CN102206128A - Separation method for low-carbon olefin prepared from oxygen-containing compound - Google Patents
Separation method for low-carbon olefin prepared from oxygen-containing compound Download PDFInfo
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- CN102206128A CN102206128A CN2011100899108A CN201110089910A CN102206128A CN 102206128 A CN102206128 A CN 102206128A CN 2011100899108 A CN2011100899108 A CN 2011100899108A CN 201110089910 A CN201110089910 A CN 201110089910A CN 102206128 A CN102206128 A CN 102206128A
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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
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
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Abstract
The invention discloses a separation method for a low-carbon olefin prepared from an oxygen-containing compound. The method comprises the following steps of: mixing a product from a reactor for preparing the low-carbon olefin from the oxygen-containing compound and/or a product from olefin catalytic pyrolysis, carrying out heat recovery, compression, purifying, cooling and the like pre-treatment steps, and separating to obtain a gas-phase hydrocarbon and a liquid-phase hydrocarbon; introducing the gas-phase hydrocarbon and the liquid-phase hydrocarbon to a depropanizer for C3<->/C4<+> separation; further condensing and cooling light components comprising three or less than carbon atoms at the depropanizer top, and introducing to a demethanizer which uses ethane or ethane and propane binary mixture as an absorbent at the demethanizer top, thus improving ethylene yield; introducing C2-C3 components at the demethanizer bottom to a dethanizer for C2 and C3 component separation; introducing C2 components to an ethylene rectifying tower, carrying out side withdrawing of ethylene, returning noncondensable gases at the tower top to a compressor, super-cooling ethane at the tower bottom and completely using as the absorbent of the demethanizer or partially using as fuel gas to withdraw; and introducing C3 components to a propylene rectifying tower, carrying out top or side withdrawing of propylene of the propylene rectifying tower, and withdrawing propane at the tower bottom to use as an LPG (liquefied petroleum gas) byproduct. Compared with traditional ethylene separation processes, the separation method uses ethane or ethane and propane binary mixture as the absorbent and employs a front-end depropanization (an intercooling demethanization) process, thus realizing high-efficiency recovery of ethylene; and simultaneously the separation method has the advantages of low energy consumption, low investment, effective utilization of byproducts and the like.
Description
Technical field
The invention belongs to the lower carbon number hydrocarbons separation technology field, relate in particular to the separation method of preparing low-carbon olefin from oxygen-containing compounds or olefins by catalytic cracking process.
Background technology
Ethene, propylene are the basic materials of petrochemical industry.The conventional production methods of ethene and propylene mainly adopts the naphtha steam cracking method to make, and petroleum resources is relied on serious.Growing tension along with oil supply, oxygenatedchemicals is produced the focus that low-carbon alkene becomes research, and obtained significant progress, oxygenatedchemicals comprises alcohol, ether, aldehyde and ketone etc., wherein methyl alcohol and dme are used more extensive, can produce by coal or Sweet natural gas, the pressure that this can alleviate oil supply to a certain extent especially meets the national conditions of China's " oil starvation, weak breath, rich coal ".
Produce in the lower carbon number hydrocarbons at naphtha steam cracking,, generally adopt deep cooling to come separation of methane and ethene, to improve yield of ethene because hydrogen, methane content are higher.Typical deep cooling separating method comprises order separation, front-end deethanization and predepropanization process, three kinds of flow processs differ from one another, but all need the deep cooling condition below-100 ℃, need ethylene compressor, even need methane compressor to provide cold for it, also higher to the ice chest requirement simultaneously, make construction investment strengthen.
The characteristics of preparing low-carbon olefin from oxygen-containing compounds product are that hydrogen, methane content are lower, and ethene, propylene content are higher, and high-carbon hydrocarbon contents such as C5+ are less, the cold that causes demethanizing tower to need is less, as adopting deep cooling separating method, to the equipment requirements height, investment is big, the energy consumption height, and economic benefit is not good.
