CN102276400B - Low carbon olefin reaction-regeneration device by using methanol - Google Patents
Low carbon olefin reaction-regeneration device by using methanol Download PDFInfo
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- CN102276400B CN102276400B CN201010199977.2A CN201010199977A CN102276400B CN 102276400 B CN102276400 B CN 102276400B CN 201010199977 A CN201010199977 A CN 201010199977A CN 102276400 B CN102276400 B CN 102276400B
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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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- Y02P20/00—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
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The invention relates to a low carbon olefin reaction-regeneration device by using methanol, which mainly solves the problem of low yield of low carbon olefin in the reaction-regeneration device in the prior art. The low carbon olefin reaction-regeneration device by using methanol comprises a methanol conveying reactor 3, a by-product conveying reactor 11, a regenerator 18, an overflow pipe 12 and a lifting pipe 10, the upper part of the by-product conveying reactor 11 is connected with the regenerator 18, the lower part of the by-product conveying reactor 11 is connected with the methanol conveying reactor 3, a degassing zone 20 is provided in the regenerator 18, a catalyst in the degassing zone 20 is entered into the by-product conveying reactor 11 through the overflow pipe 12, a catalyst outlet is opened at the lower part of the by-product conveying reactor 11 and is connected with the methanol conveying reactor 3 through the catalyst conveying tube 5, a stripping zone 6 is provided in the methanol conveying reactor 3, a catalyst in the stripping zone 6 is entered into the regenerator 18 through the lifting pipe 10, a product outlet is opened at the upper part of the methanol conveying reactor 3 and the by-product conveying reactor 11, the problem is better solved by the present invention by the technical scheme that the fume outlet is opened at the top of the regenerator 18. The present invention can be used for the industrial production of low carbon olefin.
Description
Technical field
The present invention relates to a kind of reaction for preparing light olefins from methanol-regenerating unit.
Technical background
Low-carbon alkene, i.e. ethene and propylene, is two kinds of important basic chemical industry raw materials, its demand is in continuous increase.Usually, ethene, propylene are to produce by petroleum path, but due to the limited supply of petroleum resources and higher price, the cost of being produced ethene, propylene by petroleum resources constantly increases.In recent years, people start to greatly develop the technology of alternative materials conversion ethene processed, propylene.Wherein, the important alternative materials for light olefin production of one class is oxygenatedchemicals, such as 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 technique is very ripe, can realize the industrial scale of up to a million tonnes.Due to the popularity in oxygenatedchemicals source, add and transform the economy that generates light olefin technique, so by the technique of oxygen-containing compound conversion to produce olefine (OTO), be particularly subject to increasing attention by the technique of preparing olefin by conversion of methanol (MTO).
In US4499327 patent, silicoaluminophosphamolecular molecular sieve catalyst is applied to preparing olefin by conversion of methanol technique and studies in detail, think that SAPO-34 is the first-selected catalyzer of MTO technique.SAPO-34 catalyzer has very high light olefin selectivity, and activity is also higher, and can make methanol conversion is reaction times of light olefin to be less than the degree of 10 seconds, more even reaches in the reaction time range of riser tube.
Technology and reactor that a kind of oxygenate conversion is low-carbon alkene in US6166282, are announced, adopt fast fluidized bed reactor, gas phase is after the lower Mi Xiangfanyingqu of gas speed has reacted, rise to after the fast subregion that internal diameter diminishes rapidly, adopt special gas-solid separation equipment initial gross separation to go out most entrained catalyst.Due to reaction after product gas and catalyzer sharp separation, effectively prevent the generation of secondary reaction.Through analog calculation, compared with traditional bubbling fluidization bed bioreactor, this fast fluidized bed reactor internal diameter and the required reserve of catalyzer all greatly reduce.
In CN1723262, having announced with the multiple riser reaction unit of central catalyst return is low-carbon alkene technique for oxygenate conversion, this covering device comprises multiple riser reactors, gas solid separation district, multiple offset components etc., each riser reactor has the port of injecting catalyst separately, be pooled to the disengaging zone of setting, catalyzer and gas product are separated.
Known in the field, guarantee high selectivity of light olefin, on catalyzer, need the carbon distribution of some amount, and also very responsive to processing parameters such as temperature of reaction in the methanol conversion process that is low-carbon alkene.All there is the lower problem of yield of light olefins causing greatly due to reaction zone inner catalyst carbon deposit skewness, temperature of reaction fluctuation in prior art.In addition, in the process of preparing low-carbon olefin by using methanol, inevitably can produce some by product, as carbon four above hydrocarbon etc., if these by products are further converted to object product, will improve yield and the process economy of low-carbon alkene.The present invention has solved the problems referred to above targetedly.
