CN1055872C - Removing carbon dioxide from mixed gas by compound activator - Google Patents
Removing carbon dioxide from mixed gas by compound activator Download PDFInfo
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- CN1055872C CN1055872C CN92107308A CN92107308A CN1055872C CN 1055872 C CN1055872 C CN 1055872C CN 92107308 A CN92107308 A CN 92107308A CN 92107308 A CN92107308 A CN 92107308A CN 1055872 C CN1055872 C CN 1055872C
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- solution
- gas
- absorption
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- potassium carbonate
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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
- 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
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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
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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
- 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
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Abstract
The present invention relates to a compound activating potassium carbonate solution for eliminating CO2 from mixed gases containing an acidic gas and a process improvement. The present invention adopts a compound activating agent containing steric hindrance amine for eliminating the CO2, and the compound activating agent has the characteristics of rapid speed of CO2 absorption and desorption, large capability of CO2 absorption of the solution, low heat consumption for regeneration, stable solution, etc. The solution used in the present invention comprises the following ingredients and concentration of 230 to 370 g/l of K2CO3, 10 to 20 g/l of diethanolamine, 5 to 30g/1 of 2-amino-2-methyl-1-propanol (AMP), 10 to 30g/1 of boronic acid and 5 to 10g/1 of total vanadium (measured by KVO3). The solution is used for eliminating the CO2 from the mixed gases of a raw gas for synthesizing ammonia, a city gas, a natural gas, etc.
Description
The invention belongs to operation and separate class, relate to chemical absorption divided gas flow technical field.The present invention is method and the solution that removes carbonic acid gas with a kind of multiplicity reactivation solution of potassium carbonate that contains sterically hindered amines from contain acidic mixed gas.
Solution of potassium carbonate is widely used in the gas mixtures such as synthetic ammonia and hydrogen feedstock gas, town gas, Sweet natural gas and removes carbonic acid gas.General solution of potassium carbonate contacts CO with gaseous mixture
2By solution absorption, solution enters regenerator column thereafter, makes CO with steam stripped
2From solution of potassium carbonate, desorb.With simple solution of potassium carbonate absorption and desorption CO
2, speed is slow, hear rate height, CO
2Degree of purification is low.Therefore, the home and abroad is all adopted and add various catalyzer or activator in solution of potassium carbonate, to overcome the above-mentioned defective that exists.CL545908 has reported interpolation As
2O
3Or Padil makes the G-V method and the nontoxic G-V method of catalyzer, but As
2O
3Poisonous, the Padil uptake rate is slow, the solution instability; US2886405 adds diethanolamine and makes catalyzer, and this method regeneration hear rate is big.CN85103855.7 removes CO in the gas mixture with a kind of composite catalyzing solution of potassium carbonate
2Method.In solution of potassium carbonate, add Padil, diethanolamine and boric acid etc. and made catalyzer.The solution absorption and the desorption rate of this patent is fast, hear rate is low, and is solution-stabilized, and the factory of tame large, medium and small type ammonia more than 20 applies at home, obtains promising result.
The present invention has further improved the composition of composite catalyst on this basis, replaces Padil to form new composite activating agent with a kind of sterically hindered amines such as 2-amino-2-methyl-1-propanol, and it has faster absorption and desorb CO
2Speed, solution absorption CO
2Ability also higher.
American exxon (Exxon ' s) Research And Engineering company has developed a series of about sterically hindered amines heat of activation solution of potassium carbonate decarburization technique, and a series of patents have been applied for, the sterically hindered amines activator that proposes in US4112050 (1978) and US4217237 (1980) has: 4,4,5,5-tetramethyl-diethylenetriamine; 2-amino-2-methyl-1-propanol; N-cyclohexyl-1, the 3-propanediamine; N-1,8-menthanediamine etc.But all be in solution of potassium carbonate, to add a kind of sterically hindered amines separately, to improve solution absorption CO
2Ability and mass transfer velocity coefficient.
