CN114011219B - Composite oxidation method for wet desulfurization process of carbide slag-based desulfurizing agent - Google Patents
Composite oxidation method for wet desulfurization process of carbide slag-based desulfurizing agent Download PDFInfo
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 119
- 230000023556 desulfurization Effects 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title claims abstract description 102
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 77
- 230000008569 process Effects 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 62
- 239000002893 slag Substances 0.000 title claims abstract description 55
- 230000003647 oxidation Effects 0.000 title claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 37
- 239000002002 slurry Substances 0.000 claims abstract description 67
- 238000004537 pulping Methods 0.000 claims abstract description 24
- 239000010440 gypsum Substances 0.000 claims abstract description 22
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000003814 drug Substances 0.000 claims abstract description 14
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 14
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 14
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 14
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 14
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- -1 iron ions Chemical class 0.000 claims abstract description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 5
- 238000005189 flocculation Methods 0.000 claims abstract description 5
- 230000016615 flocculation Effects 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 32
- 229910052717 sulfur Inorganic materials 0.000 claims description 32
- 239000011593 sulfur Substances 0.000 claims description 32
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 26
- 239000003546 flue gas Substances 0.000 claims description 26
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 claims description 15
- 235000010261 calcium sulphite Nutrition 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000002708 enhancing effect Effects 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 30
- 230000008676 import Effects 0.000 description 7
- 239000002585 base Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 229910009112 xH2O Inorganic materials 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention belongs to the technical field of resource recycling, and particularly relates to a composite oxidation method for a wet desulfurization process of a carbide slag-based desulfurizing agent, which comprises the steps of preparing a composite medicament from ferric sulfate, ferrous sulfate and ferrate according to a certain proportion, mixing the composite medicament with the desulfurizing agent for pulping, wherein the slurry is in an alkaline environment in the pulping process, and the oxidizing agent is used for removing reducing impurities and has a certain flocculation impurity removal function; in the desulfurization process, the slurry is in an acidic environment, the unreacted oxidant directly oxidizes the sulfite, and the catalyst and the oxidant product provide iron ions and ferrous ions for the reaction of the sulfite and oxygen as the catalyst. The method utilizes the acid-base change of slurry in the desulfurization process of the carbide slag-based desulfurizing agent, utilizes the difference of the reaction of the composite agent in the acid-base environment, has the effects of removing impurities and enhancing oxidation in the pulping and desulfurization processes, and improves the quality of the desulfurized gypsum while ensuring the desulfurization efficiency.
Description
Technical Field
The invention belongs to the technical field of resource recycling, and particularly relates to a composite oxidation method for a wet desulfurization process of a carbide slag-based desulfurizing agent.
Background
The carbide slag is solid waste generated in the process of preparing acetylene by reacting calcium carbide with water, and 1800 ten thousand tons of carbide slag are discharged by the polyvinyl chloride (PVC) industry each year. The main component of carbide slag is calcium hydroxide, the content can reach 80-90%, and unlike traditional limestone desulfurizing agent, the carbide slag-based desulfurizing agent has far higher dissolution mass transfer rate than limestone, can maintain higher desulfurizing efficiency, also reduces the circulating amount of slurry, and meanwhile, partial H 2S、PH3 and other reducing substances remain, so that it is necessary to introduce an oxidation enhancer to eliminate reducing impurities and promote the oxidation of calcium sulfite, thereby ensuring high-efficiency desulfurization and quality of desulfurized gypsum.
The invention patent of China with the application number of CN101734875A discloses a catalytic oxidation method of calcium sulfite in dry and semi-dry desulfurization ash, which has the technical scheme that manganese salt solution and hydrogen peroxide solution are added into the desulfurization ash, and the oxidation speed and limit of the calcium sulfite are improved through heat preservation and digestion, but the method is only suitable for the dry and semi-dry desulfurization process and has certain limitation.
The Chinese patent application No. CN101244360A discloses a catalytic oxidation process of calcium sulfite, which adopts the technical scheme that soluble ferrous salt, manganese salt or a mixture of the two are added into slurry after SO 2 absorption as a catalyst SO as to improve the oxidation rate of the calcium sulfite, but the process introduces additional impurity elements.
The Chinese patent application No. CN102872718A discloses an oxidation method of wet flue gas desulfurization liquid, which utilizes a fixed bed reactor to catalyze calcium sulfite, but adds a new process and additional waste catalyst to the desulfurization process.
