CN117585689A - Method for preparing sodium bicarbonate and co-producing potassium sulfate and ammonium chloride from sodium sulfate waste salt - Google Patents
Method for preparing sodium bicarbonate and co-producing potassium sulfate and ammonium chloride from sodium sulfate waste salt Download PDFInfo
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- CN117585689A CN117585689A CN202311573424.2A CN202311573424A CN117585689A CN 117585689 A CN117585689 A CN 117585689A CN 202311573424 A CN202311573424 A CN 202311573424A CN 117585689 A CN117585689 A CN 117585689A
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- sodium sulfate
- ammonium chloride
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- waste salt
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 150000003839 salts Chemical class 0.000 title claims abstract description 77
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 title claims abstract description 72
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 70
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 67
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 67
- 239000002699 waste material Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 47
- 235000019270 ammonium chloride Nutrition 0.000 title claims abstract description 44
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 title claims abstract description 36
- 235000017557 sodium bicarbonate Nutrition 0.000 title claims abstract description 36
- 229910000030 sodium bicarbonate Inorganic materials 0.000 title claims abstract description 36
- 229910052939 potassium sulfate Inorganic materials 0.000 title claims abstract description 33
- 235000011151 potassium sulphates Nutrition 0.000 title claims abstract description 33
- 239000000047 product Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000007710 freezing Methods 0.000 claims abstract description 17
- 230000008014 freezing Effects 0.000 claims abstract description 17
- 238000002425 crystallisation Methods 0.000 claims abstract description 10
- 230000008025 crystallization Effects 0.000 claims abstract description 10
- 238000004090 dissolution Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000005649 metathesis reaction Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 37
- 239000012452 mother liquor Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000010413 mother solution Substances 0.000 claims description 12
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 11
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 11
- 239000001099 ammonium carbonate Substances 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000012047 saturated solution Substances 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 238000011045 prefiltration Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000005185 salting out Methods 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000011085 pressure filtration Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 12
- 230000007062 hydrolysis Effects 0.000 abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000008020 evaporation Effects 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000002360 explosive Substances 0.000 abstract description 2
- 239000013067 intermediate product Substances 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000011265 semifinished product Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007405 data analysis Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 102200115278 rs121918085 Human genes 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
-
- 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
- C01D5/08—Preparation of sulfates by double decomposition with each other or with ammonium sulfate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for preparing sodium bicarbonate and co-producing potassium sulfate and ammonium chloride from sodium sulfate waste salt, which comprises the following steps: dissolving; purifying and carbonizing; separating and drying; secondary treatment; metathesis and hydrolysis; freezing and crystallizing. The method has the advantages of short flow, mild reaction conditions, no selection of organic chemical raw materials, no high-temperature and high-pressure reaction, easy operation control and no inflammable and explosive safety risk; all intermediate products are recycled, and no sewage is generated; the waste gas is discharged after reaching the standard after being absorbed; a small amount of solid waste comes from purifying sodium sulfate waste salt, and the environment-friendly pressure is kept; the whole chemical reaction does not adopt an evaporation crystallization process, so that the energy consumption is low; the technology of secondary dissolution, low-temperature centrifugal separation and ammonium chloride hydrolysis is adopted, so that the product conversion rate is high, the equipment investment is low, the economic benefit is good, and the method is suitable for industrial production; the obtained product has stable quality, and the waste sodium sulfate salt is purified by adopting a chemical method to remove toxicity, so that the problem of utilization of byproduct industrial salt is effectively solved.
Description
Technical Field
The invention relates to the technical field of sodium sulfate resource utilization, in particular to a method for preparing sodium bicarbonate and co-producing potassium sulfate and ammonium chloride from sodium sulfate waste salt.
