The invention discloses a technique for extracting copper ions from industrial wastewater, which comprises the following steps: 1) respectively pretreating an acidic coppery etching waste liquid and an alkaline coppery etching waste liquid; 2) neutralization and precipitation: carrying out neutralization reaction on the acidic coppery etching waste liquid and alkaline coppery etching waste liquid in a neutralizing tank, and precipitating to obtain a basic copperchloride precipitate and a filtrate; 3) adding the basic copperchloride precipitate into a reaction tank, and adding sulfuric acid to obtain a copper sulfatecrystal; 4) sending the filtrate into an ion exchange resin tower to adsorb the rest unrecovered copper ions, thereby obtaining ammonianitrogenwastewater; and 5) carrying out evaporative concentration on the ammonianitrogenwastewater by a vapor recompression technique, crystallizing the concentrate to produce an ammoniumchloride product, treating the condensation water by an ion-exchange process, and discharging after reaching the standard. The technique can greatly enhance the extraction rate of copper ions, solves the problem of environmental pollution caused by heavy metal ions, and can produce other products from the waste liquid to implement cyclic utilization, thereby saving the resources and protecting the environment.
The invention relates to a comprehensive treatment method of acidic etching waste water. Tail water treated by the existing treatment method can not conform to the standard. The method comprises the following steps: firstly adding oxydol to an acidic etching waste liquid to be treated for breaking and regeneration; then adding 98% concentrated sulfuric acid, distilling by heating, and absorbing the distilled steam with clean water to obtain dilute hydrochloric acid; dissolving residues after the distillation in a solution to generate a mother solution, throwing nano filter membranes and reverse osmosis membranes for concentration and separation, cooling and crystallizing the condensed mother solution, rinsing with water, and drying to obtain a coppersulfatecrystal product. The method comprehensively uses the resources of the acidic etching waste liquid, produces the industrial dilute hydrochloric acid and coppersulfate products, ensures that the discharged waste water conform to the standard, improves the resource recovery rate of copper, and also raises the distillation speed.
The invention provides a slow-release organic fertilizer for tea herb and a preparation method thereof. The slow-release organic fertilizer for tea herb is composed of lignin, kieselguhr, humic acid, calcium-based silicate mineral, nitrogenous fertilizer, phosphatic fertilizer, potashfertilizer, trace elements and water, wherein the trace elements contain calcium superphosphate, magnesiumsulfatecrystal, manganesesulfatecrystal and coppersulfatecrystal. The preparation method comprises the following steps: dissolving and stirring all the components, and then mixing and pelletizing, thereby obtaining the slow-release organic fertilizer for tea herb. The formula of the slow-release organic fertilizer for tea herb is reasonable; under the synergistic effect of all the components, the use ratio of organic fertilizer and the yield of tea herb are greatly increased; and meanwhile, the problem of eutrophication or nutrient deficiency symptom of the crops and the problem of water pollution caused by fertilizer loss are effectively solved, the soil is improved, the resource is saved and the cost is lowered; and the preparation method is simple and meets the requirement for large-scale industrial production.
A method for recycling sludge during waste-water treatment firstly utilizes a process of chemical coagulation to produce sludge rich in copper ions. The sludge is then leached in a sulfuric acidstorage tank with sulfuric acid of concentration 1-2N, whereby a extractive solution with copper enrichment 18-39 g / L and residues can be obtained. The extractive solution is then processed in a refrigerationcrystallization tank to form coppersulfate crystals. Further, the residues produced are added into the coagulation tank as a coagulant in the process of chemical coagulation for wastewater treatment, thereby achieving a goal of zero sludge production.
The invention relates to a preparation method of electroplating-grade coppersulfate. The preparation method comprises the following steps: step I: mixing water with industrial-grade copperoxide according to the weight ratio of 3.4-3.7: 1 and beating to form mixed slurry; step II: adding acid liquor into the mixed slurry for acidification; regulating the pH of the mixed slurry to 1-2, and stirring and reacting for 1.5-3h to form a mixed system; step III: adding the acid liquor to regulate the pH of the mixed system to below 1, and cooling and crystallizing the mixed system; and step IV: performing solid-liquid separation on the mixed system to get a coppersulfatecrystal. The preparation method disclosed by the invention has the advantages of simplicity and easiness in operation and low treatment cost; and produced electroplating-grade copper sulfate is very low content of impurities, is completely in line with a national standard, can be suitable for market demands and further has higher economic benefits.