In addition, the processes in the prior art mainly aim at the traditional dry, semi-dry and wet desulfurization processes, and cannot be well adapted to the influence of rapid ablation and high desulfurization efficiency of the carbide slag-based desulfurizing agent.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a composite oxidation method for a wet desulfurization process of a carbide slag-based desulfurizing agent, which utilizes the change of the acid and the alkali of slurry in the desulfurization process of the carbide slag-based desulfurizing agent, utilizes the difference of reactions of composite agents in an acid-alkali environment, respectively plays roles of removing impurities and enhancing oxidation in the pulping and desulfurization processes, ensures the desulfurization efficiency, improves the quality of desulfurized gypsum, has simple process, low raw material cost, does not add additional procedures, and has good economic and social values.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a composite oxidation method for a wet desulfurization process of a carbide slag-based desulfurizing agent comprises the following steps:
(1) Preparing desulfurization slurry: mixing ferric sulfate, ferrous sulfate and ferrate according to a certain proportion to prepare a composite medicament, and pulping the composite medicament and a carbide slag-based desulfurizing agent according to a certain proportion in a pulping tank to prepare desulfurization slurry;
(2) Wet desulfurizing:
And (3) delivering the desulfurization slurry obtained in the step (1) into a desulfurization reaction tower for desulfurization, and enabling the desulfurization slurry to contact and react with sulfur-containing flue gas through a spraying system to participate in the whole wet desulfurization process.
Preferably, the method is suitable for the wet desulfurization process of the carbide slag-based desulfurizing agent, the desulfurizing agent is matched with the composite agent to prepare slurry, the slurry is sent to a desulfurizing tower to carry out desulfurization, the slurry in the pulping tank is in an alkaline environment, and the slurry in the desulfurizing tower is in an acidic environment.
Preferably, the composite medicament takes ferric sulfate and ferrous sulfate as catalysts, ferrate is taken as an oxidant, the content of the catalysts (ferric sulfate and ferrous sulfate) is 0-30%, the content of the ferrate is 70-100%, and the catalysts and the oxidant can be one or a mixture of several of the medicines in any proportion.
Preferably, the compound agent participates in slurry configuration according to proportion when the desulfurization slurry is configured, and the adding proportion accounts for 0.01% -0.1% of the consumption of the desulfurization agent in the desulfurization process.
The composite medicament has the functions of removing the reducing impurities and flocculating and removing a small amount of other impurities in the pulping process.
In the pulping process, the slurry is in an alkaline environment, and ferrate reacts with residual H 2S、PH3 in the carbide slag-based desulfurizing agent as follows:
8FeO4 2-+3H2S+(4x+2)H2O＝3SO4 2-+4(Fe2O3·xH2O)+10OH-
8FeO4 2-+3PH3+(4x-1)H2O＝3PO4 3-+4(Fe2O3·xH2O)+7OH-
the formed ferric hydroxide colloid can play a certain role in flocculation.
In the desulfurization process of the composite reagent, on one hand, unreacted oxidant directly oxidizes the sulfite, and on the other hand, iron ions and ferrous ions in the catalyst and oxidation products provide a catalyst for the reaction of the sulfite and oxygen.
After entering the desulfurization process, the slurry absorbs a large amount of SO 2, and in an acidic environment, unreacted ferrate reacts with sulfite to promote the oxidation of the sulfite, and the reaction is as follows:
2FeO4 2-+3SO3 2-+4H++H2O＝2Fe(OH)3+3SO4 2-
Meanwhile, ferric ions in the reaction product and iron ions in the compound agent play a role in promoting the oxidation of the sulfite, so that the enhanced oxidation of the sulfite is realized.
Advantageous effects
The invention discloses a composite oxidation method for a wet desulfurization process of a carbide slag-based desulfurizing agent, which comprises the steps of preparing a composite medicament from ferric sulfate, ferrous sulfate and ferrate according to a certain proportion, mixing the composite medicament with the desulfurizing agent according to a certain proportion, adding the mixture into a desulfurizing agent pulping tank, and in the pulping process, enabling slurry to be in an alkaline environment, removing reducing impurities by using an oxidizing agent, and playing a certain flocculation impurity removal function; in the desulfurization process, the slurry is in an acidic environment, the unreacted oxidant directly oxidizes the sulfite, and the catalyst and the oxidant product provide iron ions and ferrous ions for the reaction of the sulfite and oxygen as the catalyst.
