CN101143286B - Method for removing COS from acid airflow - Google Patents
Method for removing COS from acid airflow Download PDFInfo
- Publication number
- CN101143286B CN101143286B CN200610041585A CN200610041585A CN101143286B CN 101143286 B CN101143286 B CN 101143286B CN 200610041585 A CN200610041585 A CN 200610041585A CN 200610041585 A CN200610041585 A CN 200610041585A CN 101143286 B CN101143286 B CN 101143286B
- Authority
- CN
- China
- Prior art keywords
- cos
- weight ratio
- diazabicylo
- remove
- absorbent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Gas Separation By Absorption (AREA)
Abstract
The invention belongs to the gas purification technology field. The invention uses a compound amine solution as absorbent, and proper amount of activator is added to totally remove H<SUB>2</SUB>S fromairflow. When the removing rate is not high, the invention can remove most of the COS, and the absorbent can be regenerated and circulating used. The invention has a higher COS removing rate than themethod by using conventional amine.
Description
Technical field:
The invention belongs to the gas purification technique field, be specifically related to from acid gas stream, remove the method for COS.This acid gas stream comprises natural gas, synthesis gas, refinery gas, liquefied petroleum gas etc.
Background technology:
Usually contain H in the industrial gasses
2S, CO
2With objectionable impurities such as COS, various mercaptan, thioethers, before further utilizing, they must removed totally, up to the present, the technology that is applied to the decarburization of qi exhaustion sulphur is descended hundreds of.Modal is that acid gas stream contacts in gas cleaning plant with organic solvent (or aqueous solution of organic solvent).A large amount of patent documentations have been arranged in these processes.Generally speaking, two kinds of different gas purification solvents are roughly arranged.
First kind is physical solvent, and what lean on is Physical Absorption.Typical physical solvent has the mixture of sulfolane and its derivative, straight chain acid amides, NMP (N-methyl pyrrolidone), N-alkyl pyrrolidone, relevant pyrrolidones, methyl alcohol and polyvinyl alcohol dialkyl ether.
Another kind is a chemical solvent.Based on chemical reaction, make sour gas generate the compound of easily removing.For instance, industrial the most frequently used chemical solvent is a hydramine, because the salt that generates decomposes easily or carried by steam gas easily, therefore amine can recycle.From air-flow, remove the MDEA that the reasonable amine of acid ingredient has monoethanolamine (MEA), diethanol amine (DEA), triethanolamine (TEA), diisopropanolamine (DIPA) (DIPA), amido ethoxy ethanol (AEE), methyl diethanolamine (MDEA) and added various activators.
Usually, above-mentioned solvent is to removing H
2S and CO
2Have higher efficient, but then there are many difficulties in COS.Physical solvent can be removed COS fully, but this process is inappropriate, because these physical solvents can absorb other linear paraffin, regeneration deals with very expensive.In the chemical solvent, primary amine and secondary amine and COS directly react the loss increase that generates metastable compound and cause effective amine, also can cause the corrosion of equipment simultaneously, and tertiary amine then only depends on physical dissolution to remove COS, and its effect is obviously very poor.
Therefore, there is Many researchers to propose suggestion, comprises removing COS:
Adopt the COS hydrolyst that COS is hydrolyzed into H
2S and CO
2, and then with alkanolamine solution with H
2S and CO
2Remove;
Air-flow is contacted with the mixed solvent of MDEA and DIPA, and here 50%～80% COS is hydrolyzed into H
2S and CO
2The remaining peralkaline amine liquid of the air communication that contains COS washs into Na
2S or Na
2CO
3At last, Yu Xia COS removes by alkali lye.This process comprises three sections, all will regenerate for every section, therefore deals with expensive;
Air-flow is contacted with the pure amine solvent that has added catalyst, and COS is hydrolyzed into H
2S and CO
2After be absorbed and remove.But this method need be at CO
2Could partly remove COS under the very high situation of removal efficiency.
Summary of the invention:
The present invention adopts a kind of varies aqueous solution to make absorbent, adds an amount of activator, can remove H from air-flow fully
2S removes most COS; And at CO
2Remove under the not high situation of rate, remove most COS, (as natural gas purification) reserve part CO in some processes
2Need.
