CN1962032A - Solvent and method for simultaneous removal of hydrogen sulphide and carbon dioxide - Google Patents
Solvent and method for simultaneous removal of hydrogen sulphide and carbon dioxide Download PDFInfo
- Publication number
- CN1962032A CN1962032A CN 200510095344 CN200510095344A CN1962032A CN 1962032 A CN1962032 A CN 1962032A CN 200510095344 CN200510095344 CN 200510095344 CN 200510095344 A CN200510095344 A CN 200510095344A CN 1962032 A CN1962032 A CN 1962032A
- Authority
- CN
- China
- Prior art keywords
- amine
- mdea
- solvent
- special construction
- aqueous solution
- 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.)
- Granted
Links
Landscapes
- Gas Separation By Absorption (AREA)
Abstract
The invention relates to a method for removing hydrogen sulfide and carbon diode, and relative solvent, wherein it uses special amine and water to form mixed water solution, to contact the target gas. The invention can hold the advantages of MDEA mixed solvent.
Description
Technical field:
The invention belongs to the gas purification technique field, be specifically related to remove at the same time solvent and the method used in the process of hydrogen sulfide and carbon dioxide.
Background technology:
Usually contain H in the industrial gasses
2S and CO
2Deng objectionable impurities, 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, and widely used also have tens of kinds, but prevailing method is the hydramine method.
The chemically reactive substance alkyl alcohol amine is adopted in the desulfurization of amine method, and what external at first exploitation was used is monoethanolamine (MEA), diethanol amine (DEA), diglycolamine (DGA), diisopropanolamine (DIPA) (DIPA) equal solvent.These solvent removals CO
2, H
2S efficient height, but for selectively removing H
2S and organic sulfur then efficient are relatively poor, and desulfurization energy consumption and operating cost are higher, and degrading solvent and equipment corrosion are serious.After 1980, methyl diethanolamine (MDEA) aqueous solution is owing to have advantages such as high selectivity, high acid gas load, low energy consumption and corrosivity, is used widely in that natural gas processing is industrial.
But, because MDEA and CO
2Reaction rate very slow, for the needs deep desulfuration and remove CO in a large number
2Occasion, adopt conventional MDEA solvent just improper.So, the mixed solvent that a certain amount of MEA or DEA form has appearred again in MDEA adding, this kind solvent utilize MEA or DEA can and CO
2Reaction and the fast reaction that generates carbaminate activates MDEA, thus overcome the defective that MDEA solvent desulfurization and decarburization exists, obtained effect preferably.But MEA or DEA and CO in this kind solvent
2Generate stable carbaminate, need more heat to decompose in regenerative process, the energy consumption that causes regenerating is bigger.Simultaneously, the corrosivity of carbamic acid salt pair equipment is stronger, can form incrustation scale again.In addition, carbaminate has also aggravated alkanolamine and CO
2Degradation reaction, produce a series of problems such as alkanolamine loss increase, decarbonization performance decline, corrosivity rising.
Summary of the invention:
The purpose of the present invention's invention is to adopt some amine with special construction and MDEA to form mixed solvent, can keep the advantage of aforementioned mixed solvent, overcomes their shortcoming simultaneously again.
The amine with special construction that the present invention adopts is secondary amine, and described special construction is meant that the alkyl that links to each other with amino in the molecule has significant space steric effect, they and CO
2The carbaminate R of reaction
1R
2Among the NCOOH, because R
1Or R
2Space steric effect, make-COO
-Extremely unstable with being connected of N atom, thus the stability of carbaminate is descended greatly.Like this, just overcome because the variety of problems that stability produced of carbaminate.
The amine with special construction that the present invention adopts is chosen as: isopropylamine base ethanol (IPAE), isopropylamine base isopropyl alcohol (IPAIP), isobutyl amine ethanol (IBAE), isobutyl amine propyl alcohol (IBAP), isobutyl amine isopropyl alcohol (IBAIP), tert-butylamine base propyl alcohol (TBAP), tert-butylamine base isopropyl alcohol (TBAIP) etc.
Amine with special construction used in the present invention mixes with MDEA when using, and suitable usage ratio is: the amine with special construction: MDEA=1: 1.2～6.5 (mol ratios), be preferably 1: 2～and 5.
In the mixed amine aqueous solution used in the present invention, suitable total amine concentration is: 20～70% (wt), but be preferably 30～50% (wt).
In the mixed amine 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%～5% (wt), and the use of these additives is that present technique field personnel are known.