A disclosed method for using a coppersulfate waste liquid to prepare high-purity spherical copperoxide is characterized by comprising the following steps: a, injecting 25-35 wt% of hydrogenperoxide into the copper-sulfate-containing waste liquid to perform oxidation; b, adding basic copper carbonatepowder into the copper sulfate solution until pH is about 3.5, standing and filtering; c, adding absolute ethanol into the copper sulfate filtrate obtained in the step b according to the volume ratio of 1:50, filtering, then adding absolute ethanol into the filtrate according to the volume ratio of 1:1, crystallizing, filtering, washing with an ethanol solution, and performing spin drying; d, dissolving copper sulfatecrystal and urea in distilled water, putting in a hydro-thermal kettle to perform hydro-thermal reaction, so as to obtain copper oxide, and washing; e, drying, sintering, grinding and screening to obtain spherical copper oxide with the purity larger than 99.0%; and f, distilling an ethanol solution generated in the step c to recover ethanol. The method is less in generated wastewater, environment friendly and low in cost.
The invention provides a micro-etching solution cyclic regeneration and copper reclamation device, and relates to a device for reclaiming copper from micro-etching waste solution and a regeneration technique for the waste solution in the printed circuit board industry. The micro-etching waste solution is generally repurchased for extracting coppersulfate crystals by a reclamation company in the current industry, and the discharge of the waste solution causes secondary pollution; and high-purity electrolytic copper is reclaimed by electrolysis technology, and the micro-etching solution can be recycled and does not need discharging so as to fulfill the aims of energy conservation, emission reduction and clean production.
The invention relates to a process for producing cathodecopper by low-grade anode plates. Low-grade high-nickeltin black copper is used as raw materials for direct electrolysis refining to prepare qualified cathodecopper; through such modes as adjustment of process conditions, selection of reasonable current density, flow and temperature, adjustment of the additive ratio and adding of modifiedpolyacrylamide, the obtained cathode copper is higher in grade, smooth in surface, clear and compact in grain, uniform in thickness and beautiful; meanwhile, the purification and replacement period ofelectrolyte is prolonged, so that the production cost is greatly reduced when the recovery rate is increased; anode mud is treated by adopting ethyl acetate and phenolic resins, so that the problem of difficult gold and silver separation of the anode mud due to adding of polyacrylamide is solved, and the daily treatment quantity of the anode mud is increased; and copper sulfatecrystal seeds areintroduced to accelerate separation of copper sulfate crystals, so that the recycling rate of metal copper and nickel is improved.
The invention discloses a protection method and device for a cathode roller after grinding and application. The invention belongs to the technical field of electrolytic copper foil production. The method is technically characterized by comprising the following steps: S1, hoisting a cathode roller from a crude foil engine, and moving the cathode roller to a grindingmachine for grinding; s2, aftergrinding, pure water is adopted for cleaning, specifically, after the grinding machine finishes grinding the cathode roller, pure water is adopted for cleaning the surface of the cathode roller; s3, after cleaning is stopped, the cathode roller continues to rotate for 1-10 min; s4, a protective layer is constructed on the surface of the cathode roller; S4, after the surface of the cathode roller is blow-dried, a coppersulfate solution is uniformly sprayed on the surface of the cathode roller; s4-2, stopping spraying the coppersulfate solution when the copper sulfate solution exists on the surface of the cathode roller; and S4-3, after copper sulfate crystals are formed on the surface of the cathode roller, the roller surface of the cathode roller is protected. According to the protectionmethod and device for the ground cathode roller and the application, the ground cathode roller surface is protected, and therefore various properties of the electrolytic copper foil are guaranteed.
The invention discloses a method for extracting nickel from high-grade matte nickel leaching residues. The method comprises the following steps of firstly, adding a crushed material of the high-grade matte nickel leaching residues into an organic solvent dissolved with sulfur, heating for reaction, carrying out solid-liquid separation to obtain first filtrate and first filter residues, adding the first filter residues into a coppersulfate solution, heating for reaction, carrying out solid-liquid separation to obtain second filtrate and second filter residues, carrying out evaporation condensation concentration on the second filtrate, and filtering to obtain coppersulfate crystals and nickel-containing filtrate. According to the method, Cu2S, Ni3S2, CuFeS2, a nickel-iron-copperalloy and the like in the high-grade matte nickel leaching residues are oxidized into CuS, NiS and FeS by utilizing the oxidability of elemental sulfur in the organic solvent, the elemental sulfur in the high-grade matte nickel leaching residues is dissolved in the solvent in the presence of the organic solvent, then NiS and FeS are replaced by more insoluble CuS by adopting a copper sulfate solution, nickel ions and ferrous ions enter the solution, and the copper content in the leaching residues is further improved. Only a small amount of sulfur and copper sulfate are consumed in the whole reaction, and the organic solvent can be recycled.
