CN111549235A

CN111549235A - Separation method of lead-containing raw material

Info

Publication number: CN111549235A
Application number: CN201910109315.2A
Authority: CN
Inventors: 张超; 武占月; 刘军飞; 任佳楠; 陈建民; 刘广辉; 刘向东; 孙建明; 王占
Original assignee: Beijing Zhongjin Ruifeng Environmental Protection Technology Co ltd
Current assignee: Beijing Zhongjin Ruifeng Environmental Protection Technology Co ltd
Priority date: 2019-02-08
Filing date: 2019-02-08
Publication date: 2020-08-18

Abstract

The invention discloses a separation method of a lead-containing raw material, belonging to the technical field of separation of lead-containing mixtures. The invention takes lead-calcium separation as a core, is matched with the separation of lead-calcium and zinc-magnesium, realizes the mutual separation of lead, calcium, magnesium and zinc components by the circulation of sulfate and alkaline gas on the premise of consuming a small amount of sulfuric acid by a lead-containing raw material, and converts the lead, calcium, magnesium and zinc components into lead carbonate, basic zinc carbonate 1, basic magnesium carbonate and calcium carbonate products. In the separation method, the lead in the lead-containing raw material is dissolved and calcium oxide is desulfurized synchronously by utilizing the difference of the dissolving capacity of the reaction liquid to lead and calcium, so that the mutual separation of lead and calcium in the same reaction liquid system is realized.

Description

Separation method of lead-containing raw material

Technical Field

The invention relates to the technical field of separation of lead-containing mixtures, in particular to a method for separating a lead-containing raw material.

Background

Lead is a common non-ferrous metal and is widely applied to industries such as storage batteries, cable sheaths, machinery manufacturing industry, ship manufacturing industry, light industry, lead oxide industry, ray protection industry and the like. At present, lead is mainly from primary lead smelted from primary ore and secondary lead recycled from scrapped lead-acid batteries, and the lead ore and the scrapped lead-acid batteries are characterized by high lead content, wherein the lead content of lead concentrate can reach 40-70%, and the lead content in the scrapped lead-acid batteries can reach more than 50%, and the two raw materials are high in lead content and low in smelting cost and are widely used as lead smelting raw materials. Besides lead concentrate with high lead content and scrapped lead-acid batteries, a large amount of low-grade lead raw materials also exist, including low-grade lead-zinc ore, lead-containing gypsum, lead sulfate mud, zinc leaching slag and the like, the content of lead in the raw materials is more different, wherein the lead content is as low as 0.5 percent and as high as 40 percent, the low-grade lead raw materials are directly smelted as raw materials due to lower lead content, and some enterprises mix the low-grade lead raw materials with some lead concentrate with high lead content and scrapped lead-acid batteries and then smelt the mixed raw materials, so that the cost can be shared, but the smelting cost is not reduced for the low-grade lead raw materials.

At present, lead smelting is mainly pyrometallurgy, and mainly adopts bottom blowing, top blowing and side blowing furnaces to smelt lead, so that a lead-containing raw material and reducing agents such as carbon are heated together at a temperature of over 1000 ℃, lead compounds are reduced into metallic lead, and metallic lead products are obtained. The pyrometallurgical process of lead is developed for more than 100 years and is relatively mature, and the smelting cost of lead approaches the bottom line after long-time efforts, so that a new process needs to be developed to be suitable for recovering low-grade lead-containing raw materials.

The existing method for treating low-grade lead-containing raw materials is to use a pyrogenic process, reduce lead compounds into metallic lead by using carbon, ensure the reaction temperature to exceed 1000 ℃, lead and impurities in the lead-containing raw material can be heated to more than 1000 ℃ together in the process, and according to different smelting processes, the energy consumption of each ton of raw material in the smelting process is hundreds of kilograms or even thousands of kilograms of standard coal, for lead-containing raw materials with higher lead content, the energy cost of the smelting process shared by each ton of metal lead is lower, it is acceptable for lead smelting enterprises, with the reduction of the lead content in the lead-containing raw material, the energy cost of the smelting process allocated by each ton of metal lead gradually increases, the smelting cost of the lead-containing raw material with the lead content of 10 percent is 5 times of the smelting cost of the lead-containing raw material with the lead content of 50 percent, for a large amount of low-grade lead-containing raw material with a lead content of less than 10%, the smelting cost per ton of metallic lead is higher.

In addition, the components in many lead-containing raw materials contain lead sulfate, the temperature in the lead smelting process reaches over 1000 ℃, the lead sulfate can be decomposed to generate sulfur dioxide gas, and flue gas containing dust, lead vapor and sulfur dioxide gas is inevitably generated. The flue gas generated in the smelting process can be discharged after being treated by a multi-stage dust removal and desulfurization system, and the cost generated in the dust removal and desulfurization process is distributed to each ton of metal lead, so that the treatment cost of the low-grade lead-containing raw material can be further improved.

Finally, the lead content in the low-grade lead-containing raw material is low, and the content of other impurity elements such as zinc, iron, calcium, magnesium, silicon and the like is high, lead and zinc can be synchronously reduced in the reduction process in the conventional pyrometallurgical process and coexist in products, and the obtained products need to be subjected to secondary processing to obtain lead and zinc products with good quality. In addition, iron, calcium, magnesium and silicon elements in the lead-containing raw material cannot volatilize in the smelting process, form a molten mass, and are converted into slag after cooling, although the slag does not belong to dangerous waste, the amount of slag generated per ton of metallic lead is increased sharply with the decrease of the lead content in the lead-containing raw material, and the increased treatment cost of the slag in the treatment process also increases the treatment cost of the low-grade lead-containing raw material.

Therefore, how to reduce the energy consumption for processing low-grade lead-containing raw materials, realize the effective separation of lead and zinc, reduce the emission of flue gas and reduce the amount of tailings is a problem to be solved urgently.

Disclosure of Invention

Aiming at the problems of difficult separation of lead and zinc of low-grade lead-containing raw materials, high separation cost of the lead-containing raw materials, high desulphurization cost of the lead-containing raw materials and the like in the prior art, the invention aims to provide the separation method of the lead-containing raw materials, which uses a cheap desulfurizer for desulphurization while separating lead and zinc, converts desulphurization byproducts into valuable products, and simultaneously uses a low-cost wet process technology to reduce the treatment cost and the flue gas emission of the low-grade lead-containing raw materials, improve the recovery rate of valuable metals such as lead and the like, and reduce the amount of tailings by recovering calcium, magnesium and iron elements.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a method for separating lead-containing raw materials is used for separating initial lead-containing raw materials, and specifically comprises the following steps:

(1) reacting a reaction solution containing a solvent, a cosolvent, a catalyst and sulfate with a lead-containing raw material, controlling the pH value of the solution to be between 5.0 and 12.0 (the pH value is preferably between 6.0 and 10.5), and separating to obtain gypsum residue and a lead-containing solution after the reaction is finished;

(2) adding a precipitator A or a solution containing the precipitator A into a lead-containing solution for reaction, controlling the pH value of the solution to be between 5.5 and 12.0 (the pH value is preferably between 7.0 and 11.0), and separating to obtain a lead-precipitating solution and a lead-containing precipitate after the reaction is finished;

(3) reacting a reaction solution containing a solvent, a cosolvent, a catalyst and sulfate with the gypsum residue obtained in the step (1), controlling the pH value of the solution to be between 5.5 and 12.0 (the pH value is preferably between 7.5 and 11.5), and separating to obtain tailings and a calcium-containing solution after the reaction is finished;

(4) adjusting pH of the calcium-containing solution to 4.0-10.0 (preferably pH of 6.0-9.0) by volatilizing alkaline gas or adding acidic compound to separate calcium sulfate solid from the calcium-containing solution, and separating to obtain calcium-containing precipitate and calcium precipitation solution.

The lead-containing raw material in the invention is lead oxide ore, galena oxidation product, zinc sulfide ore oxidation product, zinc oxide ore, lead-containing flue dust, lead-containing waste in the lead-acid battery production process, scrap lead-acid battery lead paste and thermal decomposition product thereof, scrap lead-acid battery lead paste desulfurization product, zinc hypoxide, zinc-containing smoke dust, lead-containing smoke dust, dust and wastewater treatment sludge collected by a dust collecting (removing) device in the lead-zinc copper regeneration process, wastewater treatment sludge produced in the lead-zinc copper smelting process, hot acid leaching jarosite method of zinc roasting ore in the lead-zinc smelting process, lead silver slag produced by hot acid leaching goethite method, lead oxide slag and alkali slag produced by cathode lead refining in the lead-zinc smelting process, scum and bottom mud produced in the lead smelting process, various smoke dusts collected by dry dust collectors in the lead-zinc copper smelting process, zinc slag produced by a zinc refining furnace in the lead-zinc smelting process, lead slag, Blast furnace scum generated by a blast furnace zinc smelting vapor condensation separation system in the lead-zinc smelting process, zinc oxide leaching slag generated by zinc oxide leaching treatment in the lead-zinc smelting process, casting scum generated by cathode zinc casting in the lead-zinc smelting process, sulfur slag (leaching slag) generated by zinc sulfide ore atmospheric pressure oxygen leaching or pressure oxygen leaching, jarosite slag generated by jarosite hot acid leaching of zinc roasted ore in the lead-zinc smelting process, leaching slag generated by zinc roasted ore conventional leaching method in the lead-zinc smelting process, wastewater treatment sludge generated in the crude zinc refining process, one or more of dust and wastewater treatment sludge collected by a dust collecting (removing) device in the steel smelting and processing process and lead-containing sludge; the adding amount of the lead-containing raw material in the reaction solution is 1-1000 g/L.

