CN113651480A - Regeneration system and method for tin-containing waste liquid - Google Patents
Regeneration system and method for tin-containing waste liquid Download PDFInfo
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- CN113651480A CN113651480A CN202110962709.XA CN202110962709A CN113651480A CN 113651480 A CN113651480 A CN 113651480A CN 202110962709 A CN202110962709 A CN 202110962709A CN 113651480 A CN113651480 A CN 113651480A
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- tin
- liquid
- waste liquid
- containing waste
- solid
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- 239000007788 liquid Substances 0.000 title claims abstract description 174
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 239000002699 waste material Substances 0.000 title claims abstract description 79
- 238000011069 regeneration method Methods 0.000 title claims abstract description 22
- 230000008929 regeneration Effects 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 54
- 239000000706 filtrate Substances 0.000 claims abstract description 46
- 238000000926 separation method Methods 0.000 claims abstract description 43
- 239000012535 impurity Substances 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 29
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003814 drug Substances 0.000 claims abstract description 12
- AUYOHNUMSAGWQZ-UHFFFAOYSA-L dihydroxy(oxo)tin Chemical compound O[Sn](O)=O AUYOHNUMSAGWQZ-UHFFFAOYSA-L 0.000 claims abstract description 11
- 150000001879 copper Chemical class 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims description 138
- 239000012752 auxiliary agent Substances 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 238000003860 storage Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000010425 asbestos Substances 0.000 claims description 12
- 239000001913 cellulose Substances 0.000 claims description 12
- 229920002678 cellulose Polymers 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000010451 perlite Substances 0.000 claims description 12
- 235000019362 perlite Nutrition 0.000 claims description 12
- 229910052895 riebeckite Inorganic materials 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- -1 sawdust Chemical compound 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 239000004927 clay Substances 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 7
- 239000010440 gypsum Substances 0.000 claims description 7
- 229910052602 gypsum Inorganic materials 0.000 claims description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 6
- 235000019738 Limestone Nutrition 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 6
- 239000000440 bentonite Substances 0.000 claims description 6
- 229910000278 bentonite Inorganic materials 0.000 claims description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 239000004571 lime Substances 0.000 claims description 6
- 239000006028 limestone Substances 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000011085 pressure filtration Methods 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 239000005909 Kieselgur Substances 0.000 claims description 3
- 229920001131 Pulp (paper) Polymers 0.000 claims description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 3
- 235000010980 cellulose Nutrition 0.000 claims description 3
- 210000003298 dental enamel Anatomy 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229940116315 oxalic acid Drugs 0.000 claims description 3
- 239000001508 potassium citrate Substances 0.000 claims description 3
- 229960002635 potassium citrate Drugs 0.000 claims description 3
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 3
- 235000011082 potassium citrates Nutrition 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 235000012222 talc Nutrition 0.000 claims description 3
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims 6
- 239000003513 alkali Substances 0.000 abstract description 10
- 238000006386 neutralization reaction Methods 0.000 abstract description 7
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 230000000717 retained effect Effects 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 238000011084 recovery Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241000275031 Nica Species 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- 229910021509 tin(II) hydroxide Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- 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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
- C02F1/025—Thermal hydrolysis
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention belongs to the field of resource utilization of tin-containing waste liquid, and discloses a regeneration system and a regeneration method of tin-containing waste liquid, which comprises the steps of carrying out heat treatment on the tin-containing waste liquid so as to convert tin components in the tin-containing waste liquid into metastannic acid; carrying out first solid-liquid separation on the tin-containing waste liquid after heat treatment to obtain tin mud and first filtrate; adding an impurity removing agent into the first filtrate, and performing second solid-liquid separation to obtain copper salt and second filtrate; and (3) carrying out regeneration sub-liquid blending on the second filtrate, adding a tin stripping component into the second filtrate, and returning the second filtrate to a tin stripping line to be reused as a tin stripping agent. According to the invention, tin in various forms is converted into metastannic acid through heat treatment, tin mud is obtained through solid-liquid separation, the separated liquid phase is subjected to impurity removal, solid-liquid separation and sub-liquid blending to obtain regenerated tin-containing water, alkali addition and neutralization are not required, the consumption of a large amount of liquid alkali to recover tin is avoided, and meanwhile, nitric acid in tin-stripping waste liquid is retained, so that the tin-stripping waste liquid can be recycled for regeneration and blending of tin-containing liquid medicine, the tin-stripping cost is saved, and the grade of the tin mud is improved.
