CN101676018A - Method for selectively removing COS from acid gas flow - Google Patents
Method for selectively removing COS from acid gas flow Download PDFInfo
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- CN101676018A CN101676018A CN200810156073A CN200810156073A CN101676018A CN 101676018 A CN101676018 A CN 101676018A CN 200810156073 A CN200810156073 A CN 200810156073A CN 200810156073 A CN200810156073 A CN 200810156073A CN 101676018 A CN101676018 A CN 101676018A
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- Prior art keywords
- cos
- aqueous solution
- gas
- amine
- activator
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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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- 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
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
The invention belongs to the gas purification technical field. Composite amine water solution is used as absorbent and a proper amount of activator is added and most of COS is removed when CO2 removalrate is not high and the absorbent is regenerated. The composite amine is composed of methyl diethanol amine and diisopropanolamine and the activator is 1,4-di-aza-bicyclo[2,2,2]-octane or 1,4-di-aza-bicyclo[4,3,0]-5-nonaen. The method has higher COS removal rate compared with the conventional amine method.
Description
Technical field:
The invention belongs to the gas purification technique field, be specifically related to optionally remove the method for COS from acid gas stream, 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.These physical solvents can be removed sour gas fully, also can optionally remove H
2S, but this process is inappropriate because in most of physical solvents the solubility of COS and CO
2Solubility between do not have too big difference, if from contain air-flow, optionally remove COS, difficulty relatively then, and these physical solvents can absorb other linear paraffin, regeneration deals with very expensive.
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, they are to removing H
2S and CO
2Have higher efficient, but then there are many difficulties in COS.Primary amine and secondary amine and COS directly react the loss that generates metastable compound and cause effective amine to be increased, and also can cause the corrosion of equipment simultaneously, and the reaction speed of these amines and COS than with CO
2Slow more than 100 times of reaction speed, its effect of optionally removing COS is obviously very poor.
Yet, extremely strict to the COS content requirement in the air-flow in many cases, and do not need to remove in a large number CO
2, therefore, there is Many researchers to propose suggestion to removing COS, comprising:
US patent 4482529 has disclosed from containing H
2Optionally remove the method for COS in the air-flow of S, add a spot of dicyclo tertiary amine in known physical solvent, the dicyclo tertiary amine has promoted the hydrolysis of COS.
US patent 4808765 has disclosed the method that multistep is removed sulfide suddenly from sour gas, at first removes H with MDEA and DIPA mixed solution
2S and 50% above COS, and then rest parts COS is changed into NaS or Na with basic amine solution
2CO
3, last, remove other organic sulfur compound and remaining COS with alkali-metal hydroxide aqueous solution.This technology comprises 3 absorption step, and each absorption step needs independently regenerative system again, and equipment complexity, operating cost are also very high.
US patent 4980140 has disclosed to adopt and has comprised the solvent of tertiary amine, physical solvent and low amounts of water from containing H
2Optionally remove the method for COS in the air-flow of S, effectively physical solvent comprises sulfone, sulfoxide, dihydroxylic alcohols and list and diether etc.
US patent 6852144 has disclosed and has adopted activation MDEA solvent from containing H
2Optionally remove the method for COS in the air-flow of S, its activator is piperazine, methyl piperazine and morpholine.
Summary of the invention:
The objective of the invention is to adopt a kind of varies aqueous solution to make absorbent, add an amount of activator, can be 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 COS, and aqueous solution absorbent contains the varies of percentage by weight 20-56% and the activator of percentage by weight 3-8%; Varies is made up of methyl diethanolamine MDEA and diisopropanolamine (DIPA) DIPA, and activator is 1,4-diazabicylo [2,2,2]-octane or 1,4-diazabicylo [4,3,0]-5-nine alkene.
Varies is made up of MDEA and DIPA, and suitable total amine concentration is 20～56% (weight ratios, down together), but is preferably 30～50%, and wherein, MDEA: DIPA is 2-3: 1;
Activator is 1,4-diazabicylo [2,2,2]-octane (DABCO) or 1, and 4-diazabicylo [4,3,0]-5-nine alkene (DBN), its concentration is 3-8% (weight ratio).
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 0.01%～2% (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 CO in the air-flow
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:
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.
Embodiment:
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 CO
28.6%, COS856 * 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 (5)
1. method that selectivity is removed COS from acid gas stream, it is characterized in that it adopts a kind of aqueous solution absorbent and air-flow counter current contacting and remove COS, aqueous solution absorbent contains the varies of percentage by weight 15-56% and the activator of percentage by weight 3-8%; Varies is made up of methyl diethanolamine MDEA and diisopropanolamine (DIPA) DIPA, and activator is 1,4-diazabicylo [2,2,2]-octane or 1,4-diazabicylo [4,3,0]-5-nine alkene.
2. 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.
3. according to the described method of claim 1, it is characterized in that aqueous solution absorbent is renewable.
4. according to the described method of claim 1, it is characterized in that adding in the aqueous solution absorbent corrosion inhibitor, defoamer and antisludging agent is additive.
5. according to the described method of claim 4, it is characterized in that the concentration range of additive is weight percentage 0.01%～2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810156073A CN101676018A (en) | 2008-09-19 | 2008-09-19 | Method for selectively removing COS from acid gas flow |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810156073A CN101676018A (en) | 2008-09-19 | 2008-09-19 | Method for selectively removing COS from acid gas flow |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101676018A true CN101676018A (en) | 2010-03-24 |
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ID=42028824
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810156073A Pending CN101676018A (en) | 2008-09-19 | 2008-09-19 | Method for selectively removing COS from acid gas flow |
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| CN (1) | CN101676018A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| EP2554243A4 (en) * | 2010-03-29 | 2015-06-03 | Toshiba Kk | Acidic gas absorbent, acidic gas removal device, and acidic gas removal method |
| CN105344205A (en) * | 2014-08-20 | 2016-02-24 | 中国石油化工股份有限公司 | Absorber for selectively removing H2S from CO2-containing mixing gas |
| CN108367233A (en) * | 2015-12-22 | 2018-08-03 | 株式会社神户制钢所 | The separation and recovery method of absorbent and its manufacturing method and acid compound |
| CN108722115A (en) * | 2017-04-18 | 2018-11-02 | 中国石油化工股份有限公司 | One kind removing CO from gaseous mixture2Special absorptive liquid |
| CN111757773A (en) * | 2018-02-28 | 2020-10-09 | 株式会社可乐丽 | Composition for removing sulfur-containing compounds |
-
2008
- 2008-09-19 CN CN200810156073A patent/CN101676018A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2554243A4 (en) * | 2010-03-29 | 2015-06-03 | Toshiba Kk | Acidic gas absorbent, acidic gas removal device, and acidic gas removal method |
| 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 |
| CN105344205A (en) * | 2014-08-20 | 2016-02-24 | 中国石油化工股份有限公司 | Absorber for selectively removing H2S from CO2-containing mixing gas |
| CN108367233A (en) * | 2015-12-22 | 2018-08-03 | 株式会社神户制钢所 | The separation and recovery method of absorbent and its manufacturing method and acid compound |
| CN108722115A (en) * | 2017-04-18 | 2018-11-02 | 中国石油化工股份有限公司 | One kind removing CO from gaseous mixture2Special absorptive liquid |
| CN111757773A (en) * | 2018-02-28 | 2020-10-09 | 株式会社可乐丽 | Composition for removing sulfur-containing compounds |
| US11795404B2 (en) | 2018-02-28 | 2023-10-24 | Kuraray Co., Ltd. | Composition for removing sulfur-containing compounds |
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Application publication date: 20100324 |