Background
In the fields of vanadium product processing, petrochemical industry, pesticides, herbicides, smelting, new energy sources and the like, a large amount of sodium carbonate, industrial salt and sulfuric acid are used as raw materials in the production processes of chemical reaction, flue gas desulfurization and sewage treatment by manufacturing enterprises, and a large amount of sodium sulfate waste salt is generated after concentration and salt extraction. At present, a small amount of sodium sulfate waste salt is only used for producing anhydrous sodium sulfate and sodium sulfide, a large amount of waste salt is piled up due to limited digestion capacity, and high waste salt disposal cost and environmental protection pressure make industrial waste salt a bottleneck for restricting the survival and development of enterprises.
Sodium sulfate recycling is a better method for solving the stacking problem, and a great deal of research and development work is carried out on technicians at home and abroad, for example, sodium sulfate is utilized to prepare sodium carbonate on the basis of alkali preparation by combined alkali, so that the sodium sulfate stacking pressure can be relieved to a certain extent. However, some problems remain with the prior art such as:
1. the organic matters and heavy metals cannot be effectively oxidized and separated to remove toxicity of sodium sulfate waste salt, and the conventional disposal method in the prior art comprises the following steps: (1) wet process: the industrial waste salt is dissolved in water, and a high-grade oxidation method, a catalytic oxidation method and a supercritical hydrothermal oxidation method are generally adopted. The wet treatment of waste salt has harsh reaction conditions, relates to high temperature and high pressure, has high equipment requirements and high operation cost, and has limitation in application in industrial production; (2) and (3) dry method: the organic matters are incinerated and decomposed in a molten state at 800-1200 ℃ by high-temperature incineration, organic matters are carbonized and pyrolyzed and melted at high temperature, the effect of removing the organic matters is good, but dioxin and toxic gas can be generated by high-temperature incineration, the energy consumption is high, and the equipment investment is large; (3) landfill method: the cost is high, and the risk of secondary pollution exists;
2. the conversion rate of raw materials and the quality of products cannot be effectively improved, and the method adopted by the presently disclosed invention patent comprises the following steps: (1) carbonization reaction at near normal temperature and solid-liquid separation; (2) adding sodium sulfate into the carbonized solution for the second time, and further reacting with unreacted ammonium bicarbonate; (3) adding promoter sodium nitrate, evaporating and crystallizing to obtain ammonium sulfate; (4) adding sodium chloride fine powder, salting out ammonium chloride. Disadvantages of these process schemes include low overall conversion (at 87% -92%); the salt is not thoroughly separated and mixed, and the quality of the product is unstable; adding sodium chloride fine powder, and when salting-out mother liquor enters the next recycling sleeve, the dissolved sodium sulfate waste salt is very limited, so that the purpose of recycling the sodium sulfate waste salt can not be achieved; high energy consumption of evaporation and crystallization, and loss after being put into industrial production.
Disclosure of Invention
In order to solve the problems set forth in the background art, the invention provides the following technical scheme: a process method for preparing sodium bicarbonate and co-producing potassium sulfate and ammonium chloride from sodium sulfate waste salt comprises the following steps:
step 1) dissolution: dissolving sodium sulfate waste salt to prepare sodium sulfate saturated solution, regulating the pH value by dilute sulfuric acid, adding sodium sulfide with proper amount, stirring, standing, and performing pressure filtration to obtain filtrate I;
step 2) purification and carbonization: sequentially carrying out hydrogen peroxide oxidation, ozone oxidation and activated carbon adsorption on the filtrate I, then carrying out pressurized filtration and purification to obtain filtrate II, and adding ammonium bicarbonate into the filtrate II for carbonization reaction to obtain carbonized solution;
step 3) separating and drying: cooling the carbonized solution, and performing centrifugal separation, water washing and drying to obtain mother liquor I and a first batch of sodium bicarbonate dry products;
step 4) secondary treatment: repeating the steps 1) -3) by taking the mother liquor I as a solvent to obtain a mother liquor II and a second batch of sodium bicarbonate dry products;
step 5) metathesis: freezing out salt from mother solution II, filtering to obtain mixed salt and frozen clear liquid, adding potassium chloride into the frozen clear liquid, preheating and stirring, heating and hydrolyzing, absorbing gas by using ammonium chloride solution to obtain absorption liquid, cooling and settling, centrifugally separating, collecting mother solution III and solid, adding saturated potassium sulfate solution into the solid, and washing and drying to obtain dry potassium sulfate;
step 6) freezing crystallization: and collecting the absorption liquid, and performing freezing stirring, crystallization, centrifugal separation and drying to obtain an ammonium chloride dry product.