Description
Technical Field
The invention belongs to the field of resource utilization of tin-containing waste liquid, and particularly relates to a regeneration method of tin-containing waste liquid.
Background
In the production process of Printed Circuit Boards (PCB), nitric acid type tin-containing water is commonly used for removing tin-plated layers on the circuit boards, and tin-stripping waste liquid is formed when the tin-containing water has reduced tin-etching capability. The tin stripping waste liquid is acid waste water and belongs to dangerous waste. The tin content in the tin stripping waste liquid generally reaches more than 90g/L, the copper content is 5-10 g/L, 15-20% of nitric acid residues are left, and heterocyclic compounds, polycyclic aromatic hydrocarbon compounds and polymers are also contained, so the tin stripping waste liquid has strong corrosivity and pollution, and if the tin stripping waste liquid is directly discharged without reasonable treatment, serious pollution is inevitably caused to water resources and ecological environment; meanwhile, the valuable metal tin and copper in the tin-containing waste liquid is high in content and recovery value.
At present, the treatment method of the tin-containing waste liquid mainly comprises the following steps: neutralization, distillation, metal ion removal circulation, diffusion dialysis and solvent extraction.
The neutralization method is to directly add alkaline substances such as ammonia water, sodium carbonate, liquid alkali and the like into the tin-containing waste liquid to adjust the pH value to be about neutral so as to precipitate metal ions. The alkali consumption of the method is mainly used for neutralizing the residual nitric acid, so that the alkali consumption is large, the valuable acid is wasted, a large amount of salt is produced, and the subsequent wastewater treatment cost is greatly increased; in addition, the metastannic acid obtained through neutralization is in a colloid form, the particles are fine and sticky, separation is difficult to carry out through filter pressing, the actual production efficiency is greatly influenced, impurity metal ions are subjected to coprecipitation and enter tin mud, the grade of the tin mud is lower than 20%, and the added value is greatly reduced.
The distillation method is to utilize negative pressure distillation, evaporate nitric acid, cool and recycle to prepare 10-25% nitric acid, and can be used for blending tin-containing seed solution again; and neutralizing the residual tin-containing waste liquid with weak acidity by using liquid alkali to recover metal ions. The method has strong corrosivity to equipment due to the strong corrosivity of nitric acid; in addition, the concentration of the recovered nitric acid is low, the yield is high, the nitric acid cannot be completely recycled for the preparation of the seed solution, and the outlet path is limited.
The metal ion removing circulation method is that metal ion precipitant and flocculant are added into tin-containing waste liquid to separate tin, copper and other precipitate, and proper amount of supplementary component is added into the clear liquid to obtain regenerated tin-containing water. For different batches of products, the tin stripping waste liquid of manufacturers has different components, and the addition amount can be determined only through complex analysis, so that the tin stripping waste liquid is difficult to use universally, and the application range of the tin stripping waste liquid is greatly limited.
The diffusion dialysis method is that tin-containing waste liquid and clear water are respectively added to two sides of a diffusion permeable membrane, the separation of nitric acid is realized by taking the concentration difference of the two sides as power, and the recovery rate of the nitric acid reaches more than 70%. The residual solution passes through an ion exchange membrane, and tin is recovered by an electrodeposition method. The method involves complicated process equipment, particularly the durability of the permeable membrane and the ionic membrane is difficult to ensure, the maintenance and replacement cost is high, and the economic benefit of the process is not obvious.
The solvent extraction method is characterized in that on the basis of selecting a proper extracting agent, nitric acid in tin-containing waste liquid is extracted and separated, the residual solution is electrolyzed to recover cathode copper, and most of tin ion precipitate is separated after the pH value is adjusted to 1.5 by Pb (OH) 2. It can be seen that the process is complex, and the extraction and precipitation processes require the consumption of large amounts of reagents, which makes the disposal cost high.
In summary, no recycling process which is simple to operate and low in cost and can simultaneously recover tin, copper and nitric acid in tin-containing waste liquid is available in the market.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a regeneration system and a regeneration method of tin-containing waste liquid, which improve the resource degree of the tin-containing waste liquid and the process economic benefit.