US7714180 has proposed a kind of processing method of olefin recovery.According to this method, process gas at first removes C5+ through debutanizing tower after compression, C4-further compresses again, cool off back laggard demethanizing tower, deethanizing column, depropanizing tower earlier, and hybrid C 4 goes demethanizing tower to absorb ethene in the overhead gas as absorption agent at the bottom of the depropanizing Tata, improves yield of ethene.This invention avoids adopting deep cooling process for separating, but the technology that adopts oil to absorb has reduced investment, but for oxygenatedchemicals preparing low carbon hydrocarbons technology, main component is the C1-C4 material, and a large amount of materials needs the laggard demethanizing tower of precooling, and energy consumption is bigger.And hybrid C 4 absorption agent internal circulating load is big and circulation process is long, and energy consumption is bigger.
Chinese patent 200710171098.7 has proposed the separation method of the lower hydrocarbon containing light gas that a kind of rectifying combines with solvent absorbing.Cool off the pre-separation tower again according to this method gas after pre-treatment, overhead gas enters the absorption tower to improve yield of ethene, and the mixture that uses C3 or C4 or C5 or C6 or its hydro carbons is as absorption agent.Though this invention avoids adopting ethylene compressor, has reduced investment, be to use C3 as absorption agent, its internal circulating load is big, and partially absorbs the agent meeting and remove to do fuel gas with the absorption tower overhead gas, has reduced the utility value of absorption agent itself.The hydro carbons that uses C4 or C5 or C6 is not suitable for adopting predepropanization process as absorption agent.
Chinese patent 200810201217.3 has proposed the separation method of light hydrocarbon product in a kind of MTO-MTP reaction product.According to this method, directly send into deethanizing column after the pre-treatment of lighter hydrocarbons product, cat head C2-enters the absorption tower again, makees absorption agent to improve the ethylene recovery rate with ethane.This method is similar with above-mentioned two kinds of methods, has avoided the use ethylene compressor, has adopted ethane to make absorption agent, and part ethane steams from the absorption tower cat head and makes fuel gas.But the precondition of this invention is to use the front-end deethanization flow process, is not suitable for using ethane, propane mixture to make absorption agent.
Summary of the invention
The present invention is according to the characteristics of low carbon olefin preparation by using oxygenated chemical gas composition, proposed that a kind of energy consumption is low, less investment and make full use of the lower carbon number hydrocarbons separation method that self-produced byproduct is made absorption agent.
The present invention adopts following technical scheme:
A kind of separation method of preparing low-carbon olefin from oxygen-containing compounds, it is characterized in that: before entering the deethanizing column processing, adopt depropanizing-demethanizing technical process, and when demethanizing, use the mixed alkanes of ethane or ethane and propane to make absorption agent,, specifically may further comprise the steps:
(1) will mix after behind a series of pre-treatment steps such as heat recuperation, compression, purification and cooling from the product of oxygenatedchemicals reaction for preparing light olefins device and/or from the product of olefins by catalytic cracking, be divided into gas phase hydrocarbon and hydrocarbon liquid phase, the different column plates that gas phase hydrocarbon and hydrocarbon liquid phase advance depropanizing tower respectively carry out separating of the above heavy constituent of the following light constituent of C3 and C3 and C4 and C4, the following light constituent of C3 and C3 is told by the depropanizing tower cat head, and the above heavy constituent of C4 and C4 are told at the bottom of by the depropanizing Tata;
(2) more isolated C3 of depropanizing tower cat head in the step (1) and the following light constituent of C3 further are compressed to 2.2～3.8MPa, after being cooled to-40～20 ℃, entering demethanizing tower separates with the C2-C3 material light constituents such as methane, hydrogen, carbon monoxide, nitrogen, wherein light constituent is told by the methane column overhead, the C2-C3 material is told at the bottom of by the methane Tata, the method that demethanizing tower uses ethane absorption or ethane and propane binary mixture to absorb, to improve the rate of recovery of ethene, by making fuel gas or go hydrogen manufacturing behind the isolated light constituent recovery of the cat head cold;
(3) go subsequent separation system to handle by the above heavy constituent material of isolated C4 and C4 at the bottom of the depropanizing Tata after, as byproduct output or go olefins by catalytic cracking further to produce low-carbon alkene;
(4) isolated C2-C3 material enters deethanizing column and isolates C2 and C3 at the bottom of the demethanizer, and cat head C2 goes the hydrogenation acetylene removal or directly enters ethylene rectification tower, and C3 enters propylene rectification tower at the bottom of the tower;
(5) by ethylene distillation column overhead or side line extraction ethene, enter demethanizing tower as absorption agent after all or part of cooling of ethane at the bottom of the tower;
(6) by propylene rectification tower cat head or side line extraction propylene, another component that propane all makes to do after liquefied petroleum gas (LPG) (LPG) byproduct output or the part cooling absorption agent at the bottom of the tower enters demethanizing tower.