By adopting the technical scheme, the sodium sulfate saturated solution dissolved with the sodium sulfate waste salt is treated by the technologies of acidification, vulcanization, oxidation, decoloration, adsorption and the like in the step 1) and the step 2), and organic impurities and heavy metals in the sodium sulfate waste salt can be effectively separated and removed, so that organic residues and heavy metals are not detected in the treated solution and products. Meanwhile, in the step 4), the mother liquor I is used for secondarily dissolving the sodium sulfate waste salt, so that the recycling and efficient utilization of the sodium sulfate waste salt is realized, the total conversion rate of the finally obtained sodium bicarbonate, potassium sulfate and ammonium chloride can reach 98.5%, 96% and 96%, and all quality indexes of the three products meet the national standard. Moreover, the technical scheme has mild reaction conditions, easy control, less equipment investment and low energy consumption, and is suitable for industrial application.
Preferably, the pressurizing filtration in the step 1) and the step 2) is carried out by preparing the diatomite into the water solution to be pumped into the filter to be used as a prefilter layer and then filtering. Wherein the proportion of the diatomite aqueous solution is preferably diatomite: solution = 1g:1000ml (m/v).
Preferably, in the step 2), the filtrate I is placed in a reactor, stirring is started, 25-30% hydrogen peroxide is added, stirring is stopped after oxidation for 20-30min, static oxidation is performed for 20-30min, ozone is introduced for 30-60min, heat preservation is performed for 40-45 ℃, active carbon is added, the solution is stirred, decolorized and adsorbed for 30-45min, and static adsorption is performed for 20-30min. Wherein the proportion of 25-30% concentration hydrogen peroxide is preferably hydrogen peroxide: solution = 2-3ml:100ml (v/v), the dosing ratio of ozone is preferably ozone: solution = 1g:1m 3 (m/v), the proportioning ratio of the activated carbon is preferably activated carbon: solution = 5g:1000ml (m/v).
Preferably, in the step 2), ammonium bicarbonate is slowly added into the filtrate II for a plurality of times, the temperature is raised to 30-32 ℃ while stirring, the heat is preserved and stirred for 1-1.5h for carbonization reaction, the temperature is lowered to 10-15 ℃, and the mixture is settled for 30-40min to obtain carbonized solution. Wherein the proportioning ratio of the ammonium bicarbonate is preferably ammonium bicarbonate: sodium sulfate = 1.1g:1g (m/m).
Preferably, the frozen salt precipitation in the step 5) is that the mother liquor II is placed into a freezing container, stirring is started, freezing is carried out for 3-4 hours at the temperature of 0-5 ℃, and after mixed salt precipitation, the mixed salt is transferred to the next step 2) for redissolution before ammonium bicarbonate is added.
Preferably, the temperature of the preheating stirring in the step 5) is 30-35 ℃, and the heat preservation stirring time is 1-1.5h. Wherein, the proportioning ratio of adding potassium chloride into the frozen clear liquid for preheating and stirring is preferably potassium chloride: ammonium sulfate = 1.13g:1g (m/m).
Preferably, the heating hydrolysis in the step 5) is to firstly open the cold water inlet and outlet valves of the induced draft fan and the condenser, heat up to 70-80 ℃ and then keep the temperature for hydrolysis for 1.5-2h.
Preferably, the cooling sedimentation in the step 5) is to cool to 5-10 ℃ and stand for 30-45min.