The present invention is except adding in solution of potassium carbonate a kind of sterically hindered amines (2-amino-2-methyl-1-propanol), also add non-bulky amine activator diethanolamine and boric acid, form a kind of new composite activating agent, each component role in solution of potassium carbonate is as follows:
1, sterically hindered amines: sterically hindered amines relates to hundreds of organic amine joint compounds with space steric effect, in this compounds, have at least a kind of primary amino to be connected with a tertiary carbon atom, also has the side chain that is connected with carbon atom at secondary amino group simultaneously, the selected sterically hindered amines of the present invention is 2-amino-2-methyl-1-propanol (AMP), and its molecular structural formula is:
Because of the ammonia atom that links to each other with carbon atom in the bulky amine is one to have the substituting group of side chain, thereby produced very significantly space steric effect,, made amine from different positions and CO by this effect
2Form the complex compound group of primary amino and secondary amino group, accelerated absorption CO greatly
2Speed, its net reaction is as follows:
As can be seen from the above equation, AMP can absorb CO
2Maximum capacity be 1mol CO
2/ mol amine; Receptivity is much larger than the non-space bulky amine.Because sterically hindered amines all absorbs CO with protonated stoichiometry
2So, formed the complex compound group, make its spatial branched structure that huge tension force effect be arranged.When pressurized, this tension force is obvious especially, and helps absorbing.After pressure was removed rapidly, because of the tension force effect, the amino methanol salt instability by bulky amine generates more easily lost COO
-, be easy to regeneration, therefore, bulky amine is for absorption and desorption CO
2Promoter action is all being arranged aspect the thermodynamics and dynamics two.
2, diethanolamine (DEA): it joins in the solution with AMP, evidence, these two kinds of activators and deposit, not only can not offset their activations in hot potassium carbonate solution, also play the effect of mutually promoting, adopt the activator of this combination of DEA+AMP higher by about 30% than single activator absorption speed.In the time of also can solving single use AMP bulky amine because of the big actual application problem of vapour pressure height loss.
3, boric acid: adding boric acid in solution can generate borate with amine, and it picks up very big promoter action to separating of solution, improves desorption rate, makes solution regeneration more complete, improves the absorptive capacity of solution, and can obviously reduce the regeneration hear rate.
Therefore, above-mentioned three kinds of components are formed a multiplicity reactivation system, to CO
2Absorb with desorb and play a driving role.
The concentration of compound activator solution of the present invention is: K
2CO
3230～370g/L, diethanolamine 10～20g/L, AMP 5～30g/L, boric acid 10～30g/L, total vanadium is (with KVO
3Meter) 5～10g/L.The actual strength of solution of using depends on the component of processed gas, the degree of purification of requirement and absorption temperature and pressure.
Composite activating agent of the present invention takes off CO
2Solution (2) absorbs CO in the gas with the composite catalyzing solution of potassium carbonate (1) of CN85103855.7
2Absorption rate contrast see Fig. 1,2 lines are solution absorption speed line of the present invention in Fig. 1,1 line is a CN85103855.7 solution absorption speed line, from Fig. 1 as seen, under same degree of carbonisation Fc condition, uptake rate line of the present invention (2 line) is faster than CN85103855.7 uptake rate line (1 line), and uptake rate on average improves about 20%.
Composite activating agent of the present invention takes off CO
2The desorb CO of the composite catalyzing solution of potassium carbonate (1) of solution (2) and CN85103855.7
2Fig. 2 is seen in the speed contrast, 2 lines are solution stripping speed line of the present invention in Fig. 2,1 line is a CN85103855.7 solution stripping speed line, from Fig. 2 as seen, under same degree of carbonisation Fc condition, desorption rate line of the present invention (2 line) is faster than the desorption rate line (1 line) of CN85103855.7, and the former is than the easy desorb of the latter.
The technico-economical comparison correlation data of decarbonization method of the present invention and other decarbonization methods sees Table 1.