The present invention is achieved like this: it adopts a kind of aqueous solution absorbent and air-flow counter current contacting and removes H
2S and COS, it is that 15-55% varies and weight ratio are the activator of 5-12% that absorbent contains weight ratio, varies is made up of methyl diethanolamine (MDEA) and diisopropanolamine (DIPA) (DIPA), and activator is made up of diazabicylo (DBU) and piperazine or diazabicylo (DBU) and morpholine.
The weight ratio of varies is preferably 30～50%, and wherein, MDEA: DIPA is 2-3: 1;
Activator is made up of with morpholine (MAL) diazabicylo (DBU) and piperazine (PZ) or diazabicylo (DBU), and wherein the ratio of diazabicylo and piperazine or diazabicylo (DBU) and morpholine is 1-3: 1.
In the varies aqueous solution used in the present invention, also can comprise additive as corrosion inhibitor, defoamer and similar components.Typically, the concentration range of these additives is 0%～5% (wt), and the use of these additives is that present technique field personnel are known.
Adopt the employed device of solvent removal COS of the present invention can with habituation use identical.Even the H in the air-flow
2S, CO
2And COS is removed by contacting with the mixed amine aqueous solution of the present invention.
Absorption process can one-time-reach-place, also can continuous several times carry out.Can use the solution of multiply to carry out the gas-liquid contact among the latter from the order that reduces successively by temperature to cat head at the bottom of the tower.
The rich solution that has absorbed acid gas is realized regeneration by decompression, can realize by choke valve.The energy that rich solution contains can reclaim by turbine.
Flash tank can be adopted when removing acid gas, also repeatedly flash distillation can be carried out.Rich solution passes through and further regenerates the back and then be recycled to absorption step after the flash distillation.
Any known equipment in this area may be used to absorb, regenerate and other step.
The specific embodiment:
Embodiment:
Below the invention will be further described by embodiment, its objective is in order to understand content of the present invention better, but it does not limit protection scope of the present invention.
Operating characteristics to concrete absorbent on an experimental rig is directly measured.The absorption tower internal diameter 20mm of test usefulness, interior dress φ 3 * 3 stainless steel θ ring, regenerator internal diameter 50mm, interior dress φ 6 * 6 * 1 porcelain Raschig ring, reboiler is equipped with in the regenerator bottom.
The unstripped gas for preparing (contains H
2S14%, CO
29%, COS1043 * 10
-6) entering the solution counter current contacting that absorption tower bottom and cat head enter, the acid gas in the gas is absorbed, and purified gas comes out to enter gas-liquid separator from cat head and reclaims emptying after institute's droplets entrained.
The rich solution that has absorbed acid gas leads to the regenerator top at the bottom of the absorption tower, contact and obtain regeneration with the steam counter-flow of rising in regenerator.Lean solution after the regeneration is sent into absorption tower jacking row and is absorbed after cooling.The gas that comes out from regeneration overhead enters the regeneration gas cooler with the recovery of the water vapour the gas, and regeneration gas is emptying after separating.
Certain at gas flow, the operating characteristics of different absorbents sees Table one.
Table one: the operating characteristics of different composite absorbers
Table one data show uses absorbent composition of the present invention, and its removal efficiency to COS can obviously improve.
Claims (6)
1. from acid gas stream, remove the method for COS, it is characterized in that it adopts a kind of aqueous solution absorbent and air-flow counter current contacting and remove H
2S and COS, it is that 15-55% varies and weight ratio are the activator of 5-12% that absorbent contains weight ratio, varies is made up of methyl diethanolamine MDEA and diisopropanolamine (DIPA) DIPA, and activator is made up of diazabicylo DBU and piperazine or diazabicylo (DBU) and morpholine.
2. according to the described method of claim 1, the weight ratio that it is characterized in that varies is 30～50%.
3. according to the described method of claim 1, it is characterized in that the weight ratio of MDEA and DIPA is 2-3 in the varies: 1.
4. according to the described method of claim 1, the weight ratio that it is characterized in that diazabicylo and piperazine is 1-3: 1.