In the step 5) of the technical scheme, ammonia gas and hydrogen chloride gas are released by hydrolysis of mother liquor II containing ammonium chloride under a heated state, and the two gases are collected into ammonium chloride absorption liquid through cooling to regenerate ammonium chloride, so that the ammonium chloride is thoroughly separated from potassium sulfate solution. In addition, the mother solution III obtained by centrifugal separation only contains a small amount of mixed salt, can be recycled as process water for dissolving sodium sulfate waste salt in the next circulation, achieves the purpose of utilizing the sodium sulfate waste salt, and simultaneously can be recycled, thereby being beneficial to improving the conversion rate of ammonium chloride.
Preferably, the freezing and stirring in the step 6) is to put the absorption liquid into a crystallization device, stir and freeze for 2.5-3.5 hours at 5-10 ℃, and then rest and settle for 30-40 minutes.
Preferably, the sodium sulfate waste salt in the step 1) is dissolved by taking softened water or mother liquor I or mother liquor III as a solvent, heating to 35-40 ℃ while stirring in a reactor, uniformly adding the sodium sulfate waste salt, and stirring for 0.5-1h under heat preservation until the sodium sulfate is completely dissolved. Wherein the proportion of the dissolved sodium sulfate waste salt is preferably that the sodium sulfate waste salt: demineralized water = 48g:100ml (m/v).
Preferably, the pH value of the solution is adjusted to be 5.5-6.5 by slowly adding 30% sulfuric acid solution by using dilute sulfuric acid in the step 1), and stirring is carried out for 20-30min.
In summary, the invention has the following beneficial effects:
1. the method has the advantages of short flow, mild reaction conditions, no selection of organic chemical raw materials, no high-temperature and high-pressure reaction, easy operation control and no inflammable and explosive safety risk;
2. all intermediate products are recycled, no sewage is generated, waste gas is absorbed and then discharged after reaching standards, a small amount of solid waste is from purifying sodium sulfate waste salt, and the environment-friendly pressure-maintaining performance is realized;
3. the whole-process chemical reaction does not adopt an evaporation crystallization process, has low energy consumption, adopts the technologies of secondary dissolution, low-temperature centrifugal separation and ammonium chloride hydrolysis, has high product conversion rate, less equipment investment and good economic benefit, and is suitable for large-scale industrial production;
4. the invention can thoroughly separate potassium sulfate from ammonium chloride, the quality of the obtained product is stable, the sodium bicarbonate product accords with various quality indexes of GBT1606-2008, the potassium sulfate accords with various quality indexes of GBT20406-2017, and the ammonium chloride accords with various quality indexes of GBT 2946-2018;
5. the invention adopts a chemical method to purify the sodium sulfate waste salt, detoxicates the sodium sulfate waste salt, effectively solves the utilization problem of byproduct industrial salt, can obtain considerable economic benefit, belongs to the fields of waste environmental protection comprehensive utilization and circular economy, and has great significance for developing clean production and circular economy.
Drawings
FIG. 1 is a process flow diagram of a method for preparing sodium bicarbonate and co-producing potassium sulfate and ammonium chloride from sodium sulfate waste salts of example 1 and example 2 of the present application;
fig. 2 is a flow chart of equipment of the method for preparing sodium bicarbonate and co-producing potassium sulfate and ammonium chloride from the sodium sulfate waste salt of example 1 and example 2 of the present application.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The raw materials of the examples of the present application are all commercially available in general except for the specific descriptions.
Example 1
Taking a sodium sulfate waste salt sample:
sampling unit: and (3) a medium-color large-smelting colored group smelting plant.
