CN1006041B - Composite Catalytic Potassium Carbonate Solution for Removing Carbon Dioxide in Mixed Gas - Google Patents
Composite Catalytic Potassium Carbonate Solution for Removing Carbon Dioxide in Mixed Gas Download PDFInfo
- Publication number
- CN1006041B CN1006041B CN85103855.7A CN85103855A CN1006041B CN 1006041 B CN1006041 B CN 1006041B CN 85103855 A CN85103855 A CN 85103855A CN 1006041 B CN1006041 B CN 1006041B
- Authority
- CN
- China
- Prior art keywords
- solution
- potassium carbonate
- gas
- acetic acid
- carbonate 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.)
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- 239000002131 composite material Substances 0.000 title claims abstract description 18
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 title abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title description 4
- 230000003197 catalytic effect Effects 0.000 title description 4
- 239000001569 carbon dioxide Substances 0.000 title description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 title description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 49
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 25
- 238000010521 absorption reaction Methods 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004327 boric acid Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 63
- 229940043237 diethanolamine Drugs 0.000 claims description 14
- 239000008246 gaseous mixture Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 21
- 239000007789 gas Substances 0.000 abstract description 16
- 230000008929 regeneration Effects 0.000 abstract description 14
- 238000011069 regeneration method Methods 0.000 abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract description 2
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000003345 natural gas Substances 0.000 abstract description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 abstract 2
- 239000004471 Glycine Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000009102 absorption Effects 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- AGLSQWBSHDEAHB-UHFFFAOYSA-N azane;boric acid Chemical compound N.OB(O)O AGLSQWBSHDEAHB-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- PQKYLOVVTTUCKM-UHFFFAOYSA-N carbamic acid hydrate Chemical compound O.NC(O)=O PQKYLOVVTTUCKM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- 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
Landscapes
- Gas Separation By Absorption (AREA)
Abstract
The invention relates to the removal of CO from a gas mixture containing acid gases2The invention relates to a new and more effective absorption liquid. The invention adopts potassium carbonate solution containing composite catalyst to remove CO2Compared with other potassium carbonate solution methods catalyzed by organic amine which are used in industry or reported in patent at present, the method has the advantages of absorbing and desorbing CO2The method has the characteristics of high speed, high solution absorption capacity, low heat consumption during regeneration, stable solution and the like. The component and the concentration of the invention are K2ＣＯ315-30%, diethanolamine 10-30 g/l, glycine 10-20 g/l, boric acid 15-30 g/l, total vanadium (KVO)3Calculated) 5-10 g/l. The solution is used for removing CO from mixed gas of raw gas for synthesizing ammonia, city gas, natural gas and the like2。
Description
The invention relates to from the mist of acid gas-containing and remove CO
2A kind of invention new, more effective absorbent solution.
The solution of potassium carbonate method is widely used in the gaseous mixtures such as synthetic ammonia and hydrogen feedstock gas, town gas, natural gas and removes CO
2And H
2S, the general solution of potassium carbonate that contains more than 2.5% of using contacts with admixture of gas, and solution absorbs CO
2After enter regenerator, make sour gas desorb from solution with steam stripping, but simple solution of potassium carbonate absorbs CO
2All slower with the speed of desorb, so CO
2Degree of purification is low, the hear rate height.In solution of potassium carbonate, add various catalyst and can quicken solution absorption and desorption CO
2Speed.Italian patent 545908 has been reported and added As in solution of potassium carbonate
2O
3Or amion acetic acid is made catalyst (amion acetic acid method), As
2O
3Poisonous, it is slow that amion acetic acid is made the infiltration rate of catalyst, the solution instability.United States Patent (USP) 2,886,405th is made catalyst (diethanolamine method) with diethanol amine, and hear rate is big during this method regeneration, and the solution absorbability is low.As the Cataoarb method catalyst composition that uses is maintained secrecy in addition, catalyst solution is sold to barreled and uses factory.
The objective of the invention is to adopt a kind of novel, more effective composite catalyst solution of potassium carbonate removes CO
2, it is compared with present existing other catalysis solution of potassium carbonate method, has absorption and desorption CO
2Characteristics such as speed is fast, and hear rate is low, and is solution-stabilized.
The composite catalyzing solution of potassium carbonate is to add in the alkaline matter solution of potassium carbonate by amion acetic acid, the composite catalyst that diethanol amine and boric acid are formed, and the each component role is as follows:
1. amion acetic acid: it and CO
2Very high molecular reaction velocity constant is arranged, have guiding CO
2Change the effect of liquid phase rapidly over to by gas phase, its chemical equation is as follows:
CO
2+RR′NH
RR′NCOO
-+H
+
RR′NCOO
-+H
2O
HCO
- 3+RR′NH
Be CO
2At first generate carbamate with the amion acetic acid reaction, carbamate water Jie regenerates utilizable unhindered amina then, so the hydrolysis rate of carbamate is depended in the catalytic action of amine to a great extent.
