CN102276401A - Method for removing catalyst from product gas of alkene prepared from methanol - Google Patents
Method for removing catalyst from product gas of alkene prepared from methanol Download PDFInfo
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- CN102276401A CN102276401A CN2010101997781A CN201010199778A CN102276401A CN 102276401 A CN102276401 A CN 102276401A CN 2010101997781 A CN2010101997781 A CN 2010101997781A CN 201010199778 A CN201010199778 A CN 201010199778A CN 102276401 A CN102276401 A CN 102276401A
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- catalyst
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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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- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a method for removing a catalyst from a product gas of alkene prepared from methanol, which allows a problem of low removal efficiency of the catalyst entrained in the product gas existing in prior art to be mainly solved. The method for removing the catalyst from the product gas of alkene prepared from methanol mainly comprises the following steps: 1, allowing a product gas flow I to enter a gas-solid separation apparatus which is placed in a reactor to obtain a product gas flow II with the catalyst content of less than 0.4g/m<3>; 2, allowing the product gas flow II to enter a gas-solid separation apparatus which is placed outside the reactor to obtain a product gas flow III with the catalyst content of less than 0.1g/m<3>; and 3, cooling, and quenching the product gas flow III to form a liquid-solid mixed material flow I with the concentration of a first catalyst concentration, allowing the catalyst to enter a removal apparatus to obtain a liquid-solid mixed material flow II with the concentration of less than the first catalyst concentration. A technical scheme which adopts the method of the invention allows the problem to be solved. So the method of the present invention can be used in industrial production of low carbon olefins.
Description
Technical field
The present invention relates to the removal methods of catalyzer in a kind of methanol-to-olefins product gas.
Background technology
Low-carbon alkene refers to ethene and propylene, is two kinds of important basic chemical industry raw materials, and its demand is in continuous increase.Usually, ethene, propylene are to produce by petroleum path, but because limited supply of petroleum resources and higher price, the cost of being produced ethene, propylene by petroleum resources constantly increases.In recent years, people begin to greatly develop the technology that alternative materials transforms system ethene, propylene.Wherein, the alternative materials that is used for low-carbon alkene production that one class is important is an oxygenatedchemicals, for example alcohols (methyl alcohol, ethanol), ethers (dme, methyl ethyl ether), ester class (methylcarbonate, methyl-formiate) etc., these oxygenatedchemicalss can be transformed by coal, Sweet natural gas, biomass equal energy source.Some oxygenatedchemicals can reach fairly large production, as methyl alcohol, can be made by coal or Sweet natural gas, and technology is very ripe, can realize up to a million tonnes industrial scale.Because the popularity in oxygenatedchemicals source is added and is transformed the economy that generates low-carbon alkene technology, so by the technology of oxygen-containing compound conversion to produce olefine (OTO), particularly the technology by methanol conversion system alkene (MTO) is subjected to increasing attention.
In US 4499327 patents silicoaluminophosphamolecular molecular sieves catalyzer is applied to methanol conversion system olefin process and studies in great detail, think that SAPO-34 is the first-selected catalyzer of MTO technology.The SAPO-34 catalyzer has very high selectivity of light olefin, and activity is also higher, and can make methanol conversion is the degree that was less than in reaction times of low-carbon alkene 10 seconds, more even reach in the reaction time range of riser tube.
Disclose a kind of method that makes methanol conversion become alkene in US 4338475 patents, wherein from reaction product stream, isolated catalyzer by the cyclonic separator in the reactor.Catalyzer in reactor owing to the mechanical stress fragmentation of wearing and tearing easily produces powdery granule, because its size is little, weight is lighter, cyclonic separator in the reactor can not effectively be removed catalyst fines, be entrained with reactor with reaction product stream, catalyst fines is more little, and is difficult more by conventional method separation.Therefore, catalyst removal efficient is lower in this method, loss amount is bigger.
Introduced a kind of OTO system among the US 6121504, the reaction product stream that the oxygen-containing compound conversion to produce olefine reactor produces, described reaction product stream is by interchanger efficient recovery heat, but and carries the catalyst fines that leaves reactor secretly in the undeclared how processing reaction product logistics.
