CN113651333A - Solid waste recycling method for calcium sulfate hydrate containing elemental sulfur, silicon dioxide - Google Patents
Solid waste recycling method for calcium sulfate hydrate containing elemental sulfur, silicon dioxide Download PDFInfo
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- CN113651333A CN113651333A CN202111140157.0A CN202111140157A CN113651333A CN 113651333 A CN113651333 A CN 113651333A CN 202111140157 A CN202111140157 A CN 202111140157A CN 113651333 A CN113651333 A CN 113651333A
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- CN
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- Prior art keywords
- calcium sulfate
- sulfur
- solid waste
- silicon dioxide
- elemental sulfur
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000002910 solid waste Substances 0.000 title claims abstract description 30
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 24
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 17
- ZHZFKLKREFECML-UHFFFAOYSA-L calcium;sulfate;hydrate Chemical compound O.[Ca+2].[O-]S([O-])(=O)=O ZHZFKLKREFECML-UHFFFAOYSA-L 0.000 title claims abstract description 11
- 238000004064 recycling Methods 0.000 title claims abstract description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 31
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000013081 microcrystal Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 101100289061 Drosophila melanogaster lili gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/468—Purification of calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
A method for recycling solid waste containing elemental sulfur, silicon dioxide and calcium sulfate hydrate comprises the steps of grinding carbon powder, introducing excessive oxygen for circulation, heating to convert sulfur into sulfur dioxide, converting carbon into carbon dioxide, converting mixed gas into sulfur trioxide, and simultaneously obtaining calcium sulfate with loose structure and silicon dioxide water-loss microcrystal solid.
Description
Technical Field
The invention relates to the fields of chemical industry, energy conservation and environmental protection, and discloses a resource method of sulfur-containing solid waste.
Background
The desulfurization of flue gas and coal gas is a common procedure for cleaning gas in the chemical industry, and the dry desulfurization has the advantages of small pollution, low energy consumption and the like, and is widely applied. The desulfurizer is a mixture of oxides containing iron, calcium, aluminum, silicon and the like, the desulfurizer belongs to non-hazardous chemicals and has no pollution hazard to human bodies and the environment, and the waste desulfurizer is hazardous waste due to the absorption and the aggregation of elemental sulfur.
The removed sulfides are usually H2S, SO2, COS, etc., wherein H2S is the main component, and the Fe system desulfurizing agent and the Mn system desulfurizing agent exist in the form of FeS and MnS after H2S is removed. The solid waste is treated by acid washing to generate H2S and SO2, elemental sulfur accumulated on the surface of the desulfurizer and blocking a pore channel is exposed, SiO2 in the framework of the desulfurizer is separated out, and part of CaSO4 is generated at the same time, SO that new solid waste of a mixture of elemental S, SiO2 and CaSO4 is formed.
The dissolving capacity of CS2 for S is adopted for extraction, the application cannot be realized due to the low boiling point of CS2, the performances of other solvents are not good due to the reasons of insufficient dissolving capacity and the like, and the pickling technology of the waste desulfurizing agent is not popularized and applied in a large scale at present due to the reasons. Therefore, a new method is found, which is nontoxic and environment-friendly, separates sulfur from solid waste, realizes waste digestion, produces other products as byproducts, can avoid the problem of new environmental pollution, and can obtain higher economic value.
CN111607704A lili et al announced a treatment process of waste desulfurizer, which mixes the waste desulfurizer with pyrolusite to obtain mixed solid, and leaches the mixed solid with sulfuric acid to obtain leachate; and filtering after carbonization and crystallization to obtain the manganese carbonate. The technology only recovers manganese in the waste slag, neglects the rest of the new hazardous waste of the mixture of sulfur, silicon dioxide and calcium sulfate, and does not treat the waste slag, so that the environmental protection and the economic efficiency of the technology cannot be embodied.