The technical scheme adopted by the invention is as follows: a regeneration method of tin-containing waste liquid comprises the following steps:
carrying out heat treatment on the tin-containing waste liquid so as to convert tin components in the tin-containing waste liquid into metastannic acid;
carrying out first solid-liquid separation on the tin-containing waste liquid after heat treatment to obtain tin mud and first filtrate;
adding an impurity removing agent into the first filtrate, and performing second solid-liquid separation to obtain copper salt and second filtrate;
and (3) carrying out regeneration sub-liquid blending on the second filtrate, adding a tin stripping component into the second filtrate, and returning the second filtrate to a tin stripping line to be reused as a tin stripping agent.
Optionally, in some embodiments of the present application, the heat treatment is selected from one of straight-through steam heating in the heat treatment kettle, steam heat exchange in coils in the heat treatment kettle, and jacket heat exchange in the heat treatment enamel kettle.
Optionally, in some embodiments of the present application, the temperature of the heat treatment is 30 to 120 ℃;
optionally, the heat treatment time is 0.5-5 h;
optionally, in some embodiments of the present application, the heat treatment further includes stirring the tin-containing waste liquid at a speed of 10 to 120 rpm;
optionally, in some embodiments of the present application, the first solid-liquid separation is: performing solid-liquid separation after circulation, and continuously circulating the tin-containing waste liquid after heat treatment in a solid-liquid separator until filtrate is clear; or, after precoating, carrying out solid-liquid separation, mixing the first auxiliary agent and water according to a preset proportion to form a suspension, and circulating the suspension by a circulating pump to form a precoating layer on the filter medium; or directly adding the auxiliary agent for solid-liquid separation, adding a second auxiliary agent into the tin-containing waste liquid after heat treatment, and stirring for solid-liquid separation;
optionally, in some embodiments of the present application, the temperature of the first solid-liquid separation is 30 to 120 ℃;
optionally, in some embodiments of the present application, the first auxiliary agent is selected from one or more of activated carbon, gypsum, magnesium oxide, sawdust, graphite powder, acid clay, perlite, asbestos, cellulose, diatomaceous earth, lime, limestone, talc, cellulose, asbestos fiber, perlite, pulp, bentonite, metal chips, and slag;
optionally, in some embodiments of the present application, the second auxiliary agent is selected from one or more of activated carbon, gypsum, magnesium oxide, sawdust, graphite powder, acid clay, perlite, asbestos, cellulose, diatomaceous earth, lime, limestone, talc, cellulose, asbestos fiber, perlite, pulp, bentonite, metal chips, and slag;
optionally, in some embodiments of the application, the adding mass of the second auxiliary agent is 0.01-5%;
optionally, in some embodiments of the present application, the mass ratio of the first auxiliary agent to the water is 1 to 30%, and the thickness of the precoat layer is 0.2 to 6 mm;
optionally, in some embodiments of the present application, the separation manner of the metastannic acid and the copper salt is suction filtration, pressure filtration, centrifugation or micro-filter filtration;
optionally, in some embodiments of the present application, the mesh number of the filter cloth prepared by suction filtration, pressure filtration or centrifugation is 200-1200 meshes, and the pore size of the micro filter is 0.1-10 μm;
optionally, in some embodiments of the present application, the impurity removing agent is selected from one or more of citric acid, sodium citrate, potassium citrate, ammonium citrate, oxalic acid, sodium oxalate, potassium oxalate, ammonium oxalate; and/or the adding amount of the impurity removing agent is 1.0-2.5 times of the total mass of the metal impurity ions;
optionally, in some embodiments of the present application, the tin stripping component includes hydrochloric acid, ferric chloride, nitric acid, urea, and a surfactant; wherein, the content of nitric acid is 15-35%, the content of hydrochloric acid is 0.5-10%, the content of ferric trichloride is 0.1-2%, the content of urea is 0.1-1.5%, and the content of surfactant is 0.1-0.5%;
a regeneration system of tin-containing waste liquid comprises a temporary tin-containing waste liquid storage tank, a heat treatment tank, a first solid-liquid separator, an impurity removal tank, a second solid-liquid separator, a seed liquid blending tank and a seed liquid storage tank;
optionally, in some embodiments of the present application, the tin-containing waste liquid temporary storage tank is connected to the heat treatment tank to pump the tin-containing waste liquid to the heat treatment tank; the heat treatment tank is connected with a first solid-liquid separator to carry out first solid-liquid separation; the first solid-liquid separator is connected with the impurity removal groove so as to pump the first filtrate into the impurity removal groove; the impurity removing groove is connected with a second solid-liquid separator to carry out second solid-liquid separation; the second solid-liquid separator is connected with the sub-liquid blending tank so as to pump the second filtrate to the sub-liquid blending tank to finish blending of the tin-containing liquid medicine; the seed solution blending tank is connected with the seed solution storage tank so as to pump the blended tin-containing liquid medicine into the seed solution storage tank for storage.
