CN114535264A - Recycling treatment method for industrial waste salt - Google Patents
Recycling treatment method for industrial waste salt Download PDFInfo
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- 150000003839 salts Chemical class 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000002440 industrial waste Substances 0.000 title claims abstract description 38
- 238000004064 recycling Methods 0.000 title claims description 21
- 238000000197 pyrolysis Methods 0.000 claims abstract description 103
- 239000002699 waste material Substances 0.000 claims abstract description 36
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 25
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 24
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 24
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000010521 absorption reaction Methods 0.000 claims description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 14
- 239000003546 flue gas Substances 0.000 claims description 14
- 238000010791 quenching Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 238000002485 combustion reaction Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 claims description 6
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- 239000008213 purified water Substances 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- -1 fluoride ions Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
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- 238000007599 discharging Methods 0.000 claims description 4
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000000171 quenching effect Effects 0.000 description 12
- 239000002351 wastewater Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 5
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
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- 239000000575 pesticide Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- 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
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the technical field of environmental protection, and particularly relates to a resource treatment method of industrial waste salt, which comprises the steps of sequentially crushing, mixing and compounding, anaerobic pyrolysis, aerobic pyrolysis, high-temperature crushing, replacement reaction, dissolving and impurity removal, MVR evaporation, centrifugal separation and airflow drying the industrial waste salt from first to last to obtain sodium sulfate crystals; the anaerobic pyrolysis adopts a rotary kiln baking type or spiral tube baking type heating mode, the pyrolysis time is 30-120 minutes, and the pyrolysis temperature is 400-650 ℃; the aerobic pyrolysis adopts a chain plate type reactor, ceramic fiber cloth is attached to the upper part of a chain plate of the chain plate type reactor, a heating device is arranged at the lower part of the chain plate type reactor, the aerobic pyrolysis time is 10-60 minutes, and the pyrolysis temperature is 500-700 ℃; the TOC of the waste salt after the aerobic pyrolysis is 50-800ppm, and the TOC of the waste salt after the anaerobic pyrolysis is 200-5000 ppm. The application and disposal range of the waste salt is wide, and the product after the resource treatment of the industrial waste salt is industrial class II first-class sodium sulfate, so that the product quality is excellent.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a resource treatment method for industrial waste salt.
Background
The industrial waste salt refers to a byproduct crystalline salt produced in an industrial production process, and is mainly produced in the industries of pesticides, fine chemical industry, medicines, printing and dyeing, coal chemical industry and the like. There are two main routes of industrial waste salt production: firstly, the high-salt wastewater is generated by evaporation and crystallization in the water treatment (pure water preparation, reclaimed water reuse and wastewater concentration), and secondly, the high-salt wastewater is separated out due to chemical reaction in the production process. Because the industrial waste salt is different in output ways and working procedures, a mixture containing different salt components can be generated, the industrial waste salt is various in types, complex in components, contains organic matters, has the characteristics of toxic and harmful substances, is difficult to dispose, and is qualified as dangerous solid waste.
At present, the annual output of industrial waste salt in China exceeds 2000 ten thousand tons. Especially, a large amount of chemical waste salt is generated in the production process of chemical products, and the chemical salt residues in the whole country can reach more than 500 ten thousand tons every year, wherein the pesticide accounts for 30 percent, the fine chemical industry accounts for 15 percent, the medicine accounts for 10 percent, and the others account for 45 percent.
The quantity of industrial waste salt is huge, the main treatment method at present is rigid landfill, which not only needs to occupy a large amount of landfill resources, but also causes resource waste, and therefore, the exploration and the invention of the method and the device for treating the industrial waste salt as the resource are necessary.
In view of this, the present invention is proposed.
