CN113531539A - Method for resource utilization of sodium chloride waste salt - Google Patents
Method for resource utilization of sodium chloride waste salt Download PDFInfo
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- CN113531539A CN113531539A CN202110818558.0A CN202110818558A CN113531539A CN 113531539 A CN113531539 A CN 113531539A CN 202110818558 A CN202110818558 A CN 202110818558A CN 113531539 A CN113531539 A CN 113531539A
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/02—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment
- F23G5/027—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/02—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment
- F23G5/033—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment comminuting or crushing
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/08—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating
- F23G5/14—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating including secondary combustion
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/44—Details; Accessories
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/44—Details; Accessories
- F23G5/46—Recuperation of heat
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- 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
The invention relates to the field of waste treatment, and discloses a method for resource utilization of sodium chloride waste salt, which comprises the following steps: preparing an organic matter gasification auxiliary agent, performing synergistic treatment, treating and the like; the invention discloses a method for treating waste sodium chloride salt in cooperation with a downstream rotary kiln, which utilizes the heat of the downstream rotary kiln, decomposes and gasifies organic matters in the waste sodium chloride salt, then the organic matters enter a decomposing furnace of the downstream rotary kiln to be fully combusted and then discharged in a harmless manner, so that the sodium chloride salt body can be recycled, the heat generated by combustion of the organic matters in the waste salt can be fully utilized, the energy can be supplied to the downstream rotary kiln, and the purpose of full resource utilization can be achieved; the method has the advantages of low energy consumption, high quality of the recycled sodium chloride, low carbon content and no generation of wastewater and waste gas, and is a green method for recycling the sodium chloride waste salt.
Description
Technical Field
The invention relates to the field of waste treatment, in particular to a method for resource utilization of sodium chloride waste salt.
Background
A large amount of waste salt residues are generated in the production process of a plurality of chemical products (particularly pesticides, medicines, fine chemicals, organic chemicals, dyes and the like), and the sodium chloride waste salt residues contain 2 to 15 percent of organic matters, so that the sodium chloride waste salt residues containing different organic matters show different appearance colors, emit various unpleasant smells and cause great harm to the environment and the physical and mental health of human bodies.
CN109867296A discloses a method for refining industrial sodium chloride waste salt slag, wherein the sodium chloride waste salt slag is pretreated by crushing and the like, then is subjected to heat treatment to remove organic matters, then is added with hot water and stirred to completely dissolve soluble salt and then is filtered, the obtained sodium chloride crude salt solution is subjected to purification treatment, is subjected to evaporation concentration, cooling crystallization and drying to obtain a sodium chloride product, and the evaporated and distilled water is completely recycled for dissolving the salt slag after the heat treatment. The recovery rate of sodium chloride in the method reaches more than 98 percent, the content of sodium chloride in the obtained sodium chloride product reaches more than 99 percent (wt percent), the content of impurities is extremely low and reaches more than the first-grade standard of industrial dry salt, and the sodium chloride product can be directly sold as a raw material in industries such as chlor-alkali and the like. The method realizes harmless and resource treatment of the sodium chloride waste salt slag, has remarkable economic benefit, environmental benefit and social benefit, achieves the aims of complete regeneration and recycling of sodium chloride salt resources, energy conservation and environmental protection, and is an environment-friendly technology.
CN111559749A discloses a method for recycling and fully utilizing sodium chloride waste slag salt by an esterification method. Adding acyl chloride and an alkali catalyst into the waste salt slag containing the alcohol sodium chloride, stirring, mixing, reacting and filtering; adding n-hexane into the obtained solution, stirring and mixing uniformly, standing for layering, and recovering the upper layer liquid to obtain an esterification product; adding a sodium carbonate solution into the lower-layer solution, standing and filtering, drying and recovering filter residues, adding hydrochloric acid into the filtrate, standing, heating and concentrating, separating out crystals, and drying to obtain purified sodium chloride. According to the method, the alcohol organic matters in the salt residues are efficiently and thoroughly esterified through normal-temperature treatment, the aim of purifying sodium chloride is achieved, ester substances capable of being recycled are recycled, technical support is provided for the chemical industry to achieve energy conservation and emission reduction, and sustainable coordinated development of the chemical industry is promoted.
