CN115351032A - Method for recycling industrial waste salt - Google Patents
Method for recycling industrial waste salt Download PDFInfo
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- CN115351032A CN115351032A CN202211009163.7A CN202211009163A CN115351032A CN 115351032 A CN115351032 A CN 115351032A CN 202211009163 A CN202211009163 A CN 202211009163A CN 115351032 A CN115351032 A CN 115351032A
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- brine
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- waste salt
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- 150000003839 salts Chemical class 0.000 title claims abstract description 117
- 239000002440 industrial waste Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000004064 recycling Methods 0.000 title claims abstract description 16
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 117
- 239000012267 brine Substances 0.000 claims abstract description 112
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000001704 evaporation Methods 0.000 claims abstract description 48
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 46
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 230000003647 oxidation Effects 0.000 claims abstract description 40
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 40
- 230000008020 evaporation Effects 0.000 claims abstract description 34
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 23
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 238000001471 micro-filtration Methods 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 239000011780 sodium chloride Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000002699 waste material Substances 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 239000012847 fine chemical Substances 0.000 claims description 3
- 239000003905 agrochemical Substances 0.000 claims description 2
- 238000012824 chemical production Methods 0.000 claims description 2
- 230000009615 deamination Effects 0.000 claims 1
- 238000006481 deamination reaction Methods 0.000 claims 1
- 238000009938 salting Methods 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 abstract description 11
- 239000003513 alkali Substances 0.000 abstract description 7
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 8
- 229910001424 calcium ion Inorganic materials 0.000 description 8
- 229910001425 magnesium ion Inorganic materials 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 238000003843 chloralkali process Methods 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 firstly Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011268 retreatment Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
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- 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
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- 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
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The application discloses a method for recycling industrial waste salt, which comprises the steps of firstly dissolving salt to prepare the industrial waste salt into brine, then adding NaOH into the brine until the pH value is 9-11, introducing carbon dioxide into the brine, simultaneously adding brine and carbon dioxide gas into a tubular reactor, and carrying out microfiltration on the obtained turbid brine to obtain clear brine; oxidizing the clear brine by adopting an oxygen oxidation mode, adding NaOH into the brine until the pH value is 11, stirring and preserving heat; and (3) evaporation: and finally, evaporating and dewatering the salt water, and adding the salt water into an incinerator for high-temperature incineration to obtain the industrial salt. The method is characterized in that the salt obtained by carrying out salt melting, pretreatment, advanced oxidation, ammonia evaporation, evaporation and incineration on industrial waste salt can be used for chlor-alkali electrolysis, so that the resource utilization of the industrial salt is realized.
Description
Technical Field
The application relates to the technical field of environmental protection and industrial waste treatment, in particular to a method for recycling industrial waste salt.
Background
At present, the method for treating industrial salt in domestic chemical production mainly comprises a salt washing method, specifically, the industrial salt is washed by water or an organic solvent, impurities in the industrial salt are washed away as much as possible, and the treated industrial salt is used for downstream products. The method is more suitable for sodium chloride with less impurity content and single impurity component, and has the defects of secondary pollution such as retreatment of washing water or organic solvent and the like: in addition, the content of impurities in the sodium chloride is often unstable, the dosage of washing water or solvent is difficult to control, the impurities are difficult to clean, and the industrial application is difficult to realize.
Disclosure of Invention
The application provides a method for recycling industrial waste salt, and solves the problems that in the prior art, the traditional industrial waste salt treatment mode is narrow in application range, is difficult to clean impurities in the industrial waste salt, and is difficult to realize industrial application.
