CN102304010A - Method for separating low carbon olefin mixed gas by rectifying and absorbing - Google Patents
Method for separating low carbon olefin mixed gas by rectifying and absorbing Download PDFInfo
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Abstract
The invention relates to a method for separating low carbon olefin mixed gas by rectifying and absorbing. The method utilizes a hydrocarbon or oxygen-containing organic compound absorbent to separate methane from C2; a rectifying method is used for separating C2-C4 so that polymeric layer ethylene and propylene are obtained. By utilizing the method, the ethylene is separated from the methane by using the absorbent and without setting any deep freeze refrigeration plant (such as a refrigerator, an expander and the like); the lowest operation temperature of the process is more than minus 40 DEG C and the material cost of the device is reduced. By utilizing the absorbent, the ethylene is absorbed in an absorption tower so that the separation between the ethylene and the methane is realized; as boiling points of the absorbent and the ethylene are greatly different, the absorbent is easily separated from the ethylene, the solvent loss is less, and the absorbent does not pass through other towers and does not cause incomplete separation formed by generating azeotropy with C5 and the like.
Description
Technical field
The invention belongs to the low-carbon alkene field of refinement, relate to a kind of separation of methanol prepares alkene via fluidized-bed reactor method.
Background technology
Ethene, propylene are important hardware and software platform compound of petrochemical complex and basic chemical industry raw material, nearly 200,000,000 tons of whole world annual requirement.Still there is very big breach in the production of domestic over the next several years ethene, propylene.Existing ethene, production of propylene technology rely on serious to petroleum resources.What ethylene production generally adopted is the lightweight oil cracking process, and the production of propylene about 97% is from the coproduction and the refinery by-product of cracking ethylene preparation.The raw materials cost that adopts the lightweight oil cleavage method to prepare ethene, propylene accounts for 60～80% of production cost.Existing production of propylene technology (cracking ethylene preparation coproduction and refinery's by-product) can't satisfy the requirement that the propylene consumption increases fast though ripening degree is high, and product structure is severely limited.
China has abundant relatively Sweet natural gas and coal resource.Explored coal reserves is 7,650 hundred million tons, and natural gas reserves is 38 * 10
12Cubic meter.Along with the development of gas making technology, the gas making cost reduces greatly.Utilize coal or Sweet natural gas can make cheap synthetic gas in a large number, can produce methyl alcohol via synthetic gas, and then have realistic meaning by preparing low carbon olefinic hydrocarbon with methanol.What converting methanol to prepare low carbon olefin was that development in recent years gets up is raw material with methyl alcohol, directly generates the novel process of low-carbon olefin mixed gas through catalyst.Chinese patent CN 01144188.7, CN00802040.X, CN96115333.4, CN 99815451.2 have disclosed the method for converting methanol to prepare low carbon olefin.
It is the method that raw material is produced low-carbon alkene that Chinese patent CN96115333.4 has disclosed with methyl alcohol, dme, and the process gas that reaction produces is directly through going into the ethylene/propene centrifugal station; Chinese patent CN200610144290.2 has disclosed the method that fluid catalytic cracking is produced propylene, is raw material with methyl alcohol/dme, transforms through fluidized-bed and produces propylene and just formed FMTP technology.The finished product of FMTP technology are propylene, and ethene and butylene and C5 component are as intermediates, and Returning reactor continues reaction conversion and becomes propylene.
It is the deep cooling flow process of representative with sequence flow, front-end deethanization flow process and predepropanization process that traditional low-carbon alkene separates employing.Need about-100 ℃, separate with ethene methane down with ice chest; Equipment cost is high; Chinese patent CN200610017775.5 has announced a kind of separation method of converting methanol to prepare low carbon olefin gas, has adopted improved front-end deethanization separation process separation of methanol preparing low-carbon olefin by conversion gas.The separation method of a patent ZL200810052350.7 low-carbon olefin mixed gas has adopted the absorption flow process to separate low carbon olefin gas.Use but wherein absorption agent is omnidistance, be prone to produce azeotropic with component, separates not thoroughly, and absorption agent consumption height improves for the converting methanol to prepare low carbon olefin cost of middle and small scale greatly.