In the above steps (1) and (3), the solvent in the reaction solution is ammonia, methylamine, ethylamine, ethylenediamine, propylenediamine, aniline, ethanolamine, diethanolamine, triethanolamine, imidazole, diethylenetriamine, triethylenetetramine, tetraethylpentamine, ethylenediaminetetraacetic acid, propylenediaminediacetic acid, ethylenediamine diacetic acid, ethyleneglycol diethyletherdiamine tetraacetic acid, propylenediaminetetraacetic acid, hydroxyethylethylenediamine triacetic acid, tetrahydroxypropylethylenediamine, 2-aminobenzoic acid-N, N-diacetic acid, diethylthioetherdiamine tetraacetic acid, sulfosalicylic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, cyclohexanediaminetetraacetic acid, nitrilotriacetic acid, glutamic acid, valine, histidine, aspartic acid, leucine, isoleucine, alanine, proline, serine, phenylalanine, arginine, threonine, or a mixture thereof, One or more of iminodisuccinic acid selected from glycine, lysine, asparagine, glutamine, methionine, ornithine, taurine, citrulline and sarcosine; the concentration of the solvent in the reaction liquid is 0.1-6.0 mol/L; the concentration of the solvent in the step (3) is preferably 0.5-5.0 mol/L;

the cosolvent is a sulfate, chloride, formate, acetate, malonate, benzoate, phosphate, citrate, tartrate or succinate of sodium, potassium, ammonium, magnesium, calcium, zinc, manganese, nickel, copper, chromium or lead ions; the concentration of the cosolvent in the reaction liquid is 0.1-6.0 mol/L; the concentration of the cosolvent in the step (1) is preferably 0.5-5.0 mol/L;

the sulfate is sulfate of sodium, potassium, ammonium, magnesium, calcium, zinc, manganese, nickel, copper, chromium and/or lead ions, and the concentration of the sulfate in the reaction liquid is 0.1-6.0 mol/L;

the catalyst is a variable valence metal compound, specifically one or more of ferric salt, cobalt salt, nickel salt and manganese salt, and the concentration of the catalyst in the reaction solution is 0.001-2 mol/L.

In the step (2), the precipitant A is one or more of sulfite, bisulfite, sulfurous acid, sulfur dioxide, carbonate, bicarbonate, carbon dioxide and carbon dioxide aqueous solution; the lead-containing precipitate is one or more of lead carbonate, basic sodium lead carbonate and lead sulfite.

In the steps (1) to (4), the reaction temperature is between 0 and 150 ℃; wherein: the reaction temperature in the step (1) is preferably between 20 and 100 ℃; the reaction temperature in the step (2) is preferably between 20 and 100 ℃; the reaction temperature in the step (3) is preferably between 10 and 90 ℃; the reaction temperature in the step (4) is preferably between 20 and 100 ℃;

in the step (1), the pH value of the solution is adjusted to be between 5.0 and 12.0 by using organic acid, inorganic acid, organic alkali, inorganic alkali, strong alkali weak acid salt, strong acid weak alkali salt, acid salt or volatile alkaline gas;

in the steps (2) - (3), the pH value of the solution is adjusted to be between 5.5 and 12.0 by using organic acid, inorganic acid, organic alkali, inorganic alkali, strong alkali weak acid salt, strong acid weak alkali salt, acid salt or volatile alkaline gas;

in the step (4), the acidic compound is one or more of an organic acid, an inorganic acid, a strong acid, a weak base salt and an acid salt;

the organic acid, inorganic acid, organic base, inorganic base, strong base weak acid salt, strong acid weak base salt and acid salt are hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, adipic acid, oxalic acid, malonic acid, succinic acid, maleic acid, tartaric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, caproic acid, capric acid, stearic acid, palmitic acid and acrylic acid, one or more of citric acid, ammonium sulfate, ammonium bisulfate, sodium bisulfate, potassium bisulfate, ammonium acetate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium nitrate, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, ammonia water, ammonia gas, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, barium oxide, barium hydroxide, methylamine, ethylamine, propylenediamine, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate and ammonium bicarbonate;

the alkaline gas is one or more of ammonia gas, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, methylamine, ethylamine and propylenediamine.

The calcium-containing precipitate is one or more of dihydrate gypsum, semi-hydrate gypsum and anhydrous gypsum; the alkaline gas is one or more of ammonia gas, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, methylamine, ethylamine and propylenediamine.

The acidic compound is preferably one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, adipic acid, oxalic acid, malonic acid, succinic acid, maleic acid, tartaric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, caproic acid, capric acid, stearic acid, palmitic acid, acrylic acid, citric acid, ammonium sulfate, ammonium bisulfate, sodium bisulfate, potassium bisulfate, ammonium acetate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium nitrate.

Further, more preferably, the lead precipitation solution obtained in the step (2) or the calcium precipitation solution obtained in the step (4) can be used as the reaction solution in the step (1) or the step (3);

more preferably, a reducing agent is added in the step (1) to reduce lead dioxide in the lead-containing raw material into soluble lead, wherein the reducing agent is common reducing agents such as metallic lead, sulfite, sulfur dioxide, oxalic acid, ascorbic acid, metallic iron, ferrous salt and the like;

more preferably, in the step (1), the reaction solution is reacted with the lead-containing raw material for a plurality of times or with an excessive amount of lead-containing raw material to increase the lead concentration in the lead-containing solution and decrease the calcium concentration in the lead-containing solution;

more preferably, in the step (1), the concentration of calcium in the lead-containing solution is less than 10 g/L.

More preferably, when the pH value of the solution is adjusted by using a volatile alkaline gas in the step (1), the step (2), the step (3) and the step (4), the volatilization of the alkaline gas is promoted by introducing air, inert gas or by reduced pressure evaporation, and the temperature of the reduced pressure evaporation is between 20 and 95 ℃;

more preferably, when the lead-containing raw material contains a large amount of chlorine and other soluble salts, the raw material may be contacted with water in advance to remove the soluble substances from the lead-containing raw material, and the water-washed lead-containing raw material may be used as the lead-containing raw material in the step 1).

In the step (1), the lead-containing raw material is used after being pretreated, and the pretreatment comprises the following steps:

(A) mixing a lead-containing raw material with an acidic substance or a solution containing the acidic substance for treatment to obtain a lead-containing material A;

(B) the lead-containing material A is contacted with water or a solution containing acidic substances, and a zinc-containing solution and a pretreated lead-containing raw material are obtained after separation.

In the step (a) and the step (B), the acidic substance is sulfuric acid, sulfurous acid, phosphoric acid, and the cation is one or more of sulfate, bisulfate, sulfite, bisulfite, nitrate, phosphate, dibasic phosphate, and monobasic phosphate of potassium, sodium, and ammonium ions.

In the step (A), the temperature for mixing the lead-containing raw material and the acidic substance is between 40 and 800 ℃; in the step (A), the mass ratio of the acidic substance to the lead-containing raw material is 0.0002:1 to 1: 20.

The zinc-containing solution obtained in the step (B) is treated according to the following steps:

(C) precipitating zinc in the zinc-containing solution in a solid form of zinc-containing precipitate by using a mode of evaporative crystallization, cooling crystallization or adding a precipitator B in the zinc-containing solution, and separating to obtain a zinc precipitation solution and the zinc-containing precipitate;

(D) adding a precipitator C into the zinc precipitation solution to precipitate magnesium in the zinc precipitation solution in the form of magnesium-containing precipitate, controlling the pH value of the solution to be between 6.0 and 13.0, and separating to obtain a magnesium precipitation solution and the magnesium-containing precipitate.

In the step (C), the evaporation crystallization temperature is 20-150 ℃, the cooling crystallization temperature is-50-100 ℃, and the precipitant B is one or more of sulfite, bisulfite, sulfurous acid, sulfur dioxide, carbonate, bicarbonate, carbon dioxide and carbon dioxide aqueous solution; the zinc-containing precipitate is one or more of zinc hydroxide, basic zinc sulfate, zinc sulfite, zinc carbonate, basic zinc carbonate, zinc ammonium sulfate and zinc ammonium sulfate complex.