In order to solve the technical problem, the application provides a method for recycling industrial waste salt, which comprises the following steps:
salt dissolving: adding water into industrial waste salt to prepare brine with the concentration of 200-280 g/L;
pretreatment: adding NaOH into the saline water, adjusting the pH value to 9-11, then introducing carbon dioxide gas into the saline water, simultaneously adding the saline water and the carbon dioxide gas into a tubular reactor for reaction, and performing microfiltration on turbid saline water obtained after the reaction to obtain clear saline water;
advanced oxidation: carrying out oxidation treatment on the clarified brine by adopting an oxygen oxidation mode; wherein the oxidation temperature is 200-250 ℃, the oxidation pressure is 2.5-3MPa, and the oxygen introduction amount is as follows: TOC: o is 2 =1:2.0-8.0;
Ammonia distillation: adding NaOH into the brine after advanced oxidation, adjusting the pH value to 11, keeping the temperature at 90-100 ℃ for 3-5h under the stirring state, and absorbing tail gas through micro negative pressure;
and (3) evaporation: evaporating the deaminated brine to remove water, wherein the evaporated water can be recycled to the salt dissolving step, and the evaporation temperature is 90-120 ℃;
and (3) incineration: adding the evaporated low-TOC waste salt into an incinerator for high-temperature incineration to obtain industrial salt, wherein the incineration temperature is 900-1000 ℃, and the retention time is 20-40min.
Preferably, the industrial waste salt comprises agricultural chemicals, high TOC, high ammonia nitrogen and high organic matter content industrial waste salt generated in the production process of fine chemical engineering.
Preferably, in the salt dissolving step, the concentration of the brine is 260g/L, and the water is pure water.
Preferably, in the pretreatment step, the mass ratio of the carbon dioxide to the industrial waste salt is 0.023-0.03.
Preferably, the catalyst selected in the advanced oxidation step is any one of Ni, supported Pd, supported Pt and supported Rh.
Preferably, the deaminated brine is subjected to evaporation water removal by using a triple-effect evaporator.
Preferably, in the evaporation step, the evaporation temperature is 90-100 DEG C
Compared with the prior art, the method for recycling the industrial waste salt comprises the steps of firstly dissolving the salt to prepare the industrial waste salt into brine, then adding NaOH into the brine until the PH value is 9-11, then introducing carbon dioxide into the brine, simultaneously adding the brine and the carbon dioxide gas into a tubular reactor, and performing microfiltration on the obtained turbid brine to obtain clear brine; oxidizing the clear brine by adopting an oxygen oxidation mode, adding NaOH into the brine until the pH value is 11, stirring and preserving heat; and (3) evaporation: and finally, evaporating and dewatering the brine, and adding the brine into an incinerator for high-temperature incineration to obtain the industrial salt. The pretreatment process in the method is to reduce the hardness of brine and prevent pipelines from being blocked, the TOC value of industrial waste salt can be effectively reduced in the advanced oxidation process, the ammonia nitrogen value in the industrial waste salt can be effectively reduced in the ammonia evaporation process, the two steps are preparation before the waste salt enters the incinerator, the waste salt enters the incinerator after the two steps, the treatment effect is greatly improved, the TOC and the ammonia nitrogen in the waste salt can be reduced to a very low value, and therefore the requirement of entering the chlor-alkali process is met. The evaporation step is only to evaporate water to obtain the salt. The salt obtained by the treatment of industrial waste salt through the procedures of salt melting, pretreatment, advanced oxidation, ammonia distillation, evaporation and incineration can be used for chlor-alkali electrolysis, thus realizing the resource utilization of industrial salt.
Drawings
In order to more clearly explain the technical solution of the present application, the drawings needed to be used in the embodiments are briefly described below, and it is obvious to those skilled in the art that other drawings can be obtained according to the drawings without making any inventive changes.
FIG. 1 is a schematic diagram of a method for recycling industrial waste salt according to an embodiment of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application will be described clearly and completely with reference to the accompanying drawings.
The core of the application is to provide a method for recycling industrial waste salt, which can solve the problems that the traditional industrial waste salt treatment mode in the prior art is narrow in application range, difficult to clean impurities in the industrial waste salt treatment mode and difficult to realize industrial application.
