CN101574607B - Adsorbent for selectively removing low-concentration sulfur dioxide from gas containing carbon dioxide - Google Patents
Adsorbent for selectively removing low-concentration sulfur dioxide from gas containing carbon dioxide Download PDFInfo
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- CN101574607B CN101574607B CN200910011874.6A CN200910011874A CN101574607B CN 101574607 B CN101574607 B CN 101574607B CN 200910011874 A CN200910011874 A CN 200910011874A CN 101574607 B CN101574607 B CN 101574607B
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- adsorbent
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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 invention discloses an adsorbent for selectively removing low-concentration sulfur dioxide from gas containing carbon dioxide, which belongs to the technical field of protection of natural resources and environment. The adsorbent is characterized in that the adsorbent is used in an absorption tower during the gas-liquid mass transfer, can selectively remove sulfur dioxide in low-concentration carbon dioxide feed gas, and does not lose the carbon dioxide. The content of the carbon dioxide in the feed gas which can be treated by the adsorbent is between 3 and 8 percent, and the content of the sulfur dioxide is between 0.0001 and 80 percent. The adsorbent takes 0.4 to 80 percent carboxylate or carboxylate derivative as a main absorption component, 0.01 to 4 percent of transition metal ions as a catalyst and 0.006 to 0.01 percent of sodium dodecylbenzebesuefonate as a foamer, and the balance of water. The adsorbent has the advantages that the adsorbent has high purification rate, largeabsorption capacity, small regeneration energy consumption, small corrosion on equipment, no blocking, easy regeneration and no secondary pollution. The adsorbent cannot be affected by the content of oxygen in flue gas during the absorption, has strong adaptability on fuel, and ensures that the desulfurization rate can reach more than 99 percent.
Description
Technical field
The invention belongs to protection of natural resources and environment technical field, relate to a kind of selectively removing low-concentration sulfur dioxide from carbon dioxide containing gas and retain the carbon dioxide absorbent of (being called for short " carbon-keeping desulphurization ").
Background technology
Along with industrial high speed development, bring CO 2 waste gas more and more serious to the pollution of atmosphere, and then cause greenhouse effects.Therefore recycle carbon resource for fields such as chemical industry, machinery, food, agriculturals, the blowdown presssure of extenuating carbon dioxide is significant.The source of carbon dioxide is mainly the flue gas of coal-burning power plant and pluralities of fuel Industrial Boiler, also has the ores such as calcium carbonate, magnesium carbonate to add the tail gas that thermal decomposition process discharges, and the carbonated waste gas of chemical plant emission.Wherein also be attended by the release of a small amount of sulfur dioxide, and the existence of sulfur dioxide brings impact can to recovery carbon dioxide process, cause the increase of solvent loss amount and equipment corrosion serious.Therefore, before recycling carbon dioxide, remove sulfur dioxide and there is the double meaning of optimizing carbon dioxide recovery process and protection of the environment creation economic results in society.
At present a lot of about the report that removes sulfur dioxide of flue gases, main method is dry desulfurization and wet desulphurization, wherein wet desulphurization dominate.In conventional Wet Flue Gas Desulfurization Technique, desulfurization method of limestone-gypsum technology maturation, is widely used.United States Patent (USP) U.S.3911084 has reported and has used NaSO
3-NaHSO
3cushioning liquid is as absorbent, with Ca (OH)
2neutralize regeneration, obtain by-product gypsum.Domestic East China University of Science develops Citrate Buffer flue gas desulfurization the beginning of the eighties, and desulfurization degree can reach 99%.In addition, also have ammonia process, magnesia to wash and starch the multiple wet flue gas sulfur methods such as method of reproduction.But, because sulfur dioxide and carbon dioxide all have acidity, and how conventional wet desulphurization absorbent all has alkalescence now, also absorbing carbon dioxide in sulfur dioxide absorption, bring the loss of the increase of desulfurization absorbent use amount and carbon dioxide, in existing wet flue gas sulfur method, all more or less have secondary pollution, absorbent corrosive equipment, the problems such as fouling, obstruction in addition.So now the desulfurization absorbent of use in the time that carbon dioxide exists to SO
2remove selectively not high.
Few about the report of recycling " carbon-keeping desulphurization " in carbon dioxide.The little violent low-concentration sulfur dioxide in modified activated carbon carbon dioxide removal unstripped gas of reporting of Dalian University of Technology's expense.But only report CO
2exist SO
2the impact removing.Chinese patent CN85104983A has reported with piperazinones selectively removing sulfur dioxide from carbonated and sulfur dioxide gas, has passed through thermal regeneration.Energy consumption is large, has secondary pollution.