In the step (D), the precipitant C is one or more of ammonia water, ammonia, urea, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium oxide, calcium hydroxide, methylamine, ethylamine, propylenediamine, carbonate, bicarbonate, carbon dioxide, sulfur dioxide, sulfite and bisulfite; the magnesium-containing precipitate is one or more of magnesium hydroxide, magnesium sulfite, magnesium carbonate, ammonium magnesium sulfate, basic magnesium carbonate and basic magnesium sulfate.

In the step (D), when ammonia water, ammonia gas, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium oxide, calcium hydroxide, methylamine, ethylamine or propylenediamine is used as a precipitator C, the obtained magnesium-containing precipitate is one or two of magnesium hydroxide and magnesium oxide;

in the step (D), when carbonate, bicarbonate, carbon dioxide, sulfur dioxide, sulfite and bisulfite are used as the precipitant C, the magnesium-containing precipitate is one or two of magnesium carbonate, basic magnesium carbonate and magnesium sulfite;

in the step (D), the reaction temperature is 10-150 ℃, the reaction pressure is-0.05-1.5 Mpa, and the pH value of the solution is preferably controlled to be 6.5-12.0.

In the step (1), metallic lead is added into the obtained lead-containing solution, so that metals (including copper and/or silver) which are not active to lead in the lead-containing solution react with the metallic lead and are replaced by corresponding metals, and copper ions and/or silver ions in the lead-containing solution are removed.

And (3) adding metal zinc into the calcium-containing solution obtained in the step (3) or the zinc-containing solution obtained in the step (B), so that metals (including copper, cadmium, nickel, iron, lead, cobalt and silver) without zinc activity in the solution react with the metal zinc and are replaced by corresponding metals, and metal ions (copper, cadmium, nickel, iron, lead, cobalt and silver ions) without zinc activity in the solution are removed.

Adding an oxidant to the lead-containing solution obtained in the step (1) or the solution in the process of the reaction in the step (1) or the calcium-containing solution obtained in the step (3) or the solution in the process of the reaction in the step (3) or the zinc-containing solution obtained in the step (B) or the solution in the process of the reaction in the step (B), and precipitating and separating arsenic or manganese in a solid form; the oxidant is one or more of hydrogen peroxide, manganese dioxide, potassium permanganate, air, oxygen and oxygen-enriched air; wherein: when the oxidant is added into the solution, the temperature of the solution is controlled between 40 ℃ and 100 ℃, the reaction pressure is maintained between 0 MPa and 1.5MPa, and the adding amount of the oxidant is 1 g/L to 200 g/L;

adding one or more of carbon dioxide, carbonate, bicarbonate, bisulfite, phosphate, oxalate and oxalic acid into the lead-containing solution obtained in the step (1), the lead-precipitating solution obtained in the step (2), the calcium-containing solution obtained in the step (3) or the zinc-precipitating solution obtained in the step (C), converting the lead, zinc, magnesium or calcium in the solution into carbonate, sulfite, oxalate or phosphate for precipitation, and controlling the pH value of the solution to be between 4.0 and 12.0 by using one or more of organic acid, inorganic acid, organic base, inorganic base, strong base, weak base, strong acid, weak base and acid salt in the precipitation process; wherein: the cation of the carbonate, the bicarbonate, the bisulfite, the phosphate and the oxalate is one or more of potassium, sodium and ammonium; the organic acid, inorganic acid, organic base, inorganic base, strong base and weak acid salt, strong acid and weak base salt and acid salt are hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, adipic acid, oxalic acid, malonic acid, succinic acid, maleic acid, tartaric acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, caproic acid, capric acid, stearic acid, palmitic acid and acrylic acid, one or more of citric acid, ammonium sulfate, ammonium bisulfate, sodium bisulfate, potassium bisulfate, ammonium acetate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium nitrate, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, ammonia water, ammonia gas, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, barium oxide, barium hydroxide, methylamine, ethylamine, propylenediamine, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate and ammonium bicarbonate; the adding amount of one or more of carbon dioxide, carbonate, bicarbonate, bisulfite, phosphate, oxalate and oxalic acid is 1-200 g/L. More preferably, in the process of converting zinc, magnesium or calcium in the calcium-containing solution obtained in the step 3) or the precipitated calcium solution obtained in the step 4) or the precipitated zinc solution obtained in the step C) into carbonate, sulfite, oxalate or phosphate, the reaction temperature of the solution is controlled to be 20-100 ℃, the pressure is controlled to be 0-1.5MPa, and the pH value of the solution is controlled to be 5.0-11.0;

adding an ionic strength regulator or a solution polarity regulator or a surfactant to the solution in the step (2) or the step (4) or the step (C); the ionic strength regulator is one or more of carbonate, nitrate, chloride, fluoride, acetate, oxalate, phosphate, citrate, pyrophosphate, tartrate and perchlorate of sodium, potassium, ammonium or magnesium ions, and the concentration of the ionic strength regulator is not more than 4.5 mol/L; the solution polarity regulator is one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, glycerol, N-methyl pyrrolidone, N-butanol, formaldehyde, acetaldehyde, benzaldehyde, acetone, butanone, cyclohexanone, formic acid, acetic acid and propionic acid, and the concentration is not more than 15.0 mol/L; the surfactant is anionic surfactant, cationic surfactant, zwitterionic surfactant and nonionic surfactant, and the surfactant is stearic acid, oleic acid, lauric acid, quaternary ammonium salt, cocamidopropyl betaine, dodecyl amino propionic acid, isomeric alcohol polyoxyethylene polyoxypropylene ether, polyvinylpyrrolidone, octyl phenol polyoxyethylene ether, polyethylene glycol octyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, sodium dodecyl sulfonate, sodium dodecyl sulfate, potassium dodecyl sulfate, diethyl sulfite, malonic acid, sorbitol, sodium glutamate, aluminum sulfate, hexadecyl trimethyl ammonium chloride, catechol-3, 5-sodium disulfonate, ammonium rhodizocarboxylate, sodium diethyldithiocarbamate, xylenol orange, chromic acid, chrome black T, chrome black A, sodium sulfate, sodium dodecyl sulfate, diethyl sulfite, malonic acid, sorbitol, sodium glutamate, aluminum sulfate, hexadecyl trimethyl ammonium chloride, catechol-3, 5-sodium disulfonate, ammonium rhodizole, sodium diethyldithiocarbamate, xylenol orange, chromic acid, chrome black, One or more of tetraethylenepentamine, triethylene tetramine, sodium pyrophosphate, sodium tripolyphosphate, dodecyl trimethyl ammonium chloride, benzyl triethyl ammonium chloride, gelatin, bone glue, Arabic gum, polyvinyl alcohol, polyethylene glycol, polymethyl acrylamide and alkylphenol polyoxyethylene ether, and the addition amount of the surfactant is not more than 10 g/L.

In the steps (1) to (4), when the volatile alkaline gas is used for adjusting the pH value of the solution, the generated alkaline gas is directly recycled as the alkali or is converted into the alkali again for recycling by a condensation absorption mode.

Reacting the calcium-containing precipitate obtained in the step (4), the zinc-containing precipitate obtained in the step (C) or the magnesium-containing precipitate obtained in the step (D) with a precipitator D, wherein an alkaline substance is used for controlling the pH value of the solution to be 6-12 to obtain a sulfate solution and a carbonate compound, and the sulfate solution is directly or after crystallization and is returned to the steps (1), (2), (3) and (4) to be used as sulfate; the precipitant D is one or more of carbonate, bicarbonate and carbon dioxide; the alkaline substance is one or more of ammonia water, ammonia, urea, sodium hydroxide, potassium hydroxide, methylamine, ethylamine, propylenediamine, carbonate and bicarbonate; the carbonate compound is one or more of calcium carbonate, magnesium carbonate, basic magnesium carbonate, zinc carbonate and basic zinc carbonate.

Further, more preferably, the precipitant D is one or more of carbon dioxide, carbonate with cation of potassium, sodium, ammonium, and bicarbonate;

more preferably, the alkaline substance is ammonia, ammonia gas, sodium hydroxide, potassium hydroxide, methylamine, ethylamine, propane diamine and the cation is one or more of carbonate and bicarbonate of potassium, sodium and ammonium;

more preferably, when the calcium-containing precipitate is reacted with the precipitant D, the carbonate compound is calcium carbonate;

more preferably, when magnesium-containing precipitate reacts with the precipitator D, the obtained carbonate compound is magnesium carbonate or basic magnesium carbonate;

more preferably, when the zinc-containing precipitate is reacted with the precipitant D, the resulting carbonate compound is zinc carbonate or basic zinc carbonate.