2. diethanol amine: when it joins solution of potassium carbonate with amion acetic acid, increase solution and absorb CO
2Ability, and promote the hydrolysis of above-mentioned carbamate to make the fast rapid regeneration of unhindered amina come out to be reused for to speed CO
2Absorption.
3. boric acid: boric acid picks up very big facilitation to separating of solution, improves desorption rate, makes solution regenerate more fully, and the circulation that it not only helps solution absorbs again, improves the absorption efficiency of solution, and can reduce the regeneration hear rate of solution significantly.
Actual reaction mechanism is comparatively complicated, and boric acid and hydroxyl effect generate ester and amino effect generates boric acid ammonia salt, therefore absorbs CO for solution of potassium carbonate
2Belong to comprehensive composite catalyzing effect with speeding up of desorb.
The concentration of composite catalyzing solution of potassium carbonate is: K
2CO
315～30%, diethanol amine 10～30 grams per liters, amion acetic acid 10～20 grams per liters, boric acid 15～30 grams per liters, total vanadium is (with KVO
3Meter) 5～10 grams per liters.The actual solution concentration of using depends on component, the degree of purification of requirement and the temperature and pressure of absorption of processed gas.
Absorbent solution corrosivity of the present invention is little, and side reaction is little, adds the V of 5～10 grams per liters in solution
2O
5Can suppress corrosion of Carbon Steel.
The solution of potassium carbonate of solution of the present invention and other catalysis absorbs CO
2Speed to such as table 1.The composite catalyzing solution of potassium carbonate is compared with other catalytic solution in the table and is had infiltration rate faster as seen from the table.
The desorption rate contrast of the solution of potassium carbonate of composite catalyzing and other two kinds of catalytic solutions as shown in Figure 1.What represent on Fig. 1 is that solution regeneration degree reduction value when regenerating concerns over time, and from scheming the interior at one time regeneration degree reduction value maximum of visible solution of the present invention, this expression desorption rate is the fastest.
See Table 1
The present invention generally adopts two-stage regeneration, the technological process of two sections absorptions, and flow process is illustrated as Fig. 2.Unstripped gas enters the bottom on absorption tower 1, removes CO in the gas in Ta Nei and absorbent solution counter current contacting
2Purified gas is sent to subsequent processing after cooling, that comes out from absorption tower bottom contains CO
2Enter regenerator 2 top sprays after the rich solution decompression and be heated, the solution that comes out in the regenerator middle part is semi lean solution, squeeze into middle part, absorption tower spray with semi-leanpump 3, another part solution is through the regenerator hypomere, by the further thermal regeneration of boiling device 6 vapor supplied, after squeezing into cooler 5, the lean pump 4 that comes out from regenerator bottom goes into the absorption tower top spray.
Use the solution of potassium carbonate of composite catalyzing to remove CO
2The main technique condition:
Absorption tower operating pressure 12～30 kilograms per centimeter
3(definitely)
80～90 ℃ of absorption tower lean solution temperature
105～115 ℃ of absorption tower semi lean solution temperature
Lean solution conversion ratio 20～25% Fc=0.2～0.25
Semi lean solution conversion ratio 40～45% Fc=0.4～0.45
Rich solution conversion ratio 80～90% Fc=0.8～0.9
110～125 ℃ of regenerator bottom temps
CO in the purified gas
2Content＜0.1%
CO in the regeneration gas
2Content＞98%
The composite catalyzing solution of potassium carbonate removes CO
2Technology and advanced in the world at present diethanolamine method, the technical-economic index such as the table 2 of amion acetic acid method.
As seen from Table 2, the absorption CO of solution of the present invention
2Can have the diethanolamine method of industrial use now, amion acetic acid method height, regeneration hear rate low 20～25%.
The preparation of solution of the present invention can utilize the diethanolamine method or the amion acetic acid method solution that use in the original production to add other catalyst by solution composition of the present invention, be newly prepare or utilize composite catalyst solution of potassium carbonate that old solution is mixed with all need be in a static groove slaking just can squeeze into system after about 12 hours and use, can avoid solution foaming like this.Do not need to add defoamer in the ordinary course of things.When bubbling, can open in the short time with active carbon filter to remove foamer.