The separation method of described a kind of preparing low-carbon olefin from oxygen-containing compounds is characterized in that, described flow process adopts predepropanization-demethanizing technology, and wherein depropanizing tower is the two depropanizing towers of single tower or high-low pressure, is preferably the two depropanizing towers of high-low pressure.
The separation method of described a kind of preparing low-carbon olefin from oxygen-containing compounds is characterized in that, described demethanizing tower adopts the ethane absorption agent, and the preferred temperature of absorption agent is 5～-40 ℃.
The separation method of described a kind of preparing low-carbon olefin from oxygen-containing compounds is characterized in that, described demethanizing tower adopts ethane, propane composite absorber, wherein the preferred temperature 5 of ethane absorption agent～-40 ℃.
The present invention uses-40 ℃ and above cryogen, only needs the propylene refrigeration compressor, avoids traditional ethene to separate ethylene compressor and the deep cooling ice chest that uses, and has reduced facility investment and operation easier.According to the characteristics that the preparing low-carbon olefin from oxygen-containing compounds product is formed, the present invention uses predepropanization-demethanizing flow process, can effectively cut down the consumption of energy.
Main points of the present invention are: with traditional ethene separating technology relatively, the present invention adopts ethane or ethane and propane binary mixture to make absorption agent, adopt predepropanization-in cold demethanizing tower technology, the high efficiente callback of realization ethene.
Depropanizing tower among the present invention can be traditional single tower depropanizing tower or high-low pressure double-tower depropanizing tower.Demethanizing tower of the present invention is made absorption agent with ethane or ethane and propane binary mixture, and demethanizing cat head light constituent reclaims cold after adopting throttling or expander refrigeration, and light constituent is made fuel gas or gone hydrogen manufacturing, to satisfy the hydrogenation needs of diolefine or alkynes.Make absorption agent with ethane or mixed alkanes, though compare as absorption agent with propane and above heavy constituent, more with the absorption agent of light constituents such as methane losses, do not reduce the utility value of ethane, the gas that still acts as a fuel uses; And using propane to make absorption agent, the propane of loss has reduced the utility value (propane originally can be used as liquefied petroleum gas (LPG)) of propane as fuel gas.
According to the present invention, can adopt the absorption agent of ethane as ethene in the demethanizer column overhead gas, the ethane amount that Tathagata autoreaction generates then can be replenished propane and make absorption agent, to avoid a large amount of outsourcing ethane during less than the loss amount of demethanizer column overhead ethane.
Compared with prior art, advantage of the present invention is:
The characteristics that the present invention forms according to the preparing low-carbon olefin from oxygen-containing compounds product, use predepropanization-demethanizing flow process, and use ethane or ethane, propane composite absorber, avoid adopting deep cooling ice chest and ethylene compressor, reduce facility investment and energy consumption, do not reduced absorption agent utility value originally simultaneously.
Therefore the present invention is that a kind of facility investment is low, energy consumption is low, does not reduce the method for absorbing and separating of absorption agent utility value simultaneously, and preparing low-carbon olefin from oxygen-containing compounds or olefins by catalytic cracking process are had good suitability.
Specify the intent of the present invention below in conjunction with the drawings and specific embodiments, but drawings and Examples are not construed as limiting the invention.
Description of drawings
Fig. 1 is the separation process figure of preparing low-carbon olefin from oxygen-containing compounds of the present invention.
Fig. 2 is the separation process figure of the another kind of preparing low-carbon olefin from oxygen-containing compounds of the present invention.