Summary of the invention
In order to solve the problem that exists in the prior art, the present invention provides a kind of method that adopts rectifying and absorption extraction low-carbon olefin mixed gas, solves the available technology adopting ice chest and raises the cost, separates incomplete problem.
Technical scheme of the present invention is:
A kind of method that adopts rectifying and absorption extraction low-carbon olefin mixed gas comprises the steps:
(1) will be from compression and exsiccant low-carbon olefin mixed gas and liquid feeding high pressure depropanizer; The C4+ that is rich in C3 that collects from the bottom of said high pressure depropanizer gets into the low pressure depropanizing tower, and low pressure depropanizing tower top liquid is through being pumped into high pressure depropanizer;
(2) gas of being collected by said high pressure depropanizer top feeds compressor, and the gas after boosting gets into demethanizing tower through cooling, and demethanizer column overhead gas gets into the bottom, absorption tower;
(3) feed absorption agent from top, said absorption tower; Through mass transfer; Be not absorbed the top collection of the C1 of agent absorption and lighter component from said absorption tower; Absorption agent to be generated gets into regenerator column from the bottom output on absorption tower after reclaiming cold with poor absorption agent heat exchange; In said regenerator column, C2 is realized separating with absorption agent, absorption agent recycles after reclaiming heat; Said absorption agent be contain in the molecule Sauerstoffatom, carbonatoms is that the carbonatoms of alcohols, ethers or the oxygen-free atom of 1-4 is at least a in the hydro carbons of 3-5;
(4) the resulting C2～C3 in said demethanizing tower bottom is sent into deethanizing column, in said deethanizing column, realize separating of C2 and C3, C3 gets into propylene tower, obtains propylene product at said propylene tower top, obtains the propane byproduct at the bottom of the tower;
(5) with said deethanizing column top C2 product input ethylene column, a large amount of ethene obtain at cat head in said ethylene column, together behind the recovery heat, send reactive system with the C2 gas at said regenerator column top;
(6) obtain ethane with small amount of ethylene is sent into ethane tower in said ethylene column bottom, obtain polymer grade ethylene at said ethane tower top, obtain ethane at the bottom of the tower, ethane and the said absorption overhead gas gas that together acts as a fuel is seen off behind the recovery cold;
(7) C4+ that said low pressure depropanizing tower bottom is obtained is divided into two strands, and one send C4 tower, in said C4 tower, C4 is separated with C5+, and C4 and propane are as liquefaction pneumatic transmission tank field, and C5+ send the tank field as gasoline products, another strand Returning reacting system.
Said alcohols is preferably methyl alcohol, ethanol or butanols.
Said ethers is preferably ether or dme.
Said hydro carbons is preferably propane, butane or pentane.
Propylene and the butylene volumn concentration in mixed gas is 5%～95% in the said low-carbon olefin mixed gas.
Technology of the present invention can realize the separation of coal system alkene; Can obtain products such as fuel gas, ethene, ethane, propylene, propane, liquefied petroleum gas (LPG) and gasoline; Realize the separation fully of mixed olefins; Separate the ethene and the propylene that obtain through present technique and can be used as raw material production homopolymerization or Co-polypropylene; Simultaneously; Also can produce multiple derived product such as Vilaterm, polyvinyl chloride, terepthaloyl moietie, vinyl cyanide, vinylformic acid and ester, reliable assurance is provided for the expansion and the development of coal system alkene downstream industry chain.
At present, the isolation technique of coal system alkene mainly contains predepropanization technology and order isolation technique.Present technique is predepropanization and absorption techniques, compares with other isolation technique, and present technique has the following advantages:
1) through the method realization ethene of absorption and separating of methane, deep freeze refrigeration plant (like ice chest and decompressor etc.) need be set, the minimum operation temperature of this technology is more than-40 ℃, and the Master Cost of equipment will reduce.Use through absorption agent; Ethene is absorbed in the absorption tower under the agent absorption; Realization ethene separates with methane; Because the boiling point of absorption agent and ethene differs bigger; Absorption agent separates than is easier to ethene; Solvent loss is few, and absorption agent is without other towers, can not cause with generation azeotropic such as C5 and separate not exclusively.