Anyly comprise a large amount of H simultaneously
2S and CO
2Gas can handle according to the present invention.Source of the gas is not crucial for purposes of the invention, comprises for example natural gas, synthesis gas and various refinery gas.Typically, in these air-flows, comprise a large amount of H simultaneously
2S and CO
2, wherein, H
2The content of S is greatly about 5%～90% (mol), CO
2Content greatly about 5%～50% (mol).
H in the air-flow
2S and CO
2Be removed by contacting with the mixed amine aqueous solution of the present invention.Make used absorbent regeneration simultaneously, remove all or part of H that absorbs
2S and CO
2, and then be recycled to absorption step.Any known equipment in this area may be used to absorb, regenerate and other step.
The specific embodiment:
The invention will be further described below in conjunction with embodiment, but it does not limit protection scope of the present invention.
Embodiment is according to deep desulfuration of the present invention and removes CO in a large number
2Typical technology.
Comprise a large amount of H
2S and CO
2The GAS ABSORPTION tower bottom, the mixed amine aqueous solution of coming in top in the absorption tower contacts, the H in the air-flow
2S and CO
2Be removed, satisfactory product gas enters subsequent processing.Be rich in H
2S and CO
2The mixed amine aqueous solution discharge at the bottom of the absorption tower.
Suitable column plate or filler are equipped with in the absorption tower, and the concrete device of the related use in absorption tower it is well known to those having skill in the art that.The typical operating temperature in absorption tower is greatly about 25 to 90 ℃, and pressure is greatly about 0.1 to 11MPa.
Be rich in H
2S and CO
2The mixed amine aqueous solution can pass through one or more flash tanks, a part of absorbed H
2S and CO
2From the mixed amine aqueous solution, separate, and discharge from flash drum overhead.The mixed amine aqueous solution after the flash distillation enters regenerator, is regenerated in regenerator.
The concrete device of the related use of regenerator it is well known to those having skill in the art that.The typical operating temperature of regenerator is greatly about 100 to 130 ℃, and pressure is greatly about 0.1 to 0.4MPa.
In regenerator, separated the H of sucking-off
2S and CO
2Discharge from cat head, discharge at the bottom of the mixed amine aqueous solution tower after the regeneration, go into the absorption tower and reuse through supercooling is laggard.
Embodiment one:
Operating characteristics to concrete absorbent on an experimental rig is directly measured.The absorption tower internal diameter 50mm of test usefulness, interior dress φ 6 * 6 * 1 porcelain Raschig ring, regenerator internal diameter 70mm, interior dress φ 8 * 8 * 1 porcelain Raschig ring, reboiler is equipped with in the regenerator bottom.
The unstripped gas for preparing (contains H
2S14%, CO
29%) enter 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, different amine mix the operating characteristics of forming absorbent and see Table one with MDEA.
Table one: the operating characteristics of different composite absorbers
| Absorbent is formed | Purify H in the gas of back 2S：ppmv | Purify CO in the gas of back 2：v％ | Solution internal circulating load: L/h | Reboiler: kw |
| MDEA3.8mol/l+MEA0.8mol/l | 20 | 0.4 | 20.0 | 2.20 |
| MDEA2.0mol/l+IPAE0.8mol/l | 20 | 0.3 | 19.8 | 2.10 |
| MDEA3.3mol/l+IPAIP0.8mol/l | 18 | 0.3 | 18.3 | 1.95 |
| MDEA1.5mol/l+IBAE0.3mol/l | 20 | 0.4 | 19.8 | 2.04 |
| MDEA1.8mol/l+IBAP0.7mol/l | 19 | 0.4 | 19.6 | 1.98 |
| MDEA2.8mol/l+IBAIP0.8mol/l | 20 | 0.3 | 19.0 | 2.07 |
| MDEA3.0mol/l+TBAP0.6mol/l | 19 | 0.3 | 18.4 | 1.88 |
| MDEA4.2mol/l+TBAIP0.7mol/l | 20 | 0.4 | 19.6 | 2.00 |
Table one data show uses absorbent composition of the present invention, and the mixture of its absorbent properties and MDEA and MEA is suitable, but the regeneration energy consumption descends.
Embodiment two:
This test determination solution is to the corrosion of Carbon Steel situation.Adopt A
3Carbon steel lacing film, lacing film through polishing, purify, dry, be immersed in after weighing in 100 ℃ the amine aqueous solution, and with H
2S feeds in the solution with the certain speed bubbling, and the long run test time is 72 hours, takes out lacing film afterwards, with lacing film purify, dry and weigh, measure the lacing film loss of weight.The different solution of forming see Table two to the corrosion of Carbon Steel situation.