5. according to the described method of claim 1, the weight ratio of its feature diazabicylo and morpholine is 1-3: 1.
6. according to the described method of claim 1, it is characterized in that having added in the absorbent an amount of corrosion inhibitor, defoamer and antisludging agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610041585A CN101143286B (en) | 2006-09-15 | 2006-09-15 | Method for removing COS from acid airflow |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610041585A CN101143286B (en) | 2006-09-15 | 2006-09-15 | Method for removing COS from acid airflow |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101143286A CN101143286A (en) | 2008-03-19 |
| CN101143286B true CN101143286B (en) | 2010-05-12 |
Family
ID=39206125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200610041585A Active CN101143286B (en) | 2006-09-15 | 2006-09-15 | Method for removing COS from acid airflow |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101143286B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745289B (en) * | 2008-12-12 | 2013-03-27 | 南化集团研究院 | Method for selectively removing H2S from gas mixture containing CO2 |
| CN101869824B (en) * | 2009-04-21 | 2012-06-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Flue gas desulfurizing agent and flue gas desulfurization method |
| EA019333B1 (en) * | 2009-08-04 | 2014-02-28 | Басф Се | Absorption agent for removing acidic gases from a fluid flow |
| DE102010004070A1 (en) * | 2010-01-05 | 2011-07-07 | Uhde GmbH, 44141 | CO2 removal from gases by means of aqueous amine solution with the addition of a sterically hindered amine |
| CN102343204A (en) * | 2010-08-04 | 2012-02-08 | 中国石油化工集团公司 | Method for removing sulfides from acidic gas flow |
| CN102527190A (en) * | 2010-12-24 | 2012-07-04 | 中国石油化工集团公司 | Method for removing acid gas by screw expander |
| CN104411806A (en) * | 2012-06-29 | 2015-03-11 | 陶氏环球技术有限责任公司 | Aqueous alkanolamine absorbent composition comprising piperazine for enhanced removal of hydrogen sulfide from gaseous mixtures and method for using the same |
| CN102989297B (en) * | 2012-11-30 | 2014-06-04 | 西南化工研究设计院有限公司 | Process for purification, desulfuration and decarburization of calcium carbide furnace gas and cyclic utilization of solution |
| CN104415643A (en) * | 2013-08-20 | 2015-03-18 | 中国石油化工股份有限公司 | Method for selectively removing H2S from gas flow containing CO2 |
| CN105498450A (en) * | 2014-10-14 | 2016-04-20 | 中国石油化工股份有限公司 | Desulfurization absorption liquid capable of saving energy and reducing consumption |
| CN105879602B (en) * | 2016-05-25 | 2019-10-11 | 郝天臻 | A kind of tail gas of sulphur processing desulfurization solvent and treatment process |
| CN107433108A (en) * | 2016-05-26 | 2017-12-05 | 中国石油化工股份有限公司 | A kind of lyosoption for being used for desulfurization and decarburization in plant catalytic dry gas |
| CN106479578B (en) * | 2016-11-09 | 2019-05-17 | 中石化宁波工程有限公司 | A kind of acid gas removal technique of mating coal gasification |
| CN112143536A (en) * | 2019-06-27 | 2020-12-29 | 中石化南京化工研究院有限公司 | Absorption liquid for corrosion prevention of decarburization system in natural gas |
| CN112574788B (en) * | 2019-09-29 | 2021-12-10 | 中石化南京化工研究院有限公司 | Method for purifying blast furnace gas |
| CN113786811B (en) * | 2021-10-13 | 2024-04-30 | 山东迅达催化剂有限公司 | Adsorption desulfurizing agent capable of being thermally regenerated and having COS hydrolysis function, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86107236A (en) * | 1985-10-28 | 1987-10-07 | 陶氏化学公司 | The sweetening of hydrocarbons process |
| CN1063052A (en) * | 1990-08-29 | 1992-07-29 | 兰德股份公司 | The method of selective removal of inorganic and/or sulfur-containing organic compound |
| WO2000018492A1 (en) * | 1998-09-30 | 2000-04-06 | The Dow Chemical Company | Composition and process for removal of acid gases |