Adding a desulfurizing agent or a solution containing the desulfurizing agent into the reaction solution obtained in the step (1) to convert sulfate radicals in the lead-containing raw material into gypsum precipitates; the desulfurizer is one or more of calcium oxide, barium oxide, calcium hydroxide and barium hydroxide; the solution containing the desulfurizer is obtained by separating any one of the solution in the steps (1), (2), (3), (4), (B), (C) and (D) after contacting the desulfurizer. Further, more preferably, the temperature of any one of the solutions in the steps 1), 2), 3), 4), B), C) and D) in contact with the desulfurizing agent is 0-100 ℃; more preferably, the excessive desulfurizer is used to contact with any solution in the steps 1), 2), 3), 4), B), C) and D), and the solution containing the desulfurizer is obtained after the solid is separated.

Converting iron in the zinc-containing solution obtained in the step B) into iron-containing precipitate by using a method of single cooling crystallization or multiple cooling crystallization or solution pH value adjustment or oxidant addition; the method for adjusting the pH value of the solution comprises the following steps: adjusting the pH value of the solution to 1.5-10.0 by using one or more of organic alkali, inorganic alkali and strong alkali and weak acid salt; the temperature of the cooling crystallization is-50-100 ℃; the oxidant is one or more of hydrogen peroxide, manganese dioxide, potassium permanganate, air, oxygen and oxygen-enriched air; the iron-containing precipitate is one or more of hydrated ferric oxide, ferric hydroxide, ferroferric oxide, iron vitriol, ferrous sulfate and ferric sulfate.

Further, more preferably, the organic base, the inorganic base, the strong base and the weak acid salt are one or more of ammonia water, ammonia gas, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, barium oxide, methylamine, ethylamine, propylenediamine, carbonate and bicarbonate;

more preferably, the iron-containing precipitate obtained by using a single cooling crystallization or multiple cooling crystallization method is one or more of ferrous sulfate and ferric sulfate;

more preferably, the iron-containing precipitate obtained by adjusting the pH value of the solution or adding an oxidant is one or more of hydrated iron oxide, ferric hydroxide, ferroferric oxide and iron vitriol;

more preferably, the carbonate and bicarbonate are one or more of carbonate and bicarbonate with cation of potassium, sodium and ammonium.

The design mechanism of the separation method of the invention is as follows:

the invention aims to solve the main problems of realizing low-cost desulfurization of low-grade lead-containing raw materials, extracting and separating valuable elements in the low-cost lead-containing raw materials, and converting the valuable elements into qualified products. The extraction of valuable elements in low-grade lead-containing raw materials is a difficult problem which always troubles the lead-zinc smelting industry, in the traditional lead-zinc smelting industry, the lead-containing raw materials mostly come from raw materials with high lead-zinc content, such as lead concentrate, zinc concentrate, scrapped lead-acid batteries and the like, and the low-grade lead-containing raw materials are greatly idle and lead-zinc resources in the low-grade lead-containing raw materials cannot be fully recovered.

The existing pyrometallurgical process for treating lead-containing raw materials with high lead and zinc contents is mature, lead-zinc compounds are reduced into metallic lead and zinc through reduction smelting, and the lead content in the lead-containing raw materials can not be too low due to energy consumption and additional cost caused by smelting temperature exceeding 1000 ℃. For lead-containing materials with high sulfur content, such as lead sulfate mud, lead plaster and the like, the sulfur content is high, a large amount of sulfur dioxide gas is generated by direct smelting, sulfur in raw materials needs to be removed in advance in the process of smelting lead by a pyrogenic process, desulfurizing agents such as sodium hydroxide and sodium carbonate are mostly used for desulfurization at present, and sodium sulfate with low value is produced as an additional product. Many low-grade lead-containing raw materials, such as low-grade zinc oxide ore, zinc leaching slag, blast furnace dust, and converter dust, contain not only lead but also elements such as zinc, magnesium, calcium, and iron. Generally, common metal sulfates can be dissolved in water, such as zinc, copper, nickel, cobalt, and the like, so non-ferrous metal smelting enterprises such as zinc smelting, copper smelting, and the like use sulfuric acid solution to treat raw materials containing elements such as zinc, copper, and the like, react the element compounds such as zinc, copper, and the like with sulfuric acid to convert the element compounds into soluble sulfates, and further separate and purify the soluble sulfates. However, the solubility of lead and calcium sulfate in sulfuric acid solution is low, and lead and calcium are converted into sulfate and exist in slag after being treated by the sulfuric acid solution by using various raw materials, so that the lead and calcium cannot be effectively extracted. The low-grade lead-containing raw material has complex components, particularly contains a plurality of elements such as lead, zinc, copper, iron, calcium and the like, is difficult to extract valuable metals by using a conventional sulfuric acid solution, is difficult to separate from one another, and has low recovery rate of the valuable metals, and a plurality of low-grade lead-containing raw materials do not have a good treatment method at present and are stored in a large amount.

The invention provides a separation method of a lead-containing raw material, which can separate lead, zinc, calcium, iron and magnesium in the lead-containing raw material into products one by one on the basis of lead-calcium separation, only consumes a small amount of sulfuric acid in the process, and realizes the resource recovery of the low-grade lead-containing raw material.

Specifically, a lead-containing raw material is first mixed with sulfuric acid, a sulfate or the like, and subjected to heat treatment to obtain a pretreated lead-containing raw material a, iron, zinc and magnesium in the lead-containing raw material are converted into soluble zinc sulfate, ferrous sulfate, ferric sulfate and magnesium sulfate, so that the leaching rates of zinc, iron and magnesium in the lead-containing raw material are increased, calcium carbonate and calcium oxide in the lead-containing raw material are converted into gypsum, and lead oxide and lead carbonate are converted into lead sulfate.

The pretreated lead-containing raw material A is reacted with water or an aqueous solution containing sulfate to dissolve soluble sulfate in the pretreated lead-containing raw material A, and in the process, lead and calcium elements in the pretreated lead-containing raw material A are separated from soluble zinc, iron and magnesium in the form of insoluble sulfate precipitates, so that the separation of zinc, iron and magnesium elements from lead and calcium elements in the lead-containing raw material is realized, and then a pretreated lead-containing raw material B and a zinc-containing solution containing zinc, magnesium and iron ions are obtained;

in the process of heat treatment without mixing the lead-containing raw material with sulfuric acid, sulfate and other substances, the lead-containing raw material and a solution containing sulfate are directly reacted, zinc, magnesium and iron elements in the lead-containing raw material are converted into soluble sulfate, lead and calcium are converted into insoluble sulfate, separation of zinc, iron and magnesium elements from lead and calcium elements in the lead-containing raw material is realized, and then the pretreated lead-containing raw material B and a zinc-containing solution containing zinc, magnesium and iron ions are obtained.

For a lead-containing raw material containing iron, a zinc-containing solution contains iron ions, and ferrous sulfate is separated from other sulfates (zinc sulfate, magnesium sulfate and the like) by using a single or multiple cooling crystallization, namely a recrystallization mode by utilizing the fact that a ferrous sulfate solubility temperature curve is different from that of other sulfates to obtain a ferrous sulfate product; or by utilizing the characteristic of low solubility product of ferric hydroxide (ferric oxide), adjusting the dissolved pH value by using alkali (which can be externally added alkali or alkali recovered in a system), and converting ferrous ions and ferric ions into ferric hydroxide, ferric oxide or jarosite precipitates by taking an oxidant as an auxiliary means, thereby realizing the iron removal process of the zinc-containing solution.

The raw material containing lead is widely available, besides lead, zinc, iron, calcium and magnesium elements, impurity elements such as nonferrous metals, arsenic, manganese, copper, cadmium, nickel, cobalt, silver and the like also exist, and the impurity elements also enter the magnesium-containing solution in the process of leaching the magnesium-containing raw material. In order to ensure the quality of magnesium products, impurity ions in the magnesium-containing solution need to be removed. The manganese zinc-containing solution exists in the form of divalent manganese, the arsenic exists in the form of arsenite, and manganese and arsenic can be converted into manganese dioxide and arsenate precipitates by adding oxidants such as hydrogen peroxide, potassium permanganate and the like or introducing air and oxygen for oxidation, so that manganese and arsenic ions in the zinc-containing solution are removed.

As for impurity elements such as copper, cadmium, nickel, cobalt, and silver, the impurity elements in the solution are removed by replacing elements not having zinc activity with metals such as zinc, copper, nickel, cadmium, cobalt, and silver by using metallic zinc.

The above-mentioned purification method of the zinc-containing solution can remove impurities every batch or periodically depending on the composition of the lead-containing raw material.

The zinc in the zinc-containing solution is precipitated in the form of zinc ammonium sulfate, zinc sulfate and a zinc complex by a combined method of evaporative crystallization and cooling crystallization, so that the separation of zinc and magnesium in the solution is realized.

The separated zinc-containing precipitate reacts with carbonate or carbon dioxide to convert all zinc into basic zinc carbonate, so that the aim of separating zinc from basic zinc carbonate is fulfilled, the zinc reacts with the carbonate to generate sulfate-containing solutions, and the sulfate-containing solutions can be returned to other processes needing to supplement sulfate, so that the sulfate can be recycled. The basic zinc carbonate can be used as a zinc smelting raw material or can be decomposed into a zinc oxide product by heating, so that the zinc is converted into a product meeting the standard. And for the lead-containing raw material without magnesium, after zinc is removed from the zinc-containing solution, the solution can be returned to the step A) or the step B) for recycling.

