CN102304010B - 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 low-carbon alkene field of refinement, relate to a kind of separation of methanol and via fluidized-bed reactor, prepare the method for alkene.
Background technology
Ethene, propylene are the 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 large breach in the production of domestic ethene, propylene over the next several years.Existing ethene, production of propylene technology on petroleum Resource Dependence are serious.What ethylene production generally adopted is light oil pyrolysis method, the production of propylene approximately 97% coproduction from cracking ethylene preparation and refinery by-product.The raw materials cost that adopts light oil pyrolysis method to prepare ethene, propylene accounts for 60～80% of production cost.Although ripening degree is high, product structure is severely limited existing production of propylene technology (cracking ethylene preparation coproduction and refinery's by-product), cannot meet the requirement of propylene consumption rapid growth.
China has relatively abundant Sweet natural gas and coal resource.Explored coal reserves is 7,650 hundred million tons, and natural gas reserves is 38 * 1012 cubic metres.Along with the development of Prospect of Gasification Technology, gas making cost reduces greatly.Utilize coal or Sweet natural gas can make in a large number cheap synthetic gas, via synthetic gas, can produce methyl alcohol, and then there is realistic meaning by preparing low carbon olefinic hydrocarbon with methanol.Converting methanol to prepare low carbon olefin be development in recent years get up take methyl alcohol as raw material, through catalyst, directly generate the novel process of low-carbon olefin mixed gas.Chinese patent CN01144188.7, CN00802040.X, CN96115333.4, CN99815451.2 have disclosed the method for converting methanol to prepare low carbon olefin.
Chinese patent CN96115333.4 has disclosed take the method that methyl alcohol, dme is waste low-carbon alkene, and the process gas that reaction produces is directly through entering ethylene/propene centrifugal station; Chinese patent CN200610144290.2 has disclosed the method for fluid catalytic cracking preparing propone, take methanol/dimethyl ether as raw material, transforms preparing propone just formed FMTP technique by fluidized-bed.The finished product of FMTP technique are propylene, and ethene and butylene and C5 component are as intermediates, and Returning reactor continues reaction and changes into propylene.
Traditional low-carbon alkene is separated to be adopted and take the deep cooling flow process that sequence flow, front-end deethanization flow process and predepropanization process be representative.Need under-100 ℃ of left and right, to methane, carry out separated with ethene 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 separated low carbon olefin gas of absorption flow process.But wherein absorption agent is omnidistance, use, easily, with component generation azeotropic, separation is not thorough, and absorption agent consumption is high, for the converting methanol to prepare low carbon olefin cost of middle and small scale, greatly improves.
Summary of the invention
In order to solve problems of the prior art, the invention provides a kind of method that adopts rectifying and absorption extraction low-carbon olefin mixed gas, solution available technology adopting ice chest raises the cost, separated incomplete problem.
Technical scheme of the present invention is:
A method that adopts rectifying and absorption extraction low-carbon olefin mixed gas, comprises the steps:
(1) in the future contract dry low-carbon olefin mixed gas and liquid of self-pressure passes into high pressure depropanizer, and the C4+ that is rich in C3 collecting from the bottom of described high pressure depropanizer enters low pressure depropanizing tower, and low pressure depropanizing tower top liquid is through pump
Send into high pressure depropanizer;
(2) gas of being collected by described high pressure depropanizer top passes into compressor, and the gas after boosting is through the cooling demethanizing tower that enters, and demethanizer column overhead gas enters bottom, absorption tower;
(3) from top, described absorption tower, pass into absorption agent, through mass transfer, the C1 and the lighter component that are not absorbed agent absorption are collected from the top on described absorption tower, absorption agent to be generated enters regenerator column from the bottom output on absorption tower after reclaiming cold with poor absorption agent heat exchange, C2 and absorption agent are realized separatedly in described regenerator column, absorption agent recycles after reclaiming heat; Described absorption agent is in molecule, to contain at least one in the hydro carbons that the carbonatoms that contains ethers Sauerstoffatom, that carbonatoms is 1-4 or oxygen-free atom in alcohols Sauerstoffatom, that carbonatoms is 1-4 or molecule is 3-5;
(4) the resulting C2～C3 in described demethanizing tower bottom is sent into deethanizing column, realize the separated of C2 and C3 in described deethanizing column, C3 enters propylene tower, at described propylene tower top, obtains propylene product, obtains propane byproduct at the bottom of tower;
(5) by described deethanizing column top C2 product input ethylene column, in described ethylene column, a large amount of ethene obtains at tower top, together after reclaiming heat, send reactive system with the C2 gas at described regenerator column top;
(6) in described ethylene column bottom, obtain ethane and send into ethane tower with a small amount of ethene, at described ethane tower top, obtain polymer grade ethylene, obtain ethane at the bottom of tower, ethane and described absorption overhead gas are together sent after reclaiming cold as fuel gas;
(7) C4+ described low pressure depropanizing tower bottom being obtained is divided into two strands, and one send C4 tower, in described C4 tower, C4 is separated with C5+, and C4 and propane are as liquefied gas tank sending district, and C5+ is as gasoline products tank sending district, another strand of Returning reacting system.