| CN1307498A (en) * | 1998-06-29 | 2001-08-08 | 巴斯福股份公司 | Method for removing acid gas components from gases |
| CN1421264A (en) * | 2002-12-11 | 2003-06-04 | 南化集团研究院 | Absorbing liquid for eliminating sulfide from gas mixture |
-
2006
- 2006-09-15 CN CN200610041585A patent/CN101143286B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86107236A (en) * | 1985-10-28 | 1987-10-07 | 陶氏化学公司 | The sweetening of hydrocarbons process |
| CN1063052A (en) * | 1990-08-29 | 1992-07-29 | 兰德股份公司 | The method of selective removal of inorganic and/or sulfur-containing organic compound |
| CN1307498A (en) * | 1998-06-29 | 2001-08-08 | 巴斯福股份公司 | Method for removing acid gas components from gases |
| WO2000018492A1 (en) * | 1998-09-30 | 2000-04-06 | The Dow Chemical Company | Composition and process for removal of acid gases |
| CN1421264A (en) * | 2002-12-11 | 2003-06-04 | 南化集团研究院 | Absorbing liquid for eliminating sulfide from gas mixture |
Non-Patent Citations (2)
| Title |
|---|
| 李新学等.羰基硫脱除技术.现代化工24 8.2004,24(8),第19-20页第1部分. |
| 李新学等.羰基硫脱除技术.现代化工24 8.2004,24(8),第19-20页第1部分. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101143286A (en) | 2008-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101143286B (en) | Method for removing COS from acid airflow | |
| JP4634384B2 (en) | Absorption liquid, CO2 and / or H2S removal method and apparatus | |
| RU2534765C2 (en) | Self-concentrating absorbent for separation of acidic gas | |
| AU2013281027B2 (en) | Aqueous alkanolamine absorbent composition comprising piperazine for enhanced removal of hydrogen sulfide from gaseous mixtures and method for using the same | |
| EP0796646B1 (en) | Method for the removal of carbon dioxide present in gases and absorbent | |
| CN101455932A (en) | Absorbing agent capable of removing sulfide from acid gas flow and method thereof | |
| CA2870164C (en) | Aqueous alkanolamine solution and process for the removal of h2s from gaseous mixtures | |
| CN100584432C (en) | From acid gas stream, remove the absorbent and the method for mercaptan | |
| CN101745289B (en) | Method for selectively removing H2S from gas mixture containing CO2 | |
| US7387768B2 (en) | Method for purifying gases | |
| CN101844035A (en) | High-efficient desulfurizing agent for removing hydrogen sulfide and organic mercaptan from mixed gas | |
| CN100427178C (en) | Solvent and method for simultaneous removal of hydrogen sulphide and carbon dioxide | |
| CN101676018A (en) | Method for selectively removing COS from acid gas flow | |
| CN108310915B (en) | Composite desulfurizing agent and method for deep desulfurization of sulfur-containing gas | |
| CN104815525A (en) | Treating agent for mixing acid components in mixed gases | |
| CN111925846A (en) | High-efficiency thioether and thiophene removal solvent and application thereof | |
| KR101038764B1 (en) | Appraratus and method for solvent scrubbing co2 capture system | |
| CN106794415B (en) | Process for removing acid gases from gas mixtures using aqueous solutions of 2-dimethylamino-2-hydroxymethyl-1, 3-propanediol | |
| CN102049174A (en) | Method for partially separating carbon dioxide from gas mixture | |
| CN102343204A (en) | Method for removing sulfides from acidic gas flow | |
| CA2986035C (en) | An aqueous alkanolamine composition and process for the selective removal of hydrogen sulfide from gaseous mixtures | |
| CN101422684B (en) | Solvent capable removing COS from acid gas flow | |
| CN109420409B (en) | Selective removal of H-containing compounds from gas streams2S and CO2And method for absorbing acid gas | |
| CN104069716B (en) | Solvent for removing CO2 and sulfides in acidic airflow, and application thereof | |
| CN102451608A (en) | Tail gas treatment process applied to high-sulfur natural gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: Nanhua Group Research Institute |
|
| CP01 | Change in the name or title of a patent holder |