Table two, corrosion rate are relatively
| Solution composition | MDEA3.5mol/l +MEA0.8mol/l | MDEA3.5mol/l +TBAP0.8mol/l | MDEA3.5mol/l +IPAE0.8mol/l | MDEA3.5mol/l +TBAIP0.8mol/l |
| Corrosion rate mm/a | 0.058 | 0.043 | 0.032 | 0.038 |
Table two data show uses absorbent composition of the present invention, and its corrosivity reduces.
Claims (5)
1, a kind of solvent that is used for removing simultaneously hydrogen sulfide and carbon dioxide, it is characterized in that adopting some amine with special construction and MDEA to form mixed aqueous solution, employed amine with special construction is: isopropylamine base ethanol (IPAE), isopropylamine base isopropyl alcohol (IPAIP), isobutyl amine ethanol (IBAE), isobutyl amine propyl alcohol (IBAP), isobutyl amine isopropyl alcohol (IBAIP), tert-butylamine base propyl alcohol (TBAP), tert-butylamine base isopropyl alcohol (TBAIP).
2, solvent according to claim 1 is characterized in that employed amine with special construction mixes with MDEA when using, and the mol ratio of use is: the amine with special construction: MDEA=1: 1.2～6.5.
3, solvent according to claim 1 is characterized in that employed amine with special construction mixes with MDEA when using, and the mol ratio of use is: the amine with special construction: MDEA=1: 2～5.
4, solvent according to claim 1, it is characterized in that to use in the mixed aqueous solution total amine concentration weight ratio be 30～60%.
5, a kind of method that is used for removing simultaneously hydrogen sulfide and carbon dioxide is characterized in that comprising with the described mixed aqueous solution of claim 1 contacting with processed gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100953446A CN100427178C (en) | 2005-11-09 | 2005-11-09 | Solvent and method for simultaneous removal of hydrogen sulphide and carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100953446A CN100427178C (en) | 2005-11-09 | 2005-11-09 | Solvent and method for simultaneous removal of hydrogen sulphide and carbon dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1962032A true CN1962032A (en) | 2007-05-16 |
| CN100427178C CN100427178C (en) | 2008-10-22 |
Family
ID=38081361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100953446A Active CN100427178C (en) | 2005-11-09 | 2005-11-09 | Solvent and method for simultaneous removal of hydrogen sulphide and carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100427178C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009001804A1 (en) * | 2007-06-28 | 2008-12-31 | Research Institute Of Innovative Technology For The Earth | Method for efficiently recovering carbon dioxide in gas |
| CN102151456A (en) * | 2011-01-28 | 2011-08-17 | 北京化工大学 | Method and device for removing CO2 and H2S in sewage gas and similar gas resources by chemical reagent process |
| CN102898317A (en) * | 2012-10-12 | 2013-01-30 | 四川农业大学 | Organic amino compounds serving as immunopotentiators, metabolic enhancers or roborants and preparation method and use thereof |
| CN102989297A (en) * | 2012-11-30 | 2013-03-27 | 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 |
| CN104403688A (en) * | 2014-12-16 | 2015-03-11 | 西安石油大学 | Deep desulfurization and refining combined technology for liquefied petroleum gas |
| 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 |
| CN107866132A (en) * | 2016-09-28 | 2018-04-03 | 中国石油化工股份有限公司 | SO in one kind processing Claus tail gas2Absorbing liquid and processing method |
| CN112774418A (en) * | 2019-11-07 | 2021-05-11 | 江苏汉光实业股份有限公司 | Deep desulfurization and decarburization solvent and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171659C (en) * | 2001-09-26 | 2004-10-20 | 南化集团研究院 | Solvent for selectively removing sulfide from CO2-contained gas mixture |
| CN1164349C (en) * | 2001-10-30 | 2004-09-01 | 南化集团研究院 | Compound amine solvent for recovering low fractional pressure carbon dioxide |
| CN1219579C (en) * | 2002-12-11 | 2005-09-21 | 南化集团研究院 | Absorbing liquid for eliminating sulfide from gas mixture |
-
2005
- 2005-11-09 CN CNB2005100953446A patent/CN100427178C/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009001804A1 (en) * | 2007-06-28 | 2008-12-31 | Research Institute Of Innovative Technology For The Earth | Method for efficiently recovering carbon dioxide in gas |