Disclosure of Invention
The invention relates to a method for recycling solid wastes containing elemental sulfur, silicon dioxide and calcium sulfate hydrate, which is characterized by comprising the following steps: the solid waste contains 4-20% of elemental sulfur, 4-20% of silicon dioxide and the balance of calcium sulfate. Feeding the carbon powder and the carbon powder into a closed reactor at a ratio of 0.05-0.1: 1, introducing 4-12 times excess oxygen (or air or oxygen-enriched air) for circulation, and keeping the mixture at 250-280 ℃ for 20-180 minutes. Elemental sulfur is converted into sulfur dioxide, carbon is converted into carbon dioxide, mixed gas containing the sulfur dioxide, the carbon dioxide and oxygen is obtained and sent to a sulfur trioxide synthesis process, and silicon dioxide and calcium sulfate water loss microcrystal solid which does not contain the elemental sulfur and has a loose structure is obtained.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a method for recycling solid waste containing elemental sulfur, silicon dioxide and calcium sulfate hydrate, wherein the solid acid-washing waste desulfurizer becomes a feasible disposal method, and the waste-free full utilization is realized;
(2) the invention provides a method for recycling solid waste containing elemental sulfur, silicon dioxide and calcium sulfate hydrate, wherein the microcrystalline solid has better strength than anhydrous gypsum after being formed by adding water, and can be directly sold as a product, so that the solid waste is recycled;
(3) the invention provides a method for recycling solid waste containing elemental sulfur, silicon dioxide and calcium sulfate hydrate, wherein S is oxidized into SO2Then converted into SO3And the sulfuric acid can be prepared and repeatedly used in the pickling section.
Detailed Description
Example 1: a calcium sulfate hydrate solid waste containing elemental sulfur, silicon dioxide and calcium sulfate, wherein the solid waste contains 10% of elemental sulfur, 16% of silicon dioxide and the balance calcium sulfate, carbon powder which is 10% of the weight of the solid waste and is ground is added, the solid waste is sent into a closed container, 8 times of excessive oxygen (or air or oxygen-enriched air) is introduced for circulation, the solid waste is heated to 250 ℃ and is kept for 160 minutes, elemental sulfur and oxygen react to generate sulfur dioxide gas, the carbon and the oxygen react to generate carbon dioxide, and the obtained circulation gas contains sulfur dioxide, and the carbon dioxide and the oxygen are sent into the gas to be synthesized into sulfur trioxide by utilizing the working procedure; and simultaneously, the water-loss microcrystalline solid of calcium sulfate and silicon dioxide which does not contain elemental sulfur and has a loose structure is obtained, and the microcrystalline solid has better strength than that of anhydrous gypsum after being formed by adding water.
Example 2: solid waste containing elemental sulfur, silicon dioxide and calcium sulfate hydrate, wherein the solid waste contains 8% of elemental sulfur, 14% of silicon dioxide and the balance calcium sulfate, carbon powder which is 7% of the weight of the solid waste and is ground is added, the solid waste is sent into a closed container, excess 6 times of oxygen (or air or oxygen-enriched air) is introduced for circulation, the solid waste is heated to 260 ℃ and is kept for 120 minutes, elemental sulfur and the oxygen react to generate sulfur dioxide gas, the carbon and the oxygen react to generate carbon dioxide, and the obtained circulating gas contains sulfur dioxide, and the carbon dioxide and the oxygen are sent into the gas to be synthesized into sulfur trioxide by utilizing the working procedure; and simultaneously, the water-loss microcrystalline solid of calcium sulfate and silicon dioxide which does not contain elemental sulfur and has a loose structure is obtained, and the microcrystalline solid has better strength than that of anhydrous gypsum after being formed by adding water.
Example 3: solid waste containing elemental sulfur, silicon dioxide and calcium sulfate hydrate is prepared by adding carbon powder which is 5% of the weight of the solid waste and is ground, sending the solid waste into a closed container, introducing excess 4 times of oxygen (or air or oxygen-enriched air) for circulation, heating to 280 ℃ for 90 minutes, reacting elemental sulfur with oxygen to generate sulfur dioxide gas, reacting carbon with oxygen to generate carbon dioxide, and sending the obtained circulating gas containing sulfur dioxide, carbon dioxide and oxygen into a gas utilization process to synthesize sulfur trioxide; and simultaneously, the water-loss microcrystalline solid of calcium sulfate and silicon dioxide which does not contain elemental sulfur and has a loose structure is obtained, and the microcrystalline solid has better strength than that of anhydrous gypsum after being formed by adding water.