The granules of catalyst of carrying secretly with reaction product stream can deposit on some separation circuit equipment of whole technology if can not in time remove, and causes burden.Simultaneously since the methanol-to-olefins catalyzer cost an arm and a leg, therefore, the granules of catalyst that needs recovery reaction product stream as much as possible to carry secretly, and it is removed from the primary product logistics.Prior art does not all address this problem preferably.The present invention has solved this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the lower problem of entrained catalyst removal efficiency in the product gas that exists in the prior art, the removal methods of catalyzer in a kind of new methanol-to-olefins product gas is provided, and this method has entrained catalyst removal efficiency advantage of higher in the product gas.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the removal methods of catalyzer in a kind of methanol-to-olefins product gas, comprise the steps: that mainly (1) carry the product gas logistics I of catalyzer and enter the gas-solid separation equipment that is built in reactor, obtain catalyst content less than 0.4 gram/rice
3Product gas logistics II; (2) described product gas logistics II enters the gas-solid separation equipment that is placed on reactor, obtains catalyst content less than 0.1 gram/rice
3Product gas logistics III; (3) described product stream III forms the liquid-solid mixture flow I of first catalyst concn behind cooling, chilling, enters catalyst removal equipment, obtains to be lower than the liquid-solid mixture flow II of first catalyst concn.
In the technique scheme, described catalyzer comprises SAPO-34; The described gas-solid separation equipment that is built in reactor is the cyclonic separator that is at least one-level; The described gas-solid separation equipment that is placed on reactor is a cyclonic separator, built-in at least 100 vertical pipe type efficient cyclone pipes; The medium that described cooling, quenching process adopt is a water; Described first catalyst concn is at 0.3～2.0 gram/kilogram; Catalyst concn is less than 0.2 gram/kilogram in the described liquid-solid mixture flow II; In described catalyst removal equipment, remove the method that adopts filtration or wash in the process of catalyzer.
Among the present invention, the product stream III enters quench tower then through being cooled to after the heat exchange below 300 ℃ with water vapour in interchanger, and described quench tower is a tray column, is selected from sieve-tray tower or bubble-plate column.Quenching medium adopts water, quench tower ejects product gas, form the liquid-solid mixture flow I of 35～60 ℃ first catalyst concn at the bottom of the tower, squeeze into catalyst removal equipment with pump then, can adopt the method for filtering or washing, remove the granules of catalyst of carrying secretly in the mixture flow I, form the liquid-solid mixture flow II and the slag slurry that are lower than first catalyst concn simultaneously.At least 90% the granules of catalyst that contains in the described slag slurry that product gas carries secretly.
Among the present invention, the removal efficiency of catalyzer=(catalyst quality in catalyst quality in the liquid-solid mixture flow II of 1-/product gas logistics II) * 100%.
Adopt method of the present invention, except that the traditional cyclonic separator that is built in reactor, also outside reactor, be provided with the cyclonic separator of built-in efficient cyclone pipe, this cyclonic separator is similar to " three-stage cyclone separator " on the catalytic cracking flue gas pipeline, can guarantee the effective elimination of the catalyst fines about 10 microns.In addition, the catalyst fines that cyclonic separator can not remove enters cooling, chilling operation with logistics, enters catalyst removal equipment again with the liquid stream catalyst fines that gets off that is cooled, and adopts to filter or the method for washing finally removes.Therefore, adopt method of the present invention, efficient recovery the catalyst fines that carries of product stream, reduced the catalyst consumption of methanol-to-olefins technology.
