CN110257640B - Method for comprehensively recycling circuit board incineration ash - Google Patents

Method for comprehensively recycling circuit board incineration ash Download PDF

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CN110257640B
CN110257640B CN201910678545.0A CN201910678545A CN110257640B CN 110257640 B CN110257640 B CN 110257640B CN 201910678545 A CN201910678545 A CN 201910678545A CN 110257640 B CN110257640 B CN 110257640B
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zinc
circuit board
copper
lead
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CN110257640A (en
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刘勇
吕昊子
陈志强
吕建芳
吕先瑾
胡红喜
饶金山
刘超
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Institute of Resource Utilization and Rare Earth Development of Guangdong Academy of Sciences
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Guangdong Institute of Resources Comprehensive Utilization
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00—Obtaining lead
    • C22B13/04—Obtaining lead by wet processes
    • C22B13/045—Recovery from waste materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C22B15/0091—Treating solutions by chemical methods by cementation
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B25/00—Obtaining tin
    • C22B25/04—Obtaining tin by wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B25/00—Obtaining tin
    • C22B25/06—Obtaining tin from scrap, especially tin scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02—Working-up flue dust
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a method for comprehensively recycling circuit board incineration ash, which comprises the steps of concentrated sulfuric acid mixing, heating dry distillation, cooling absorption, chlorine gas replacement, lime slurry absorption, water dissolution, zinc oxide neutralization, zinc powder replacement and ammonium acetate dissolution. The invention has the advantages of high comprehensive utilization rate, high added value, low toxicity, harmlessness and the like, has wider adaptability to raw materials, does not relate to high-temperature and high-alkali operation, is easy to implement and control, has higher economic feasibility and has favorable application prospect.

Description

Method for comprehensively recycling circuit board incineration ash
Technical Field
The invention relates to a method for comprehensively recycling circuit board incineration ash, belonging to the technical field of comprehensive utilization of industrial solid waste resources.
Background
The circuit board is a support body for most widely used electronic components and is an important carrier for mutual connection of the electronic components. With the continuous development of electronic manufacturing technology, a large number of old manufactured electric appliances are discarded, and a large number of waste circuit boards requiring urgent treatment are generated. The waste circuit board contains valuable metals such as copper, lead, zinc, tin, gold, silver, palladium and the like, and has comprehensive recovery value. The recovery process of valuable metals of the waste circuit boards mainly comprises mechanical sorting, heat treatment, chemical treatment, microbial treatment and the like, the heat treatment method is the most widely applied circuit board treatment process at present, and the incineration method is the most main heat treatment method. A large amount of incineration ash can be generated in the circuit board incineration process, and a large amount of copper, lead, zinc, tin, gold, silver, palladium and other metals are enriched in the part of ash, the content of the ash is far higher than that of common mineral resources, and the ash has extremely high comprehensive utilization value.
According to statistics, the amount of waste circuit boards treated in China is more than million tons every year, and the yield of related incineration ash is about 2 million tons. Because the circuit board contains a large amount of resin organic matters containing bromine and chlorine, the content of chlorine and bromine in the incineration ash is generally higher. The existence of chlorine and bromine can bring adverse effect to the recovery of valuable metals in the ash, and the existing recovery process is difficult to realize the high-efficiency comprehensive recovery of various valuable metals in the incineration ash. In order to realize the high-efficiency comprehensive recovery of nonferrous metals such as copper, lead, zinc, tin, gold, silver, palladium and the like and noble metals, the pretreatment of the circuit board incineration ash needs to be carried out by adopting a proper bromine and chlorine removal process.
Disclosure of Invention
The invention provides a method for comprehensively recycling circuit board incineration ash, which is used for removing and recycling bromine and chlorine in the circuit board incineration ash by adopting a sulfuric acid low-temperature dry distillation technology, then respectively recycling copper, lead, zinc and tin one by adopting a targeted technical scheme, and realizing the high-efficiency enrichment of precious metals such as cash, silver, palladium and the like. The invention has the advantages of high comprehensive utilization rate, high added value, low toxicity, harmlessness and the like.