CN108423692B proposes a method for purifying and refining sodium chloride by using waste salt generated in vitamin C production, which comprises the following steps: 1) dissolving waste salt generated in the production process of vitamin C in water, and adding a precipitator or a precipitator and a precipitation auxiliary agent to precipitate impurities; the precipitator is a sodium hydroxide solution, and the precipitation auxiliary agent is one or more of a sodium carbonate solution, a calcium chloride solution and an ammonium carbonate solution; 2) decolorizing with active carbon, and filtering; 3) concentrating the filtrate under reduced pressure, recovering purified water, centrifuging the materials, and recovering the centrifuged mother liquor; and drying the dehydrated wet product to obtain the product sodium chloride. The invention refines and purifies the waste salt generated in the vitamin C production process to obtain the method for producing industrial salt, and solves the problem of recycling solid waste in the vitamin C production process. The purification and refining process is simple, the mother liquor and the purified water are recycled, the refining cost is low, and the product purity is high.
The method and the prior art adopt the method of dissolving the waste salt by water, evaporating, concentrating, cooling and crystallizing, and are subject to the waste salt of sodium chloride, and the method has the discharge of a large amount of waste water and organic waste and is easy to cause secondary pollution.
Disclosure of Invention
In order to solve the problems, the invention provides a method for resource utilization of sodium chloride waste salt. The invention discloses a method for recycling sodium chloride waste salt, which utilizes the heat of a downstream rotary kiln, decomposes and gasifies organic matters in the sodium chloride waste salt, then the organic matters enter a decomposing furnace of the downstream rotary kiln to be fully combusted and then discharged harmlessly, can recycle sodium chloride salt bodies, and can also fully utilize the heat generated by the combustion of the organic matters in the waste salt to supply energy to the downstream rotary kiln, thereby achieving the purpose of full recycling; the waste salt balls are ignited by the igniter to form a combustion layer, the waste salt balls are gradually combusted under the action of air draft, the combustion layer is gradually pushed downwards until the bottom of the material layer, the incineration of all the material layers is completed, the smoke enters the lower material layer under the action of negative pressure, and the heat of the smoke dries and preheats the lower pellets to be incinerated, so that the thermal efficiency in the incineration disposal process is improved.
Preparing an organic matter gasification auxiliary agent:
adding 3-7 parts of vinylpyridine, 5-12 parts of methyl silicon (glycol) diacetate, 0.3-1.8 parts of tetratriphenyl phosphorus palladium and 130 parts of 105-plus organic solvent into a reaction kettle, controlling the temperature to 80-90 ℃, carrying out reflux reaction for 3-8h, adding 12.3-14.8 parts of transition metal chloride salt after the reaction is finished, controlling the temperature to 80-90 ℃, stirring for 1-5h, evaporating the solvent, adding 10-16 parts of organic Lewis acid and 38-52 parts of phosphate, uniformly mixing, drying at 80-105 ℃, cooling, carrying out high-speed ball milling treatment on the mixed group at 0-10 ℃ to obtain a powdery material with the average particle size of 200 plus 500 mu m, adding 5-12 parts of manganese acetate, carrying out low-speed ball milling treatment at 10-40 ℃, so as to obtain the organic matter gasification auxiliary agent;
a method for resource utilization of sodium chloride waste salt comprises the following steps:
step one, cooperative treatment: uniformly mixing 180 parts of sodium chloride waste salt 100 plus materials with 0.5-3 parts of organic gasification auxiliary agent to obtain a mixed material, sending the mixed material into pyrolysis equipment, wherein the pyrolysis equipment is provided with a heating layer and a material chamber, the heating layer is connected with a downstream rotary kiln decomposition system, introducing heat of the downstream rotary kiln into the pyrolysis equipment, heating the sodium chloride waste salt mixed material in the material chamber, treating the mixed material at 450 ℃ of 250 plus materials for 10-30min, and then heating the mixed material to 1000 ℃ of 850 plus materials, and the reaction time is 20-60 min; the material chamber be in anaerobic heating state, the flue gas and the air that the organic matter produced according to the volume ratio 0.8: mixing in the ratio of 0.6-1.2, feeding into a downstream rotary kiln decomposing furnace through a pipeline, and feeding into a secondary combustion chamber after full combustion;
step two, secondary incineration
The secondary combustion chamber is used for further thoroughly decomposing and destroying harmful substances which are not burnt out in the smoke generated by the primary combustion, and the burner is arranged at the lower part of the secondary combustion chamber, so that the fuel gas and the smoke can be fully mixed. The second combustion chamber adopts a cylindrical structure, the inner part is a fire-resistant layer, the heat-insulating layer and the outer layer are sequentially coated with steel plates. In order to fully mix the smoke and the secondary air supply, the secondary air speed is 30-50m/s, the temperature of the gas at the outlet of the secondary incineration chamber is 1100-1500 ℃, the retention time of the smoke in the secondary incineration chamber is more than 2 seconds, and the oxygen content at the outlet is 6-11%.