Waste salt source: wet desulfurization of copper smelting fume
Detection result:
| main component | Sodium sulfate | Moisture content | Pb | Ash content | Sodium sulfite |
| Content (%) | 90 | 4 | 0.07 | 4 | 1.95 |
(II) the process steps:
step 1) dissolution:
1.1, pretreatment: placing 80L of softened water in a No. 1 glass stirring tank, starting stirring, adding 43kg of sodium sulfate waste salt, heating to 40 ℃ while stirring, keeping the temperature and stirring for 1h until the sodium sulfate waste salt is completely dissolved, regulating the pH value to 6.0 by 30% dilute sulfuric acid, adding 110g of sodium sulfide, keeping the temperature and stirring for 30min, and preparing a sodium sulfate saturated solution;
1.2, filtering: weighing 100g of diatomite to prepare a water solution, pumping the water solution into a stainless steel pilot panel frame to serve as a prefilter layer, and drying the water content by compressed air; pumping the sodium sulfate saturated solution into a stainless steel pilot-board frame for pressurizing and filtering. Drying the water content by compressed air after filtering to obtain 1.3kg of filter residue and filtrate I88L; step 2) purification and carbonization:
2.1, purifying: placing the filtrate I into a No. 1 glass stirring tank, starting stirring, adding 2.8L hydrogen peroxide, stirring at 35 ℃ for 30min, and standing for oxidation for 30min; stirring is started, 16g of ozone is introduced, and stirring is carried out for 1h; standing for oxidation for 30min, adding 440g of powdery active carbon, stirring at 45deg.C for 45min, and standing for adsorption for 30min;
2.2, filtering: weighing 100g of diatomite to prepare a water solution, pumping the water solution into a stainless steel pilot panel frame to serve as a prefilter layer, and drying the water content by compressed air; pumping the filtrate I into a stainless steel pilot-board frame for pressurizing and filtering, and drying the water after the filtering by compressed air to obtain 1.2kg of filter residue and 87.6L of filtrate II;
2.3, carbonization: placing the filtrate II into a No. 2 glass stirring tank, starting stirring, controlling the temperature to be 32 ℃, adding 43kg of ammonium bicarbonate for 4 times, heating to be 32 ℃, keeping the temperature, stirring for 1.5 hours, cooling to 13 ℃, standing, settling for 40 minutes, and extracting the supernatant to obtain a carbonized solution;
step 3) separating and drying: stirring is started, the carbonized solution is put into a stainless steel centrifuge for centrifugation, and mother liquor is dried; washing with 5L of softened water, spin-drying the water, taking out a sodium bicarbonate semi-finished product, and performing secondary centrifugation on the carbonized solution;
the first time a product is obtained: 31.5kg of first batch of wet sodium bicarbonate and 96L of mother liquor I;
step 4) secondary treatment:
putting the mother liquor I into a No. 1 glass stirring tank, adding 21.5kg of sodium sulfate waste salt, performing secondary dissolution, pretreatment, purification and carbonization, and repeating the operation processes of the steps 1) to 3);
wherein the second feeding amount is as follows: 21.5kg of sodium sulfate waste salt, 55g of sodium sulfide, 200g of activated carbon, 1.5L of hydrogen peroxide, 9g of ozone, 200g of diatomite and 23.7kg of ammonium bicarbonate;
the second time of the reaction yields the product: a second batch of sodium bicarbonate wet 25.3kg and mother liquor II 103L.
The analysis results show that:
(1) Adding 64.5kg of sodium sulfate waste salt and 58kg of pure sodium sulfate for the second time;
(2) Obtaining 56.8kg of wet sodium bicarbonate product in total for the second time, and drying the wet sodium bicarbonate product in an oven to obtain 49.3kg of dry sodium bicarbonate product;
(3) 103L multiplied by 0.076=7.8 kg exists in the second carbonization solution, and the solution can be recycled to the next batch; (4) The single pass conversion of sodium bicarbonate was 49.3/58×100% =85%;
(5) The sodium bicarbonate sampling detection result is 98.6 percent of total alkali (w/%) and 0.18 percent of water, and the pH value is 8.6 and the chloride content is 0.3 percent; sulfate 0.04%, arsenic (As) and heavy metal (Pb) were not detected, meeting industry III standards.
Step 5) metathesis:
5.1, freeze salting out: placing mother liquor II in a No. 2 tank, starting stirring, controlling the temperature to be 2-6 ℃ and freezing for 3 hours, then pressurizing and filtering by a stainless steel plate frame, and drying the water by compressed air after filtering to obtain 3.9kg of mixed salt crystals and 99L of frozen clear liquid;
5.2, preheating and stirring:
preparation: (1) the mother liquor II is sent to sample to detect that the ammonium sulfate content is 54.5 percent; (2) thoroughly cleaning the No. 1 and No. 2 glass stirring tanks; (3) the No. 2 glass stirring tank is filled with softened water 70L, a hose for exhausting the No. 1 glass stirring tank is introduced into the No. 2 glass stirring tank, and the hose is inserted to a position 150mm below the liquid level.