Table 1, the technico-economical comparison contrast of several decarbonization methods
As seen from Table 1: solution absorption ability of the present invention is 28～30Nm
3CO
2/ m
3Solution, all bigger than other several solns receptivities, therefore, the solution circulated amount is few, and power consumption is also few.The present invention hear rate～3762KJ/Nm that regenerates
3CO
2, all lack than the regeneration hear rate of other several solns, more save energy.
Technical process of the present invention as shown in Figure 3.Unstripped gas enters the bottom on absorption tower 1 through cooling separator 13, removes CO in the gas in Ta Nei and composite activating agent absorbent solution counter current contact
2, purified gas is drawn through water cooler 11, separator 12 and is sent to subsequent processing in 1 top from the absorption tower.CO is come out to contain in 1 bottom from the absorption tower
2Rich solution after 10 decompressions are cut down in decompression, enter regenerator column 2 napexes sprays and be heated.The regenerator column 2 middle parts solution that comes out is semi lean solution, and semi lean solution is squeezed into 1 middle part, absorption tower spray with semi-leanpump 3.Another part solution flows into the regenerator column hypomere in the regenerator column 2, by the further thermal regeneration of boiling device 6 supply steam.The lean solution of coming out from regenerator column 2 bottoms is sent into absorption tower 1 top spray with lean pump 4 after water cooler 5 coolings.The gas that comes out from regenerator column 2 tops is gone into separator 8, the high-content CO behind the cooling condensation after condenser 7 coolings
2Gas uses for the user, and the water of condensation that comes out from condenser 7 and separator 8 bottoms is squeezed into regenerator column 2 backflows with condensate pump 9.
The composite activating agent decarburization that use contains the AMP bulky amine is that purified gas and resurgent gases all will be cooled to about 40 ℃ in technologic key, and water of condensation goes back to system.Particularly do not allow a large amount of intrasystem water of condensation to discharge outward, reduce owing to the high loss that causes of AMP vapour pressure.If system's moisture content imbalance can suitably reduce the temperature of the unstripped gas that enters absorption tower 1, reduce the saturation water content that unstripped gas is brought into.Promptly increase cooling separator 13 loads.
The present invention uses the composite activating agent that contains the AMP bulky amine to remove CO
2The main technique condition be:
Absorption tower working pressure 1.2～3.0MPa (definitely)
80～90 ℃ of absorption tower lean solution temperature
105～115 ℃ of absorption tower semi lean solution temperature
Regenerator column base pressure 0.12～0.2MPa (definitely)
110～125 ℃ of regenerator column bottom temps
Purge gas cooling back temperature≤40 ℃
Regeneration gas cooling back temperature≤40 ℃
CO in the purified gas
2Content＜0.1%
CO in the resurgent gases
2Content＞98%
Solution absorption CO
2Ability 28～30Nm
3CO
2/ m
3
Regeneration hear rate 3762KJ/Nm
3CO
2
Solutions employed of the present invention is founded the factory newly and can be prepared by the above-mentioned requirements composition when using, the solution of potassium carbonate at activators such as diethanolamine, Padil, diethylenetriamines that in modernizing and expanding the existing factory, also can utilize original production to use, add other activators by solution component of the present invention, stop to add no activator.But no matter be newly to prepare or utilize old solution to be mixed with new compound activator solution, all need in a static groove slaking just can squeeze into system after 12 hours and use, bubble when preventing the solution running.
In sum, advantage of the present invention is: absorption and desorption CO
2Speed is fast; Solution absorption CO
2Ability improves, and the regeneration energy consumption is low; Solution-stabilized, can utilize equipment, the pipeline of original hot potash decarbonization, do not changing greatly under the prerequisite, on original hot potassium carbonate solution decarburization flow process, carry out the solution preparation and transform, can improve the decarbonization system ability, save energy consumption, remarkable in economical benefits.