And step three, discharging purified salt obtained after the thermal decomposition of the waste sodium chloride salt from a salt discharge port, dissolving, filtering and evaporating to obtain the recycled sodium chloride salt.
The transition metal chloride is cobalt chloride or ferric chloride or copper chloride.
The organic solvent is methanol or ethanol or isopropanol.
The organic Lewis acid is formic acid or oxalic acid or citric acid.
The phosphate is ammonium phosphate or triethylamine phosphate or phosphoric acid-1, 2-ethylenediamine salt.
The sodium chloride waste salt incineration process mainly comprises the following main units: a feeding system: comprises a hydraulic station, a feeding system, a weighing system, a crusher and a pushing mechanism. An incineration system: comprises a downstream rotary kiln, a secondary combustion chamber system, a waste liquid feeding system and a burner. A waste heat recovery system: comprises a waste heat boiler (in SNCR furnace denitration), auxiliary equipment and the like. Flue gas purification system: the flue gas in the incinerator is cooled, harmful substances are removed, and the flue gas is discharged after reaching the discharge requirement. Comprises a quench tower, a lime feeding system, an active carbon feeding system, a cloth bag dust removing system, a wet tower and the like. A flue gas discharge system: the system comprises an induced draft fan, a chimney and an online monitoring system.
The vinylpyridine and the methyl silicon (glycol) diacetate are subjected to hydrosilylation reaction, and the formula is shown as follows:
according to the invention, the organic matter gasification auxiliary agent added into the waste salt can promote the organic matter to be decomposed into small molecules, so that the organic matter is volatilized, the carbide residue in the waste salt is reduced, and the quality of the recovered waste salt is improved; the method of the invention fully utilizes the heat generated by the downstream rotary kiln to decompose the organic matters in the waste salt, and then the decomposed organic matters enter the downstream rotary kiln to be fully combusted to provide heat for the downstream rotary kiln, thereby achieving the purpose of green treatment. The method has the advantages of low energy consumption, high quality of the recycled sodium chloride, low carbon content and no generation of wastewater and waste gas, and is a green method for recycling the sodium chloride waste salt.
The purity product of the sodium chloride regenerated salt obtained after the chemical waste salt is treated by the item meets the standard of refined dry salt for ionic membrane caustic soda in ionic membrane caustic soda salt (QB/T5270-2018), and the TOC is less than or equal to 10 mg/kg.
Drawings
FIG. 1 is an electron micrograph of SU8010 of waste salts.
FIG. 2 is an electron micrograph of SU8010 of waste salts.
FIG. 3 is a thermogravimetric analysis chart of spent salt.
As can be seen from fig. 3: the waste salt contains a plurality of exothermic peaks and is judged to contain a plurality of organic matters; the exothermic peaks are all <800 ℃.