Through the technical scheme, the invention has the beneficial effects that: the tin in each form is converted into metastannic acid through heat treatment, tin mud is obtained through solid-liquid separation, the separated liquid phase is subjected to impurity removal, solid-liquid separation and sub-liquid blending to obtain regenerated tin-containing water, alkali neutralization is not needed, tin is prevented from being recovered by consuming a large amount of liquid alkali, nitric acid in tin-stripping waste liquid is reserved, the regenerated tin-containing water can be recycled for regeneration and blending of tin-containing liquid medicine, the tin-stripping cost is saved, impurity ions do not enter a tin product due to alkali neutralization, the grade of the tin mud is improved, in addition, the solid-liquid separation mode can ensure that the metastannic acid does not leak when passing through filter cloth, the tin recovery rate is improved, the filtrate is clarified, the tin-stripping sub-liquid can be directly blended, and the resource degree of the tin-containing waste liquid is improved.
Drawings
FIG. 1 is a block flow diagram of the regeneration process of the present invention.
The implementation, functional features and advantages of the objectives of the present application will be further explained with reference to the accompanying drawings.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
For a better understanding of the above technical solutions, exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
In order to better understand the technical solution, the technical solution will be described in detail with reference to the drawings and the specific embodiments.
A regeneration method of tin-containing waste liquid is characterized in that:
carrying out heat treatment on the tin-containing waste liquid so as to convert tin components in the tin-containing waste liquid into metastannic acid;
carrying out first solid-liquid separation on the tin-containing waste liquid after heat treatment to obtain tin mud and first filtrate;
adding an impurity removing agent into the first filtrate, and performing second solid-liquid separation to obtain copper salt and second filtrate;
and (3) carrying out regeneration sub-liquid blending on the second filtrate, adding a tin stripping component into the second filtrate, and returning the second filtrate to a tin stripping line to be reused as a tin stripping agent. The invention innovatively treats various forms of tin such as Sn in the tin-containing waste liquid through heat treatment2+、Sn4+、Sn(OH)2、Sn(OH)4The metatitanic acid existing in a colloid form can be effectively subjected to solid-liquid separation under the aid, so that the high auxiliary material cost of a process for neutralizing and recovering tin by adding alkali is avoided, tin is efficiently separated from impurity metal ions under the condition of not introducing new substances, and the grade of a tin product is improved; and the residual nitric acid in the tin-containing waste liquid is reserved to the greatest extent, and the method can be used for preparing the tin-containing sub-liquid and reduces the tin stripping cost.
Further, the heat treatment heating mode of the tin-containing waste liquid is direct steam heating in a heat treatment kettle, steam heat exchange of a coil pipe in the heat treatment kettle or heat exchange of a jacket of an enamel kettle.
Further, the heat treatment temperature is 30-120 ℃, the heat treatment time is 0.5-5 h, and the stirring speed is 10-120 rpm.
In the process for recovering tin by a neutralization method, the obtained tin product is tin hydroxide, is a viscous colloidal substance, has fine particles, is easy to permeate through filter cloth and is difficult to realize solid-liquid separation, so that the recovery rate of tin is low.
Further, the rigid filter cake layer is formed in a mode of solid-liquid separation after circulation: continuously circulating the tin-containing waste liquid after heat treatment in a solid-liquid separator until the filtrate is clear; or, solid-liquid separation after precoating: mixing the first auxiliary agent and water according to a preset proportion to form a suspension, and circulating the suspension by a circulating pump to form a precoating layer on a filter medium; or, after directly adding the auxiliary agent, carrying out solid-liquid separation: adding a second auxiliary agent into the tin-containing waste liquid after heat treatment, and carrying out solid-liquid separation after stirring; .
Further, the temperature of the first solid-liquid separation is 30-120 ℃.