Adopt technical scheme of the present invention: described catalyzer comprises SAPO-34; The described gas-solid separation equipment that is built in reactor is the cyclonic separator that is at least one-level; The described gas-solid separation equipment that is placed on reactor is a cyclonic separator, built-in at least 100 vertical pipe type efficient cyclone pipes; The medium that described cooling, quenching process adopt is a water; Described first catalyst concn is at 0.3～2.0 gram/kilogram; Catalyst concn is less than 0.2 gram/kilogram in the described liquid-solid mixture flow II; Remove the method that adopts filtration or wash in the process of catalyzer in described catalyst removal equipment, the removal efficiency of entrained catalyst reaches 98.2% in the product gas, has obtained better technical effect.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
In the methanol to olefins reaction system, reactor adopts fast fluidized bed, catalyzer adopts SAPO-34, it with purity 99.5% methanol feeding, inlet amount is 4.2 tons/hour, and temperature of reaction is 465 ℃, and reaction zone gas phase linear speed is 1.25 meter per seconds, be provided with the two stage cyclone separator in the reactor settling section, two stage cyclone separator outlet catalyst content is about 0.21 gram/rice
3, outside reactor, being provided with the cyclonic separator of built-in 100 efficient cyclone pipes, tornadotron is a vertical pipe type, but the catalyst fines of efficient recovery more than 7 microns, external cyclone water-separator outlet catalyst content is about 0.05 gram/rice
3Product air cooling but, the medium that adopts of chilling operation is water, about 40 ℃ of the temperature of the liquid-solid mixture flow I that forms, wherein first catalyst concn is 0.8 gram/kilogram, enter catalyst removal equipment, adopt filtration method to carry out removing of catalyzer in the liquid-solid materials flow, two liquid-solid materials flow strainers are set, one opens one is equipped with, obtain liquid-solid mixture flow II, catalyst concentration is about 0.08 gram/kilogram in the liquid-solid mixture flow II.After catalyzer in the product gas removed through whole steps, the removal efficiency of the catalyzer that product gas is carried secretly was 98.2%.
[embodiment 2]
Under as embodiment 1 described condition, reducing the methanol feeding amount is 2.86 tons/hour, and adds water vapour in methanol feeding, and the mass ratio of water vapour and methyl alcohol is 0.12, reaction zone gas phase linear speed is 0.98 meter per second, and built-in cyclonic separator outlet catalyst content is about 0.38 gram/rice
3, external cyclone water-separator outlet catalyst content is about 0.097 gram/rice
3First catalyst concn is 1.94 gram/kilograms in the liquid-solid mixture flow I, and catalyst concentration is about 0.17 gram/kilogram in the liquid-solid mixture flow II.After catalyzer in the product gas removed through whole steps, the removal efficiency of the catalyzer that product gas is carried secretly was 93.4%.
[comparative example 1]
Under as embodiment 1 described condition, cyclonic separator just is not set outside reactor, built-in cyclonic separator outlet catalyst content is about 0.23 gram/rice
3, first catalyst concn is 1.23 gram/kilograms in the liquid-solid mixture flow I, catalyst concentration is about 0.25 gram/kilogram in the liquid-solid mixture flow II.After catalyzer in the product gas removed through whole steps, the removal efficiency of the catalyzer that product gas is carried secretly was 89.5%.
Obviously, adopt method of the present invention, effective elimination the catalyst fines of carrying secretly in the product gas, have bigger technical superiority, can be used in the industrial production of low-carbon alkene.
Claims (7)
1. the removal methods of catalyzer in the methanol-to-olefins product gas mainly may further comprise the steps:
(1) the product gas logistics I of carrying catalyzer enters the gas-solid separation equipment that is built in reactor, obtains catalyst content less than 0.4 gram/rice
3Product gas logistics II;
(2) described product gas logistics II enters the gas-solid separation equipment that is placed on reactor, obtains catalyst content less than 0.1 gram/rice
3Product gas logistics III;
(3) described product stream III forms the liquid-solid mixture flow I of first catalyst concn behind cooling, chilling, enters catalyst removal equipment, obtains to be lower than the liquid-solid mixture flow II of first catalyst concn.
2. according to the removal methods of catalyzer in the described methanol-to-olefins product of claim 1 gas, it is characterized in that described catalyzer comprises SAPO-34.
3. according to the removal methods of catalyzer in the described methanol-to-olefins product of claim 1 gas, it is characterized in that the described gas-solid separation equipment that is built in reactor is the cyclonic separator that is at least one-level; The described gas-solid separation equipment that is placed on reactor is a cyclonic separator, built-in at least 100 vertical pipe type efficient cyclone pipes.