Detailed Description
The invention is further illustrated by the following specific examples:
analysis of chemical composition of sodium chloride waste salt part
| Cl(%) | Ca(%) | Mg(%) | S04 2-(%) | K2O(%) | Na2O(%) |
| 35.7 | 0.366 | 0 | 15.04 | 0 | 26.81 |
The organic content was 15200 ppm.
Example 1
A method for resource utilization of sodium chloride waste salt comprises the following steps:
preparing an organic matter gasification auxiliary agent:
adding 3kg of vinylpyridine, 5kg of methyl silicon (glycol) diacetate, 0.3kg of tetratriphenyl phosphine palladium and 105kg of organic solvent into a reaction kettle, controlling the temperature to 80 ℃, carrying out reflux reaction for 3 hours, adding 12.3kg of transition metal chloride salt after the reaction is finished, controlling the temperature to 80 ℃, stirring for 1 hour, evaporating the solvent, adding 10kg of organic Lewis acid and 38kg of phosphate, uniformly mixing, drying at 80 ℃, cooling, carrying out high-speed ball milling treatment on the mixed group at 0 ℃ to obtain a powdery material with the average particle size of 200 mu m, adding 5kg of manganese acetate, and carrying out low-speed ball milling treatment at 10 ℃ to obtain a gasification organic auxiliary agent;
a method for resource utilization of sodium chloride waste salt comprises the following steps:
step one, cooperative treatment: uniformly mixing 100kg of sodium chloride waste salt with 0.5kg of organic matter gasification auxiliary agent to obtain a mixed material, feeding the mixed material into pyrolysis equipment, wherein the pyrolysis equipment is provided with a heating layer and a material chamber, the heating layer is connected with a downstream rotary kiln decomposition system, the heat of the downstream rotary kiln is introduced into the pyrolysis equipment, the sodium chloride waste salt mixed material in the material chamber is heated, firstly treated at 250 ℃ for 10min, then heated to 850 ℃, and the reaction time is 20 min; the material chamber be in anaerobic heating state, the flue gas and the air that the organic matter produced according to the volume ratio 0.8: the mixture with the proportion of 0.6 enters a downstream rotary kiln decomposing furnace through a pipeline, and enters a secondary burning chamber after being fully burned;
step two, secondary incineration
The secondary combustion chamber is used for further thoroughly decomposing and destroying harmful substances which are not burnt out in the smoke generated by the primary combustion, and the burner is arranged at the lower part of the secondary combustion chamber, so that the fuel gas and the smoke can be fully mixed. The second combustion chamber adopts a cylindrical structure, the inner part is a fire-resistant layer, the heat-insulating layer and the outer layer are sequentially coated with steel plates. In order to fully mix the smoke and secondary air supply, the secondary air speed is 30m/s, the temperature of gas at the outlet of the secondary incineration chamber is 1100 ℃, the retention time of the smoke in the secondary incineration chamber is more than 2 seconds, and the oxygen content at the outlet is 6 percent.
And step three, discharging purified salt obtained after the thermal decomposition of the waste sodium chloride salt from a salt discharge port, dissolving, filtering and evaporating to obtain the recycled sodium chloride salt.
The transition metal chloride is cobalt chloride.
The organic solvent is methanol.
The organic Lewis acid is formic acid.
The phosphate is ammonium phosphate.
The lower temperature is 250 ℃.
