CN112212348A - Resource treatment method of industrial waste salt - Google Patents
Resource treatment method of industrial waste salt Download PDFInfo
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- CN112212348A CN112212348A CN202011188671.7A CN202011188671A CN112212348A CN 112212348 A CN112212348 A CN 112212348A CN 202011188671 A CN202011188671 A CN 202011188671A CN 112212348 A CN112212348 A CN 112212348A
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- 150000003839 salts Chemical class 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000002440 industrial waste Substances 0.000 title claims abstract description 21
- 235000002639 sodium chloride Nutrition 0.000 claims description 71
- 239000002699 waste material Substances 0.000 claims description 28
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 12
- 239000012433 hydrogen halide Substances 0.000 claims description 12
- 238000004064 recycling Methods 0.000 claims description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 10
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 239000003444 phase transfer catalyst Substances 0.000 claims description 7
- 239000002893 slag Substances 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- 239000008394 flocculating agent Substances 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 235000003270 potassium fluoride Nutrition 0.000 claims description 4
- 239000011698 potassium fluoride Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 229940045872 sodium percarbonate Drugs 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000010842 industrial wastewater Substances 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- 239000002920 hazardous waste Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical class [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 4
- 238000003889 chemical engineering Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 229940097068 glyphosate Drugs 0.000 description 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- -1 printing and dyeing Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229960005076 sodium hypochlorite Drugs 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/04—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste liquors, e.g. sulfite liquors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/035—Preparation of hydrogen chloride from chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
- C01B7/093—Hydrogen bromide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/06—Preparation of sulfates by double decomposition
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
- C02F2301/046—Recirculation with an external loop
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/06—Pressure conditions
- C02F2301/063—Underpressure, vacuum
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention belongs to the technical field of industrial waste salt treatment and resource utilization, and particularly relates to a resource treatment method of industrial waste salt.
Description
Technical Field
The invention belongs to the technical field of industrial waste salt treatment and resource utilization, and particularly relates to an industrial halogenated salt slag treatment and resource utilization technology.
Background
China is a large industrial country, and with the development of economy, the demand of industrial salt is greatly increased, so that a large amount of byproduct waste salt is generated. The waste salt is industrial waste salt mainly comprising halogenated salt such as sodium chloride, potassium chloride, sodium fluoride, potassium fluoride, sodium bromide, potassium bromide and the like as main components, and the industrial waste salt is mainly from various industries such as coal chemical industry, pesticides, medicines, fine chemical industry, dyes, chemical fertilizers and the like. According to incomplete statistics, the annual waste salt production in China exceeds 2000 million tons, wherein the waste salt with halogenated salt as a main component accounts for 500 million tons/year. The waste salt is often unable to be directly reused in industrial production due to the large amount of organic substances and toxic and harmful components, and the national relevant legal documents also classify the waste salt as dangerous waste. And because the hazardous waste contains complex components and is high in hazard, the cost of self-treatment and entrustment treatment of enterprises is very high, and huge economic burden and potential safety hazard are brought to enterprise operation.
Among such a large number of industrial waste salt residues, the most common waste salt residues are halogenated waste salts such as sodium chloride and potassium chloride. In general, in waste water generated by acid-base neutralization in the industries of fine chemicals, medicines, pesticides, dyes and the like, common biochemical treatment cannot be carried out due to the fact that the waste water contains a large amount of inorganic salts and high-content organic matters, the waste water is required to be burnt into burnt residues after passing through an incinerator, the main components of the residues are halogenated salts, the content of the halogenated salts is over 70%, and the other waste water contains burning ash, inorganic salts and a small amount of organic matters. The incinerated salt ash is generally disposed of in landfills after being paid and stored by a third party with disposal qualification as dangerous solid waste. Moreover, the landfill treatment not only occupies a large amount of land resources, but also often causes secondary pollution and potential safety hazard of land and underground water resource environments due to different characteristics of hazardous wastes, and entrusted treatment cost and environmental protection pressure of the landfill treatment also often become important factors restricting sustainable development of enterprises.