The invention provides a method for etching the front surface of silica glass with the assistance of a chemical salt film, belonging to the field of non-traditional machining. The machining method provided by the invention mainly comprises the four steps that (1), the silica glass is heated by an electric heating wire; a saturated coppersulfate solution is slowly added to the surface of the silica glass; coppersulfate crystals are continuously precipitated in the solution on the surface of the silica glass until a layer of very thin and uniform chemical salt film is formed on the surface of the silica glass; (2), the silica glass is clamped on a laser worktable, and lasersystem technological parameters of laser for etching the silica glass are determined; (3), a laser scanning path and laser scanning speed are determined; and (4), the silica glass of which the surface is provided with the chemical salt film is etched through the laser according to the scanning path. According to the method, laser energy is mainly absorbed by the chemical salt film in an assistant manner, so that a laser beam is prevented from being transmitted through the silica glass, and the laser beam emitted by a solid laser can perform etching on the surface of the silica glass. By adopting the method provided by the invention, obvious slags and edge breakage do not exist on the surfaces of grooves etched on the surface of the silica glass, and the surfaces are smooth and clean; and a good machining effect is reached.
The invention discloses a method for removing lead in a cupper sulfate preparation process. The method is characterized by comprising the following steps: a, preparing a lead-dissolving reagent by utilizing acetic acid or one or more water-soluble acetates, wherein the molar weight of acetate in the lead-dissolving reagent is 2 times larger than that of lead in a cupper sulfate preparation solution to be treated; b, adding the lead-dissolving reagent into the lead-containing cupper sulfate preparation solution to be treated so that acetate in the lead-dissolving reagent and lead form soluble lead acetate; c, crystallizing and precipitating out cupper sulfate in the cupper sulfate preparation solution; and d, separating cupper sulfate crystal obtained by crystallization and precipitation from the treated cupper sulfate preparation solution. The method disclosed by the invention has the beneficial effects that the lead-removing process is wide in application range, the lead-removing cost is low, a deep lead-removing effect is good, the quality is stable, the efficiency is high, and equipment dose not need to be added and changed.
The invention discloses a corrosion inhibiting modified double coated thermal-stabilized water-based aluminum pigment. The corrosion inhibiting modified double coated thermal-stabilized water-based aluminum pigment is prepared from, by weight, 40-45 parts of flaky aluminum powder, 100-110 parts of isopropanol, 0.3-0.35 part of coppersulfate crystals, a proper amount of deionized water, 4-4.5 parts of phenolic ether type phosphate, a proper amount of absolute ethyl alcohol, 9-10 parts of tetraethoxysilane, 6-7 parts of vinyltriethoxysilane, 9-10 parts of ammoniumhydroxide with the concentration being 20 wt%, 200-220 parts of butyl acetate, 5-6 parts of crylic acid, 5-6 parts of methacrylic acid, 0.6-0.65 part of dibenzoyl peroxide, 13-15 parts of propylene glycolmonomethyl ether, 4-5 parts of aluminum hydroxide, 3-4 parts of antimonous oxide, 0.8-1 part of silanecoupling agent KH-550, 1.2-1.5 parts of alkylphenol ethoxylates, 0.5-0.6 part of span-80 and 0.8-1 part of polyethylenewax. A product prepared from the corrosion inhibiting modified double coated thermal-stabilized water-based aluminum pigment can be evenly dispersed in a coating, and high stability is achieved.
The invention relates to an environment friendly acid solution for removing copper sheets on titanium and titaniumalloy extruded tube blanks. The environment friendly acid solution for removing the copper sheets on the titanium and titanium alloy extruded tube blanks is characterized by comprising the following raw materials in percentage by mass: 15-20% of H2SO4, 5-10% of HNO3, 5-10% of H2O2 and the balance of water. By using the environment friendly acid solution for removing the copper sheets on the titanium and titanium alloy extruded tube blanks, provided by the invention, the using amount of the nitric acid is reduced, the using amount of the hydrogenperoxide is increased, brownish rednitric oxide (NO2) as a poisonous gas is prevented from being generated, and excessive cupric ions and nitrate ions are prevented from being generated, and waste gases and waste solutions can meet environment friendliness requirements, so that the environment friendly acid solution has a practical application value; and meanwhile, the economic benefit is increased by recovery of copper sulfatecrystal substances, so that the environment friendly acid solution can be widely used by enterprises adopting the conventional technique (sulfuric acid and nitric acid, water or nitric acid and water) through slightly changing the conventional technique and equipment.