Fig. 1 is a schematic diagram of a method for recycling industrial waste salt according to an embodiment of the present invention, as shown in fig. 1, including:
salt dissolving: adding water into the industrial waste salt to prepare brine with the concentration of 200-280 g/L.
The industrial waste salt comprises industrial waste salt with high TOC, high ammonia nitrogen and high organic matter content generated in the production process of pesticides and fine chemicals. The concentration of the brine is 260g/L, and the water is pure water.
Pretreatment: adding NaOH into the saline water, adjusting the pH value to 9-11, then introducing carbon dioxide gas into the saline water, simultaneously adding the saline water and the carbon dioxide gas into a tubular reactor for reaction, and performing microfiltration on turbid saline water obtained after the reaction to obtain clear saline water. In the step, the mass ratio of the carbon dioxide to the industrial waste salt is 0.023-0.03. The pH in this step is preferably 11.
Advanced oxidation: oxidizing the clarified brine by adopting an oxygen oxidation mode; wherein the oxidation temperature is 200-250 ℃, the oxidation pressure is 2.5-3MPa, and the oxygen introduction amount is as follows: TOC: o is 2 =1:2.0-8.0. The step needs to use a catalyst, and the selected catalyst is any one of Ni, loaded Pd, loaded Pt and loaded Rh. TOC is called total organic carbon and is a value generally used to indicate the content of organic matter in waste salts and waste water.
Ammonia distillation: adding NaOH into the saline water after advanced oxidation, adjusting the pH value to 11, keeping the temperature at 90-100 ℃ for 3-5h under the stirring state, and absorbing tail gas through micro negative pressure. The brine in this step was added to the NaOH via a baffle. The baffling groove is a device, can increase the surface area of two material contacts, and is more high-efficient, more space-saving for ordinary mixing tank.
And (3) evaporation: and (3) evaporating the deaminated brine to remove water, wherein the evaporated water can be recycled to the salt dissolving step, and the evaporation temperature is 90-120 ℃. Specifically, the energy consumption and time can be greatly shortened by using a triple-effect evaporator to evaporate and remove water from the deaminated brine, and the evaporation temperature is preferably 90-100 ℃.
And (3) incineration: and adding the evaporated low-TOC waste salt into an incinerator for high-temperature incineration to obtain industrial salt, wherein the incineration temperature is 900-1000 ℃, and the retention time is 20-40min. The incineration temperature is preferably 950 ℃ and the retention time is 25min. The industrial waste salt is treated in the previous steps, and the TOC value is reduced, so the industrial waste salt is called low-TOC waste salt.
The first embodiment is as follows:
salt dissolving: 2.5kg of industrial waste salt is prepared into brine with the concentration of 260g/L by pure water for standby.
Pretreatment: adding 30% sodium hydroxide aqueous solution into the brine prepared in the previous step, adjusting the pH value to 11, introducing 65g of carbon dioxide gas into the brine after the adjustment is finished, simultaneously adding the brine and the carbon dioxide gas into a tubular reactor for reaction, carrying out microfiltration on turbid brine obtained after the reaction to obtain clear brine for later use. The content of calcium and magnesium ions in the brine sample is analyzed as follows: calcium ion: 7ppm, magnesium ion: 5ppm of the total amount of the reaction product.
Advanced oxidation: placing the clear brine into a high-pressure kettle, adding a Pd catalyst with the mass fraction of 1%, setting the temperature at 250 ℃, the pressure at 2.5MPa, and the oxygen introduction amount: TOC: o is 2 =1:2.8 (brine TOC:21403 ppm), and after the same is completed, the brine is taken out, analyzed for TOC, and subjected to advanced oxidation to TOC:248ppm.
Ammonia distillation: adjusting the pH value of the brine subjected to advanced oxidation to 11, then putting the brine into a stirring kettle, setting the temperature to be 100 ℃, keeping the temperature for 3 hours in a stirring opening state, taking out the brine after heat preservation, analyzing ammonia nitrogen in the brine, and evaporating the ammonia in the brine: 379ppm (ammonia nitrogen of the saline after advanced oxidation: 6700 ppm).
