CN114367170A - Method for enriching sulfur dioxide in flue gas - Google Patents
Method for enriching sulfur dioxide in flue gas Download PDFInfo
- Publication number
- CN114367170A CN114367170A CN202111520632.7A CN202111520632A CN114367170A CN 114367170 A CN114367170 A CN 114367170A CN 202111520632 A CN202111520632 A CN 202111520632A CN 114367170 A CN114367170 A CN 114367170A
- Authority
- CN
- China
- Prior art keywords
- sulfur dioxide
- flue gas
- absorption liquid
- pressure
- sulfite
- 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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- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000003546 flue gas Substances 0.000 title claims abstract description 46
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000010521 absorption reaction Methods 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 3
- 239000010452 phosphate Substances 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 9
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 9
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229940059867 sulfur containing product ectoparasiticides Drugs 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 2
- 230000006837 decompression Effects 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 abstract description 2
- 235000010269 sulphur dioxide Nutrition 0.000 description 47
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 20
- 235000010265 sodium sulphite Nutrition 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1481—Removing sulfur dioxide or sulfur trioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1418—Recovery of products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/10—Inorganic absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a method for enriching sulfur dioxide in flue gas, which comprises the following steps: 1) pressurizing the flue gas with the sulfur dioxide volume percentage content of 7-10%; 2) introducing the pressurized flue gas into an absorption liquid, wherein the absorption liquid is a supersaturated solution containing dihydric phosphate; 3) and after the absorption liquid is fully absorbed, reducing the pressure, releasing and collecting sulfur dioxide. According to the invention, the sulfur dioxide flue gas is pressurized and then introduced into the absorption liquid, on one hand, sulfur dioxide can be easily separated from the flue gas through the reaction with dihydrogen phosphate and is enriched in the form of sulfite, and on the other hand, as the absorption liquid is supersaturated dihydrogen phosphate solution, sulfite is difficult to be oxidized into sulfate radicals through the reaction with oxygen in the flue gas; and then decompression operation is carried out to force sulfite to be reversibly converted into sulfur dioxide, so that high-purity sulfur dioxide is enriched and obtained. The production process is simple, the equipment investment is low, and the obtained high-purity sulfur dioxide can be used for preparing sulfur-containing products.
Description
Technical Field
The invention belongs to the technical field of flue gas desulfurization, and particularly relates to a method for enriching sulfur dioxide in flue gas.
Technical Field
The sulfur dioxide flue gas is mainly derived from industrial waste gas and combustion flue gas. Sulfur dioxide is smelly and soluble in water. When the sulfur dioxide content in the air exceeds the allowable standard, the method not only can directly harm human health and the growth of animals and plants, but also can form acid mist and acid rain, and causes greater harm to the ecological environment such as air, water quality, soil and the like. Flue gas desulfurization methods are roughly classified into two categories: (1) wet processes, i.e. washing with liquid absorbents such as water or alkali solutions to remove sulphur dioxide; (2) dry processes, using powdered or granular absorbents, adsorbents, or catalysts to remove sulfur dioxide.
There are currently different options for treating sulfur-containing flue gases:
one idea is to directly desulfurize the flue gas. For example, when a liquid absorbent such as lye is used directly to remove sulfur dioxide, or a limestone slurry is used to absorb sulfur dioxide from flue gas, the resulting sulfite (e.g., calcium sulfite) is easily oxidized further due to the oxygen-rich content of flue gas, resulting in a sulfate byproduct (e.g., gypsum).
The other idea is to respectively treat and effectively recover the sulfur dioxide according to the concentration of the sulfur dioxide:
for SO2In the smelting flue gas with the concentration of more than 1 percent and less than 2.5 percent, the sulfur dioxide can be enriched by methods of absorption, adsorption and the like to obtain high-concentration sulfur dioxide gas or pure sulfur dioxide gas and then be utilized. The flue gas with the sulfur dioxide concentration of more than 3 percent can be prepared into sulfuric acid by a standard contact method. The flue gas with the concentration of sulfur dioxide more than 5 percent can be used as a raw material for preparing sulfur, and the process is only mastered by a few factories in the world.
However, the above methods all have various drawbacks: the gypsum method has the advantages of mature technology, wide source of main raw material lime, simple process and low treatment cost, but the treated gypsum has low economic value and even can not be utilized and can only be used as a tailing treatment filler or directly discarded.
If sulfur dioxide in flue gas is used for directly preparing elemental sulfur, high value can be generated, but related technologies are not obtained, and the early investment is very large. Moreover, although the method for preparing the sulfuric acid is simple, the yield of the sulfuric acid is excessive, and the value is not high.