Firstly, putting the frozen clear liquid into a No. 1 glass stirring tank, starting stirring, heating to 33 ℃, then adding 61kg of potassium chloride, and carrying out heat preservation stirring for 1.5 hours;
5.3, hydrolysis: heating the No. 1 tank while stirring, starting a draught fan, when the temperature is raised to 55 ℃, allowing gas to enter the No. 2 tank through a No. 1 tank exhaust hose, and when the temperature of the No. 1 tank is raised to 72 ℃, stopping heating, wherein the temperature in the No. 2 tank is slowly raised, starting to cool, and keeping the temperature between 30 and 35 ℃. 1. Maintaining the heat preservation of the No. 2 tank for 2 hours;
5.4 cooling and centrifuging: cooling the double decomposition liquid in the No. 1 tank to 8 ℃, standing and settling for 40min, and extracting supernatant; stirring is started, the lower sedimentation liquid is put into a stainless steel centrifuge for centrifugation, and mother liquid is dried; leaching with 5L saturated potassium sulfate solution, spin-drying mother liquor, taking out potassium sulfate semi-finished product, and centrifuging the batch for four times;
the product is obtained: 76.3kg of potassium sulfate semi-finished product and 94L of mother liquor III which can be used for dissolving sodium sulfate waste salt in the next batch.
Step 6) freezing crystallization:
stirring and cooling the absorption liquid in the No. 2 tank to 5 ℃, standing and freezing for 2 hours, and extracting supernatant; stirring is started, the lower sedimentation liquid is put into a pilot-scale stainless steel centrifuge for centrifugation, mother liquid is spin-dried, and an ammonium chloride wet product is taken out, and the batch is subjected to secondary centrifugation;
the product is obtained: 22kg of wet ammonium chloride and 82L of mother liquor, and the mother liquor is reused in batches.
The analysis results show that:
(1) 76.3kg of wet potassium sulfate product is dried to obtain 63.6kg, the theoretical amount of potassium sulfate is 74.06kg, and the single pass conversion rate is 85.88%; the mother liquor contains 9.46kg;
(2) 22kg of wet ammonium chloride product is dried to obtain 18.4kg of product, the theoretical amount of ammonium chloride is 45.47kg, and the single pass conversion rate is 40.53%; the mother liquor contains 25.32kg;
(3) The potassium sulfate product is in powder form, and K is detected by sample feeding 2 The O content is 46%, the sulfur (S) content is 14.9%, the standard is close, and other indexes are not out of standard, so that the standard of qualified products is achieved;
(4) The ammonium chloride product is crystal powder, and the content of ammonium chloride (NH 4 Cl) is 99.4% through sample feeding detection, and other indexes are not out of standard, so that the product reaches the industrial qualified product standard.
Example 2
Taking a sodium sulfate waste salt sample: the same as in example 1;
(II) the process steps:
step 1) to step 6) are all operated according to the process steps of example 1, and mother liquor involved in example 1 is recycled on the basis of the process steps, and the process is specifically as follows:
(1) the mother liquor III in the metathesis of step 5) of example 1 was used in the pretreatment process in the dissolution of step 1) of this example, replacing the demineralized water for the dissolution of sodium sulphate waste salts;
(2) the hydrolysis mother liquor in the metathesis of step 5) of example 1 was used in the hydrolysis process of the metathesis of step 5) of this example, substituting tank No. 2 softened water as an absorption liquid;
(3) the mixed salt precipitated after freezing the mother liquor II in the double decomposition in the step 5) of the example 1 is used in the carbonization process of the step 2) of the embodiment, and is redissolved and recycled before adding ammonium bicarbonate. The analysis results show that:
(1) Sodium sulfate waste salt adding amount:
| step by step | Weighing scale (kg) | Content (%) | Folding pure (kg) |
| First time | 40 | 90 | 36 |
| Second time | 20 | 90 | 18 |
| Totalizing | 60 | 54 |
(2) Sodium bicarbonate yield:
| step by step | Wet weight (kg) | Dry weight (%) |
| First time | 50.3 | 41.8 |
| Second time | 25.3 | 21 |
| Totalizing | 75.6 | 62.8 |
Data analysis: theoretical yield of sodium bicarbonate: 54×1.18= 63.72kg;
the actual dry product yield is as follows: 62.8kg;
single pass conversion: 62.8/63.72 ×100% =98.56%.