Therefore, how to develop a proper process technology, and the harmless treatment and resource utilization of the industrial waste salt with low investment, low cost and environmental protection are not only the requirements of sustainable environment-friendly development of enterprises are met, but also the technical problem of resource treatment of the halogenated waste salt in the environment-friendly industry is solved, and the method accords with the national relevant environmental protection industrial policies and has important significance.
At present, the treatment of the part of the industrial waste salt after incineration mainly comprises the following technologies:
(1) direct harmless landfill disposal
The method is that various waste salts are mixed and solidified by a curing agent, and then the waste salts are treated according to relevant regulations of national hazardous waste management and disposal
And special landfill disposal is carried out according to technical specifications. The method not only occupies a large land area, but also is easy to generate secondary pollution and potential safety hazard of the environment.
(2) Dissolving impurity-removing evaporation crystallization method
The method is to re-dissolve the industrial waste salt residue in clean water and then remove the salt residue by a physical method (filtration, membrane treatment and the like)
After mechanical impurities, organic matters are removed by a chemical method, and inorganic salt is recovered by multi-effect evaporation crystallization. The method has complex treatment process and high treatment cost, and the inorganic salt obtained by the method has low purity, and particularly for industrial halogenated salt, the recovered halogenated salt cannot be widely applied due to low use and economic value.
For example, patent CN109570194 discloses a full recycling treatment technology for waste salt slag, in which waste salt is re-dissolved in clean water after being roasted at high temperature, and then is recycled by a series of complicated processes and expensive chemical materials, so that the economic value and the practicability are not high. Patent 201610630083.1 discloses a method for recovering high-concentration sodium sulfate and sodium chloride contained in high-salinity wastewater, which is a method for obtaining high-purity sodium chloride and sodium sulfate industrial salt by complex processes such as softening, removing calcium and magnesium ions, then carrying out salt separation treatment by a sodium filter membrane, electrodialysis, electrolysis, oxidation and the like.
(3) Advanced oxidation process
Mainly dissolving waste salt slag in water, and adding oxidant to oxidize residual organic matters in the solution to extract
And (4) pure recovery of inorganic salts. For example, patent CN104163519A discloses a method for purifying and recovering waste salt by fenton oxidation and adding chemical agents such as hydrogen peroxide and sodium hypochlorite into glyphosate waste water.
(4) Mannheim method
The Mannheim method was successfully developed by the German scholars Mannheim, Klin at the end of the nineteenth century and is thus named. The method has reliable technology and simple process. But has the disadvantages of high reaction temperature (500-.
Disclosure of Invention
The invention aims to provide a method for resource utilization of by-products, namely halogen acid, hydrogen halide gas and sulfate, of refined industrial halogenated waste salt residues. The method has wide applicability, so that a large amount of halogenated waste salt (slag) containing ash and organic matters generated in the industries of chemical engineering and the like is recycled by a simple, economic and environment-friendly method, the recycled halogen acid, the hydrogen halide gas and the sulfate reach the industrial grade, the method can be widely applied to the industries of chemical engineering, metallurgy, steel, printing and dyeing, petroleum and the like, the halogenated waste salt is completely digested in the industrial production, waste is changed into valuable, the environmental problem of the generated hazardous waste is solved, the hazardous waste is recycled, considerable economic benefits are generated, the healthy, continuous and stable development of the chemical industry is promoted, and the recycling economy, energy conservation and environmental protection are really realized.
The invention provides a method for producing by-products of halogen acid, hydrogen halide gas and sulfate by refining industrial halogenated waste salt residues. The method is characterized by comprising the following steps:
step (1): firstly, dissolving halogenated salt ash generated after industrial wastewater is incinerated by a boiler in clear water, adding a proper amount of flocculant and oxidant, stirring and completely dissolving, standing and precipitating for a period of time, filtering most of residual carbon ash by using a plate-and-frame filter press, filtering residual ash by using a precision filter, obtaining a crude halogenated salt solid from a mother liquor by using a vacuum single-effect evaporator, and mechanically applying the crude halogenated salt solid to the next batch after the distillate enters a storage tank.