In view of the above, the present invention provides a method for enriching and releasing sulfur dioxide in flue gas by using pressure difference, wherein high-concentration sulfur dioxide flue gas is pressurized and then introduced into absorption liquid, and the sulfur dioxide is forced to be separated and enriched from the flue gas by pressure reduction operation. The whole production process is simple and the equipment investment is low. The obtained high-purity sulfur dioxide can be used for preparing various high-value sulfur-containing products.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for enriching sulfur dioxide in flue gas, which avoids the problem of low-value utilization of sulfur resources in the prior art when sulfur-containing flue gas is treated by separating and enriching sulfur-containing flue gas, and the obtained high-purity sulfur dioxide can be used for preparing other chemical products.
In order to solve the technical problems, the technical scheme provided by the invention comprises the following steps:
1) pressurizing the flue gas containing sulfur dioxide;
2) introducing the pressurized flue gas into an absorption liquid, wherein the absorption liquid is a supersaturated solution containing dihydric phosphate;
3) after the absorption liquid is fully absorbed, reducing the pressure, releasing and collecting sulfur dioxide;
in the step 1), the sulfur dioxide content in the flue gas is 7-10% by volume.
Further, in the step 2), the absorption solution is a supersaturated solution containing sodium dihydrogen phosphate or potassium dihydrogen phosphate.
Further, in the step 1), the pressure intensity of the pressurization is 10 MPa-20 MPa.
Further, in the step 3), the pressure of the reduced pressure is 0.01MPa or less. Furthermore, in the step 3), the pressure for reducing the pressure is 0.001-0.01 MPa.
According to the invention, the sulfur dioxide flue gas is pressurized and then introduced into the absorption liquid, on one hand, sulfur dioxide can be easily separated from the flue gas through the reaction with dihydrogen phosphate and is enriched in the form of sulfite, and on the other hand, as the absorption liquid is supersaturated dihydrogen phosphate solution, sulfite is difficult to be oxidized into sulfate radicals through the reaction with oxygen in the flue gas; and then decompression operation is carried out to force sulfite to be reversibly converted into sulfur dioxide, so that high-purity sulfur dioxide is enriched and obtained. The whole production process is simple and the equipment investment is low. The obtained high-purity sulfur dioxide can be used for preparing various high-value sulfur-containing products.
Detailed Description
The present invention will be further described with reference to the following detailed description, but the invention is not limited thereto.
Example 1
Pressurizing the flue gas containing 7% of sulfur dioxide to 10Mpa, introducing into supersaturated absorption liquid of sodium dihydrogen phosphate, after the absorption liquid is fully absorbed to form sodium sulfite, reducing the pressure to 0.01Mpa, and reversibly converting the sodium sulfite into sulfur dioxide and releasing from the absorption liquid, and collecting with a sealed gas storage bottle to obtain high-purity sulfur dioxide.
Example 2
Pressurizing the flue gas containing 8% of sulfur dioxide to 10Mpa, introducing into supersaturated absorption liquid of sodium dihydrogen phosphate, reducing pressure to 0.001Mpa after the absorption liquid fully absorbs to form sodium sulfite, reversibly converting the sodium sulfite into sulfur dioxide, releasing from the absorption liquid, and collecting with a sealed gas cylinder to obtain high-purity sulfur dioxide.
Example 3
Pressurizing the flue gas containing 9% of sulfur dioxide to 12Mpa, introducing into supersaturated absorption liquid of sodium dihydrogen phosphate, reducing pressure to 0.01Mpa after the absorption liquid fully absorbs to form sodium sulfite, reversibly converting the sodium sulfite into sulfur dioxide, releasing from the absorption liquid, and collecting with a sealed gas cylinder to obtain high-purity sulfur dioxide.
Example 4
Pressurizing the flue gas containing 10% sulfur dioxide to 15Mpa, introducing into supersaturated absorption liquid of sodium dihydrogen phosphate, reducing pressure to 0.01Mpa after the absorption liquid fully absorbs to form sodium sulfite, reversibly converting sodium sulfite into sulfur dioxide, releasing from the absorption liquid, and collecting with sealed gas bomb to obtain high purity sulfur dioxide.
Example 5
Pressurizing the flue gas containing 9% sulfur dioxide to 20Mpa, introducing into supersaturated solution of sodium dihydrogen phosphate, fully absorbing by sodium dihydrogen phosphate solution to obtain mixed solution of sodium dihydrogen phosphate and sodium sulfite, reducing pressure to 0.001Mpa, reversibly converting the formed sodium sulfite into sulfur dioxide, releasing from the solution, and collecting with sealed gas cylinder to obtain high-purity sulfur dioxide. .
The sulfur dioxide enrichment rate of each example is more than 60%.
