thereof |
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