The above data indicate that: after the mixed salt precipitated from the mother solution II generated in the example 1 and the double decomposition mother solution III are recycled and reused, the single pass conversion rate of sodium bicarbonate is improved to 98.56% from 85% in the example 1, and the design conversion rate of the invention is achieved. The main reason is that sodium bicarbonate and sodium sulfate in the mixed salt and the double decomposition mother solution III are effectively recycled, and meanwhile, the fact that the sodium bicarbonate in the double decomposition mother solution III is not obviously decomposed at 70-80 ℃ is verified.
(3) Sodium bicarbonate and potassium chloride addition:
(4) The volume of mother liquor of each step:
the table above shows that: after the mother solution is applied mechanically, the total water balance can be maintained, and the double decomposition mother solution amount is not increased compared with the example 1;
(5) Yield of potassium sulfate and ammonium chloride:
| material name | Wet weight (kg) | Dry weight (kg) | Theoretical weight (kg) |
| Potassium sulfate | 76.4 | 63.7 | 66.2 |
| Ammonium chloride | 46.7 | 39 | 40.6 |
Data analysis: single pass conversion of potassium sulfate: 63.7/66.2×100% = 96.22%;
single pass conversion of ammonium chloride: 39/40.6x100% = 96.06%;
because the double decomposition mother liquor III and the ammonium chloride absorption liquid of the previous batch are recycled in the batch, the potassium sulfate and the ammonium chloride in the mother liquor are effectively utilized, and the single pass conversion rate of the potassium sulfate is improved to 96.22 percent from 85.88 percent of the example 1; the per pass conversion of ammonium chloride was increased from 40.53% of example 1 to 96.06%; the product fractions in the mother liquor of example 1 are counteracted.
(6) Product quality
The batch only detects the main content and heavy metals of three products, and other items are not detected:
the product quality detection result shows that: the technology for separating and removing organic matters and heavy metals can realize efficient resource utilization of sodium sulfate waste salt generated by flue gas desulfurization of a treatment smelting plant.
While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations may be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The method for preparing sodium bicarbonate and co-producing potassium sulfate and ammonium chloride from sodium sulfate waste salt is characterized by comprising the following steps:
step 1) dissolution: dissolving sodium sulfate waste salt to prepare sodium sulfate saturated solution, regulating the pH value by dilute sulfuric acid, adding sodium sulfide with proper amount, stirring, standing, and performing pressure filtration to obtain filtrate I;
step 2) purification and carbonization: sequentially carrying out hydrogen peroxide oxidation, ozone oxidation and activated carbon adsorption on the filtrate I, then carrying out pressurized filtration and purification to obtain filtrate II, and adding ammonium bicarbonate into the filtrate II for carbonization reaction to obtain carbonized solution;
step 3) separating and drying: cooling the carbonized solution, and performing centrifugal separation, water washing and drying to obtain mother liquor I and a first batch of sodium bicarbonate dry products;
step 4) secondary treatment: repeating the steps 1) -3) by taking the mother liquor I as a solvent to obtain a mother liquor II and a second batch of sodium bicarbonate dry products;
step 5) metathesis: freezing out salt from mother solution II, filtering to obtain mixed salt and frozen clear liquid, adding potassium chloride into the frozen clear liquid, preheating and stirring, heating and hydrolyzing, absorbing gas by using ammonium chloride solution to obtain absorption liquid, cooling and settling, centrifugally separating, collecting mother solution III and solid, adding saturated potassium sulfate solution into the solid, and washing and drying to obtain dry potassium sulfate;
step 6) freezing crystallization: and collecting the absorption liquid, and performing freezing stirring, crystallization, centrifugal separation and drying to obtain an ammonium chloride dry product.