Step (2): dissolving the crude haloid obtained in the step 1 in a pre-prepared saturated sulfate solution, adding concentrated sulfuric acid and a phase transfer catalyst in a certain proportion, heating to a certain temperature, reacting for a period of time to volatilize the generated hydrogen halide gas, absorbing the volatilized hydrogen halide gas into hydrohalic acid by using water, adjusting the hydrogen halide acid to be neutral by using alkali after the reaction is finished, and centrifuging the rest materials to obtain sulfate with qualified purity.
The chemical reactions involved are:
in the step (2), R is Na or K in alkali metal elements, X is F, Cl or Br in halogen elements, and RX is the combination of the sequences.
Preferably, the halogenated salt in step (1) is one of sodium chloride, potassium chloride, sodium fluoride, potassium fluoride, sodium bromide and potassium bromide.
Preferably, the flocculating agent in the step (1) is one or more of polyaluminium chloride, anionic polyacrylamide, cationic polyacrylamide, nonionic polyacrylamide, zwitterionic polyacrylamide and polymeric flocculating agent; the addition amount of the flocculant is 0.5-5% (wt%). Further the flocculant is added in the step (1) in an amount of 0.5 to 3% (wt%).
Preferably, the oxidant in the step (1) is one or more of hydrogen peroxide, sodium hypochlorite, sodium percarbonate and sodium percarbonate; the amount of oxidant added is 1% to 10% (wt%). Further, in the step (1), the addition amount of the oxidant is 1-5% (wt%).
Preferably, in the step (1), the stirring time is 1-5 hours, and the standing time is 1-10 hours; in the step (1), the stirring time is 1-3 hours, and the standing time is 1-5 hours.
Preferably, the molar ratio of the added amount of the sulfuric acid to the halogenated salt in the step (2) is as follows: 1.5:2. In the further step (2), the molar ratio of the added sulfuric acid to the halogenated salt is 1.1-1.3: 2.
Preferably, the phase transfer catalyst in step (2) is some organic ammonium salts and organic catalysts, such as: benzyltriethylammonium chloride, tetrabutylammonium bromide, dodecyltrimethylammonium chloride, tributylamine, 18 crown 6, PEG-400, PEG-600, ionic liquid and the like.
Preferably, the phase transfer catalyst is added in an amount of 0.1-5% (wt%) in step (2), and further the phase transfer catalyst is added in an amount of 0.1-3% (wt%) in step (2).
Preferably, the reaction temperature in the step (2) is controlled to be 100-180 ℃; the reaction time is 3-20 hs; further, the reaction temperature in the step (2) is controlled to be 100-150 ℃; the reaction time is 3-10 hs.
The invention has the beneficial effects that: the invention provides a method for resource utilization of by-products, namely halogen acid, hydrogen halide gas and sulfate, of refined industrial halogenated waste salt residues. The method has wide applicability, so that a large amount of ash-slag-containing halogenated waste salt (slag) generated in the industries of chemical engineering and the like can be recycled by a simple, economic and environment-friendly method, the recycled halogen acid, the hydrogen halide gas and the sulfate reach the industrial grade, the halogenated waste salt is changed into valuable, the environmental problem of hazardous waste is solved, the hazardous waste is recycled, considerable economic benefit is generated, and the recycling economy, energy conservation and environmental protection are really realized, so that the industrial production is facilitated.
Drawings
FIG. 1 is a schematic process flow diagram.
Detailed Description
The technical solutions of the present invention are described below by way of specific examples, but the scope of the present invention is not limited thereto.