Further, the first auxiliary agent is one or more of activated carbon, gypsum, magnesium oxide, sawdust, graphite powder, acid clay, perlite, asbestos, cellulose, diatomite, lime, limestone, talcum powder, cellulose, asbestos fiber, perlite, paper pulp, bentonite, metal chips and furnace slag.
Further, the second auxiliary agent is one or more of activated carbon, gypsum, magnesium oxide, sawdust, graphite powder, acid clay, perlite, asbestos, cellulose, diatomite, lime, limestone, talcum powder, cellulose, asbestos fiber, perlite, paper pulp, bentonite, metal chips and furnace slag.
Further, the adding mass of the second auxiliary agent is 0.01-5%.
Further, the mass ratio of the first auxiliary agent to the water is 1-30%, and the thickness of the precoating layer is 0.2-6 mm.
Further, the separation mode of the metastannic acid is suction filtration, filter pressing, centrifugation or micro-filter filtration.
Furthermore, the mesh number of the filter cloth prepared by suction filtration, filter pressing or centrifugation is 200-1200 meshes, and the aperture of the microfilter is 0.1-10 mu m. The clear solution after heat treatment for tin removal contains metal impurities, and the existence of the metal impurities can cause the corrosion of a copper layer of a PCB substrate to influence the conductivity of the PCB substrate; in addition, the clear liquid also contains high-concentration nitric acid, and in order to effectively utilize the nitric acid in the clear liquid, a citric acid-series or oxalic acid-series precipitator is added, so that copper can be recovered and iron can be removed under the strong acid condition.
2Fe3++3RCA＝Fe2(CA)3+6H+
Ni2++RCA＝NiCA+2H+
Mn2++RCA＝MnCA+2H+
2Cr3++3RCA＝Cr2(CA)3+6H+
Further, the impurity removing agent is selected from one or more of citric acid, sodium citrate, potassium citrate, ammonium citrate, oxalic acid, sodium oxalate, potassium oxalate and ammonium oxalate.
Furthermore, the adding amount of the impurity removing agent is 1.0-2.5 times of the total mass of the metal impurity ions.
Further, the tin stripping component comprises hydrochloric acid, ferric trichloride, nitric acid, urea and a surfactant; wherein, the content of nitric acid is 15-35%, the content of hydrochloric acid is 0.5-10%, the content of ferric trichloride is 0.1-2%, the content of urea is 0.1-1.5%, and the content of surfactant is 0.1-0.5%.
The regeneration system of the tin-containing waste liquid is characterized by comprising a temporary tin-containing waste liquid storage tank, a heat treatment tank, a first solid-liquid separator, an impurity removal tank, a second solid-liquid separator, a seed liquid blending tank and a seed liquid storage tank.
Further, the tin-containing waste liquid temporary storage tank is connected with the heat treatment tank so as to pump the tin-containing waste liquid to the heat treatment tank; the heat treatment tank is connected with a first solid-liquid separator to carry out first solid-liquid separation; the first solid-liquid separator is connected with the impurity removal groove so as to pump the first filtrate into the impurity removal groove; the impurity removing groove is connected with a second solid-liquid separator to carry out second solid-liquid separation; the second solid-liquid separator is connected with the sub-liquid blending tank so as to pump the second filtrate to the sub-liquid blending tank to finish blending of the tin-containing liquid medicine; the seed solution blending tank is connected with the seed solution storage tank so as to pump the blended tin-containing liquid medicine into the seed solution storage tank for storage.
Example 1
The tin-containing waste liquid used in the present example comprises the following main components and contents: sn, 7.82%; 1.84% of Cu; fe, 0.82%, HNO3，15.4％。
Introducing steam into 1000g of tin-containing waste liquid, heating to 120 ℃, maintaining for 4h, and stirring at the speed of 60 rpm; adding 30g of gypsum into the heat-treated material, uniformly mixing, cooling the material to 50 ℃, and performing filter pressing in a filter press with 1200-mesh filter cloth to obtain 272.5g of first filter mud and first filtrate; and adding 12g of sodium citrate into the first filtrate, and then carrying out filter pressing on the first filtrate by a second filter press to obtain 76.3g of second filter mud and second filtrate, wherein the tin recovery rate is 98.7%, the tin content in the second filtrate is 129.5mg/L, and the copper content in the second filtrate is 271.3 mg/L. And adding 1.3g of urea, 45.3g of ferric trichloride, 5.2g of hydrochloric acid, 35.7g of nitric acid and 1.9g of surfactant into the second filtrate to obtain regenerated tin-containing seed solution.