Although embodiments of the present invention have been described in detail above, those of ordinary skill in the art will understand that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (5)
1. A method for enriching sulfur dioxide in flue gas is characterized by comprising the following steps:
1) pressurizing the flue gas containing sulfur dioxide;
2) introducing the pressurized flue gas into an absorption liquid, wherein the absorption liquid is a supersaturated solution containing dihydric phosphate;
3) after the absorption liquid is fully absorbed, reducing the pressure, releasing and collecting sulfur dioxide;
in the step 1), the sulfur dioxide content in the flue gas is 7-10% by volume.
2. The method for sulfur dioxide in flue gas according to claim 1,
in the step 2), the absorption liquid is supersaturated solution containing sodium dihydrogen phosphate or potassium dihydrogen phosphate.
3. The method for removing sulfur dioxide from flue gas according to claim 1 or 2, wherein the pressurizing pressure in the step 1) is 10 Mpa-20 Mpa.
4. The method for removing sulfur dioxide from flue gas according to claim 1 or 2, wherein in the step 3), the pressure for pressure reduction is below 0.01 MPa.
5. The method for removing sulfur dioxide from flue gas as recited in claim 4, wherein in the step 3), the pressure of the pressure reduction is 0.001-0.01 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111520632.7A CN114367170B (en) | 2021-12-13 | 2021-12-13 | Method for enriching sulfur dioxide in flue gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111520632.7A CN114367170B (en) | 2021-12-13 | 2021-12-13 | Method for enriching sulfur dioxide in flue gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114367170A true CN114367170A (en) | 2022-04-19 |
| CN114367170B CN114367170B (en) | 2024-08-09 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111520632.7A Active CN114367170B (en) | 2021-12-13 | 2021-12-13 | Method for enriching sulfur dioxide in flue gas |
Country Status (1)
| Country | Link |
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| CN (1) | CN114367170B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2454407A1 (en) * | 1974-11-16 | 1976-05-20 | United States Filter Corp | METHOD AND APPARATUS FOR SEPARATING SULFUR DIOXYDE FROM GASEOUS CARRIER STREAMS |
| GB1486606A (en) * | 1973-10-29 | 1977-09-21 | United States Filter Corp | Method of removing sulphur dioxide from gaseous carriers |
| US5690899A (en) * | 1995-07-29 | 1997-11-25 | Lentjes Bischoff Gmbh | Process for removing sulphur dioxide from flue gas |
| CN1416360A (en) * | 2000-03-06 | 2003-05-07 | 奥拉夫·埃加 | Process for purifying aqueous buffer solutions |
| CN102068876A (en) * | 2009-11-20 | 2011-05-25 | 北京化工大学 | Flue gas desulfurization process |
| CN103480259A (en) * | 2013-09-07 | 2014-01-01 | 中北大学 | Flue gas desulfurization device and process |
| CN103495340A (en) * | 2013-10-15 | 2014-01-08 | 北京博源恒升高科技有限公司 | Method of removing SOx in gas by compound alkanolamine solution |
| CN107198943A (en) * | 2017-05-02 | 2017-09-26 | 山西艾珂灵环境科技有限公司 | A kind of tail gas absorption liquid |
| CN107297123A (en) * | 2017-08-21 | 2017-10-27 | 太原师范学院 | A kind of use carboxylic acid salt solution absorbing sulfur dioxide in flue and the process of equality of temperature regeneration |
-
2021
- 2021-12-13 CN CN202111520632.7A patent/CN114367170B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1486606A (en) * | 1973-10-29 | 1977-09-21 | United States Filter Corp | Method of removing sulphur dioxide from gaseous carriers |
| DE2454407A1 (en) * | 1974-11-16 | 1976-05-20 | United States Filter Corp | METHOD AND APPARATUS FOR SEPARATING SULFUR DIOXYDE FROM GASEOUS CARRIER STREAMS |
| US5690899A (en) * | 1995-07-29 | 1997-11-25 | Lentjes Bischoff Gmbh | Process for removing sulphur dioxide from flue gas |
| CN1416360A (en) * | 2000-03-06 | 2003-05-07 | 奥拉夫·埃加 | Process for purifying aqueous buffer solutions |
| CN102068876A (en) * | 2009-11-20 | 2011-05-25 | 北京化工大学 | Flue gas desulfurization process |
| CN103480259A (en) * | 2013-09-07 | 2014-01-01 | 中北大学 | Flue gas desulfurization device and process |
| CN103495340A (en) * | 2013-10-15 | 2014-01-08 | 北京博源恒升高科技有限公司 | Method of removing SOx in gas by compound alkanolamine solution |
| CN107198943A (en) * | 2017-05-02 | 2017-09-26 | 山西艾珂灵环境科技有限公司 | A kind of tail gas absorption liquid |
| CN107297123A (en) * | 2017-08-21 | 2017-10-27 | 太原师范学院 | A kind of use carboxylic acid salt solution absorbing sulfur dioxide in flue and the process of equality of temperature regeneration |
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| Publication number | Publication date |
|---|---|
| CN114367170B (en) | 2024-08-09 |
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