Example 1
The method comprises the following steps of directly feeding 1000Kg of sodium chloride salt ash waste residue discharged from an incinerator into a 10-cube dissolving tank through a hopper, adding 5Kg of cationic polyacrylamide solution and 10 Kg of sodium hypochlorite solution, stirring for 2 hours, standing for 2 hours, removing insoluble carbon residues and other insoluble substances from feed liquid through plate-and-frame filter pressing (removing an incineration system after a filter cake is pressed dry), feeding filtrate into a 100-cube filtrate storage tank after passing through a 5nm precision filter, and evaporating by using a vacuum single-effect evaporator to obtain sodium chloride crude salt. The distillate is reused in the next batch after entering the storage tank.
Putting 1000Kg of crude sodium chloride salt obtained in the last step into a prepared saturated sodium sulfate solution in a 5 cubic reaction kettle, adding 1Kg of tetrabutylammonium bromide serving as a catalyst, slowly dropwise adding 958Kg of concentrated sulfuric acid, absorbing the generated hydrogen chloride gas with water to prepare hydrochloric acid, heating to 130 ℃ after dropwise adding for reaction for 3 hours, slowly cooling to 30 ℃, removing the residual hydrogen chloride gas by using low vacuum, adjusting the pH to 7 by using 32% liquid alkali, and centrifuging the precipitated salt to obtain a refined sodium sulfate solid. The mother liquid is mechanically applied to the next batch.
Example 2
The method comprises the following steps of directly feeding 1500Kg of potassium chloride salt ash waste residues discharged from an incinerator into a 10-cube dissolving tank through a hopper, adding 7.5 kilograms of polymeric flocculant solution and 15 kilograms of hydrogen peroxide solution, stirring for 3 hours, standing for 3 hours, removing insoluble carbon residue and other insoluble substances from feed liquid through plate-and-frame filter pressing (removing a burning system after a filter cake is pressed dry), feeding filtrate into a 100-cube filtrate storage tank after passing through a 5nm precision filter, and evaporating by using a vacuum single-effect evaporator to obtain crude potassium chloride salt. The distillate is reused in the next batch after entering the storage tank.
Putting 1500Kg of crude potassium chloride salt obtained in the last step into a prepared saturated potassium sulfate solution in a 5 cubic reaction kettle, adding 1.5Kg of dodecyl trimethyl ammonium chloride serving as a catalyst, slowly dropwise adding 1437Kg of concentrated sulfuric acid, absorbing the generated hydrogen chloride gas with water to prepare hydrochloric acid, heating to 150 ℃ after dropwise adding, reacting for 5 hours, slowly cooling to 30 ℃, removing the residual hydrogen chloride gas by using low vacuum, adjusting the pH to 7 by using 32% liquid alkali, and centrifuging the separated salt to obtain the refined potassium sulfate solid. The mother liquid is mechanically applied to the next batch.
Example 3
1500Kg potassium fluoride salt ash waste residue that burns out of burning furnace directly gets into 10 cubic dissolving tanks from the hopper, add 7.5 kilograms of anion polyacrylamide flocculant solution and 15 kilograms of inferior sodium peroxide solution, stir 3 hours after, stand for 3 hours, feed liquid gets rid of insoluble undissolved insoluble such as carbon residue through plate and frame filter pressing (the filter cake gets rid of the burning system after being pressed dry), filtrate is thrown into 100 cubic filtrate storage tanks after 5nm precision filter again, get potassium fluoride coarse salt through the evaporation of vacuum single effect evaporator. The distillate is reused in the next batch after entering the storage tank.