The spraying method is adopted to verify the tin stripping performance of the regenerated medicament, and the detection shows that the tin dissolving amount reaches 95g/L, the tin stripping rate reaches 10.8 mu m/min, and the copper corrosion rate is 0.5 mu m/min, which is equivalent to the tin stripping performance of fresh tin-containing liquid medicine and can meet the recycling requirement.
Example 2
The tin-containing waste liquid used in the present example comprises the following main components and contents: sn, 7.82%; 1.84% of Cu; fe, 0.82%, HNO3，15.4％。
Introducing steam into 1000g of tin-containing waste liquid, heating to 70 ℃, maintaining for 5h, and stirring at the speed of 90 rpm; adding 60g of acid clay into the heat-treated material, uniformly mixing, cooling the material to 50 ℃, and centrifuging in a centrifuge with 1000-mesh filter cloth to obtain 268.3g of first filter mud and first filtrate; and adding 17.3g of potassium oxalate into the first filtrate, and performing pressure filtration by using a second pressure filter to obtain 66.9g of second filter mud and second filtrate, wherein the tin recovery rate is 98.5%, the tin content in the second filtrate is 134.7mg/L, and the copper content is 209.6 mg/L. And adding 1.8g of urea, 34.5g of ferric trichloride, 6.3g of hydrochloric acid, 25.9g of nitric acid and 1.7g of surfactant into the second filtrate to obtain regenerated tin-containing seed solution.
The spraying method is adopted to verify the tin-containing performance of the regenerated medicament, and the detection shows that the tin dissolving amount reaches 94.6g/L, the tin stripping rate reaches 10.4 mu m/min, and the copper corrosion rate is 0.4 mu m/min, which is equivalent to the tin-containing performance of fresh tin stripping liquid medicine and can meet the recycling requirement.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above-mentioned serial numbers of the embodiments of the present application are merely for description and do not represent the merits of the embodiments.
The above description is only a preferred embodiment of the present application, and not intended to limit the scope of the present application, and all modifications of equivalent structures and equivalent processes, which are made by the contents of the specification and the drawings of the present application, or which are directly or indirectly applied to other related technical fields, are included in the scope of the present application.
Claims (10)
1. The regeneration method of the tin-containing waste liquid is characterized by comprising the following steps:
carrying out heat treatment on the tin-containing waste liquid so as to convert tin components in the tin-containing waste liquid into metastannic acid;
carrying out first solid-liquid separation on the tin-containing waste liquid after heat treatment to obtain tin mud and first filtrate;
adding an impurity removing agent into the first filtrate, and performing second solid-liquid separation to obtain copper salt and second filtrate;
and (3) carrying out regeneration sub-liquid blending on the second filtrate, adding a tin stripping component into the second filtrate, and returning the second filtrate to a tin stripping line to be reused as a tin stripping agent.
2. The method for regenerating a tin-containing waste liquid as claimed in claim 1, wherein the heat treatment is selected from one of straight-through steam heating in a heat treatment kettle, steam heat exchange of a coil in the heat treatment kettle, and heat exchange of a jacket of an enamel kettle for heat treatment;
and/or the temperature of the heat treatment is 30-120 ℃;
and/or the time of the heat treatment is 0.5-5 h;
and/or stirring the tin-containing waste liquid at the stirring speed of 10-120 rpm.
3. The method for regenerating a tin-containing waste liquid according to claim 1, wherein the first solid-liquid separation is: performing solid-liquid separation after circulation, and continuously circulating the tin-containing waste liquid after heat treatment in a solid-liquid separator until filtrate is clear; or, after precoating, carrying out solid-liquid separation, mixing the first auxiliary agent and water according to a preset proportion to form a suspension, and circulating the suspension by a circulating pump to form a precoating layer on the filter medium; or directly adding the auxiliary agent for solid-liquid separation, adding a second auxiliary agent into the tin-containing waste liquid after heat treatment, and stirring for solid-liquid separation.
4. The method for regenerating a tin-containing waste liquid according to claim 1, wherein the temperature of the first solid-liquid separation is 30 to 120 ℃.