2) all devices is conventional unit equipment, can realize production domesticization.
3) the absorption agent consumption is little, and consumption only is omnidistance about 10% of the absorption agent separating technology that uses, and reduces greatly for the converting methanol to prepare low carbon olefin cost of middle and small scale, and facility investment is low.
4) absorption agent loss is few, absorbs, desorb is easy, helps the operational condition of optimized Separation, and the process form for portion gas (being generally ethene) Returning reactor being continued reaction help analyzing the influence of absorption agent for reaction workshop section.
5) technology is reliable, and is simple to operate.
6) can make in the gas that absorbs cat head ethylene content less than 0.5% (V) through optimization to operational condition.
The inventive method particularly for the converting methanol to prepare low carbon olefin technology of middle and small scale, has very strong economic and practical.
Description of drawings
Fig. 1 is the process flow diagram of the separation method of low-carbon olefin mixed gas of the present invention;
Wherein: 1-high pressure depropanizer, 2-low pressure depropanizing tower, 3-demethanizing tower, 4-absorption tower; The 5-regenerator column, 6-deethanizing column, 7-ethylene column, 8-ethane tower; The 9-propylene tower, 10-C4 tower, the rich or poor absorption agent interchanger of 11-; 12-process gas compression machine, A-process gas, B-fuel gas; C-C2, D-polymer grade ethylene, E-polymerization-grade propylene; F-C4+, G-C5+, H-LPG.
Embodiment
Further describe through concrete embodiment below in conjunction with 1 pair of technical process of the present invention of accompanying drawing.
Adopt the method for rectifying and absorption extraction low-carbon olefin mixed gas; Comprising the steps: will be from compression and exsiccant low-carbon olefin mixed gas A and liquid feeding high pressure depropanizer 1; The C4+ that is rich in C3 that collects from the bottom of high pressure depropanizer 1 gets into low pressure depropanizing tower 2, and low pressure depropanizing tower 2 top liquid are through being pumped into high pressure depropanizer 1.The gas of being collected by high pressure depropanizer 1 top feeds process gas compression machine 12; Gas after boosting gets into domethanizing column 3 through cooling; Demethanation 3 column overhead gases get into 4 bottoms, absorption tower; 4 tops feed absorbent from the absorption tower; Through mass transfer; Not being absorbed C1 that agent absorbs and lighter component B 4 top collects from the absorption tower; Treat that absorbent regeneration gets into regenerator 5 after the bottom output on absorption tower 4 is reclaimed cold through rich or poor absorbent heat exchanger 11; In regenerator 5, C2 is realized separating with absorbent; Absorbent recycles after reclaiming heat; Resulting C2～the C3 in 3 bottoms sends into dethanizer 6 with said domethanizing column; In said dethanizer 6, realize separating of C2 and C3; C3 gets into propylene tower 9, obtains propylene product E at said propylene tower 9 tops, obtains propane byproduct H at the bottom of the tower.With said deethanizing column 6 top C2 products input ethylene columns 7, a large amount of ethene obtain at cat head in said ethylene column 7, together behind the recovery heat, send reactive system with the C2 gas at said regenerator column 5 tops.Obtain ethane in said ethylene column 7 bottoms and small amount of ethylene is sent into ethane tower 8, obtain polymer grade ethylene D at said ethane tower 8 tops, obtain ethane at the bottom of the tower, ethane and said absorption tower 4 top gases together act as a fuel and see off after gas reclaims cold.The C4+F that said low pressure depropanizing tower 2 bottoms are obtained is divided into two strands, and one send C4 tower 10, in said C4 tower 10, C4 is separated with C5+, and C4 and propane are as liquefaction pneumatic transmission tank field, and C5+G send the tank field as gasoline products, another strand Returning reacting system.Said absorption agent is one or more mixing in methyl alcohol, ethanol, butanols, ether, dme, propane, butane or the pentane.Propylene and the butylene volumn concentration in mixed gas is 5%～95% in the said low-carbon olefin mixed gas.