Disclosure of Invention
The invention hopes to provide a resource treatment method for industrial waste salt, and the specific scheme is as follows:
a method for recycling industrial waste salt comprises the steps of sequentially crushing, mixing and compounding the industrial waste salt from first to last, carrying out anaerobic pyrolysis, aerobic pyrolysis, high-temperature crushing, replacement reaction, dissolving and impurity removal, MVR evaporation, centrifugal separation and airflow drying on the industrial waste salt, and finally obtaining sodium sulfate crystals; the anaerobic pyrolysis adopts a rotary kiln baking type or spiral tube baking type heating mode, the pyrolysis time is 30-120 minutes, and the pyrolysis temperature is 400-650 ℃; the aerobic pyrolysis adopts a chain plate type reactor, ceramic fiber cloth is attached to the upper part of a chain plate of the chain plate type reactor, a heating device is arranged at the lower part of the chain plate type reactor, the aerobic pyrolysis time is 10-60 minutes, and the pyrolysis temperature is 500-700 ℃; the TOC (total organic carbon) of the waste salt after anaerobic pyrolysis is 5000ppm, the TOC of the waste salt after aerobic pyrolysis is 50-800ppm, the TOC of the waste salt after high-temperature crushing is less than or equal to 250ppm, and the TOC of the waste salt after replacement reaction is less than or equal to 100 ppm.
Pyrolysis gas generated in the aerobic pyrolysis and the anaerobic pyrolysis is introduced into a secondary combustion chamber, high-temperature flue gas generated in the secondary combustion chamber is used for anaerobic pyrolysis, the temperature for treating the flue gas is more than 1100 ℃, the retention time is more than 2.5 seconds, and the resource consumption is reduced.
The flue gas generated in the anaerobic pyrolysis is subjected to quenching tower, cloth bag dust removal and tail gas purification treatment, and finally discharged into the atmosphere through a chimney, tail gas purified water generated after the tail gas purification treatment is introduced into the quenching tower for recycling, and a quenching medium in the quenching tower is alkaline tail gas purified water generated after the tail gas is purified, so that the waste water is not generated integrally under the synergistic effect of the quenching medium and the alkaline tail gas purified water.
Washing and purifying tail gas generated in the displacement reaction and carrying out tail gas countercurrent absorption treatment, discharging the residual tail gas into the atmosphere after alkali absorption, wherein the tail gas countercurrent absorption reagent is pure water, the absorption mode is countercurrent multistage absorption, and the countercurrent multistage absorption is carried out to obtain first-grade hydrochloric acid (the index requirement refers to the national standard); the washing and purifying reagent is final-stage absorption liquid in countercurrent multistage absorption, the washing and purifying mode is circulating concurrent washing, and qualified hydrochloric acid is obtained through washing and purifying (the index requirement refers to the national standard).
The high-temperature flue gas generated in the replacement reaction is used for airflow drying, so that the energy consumption is reduced.
The replacement reagent in the replacement reaction is sulfuric acid, the concentration of the sulfuric acid is 80-100%, the replacement time is 2-6 hours, and the replacement temperature is 400-600 ℃.
The replacement time is 3-4 hours, the replacement temperature is 450-500 ℃, and the replacement effect is optimal when the replacement time and the replacement temperature are selected.
The cooling water obtained by MVR evaporation is introduced into the dissolution and impurity removal for recycling, and water resources are recycled, so that no wastewater is generated in the whole system.
The compounding parameters in the mixed compounding are that TOC is less than or equal to 30%, water is less than or equal to 20%, total nitrogen is less than or equal to 5%, potassium ions are less than or equal to 4%, calcium and magnesium ions are less than or equal to 5%, heavy metals are less than or equal to 5%, fluoride ions are less than or equal to 1%, bromide ions are less than or equal to 1%, sodium ions, sulfate ions and chloride ions are more than or equal to 85%, feeding is more uniform during pyrolysis of the industrial waste salt after compounding treatment, and only the industrial waste salt meeting the compounding requirement can be recycled through the combined method of aerobic pyrolysis and anaerobic pyrolysis.