The process utilizes the acid-base change of slurry in the desulfurization process of the carbide slag-based desulfurizing agent, utilizes the difference of the reaction of the composite agent in the acid-base environment, has the effects of removing impurities and enhancing oxidation in the pulping and desulfurization processes, ensures the desulfurization efficiency and improves the quality of the desulfurized gypsum.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The method for enhancing oxidation by using the sulfite radical in the desulfurization process of the carbide slag-based desulfurizing agent provided by the invention enhances the oxidation of calcium sulfite in the desulfurization process of the carbide slag-based desulfurizing agent, and improves the quality of desulfurized gypsum;
(2) The method for enhancing the oxidation of the sulfite in the desulfurization process of the carbide slag-based desulfurizing agent has the advantages of simple process, low cost and good economic and social values;
(3) The method for enhancing the oxidation of the sulfite in the desulfurization process of the carbide slag-based desulfurizer provided by the invention accords with the variation characteristics of slurry components, reaction speed, pH value and other conditions in the desulfurization process of the carbide slag-based desulfurizer, and is suitable for the wet desulfurization process of the carbide slag-based desulfurizer.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description, it is to be understood that the terms used in this specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description set forth herein is merely a preferred example for the purpose of illustration and is not intended to limit the scope of the invention, so that it should be understood that other equivalents or modifications may be made thereto without departing from the spirit and scope of the invention.
The following examples are merely illustrative of embodiments of the present invention and are not intended to limit the invention in any way, and those skilled in the art will appreciate that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Example 1
A composite oxidation method for a wet desulfurization process of a carbide slag-based desulfurizing agent comprises the following steps:
(1) Preparing desulfurization slurry: mixing ferric sulfate, ferrous sulfate and ferrate according to the proportion of 10%, 20% and 70% to prepare a composite reagent, adding water into the composite reagent and a carbide slag-based desulfurizing agent to pulp to prepare desulfurizing slurry, controlling the pH of the desulfurizing slurry in the pulping process to be 12.3, adding the composite reagent according to the proportion of 0.01% of the carbide slag-based desulfurizing agent, and after adding the composite reagent, keeping the parameters such as pH, import and export sulfur content and the like unchanged.
(2) Wet desulfurizing: and (3) sending the desulfurization slurry obtained in the step (1) into a desulfurization reaction tower, carrying out wet desulfurization by contacting and reacting with sulfur-containing flue gas through a spraying system, and dehydrating to obtain the desulfurization gypsum. The pH of the slurry in the desulfurization process is controlled at 5.0, the sulfur content of the inlet flue gas is 3200ppm, the sulfur content of the outlet flue gas is 15ppm, and the content of calcium sulfite in the desulfurization gypsum is reduced from 0.14% to 0.11%.
Example 2
A composite oxidation method for a wet desulfurization process of a carbide slag-based desulfurizing agent comprises the following steps:
(1) Preparing desulfurization slurry: mixing ferric sulfate, ferrous sulfate and ferrate according to the proportion of 10%, 0% and 90% to prepare a composite reagent, adding water into the composite reagent and a carbide slag-based desulfurizing agent to pulp to prepare desulfurizing slurry, controlling the pH of the desulfurizing slurry in the pulping process to be 12.4, adding the composite reagent according to the proportion of 0.1% of the carbide slag-based desulfurizing agent, and after adding the composite reagent, keeping the parameters such as pH, import and export sulfur content and the like unchanged.
(2) Wet desulfurizing: and (3) sending the desulfurization slurry obtained in the step (1) into a desulfurization reaction tower, carrying out wet desulfurization by contacting and reacting with sulfur-containing flue gas through a spraying system, and dehydrating to obtain the desulfurization gypsum. The pH of the slurry in the desulfurization process is controlled at 4.7, the sulfur content of the inlet flue gas is 4600ppm, the sulfur content of the outlet flue gas is 12ppm, and the content of calcium sulfite in the desulfurized gypsum is reduced from 0.53 percent to 0.32 percent.
Example 3
A composite oxidation method for a wet desulfurization process of a carbide slag-based desulfurizing agent comprises the following steps:
(1) Preparing desulfurization slurry: mixing ferric sulfate, ferrous sulfate and ferrate according to the proportion of 0%, 30% and 70% to prepare a composite reagent, adding water into the composite reagent and a carbide slag-based desulfurizing agent to pulp to prepare desulfurizing slurry, controlling the pH of the desulfurizing slurry in the pulping process to be 12.2, adding the composite reagent according to the proportion of 0.03% of the carbide slag-based desulfurizing agent, and after adding the composite reagent, keeping the parameters such as pH, import and export sulfur content and the like unchanged.