Example 2
Preparing an organic matter gasification auxiliary agent:
adding 5kg of vinylpyridine, 8kg of methyl silicon (glycol) diacetate, 1.1kg of tetratriphenyl phosphine palladium and 118kg of organic solvent into a reaction kettle, controlling the temperature to 85 ℃, carrying out reflux reaction for 6 hours, adding 13.5kg of transition metal chloride salt after the reaction is finished, controlling the temperature to 85 ℃, stirring for 3 hours, evaporating the solvent, adding 13kg of organic Lewis acid and 45kg of phosphate, uniformly mixing, drying at 92 ℃, cooling, carrying out high-speed ball milling treatment on the mixed group at 5 ℃ to obtain a powdery material with the average particle size of 350 mu m, adding 8kg of manganese acetate, and carrying out low-speed ball milling treatment at 25 ℃ to obtain a gasification organic auxiliary agent;
a method for resource utilization of sodium chloride waste salt comprises the following steps:
step one, cooperative treatment: uniformly mixing 140kg of sodium chloride waste salt with 1.8kg of organic matter gasification auxiliary agent to obtain a mixed material, feeding the mixed material into pyrolysis equipment, wherein the pyrolysis equipment is provided with a heating layer and a material chamber, the heating layer is connected with a downstream rotary kiln decomposition system, the heat of the downstream rotary kiln is introduced into the pyrolysis equipment, the sodium chloride waste salt mixed material in the material chamber is heated, firstly treated at 350 ℃ for 20min, then heated to 925 ℃ and reacted for 40 min; the material chamber be in anaerobic heating state, the flue gas and the air that the organic matter produced according to the volume ratio 0.8: 0.9 of the mixture enters a downstream rotary kiln decomposing furnace through a pipeline, and enters a secondary burning chamber after being fully burned;
step two, secondary incineration
The secondary combustion chamber is used for further thoroughly decomposing and destroying harmful substances which are not burnt out in the smoke generated by the primary combustion, and the burner is arranged at the lower part of the secondary combustion chamber, so that the fuel gas and the smoke can be fully mixed. The second combustion chamber adopts a cylindrical structure, the inner part is a fire-resistant layer, the heat-insulating layer and the outer layer are sequentially coated with steel plates. In order to fully mix the smoke and the secondary air supply, the secondary air speed is 40m/s, the temperature of the gas at the outlet of the secondary incineration chamber is 1300 ℃, the retention time of the smoke in the secondary incineration chamber is more than 2 seconds, and the oxygen content at the outlet is 8 percent.
And step three, discharging purified salt obtained after the thermal decomposition of the waste sodium chloride salt from a salt discharge port, dissolving, filtering and evaporating to obtain the recycled sodium chloride salt. The transition metal chloride is ferric chloride.
The organic solvent is ethanol.
The organic Lewis acid is oxalic acid.
The phosphate is triethylamine phosphate.
The lower temperature is 350 ℃.
Example 3
A method for resource utilization of sodium chloride waste salt comprises the following steps:
preparing an organic matter gasification auxiliary agent:
adding 7kg of vinylpyridine, 12kg of methyl silicon (glycol) diacetate, 1.8kg of tetratriphenyl phosphine palladium and 130kg of organic solvent into a reaction kettle, controlling the temperature to 90 ℃, carrying out reflux reaction for 8 hours, adding 14.8kg of transition metal chloride salt after the reaction is finished, controlling the temperature to 90 ℃, stirring for 5 hours, evaporating the solvent, adding 16kg of organic Lewis acid and 52kg of phosphate, uniformly mixing, drying at 105 ℃, cooling, carrying out high-speed ball milling treatment on the mixed group at 10 ℃ to obtain a powdery material with the average particle size of 500 mu m, adding 12kg of manganese acetate, and carrying out low-speed ball milling treatment at 40 ℃ to obtain a gasification organic auxiliary agent;
a method for resource utilization of sodium chloride waste salt comprises the following steps:
step one, cooperative treatment: uniformly mixing 180kg of sodium chloride waste salt with 3kg of organic matter gasification auxiliary agent to obtain a mixed material, feeding the mixed material into pyrolysis equipment, wherein the pyrolysis equipment is provided with a heating layer and a material chamber, the heating layer is connected with a downstream rotary kiln decomposition system, the heat of the downstream rotary kiln is introduced into the pyrolysis equipment, the sodium chloride waste salt mixed material in the material chamber is heated, firstly treated at 450 ℃ for 30min, then heated to 1000 ℃, and the reaction time is 60 min; the material chamber be in anaerobic heating state, the flue gas and the air that the organic matter produced according to the volume ratio 0.8: 1.2, the mixture enters a downstream rotary kiln decomposing furnace through a pipeline, and enters a secondary combustion chamber after being fully combusted;
step two, secondary incineration
The secondary combustion chamber is used for further thoroughly decomposing and destroying harmful substances which are not burnt out in the smoke generated by the primary combustion, and the burner is arranged at the lower part of the secondary combustion chamber, so that the fuel gas and the smoke can be fully mixed. The second combustion chamber adopts a cylindrical structure, the inner part is a fire-resistant layer, the heat-insulating layer and the outer layer are sequentially coated with steel plates. In order to fully mix the smoke and the secondary air supply, the secondary air speed is 50m/s, the temperature of the gas at the outlet of the secondary incineration chamber is 1500 ℃, the retention time of the smoke in the secondary incineration chamber is more than 2 seconds, and the oxygen content at the outlet is 11 percent.