In order to achieve the technical aim, the invention adopts the technical scheme that: a method for comprehensively utilizing circuit board incineration ash comprises the following specific steps:
(1) mixing concentrated sulfuric acid: uniformly mixing the circuit board incineration ash and concentrated sulfuric acid, wherein the mass ratio of the circuit board incineration ash to the concentrated sulfuric acid is 1: 0.8-1: 1.2, and obtaining an ash acid mixture;
(2) heating and dry distillation: heating and dry distilling the ash acid mixture obtained in the step (1), wherein gas generated in the dry distilling process is called dry distilling gas, and the residue of the dry distilling is dry distillation slag;
(3) cooling and absorbing: carrying out gas cooling and spray water cyclic absorption on the dry distillation gas in the step (2), wherein the obtained acid solution is bromine and chloric acid solution, and the residual waste gas after cyclic absorption of the spray water is SO2An exhaust gas;
(4) replacement with chlorine gas: introducing circulating chlorine gas into the bromine and chloric acid solution obtained in the step (3) to carry out a chlorine gas displacement reaction, wherein the displaced bromine is precipitated at the bottom in a liquid state, and the aqueous solution at the upper part is a hydrochloric acid solution;
(5) lime slurry absorption: SO obtained in the step (3)2Introducing the waste gas into lime slurry to obtain lime slurry precipitate, wherein the lime slurry precipitate is calcium sulfite;
(6) dissolving in water: adding water into the dry distillation residues in the step (2) to dissolve soluble substances to obtain a dissolved solution and undissolved residual substances, wherein the undissolved residual substances are crude lead residues mainly containing lead sulfate, and the dissolved solution is acidic polymetallic liquid containing copper, zinc and tin;
(7) zinc oxide neutralization: adding fine-grained zinc oxide into the acidic multi-metal liquid obtained in the step (6) for neutralization, wherein the obtained nascent precipitate is a tin-containing precipitate mainly containing tin basic sulfate, and the neutralized solution is a copper-zinc solution mainly containing copper sulfate and zinc sulfate;
(8) zinc powder replacement: adding zinc powder into the copper-zinc solution obtained in the step (7) for copper replacement, wherein the replaced simple substance copper forms a precipitate, and the solution after copper replacement is zinc sulfate crude solution mainly containing zinc sulfate;
(9) dissolving ammonium acetate: and (4) dissolving the crude lead slag obtained in the step (6) by using an ammonium acetate solution to obtain a final insoluble substance and an ammonium lead crude liquid, wherein the final insoluble substance is the precious metal slag with highly enriched precious metals such as gold, silver and the like, and lead is mainly added into the ammonium lead crude liquid.
In the step (2), the heating and dry distillation are carried out at the dry distillation temperature of 150-250 ℃ for 1.5-2.0 h.
And (4) circularly absorbing by using the spray water in the step (3) until the pH of the absorption liquid reaches-0.6 to-0.8.
The chlorine gas introducing speed in the step (4) is 2.5-3L/(L.min), namely the gas introducing amount of 1L bromine and chloric acid liquid per minute is 2.5-3L, and the chlorine gas replacement reaction time is 30-45 min.
In the step (5), the concentration of the lime slurry is 40-50%, and the dosage of the lime slurry is 5-7L/m3。
In the step (6), the mass ratio of the dry distillation residues to the water is 1: 3-1: 5.
And (4) adding zinc sulfate to neutralize in the step (7), wherein the pH value of the solution is 4.5-5 at the end point of neutralization.
In the step (9), the concentration of the ammonium acetate solution is 10-15%, and the dosage of the ammonium acetate solution is 7-8L/kg relative to the crude lead slag.
The principle of the invention is as follows: under the strong acid environment, bromine, chlorine and H can react+HBr and HCl are formed in combination, the HBr and HCl being volatile substances, H2SO4(sulfuric acid) belongs to a substance which is difficult to volatilize, HBr and HCl can be volatilized relatively stably and efficiently at the dry distillation temperature of 150-250 ℃ limited by the invention, and SO is generated as little as possible2And when the exhaust gas is exhausted, the volatilized HBr and HCl can be efficiently absorbed and collected by water, so that the bromine and chlorine in the soot can be removed.
The invention has the beneficial effects that:
(1) according to the method for comprehensively utilizing the circuit board incineration ash, bromine and chlorine in the ash are removed by a low-temperature dry distillation technology for the first time, and a targeted recovery process is used in cooperation, so that independent products of bromine, chlorine, tin, copper, zinc and lead can be obtained respectively, highly enriched precious metal slag can be obtained, and the high-efficiency utilization of the circuit board incineration ash is finally realized.
(2) The method has the advantages of reasonable process flow, wide adaptability to raw materials, no high-temperature and high-alkali operation, easy implementation and control, high economic feasibility and good industrial prospect.
(3) The method not only comprehensively utilizes the circuit board incineration ash, but also is environment-friendly, low in toxicity and harmless, is beneficial to the environment, and provides technical support for efficient and comprehensive utilization of the circuit board incineration ash.
(4) The invention has high economic feasibility and good application prospect.
Drawings
FIG. 1 is a flow chart of the method for comprehensively recycling the incineration ash of the circuit board.