And (3) evaporation: putting the brine after ammonia evaporation into a triple-effect evaporator, evaporating water at 100 ℃ to obtain 1.9kg of industrial salt, and sending a sample to analyze TOC:248ppm, ammonia nitrogen: 379ppm, nitrate: 139ppm.
And (3) incineration: and (3) placing the industrial salt obtained after evaporation in a muffle furnace, burning for 25min at 950 ℃ to obtain 1.82kg of industrial salt, and carrying out sample analysis: TOC:21ppm, ammonia nitrogen: 5ppm, nitrate radical: 0.036ppm. The analysis data accords with the conditions of the chlor-alkali electrolysis process, and the industrial waste salt treated by the process can be conveyed to the chlor-alkali process for electrolysis, so that the resource utilization is achieved.
Example two:
salt dissolving: 2.5kg of industrial waste salt is prepared into brine with the concentration of 260g/L by pure water for standby.
Pretreatment: adding 30% sodium hydroxide aqueous solution into the prepared brine in the previous step, adjusting the pH value to 11, introducing 65g of carbon dioxide gas into the brine after the adjustment is finished, simultaneously adding the brine and the carbon dioxide gas into a tubular reactor for reaction, and performing microfiltration on turbid brine obtained after the reaction to obtain clear brine for later use. The content of calcium and magnesium ions in the brine sample is analyzed as follows: calcium ion: 7ppm, magnesium ion: 5ppm of the total amount of the reaction product.
Advanced oxidation: placing the clear brine into a high-pressure kettle, adding a Pd catalyst with the mass fraction of 1%, setting the temperature at 200 ℃, the pressure at 2.5MPa, and the oxygen introduction amount: TOC: o is 2 =1:3 (brine TOC:22500 ppm), likewise after completion, the brine is taken out, analyzed for TOC, brine TOC after advanced oxidation: 294ppm.
Ammonia distillation: adjusting the pH value of the brine subjected to advanced oxidation to 11, then putting the brine into a stirring kettle, setting the temperature to be 100 ℃, keeping the temperature for 3 hours in a stirring starting state, taking out the brine, analyzing ammonia nitrogen in the brine, and evaporating the ammonia in the brine to obtain the ammonia nitrogen: 379ppm (ammonia nitrogen of the saline water after advanced oxidation: 6810 ppm).
And (3) evaporation: and (3) putting the brine after ammonia distillation into a triple-effect evaporator, evaporating water at 100 ℃ to obtain 1.9kg of industrial salt, and analyzing the sample with TOC of 294ppm, ammonia nitrogen: 379ppm, nitrate: 139ppm.
And (3) incineration: and (3) placing the industrial salt obtained after evaporation in a muffle furnace, burning for 30min at 1000 ℃ to obtain 1.80kg of industrial salt, and carrying out sample analysis: TOC:22ppm, ammonia nitrogen: 7ppm, nitrate: it was not detected. The analysis data accords with the conditions of the chlor-alkali electrolysis process, and the industrial waste salt treated by the process can be conveyed to the chlor-alkali process for electrolysis, so that the resource utilization is achieved.
Example three:
salt dissolving: 2.5kg of industrial waste salt is prepared into brine with the concentration of 260g/L by pure water for standby.
Pretreatment: adding 30% sodium hydroxide aqueous solution into the brine prepared in the previous step, adjusting the pH value to 11, introducing 65g of carbon dioxide gas into the brine after the adjustment is finished, simultaneously adding the brine and the carbon dioxide gas into a tubular reactor for reaction, carrying out microfiltration on turbid brine obtained after the reaction to obtain clear brine for later use. The content of calcium and magnesium ions in the brine sample is analyzed as follows: calcium ion: 10ppm, magnesium ion: 8ppm.