2. The method for preparing sodium bicarbonate and co-producing potassium sulfate and ammonium chloride from sodium sulfate waste salt according to claim 1, which is characterized by comprising the following steps: the pressurizing filtration in the step 1) and the step 2) is to prepare water solution by diatomite and pump the water solution into a filter to be used as a prefilter layer, and then to filter.
3. The method for preparing sodium bicarbonate and co-producing potassium sulfate and ammonium chloride from sodium sulfate waste salt according to claim 1, which is characterized by comprising the following steps: in the step 2), the filtrate I is placed in a reactor, firstly, stirring is started, then 25-30% hydrogen peroxide is added, stirring is stopped after oxidation is carried out for 20-30min, still oxidation is carried out for 20-30min, then ozone is introduced for 30-60min, heat preservation is carried out for 40-45 ℃, then active carbon is added, the solution is stirred, decolorized and adsorbed for 30-45min, and still adsorption is carried out for 20-30min.
4. The method for preparing sodium bicarbonate and co-producing potassium sulfate and ammonium chloride from sodium sulfate waste salt according to claim 1, which is characterized by comprising the following steps: and 5) the freezing and salting-out step is to put the mother solution II into a freezing container, start stirring and freeze for 3-4 hours at 0-5 ℃, transfer the mixed salt to the next step 2) after precipitating the mixed salt, and re-dissolve the mixed salt before adding ammonium bicarbonate.
5. The method for preparing sodium bicarbonate and co-producing potassium sulfate and ammonium chloride from sodium sulfate waste salt according to claim 1, which is characterized by comprising the following steps: the temperature of the preheating stirring in the step 5) is 30-35 ℃, and the heat preservation stirring time is 1-1.5h.
6. The method for preparing sodium bicarbonate and co-producing potassium sulfate and ammonium chloride from sodium sulfate waste salt according to claim 1, which is characterized by comprising the following steps: and 5) heating and hydrolyzing to open cold water inlet and outlet valves of the induced draft fan and the condenser, heating to 70-80 ℃, and preserving heat and hydrolyzing for 1.5-2h.
7. The method for preparing sodium bicarbonate and co-producing potassium sulfate and ammonium chloride from sodium sulfate waste salt according to claim 1, which is characterized by comprising the following steps: and (3) cooling and settling in the step (5) to 5-10 ℃, and standing for 30-45min.
8. The method for preparing sodium bicarbonate and co-producing potassium sulfate and ammonium chloride from sodium sulfate waste salt according to claim 1, which is characterized by comprising the following steps: the freezing and stirring in the step 6) is to put the absorption liquid into a crystallization device, stir and freeze for 2.5-3.5h at 5-10 ℃, and then rest and settle for 30-40min.
9. The method for preparing sodium bicarbonate and co-producing potassium sulfate and ammonium chloride from sodium sulfate waste salt according to claim 1, which is characterized by comprising the following steps: dissolving the sodium sulfate waste salt in the step 1) by taking softened water or mother liquor I or mother liquor III as a solvent, heating to 35-40 ℃ while stirring in a reactor, uniformly adding the sodium sulfate waste salt, and stirring for 0.5-1h under heat preservation until the sodium sulfate is completely dissolved.
10. The method for preparing sodium bicarbonate and co-producing potassium sulfate and ammonium chloride from sodium sulfate waste salt according to claim 1, which is characterized by comprising the following steps: the pH value of the solution in the step 1) is regulated by dilute sulfuric acid, 30 percent sulfuric acid solution is slowly added to regulate the pH value of the solution to 5.5-6.5, and the solution is stirred for 20-30min.
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