One factory processes tolerance 2700Nm
3The full scale plant of/h, absorption pressure 1.5MPa used K originally
2O200g/L, the solution of diethylenetriamine 20g/L removes CO
2, air inlet unstripped gas CO
2Concentration 25%, purified gas CO
21.2%, the solution absorption ability is 20Nm
3CO
2/ m
3Solution.Use compound activator solution decarburization of the present invention instead, solution component is K
2O200g/L, diethanolamine 20g/L, AMP5g/L, boric acid 6g/L handle the ammonia amount and are increased to 31000Nm
3/ h, purified gas CO
2Reduce to 1%, the solution absorption ability increases to 30Nm
3CO
2/ m
3Liquid.
One produces 300000 tons of synthetic ammonia factories per year, removes CO with diethanolamine heat of activation solution of potassium carbonate originally
2, processing tolerance is 150000Nm
3/ h, solution compolision is K
2O250g/L, diethanolamine 30g/L, V
2O
5G/L7g/L, solution absorption ability 24Nm
3CO
2/ m
3Liquid.Purified gas CO
2＜0.1%.Use compound activator solution of the present invention instead, solution component K
2O250g/L, diethanolamine 15g/L, AMP15g/L, boric acid 20g/L is with this solution absorption CO
2, solution absorption CO
2Ability increases to 30Nm
3CO
2/ m
3Liquid, purified gas CO
2＜0.1%, handle tolerance and increase to 172500Nm
3/ h.Use original equipment Ammonia Production ability to increase 15%.
Claims (1)
1, a kind of compound activator solution that removes carbonic acid gas in the gas mixture, it is characterized in that this compound activator solution is made up of salt of wormwood, 2-amino-2-methyl-1-propanol, diethanolamine and boric acid, and in solution, add vanadium as inhibiter, the solution component is: salt of wormwood 230～370g/L, 2-amino-2-methyl-1-propanol 5～30g/L, diethanolamine 10～20g/L, boric acid 10～30g/L, total vanadium (in Vanadium Pentoxide in FLAKES) 5～10g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92107308A CN1055872C (en) | 1992-03-14 | 1992-03-14 | Removing carbon dioxide from mixed gas by compound activator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92107308A CN1055872C (en) | 1992-03-14 | 1992-03-14 | Removing carbon dioxide from mixed gas by compound activator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1076380A CN1076380A (en) | 1993-09-22 |
| CN1055872C true CN1055872C (en) | 2000-08-30 |
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ID=4942800
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92107308A Expired - Fee Related CN1055872C (en) | 1992-03-14 | 1992-03-14 | Removing carbon dioxide from mixed gas by compound activator |
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| Country | Link |
|---|---|
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Cited By (1)
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|---|---|---|---|---|
| CN101637689B (en) * | 2009-01-09 | 2012-03-28 | 清华大学 | Absorption solvent used for catching or separating carbon dioxide |
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| CN109701362A (en) * | 2019-02-28 | 2019-05-03 | 华能国际电力股份有限公司 | It is a kind of for the liquid-solid phase transformation absorbent of collecting carbonic anhydride and its application |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4112050A (en) * | 1975-06-26 | 1978-09-05 | Exxon Research & Engineering Co. | Process for removing carbon dioxide containing acidic gases from gaseous mixtures using a basic salt activated with a hindered amine |
| CN85103423A (en) * | 1985-04-20 | 1986-12-31 | 华东化工学院 | Separating carbon dioxide from admixture of gas |
-
1992
- 1992-03-14 CN CN92107308A patent/CN1055872C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4112050A (en) * | 1975-06-26 | 1978-09-05 | Exxon Research & Engineering Co. | Process for removing carbon dioxide containing acidic gases from gaseous mixtures using a basic salt activated with a hindered amine |
| CN85103423A (en) * | 1985-04-20 | 1986-12-31 | 华东化工学院 | Separating carbon dioxide from admixture of gas |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101637689B (en) * | 2009-01-09 | 2012-03-28 | 清华大学 | Absorption solvent used for catching or separating carbon dioxide |
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| Publication number | Publication date |
|---|---|
| CN1076380A (en) | 1993-09-22 |
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