Summary of the invention
The technical problem to be solved in the present invention is to obtain high-performance carbon-keeping desulphurization absorbent.In wet desulfurizing process, this absorbent not only requires the purifying rate of sulfur dioxide high, and absorptive capacity is large, and regeneration is easy, and non-secondary pollution is little to equipment corrosion; And to SO
2absorption selectivity high and do not absorb CO
2, so just prepare food-class high-purity CO for reclaiming
2feasible key technology is provided, has promoted CO
2recycle, be conducive to environmental protection and promote the well-being of mankind.
Technical scheme of the present invention has been to provide a kind of " carbon-keeping desulphurization " absorbent, can only absorb the sulfur dioxide in carbon dioxide containing gas, and absorbing carbon dioxide not.Composition and the renovation process of unstripped gas and absorbent are as follows:
(1) in the unstripped gas of processing, carbon dioxide content is 3%-80%, and content of sulfur dioxide is 0.0001%-80%;
(2) absorbent composition and content
A, main absorbent components are one or more of compound with following chemical formula:
(RCOO)
nM
In formula, R is hydrogen atom, C
1～C
3alkyl, fragrant alkyl, the one in alkylene or halogen; M is Li
+, Na
+, K
+, Mn
2+, Mg
2+, Ca
2+one in ion.
The content of main absorbent components is 0.4%-80%;
B, catalyst are metal ions M n
2+, Fe
3+, Cr
3+, Cu
2+, Co
2+, Zn
2+, Ni
2+in one, its content is at 0.01-4%;
C, foaming agent are neopelexes, and its content is at 0.006-0.01%;
D, except main absorbent components, catalyst, foaming agent, all the other are water.
(3) absorbent regeneration method
When the pH of absorption liquid value is lower than 4 time, pass into air and carry out forced oxidation, after oxidation, add lime stone to carry out reducing/regenerating, filter to obtain by-product calcium sulfate gypsum, reclaim sulphur with the form of sulfate, the filtrate of having regenerated continues to recycle as absorbent.
A kind of absorption and regeneration principle of selecting the absorbent that removes low-concentration sulfur dioxide from carbon dioxide containing gas of the present invention:
1. when thering is (RCOO)
nsO in compound water solution and the gas phase of M chemical formula
2in absorption tower, when counter current contacting, there is following chemical reaction
(RCOO)
nM+nSO
2+nH
2O→M(HSO
3)
n+nRCOOH
Wherein, the Catalysis Principles of catalyst is
2. absorption liquid pH value, lower than 4 o'clock, passes into force air oxidation.Chemical reaction is as follows
M(HSO
3)
n+n/2O
2+M(RCOO)
n→M
2(SO
4)
n+nRCOOH
3. absorbent regeneration reaction
nCaCO
3+nRCOOH+nH
2O+M
2(SO
4)
n→nCaSO
4·2H
2O+nCO
2+2M(RCOO)
n
Effect of the present invention and benefit are:
Absorbent of the present invention is strong base-weak acid salt, has good pH value buffer capacity.The ionization equilibrium constant of corresponding weak acid, therefore can well sulfur dioxide absorption, not absorbing carbon dioxide between carbonic acid and sulfurous acid.This absorbent purifying rate is high, and internal circulating load is little, saves power consumption, little to equipment corrosion, does not stop up, and regeneration is easy, non-secondary pollution.Absorbent can not be subject to the impact of oxygen content in flue gas in absorption process, to the strong adaptability of fuel, low concentration unstripped gas is the flue gas of coal combustion, gaseous fuel, oily fuel, the discharge of plant fuel process, the tail gas of heating decomposing ore process, the carbonated of chemical process discharge and the waste gas of sulfur dioxide, desulfurization degree all can reach more than 99%.
Detailed description of the invention
Describe the specific embodiment of the present invention in detail below in conjunction with technical scheme.
Embodiment 1
In step 1 .60g water, add 0.2461g sodium acetate, 0.2g manganese sulfate and 0.005g neopelex as initial absorption liquid, under 40 DEG C of conditions of temperature, pass into containing SO
2the CO of 2000ppm
2gas and air absorb, and detect the variation of absorption liquid pH value and outlet SO every ten minutes
2change in concentration, absorbs 70 minutes with inner outlet concentration all below 50ppm, and absorptivity is up to more than 99%.Absorb and after 160 minutes, absorb saturatedly, absorption liquid pH value is 3.48.Stop logical SO
2and CO
2mist.Stop the body of ventilating, and detect sulfate radical content in absorption liquid.