Claims (1)
1. A method for recycling solid waste containing elemental sulfur, silicon dioxide and calcium sulfate hydrate is characterized in that the solid waste contains 4-20% of elemental sulfur, 4-20% of silicon dioxide and the balance of calcium sulfate, finely ground carbon powder accounting for 5-10% of the weight of the solid waste is added, the solid waste is sent into a closed container, excess 4-12 times of oxygen (or air or oxygen-enriched air) is introduced for circulation, the mixture is heated to 250-280 ℃ and kept for 20-180 minutes, the elemental sulfur and the oxygen react to generate sulfur dioxide gas, the carbon and the oxygen react to generate carbon dioxide, and the obtained circulation gas contains sulfur dioxide, and the carbon dioxide and the oxygen are sent into the gas to be utilized to synthesize sulfur trioxide; and simultaneously, the water-loss microcrystalline solid of calcium sulfate and silicon dioxide which does not contain elemental sulfur and has a loose structure is obtained, and the microcrystalline solid has better strength than that of anhydrous gypsum after being formed by adding water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111140157.0A CN113651333A (en) | 2021-09-28 | 2021-09-28 | Solid waste recycling method for calcium sulfate hydrate containing elemental sulfur, silicon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111140157.0A CN113651333A (en) | 2021-09-28 | 2021-09-28 | Solid waste recycling method for calcium sulfate hydrate containing elemental sulfur, silicon dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113651333A true CN113651333A (en) | 2021-11-16 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111140157.0A Pending CN113651333A (en) | 2021-09-28 | 2021-09-28 | Solid waste recycling method for calcium sulfate hydrate containing elemental sulfur, silicon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113651333A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4520002A (en) * | 1984-01-20 | 1985-05-28 | Merichem Company | Method for preparing elemental sulfur as a diffusion-resistant gas and methods for its use in making lime, sulfur dioxide and sulfuric acid from waste gypsum |
| JPH04219120A (en) * | 1990-12-18 | 1992-08-10 | Kawasaki Steel Corp | Method for making spent desulfurizing agent harmless |
| CN101020570A (en) * | 2006-03-22 | 2007-08-22 | 蒋胜 | Production process of eliminating simple substance sulphur from SO2 gas |
| CN101570341A (en) * | 2009-05-26 | 2009-11-04 | 华中科技大学 | Method for utilizing comprehensive resource of sulfur-containing solid waste |
| CN102502524A (en) * | 2011-10-28 | 2012-06-20 | 云南云天化国际化工股份有限公司 | Method for producing sulfur dioxide from calcium sulfate and sulfur |
| CN103962115A (en) * | 2014-05-21 | 2014-08-06 | 杨皓 | Desulphurization activated carbon regeneration process combined with Claus device |
| CN107902631A (en) * | 2017-11-11 | 2018-04-13 | 四川大学 | One kind utilizes hot carbon reduction ardealite coupling thermal activation potash feldspar ore CO2The method of co-production sulfur dioxide and potassium sulfate |
| CN109052335A (en) * | 2018-07-24 | 2018-12-21 | 上海三夫工程技术有限公司 | A kind of method of sulfur gas reduction Waste Sulfuric Acid sulfur dioxide liquid and sulfuric acid |
| CN109573957A (en) * | 2018-12-28 | 2019-04-05 | 华陆工程科技有限责任公司 | A kind of sulphur produces the sulfur dioxide of various concentration and the co-production of sulfuric acid simultaneously |
-
2021
- 2021-09-28 CN CN202111140157.0A patent/CN113651333A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4520002A (en) * | 1984-01-20 | 1985-05-28 | Merichem Company | Method for preparing elemental sulfur as a diffusion-resistant gas and methods for its use in making lime, sulfur dioxide and sulfuric acid from waste gypsum |
| JPH04219120A (en) * | 1990-12-18 | 1992-08-10 | Kawasaki Steel Corp | Method for making spent desulfurizing agent harmless |
| CN101020570A (en) * | 2006-03-22 | 2007-08-22 | 蒋胜 | Production process of eliminating simple substance sulphur from SO2 gas |
| CN101570341A (en) * | 2009-05-26 | 2009-11-04 | 华中科技大学 | Method for utilizing comprehensive resource of sulfur-containing solid waste |
| CN102502524A (en) * | 2011-10-28 | 2012-06-20 | 云南云天化国际化工股份有限公司 | Method for producing sulfur dioxide from calcium sulfate and sulfur |
| CN103962115A (en) * | 2014-05-21 | 2014-08-06 | 杨皓 | Desulphurization activated carbon regeneration process combined with Claus device |
| CN107902631A (en) * | 2017-11-11 | 2018-04-13 | 四川大学 | One kind utilizes hot carbon reduction ardealite coupling thermal activation potash feldspar ore CO2The method of co-production sulfur dioxide and potassium sulfate |
| CN109052335A (en) * | 2018-07-24 | 2018-12-21 | 上海三夫工程技术有限公司 | A kind of method of sulfur gas reduction Waste Sulfuric Acid sulfur dioxide liquid and sulfuric acid |
| CN109573957A (en) * | 2018-12-28 | 2019-04-05 | 华陆工程科技有限责任公司 | A kind of sulphur produces the sulfur dioxide of various concentration and the co-production of sulfuric acid simultaneously |
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