Embodiment
As Fig. 1, from the product of preparing low-carbon olefin from oxygen-containing compounds reactor with or mix after behind a series of pre-treatment steps such as heat recuperation, compression, purification and cooling, be divided into gas phase hydrocarbon and hydrocarbon liquid phase from the product of olefins by catalytic cracking.Gas phase hydrocarbon and hydrocarbon liquid phase advance depropanizing tower to carry out C3-/C4+ and separates, and wherein depropanizing tower can be single tower or double tower.The following light constituent of depropanizing tower cat head C3 and C3 further compresses the laggard demethanizing tower of cooling, and the very useful ethane of demethanizer is made absorption agent, to improve yield of ethene.The C4+ heavy constituent are handled the back as gasoline and LPG byproduct or directly return the output of olefin reactor with raising ethene, propylene through subsequent separation system at the bottom of the depropanizing tower.C2-C3 removes deethanizing column separation of C 2 and C3 at the bottom of the demethanizer.C2 advances ethylene rectification tower, side line extraction ethene, and the compressed machine of cat head non-condensable gas returns, and the whole mistakes of ethane are done the gas extraction that acts as a fuel of demethanizing tower absorption agent or part after cold at the bottom of the tower.C3 removes propylene rectification tower, cat head extraction propylene, and extraction propane is made the LPG byproduct at the bottom of the tower.
Fig. 2 separation process and Fig. 1 flow process are basic identical, difference is to have used ethane, propane composite absorber, the ethane amount that this flow process is suitable for producing in reaction process is less than in the operating mode of demethanizer column overhead with the ethane amount of light constituent loss, need propane to make another component of absorption agent this moment, to avoid outsourcing ethane, reduce cost.
As Fig. 1, come self-reacting lower carbon number hydrocarbons through heat recuperation, compression and purification postcooling, under 2.1MPa, 15 ℃ condition, at first advance depropanizing tower, depropanizing cat head gas phase is compressed to 3.4MPa, be cooled to-30 ℃ advances demethanizing tower, demethanizing tower adopts ethane to make absorption agent, and wherein ethane absorption agent temperature is-24 ℃.Table 1 is an example calculation result, as can be seen from the table, when the ethene mass rate is identical in the control light constituent, the ethane absorption agent that needs lacks than propane absorbent, the ethane mass rate only is 2/3 of a propane, though far more than the propane losses amount, the ethane of loss does not reduce its utility value to ethane with the light constituent loss, still can be used as fuel gas and uses.And use propane to make absorption agent, and the loss amount of propane is 672kg/h, and a year loss amount is 5376t, and script propane can be used as the LPG byproduct and sells, but can only make fuel gas this moment uses, and has reduced its utility value.
Embodiment 2
As Fig. 2, come self-reacting lower carbon number hydrocarbons through heat recuperation, compression and purification postcooling, under 2.1MPa, 15 ℃ condition, at first advance depropanizing tower, depropanizing cat head gas phase compressed to 3.4MPa, be cooled to-30 ℃ and advance demethanizing tower, because the ethane selectivity is low in the product, as making absorption agent with ethane, with the ethane amount of light constituent loss greater than product ethane, make absorption agent as whole use ethane, need outsourcing part ethane, consider that replenishing propane makes absorption agent this moment.From table 2 also as can be seen, compare as absorption agent with using propane fully, the absorption agent consumption is less, and propane losses amount minimizing 560kg/h, and the about 4480t of propane reduces the loss in year.
Table 1 embodiment 1 calculation result with make absorption agent relatively with propane fully
Table 2 embodiment 2 calculation result with make absorption agent relatively with propane fully
Claims (4)
1. the separation method of a preparing low-carbon olefin from oxygen-containing compounds, it is characterized in that: before entering the deethanizing column processing, adopt depropanizing-demethanizing technical process, and when demethanizing, use the binary mixed alkanes of ethane or ethane and propane to make absorption agent, specifically may further comprise the steps:
(1) will mix after behind a series of pre-treatment steps such as heat recuperation, compression, purification and cooling from the product of oxygenatedchemicals reaction for preparing light olefins device and/or from the product of olefins by catalytic cracking, be divided into gas phase hydrocarbon and hydrocarbon liquid phase, gas phase hydrocarbon and hydrocarbon liquid phase advance depropanizing tower and carry out separating of the above heavy constituent of the following light constituent of C3 and C3 and C4 and C4, the following light constituent of C3 and C3 is told by the depropanizing tower cat head, and the above heavy constituent of C4 and C4 are told at the bottom of by the depropanizing Tata;
(2) more isolated C3 of depropanizing tower cat head in the step (1) and the following light constituent of C3 further are compressed to 2.2～3.8MPa, after being cooled to-40～20 ℃, entering demethanizing tower separates with the C2-C3 material light constituents such as methane, hydrogen, carbon monoxide, nitrogen, wherein light constituent is told by demethanizer column overhead, the C2-C3 material is told at the bottom of by demethanizer, demethanizing tower uses ethane absorption or ethane and propane binary composite absorber, to improve yield of ethene, by making fuel gas or remove hydrogen generating system behind the isolated light constituent recovery of the cat head cold;
(3) by the above heavy constituent material of isolated C4 and C4 at the bottom of the depropanizing Tata, after subsequent separation system is handled, as byproduct output or go olefins by catalytic cracking further to produce low-carbon alkene;
(4) isolated C2-C3 material enters deethanizing column and isolates C2 and C3 at the bottom of the demethanizer, and cat head C2 removes hydrogenation or directly enters ethylene rectification tower, and C3 enters propylene rectification tower at the bottom of the tower;
(5) by ethylene distillation column overhead or side line extraction ethene, enter demethanizing tower as absorption agent after all or part of cooling of ethane at the bottom of the tower;
(6) by propylene rectification tower cat head or side line extraction propylene, another component that propane all makes to do after liquefied petroleum gas (LPG) (LPG) byproduct output or the part cooling absorption agent at the bottom of the tower enters demethanizing tower.