The lead-containing raw material basically contains calcium element, calcium can be converted into slightly soluble calcium sulfate in the zinc soaking process, the solubility of the calcium sulfate in an aqueous solution is not high, but the concentration can still reach 2g/L, and products such as basic magnesium carbonate, magnesium oxide and the like have high calcium content, for example, the calcium oxide content of first-class products in the basic magnesium carbonate is required to be lower than 0.7%, so that the calcium in a zinc-containing solution needs to be subjected to impurity removal. For calcium in the zinc-containing solution, carbonate is used to react with calcium to convert the calcium into calcium carbonate precipitate, and in order to obtain better calcium removal effect, the pH value of the solution is controlled between 7.5 and 9.5 as much as possible during calcium precipitation on the premise that magnesium does not precipitate. Although calcium is removed, the zinc-containing solution still contains a small amount of calcium which cannot be completely precipitated.

For the downstream basic magnesium carbonate product with loose calcium content requirement, the zinc-containing solution can directly react with carbonate or carbon dioxide without removing calcium, magnesium is converted into the basic magnesium carbonate product and reacts with sulfate solution, and the sulfate solution supplements the reaction requirement. Downstream basic magnesium carbonate products with strict requirements on calcium content need to further reduce the calcium content, a zinc-containing solution reacts with alkali to convert magnesium into magnesium hydroxide precipitate, free carbonate does not exist in the solution at the moment, calcium still exists in the form of soluble ions, complete separation of calcium and magnesium is realized, magnesium hydroxide precipitate and sulfate solution are obtained, and the sulfate solution meets the reaction requirements. The obtained magnesium hydroxide solid reacts with carbonate and carbon dioxide to obtain basic magnesium carbonate products.

Lead-containing raw materials often contain fluorine and chlorine ions, and the fluorine ions are converted into calcium fluoride with calcium to enter slag when calcium oxide is used for desulfurization; most of chloride ions are soluble compounds, water can be used for mixing with the lead-containing raw materials in advance, the chloride ions are transferred into the water, and the water containing the chloride ions is subjected to evaporation concentration or reverse osmosis concentration to realize the recycling of the water. For the accumulated chloride ions in the system, chlorine in the system solution can be separated by using ultrafiltration, nanofiltration and reverse osmosis membrane treatment.

And (2) converting the lead-containing raw material into a pretreated lead-containing raw material B after the lead-containing raw material is treated in the steps A) and B), and allowing the pretreated lead-containing raw material B to enter the step 1) to react with a reaction solution containing a solvent and a cosolvent to obtain a lead-containing solution and gypsum residues. In the process, alkali or acid is used for adjusting the pH value of the reaction liquid, and a desulfurizing agent is added to convert lead sulfate in the lead-containing raw material into soluble lead and gypsum precipitate, wherein the desulfurizing agent can be solid directly added into the reaction in the step 1), or a lead precipitation solution or other reaction liquid is pre-reacted with a desulfurizing agent such as calcium oxide, and after impurities are separated, a high-calcium solution with high calcium content is obtained and added into the step 1), so that the exchange of lead and calcium elements in the reaction liquid is realized. After the reaction in the step 1), separating to obtain a lead-containing solution and gypsum residues. The lead-containing solution is then reacted with carbon dioxide (sulfur dioxide, carbonate, sulfite can achieve the same technical effect) to convert lead into lead carbonate (or other lead salt) precipitate. For lead-containing raw materials containing a small amount of or no zinc, magnesium, etc., the lead-containing raw materials may be directly used as the lead-containing raw materials in the step 1) without passing through the steps A), B) and C).

And (3) carrying out a gypsum separation process on the gypsum residues, carrying out step 3) on the gypsum residues, dissolving the gypsum by using the reaction liquid containing the same solvent and cosolvent as the step 1), and controlling the pH value of the reaction liquid by using acid or alkali. Filtering and separating to obtain calcium-containing solution and final tailings. And evaporating the calcium-containing solution, and controlling the ionic strength, the solvent concentration and the like of the calcium-containing solution to realize the crystallization of the gypsum.

In the invention, the solvents and the cosolvent used in the steps 1) and 3) are the same, the solvents play a role in complexing and dissolving, the cosolvent plays a role in regulating ionic strength and the complexing ability of the complexing agent, the reaction solution consisting of the solvents and the cosolvent has better dissolving capacity for elements such as lead, zinc, calcium, copper, nickel, cobalt, cadmium and the like, particularly the dissolving capacity of the reaction solution for calcium is similar to the precipitation capacity of sulfate radicals for calcium, the dissolving-separating process of calcium sulfate in the reaction solution can be realized by regulating the ionic strength of the solution, the concentrations of the solvents and the cosolvent, and meanwhile, the dissolving capacity of the reaction solution for lead is far higher than that of calcium, and the dissolving capacity for lead is far higher than that of lead sulfate and lower than that of lead carbonate. The reaction solution of the invention utilizes the characteristic that excessive lead reacts with the reaction solution, the dissolving capacity of the reaction solution to lead is far higher than that of calcium, the reaction solution is in a state of dissolving lead and insoluble calcium when the excessive lead exists, sulfate radicals in the lead-containing raw material react with calcium to be converted into gypsum precipitate, the dissolution and the desulfurization of lead are synchronously carried out, the lead-containing raw material and the reaction solution are in countercurrent multiple contact, the concentration of calcium in the lead-containing solution is as low as possible, and the content of lead in gypsum residues is as low as possible. After the lead in the lead-containing raw material is leached, the residual gypsum reacts with the reaction solution again, the content of the lead in the gypsum residue is low, and the gypsum is separated and purified by utilizing the controllable dissolution of the reaction solution.

The lead-containing raw material contains a small amount of arsenic, manganese and other impurity elements, and an oxidant can be added into the lead-containing raw material leaching process, the lead-containing solution, the lead precipitation solution, the gypsum residue leaching process, the calcium-containing solution and the calcium precipitation solution to oxidize and convert the arsenic and manganese elements into solids so as to realize separation.

The lead-containing solution contains a small amount of calcium and magnesium, and a precipitator containing oxalate, carbonate, sulfite and the like can be added into the lead-containing solution to convert calcium and magnesium elements in the lead-containing solution into precipitates, so that the quality of lead carbonate products is ensured.

A small amount of lead, zinc and magnesium contained in the gypsum residues are gradually enriched in the solution, and metal ions such as lead, copper, silver and the like can be converted into metal for separation by adding metal zinc into a calcium-containing solution and a calcium-precipitating solution; or adding carbonate or carbon dioxide precipitator into the calcium-containing solution and the calcium precipitation solution to precipitate lead, zinc, magnesium and calcium together to obtain a mixture of lead carbonate, zinc carbonate, magnesium carbonate and calcium carbonate, so as to remove lead, zinc and magnesium elements in the calcium-containing solution and the calcium precipitation solution.

In the process of precipitating magnesium by reacting a magnesium-containing solution with a precipitator and precipitating gypsum by using a calcium-containing solution, in order to obtain a better crystal form of a calcium-magnesium product, a surfactant can be added to control the precipitated crystal form, so that the product has a better micro-morphology.

The calcium carbonate in the lead-containing raw material is converted into gypsum with sulfate and sulfuric acid in the steps A), B) and 1), the sulfate and the sulfuric acid are consumed, the gypsum product has low value, so that part of the calcium sulfate product reacts with carbonate and carbon dioxide according to the consumption condition of the sulfate to be converted into the calcium carbonate product and the sulfate, and the sulfate replenishes the sulfate consumed in the reaction process of the lead-containing raw material.

According to the invention, through the circulation of sulfate and alkali, the lead-calcium separation characteristic of reaction liquid and the combination of the separation technology of zinc, magnesium and lead-calcium, lead-containing raw materials are separated into products of lead carbonate, zinc carbonate, basic magnesium carbonate and calcium carbonate which meet market standards on the premise of consuming a small amount of sulfuric acid.

The invention has the following advantages and beneficial effects:

in the process of treating the lead-containing raw material, the energy consumption cost of the process of treating the lead-containing raw material is reduced by a wet method technology, low-grade valuable elements in the lead-containing raw material are separated and extracted and converted into corresponding high-quality products by mutual separation of lead, calcium, magnesium and zinc, and simultaneously, the low-cost calcium oxide is used for desulfurization, so that the desulfurization cost of the lead-containing raw material is reduced; on the other hand, the method utilizes the sulfate and the alkaline gas discharged by the lead-containing raw material and the sulfate generated in the product carbonization process to realize the circulation of the sulfate and the alkaline gas in the system, reduces the acid and alkali consumed in the treatment process of the lead-containing raw material, realizes the mutual separation of the components in the lead-magnesium raw material by only consuming a small amount of sulfuric acid and heat energy, and has the advantages of low cost and low energy consumption.