A method for recycling sludge during waste-water treatment firstly utilizes a process of chemical coagulation to produce sludge rich in copper ions. The sludge is then leached in a sulfuric acidstorage tank with sulfuric acid of concentration 1-2N, whereby a extractive solution with copper enrichment 18-39 g / L and residues can be obtained. The extractive solution is then processed in a refrigerationcrystallization tank to form coppersulfate crystals. Further, the residues produced are added into the coagulation tank as a coagulant in the process of chemical coagulation for wastewater treatment, thereby achieving a goal of zero sludge production.
The invention provides a waste coppersulfateelectrolyte purification system and a waste coppersulfateelectrolyte purification method realized by using the system. The system comprises a waste electrolytestorage tank, a waste electrolyte pump, a plate filter, a waste filtrate storage tank, a waste filtrate pump, a plate heat exchanger, a vacuum evaporator set, a coppersulfatewater coolingcrystallization tank, a belt filter and a suction filtration tank which are sequentially connected, wherein the suction filtration tank comprises a tank body; the upper part of the tank body is opened; the middle of the tank body is provided with a pore plate; the tank body is partitioned into a material chamber and a suction filtration chamber by the pore plate; filter cloth covers on the pore plate; the suction filtration chamber is connected with a vacuum pump. According to the invention, devices such as the plate heat exchanger and the like are not easy to scale, so that the safety use of the equipment is ensured; meanwhile, waste electrolyte entering the vacuum evaporator set is low in impurity content, so that the purity of a final product is improved; secondary suction filtration is realized by the suction filtration tank, so that the water and acid contents of a copper sulfatecrystal product are effectively reduced, and the quality of the product is improved.
The invention discloses a resource utilization method suitable for PCB deplating waste liquor. The deplating waste liquor is coppernitrate waste liquor. The method comprises the following steps of pretreatment, wherein the coppernitrate waste liquor is filtered to remove impurities, a sulfuric acid solution is added into the filtered coppernitrate waste liquor, and the acid concentration of thesystem is adjusted to obtain an inorganic phase for use; extraction, wherein the inorganic phase is put into an extraction device, an extraction agent TBP is added, and the extraction condition is controlled for extracting nitric acid to obtain an extract phase and a raffinate phase; back extraction, wherein the extract phase is put into the extraction device, water is added, and the back extraction condition is controlled for back-extracting nitric acid to obtain a nitric acid solution; crystallization, wherein a copper oxide or copper hydroxidesolid is added into the raffinate phase to neutralize redundant acid, the pH of the system is adjusted to 2-3, filtering is conducted, a filtrate is crystallized, and then a copper sulfatecrystal is obtained. According to the resource utilization method, copper and waste liquor are recycled under normal temperature and normal pressure, the energy consumption is lowered, the waste of resources is avoided, the environmental pollution is prevented, and the production cost is lowered.
The invention relates to the technical field of wastewater treatment, and provides a method and system for treating a copper-containing etching waste liquid. The method comprises the following steps:mixing an acidic etching waste liquid with an alkaline etching waste liquid to obtain a neutralized liquid; contacting the neutralized liquid with oxygen to obtain an oxidizing liquid; performing pressure filtration on the oxidizing liquid; beating the above obtained first filter cake, and carrying out pressure filtration on the above obtained first slurry; beating the obtained second filter cake,and reacting the obtained second slurry with concentrated sulfuric acid; and sequentially carrying out cooling crystallization and solid-liquid separation on the obtained coppersulfate-containing reaction liquid to obtain coppersulfate crystals and a copper sulfatemother liquor. The copper-containing acidic etching waste liquid is neutralized, then the neutralized liquid is aerated, cuprous ions in the neutralized liquid and chloride ions form a complex, cuprous ions are rapidly oxidized in an aeration state to form copper ions in order to form a basic copper chloride precipitate, and thebasic copper chloride precipitate is recovered by pressure filtration and used to prepare copper sulfate, so the copper concentration of the wastewater is reduced, and the copper recovery rate is increased.