Described alcohols is preferably methyl alcohol, ethanol or butanols.
Described ethers is preferably ether or dme.
Described hydro carbons is preferably propane, butane or pentane.
In described low-carbon olefin mixed gas, propylene and the butylene volumn concentration in mixed gas is 5%～95%.
The technology of the present invention can realize the separation of olefin hydrocarbon making by coal, can obtain the products such as fuel gas, ethene, ethane, propylene, propane, liquefied petroleum gas (LPG) and gasoline, realize the complete separation of mixed olefins, the ethene obtaining through present technique separation and propylene can be used as raw material production homopolymerization or Co-polypropylene, simultaneously, also can produce the multiple derived product such as polyethylene, polyvinyl chloride, ethylene glycol, vinyl cyanide, acrylic acid and propynoic acid ester, for expansion and the development of olefin hydrocarbon making by coal downstream industry chain, provide reliable assurance.
At present, the isolation technique of olefin hydrocarbon making by coal mainly contains predepropanization technology and order isolation technique.Present technique is predepropanization and absorption techniques, with other isolation technique, compares, and present technique has the following advantages:
1) by the method absorbing, realize the separated of ethene and methane, do not need to arrange deep freeze refrigeration plant (as ice chest and decompressor etc.), the minimum operation temperature of this technique is more than-40 ℃, and the Master Cost of equipment will reduce.By the use of absorption agent, ethene is absorbed under agent absorption in absorption tower, realize the separated of ethene and methane, because the boiling point of absorption agent and ethene differs larger, absorption agent is easier to the separated ratio of ethene, solvent loss is few, and absorption agent is without other towers, not can with the generation azeotropic such as C5 cause separated not exclusively.
2) all devices is standard element equipment, can realize production domesticization.
3) absorption agent consumption is little, and consumption is only omnidistance 10% left and right of using absorption agent separating technology, for the converting methanol to prepare low carbon olefin cost of middle and small scale, greatly reduces, and facility investment is low.
4) absorption agent loss is few, absorbs, desorb is easy, is conducive to the operational condition of optimized Separation, for portion gas (being generally ethene) Returning reactor being continued to the process form of reaction, be conducive to analyze absorption agent for the impact of reaction workshop section.
5) process, simple to operate.
6) can be less than 0.5% (V) by the optimization of operational condition being made to absorb ethylene content in the gas of tower top.
The inventive method, particularly, for the converting methanol to prepare low carbon olefin technique of middle and small scale, has very strong economic and practical.
Accompanying drawing explanation
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, 5-regenerator column, 6-deethanizing column, 7-ethylene column, 8-ethane tower, 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
Below in conjunction with 1 pair of technical process of the present invention of accompanying drawing, by specific embodiment, further describe.
Adopt the method for rectifying and absorption extraction low-carbon olefin mixed gas, comprise the steps: that self-pressure contracts dry in the future low-carbon olefin mixed gas A and liquid pass into high pressure depropanizer 1, the C4+ that is rich in C3 collecting from the bottom of high pressure depropanizer 1 enters 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 passes into process gas compression machine 12, gas after boosting is through the cooling demethanizing tower 3 that enters, demethanizing 3 column overhead gases enter 4 bottoms, absorption tower, from absorption tower, 4 tops pass into absorption agent, through mass transfer, not being absorbed C1 that agent absorbs and lighter component B 4 top collects from absorption tower, until absorbent regeneration, from the bottom output on absorption tower 4, after reclaiming cold, rich or poor absorption agent interchanger 11 enters regenerator column 5, in regenerator column 5, C2 is realized separated with absorption agent, absorption agent recycles after reclaiming heat, the described demethanizing tower 3 resulting C2～C3 in bottom are sent into deethanizing column 6, in described deethanizing column 6, realize the separated of C2 and C3, C3 enters propylene tower 9, at described propylene tower 9 tops, obtain propylene product E, at the bottom of tower, obtain propane byproduct H.By described deethanizing column 6 top C2 product input ethylene columns 7, in described ethylene column 7, a large amount of ethene obtains at tower top, together after reclaiming heat, send reactive system with the C2 gas at described regenerator column 5 tops.In described ethylene column 7 bottoms, obtain ethane and send into ethane tower 8 with a small amount of ethene, at described ethane tower 8 tops, obtain polymer grade ethylene D, obtain ethane at the bottom of tower, ethane and described absorption tower 4 top gas bodies are sent after together reclaiming cold as fuel gas.The C4+F that described low pressure depropanizing tower 2 bottoms are obtained is divided into two strands, and one send C4 tower 10, in described C4 tower 10, C4 is separated with C5+, and C4 and propane are as liquefied gas tank sending district, and C5+G is as gasoline products tank sending district, another strand of Returning reacting system.Described absorption agent is one or more mixing in methyl alcohol, ethanol, butanols, ether, dme, propane, butane or pentane.In described low-carbon olefin mixed gas, propylene and the butylene volumn concentration in mixed gas is 5%～95%.