(2) Wet desulfurizing: and (3) sending the desulfurization slurry obtained in the step (1) into a desulfurization reaction tower, carrying out wet desulfurization by contacting and reacting with sulfur-containing flue gas through a spraying system, and dehydrating to obtain the desulfurization gypsum. The pH of the slurry in the desulfurization process is controlled at 5.5, the sulfur content of the inlet flue gas is 1200ppm, the sulfur content of the outlet flue gas is 8ppm, and the content of calcium sulfite in the desulfurized gypsum is reduced from 0.38 percent to 0.30 percent.
Example 4
A composite oxidation method for a wet desulfurization process of a carbide slag-based desulfurizing agent comprises the following steps:
(1) Preparing desulfurization slurry: mixing ferric sulfate, ferrous sulfate and ferrate according to the proportion of 5%, 5% and 90% to prepare a composite reagent, adding water into the composite reagent and a carbide slag-based desulfurizing agent to pulp to prepare desulfurizing slurry, controlling the pH of the desulfurizing slurry in the pulping process to be 12.4, adding the composite reagent according to the proportion of 0.05% of the carbide slag-based desulfurizing agent, and after adding the composite reagent, keeping the parameters such as pH, import and export sulfur content and the like unchanged.
(2) Wet desulfurizing: and (3) sending the desulfurization slurry obtained in the step (1) into a desulfurization reaction tower, carrying out wet desulfurization by contacting and reacting with sulfur-containing flue gas through a spraying system, and dehydrating to obtain the desulfurization gypsum. The pH of the slurry in the desulfurization process is controlled at 5.8, the sulfur content of the inlet flue gas is 1700ppm, the sulfur content of the outlet flue gas is 12ppm, and the content of calcium sulfite in the desulfurized gypsum is reduced from 0.22 percent to 0.12 percent.
Example 5
A composite oxidation method for a wet desulfurization process of a carbide slag-based desulfurizing agent comprises the following steps:
(1) Preparing desulfurization slurry: mixing ferric sulfate, ferrous sulfate and ferrate according to the proportion of 0%, 0% and 100% to prepare a composite reagent, adding water into the composite reagent and a carbide slag-based desulfurizing agent to pulp to prepare desulfurizing slurry, controlling the pH of the desulfurizing slurry in the pulping process to be 12.5, adding the composite reagent according to the proportion of 0.1% of the carbide slag-based desulfurizing agent, and after adding the composite reagent, keeping the parameters such as pH, import and export sulfur content and the like unchanged.
(2) Wet desulfurizing: and (3) sending the desulfurization slurry obtained in the step (1) into a desulfurization reaction tower, carrying out wet desulfurization by contacting and reacting with sulfur-containing flue gas through a spraying system, and dehydrating to obtain the desulfurization gypsum. The pH of the slurry in the desulfurization process is controlled at 6.0, the sulfur content of the inlet flue gas is 4200ppm, the sulfur content of the outlet flue gas is 24ppm, and the content of calcium sulfite in the desulfurized gypsum is reduced from 0.19% to 0.05%.
Example 6
A composite oxidation method for a wet desulfurization process of a carbide slag-based desulfurizing agent comprises the following steps:
(1) Preparing desulfurization slurry: mixing ferric sulfate, ferrous sulfate and ferrate according to the proportion of 5%, 10% and 85% to prepare a composite reagent, adding water into the composite reagent and a carbide slag-based desulfurizing agent to pulp to prepare desulfurizing slurry, controlling the pH of the desulfurizing slurry in the pulping process to be 12.5, adding the composite reagent according to the proportion of 0.07% of the carbide slag-based desulfurizing agent, and after adding the composite reagent, keeping the parameters such as pH, import and export sulfur content and the like unchanged.
(2) Wet desulfurizing: and (3) sending the desulfurization slurry obtained in the step (1) into a desulfurization reaction tower, carrying out wet desulfurization by contacting and reacting with sulfur-containing flue gas through a spraying system, and dehydrating to obtain the desulfurization gypsum. The pH of the slurry in the desulfurization process is controlled at 4.0, the sulfur content of the inlet flue gas is 3200ppm, the sulfur content of the outlet flue gas is 6ppm, and the content of calcium sulfite in the desulfurization gypsum is reduced from 0.85% to 0.61%.