In conclusion, the method for treating the lead-containing raw material can effectively recover the low-grade lead-containing raw material which cannot be recovered by the conventional method, and has wide market application prospect.

Drawings

FIG. 1 is a process flow diagram of the present invention.

Detailed Description

For a further understanding of the present invention, reference is made to the following description taken in conjunction with the accompanying drawings and examples, which are provided for purposes of illustration and are not intended to limit the scope of the invention.

Example 1:

(1) adding 10kg of zinc oxide ore (containing zinc 7.5%, lead 1.1%, calcium 10.4% and magnesium 1.5%) into a 50L reaction kettle, adding water to a constant volume of 50L, adjusting the pH value to 1.0-1.2 by using sulfuric acid, reacting at 50 ℃ for 5h, and filtering to obtain 45L of zinc-containing solution and 11.5kg of filter residue;

(2) adjusting the pH value of the filtrate obtained in the step (1) to 3.0 by using sodium hydroxide, reacting for 5 hours at 100 ℃, and filtering to obtain iron oxide slag and filtrate;

(3) adding 50g of zinc powder into the filtrate obtained in the step (2), reacting for 4 hours, and filtering to obtain purified slag and filtrate;

(4) adding 100ml of 30% hydrogen peroxide and 700g of ammonium carbonate into the filtrate obtained in the step (3), reacting for 3 hours at the temperature of 60 ℃, and filtering to obtain filtrate and purified residues;

(5) adding the filtrate obtained in the step (4) into another reaction kettle, heating and evaporating to 25L, cooling to 20 ℃, and filtering to obtain zinc ammonium sulfate solid and filtrate;

(6) transferring the ammonium zinc sulfate solid obtained in the step (5) into another reaction kettle, adding 25L of water, adjusting the pH value to be between 8.5 and 8.8 by using ammonia water, introducing carbon dioxide for 5 hours at 1000ml/min, filtering, washing and drying to obtain 1.15kg of basic zinc carbonate product;

(7) transferring the filtrate obtained in the step (6) into another reaction kettle, adding 5L of 30% ammonia water, maintaining the reaction temperature at 90 ℃, the reaction pressure at 0.15MPa and the reaction time for 5h, and filtering to obtain magnesium hydroxide precipitate and sulfate filtrate;

(8) and (4) transferring the magnesium hydroxide precipitate obtained in the step (7) into another reaction kettle, adding 5L of water, adjusting the pH value to be 9.5-9.7 by using 30% ammonia water, introducing carbon dioxide at 1000ml/min, reacting for 5 hours, separating, washing and drying to obtain 490g of basic magnesium carbonate product.

(9) Adding 150g of ammonium sulfate, 30g of magnesium sulfate, 30g of copper sulfate, 30g of zinc sulfate, 70g of calcium chloride, 25g of mirabilite, 15g of citric acid, 50g of ethylenediamine tetraacetic acid, 100g of diethylenetriamine pentaacetic acid and 150g of triethylenetetramine hexaacetic acid into a 2L reaction kettle, and adding water to a constant volume of 2L;

(10) adding the filter residue of 1/10 obtained in the step (1) and 50g of calcium oxide into the solution obtained in the step (9), heating to 80 ℃, stirring for reaction for 1h, adjusting the pH value of the solution to 9.8-10.0 by using sodium hydroxide, and filtering to obtain gypsum residue and a lead-containing solution;

(11) using the lead-containing solution obtained in the step (10) as the solution obtained in the step (9) in the step (10), and circularly reacting for 9 times to obtain the lead-containing solution and gypsum residues;

(12) adding 5g of oxalic acid and 5g of phosphoric acid into the lead-containing solution obtained in the step (11), reacting for 5 hours at 60 ℃, and filtering to obtain filtrate and purification residues;

(13) introducing carbon dioxide into the solution obtained in the step (12) at a speed of 200ml/L, adjusting the pH value of the solution to 8.5-8.8 by using potassium hydroxide, reacting at the temperature of 80 ℃ for 5 hours, and after the reaction is finished, separating, washing and drying to obtain 180g of lead carbonate products;

(14) transferring the gypsum residue obtained in the step (11) into a 40L reaction kettle, adding 3kg of ammonium sulfate, 600g of magnesium sulfate, 600g of copper sulfate, 600g of zinc sulfate, 1400g of calcium chloride, 1000g of mirabilite, 300g of citric acid, 1000g of ethylene diamine tetraacetic acid, 2000g of diethylenetriamine pentaacetic acid, 3000g of triethylenetetramine hexaacetic acid, adding water to a constant volume of 40L, adjusting the pH value of the solution to 10.0 +/-0.1 by using ethanolamine, reacting at the temperature of 80 ℃, reacting for 5 hours, and filtering to obtain filtrate and tailings;

(15) and (4) adding sulfuric acid into the filtrate obtained in the step (14), adjusting the pH value of the solution to be 7.0-7.5, separating out gypsum, reacting at the temperature of 80 ℃ for 5 hours, separating, washing and drying to obtain 4.05kg of gypsum product.

Example 2:

(1) adding 100g of lead paste (containing 70.5% lead) of a scrapped lead-acid battery into a 1L reaction kettle, adding 50g of sodium sulfate, 35g of cobalt chloride, 15g of nickel nitrate, 25g of nitrilotriacetic acid, 100g of hydroxyethyl ethylenediamine triacetic acid, 25g of ethylenediamine and 100g of diethylenetriamine, adding water to a constant volume of 1L, adjusting the pH value to be 9.9-10.5 by using sodium hydroxide, adding 30g of calcium oxide, reacting at the reaction temperature of 60 ℃ for 5h, and filtering to obtain 1L of lead-containing solution and 70g of filter residue;

(2) adding 5g of sodium carbonate into the lead-containing solution obtained in the step (1), reacting for 1h at 70 ℃, and filtering to obtain filtrate and purification residues;

(3) introducing carbon dioxide into the solution obtained in the step (2) at a speed of 290ml/L, adjusting the pH value of the solution to 7.0-7.5 by using sodium hydroxide, reacting at the temperature of 50 ℃ for 4 hours, and after the reaction is finished, separating, washing and drying to obtain 98g of lead carbonate products;

(4) transferring the gypsum residue obtained in the step (1) into a 1L reaction kettle, adding 50g of sodium sulfate, 35g of cobalt chloride, 15g of nickel nitrate, 25g of nitrilotriacetic acid, 100g of hydroxyethyl ethylenediamine triacetic acid, 25g of ethylenediamine and 100g of diethylenetriamine, adding water to a constant volume of 1L, adjusting the pH value to be 10.4-10.9 by using sodium hydroxide, reacting at the temperature of 40 ℃ for 2h, and filtering to obtain filtrate and tailings;

(5) and (4) heating the filtrate obtained in the step (4) to boiling, reducing the pH value of the solution to 7.6-7.8, separating out gypsum, reacting at the temperature of 110 ℃ for 4 hours, separating, washing and drying to obtain 160g of gypsum product.

Example 3:

(1) mixing 50kg of blast furnace dust (containing 9.1% zinc, 2.3% lead, 40.5% iron and 2.7% calcium) with 20kg of ammonium sulfate, performing heat treatment at 200 deg.C for 5h, heating to 500 deg.C, continuing heat treatment for 5h, absorbing gas generated during heat treatment with water as alkali solution, and cooling;

(2) adding the treated blast furnace ash obtained in the step (1) into a 100L reaction kettle, adding 1kg of sodium sulfate, adding water to a constant volume of 100L, adjusting the pH value to be between 0.8 and 1.0 by using sulfuric acid, reacting at the temperature of 90 ℃ for 5h, filtering, and washing a filter cake by using 20L of water to obtain 100L of zinc-containing solution and 41kg of filter residue;

(3) adjusting the pH value of the filtrate obtained in the step (2) to be more than 4.0 by using alkali liquor, reacting for 4 hours at 95 ℃, and filtering to obtain jarosite slag and filtrate;

(4) adding 1kg of zinc powder into the filtrate obtained in the step (3), reacting for 4h, and filtering to obtain purified slag and filtrate;

(5) adding 600ml of 30% hydrogen peroxide into the filtrate obtained in the step (4), reacting for 5 hours at 50 ℃, and filtering to obtain filtrate and purification residues;

(6) adding the filtrate obtained in the step (5) into another reaction kettle, heating and evaporating to 80L, cooling to-10 ℃, and filtering to obtain zinc-ammonium complex solid and filtrate;

(7) transferring the zinc ammonium complex obtained in the step (6) into another reaction kettle, adding 50L of water, adjusting the pH value to 7.0-7.8 by using sodium hydroxide, adding 8kg of ammonium carbonate, reacting for 7 hours at 40 ℃, filtering, washing and drying to obtain 7.75kg of basic zinc carbonate product;