| US8419831B2 (en) | 2007-06-28 | 2013-04-16 | Research Institute Of Innovative Technology For The Earth | Method for efficiently recovering carbon dioxide in gas |
| JP5452222B2 (en) * | 2007-06-28 | 2014-03-26 | 公益財団法人地球環境産業技術研究機構 | Method for efficiently recovering carbon dioxide in gas |
| CN102151456A (en) * | 2011-01-28 | 2011-08-17 | 北京化工大学 | Method and device for removing CO2 and H2S in sewage gas and similar gas resources by chemical reagent process |
| CN102898317A (en) * | 2012-10-12 | 2013-01-30 | 四川农业大学 | Organic amino compounds serving as immunopotentiators, metabolic enhancers or roborants and preparation method and use thereof |
| CN102898317B (en) * | 2012-10-12 | 2015-04-22 | 四川农业大学 | Organic amino compounds serving as immunopotentiators, metabolic enhancers or roborants and preparation method and use thereof |
| CN102989297A (en) * | 2012-11-30 | 2013-03-27 | 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 |
| CN104403688A (en) * | 2014-12-16 | 2015-03-11 | 西安石油大学 | Deep desulfurization and refining combined technology for liquefied petroleum gas |
| CN104403688B (en) * | 2014-12-16 | 2016-05-11 | 西安石油大学 | A kind of oil liquefied gas deep desulfuration purification group technology |
| CN107866132A (en) * | 2016-09-28 | 2018-04-03 | 中国石油化工股份有限公司 | SO in one kind processing Claus tail gas2Absorbing liquid and processing method |
| CN112774418A (en) * | 2019-11-07 | 2021-05-11 | 江苏汉光实业股份有限公司 | Deep desulfurization and decarburization solvent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100427178C (en) | 2008-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101143286B (en) | Method for removing COS from acid airflow | |
| CN100427178C (en) | Solvent and method for simultaneous removal of hydrogen sulphide and carbon dioxide | |
| RU2239488C2 (en) | Absorbing compositions for removing acid gases from gas streams | |
| EP0796646B1 (en) | Method for the removal of carbon dioxide present in gases and absorbent | |
| EP2866919B1 (en) | Aqueous alkanolamine solution and process for the removal of h2s from gaseous mixtures | |
| US7387768B2 (en) | Method for purifying gases | |
| JPS6312648B2 (en) | ||
| CN101455932A (en) | Absorbing agent capable of removing sulfide from acid gas flow and method thereof | |
| CN100584432C (en) | From acid gas stream, remove the absorbent and the method for mercaptan | |
| CN101676018A (en) | Method for selectively removing COS from acid gas flow | |
| WO1993010883A1 (en) | Lean acid gas enrichment with selective hindered amines | |
| KR20080033534A (en) | Tetraorganoammonium and tetraorganophosphonium salts for acid gas scrubbing process | |
| KR20170067782A (en) | Aqueous solution of 2-dimethylamino-2-hydroxymethyl-1,3-propanediol useful for acid gas removal from gaseous mixtures | |
| KR20170067788A (en) | Process for the removal of acid gases from gaseous mixtures using an aqueous solution of 2-dimethylamino-2-hydroxymethyl-1,3-propanediol | |
| US8337596B2 (en) | Polyalkyleneacrylamide salt for acid gas scrubbing process | |
| CN102343204A (en) | Method for removing sulfides from acidic gas flow | |
| JP2018516747A (en) | Water-soluble alkanolamine composition and process for selective removal of hydrogen sulfide from gaseous mixtures | |
| CN105344205A (en) | Absorber for selectively removing H2S from CO2-containing mixing gas | |
| CN104069716B (en) | Solvent for removing CO2 and sulfides in acidic airflow, and application thereof | |
| CN102049173B (en) | Method for deeply removing carbon dioxide from gas mixture | |
| CN109420409A (en) | It is selectively removed from air-flow containing H2S and CO2Sour gas absorbent and method | |
| JP4977704B2 (en) | Hindered cyclic polyamines and their salts for acid gas cleaning processes | |
| CN101422684B (en) | Solvent capable removing COS from acid gas flow | |
| KR20230121098A (en) | Aqueous absorption media for removing acid gases | |
| CN117065520A (en) | Combined absorbent for removing acid gas and application thereof |
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 | ||
| 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 |