Step 2. continue, under 40 DEG C of conditions of temperature, to fill into 0.2461g sodium acetate solid, pass into force air oxidation 120 minutes, spectrophotometry SO
4 2-content.
Step 3. will in the absorption liquid after forced oxidation, add 0.2gCaCO
3, fully stir, filter.Filtrate is continued to pass into containing SO as stated above
2the CO of 2000ppm
2gas absorbs, and after 180 minutes, stops.Filter cake is measured CaSO by titration after drying
42H
2the content of O.
Embodiment 2
In step 1 .60g water, add 0.2889g sodium propionate, 0.2g manganese sulfate and 0.005g neopelex as initial absorption liquid, under 40 DEG C of conditions of temperature, pass into containing SO
2the CO of 2000ppm
2gas and air absorb, and detect the variation of absorption liquid pH value and outlet SO every ten minutes
2change in concentration, absorbs 70 minutes with inner outlet concentration all below 100ppm, and absorptivity is up to 96%.Absorb and after 180 minutes, absorb saturatedly, absorption liquid pH value is 3.56.Stop the body of ventilating, and detect sulfate radical content in absorption liquid.
Step 2 and step 3 are with embodiment 1, and the sodium propionate amount filling into is 0.2889g.
Embodiment 3
In step 1 .60g water, add 0.46g sodium succinate, 0.2g manganese sulfate and 0.005g neopelex as initial absorption liquid, under 40 DEG C of conditions of temperature, pass into containing SO
2the CO of 2000ppm
2gas absorbs, and detects the variation of absorption liquid pH value and outlet SO every ten minutes
2change in concentration, absorbs 40 minutes with inner outlet concentration all below 90ppm, and absorptivity is up to 99%.Absorb and after 150 minutes, absorb saturatedly, absorption liquid pH value is 3.78.Stop the body of ventilating, and detect sulfate radical content in absorption liquid.
Step 2 and step 3 are with embodiment 1, and the sodium succinate amount filling into is 0.46g.
Embodiment 4
In step 1 .60g water, add 0.6125 manganese acetate and 0.005g neopelex as initial absorption liquid, under 40 DEG C of conditions of temperature, pass into containing SO
2the CO of 2000ppm
2gas absorbs, and detects the variation of absorption liquid pH value and outlet SO every ten minutes
2change in concentration, absorbs 90 minutes with inner outlet concentration all below 50ppm, and absorptivity is up to 99%.Absorb and after 280 minutes, absorb saturatedly, absorption liquid pH value is 3.34.Stop the body of ventilating, and detect sulfate radical content in absorption liquid.
Step 2 and step 3 are with embodiment 1, and the manganese acetate amount filling into is 0.6125g.
Embodiment 5
In step 1 .60g water, add 0.2944 potassium acetate, 0.2g manganese sulfate and 0.005g neopelex as initial absorption liquid, under 40 DEG C of conditions of temperature, pass into containing SO
2the CO of 2000ppm
2gas and air absorb, and detect the variation of absorption liquid pH value and outlet SO every ten minutes
2change in concentration, absorbs 25 minutes with inner outlet concentration all below 5ppm, and absorptivity is up to 99.999%.Absorb and after 170 minutes, absorb saturatedly, absorption liquid pH value is 3.58.Stop the body of ventilating, and detect sulfate radical content in absorption liquid.
Step 2 and step 3 are with embodiment 1, and the potassium acetate amount filling into is 0.2944g.
It is 99.9% CO that absorption liquid in above implementation column is all under equal conditions absorbed to purity
2gas, absorbs result and shows, above absorbent is to SO
2absorption selectivity be greater than 99.99%.
Unlisted data in above embodiment see attached list.
Embodiment 6:
Liaohe Oil Field designs and produces a set of 30,000 tons of flue gases and reclaims carbon dioxide plant, and 4.0 meters of desulfuration absorbing tower diameters are high 8.5 meters, absorption liquid flow 200Nm
3/ h, wherein sodium acetate concentration 1.2～2.2%, manganese sulfate content 0.8～1.2%, neopelex 0.2～0.5%, all the other are water, sulfur dioxide concentration 1120ppm～1960ppm in flue gas, carbon dioxide content 9.52～12.2%, after desulfurizing tower, sulfur dioxide in tail gas content is reduced to below 20ppm, and actual removal efficiency is 98%～99%, carbon dioxide content is 9.48～11.9%, and loss late only has 3%.