The solid content of the dissolved brine in the dissolving and impurity removing process is 22-25%, the impurity removing and refining agents are liquid caustic soda, soda ash and activated carbon, the pH of the refined brine is =7-10, the sum of sodium ions and sulfate ions is not less than 95%, the sum of calcium ions and magnesium ions is not more than 50ppm, and the TOC is not more than 30ppm, ion detection and TOC detection are carried out before the final product sodium sulfate is obtained, and the product is the industrial class II first-class sodium sulfate with excellent quality after the industrial waste salt is treated as a resource.
The invention has the following beneficial effects:
1. the industrial waste salt which meets the compounding requirement can be subjected to resource treatment, the application and treatment range of the waste salt is wide, and the product after the resource treatment of the industrial waste salt is industrial class II first-class sodium sulfate salt, so that the product quality is excellent;
2. according to the invention, the organic matters in the waste salt can be better removed by combining anaerobic pyrolysis and aerobic pyrolysis;
3. the anaerobic pyrolysis temperature in the invention is slightly low, so that waste salt is prevented from melting in the pyrolysis process, and most of organic matters are removed; the aerobic pyrolysis temperature is increased, organic matters are completely removed as far as possible, and the pyrolysis equipment is provided with a ceramic fiber cloth lining layer, so that waste salt can be prevented from being melted and bonded;
4. high-temperature crushing is adopted after pyrolysis, and the heat of waste salt can be utilized to further remove organic matters during crushing; pyrolysis gas generated by anaerobic pyrolysis and aerobic pyrolysis replaces partial natural gas to be used as a combustion source, so that the treatment temperature of flue gas is higher than 1100 ℃, the retention time is longer than 2.5 seconds, and the resource consumption is reduced; the high-temperature flue gas treated by the second combustion chamber is used as a heat source for anaerobic pyrolysis, so that the energy consumption is reduced; inorganic carbon generated in the pyrolysis process can replace part of purified and refined active carbon, so that the consumption of raw materials is reduced; the drying heat source of the air flow drying is hot air utilized in the replacement process, so that the energy consumption is reduced;
5. the waste salt crushed at high temperature is used in the replacement reaction, so that the reaction temperature rise time can be shortened, and the energy consumption can be reduced. Waste salt is in a fine particle state during reaction, and organic matters wrapped in the processes of anaerobic pyrolysis and aerobic pyrolysis are further removed;
6. the quenching medium in the quenching tower is alkaline tail gas purified water generated after tail gas purification, and the alkaline tail gas purified water have synergistic effect, so that dissolved salt water obtained by dissolving, removing impurities and refining and evaporated water generated by evaporation and concentration are recycled, resources are utilized to the maximum extent, and no waste water is generated in the whole process.
Drawings
FIG. 1 is a schematic flow chart of a method for recycling industrial waste salt according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
As shown in fig. 1, a recycling treatment method of industrial waste salt comprises the steps of sequentially crushing, mixing and compounding, anaerobic pyrolysis, aerobic pyrolysis, high-temperature crushing, replacement reaction, dissolution and impurity removal, MVR evaporation, centrifugal separation and airflow drying the industrial waste salt from first to last to obtain sodium sulfate crystals; the anaerobic pyrolysis adopts a rotary kiln baking type or spiral tube baking type heating mode, the pyrolysis time is 60 minutes, and the pyrolysis temperature is 500 ℃; the aerobic pyrolysis adopts a chain plate type reactor, the upper part of a chain plate of the chain plate type reactor is attached with ceramic fiber cloth, the lower part of the chain plate is provided with a heating device, the aerobic pyrolysis time is 40 minutes, the pyrolysis temperature is 600 ℃, the TOC of waste salt after the aerobic pyrolysis is below 600ppm, the TOC of waste salt after the anaerobic pyrolysis is below 3000ppm, the TOC of waste salt after the high-temperature crushing is below 250ppm, and the TOC of waste salt after the replacement reaction is below 100 ppm.