Summary of the invention
Technical problem to be solved by this invention is the not high problem of yield of light olefins existing in prior art, and a kind of new reaction for preparing light olefins from methanol-regenerating unit is provided.This device, for the production of low-carbon alkene, has advantages of that yield of light olefins is higher.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of reaction for preparing light olefins from methanol-regenerating unit, mainly comprise methanol conversion 3, by product conversion reactor 11, revivifier 18, upflow tube 12, riser tube 10, by product conversion reactor 11 tops are connected with revivifier 18, bottom is connected with methanol conversion 3, revivifier 18 inside are provided with degas zone 20, degas zone 20 inner catalysts enter by product conversion reactor 11 by upflow tube 12, by product conversion reactor 11 bottoms have catalyst outlet, be connected with methanol conversion 3 by catalyst transport 5, methanol conversion 3 inside are provided with stripping zone 6, stripping zone 6 inner catalysts enter revivifier 18 by riser tube 10, methanol conversion 3 and by product conversion reactor 11 tops have products export, revivifier 18 tops have exhanst gas outlet.
In technique scheme, described catalyzer comprises SAPO-34 molecular sieve; Gas-solid cyclone separator is all set before described products export and exhanst gas outlet; The degassed medium in described degas zone 20 is selected from water vapour, and stripping zone 6 stripping media are selected from water vapour, and riser tube 10 promotes medium and is selected from water vapour; Described revivifier 18 is by built-in heat collector control regeneration temperature; Described methanol conversion 3 can arrange external or built-in heat collector control temperature of reaction; Described degas zone 20 and stripping zone 6 side wall upper part have at least one catalyst inlet; Described by product conversion reactor 11 products and methanol conversion 3 products share a set of separation process; Described by product is carbon four～carbon six hydrocarbon mixtures; In described hydrocarbon mixture, carbon four hydrocarbon mass content are greater than 80%, and alkene mass content is greater than 60%.
In reaction for preparing light olefins from methanol process, inevitably can produce the by products such as carbon four above hydrocarbon, this part by-product yields is high and olefin(e) centent is high, find by research, the above hydrocarbon mixture of carbon four that this part olefin(e) centent is very high is the raw material of well producing low-carbon alkene.Adopt method of the present invention, a by product convertor is set, be mainly used in transforming the carbon four～carbon six hydrocarbon by products that form in preparing low carbon olefin hydrocarbon by methanol, for increased low carbon olefine output.The catalyzer of by product convertor, directly from revivifier, is conducive to guarantee that the above hydrocarbon of carbon four transforms required temperature of reaction and catalyst activity.The inventor finds by research, and the above hydrocarbon conversion of carbon four meeting generates carbon distribution on catalyzer, and the carbon distribution generating has significantly improved selectivity of catalyst, is conducive to the production low-carbon alkene of methyl alcohol highly selective.Meanwhile, high-temperature regenerated catalyst is by after by product convertor, and temperature decreases, the corresponding heat-obtaining load that has reduced methanol conversion.In addition, prior art generally all adopts reactor, revivifier to be arranged in juxtaposition, and occupation of land space is large, catalyst transport pipeline is longer.In the present invention, adopt revivifier, by product convertor, methanol conversion coaxially arranged, greatly reduced the occupation of land space of traditional reaction-regenerative device, catalyst transport pipeline shortens greatly simultaneously.
Adopt technical scheme of the present invention: described catalyzer comprises SAPO-34 molecular sieve; Gas-solid cyclone separator is all set before described products export and exhanst gas outlet; The degassed medium in described degas zone 20 is selected from water vapour, and stripping zone 6 stripping media are selected from water vapour, and riser tube 10 promotes medium and is selected from water vapour; Described revivifier 18 is by built-in heat collector control regeneration temperature; Described methanol conversion 3 can arrange external or built-in heat collector control temperature of reaction; Described degas zone 20 and stripping zone 6 side wall upper part have at least one catalyst inlet; Described by product conversion reactor 11 products and methanol conversion 3 products share a set of separation process; Described by product is carbon four～carbon six hydrocarbon mixtures; In described hydrocarbon mixture, carbon four hydrocarbon mass content are greater than 80%, alkene mass content is greater than 60%, in methanol conversion exported product, low-carbon alkene carbon base absorption rate reaches 80.67% (weight), in by product conversion reactor exported product, yield of light olefins reaches 35.47% (weight), has obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method for the invention.