The composite distribution that in table 1, data are feed gas.
Data major equipment operating parameters in table 2.
Low-carbon olefin mixed gas to be separated in certain technique of table 1 forms
| Product component | Flow |
| Component | Molecular formula | Molecular weight | Kg/h | (wt)％ |
| Hydrogen | 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) in the future contract dry low-carbon olefin mixed gas and liquid of self-pressure passes into high pressure depropanizer, the C4+ that is rich in C3 collecting from the bottom of described high pressure depropanizer enters 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 described high pressure depropanizer top passes into compressor, and the gas after boosting is through the cooling demethanizing tower that enters, and demethanizer column overhead gas enters bottom, absorption tower;
(3) from top, described absorption tower, pass into absorption agent, through mass transfer, the C1 and the lighter component that are not absorbed agent absorption are collected from the top on described absorption tower, absorption agent to be generated enters regenerator column from the bottom output on absorption tower after reclaiming cold with poor absorption agent heat exchange, C2 and absorption agent are realized separatedly in described regenerator column, absorption agent recycles after reclaiming heat; Described absorption agent is in molecule, to contain at least one in the hydro carbons that the carbonatoms that contains ethers Sauerstoffatom, that carbonatoms is 1-4 or oxygen-free atom in alcohols Sauerstoffatom, that carbonatoms is 1-4 or molecule is 3-5;
(4) the resulting C2～C3 in described demethanizing tower bottom is sent into deethanizing column, realize the separated of C2 and C3 in described deethanizing column, C3 enters propylene tower, at described propylene tower top, obtains propylene product, obtains propane byproduct at the bottom of tower;
(5) by described deethanizing column top C2 product input ethylene column, in described ethylene column, a large amount of ethene obtains at tower top, together after reclaiming heat, send reactive system with the C2 gas at described regenerator column top;
(6) in described ethylene column bottom, obtain ethane and send into ethane tower with a small amount of ethene, at described ethane tower top, obtain polymer grade ethylene, obtain ethane at the bottom of tower, ethane and described absorption overhead gas are together sent after reclaiming cold as fuel gas;
(7) C4+ described low pressure depropanizing tower bottom being obtained is divided into two strands, and one send C4 tower, in described C4 tower, C4 is separated with C5+, and C4 and propane are as liquefied gas tank sending district, and C5+ is as gasoline products tank sending district, another strand of Returning reacting system;
In aforesaid method, the pressure and temperature parameter of each equipment is as follows:
。
2. the method for employing rectifying according to claim 1 and absorption extraction low-carbon olefin mixed gas, is characterized in that described 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 described 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 described 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 in described low-carbon olefin mixed gas that propylene and the volumn concentration of butylene in mixed gas are 5%～95%.
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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 |
| CN105985214B (en) * | 2015-01-29 | 2018-11-06 | 上海碧科清洁能源技术有限公司 | A kind of method recycling ethylene and a kind of method of separation hydrocarbon mixture |
| 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 |
| 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 |
| CN113354502B (en) * | 2021-03-19 | 2022-11-08 | 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 |
| CN113354501B (en) * | 2021-03-19 | 2022-11-08 | 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 |
| 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 |
| 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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| US5326929A (en) * | 1992-02-19 | 1994-07-05 | Advanced Extraction Technologies, Inc. | Absorption process for hydrogen and ethylene recovery |
| US6303841B1 (en) * | 1999-10-04 | 2001-10-16 | Uop Llc | Process for producing ethylene |
| CN101353286B (en) * | 2007-07-25 | 2011-12-07 | 惠生工程（中国）有限公司 | Non-copious cooling lower carbon number hydrocarbons separation method containing light gas |
| CN101445419B (en) * | 2007-11-27 | 2012-10-31 | 惠生工程（中国）有限公司 | Method for separating lower hydrocarbon containing light gas by combining distillation and solvent absorption |
| CN101234946B (en) * | 2008-02-29 | 2010-11-24 | 中国天辰工程有限公司 | Method for separating low-carbon olefin mixed gas |
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