4. according to the removal methods of catalyzer in the described methanol-to-olefins product of claim 1 gas, it is characterized in that the medium that described cooling, quenching process adopt is a water.
5. according to the removal methods of catalyzer in the described methanol-to-olefins product of claim 1 gas, it is characterized in that described first catalyst concn is at 0.3～2.0 gram/kilogram.
6. according to the removal methods of catalyzer in the described methanol-to-olefins product of claim 1 gas, it is characterized in that catalyst concn is less than 0.2 gram/kilogram in the described liquid-solid mixture flow II.
7. according to the removal methods of catalyzer in the described methanol-to-olefins product of claim 1 gas, it is characterized in that in described catalyst removal equipment, removing the method that adopts filtration or wash in the process of catalyzer.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010101997781A CN102276401B (en) | 2010-06-11 | 2010-06-11 | Method for removing catalyst from product gas of alkene prepared from methanol |
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| CN2010101997781A CN102276401B (en) | 2010-06-11 | 2010-06-11 | Method for removing catalyst from product gas of alkene prepared from methanol |
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| CN102276401A true CN102276401A (en) | 2011-12-14 |
| CN102276401B CN102276401B (en) | 2013-12-25 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007834A (en) * | 2012-11-27 | 2013-04-03 | 飞潮（无锡）过滤技术有限公司 | Device and method for recycling gas phase catalyst by utilizing ceramic screen pipe filter |
| CN103214333A (en) * | 2013-05-10 | 2013-07-24 | 神华集团有限责任公司 | System and process for gas-solid separation and heat exchange of alkene product prepared from organic oxygen-containing compound |
| CN106943965A (en) * | 2017-03-25 | 2017-07-14 | 青岛京润石化设计研究院有限公司 | A kind of gas-solid fluidized bed reactor gas-solid separating method |
Citations (3)
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|---|---|---|---|---|
| US6166282A (en) * | 1999-08-20 | 2000-12-26 | Uop Llc | Fast-fluidized bed reactor for MTO process |
| CN101270019A (en) * | 2008-04-11 | 2008-09-24 | 中国石油化工股份有限公司 | Method for preparing low carbon olefin hydrocarbon with methanol or dimethyl ether |
| CN101384685A (en) * | 2006-02-17 | 2009-03-11 | 埃克森美孚化学专利公司 | Removal of catalyst fines from a reaction system |
-
2010
- 2010-06-11 CN CN2010101997781A patent/CN102276401B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6166282A (en) * | 1999-08-20 | 2000-12-26 | Uop Llc | Fast-fluidized bed reactor for MTO process |
| CN101384685A (en) * | 2006-02-17 | 2009-03-11 | 埃克森美孚化学专利公司 | Removal of catalyst fines from a reaction system |
| CN101270019A (en) * | 2008-04-11 | 2008-09-24 | 中国石油化工股份有限公司 | Method for preparing low carbon olefin hydrocarbon with methanol or dimethyl ether |
Non-Patent Citations (1)
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| 张善全: "MTO技术的发展情况及工艺简介", 《内蒙古石油化工》, no. 11, 2006 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007834A (en) * | 2012-11-27 | 2013-04-03 | 飞潮（无锡）过滤技术有限公司 | Device and method for recycling gas phase catalyst by utilizing ceramic screen pipe filter |
| CN103007834B (en) * | 2012-11-27 | 2015-03-18 | 飞潮（无锡）过滤技术有限公司 | Device and method for recycling gas phase catalyst by utilizing ceramic screen pipe filter |
| CN103214333A (en) * | 2013-05-10 | 2013-07-24 | 神华集团有限责任公司 | System and process for gas-solid separation and heat exchange of alkene product prepared from organic oxygen-containing compound |
| CN106943965A (en) * | 2017-03-25 | 2017-07-14 | 青岛京润石化设计研究院有限公司 | A kind of gas-solid fluidized bed reactor gas-solid separating method |
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