The particle size of the crushed waste salt meets the subsequent resource requirement, and the crushed particle size is below 25 mm. The crushing device of the waste salt adopts a roller crusher. The compounding parameters in the mixed compounding are that TOC is less than or equal to 30%, water is less than or equal to 20%, total nitrogen is less than or equal to 5%, potassium ions are less than or equal to 4%, calcium and magnesium ions are less than or equal to 5%, heavy metals are less than or equal to 5%, fluoride ions are less than or equal to 1%, bromide ions are less than or equal to 1%, sodium ions, sulfate ions and chloride ions are more than or equal to 85%, feeding is more uniform during pyrolysis of the industrial waste salt after the compounding treatment, and only the industrial waste salt meeting the compounding requirement can be subjected to resource treatment by the combined method of aerobic pyrolysis and anaerobic pyrolysis. The waste salt after mixing and compounding is loaded in a compound salt mixing storage device, and the mixing device has a frequency conversion stirring and mixing function. Preferably, a conical mixer or a carriage mixer silo with a volume of 20 cubic meters is used.
Pyrolysis gas generated in the aerobic pyrolysis and the anaerobic pyrolysis is introduced into a secondary combustion chamber, high-temperature flue gas generated in the secondary combustion chamber is used for the anaerobic pyrolysis, the temperature for treating the flue gas is 1200 ℃, the retention time is more than 2.5 seconds, and the resource consumption is reduced. The flue gas generated in the anaerobic pyrolysis is subjected to quenching tower, cloth bag dust removal and tail gas purification treatment, and finally discharged into the atmosphere through a chimney, tail gas purification water generated after the tail gas purification treatment is introduced into the quenching tower for recycling, and a quenching medium in the quenching tower is alkaline tail gas purification water generated after the tail gas purification, so that the waste water is not generated integrally under the synergistic effect of the quenching medium and the alkaline tail gas purification water. The waste salt is pyrolyzed and then needs to be crushed at high temperature, and the particle size of the crushed waste salt is smaller than 150 meshes. The high-temperature ball mill is adopted as the crushing equipment, and the particle size after crushing is 20-40 meshes. Waste salt TOC after anaerobic pyrolysis is about 3000 ppm; the TOC of the waste salt after aerobic pyrolysis is about 300 ppm. The waste salt is still in pyrolysis during high-temperature crushing, organic matters which cannot be removed when the waste salt is wrapped in the caking waste salt during anaerobic pyrolysis and aerobic pyrolysis can be removed, and the TOC after crushing is 150 ppm.
And (3) carrying out washing purification and tail gas countercurrent absorption treatment on tail gas generated in the displacement reaction, discharging the residual tail gas into the atmosphere through a chimney, washing and purifying to obtain a qualified product hydrochloric acid, and carrying out tail gas countercurrent absorption treatment to obtain an first-grade product hydrochloric acid. The equipment for the displacement reaction is a kiln with baking heating and rake teeth stirring, preferably a Mannheim furnace is selected, and the heat source for baking heating is natural gas. The substitution reagent is sulfuric acid, preferably 90% concentrated sulfuric acid. The displacement time was 4 hours and the displacement temperature was 500 ℃. Waste salt is fine particles during the replacement reaction, and residual organic matters are still subjected to high-temperature pyrolysis during high-temperature replacement, so that organic matters wrapped in the processes of anaerobic pyrolysis and aerobic pyrolysis can be further removed. The TOC of the waste salt after completion of the replacement was 60 ppm. High-temperature flue gas generated in the replacement reaction is used for airflow drying, and energy consumption is reduced. The cooling water obtained by MVR evaporation is introduced into the dissolution and impurity removal for recycling, and water resources are recycled, so that no wastewater is generated in the whole process.
The solid content of the dissolved saline water is 24%, the impurity removal refined medicament is caustic soda liquid, soda ash and activated carbon, the pH of the refined saline water is =8.5, the sodium ion and sulfate ion content is 97%, the calcium and magnesium ion content is 35ppm, and the TOC content is 18 ppm. In the pyrolysis process, organic matters are decomposed to generate inorganic carbon particles, and the inorganic carbon particles can replace part of purified and refined active carbon to adsorb residual organic matters in waste salt. The produced salt is dried at high temperature, preferably, the selected drying equipment is air flow drying, and the used drying heat source is hot air used after baking and heating in the replacement process. The product obtained by drying is industrial class II first-class sodium sulfate.