The assimilation effect data of subordinate list embodiment 1-5
| Embodiment | Uptake/mg | Gypsum production rate/% | Regenerated liquid absorptivity/% | Regenerated liquid uptake/mg |
| 1 | 482.11 | 83.1 | 99 | 475.12 |
| 2 | 417.31 | 79.1 | 95 | 420.09 |
| 3 | 399.35 | 82.2 | 95 | 308.34 |
| 4 | 469.83 | 81.9 | 97 | 456.25 |
| 5 | 409.99 | 81.4 | 98 | 410.46 |
Claims (2)
1. from carbon dioxide containing gas, select to remove the absorbent of low-concentration sulfur dioxide for one kind, for the absorption tower of mass-transfer progress, sulfur dioxide in can selectively removing CO 2 raw material gas, and do not lose carbon dioxide, this absorbent is made up of main absorbent components, catalyst, foaming agent and water, it is characterized in that:
(1) in the unstripped gas of processing, carbon dioxide content is 3%-80%, and content of sulfur dioxide is 0.0001%-80%;
(2) main absorbent components is one or more of compound with following chemical formula:
(RCOO)
nM
Wherein, R is hydrogen atom, C
1～C
3alkyl, fragrant alkyl, alkylene or halogen, M is Li
+, Na
+, K
+, Mn
2+, Mg
2+, Ca
2+one in ion, its content is at 0.4%-80%;
(3) catalyst is metal ions M n
2+, its content is at 0.01%-4%;
(4) foaming agent is neopelex, and its content is at 0.006%-0.01%;
(5), except main absorbent components, catalyst, foaming agent, all the other are water.
2. according to a kind of absorbent of selecting to remove low-concentration sulfur dioxide from carbon dioxide containing gas claimed in claim 1, it is characterized in that: absorbed the absorbent of sulfur dioxide in subsequent production process, reclaimed sulphur with the form of sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910011874.6A CN101574607B (en) | 2009-06-04 | 2009-06-04 | Adsorbent for selectively removing low-concentration sulfur dioxide from gas containing carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910011874.6A CN101574607B (en) | 2009-06-04 | 2009-06-04 | Adsorbent for selectively removing low-concentration sulfur dioxide from gas containing carbon dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101574607A CN101574607A (en) | 2009-11-11 |
| CN101574607B true CN101574607B (en) | 2014-06-11 |
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ID=41269758
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910011874.6A Active CN101574607B (en) | 2009-06-04 | 2009-06-04 | Adsorbent for selectively removing low-concentration sulfur dioxide from gas containing carbon dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109336113A (en) * | 2018-12-13 | 2019-02-15 | 上海启元空分技术发展股份有限公司 | A kind of production method and products thereof of the ultrapure carbon dioxide of electron level |
| CN114432845A (en) * | 2020-11-03 | 2022-05-06 | 财团法人工业技术研究院 | Method and device for removing sulfur dioxide in flue gas |
| TWI769913B (en) | 2021-08-24 | 2022-07-01 | 財團法人工業技術研究院 | Ceramic composite and method of preparing the same |
| CN114351188B (en) * | 2022-01-10 | 2023-08-01 | 青岛中石大环境与安全技术中心有限公司 | Method and device for producing hydrogen by electrolysis of water and capturing carbon dioxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4170628A (en) * | 1977-03-25 | 1979-10-09 | Union Carbide Corporation | Process for removing SO2 from effluent gases and for removing heat stable salts from systems in which they accumulate using an anion exchange resin |
| CN85104983A (en) * | 1983-12-19 | 1986-12-31 | 陶氏化学公司 | From the gas that contains sulfurous gas and carbonic acid gas, optionally absorb sulfurous gas |
-
2009
- 2009-06-04 CN CN200910011874.6A patent/CN101574607B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4170628A (en) * | 1977-03-25 | 1979-10-09 | Union Carbide Corporation | Process for removing SO2 from effluent gases and for removing heat stable salts from systems in which they accumulate using an anion exchange resin |
| CN85104983A (en) * | 1983-12-19 | 1986-12-31 | 陶氏化学公司 | From the gas that contains sulfurous gas and carbonic acid gas, optionally absorb sulfurous gas |
Non-Patent Citations (1)
| Title |
|---|
| 李华等.有机溶剂吸收法脱除烟气中二氧化硫的研究.《煤炭转化》.2005,第28卷(第4期), * |
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|---|---|
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Effective date of registration: 20230420 Address after: 2416-8, 24/F, Tencent Building, 26 Jingxian Street, High-tech Industrial Park, Dalian, Liaoning Province, 116085 Patentee after: Zhongfeng Xinhe (Dalian) Technology Co.,Ltd. Address before: 116024 No. 2 Ling Road, Ganjingzi District, Liaoning, Dalian Patentee before: DALIAN University OF TECHNOLOGY |