In Fig. 1,1 is the charging of riser tube lifting medium; 2 is the charging of stripping medium; 3 is methanol conversion; 4 is methanol feedstock charging; 5 is catalyst transport; 6 is stripping zone; 7 is stripping zone sidewall catalyst inlet; 8 is reactor external warmer; 9 is gas-solid cyclone separator; 10 is riser tube; 11 is by product conversion reactor; 12 is upflow tube; 13 is gas-solid cyclone separator; 14 is by product charging; 15 is products export; 16 is collection chamber; 17 is regenerating medium charging; 18 is revivifier; 19 is degassed medium charging; 20 is degas zone; 21 is revivifier heat collector; 22 is gas-solid cyclone separator; 23 is exhanst gas outlet.
Raw material enters in methanol conversion 3 through feeding line 4, contact with molecular sieve catalyst, reaction generates the product that contains low-carbon alkene, after separating, gas-solid sharp separation equipment 9 enters collection chamber 16, decaying catalyst enters revivifier 18 by riser tube 10 and regenerates after 6 strippings of stripping zone, regenerated catalyst enters in by product conversion reactor 11 by upflow tube 12, contact with by products such as carbon four above hydrocarbon, the product generating enters collection chamber after gas-solid cyclone separator 13 separates, catalyzer in by product conversion reactor enters in methanol conversion 3 by catalyst transport 5, continue to react with methyl alcohol.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
In reaction-regenerative device as shown in Figure 1, collection chamber is not just set, methanol conversion product and by product conversion reactor product separate on-line analysis.The medial temperature of methanol conversion is 450 ℃, and bed density is 170 kilograms per cubic meter, and the medial temperature of by product conversion reactor is 552 ℃, and bed density is 220 kilograms per cubic meter.Reaction-regeneration system pressure is normal pressure, the methanol feeding of methanol conversion take purity as 99.5%, charging is 1 kg/hr, catalyzer is SAPO-34, stripping zone stripping medium, the degassed medium in degas zone, riser tube promote medium and are water vapour, revivifier arranges interior heat production coil pipe control regeneration temperature, and regeneration temperature is 674 ℃.The charging of by product conversion reactor is the above hydrocarbon mixture of carbon four, wherein carbon four hydrocarbon mass content are 91%, alkene mass content is 87%, regenerated catalyst carbon deposition quantity is 0.47%, from by product conversion reactor, carbon deposition quantity of catalyst is out 1.6%, keep the stability of catalyst flow control, reactor outlet product all adopts online gas chromatographic analysis, in methanol conversion exported product, low-carbon alkene carbon base absorption rate is 80.67% (weight), and in by product conversion reactor exported product, yield of light olefins is 35.47% (weight).
[embodiment 2]
According to the condition described in embodiment 1, the charging of by product conversion reactor is the above hydrocarbon mixture of carbon four, wherein carbon four hydrocarbon mass content are 80%, alkene mass content is 60%, regenerated catalyst carbon deposition quantity is 0.27%, from by product conversion reactor, carbon deposition quantity of catalyst is out 1.18%, keep the stability of catalyst flow control, reactor outlet product all adopts online gas chromatographic analysis, in methanol conversion exported product, low-carbon alkene carbon base absorption rate is 80.48% (weight), in by product conversion reactor exported product, yield of light olefins is 30.61% (weight).
[comparative example 1]
According to the condition described in embodiment 1, do not establish by product conversion reactor, regenerated catalyst directly turns back to methanol conversion bottom, and low-carbon alkene carbon base absorption rate is 79.63% weight.
Obviously, adopt method of the present invention, can reach the object that improves yield of light olefins, there is larger technical superiority, can be used in the industrial production of low-carbon alkene.