Example 2
The other steps were unchanged compared to example 1, the oxygen-free pyrolysis and its related steps were omitted, and the purity of the sodium sulfate crystals and the TOC concentration were determined.
Example 3
The other steps were unchanged compared to example 1, the aerobic pyrolysis and its related steps were omitted, and the purity of the sodium sulfate crystals and the TOC concentration were determined.
Example 4
The other steps were unchanged compared to example 1, the steps associated with anaerobic and aerobic pyrolysis and both were omitted, and the purity of the sodium sulfate crystals and the concentration of TOC were determined.
Example 5
Compared with example 1, the other steps were not changed, the time for aerobic pyrolysis was set to 40 minutes, the pyrolysis temperature was 400 ℃, and the purity of the resulting sodium sulfate crystals and the TOC concentration were measured.
Example 6
Compared with example 1, the other steps are unchanged, the time of aerobic pyrolysis is set to be 40 minutes, the pyrolysis temperature is 800 ℃, and the purity of the obtained sodium sulfate crystals and the concentration of TOC are detected.
Example 7
Compared with the example 1, other steps are unchanged, the time of aerobic pyrolysis is set to be 20 minutes, the pyrolysis temperature is 600 ℃, and the purity of the obtained sodium sulfate crystals and the concentration of TOC are detected.
Example 8
Compared with the example 1, other steps are unchanged, the time of aerobic pyrolysis is set to be 130 minutes, the pyrolysis temperature is 600 ℃, and the purity of the obtained sodium sulfate crystals and the concentration of TOC are detected.
Example 9
Compared with the example 1, other steps are unchanged, the time of anaerobic pyrolysis is set to be 20 minutes, the pyrolysis temperature is 500 ℃, and the purity of the obtained sodium sulfate crystals and the concentration of TOC are detected.
Example 10
Compared with the example 1, other steps are unchanged, the time of anaerobic pyrolysis is set to be 130 minutes, the pyrolysis temperature is 500 ℃, and the purity of the obtained sodium sulfate crystals and the concentration of TOC are detected.
Example 11
Compared with the example 1, other steps are unchanged, the time of anaerobic pyrolysis is set to be 60 minutes, the pyrolysis temperature is 300 ℃, and the purity of the obtained sodium sulfate crystals and the concentration of TOC are detected.
Example 12
Compared with the example 1, other steps are unchanged, the time of anaerobic pyrolysis is set to be 60 minutes, the pyrolysis temperature is 700 ℃, and the purity of the obtained sodium sulfate crystals and the concentration of TOC are detected.
Example 13
The other steps were unchanged from example 1, the replacement temperature was set at 400 ℃, and the purity of the resulting sodium sulfate crystals and the TOC concentration were examined.
Example 14
The other steps were unchanged from example 1, the replacement temperature was set at 600 ℃, and the purity of the sodium sulfate crystals and the TOC concentration were measured.
Example 15
The other steps were not changed, the substitution time was set to 2 hours, and the purity of the obtained sodium sulfate crystals and the TOC concentration were measured, as compared with example 1.
Example 16
The purity of the sodium sulfate crystals and the TOC concentration were measured in the same manner as in example 1 except that the other steps were not changed and the substitution time was set to 6 hours.