Putting 1500Kg of crude potassium fluoride salt obtained in the last step into a prepared saturated potassium sulfate solution in a 5 cubic reaction kettle, adding 1.5Kg of tributylamine catalyst, slowly dropwise adding 1437Kg of concentrated sulfuric acid, absorbing the generated hydrogen fluoride gas with water to prepare hydrofluoric acid, heating to 160 ℃ after dropwise adding, reacting for 5 hours, slowly cooling to 30 ℃, removing the residual hydrogen fluoride gas with low vacuum, adjusting the pH to 7 with 32% liquid alkali, and centrifuging the precipitated salt to obtain the refined potassium sulfate solid. The mother liquid is mechanically applied to the next batch.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. A resource treatment method of industrial waste salt is characterized in that: refining industrial halogenated waste salt slag to obtain by-products, namely halogen acid, hydrogen halide gas and sulfate; the method comprises the following specific steps:
step (1): firstly, dissolving halogenated salt ash generated after industrial wastewater is incinerated by a boiler in clear water, adding a proper amount of flocculant and oxidant, stirring and completely dissolving, standing and precipitating for a period of time, filtering most of residual carbon ash by using a plate-and-frame filter press, filtering the residual ash by using a precise filter, allowing a mother liquor to pass through a vacuum single-effect evaporator to obtain a crude halogenated salt solid, and allowing a distillate to enter a storage tank and be applied to the next batch;
step (2): dissolving the crude haloid obtained in the step 1 in a pre-prepared saturated sulfate solution, adding concentrated sulfuric acid and a phase transfer catalyst in a certain proportion, heating to a certain temperature, reacting for a period of time to volatilize the generated hydrogen halide gas, absorbing the volatilized hydrogen halide gas into hydrohalic acid by using water, adjusting the hydrogen halide acid to be neutral by using alkali after the reaction is finished, and centrifuging the rest materials to obtain sulfate with qualified purity.
2. The method for recycling industrial waste salt as claimed in claim 1, wherein the method comprises the following steps: in the step (2), R is Na or K in alkali metal elements, X is F, Cl or Br in halogen elements, and RX is the combination of the sequences.
3. The method for recycling industrial waste salt as claimed in claim 1, wherein the method comprises the following steps: the halogenated salt in the step (1) is one of sodium chloride, potassium chloride, sodium fluoride, potassium fluoride, sodium bromide and potassium bromide.
4. The method for recycling industrial waste salt as claimed in claim 1, wherein the method comprises the following steps: the flocculating agent in the step (1) is one or more of polyaluminium chloride, anionic polyacrylamide, cationic polyacrylamide, nonionic polyacrylamide, zwitterionic polyacrylamide and a polymeric flocculating agent; the addition amount of the flocculant is 0.5-5% (wt%).
5. The method for recycling industrial waste salt as claimed in claim 1, wherein the method comprises the following steps: the oxidant in the step (1) is one or more of hydrogen peroxide, sodium hypochlorite, sodium percarbonate and sodium hypochlorite; the amount of oxidant added is 1% to 10% (wt%).
6. The method for recycling industrial waste salt as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the stirring time is 1-5 hours, and the standing time is 1-10 hours; in the step (1), the stirring time is 1-3 hours, and the standing time is 1-5 hours.
7. The method for recycling industrial waste salt as claimed in claim 1, wherein the method comprises the following steps: the molar ratio of the addition amount of the sulfuric acid to the halogenated salt in the step (2) is as follows: 1.5:2.
8. The method for recycling industrial waste salt as claimed in claim 1, wherein the method comprises the following steps: the phase transfer catalyst in the step (2) is a plurality of organic ammonium salts and organic catalysts.
9. The method for recycling industrial waste salt as claimed in claim 1, wherein the method comprises the following steps: the addition amount of the phase transfer catalyst in the step (2) is 0.1-5% (wt%).
10. The method for recycling industrial waste salt as claimed in claim 1, wherein the method comprises the following steps: the reaction temperature in the step (2) is controlled to be 100-180 ℃; the reaction time is 3-20 hs; further, the reaction temperature in the step (2) is controlled to be 100-150 ℃; the reaction time is 3-10 hs.
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| CN115246649A (en) * | 2021-08-09 | 2022-10-28 | 江苏美东环境科技有限公司 | Method for preparing fertilizer-grade potassium chloride from potassium chloride organic hazardous waste salt |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115246649A (en) * | 2021-08-09 | 2022-10-28 | 江苏美东环境科技有限公司 | Method for preparing fertilizer-grade potassium chloride from potassium chloride organic hazardous waste salt |
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Application publication date: 20210112 |