Advanced oxidation: and (3) putting the clear brine into an autoclave, adding a Pt catalyst with the mass fraction of 1%, setting the temperature to be 250 ℃, the pressure to be 2.5MPa, and the oxygen introduction amount to be as follows: TOC: o is 2 =1:3 (brine TOC:21500 ppm), and after the same is finished, the brine is taken out, analyzed for TOC, and after advanced oxidation, brine TOC:262ppm.
Ammonia distillation: adjusting the pH value of the brine subjected to advanced oxidation to 11, then putting the brine into a stirring kettle, setting the temperature to be 100 ℃, keeping the temperature for 3 hours in a stirring opening state, taking out the brine after heat preservation, analyzing ammonia nitrogen in the brine, and evaporating the ammonia in the brine: 341ppm (ammonia nitrogen of the salt water after advanced oxidation: 6725 ppm).
And (3) evaporation: and (3) putting the brine after ammonia evaporation into a triple-effect evaporator, evaporating water at 100 ℃ to obtain 1.92kg of industrial salt, and sending a sample to analyze TOC:262ppm, ammonia nitrogen: 341ppm, nitrate group: 128ppm.
And (3) incineration: and (3) placing the industrial salt obtained after evaporation in a muffle furnace, burning for 30min at 950 ℃ to obtain 1.80kg of industrial salt, and sending the sample for analysis: TOC 18ppm, ammonia nitrogen: 5ppm nitrate group: 0.01ppm. The analysis data accords with the conditions of the chlor-alkali electrolysis process, and the industrial waste salt treated by the process can be conveyed to the chlor-alkali process for electrolysis, so that the resource utilization is achieved.
Example four:
salt dissolving: 2.5kg of industrial waste salt is prepared into brine with the concentration of 260g/L by pure water for standby.
Pretreatment: adding 30% sodium hydroxide aqueous solution into the brine prepared in the previous step, adjusting the pH value to 11, introducing 65g of carbon dioxide gas into the brine after the adjustment is finished, simultaneously adding the brine and the carbon dioxide gas into a tubular reactor for reaction, carrying out microfiltration on turbid brine obtained after the reaction to obtain clear brine for later use. The content of calcium and magnesium ions in the brine sample is analyzed as follows: calcium ion: 8ppm, magnesium ion: 6ppm.
Advanced oxidation: placing the clear brine into a high-pressure kettle, adding a Ni catalyst with the mass fraction of 1%, setting the temperature at 250 ℃, the pressure at 3MPa, and introducingOxygen amount: TOC: o is 2 =1:3 (brine TOC:23500 ppm), brine taken out after the same end, analyzed for TOC, brine TOC after advanced oxidation: 281ppm.
Ammonia distillation: adjusting the pH value of the brine subjected to advanced oxidation to 11, then putting the brine into a stirring kettle, setting the temperature to be 100 ℃, keeping the temperature for 3 hours in a stirring starting state, taking out the brine, analyzing ammonia nitrogen in the brine, and evaporating the ammonia in the brine to obtain the ammonia nitrogen: 334ppm (ammonia nitrogen of the salt water after advanced oxidation: 6840 ppm).
And (3) evaporation: putting the brine after ammonia evaporation into a triple-effect evaporator, evaporating water at 100 ℃ to obtain 1.90kg of industrial salt, and sending a sample to analyze TOC:281ppm, ammonia nitrogen: 334ppm, nitrate radical: 134ppm.
And (3) incineration: and (3) placing the industrial salt obtained after evaporation in a muffle furnace, burning for 30min at 950 ℃ to obtain 1.82kg of industrial salt, and sending the sample for analysis: TOC:21ppm, ammonia nitrogen: 7ppm, nitrate radical: it was not detected. The analysis data accords with the conditions of the chlor-alkali electrolysis process, and the industrial waste salt treated by the process can be conveyed to the chlor-alkali process for electrolysis, so that the resource utilization is achieved.