Table 1: example 1-example 16 sodium sulfate Crystal purity and TOC concentration
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A method for recycling industrial waste salt is characterized by comprising the following steps: sequentially crushing, mixing and compounding, anaerobic pyrolysis, aerobic pyrolysis, high-temperature crushing, replacement reaction, dissolving and impurity removal, MVR evaporation, centrifugal separation and airflow drying the industrial waste salt from first to last to obtain a sodium sulfate crystal; the anaerobic pyrolysis adopts a rotary kiln baking type or spiral tube baking type heating mode, the pyrolysis time is 30-120 minutes, and the pyrolysis temperature is 400-650 ℃; the aerobic pyrolysis adopts a chain plate type reactor, ceramic fiber cloth is attached to the upper part of a chain plate of the chain plate type reactor, a heating device is arranged at the lower part of the chain plate type reactor, the aerobic pyrolysis time is 10-60 minutes, and the pyrolysis temperature is 500-700 ℃; the TOC of the waste salt after the anaerobic pyrolysis is 5000-5000 ppm, the TOC of the waste salt after the aerobic pyrolysis is 50-800ppm, the TOC of the waste salt after the high-temperature crushing is less than or equal to 250ppm, and the TOC of the waste salt after the replacement reaction is less than or equal to 100 ppm.
2. The method for recycling industrial waste salt as claimed in claim 1, wherein the method comprises the following steps: and pyrolysis gas generated in the aerobic pyrolysis and the anaerobic pyrolysis is introduced into a secondary combustion chamber, and high-temperature flue gas generated in the secondary combustion chamber is used as a heat source for the anaerobic pyrolysis.
3. The method for recycling industrial waste salt as claimed in claim 2, wherein the method comprises the following steps: and introducing the high-temperature flue gas after anaerobic pyrolysis heat exchange into a quench tower, performing cloth bag dust removal and tail gas purification treatment, and finally discharging the high-temperature flue gas into the atmosphere through a chimney, wherein tail gas purified water generated after the tail gas purification treatment is introduced into the quench tower for recycling.
4. The method for recycling industrial waste salt as claimed in claim 1, wherein the method comprises the following steps: washing and purifying tail gas generated in the displacement reaction and carrying out tail gas countercurrent absorption treatment, discharging the residual tail gas into the atmosphere after alkali absorption, wherein the tail gas countercurrent absorption reagent is pure water, the absorption mode is countercurrent multistage absorption, and the countercurrent multistage absorption is carried out to obtain first-grade hydrochloric acid; the washing and purifying reagent is final-stage absorption liquid in countercurrent multistage absorption, the washing and purifying mode is circulating concurrent washing, and qualified hydrochloric acid is obtained through washing and purifying.
5. The method for recycling industrial waste salt as claimed in claim 1, wherein the method comprises the following steps: and the high-temperature flue gas generated in the replacement reaction is used for air flow drying.
6. The method for recycling industrial waste salt as claimed in claim 1, wherein the method comprises the following steps: the replacement reagent in the replacement reaction is sulfuric acid, the concentration of the sulfuric acid is 80-100%, the replacement time is 2-6 hours, and the replacement temperature is 400-600 ℃.
7. The method for recycling industrial waste salt as claimed in claim 6, wherein the method comprises the following steps: the replacement time is 3-4 hours, and the replacement temperature is 450-500 ℃.
8. The method for recycling industrial waste salt as claimed in claim 1, wherein the method comprises the following steps: and introducing cooling water obtained by MVR evaporation into the dissolving and impurity removing process for recycling.
9. The method for recycling industrial waste salt as claimed in claim 1, wherein the method comprises the following steps: the compounding parameters in the mixed compounding are that TOC is less than or equal to 30%, water is less than or equal to 20%, total nitrogen is less than or equal to 5%, potassium ions are less than or equal to 4%, calcium and magnesium ions are less than or equal to 5%, heavy metals are less than or equal to 5%, fluoride ions are less than or equal to 1%, bromide ions are less than or equal to 1%, and sodium ions, sulfate ions and chloride ions are more than or equal to 85%.
10. The method for recycling industrial waste salt as claimed in claim 1, wherein the method comprises the following steps: the solid content of the dissolved brine in the dissolving and impurity removing process is 22-25%, the impurity removing refined medicament is liquid alkali, calcined soda and active carbon, the pH of the refined brine is =7-10, the content of sodium ions and sulfate ions is more than or equal to 95%, the content of calcium and magnesium ions is less than or equal to 50ppm, and the content of TOC is less than or equal to 30 ppm.
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