In sum, solution advantage of the present invention is: absorption and desorption CO
2Speed fast, solution absorbs CO
2The ability height, the regeneration energy consumption is low, solution-stabilized, can utilize the preparation of former amion acetic acid solution or diethanolamine solution.
Example 1:
Handling tolerance is 34000NM
3In the commercial plant of/hr, absorption pressure is 18 kilograms per centimeter
2, adopt the technological process of two sections absorptions and two-stage regeneration, adopted K originally
2The O200 grams per liter, the solution of amion acetic acid 50 grams per liter compositions (amion acetic acid method) removes CO
2, air inlet CO
228%, CO in the purified gas
2Content＞0.3% is used composite catalyzing hot potassium carbonate solution instead, and solution compolision is K
2The O200 grams per liter, amion acetic acid 15 grams per liters, diethanol amine 20 grams per liters, boric acid 20 grams per liters, vanadium is (with KVO
3Meter) 10 grams per liters, CO in the purified gas
2Reduce to＜0.1%.
Example 2:
One factory processes tolerance 36000NM
3The commercial plant of/hr, absorption pressure 18 kilograms per centimeter
2, used K originally
2The O200 grams per liter, the amion acetic acid catalysis solution of potassium carbonate of amion acetic acid 30 grams per liters removes CO
2Air inlet CO
227%, CO in the clarifier
21%, the regeneration hear rate is 1200Kcal/NM
3, now use the composite catalyst solution of potassium carbonate instead, solution compolision is K
2The O200 grams per liter, amion acetic acid 15 grams per liters, diethanol amine 15 grams per liters, boric acid 20 grams per liters are being kept under the origin operation situation CO in the clarifier
2Reduce to 0.6%, the regeneration hear rate is reduced to 850Kcal/NM
3CO
2
Claims (2)
1, adopt the composite catalyst solution of potassium carbonate to remove CO in the gaseous mixture
2, its characteristics are that this composite catalyst is made up of amion acetic acid, diethanol amine and boric acid, and add vanadium as corrosion inhibiter in solution, the component of absorption liquid is: K
2CO
315～30%, diethanol amine 10～30g/L, amion acetic acid 10～20g/L, boric acid 15～30g/L, total vanadium is (with KVO
3Meter) 5～10g/L.
2, can utilize original production factory to use the solution of potassium carbonate of single catalyst (as amion acetic acid or diethanol amine) to add other compositions by first component preparation composite catalyst solution of potassium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85103855.7A CN1006041B (en) | 1985-05-08 | 1985-05-08 | Composite Catalytic Potassium Carbonate Solution for Removing Carbon Dioxide in Mixed Gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85103855.7A CN1006041B (en) | 1985-05-08 | 1985-05-08 | Composite Catalytic Potassium Carbonate Solution for Removing Carbon Dioxide in Mixed Gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85103855A CN85103855A (en) | 1986-11-05 |
| CN1006041B true CN1006041B (en) | 1989-12-13 |
Family
ID=4793482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85103855.7A Expired CN1006041B (en) | 1985-05-08 | 1985-05-08 | Composite Catalytic Potassium Carbonate Solution for Removing Carbon Dioxide in Mixed Gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1006041B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415345C (en) * | 2005-07-12 | 2008-09-03 | 南京理工大学 | Preparation of composite acid gas absorbent |
| CN101856579B (en) * | 2010-06-02 | 2012-11-14 | 清华大学 | Novel energy-saving CO2 trapping process of improved potassium carbonate |
| CN101862666B (en) * | 2010-06-13 | 2012-04-11 | 东南大学 | Carbon dioxide solid absorbent |
| EP2729237A4 (en) * | 2011-06-10 | 2015-03-04 | Co2 Solutions Inc | Enhanced enzymatic co2 capture techniques according to solution pka temperature and/or enzyme character |
| CN102350368A (en) * | 2011-06-22 | 2012-02-15 | 河北科技大学 | Potassium carbonate solution based catalytic system used for removing CO2 in fume |
| CN102389686B (en) * | 2011-09-22 | 2014-07-30 | 中国石油大学(北京) | Separating method for CO2-containing mixed gas |
| CN109420409B (en) * | 2017-08-22 | 2021-08-06 | 中国石油化工股份有限公司 | Selective removal of H-containing compounds from gas streams2S and CO2And method for absorbing acid gas |
| CN114053835A (en) * | 2021-11-11 | 2022-02-18 | 西南化工研究设计院有限公司 | Composite potassium carbonate absorbent for removing carbon dioxide and application thereof |
-
1985
- 1985-05-08 CN CN85103855.7A patent/CN1006041B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85103855A (en) | 1986-11-05 |
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