And step three, discharging purified salt obtained after the thermal decomposition of the waste sodium chloride salt from a salt discharge port, dissolving, filtering and evaporating to obtain the recycled sodium chloride salt. The transition metal chloride is copper chloride.
The organic solvent is isopropanol.
The organic Lewis acid is citric acid.
The phosphate is 1, 2-ethylenediamine phosphate.
The lower temperature is 450 ℃.
The purity product of the sodium chloride regenerated salt obtained by treating the chemical waste salt in the embodiments 1,2 and 3 by the item meets the standard of refined dry salt for ionic membrane caustic soda (QB/T5270-2018) ionic membrane caustic soda, and the TOC is less than or equal to 10 mg/kg.
Comparative example 1
A method for resource utilization of sodium chloride waste salt comprises the following steps:
a method for resource utilization of sodium chloride waste salt comprises the following steps:
step one, cooperative treatment: 100kg of sodium chloride waste salt is fed into pyrolysis equipment, the pyrolysis equipment is provided with a heating layer and a material chamber, the heating layer is connected with a downstream rotary kiln decomposition system, the heat of the downstream rotary kiln is led into the pyrolysis equipment, the sodium chloride waste salt mixed material in the material chamber is heated, the sodium chloride waste salt mixed material is firstly treated at 250 ℃ for 10min and then heated to 850 ℃, and the reaction time is 20 min; the material chamber be in anaerobic heating state, the flue gas and the air that the organic matter produced according to the volume ratio 0.8: the mixture with the proportion of 0.6 enters a downstream rotary kiln decomposing furnace through a pipeline, and enters a secondary burning chamber after being fully burned;
step two, secondary incineration
The secondary combustion chamber is used for further thoroughly decomposing and destroying harmful substances which are not burnt out in the smoke generated by the primary combustion, and the burner is arranged at the lower part of the secondary combustion chamber, so that the fuel gas and the smoke can be fully mixed. The second combustion chamber adopts a cylindrical structure, the inner part is a fire-resistant layer, the heat-insulating layer and the outer layer are sequentially coated with steel plates. In order to fully mix the smoke and the secondary air supply, the secondary air speed is 30m/s, the temperature of the gas at the outlet of the secondary incineration chamber is 1100 ℃, the retention time of the smoke in the secondary incineration chamber is more than 2 seconds, and the oxygen content at the outlet is 6 percent.
And step three, discharging purified salt obtained after the thermal decomposition of the waste sodium chloride salt from a salt discharge port, dissolving, filtering and evaporating to obtain the recycled sodium chloride salt. The transition metal chloride is cobalt chloride.
The organic solvent is methanol.
The organic Lewis acid is formic acid.
The phosphate is ammonium phosphate.
The lower temperature is 250 ℃.