Data are the component distribution of feed gas in the table 1.
Data owner is wanted equipment operation parameter in the table 2.
Treat isolating low-carbon olefin mixed gas composition in certain technology of table 1
| The product component | Flow |
| Component | Molecular formula | Molecular weight | Kg/h | (wt)％ | |
| | H2 | 2 | 104.57 | 0.11 | |
| Carbon monoxide | CO | 28 | 14.51 | 0.01 | |
| Nitrogen | N2 | 28 | 390.86 | 0.40 | |
| Methane | CH4 | 16 | 1101.16 | 1.13 | |
| Ethene | C2H4 | 28 | 27729.68 | 28.37 | |
| Ethane | C2H6 | 30 | 577.82 | 0.59 | |
| Propylene | C3H6 | 42 | 23375.17 | 23.92 | |
| Propane | C3H8 | 44 | 2270.49 | 2.32 | |
| Butylene | C4H8 | 56 | 21308.03 | 21.80 | |
| Divinyl | C4H6 | 54 | 199.55 | 0.20 | |
| Butane | C4H10 | 58 | 10360.76 | 10.60 | |
| Amylene | C5H10 | 70 | 6020.61 | 6.16 | |
| Pentane | C5H12 | 72 | 3079.76 | 3.15 | |
| Hexene | C6H12 | 84 | 1201.76 | 1.23 | |
| Amount to | 97734.73 | 100.00 |
Table 2 major equipment operating parameters
Claims (5)
1. a method that adopts rectifying and absorption extraction low-carbon olefin mixed gas is characterized in that, comprises the steps:
(1) will be from compression and exsiccant low-carbon olefin mixed gas and liquid feeding high pressure depropanizer; The C4+ that is rich in C3 that collects from the bottom of said high pressure depropanizer gets into the low pressure depropanizing tower, and low pressure depropanizing tower top liquid is through being pumped into high pressure depropanizer;
(2) gas of being collected by said high pressure depropanizer top feeds compressor, and the gas after boosting gets into demethanizing tower through cooling, and demethanizer column overhead gas gets into the bottom, absorption tower;
(3) feed absorption agent from top, said absorption tower; Through mass transfer; Be not absorbed the top collection of the C1 of agent absorption and lighter component from said absorption tower; Absorption agent to be generated gets into regenerator column from the bottom output on absorption tower after reclaiming cold with poor absorption agent heat exchange; In said regenerator column, C2 is realized separating with absorption agent, absorption agent recycles after reclaiming heat; Said absorption agent be contain in the molecule Sauerstoffatom, carbonatoms is that the carbonatoms of alcohols, ethers or the oxygen-free atom of 1-4 is at least a in the hydro carbons of 3-5;
(4) the resulting C2～C3 in said demethanizing tower bottom is sent into deethanizing column, in said deethanizing column, realize separating of C2 and C3, C3 gets into propylene tower, obtains propylene product at said propylene tower top, obtains the propane byproduct at the bottom of the tower;
(5) with said deethanizing column top C2 product input ethylene column, a large amount of ethene obtain at cat head in said ethylene column, together behind the recovery heat, send reactive system with the C2 gas at said regenerator column top;
(6) obtain ethane with small amount of ethylene is sent into ethane tower in said ethylene column bottom, obtain polymer grade ethylene at said ethane tower top, obtain ethane at the bottom of the tower, ethane and the said absorption overhead gas gas that together acts as a fuel is seen off behind the recovery cold;
(7) C4+ that said low pressure depropanizing tower bottom is obtained is divided into two strands, and one send C4 tower, in said C4 tower, C4 is separated with C5+, and C4 and propane are as liquefaction pneumatic transmission tank field, and C5+ send the tank field as gasoline products, another strand Returning reacting system.