2. the separation method of a kind of preparing low-carbon olefin from oxygen-containing compounds according to claim 1, it is characterized in that, described flow process adopts predepropanization-demethanizing technology, and wherein depropanizing tower is the two depropanizing towers of single tower or high-low pressure, is preferably the two depropanizing towers of high-low pressure.
3. the separation method of a kind of preparing low-carbon olefin from oxygen-containing compounds according to claim 1 is characterized in that, described demethanizing tower adopts the ethane absorption agent, and the preferred temperature of absorption agent is 5～-40 ℃.
4. the separation method of a kind of preparing low-carbon olefin from oxygen-containing compounds according to claim 1 is characterized in that, described demethanizing tower adopts ethane, propane binary composite absorber, and the preferred temperature of absorption agent is 5～-40 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102491866A (en) * | 2011-11-30 | 2012-06-13 | 神华集团有限责任公司 | Olefin separation process and system |
| CN111174529A (en) * | 2020-03-05 | 2020-05-19 | 赖家俊 | System and method for removing hydrocarbon and carbon by using cold energy of liquefied natural gas |
| CN114409492A (en) * | 2021-12-15 | 2022-04-29 | 国家能源集团宁夏煤业有限责任公司 | Device and method for preparing low-carbon olefin from methanol |
| CN115340436A (en) * | 2021-05-14 | 2022-11-15 | 中国石油天然气集团有限公司 | Separation device and separation method for olefin catalytic cracking |
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| CN101973831A (en) * | 2010-10-14 | 2011-02-16 | 东华工程科技股份有限公司 | Separation method for producing light olefins from oxygenated chemicals |
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| CN101973831A (en) * | 2010-10-14 | 2011-02-16 | 东华工程科技股份有限公司 | Separation method for producing light olefins from oxygenated chemicals |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491866A (en) * | 2011-11-30 | 2012-06-13 | 神华集团有限责任公司 | Olefin separation process and system |
| CN102491866B (en) * | 2011-11-30 | 2014-07-23 | 神华集团有限责任公司 | Olefin separation process and system |
| CN111174529A (en) * | 2020-03-05 | 2020-05-19 | 赖家俊 | System and method for removing hydrocarbon and carbon by using cold energy of liquefied natural gas |
| CN111174529B (en) * | 2020-03-05 | 2024-08-27 | 广东丰乐能源科技有限公司 | System and method for hydrocarbon removal and decarbonization by utilizing liquefied natural gas cold energy |
| CN115340436A (en) * | 2021-05-14 | 2022-11-15 | 中国石油天然气集团有限公司 | Separation device and separation method for olefin catalytic cracking |
| CN114409492A (en) * | 2021-12-15 | 2022-04-29 | 国家能源集团宁夏煤业有限责任公司 | Device and method for preparing low-carbon olefin from methanol |
| CN114409492B (en) * | 2021-12-15 | 2023-12-22 | 国家能源集团宁夏煤业有限责任公司 | Device and method for preparing low-carbon olefin from methanol |
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| CN101973831A (en) | 2011-02-16 |
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