(8) adding 50g of magnesium chloride, 50g of sodium sulfate, 50g of potassium sulfate, 150g of sodium chloride, 25g of diethanolamine, 100g of histidine, 45g of glycine, 2g of tetrahydroxypropyl ethylenediamine and 15g of methylenehydroxy phosphate into a 2L reaction kettle, and adding water to fix the volume to 2L;

(9) adding the filter residue of 1/40 obtained in the step (2) and 7g of calcium oxide into the solution obtained in the step (8), heating to 80 ℃, stirring for reaction for 2h, adjusting the pH value of the solution to 8.2-8.5 by using alkali liquor, and filtering to obtain gypsum residue and a lead-containing solution;

(10) using the lead-containing solution obtained in the step (9) as the solution obtained in the step (8) in the step (9), and circularly reacting until the concentration of calcium in the lead-containing solution is lower than 5g/L to obtain the lead-containing solution and gypsum residues;

(11) adding 10g of trisodium phosphate into the lead-containing solution obtained in the step (10), reacting for 2 hours at 80 ℃, and filtering to obtain filtrate and purification residues;

(12) introducing carbon dioxide into the solution obtained in the step (11) at the speed of 500ml/min, adjusting the pH value of the solution to 9.3-9.8 by using potassium hydroxide, reacting at the temperature of 30 ℃ for 2h, and after the reaction is finished, separating, washing and drying to obtain 430g of lead carbonate products;

(13) transferring 1kg of gypsum residue obtained in the step (10) into a 5L reaction kettle, adding 20g of magnesium chloride, 50g of sodium sulfate, 75g of potassium sulfate, 10g of potassium chloride, 5g of triethanolamine, 10g of alanine, 200g of glycine and 5g of tartaric acid, adding water to a constant volume of 2L, adjusting the pH value of the solution to 8.5 +/-0.1 by using ammonia water, reacting at the temperature of 60 ℃ for 4h, and filtering to obtain filtrate and tailings;

(14) and (4) adding hydrochloric acid into the filtrate obtained in the step (13), adjusting the pH value of the solution to be 7.1-7.3, separating out gypsum, reacting at the temperature of 60 ℃ for 5 hours, separating, washing and drying to obtain 0.3kg of gypsum product.

Example 4:

(1) adding 1000g of lead sulfate mud (containing 26.8% of lead, 5.5% of zinc and 1.9% of calcium) into a 2L reaction kettle, adding 100g of ammonium acetate, 5g of copper chloride, 20g of nickel sulfate, 200g of alanine, 20g of tetraethyl amine, 50g of serine, 10g of nitrilotriacetic acid and 20g of ethylene glycol diethyl ether diamine tetraacetic acid, adding water to a constant volume of 2L, adjusting the pH value to be between 7.0 and 7.5 by using ammonia gas, adding 100g of calcium oxide, reacting at the reaction temperature of 30 ℃ for 4h, and filtering to obtain 2L of lead-containing solution and filter residue;

(2) adding 20g of oxalic acid into the lead-containing solution obtained in the step (1), reacting for 1h at 60 ℃, and filtering to obtain filtrate and purification residues;

(3) introducing carbon dioxide into the solution obtained in the step (2) at the speed of 1L/min, adjusting the pH value of the solution to 6.0-6.5 by using sodium hydroxide, reacting at the temperature of 30 ℃ for 2h, and after the reaction is finished, separating, washing and drying to obtain 309g of lead carbonate product;

(4) transferring the gypsum residue obtained in the step (1) into a 2L reaction kettle, adding 100g of ammonium acetate, 5g of copper chloride, 20g of nickel sulfate, 200g of alanine, 20g of tetraethylpentamine, 50g of serine, 10g of nitrilotriacetic acid and 20g of ethylene glycol diethyl ether diamine tetraacetic acid, adding water to a constant volume of 2L, adjusting the pH value to be 7.9-8.2 by using sodium hydroxide, reacting at the temperature of 20 ℃ for 5h, and filtering to obtain filtrate and tailings;

(5) and (4) heating the filtrate obtained in the step (4) at 40 ℃ and reducing the pressure to boil, stopping the reaction when the concentration of calcium ions in the solution is reduced to be below 5g/L, separating, washing and drying to obtain 247g of gypsum product.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for separating a lead-containing raw material is characterized by comprising the following steps: the method is used for separating lead-containing raw materials, and specifically comprises the following steps:

(1) reacting a reaction solution containing a solvent, a cosolvent, a catalyst and sulfate with a lead-containing raw material, controlling the pH value of the solution to be between 5.0 and 12.0, and separating to obtain gypsum residues and a lead-containing solution after the reaction is finished;

(2) adding a precipitator A or a solution containing the precipitator A into a lead-containing solution for reaction, controlling the pH value of the solution to be between 5.5 and 12.0, and separating after the reaction is finished to obtain a lead precipitation solution and a lead-containing precipitate;

(3) reacting a reaction solution containing a solvent, a cosolvent, a catalyst and sulfate with the gypsum residue obtained in the step (1), controlling the pH value of the solution to be 5.5-12.0, and separating to obtain tailings and a calcium-containing solution after the reaction is finished;

(4) adjusting the pH value of the calcium-containing solution to 4.0-10.0 by volatilizing alkaline gas or adding acidic compound to separate calcium sulfate solid from the calcium-containing solution, and separating to obtain calcium-containing precipitate and calcium precipitation solution.

2. The method for separating a lead-containing raw material according to claim 1, wherein: the lead-containing raw material comprises lead oxide ore, oxide product of galena, zinc sulfide ore, oxide product of zinc sulfide ore, zinc oxide ore, flue ash containing lead, lead-containing waste material in the production process of lead-acid battery, lead plaster of scrap lead-acid battery and thermal decomposition product thereof, desulfurization product of lead plaster of scrap lead-acid battery, zinc hypoxide, zinc-containing smoke dust, lead-containing smoke dust, dust and wastewater treatment sludge collected by a dust collector (removing) device in the regeneration process of lead-zinc copper, wastewater treatment sludge produced in the smelting process of lead-zinc copper, hot acid leaching jarosite method of zinc roasting ore in the smelting process of lead-zinc, lead-silver slag produced by hot acid leaching goethite method, lead oxide slag and alkali slag produced by cathode refining in the smelting process of lead, scum and bottom mud produced in the smelting process of lead, various types of smoke dust collected by dry type dust collectors in the smelting process of lead-zinc, zinc slag produced by a zinc rectifying furnace in the smelting process of lead-zinc, Blast furnace scum generated by a blast furnace zinc smelting vapor condensation separation system in the lead-zinc smelting process, zinc oxide leaching slag generated by zinc oxide leaching treatment in the lead-zinc smelting process, casting scum generated by cathode zinc casting in the lead-zinc smelting process, sulfur slag (leaching slag) generated by zinc sulfide ore atmospheric pressure oxygen leaching or pressure oxygen leaching, jarosite slag generated by jarosite hot acid leaching of zinc roasted ore in the lead-zinc smelting process, leaching slag generated by zinc roasted ore conventional leaching method in the lead-zinc smelting process, wastewater treatment sludge generated in the crude zinc refining process, one or more of dust and wastewater treatment sludge collected by a dust collecting (removing) device in the steel smelting and processing process and lead-containing sludge; the adding amount of the lead-containing raw material in the reaction solution is 1-1000 g/L.

3. The method for separating a lead-containing raw material according to claim 1, wherein: in the steps (1) and (3), the solvent in the reaction solution is ammonia, methylamine, ethylamine, ethylenediamine, propylenediamine, aniline, ethanolamine, diethanolamine, triethanolamine, imidazole, diethylenetriamine, triethylenetetramine, tetraethylpentamine, ethylenediaminetetraacetic acid, propylenediaminediacetic acid, ethylenediamine diacetic acid, ethyleneglycoldimethylethylenediamine tetraacetic acid, diethyletherdiamine tetraacetic acid, propylenediaminetetraacetic acid, hydroxyethylethylenediamine triacetic acid, tetrahydroxypropylethylenediamine, 2-aminobenzoic acid-N, N-diacetic acid, diethylthioetherdiamine tetraacetic acid, sulfosalicylic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, cyclohexanediaminetetraacetic acid, nitrilotriacetic acid, glutamic acid, valine, histidine, aspartic acid, leucine, isoleucine, alanine, proline, serine, phenylalanine, arginine, threonine, glycine, leucine, isoleucine, alanine, proline, serine, phenylalanine, arginine, threonine, glycine, or a mixture thereof, One or more of imino disuccinic acid selected from lysine, asparagine, glutamine, methionine, ornithine, taurine, citrulline and sarcosine; the concentration of the solvent in the reaction liquid is 0.1-6.0 mol/L;

the cosolvent is a sulfate, chloride, formate, acetate, malonate, benzoate, phosphate, citrate, tartrate or succinate of sodium, potassium, ammonium, magnesium, calcium, zinc, manganese, nickel, copper, chromium or lead ions; the concentration of the cosolvent in the reaction liquid is 0.1-6.0 mol/L;

4. The method for separating a lead-containing raw material according to claim 1, wherein: in the step (2), the precipitant A is one or more of sulfite, bisulfite, sulfurous acid, sulfur dioxide, carbonate, bicarbonate, carbon dioxide and carbon dioxide aqueous solution;

in the step (2), the lead-containing precipitate is one or more of lead carbonate, basic sodium lead carbonate and lead sulfite;

in the steps (1) to (4), the acidic compound is one or more of organic acid, inorganic acid, strong acid, weak base salt and acid salt;

in the steps (1) to (4), the calcium-containing precipitate is one or more of dihydrate gypsum, semi-hydrate gypsum and anhydrous gypsum; the alkaline gas is one or more of ammonia gas, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, methylamine, ethylamine and propylenediamine.