Claims (1)
1. reaction for preparing light olefins from methanol method, described method is carried out in reaction-regenerative device, and position and material that described reaction-regenerative device relates to are as follows: riser tube promotes medium charging (1), stripping medium charging (2), methanol conversion (3), methanol feedstock charging (4), catalyst transport (5), stripping zone (6), stripping zone sidewall catalyst inlet (7), reactor external warmer (8), gas-solid cyclone separator (9) in methanol conversion, riser tube (10), by product conversion reactor (11), upflow tube (12), gas-solid cyclone separator (13) in by product conversion reactor, by product charging (14), products export (15), regenerating medium charging (17), revivifier (18), degassed medium charging (19), degas zone (20), revivifier heat collector (21), gas-solid cyclone separator (22) in revivifier, exhanst gas outlet (23), in methanol conversion, the outlet of gas-solid cyclone separator (9) is connected with the products export of methanol conversion, in by product conversion reactor, the outlet of gas-solid cyclone separator (13) is connected with the products export of by product conversion reactor, in revivifier, gas-solid cyclone separator (22) outlet is connected with exhanst gas outlet,
By product conversion reactor (11) top is connected with revivifier (18), bottom is connected with methanol conversion (3), degas zone (20) is arranged on revivifier (18) inside, degas zone (20) inner catalyst enters by product conversion reactor (11) by upflow tube (12), by product conversion reactor (11) bottom has catalyst outlet, be connected with methanol conversion (3) by catalyst transport (5), described stripping zone (6) is located at methanol conversion (3) inside, stripping zone (6) inner catalyst enters revivifier (18) by riser tube (10), methanol conversion (3) and by product conversion reactor (11) top have products export, exhanst gas outlet (23) is arranged on revivifier (18) top,
The technical process that described reaction-regenerative device adopts is: methanol feedstock charging (4) enters in methanol conversion (3), contact with molecular sieve catalyst, reaction generates the product that contains low-carbon alkene, separate through gas-solid cyclone separator (9) in methanol conversion, decaying catalyst enters revivifier (18) regeneration by riser tube (10) after the stripping of stripping zone (6), regenerated catalyst enters in by product conversion reactor (11) by upflow tube (12), contact with the above hydrocarbon by product of carbon four, the product generating separates through gas-solid cyclone separator (13) in by product conversion reactor, catalyzer in by product conversion reactor enters in methanol conversion (3) by catalyst transport (5), continue to react with methyl alcohol,
Specific operation process and processing condition are as follows: methanol conversion product and by product conversion reactor product separate on-line analysis, the medial temperature of methanol conversion is 450 ℃, bed density is 170 kilograms per cubic meter, the medial temperature of by product conversion reactor is 552 ℃, and bed density is 220 kilograms per cubic meter; Reaction-regeneration system pressure is normal pressure, the methanol feeding of methanol conversion take purity as 99.5%, charging is 1 kg/hr, catalyzer is SAPO-34, stripping zone stripping medium, the degassed medium in degas zone, riser tube promote medium and are water vapour, revivifier arranges interior heat production coil pipe control regeneration temperature, and regeneration temperature is 674 ℃; The charging of by product conversion reactor is the above hydrocarbon mixture of carbon four, wherein carbon four hydrocarbon mass content are 91%, alkene mass content is 87%, regenerated catalyst carbon deposition quantity is 0.47%, from by product conversion reactor, carbon deposition quantity of catalyst is out 1.6%, keep the stability of catalyst flow control, reactor outlet product all adopts online gas chromatographic analysis, in methanol conversion exported product, low-carbon alkene carbon base absorption rate is 80.67% weight, and in by product conversion reactor exported product, yield of light olefins is 35.47% weight.
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| CN102872770B (en) * | 2011-07-12 | 2015-04-08 | 中国石油化工股份有限公司 | Reaction unit for preparing low-carbon olefins |
| CN103537235B (en) * | 2012-07-12 | 2016-04-13 | 中国石油化工股份有限公司 | The reaction unit of preparing low-carbon olefin from oxygen-containing compounds |
| CN111871343A (en) * | 2020-07-10 | 2020-11-03 | 中石化洛阳工程有限公司 | Device for producing low-carbon olefin by using oxygen-containing compound |
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 |
| CN1962573A (en) * | 2006-12-01 | 2007-05-16 | 中国化学工程集团公司 | Method and reactor for catalytic cracking for producing propylene using fluid bed |
| CN101402538A (en) * | 2008-11-21 | 2009-04-08 | 中国石油化工股份有限公司 | Method for improving yield of light olefins |
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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 |
| CN1962573A (en) * | 2006-12-01 | 2007-05-16 | 中国化学工程集团公司 | Method and reactor for catalytic cracking for producing propylene using fluid bed |
| CN101402538A (en) * | 2008-11-21 | 2009-04-08 | 中国石油化工股份有限公司 | Method for improving yield of light olefins |
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