2. the method for employing rectifying according to claim 1 and absorption extraction low-carbon olefin mixed gas is characterized in that said alcohols is methyl alcohol, ethanol or butanols.
3. the method for employing rectifying according to claim 1 and absorption extraction low-carbon olefin mixed gas is characterized in that said ethers is ether or dme.
4. the method for employing rectifying according to claim 1 and absorption extraction low-carbon olefin mixed gas is characterized in that said hydro carbons is propane, butane or pentane.
5. the method for employing rectifying according to claim 1 and absorption extraction low-carbon olefin mixed gas is characterized in that propylene and the volumn concentration of butylene in mixed gas are 5%～95% in the said low-carbon olefin mixed gas.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103880577A (en) * | 2014-03-20 | 2014-06-25 | 中国石油集团东北炼化工程有限公司吉林设计院 | Reaction product separation system for production of propylene and olefins by using methanol |
| CN105985214A (en) * | 2015-01-29 | 2016-10-05 | 上海碧科清洁能源技术有限公司 | Method for recycling ethylene and method for separating mixed hydrocarbons |
| CN110092701A (en) * | 2018-01-31 | 2019-08-06 | 中国寰球工程有限公司 | The lighter hydrocarbons separation system and method for MTO product mix gas |
| CN111116298A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Separation method and device for preparing olefin from synthesis gas |
| CN113354501A (en) * | 2021-03-19 | 2021-09-07 | 北京欧谊德科技有限公司 | Separation method for recovering C1, C2 and C3 in catalytic rich gas by combined absorption method |
| CN113354502A (en) * | 2021-03-19 | 2021-09-07 | 北京欧谊德科技有限公司 | Method for separating low-carbon hydrocarbon from unsaturated dry gas by combined absorption and recovery |
| CN113387769A (en) * | 2021-03-19 | 2021-09-14 | 北京欧谊德科技有限公司 | Separation method for recovering C1, C2 and C3 in refinery saturated dry gas by combined absorption method |
| 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 |
| CN115999328A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | Method and system for preparing ethylene by combining membrane separation with rectification |
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| CN103880577B (en) * | 2014-03-20 | 2016-03-30 | 中国石油集团东北炼化工程有限公司吉林设计院 | For the reaction product separation system of preparing propylene from methanol and methanol-to-olefins |
| CN103880577A (en) * | 2014-03-20 | 2014-06-25 | 中国石油集团东北炼化工程有限公司吉林设计院 | Reaction product separation system for production of propylene and olefins by using methanol |
| CN105985214A (en) * | 2015-01-29 | 2016-10-05 | 上海碧科清洁能源技术有限公司 | Method for recycling ethylene and method for separating mixed hydrocarbons |
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| CN110092701B (en) * | 2018-01-31 | 2023-08-15 | 中国寰球工程有限公司 | Light hydrocarbon separation method for MTO product mixed gas |
| CN110092701A (en) * | 2018-01-31 | 2019-08-06 | 中国寰球工程有限公司 | The lighter hydrocarbons separation system and method for MTO product mix gas |
| CN111116298A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Separation method and device for preparing olefin from synthesis gas |
| CN113354501A (en) * | 2021-03-19 | 2021-09-07 | 北京欧谊德科技有限公司 | Separation method for recovering C1, C2 and C3 in catalytic rich gas by combined absorption method |
| CN113387769A (en) * | 2021-03-19 | 2021-09-14 | 北京欧谊德科技有限公司 | Separation method for recovering C1, C2 and C3 in refinery saturated dry gas by combined absorption method |
| CN113354502A (en) * | 2021-03-19 | 2021-09-07 | 北京欧谊德科技有限公司 | Method for separating low-carbon hydrocarbon from unsaturated dry gas by combined absorption and recovery |
| CN115999328A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | Method and system for preparing ethylene by combining membrane separation with rectification |
| 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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