According to the method for recycling the industrial waste salt, firstly, salt is melted to prepare the industrial waste salt into brine, then NaOH is added into the brine until the PH value is 9-11, then carbon dioxide is introduced into the brine, the brine and carbon dioxide gas are simultaneously added into a tubular reactor, and microfiltration is carried out on the obtained turbid brine to obtain clear brine; oxidizing the clear brine by adopting an oxygen oxidation mode, adding NaOH into the brine until the pH value is 11, stirring and preserving heat; and (3) evaporation: and finally, evaporating and dewatering the salt water, and adding the salt water into an incinerator for high-temperature incineration to obtain the industrial salt. The pretreatment process in the method is to reduce the hardness of brine and prevent pipelines from being blocked, the TOC value of industrial waste salt can be effectively reduced in the advanced oxidation process, the ammonia nitrogen value in the industrial waste salt can be effectively reduced in the ammonia evaporation process, the two steps are preparation before the waste salt enters the incinerator, the waste salt enters the incinerator after the two steps, the treatment effect is greatly improved, the TOC and the ammonia nitrogen in the waste salt can be reduced to a very low value, and therefore the requirement of entering the chlor-alkali process is met. The evaporation step is only to evaporate water to obtain the salt. The salt obtained by treating the industrial waste salt through the procedures of salt melting, pretreatment, advanced oxidation, ammonia evaporation, evaporation and incineration can be used for chlor-alkali electrolysis, and the resource utilization of the industrial salt is realized.
Other embodiments of the present application will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice in the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope of the disclosure being indicated by the following claims.
It will be understood that the present application is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof. The above-described embodiments of the present application do not limit the scope of the present application.
Claims (7)
1. A method for recycling industrial waste salt is characterized by comprising the following steps:
salt dissolving: adding water into industrial waste salt to prepare brine with the concentration of 200-280 g/L;
pretreatment: adding NaOH into the brine, adjusting the pH value to 9-11, then introducing carbon dioxide gas into the brine, simultaneously adding the brine and the carbon dioxide gas into a tubular reactor for reaction, and performing microfiltration on turbid brine obtained after the reaction to obtain clear brine;
advanced oxidation: oxidizing the clarified brine by an oxygen oxidation mode; wherein the oxidation temperature is 200-250 ℃, the oxidation pressure is 2.5-3MPa, and the oxygen introduction amount is as follows: TOC: o is 2 =1:2.0-8.0;
Ammonia distillation: adding NaOH into the saline water after advanced oxidation, adjusting the pH value to 11, keeping the temperature at 90-100 ℃ for 3-5h under the stirring state, and absorbing tail gas through micro negative pressure;
and (3) evaporation: evaporating the deamination brine to remove water, wherein the evaporated water can be recycled to the salt dissolving step, and the evaporation temperature is 90-120 ℃;
and (3) incineration: adding the evaporated low-TOC waste salt into an incinerator for high-temperature incineration to obtain industrial salt, wherein the incineration temperature is 900-1000 ℃, and the retention time is 20-40min.
2. The method for recycling industrial waste salt as claimed in claim 1, wherein the industrial waste salt comprises agricultural chemicals, high TOC, high ammonia nitrogen and high organic content industrial waste salt generated in fine chemical production process.
3. The method for recycling industrial waste salt as claimed in claim 1, wherein in the step of salting, the concentration of the brine is 260g/L, and the water is pure water.
4. The method for recycling industrial waste salt as claimed in claim 1, wherein the mass ratio of the carbon dioxide to the industrial waste salt in the pretreatment step is 0.023-0.03.
5. The method according to claim 1, wherein the catalyst used in the advanced oxidation step is any one of Ni, pd, pt, and Rh.
6. The method for recycling industrial waste salt as claimed in claim 1, wherein a triple effect evaporator is used to evaporate and remove water from the deaminated brine.
7. The method as claimed in claim 6, wherein the evaporation temperature is 90-100 ℃.
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