Comparative example 2
Preparing an organic matter gasification auxiliary agent:
adding 3kg of vinylpyridine, 5kg of methyl silicon (glycol) diacetate, 0.3kg of tetratriphenyl phosphine palladium and 105kg of organic solvent into a reaction kettle, controlling the temperature to 80 ℃, carrying out reflux reaction for 3 hours, adding 12.3kg of transition metal chloride salt after the reaction is finished, controlling the temperature to 80 ℃, stirring for 1 hour, evaporating the solvent, adding 10kg of organic Lewis acid and 38kg of phosphate, uniformly mixing, drying at 80 ℃, cooling, carrying out high-speed ball milling treatment on the mixed group at 0 ℃ to obtain a powdery material with the average particle size of 200 mu m, adding 5kg of manganese acetate, and carrying out low-speed ball milling treatment at 10 ℃ to obtain a gasification organic auxiliary agent;
a method for resource utilization of sodium chloride waste salt comprises the following steps:
step one, cooperative treatment: uniformly mixing 100kg of sodium chloride waste salt with 0.5kg of organic matter gasification auxiliary agent to obtain a mixed material, feeding the mixed material into pyrolysis equipment, wherein the pyrolysis equipment is provided with a heating layer and a material chamber, the heating layer is connected with a downstream rotary kiln decomposition system, the heat of the downstream rotary kiln is introduced into the pyrolysis equipment, the sodium chloride waste salt mixed material in the material chamber is heated, firstly treated at 250 ℃ for 10min, then heated to 850 ℃, and the reaction time is 20 min; the material chamber be in anaerobic heating state, the flue gas and the air that the organic matter produced according to the volume ratio 0.8: the mixture with the proportion of 0.6 enters a downstream rotary kiln decomposing furnace through a pipeline, and enters a secondary burning chamber after being fully burned;
and step three, discharging purified salt obtained after the thermal decomposition of the waste sodium chloride salt from a salt discharge port, dissolving, filtering and evaporating to obtain the recycled sodium chloride salt. The transition metal chloride is cobalt chloride.
The organic solvent is methanol.
The organic Lewis acid is formic acid.
The lower temperature is 250 ℃.
Comparative example 3
A method for resource utilization of sodium chloride waste salt comprises the following steps:
and (3) cooperative treatment: 100kg of sodium chloride waste salt is fed into pyrolysis equipment, the pyrolysis equipment is provided with a heating layer and a material chamber, the heating layer is connected with a downstream rotary kiln decomposition system, the heat of the downstream rotary kiln is introduced into the pyrolysis equipment to heat the sodium chloride waste salt mixed material in the material chamber, the sodium chloride waste salt mixed material is firstly treated at a lower temperature for 10min and then heated to 850 ℃, and the reaction time is 20 min; the material chamber be in anaerobic heating state, the flue gas and the air that the organic matter produced according to the volume ratio 0.8: the mixture with the proportion of 0.6 enters a downstream rotary kiln decomposing furnace through a pipeline, and enters a downstream rotary kiln waste gas system after being fully combusted;
discharging purified salt obtained after the thermal decomposition of the waste sodium chloride salt from a salt discharge port to obtain the recycled sodium chloride salt.
The lower temperature is 250 ℃.
A thermogravimetric analyzer, STA 449F 3 from Chiari corporation was used. The adopted atmosphere is nitrogen and air, the mass of the sample is about 16mg every time, the sample is placed in an alumina crucible for testing during analysis, and the flow rate of carrier gas is 50 ml/min. The organic matter residue of the waste salt after the weight reduction reaction treatment in the nitrogen atmosphere, and the carbide residue of the waste salt after the weight reduction reaction treatment in the air atmosphere. The test results are shown in the following table:
the results of the performance test for treating waste sodium chloride salt of the comparative example are shown in the following table:
| organic matter residual TOC mg/kg | Carbide (%) | |
| Example 1 | 4 | 0.5 |
| Example 2 | 2 | 0.4 |
| Example 3 | 1 | 0.2 |
| Comparative example 1 | 13 | 2.91 |
| Comparative example 2 | 59 | 6.21 |
| Comparative example 3 | 124 | 10.74 |
Claims (5)
1. A method for resource utilization of sodium chloride waste salt is characterized by comprising the following steps:
step one, cooperative treatment: uniformly mixing 180 parts of sodium chloride waste salt 100 plus materials with 0.5-3 parts of organic gasification auxiliary agent to obtain a mixed material, sending the mixed material into pyrolysis equipment, wherein the pyrolysis equipment is provided with a heating layer and a material chamber, the heating layer is connected with a downstream rotary kiln decomposition system, introducing heat of the downstream rotary kiln into the pyrolysis equipment, heating the sodium chloride waste salt mixed material in the material chamber, treating the mixed material at 450 ℃ of 250 plus materials for 10-30min, and then heating the mixed material to 1000 ℃ of 850 plus materials, and the reaction time is 20-60 min; the material chamber be in anaerobic heating state, the flue gas and the air that the organic matter produced according to the volume ratio 0.8: mixing in the ratio of 0.6-1.2, feeding into a downstream rotary kiln decomposing furnace through a pipeline, and feeding into a secondary combustion chamber after full combustion;
step two, secondary incineration
The secondary combustion chamber is used for further thoroughly decomposing and destroying harmful substances which are not burnt out in the flue gas generated by the primary combustion, and the burner is arranged at the lower part of the secondary combustion chamber, so that the fuel gas and the flue gas can be fully mixed;
the second combustion chamber adopts a cylindrical structure, the inner part is a fire-resistant layer, the heat-insulating layer and the outer layer are sequentially coated with steel plates;
in order to fully mix the smoke and the secondary air supply, the secondary air speed is 30-50m/s, the temperature of the gas at the outlet of the secondary incineration chamber is 1100-1500 ℃, the retention time of the smoke in the secondary incineration chamber is more than 2 seconds, and the oxygen content at the outlet is 6-11 percent;
and step three, discharging purified salt obtained after the thermal decomposition of the waste sodium chloride salt from a salt discharge port, dissolving, filtering and evaporating to obtain the recycled sodium chloride salt.
2. The method for resource utilization of sodium chloride waste salt according to claim 1, which is characterized in that: the preparation of the organic matter gasification auxiliary agent comprises the following steps: adding 3-7 parts of vinylpyridine, 5-12 parts of methyl silicon (glycol) diacetate, 0.3-1.8 parts of tetratriphenyl phosphorus palladium and 130 parts of 105-plus organic solvent into a reaction kettle, controlling the temperature to 80-90 ℃, carrying out reflux reaction for 3-8h, adding 12.3-14.8 parts of transition metal chloride salt after the reaction is finished, controlling the temperature to 80-90 ℃, stirring for 1-5h, evaporating the solvent, adding 10-16 parts of organic Lewis acid and 38-52 parts of phosphate, uniformly mixing, drying at 80-105 ℃, cooling, carrying out high-speed ball milling treatment on the mixed group at 0-10 ℃ to obtain a powdery material with the average particle size of 200 plus 500 mu m, adding 5-12 parts of manganese acetate, carrying out low-speed ball milling treatment at 10-40 ℃, and obtaining the organic matter gasification auxiliary agent.
3. The method for resource utilization of sodium chloride waste salt according to claim 1, which is characterized in that: the organic solvent is methanol or ethanol or isopropanol.
4. The method for resource utilization of sodium chloride waste salt according to claim 1, which is characterized in that: the organic Lewis acid is formic acid or oxalic acid or citric acid.
5. The method for resource utilization of sodium chloride waste salt according to claim 1, which is characterized in that: the phosphate is ammonium phosphate or triethylamine phosphate or phosphoric acid-1, 2-ethylenediamine salt.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116768239A (en) * | 2023-05-30 | 2023-09-19 | 湖南省湘衡盐化有限责任公司 | Large-particle salt upgrading equipment capable of removing sundries in raw salt |
| CN116768239B (en) * | 2023-05-30 | 2024-04-26 | 湖南省湘衡盐化有限责任公司 | Large-particle salt upgrading equipment capable of removing sundries in raw salt |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116768239A (en) * | 2023-05-30 | 2023-09-19 | 湖南省湘衡盐化有限责任公司 | Large-particle salt upgrading equipment capable of removing sundries in raw salt |
| CN116768239B (en) * | 2023-05-30 | 2024-04-26 | 湖南省湘衡盐化有限责任公司 | Large-particle salt upgrading equipment capable of removing sundries in raw salt |
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