5. The method for regenerating tin-containing waste liquid as claimed in claim 3, wherein the first auxiliary agent is selected from one or more of activated carbon, gypsum, magnesium oxide, sawdust, graphite powder, acid clay, perlite, asbestos, cellulose, diatomaceous earth, lime, limestone, talc, cellulose, asbestos fiber, perlite, pulp, bentonite, metal chips, and slag; the second auxiliary agent is selected from one or more of activated carbon, gypsum, magnesium oxide, sawdust, graphite powder, acid clay, perlite, asbestos, cellulose, diatomite, lime, limestone, talcum powder, cellulose, asbestos fiber, perlite, paper pulp, bentonite, metal chips and furnace slag.
6. The regeneration method of the tin-containing waste liquid as claimed in claim 3, wherein the adding mass of the second auxiliary agent is 0.01-5%; and/or the mass ratio of the first auxiliary agent to water is 1-30%, and the thickness of the precoating layer is 0.2-6 mm.
7. The regeneration method of the tin-containing waste liquid according to claim 1, wherein the separation manner of the metastannic acid and the copper salt is suction filtration, pressure filtration, centrifugation or micro-filter filtration; and/or the mesh number of the filter cloth prepared by suction filtration, filter pressing or centrifugation is 200-1200 meshes, and the pore diameter of the micro filter is 0.1-10 mu m.
8. The method for regenerating the tin-containing waste liquid according to claim 1, wherein the impurity removing agent is one or more selected from citric acid, sodium citrate, potassium citrate, ammonium citrate, oxalic acid, sodium oxalate, potassium oxalate and ammonium oxalate; and/or the adding amount of the impurity removing agent is 1.0-2.5 times of the total mass of the metal impurity ions; and/or the tin stripping component comprises hydrochloric acid, ferric trichloride, nitric acid, urea and a surfactant; wherein, the content of nitric acid is 15-35%, the content of hydrochloric acid is 0.5-10%, the content of ferric trichloride is 0.1-2%, the content of urea is 0.1-1.5%, and the content of surfactant is 0.1-0.5%.
9. The regeneration system of the tin-containing waste liquid is characterized by comprising a temporary tin-containing waste liquid storage tank, a heat treatment tank, a first solid-liquid separator, an impurity removal tank, a second solid-liquid separator, a seed liquid blending tank and a seed liquid storage tank.
10. The system for regenerating tin-containing waste liquid as claimed in claim 9, wherein the tin-containing waste liquid temporary storage tank is connected to the heat treatment tank to pump the tin-containing waste liquid to the heat treatment tank; the heat treatment tank is connected with a first solid-liquid separator to carry out first solid-liquid separation; the first solid-liquid separator is connected with the impurity removal groove so as to pump the first filtrate into the impurity removal groove; the impurity removing groove is connected with a second solid-liquid separator to carry out second solid-liquid separation; the second solid-liquid separator is connected with the sub-liquid blending tank so as to pump the second filtrate to the sub-liquid blending tank to finish blending of the tin-containing liquid medicine; the seed solution blending tank is connected with the seed solution storage tank so as to pump the blended tin-containing liquid medicine into the seed solution storage tank for storage.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114277249A (en) * | 2021-11-26 | 2022-04-05 | 江西瑞亿电子科技有限公司 | Treatment method for recycling tin, copper and waste gas from PCB tin waste liquid in recycling mode |
| CN114798194A (en) * | 2022-04-28 | 2022-07-29 | 深圳崇达多层线路板有限公司 | Method and equipment for solid-liquid separation and regeneration cyclic utilization of PCB film stripping waste liquid |
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2021
- 2021-08-20 CN CN202110962709.XA patent/CN113651480A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114277249A (en) * | 2021-11-26 | 2022-04-05 | 江西瑞亿电子科技有限公司 | Treatment method for recycling tin, copper and waste gas from PCB tin waste liquid in recycling mode |
| CN114798194A (en) * | 2022-04-28 | 2022-07-29 | 深圳崇达多层线路板有限公司 | Method and equipment for solid-liquid separation and regeneration cyclic utilization of PCB film stripping waste liquid |
| CN114798194B (en) * | 2022-04-28 | 2023-09-01 | 深圳崇达多层线路板有限公司 | Method and equipment for solid-liquid separation and regeneration recycling of PCB film-stripping waste liquid |
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