5. The method for separating a lead-containing raw material according to claim 1, wherein: in the step (1), the lead-containing raw material is used after being pretreated, and the pretreatment comprises the following steps:

6. The method for separating a lead-containing raw material according to claim 5, wherein: treating the zinc-containing solution obtained in the step (B) according to the following steps:

7. The method for separating a lead-containing raw material according to claim 6, wherein: in the step (C), the evaporation crystallization temperature is 20-150 ℃, the cooling crystallization temperature is-50-100 ℃, and the precipitant B is one or more of sulfite, bisulfite, sulfurous acid, sulfur dioxide, carbonate, bicarbonate, carbon dioxide and carbon dioxide aqueous solution; the zinc-containing precipitate is one or more of zinc hydroxide, basic zinc sulfate, zinc sulfite, zinc carbonate, basic zinc carbonate, zinc ammonium sulfate and zinc ammonium sulfate complex;

in the step (D), the precipitant C is one or more of ammonia water, ammonia, urea, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium oxide, calcium hydroxide, methylamine, ethylamine, propylenediamine, carbonate, bicarbonate, carbon dioxide, sulfur dioxide, sulfite and bisulfite; the magnesium-containing precipitate is one or more of magnesium hydroxide, magnesium sulfite, ammonium magnesium sulfate, magnesium carbonate, basic magnesium carbonate and basic magnesium sulfate.

8. The method for separating a lead-containing raw material according to claim 1, wherein: in the step (1), metal lead is added into the obtained lead-containing solution, so that metal copper and/or silver which is not active by lead in the lead-containing solution reacts with the metal lead and is replaced by corresponding metal, and copper and/or silver ions in the lead-containing solution are removed.

9. The method for separating a lead-containing raw material according to claim 5, wherein: adding metal zinc into the calcium-containing solution obtained in the step (3) or the zinc-containing solution obtained in the step (B), so that metals (including copper, cadmium, nickel, iron, lead, cobalt and silver) without zinc activity in the solution react with the metal zinc and are replaced by corresponding metals to remove metal ions (copper, cadmium, nickel, iron, lead, cobalt and silver ions) without zinc activity in the solution;

adding an oxidant to the lead-containing solution obtained in the step (1) or the solution in the process of the reaction in the step (1) or the calcium-containing solution obtained in the step (3) or the solution in the process of the reaction in the step (3) or the zinc-containing solution obtained in the step (B) or the solution in the process of the reaction in the step (B), and precipitating and separating arsenic or manganese in a solid form; the oxidant is one or more of hydrogen peroxide, manganese dioxide, potassium permanganate, air, oxygen and oxygen-enriched air.

10. The method for separating a lead-containing raw material according to claim 6, wherein: adding one or more of carbon dioxide, carbonate, bicarbonate, bisulfite, phosphate, oxalate and oxalic acid into the lead-containing solution obtained in the step (1), the lead-precipitating solution obtained in the step (2), the calcium-containing solution obtained in the step (3) or the zinc-precipitating solution obtained in the step (C), converting the lead, zinc, magnesium or calcium in the solution into carbonate, sulfite, oxalate or phosphate for precipitation, and controlling the pH value of the solution to be between 4.0 and 12.0 by using one or more of organic acid, inorganic acid, organic base, inorganic base, strong base, weak base, strong acid, weak base and acid salt in the precipitation process.

11. The method for separating a lead-containing raw material according to claim 6, wherein: adding an ionic strength regulator or a solution polarity regulator or a surfactant to the solution in the step (2) or the step (4) or the step (C); the ionic strength regulator is one or more of carbonate, nitrate, chloride, fluoride, acetate, oxalate, phosphate, citrate, pyrophosphate, tartrate and perchlorate of sodium, potassium, ammonium or magnesium ions, and the concentration of the ionic strength regulator is not more than 4.5 mol/L; the solution polarity regulator is one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, glycerol, N-methyl pyrrolidone, N-butanol, formaldehyde, acetaldehyde, benzaldehyde, acetone, butanone, cyclohexanone, formic acid, acetic acid and propionic acid, and the concentration is not more than 15.0 mol/L; the surfactant is anionic surfactant, cationic surfactant, zwitterionic surfactant or nonionic surfactant; the surfactant is stearic acid, oleic acid, lauric acid, quaternary ammonium salt, cocamidopropyl betaine, dodecyl amino propionic acid, isomeric alcohol polyoxyethylene polyoxypropylene ether, polyvinylpyrrolidone, octylphenol polyoxyethylene ether, polyethylene glycol octylphenyl ether, polyoxyethylene sorbitan fatty acid ester, sodium dodecyl sulfonate, sodium dodecyl sulfate, potassium dodecyl sulfate, diethyl sulfite, malonic acid, sorbitol, sodium glutamate, aluminum sulfate, hexadecyl trimethyl ammonium chloride, catechol-3, 5-sodium disulfonate, rose red ammonium tricarboxylate, sodium diethyldithiocarbamate, xylenol orange, chromotropic acid, chrome black T, chrome black A, tetraethylene pentamine, triethylene tetramine, sodium pyrophosphate, sodium tripolyphosphate, dodecyl trimethyl ammonium chloride, benzyl triethyl ammonium chloride, gelatin, sodium lauryl sulfate, sodium dodecyl sulfate, diethyl sulfite, sorbitol, sodium glutamate, aluminum sulfate, hexadecyl trimethyl ammonium chloride, catechol-3, 5-sodium disulfonate, rose red ammonium tricarboxylate, sodium diethyldithiocarbamate, One or more of bone glue, Arabic gum, polyvinyl alcohol, polyethylene glycol, polymethyl acrylamide and alkylphenol polyoxyethylene, and the adding amount is not more than 10 g/L.

12. The method for separating a lead-containing raw material according to claim 6, wherein: reacting the calcium-containing precipitate obtained in the step (4), the zinc-containing precipitate obtained in the step (C) or the magnesium-containing precipitate obtained in the step (D) with a precipitator D, wherein an alkaline substance is used for controlling the pH value of the solution to be 6-12 to obtain a sulfate solution and a carbonate compound, and the sulfate solution is directly or after crystallization and is returned to the steps (1), (2), (3) and (4) to be used as sulfate; the precipitant D is one or more of carbonate, bicarbonate and carbon dioxide; the alkaline substance is one or more of ammonia water, ammonia gas, urea, sodium hydroxide, potassium hydroxide, methylamine, ethylamine, propylenediamine, carbonate and bicarbonate; the carbonate compound is one or more of calcium carbonate, magnesium carbonate, basic magnesium carbonate, zinc carbonate and basic zinc carbonate.

13. The method for separating a lead-containing raw material according to claim 6, wherein: adding a desulfurizing agent or a solution containing the desulfurizing agent into the reaction solution obtained in the step (1) to convert sulfate radicals in the lead-containing raw material into gypsum precipitates; the desulfurizer is one or more of calcium oxide, barium oxide, calcium hydroxide and barium hydroxide; the solution containing the desulfurizer is obtained by separating any one of the solution in the steps (1), (2), (3), (4), (B), (C) and (D) after contacting the desulfurizer.

14. The method for separating a lead-containing raw material according to claim 6, wherein: converting iron in the zinc-containing solution obtained in the step (B) into iron-containing precipitate by using a method of single cooling crystallization or multiple cooling crystallization or solution pH value adjustment or oxidant addition; the method for adjusting the pH value of the solution comprises the following steps; adjusting the pH value of the solution to 1.5-10.0 by using one or more of organic alkali, inorganic alkali and strong alkali and weak acid salt; the temperature of the cooling crystallization is-50-100 ℃; the oxidant is one or more of hydrogen peroxide, manganese dioxide, potassium permanganate, air, oxygen and oxygen-enriched air; the iron-containing precipitate is one or more of hydrated ferric oxide, ferric hydroxide, ferroferric oxide, iron vitriol, ferrous sulfate and ferric sulfate.