Example 7
A composite oxidation method for a wet desulfurization process of a carbide slag-based desulfurizing agent comprises the following steps:
(1) Preparing desulfurization slurry: mixing ferric sulfate, ferrous sulfate and ferrate according to the proportion of 15%, 10% and 75% to prepare a composite reagent, adding water into the composite reagent and a carbide slag-based desulfurizing agent to pulp to prepare desulfurizing slurry, controlling the pH of the desulfurizing slurry in the pulping process to be 12.4, adding the composite reagent according to the proportion of 0.02% of the carbide slag-based desulfurizing agent, and after adding the composite reagent, keeping the parameters such as pH, import and export sulfur content and the like unchanged.
(2) Wet desulfurizing: and (3) sending the desulfurization slurry obtained in the step (1) into a desulfurization reaction tower, carrying out wet desulfurization by contacting and reacting with sulfur-containing flue gas through a spraying system, and dehydrating to obtain the desulfurization gypsum. The pH of the slurry in the desulfurization process is controlled at 3.8, the sulfur content of the inlet flue gas is 2100ppm, the sulfur content of the outlet flue gas is 5ppm, and the content of calcium sulfite in the desulfurized gypsum is reduced from 0.33% to 0.27%.
The invention prepares the composite medicament of ferric sulfate, ferrous sulfate and ferrate according to a certain proportion, mixes the composite medicament with the desulfurizing agent according to a certain proportion, adds the mixture into a desulfurizing agent pulping tank, and the slurry is in alkaline environment and the oxidizing agent removes reducing impurities and plays a certain role in flocculation impurity removal in the pulping process; in the desulfurization process, the slurry is in an acidic environment, the unreacted oxidant directly oxidizes the sulfite, and the catalyst and the oxidant product provide iron ions and ferrous ions for the reaction of the sulfite and oxygen as the catalyst.
The process utilizes the acid-base change of slurry in the desulfurization process of the carbide slag-based desulfurizing agent, utilizes the difference of the reaction of the composite agent in the acid-base environment, has the effects of removing impurities and enhancing oxidation in the pulping and desulfurization processes, ensures the desulfurization efficiency and improves the quality of the desulfurized gypsum.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be apparent to one skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (4)
1. The composite oxidation method for the wet desulfurization process of the carbide slag-based desulfurizing agent is characterized by comprising the following steps of:
(1) Preparing desulfurization slurry: adding water into a composite medicament and a carbide slag-based desulfurizing agent to prepare desulfurization slurry, wherein the composite medicament comprises the following components in parts by weight: 0-30 parts of catalyst and 70-100 parts of oxidant;
(2) Wet desulfurizing: feeding the desulfurization slurry obtained in the step (1) into a desulfurization reaction tower, carrying out wet desulfurization by contacting and reacting with sulfur-containing flue gas through a spraying system, and dehydrating to obtain desulfurized gypsum; wherein,
The adding amount of the composite medicament is 0.01-0.1% of the mass of the carbide slag-based desulfurizing agent;
the catalyst comprises one or a combination of two of ferric sulfate and ferrous sulfate, and the oxidant is ferrate;
In the pulping process, the slurry is in an alkaline environment, and the oxidizing agent removes reducing impurities and plays a certain role in flocculation and impurity removal; in the desulfurization process, the slurry is in an acidic environment, the unreacted oxidant directly oxidizes the sulfite, and meanwhile, the catalyst and the oxidant product provide iron ions and ferrous ions for the reaction of the sulfite and oxygen as the catalyst;
the pH value of the desulfurization slurry is controlled to be 12.2-12.5 in the pulping process, and the pH value of the desulfurization slurry is controlled to be 3.8-6.0 in the desulfurization process.
2. The composite oxidation method for a wet desulfurization process of a carbide slag-based desulfurization agent according to claim 1, wherein the carbide slag-based desulfurization agent is obtained by a carbide slag pretreatment, the carbide slag being produced by a dry or wet acetylene production process.
3. The composite oxidation method for a wet desulfurization process of a carbide slag-based desulfurizing agent according to claim 1, wherein the sulfur content of the inlet flue gas of the desulfurization reaction tower is 1200-4600 ppm, and the sulfur content of the outlet flue gas after desulfurization is 5-25 ppm.
4. The composite oxidation method for a wet desulfurization process of a carbide slag-based desulfurization agent according to claim 1, wherein the content of calcium sulfite in the desulfurized gypsum is reduced by 20% to 80%.
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