Detailed Description
The invention is further illustrated by the following figures and examples.
Example 1: the soot sample of this example is from an environmental protection company in corridor city of Hebei, and the contents of bromine, chlorine, copper, lead, zinc and tin are respectively 28.4%, 12.1%, 5.4%, 4.6%, 6.4% and 8.5%, and the contents of noble metals gold and silver are respectively 16g/t and 153g/t, as shown in FIG. 1, and the soot sample is recovered according to the following steps:
(1) mixing concentrated sulfuric acid: uniformly mixing the circuit board incineration soot (hereinafter referred to as soot) and concentrated sulfuric acid, wherein the mass ratio of the soot to the concentrated sulfuric acid is 1:1.2, and uniformly mixing to obtain an ash acid mixture;
(2) heating and dry distillation: heating and dry distilling the ash acid mixture obtained in the step (1), wherein the dry distilling temperature is 250 ℃, the dry distilling time is 2.0 hours, the gas generated in the dry distilling process is dry distilling gas, and the residue of the dry distilling is dry distilling slag;
(3) cooling and absorbing: performing gas cooling and spray water cyclic absorption on the dry distillation gas in the step (2), wherein the absorption cyclic end point is that the pH value of absorption liquid reaches-0.6, the obtained acid solution is bromine and chloric acid liquid, and the residual waste gas after absorption is SO2An exhaust gas;
(4) replacement with chlorine gas: introducing circulating chlorine into the bromine and chloric acid solution obtained in the step (3), wherein the introducing speed of the chlorine is 3L/(L.min) relative to the chlorine bromine and chloric acid solution, the displacement reaction time of the chlorine is 45min, the displaced bromine is precipitated at the bottom in a liquid state, and the aqueous solution at the upper part is hydrochloric acid solution;
(5) lime slurry absorption: will be provided withSO of step (3)2Introducing the waste gas into lime slurry to obtain lime slurry precipitate, wherein the concentration of the lime slurry is 50%, and the dosage of the lime slurry is 7L/m3The lime slurry precipitate is calcium sulfite;
(6) dissolving in water: adding water into the dry distillation residues in the step (2) for soluble substance dissolution to obtain a dissolved solution and undissolved residual substances, wherein the mass ratio of the dry distillation residues to the water is 1:3, the undissolved residual substances are crude lead residues mainly containing lead sulfate, and the dissolved solution is acidic polymetallic liquid mainly containing copper, zinc and tin;
(7) zinc oxide neutralization: adding fine-grained zinc oxide into the acidic multi-metal liquid obtained in the step (6) for neutralization, wherein the end point of the neutralization is that the pH of the solution is 4.5, the obtained nascent precipitate is a tin-containing precipitate mainly containing tin basic sulfate, and the neutralized solution is a copper-zinc solution mainly containing copper sulfate and zinc sulfate;
(8) zinc powder replacement: adding zinc powder into the copper-zinc solution obtained in the step (7) for copper replacement, wherein the replaced simple substance copper forms a precipitate, and the solution after copper replacement is zinc sulfate crude solution mainly containing zinc sulfate;
(9) dissolving ammonium acetate: and (3) dissolving the crude lead slag obtained in the step (6) by using an ammonium acetate solution, wherein the concentration of the ammonium sulfate solution is 15%, and the using amount of the ammonium acetate solution is 8L/kg relative to the crude lead slag, so as to obtain a final insoluble substance and an ammonium lead crude liquid, wherein the final insoluble substance is the precious metal slag highly enriched in precious metals such as gold, silver and the like, and lead is mainly added into the ammonium lead crude liquid.
Finally, in the obtained different products, the bromine recovery rate is 90.31%, the chlorine recovery rate is 91.45%, the tin recovery rate is 92.16%, the copper recovery rate is 93.21%, the zinc recovery rate is 96.2%, the lead recovery rate is 90.15%, and gold and silver in the noble metal slag can be respectively enriched to 476g/t and 4518 g/t.
Example 2: the soot sample of this example is from environmental protection company of Chongqing city, and the content of bromine, chlorine, copper, lead, zinc and tin is respectively 18.9%, 6.7%, 8.2%, 5.8%, 3.3% and 6.5%, and the content of noble metal gold and silver is respectively 18g/t and 242g/t, and the soot sample is recovered according to the following steps:
(1) mixing concentrated sulfuric acid: uniformly mixing the circuit board incineration soot (hereinafter referred to as soot) and concentrated sulfuric acid, wherein the mass ratio of the soot to the concentrated sulfuric acid is 1:0.8, and uniformly mixing to obtain an ash acid mixture;
(2) heating and dry distillation: heating and dry distilling the ash acid mixture obtained in the step (1), wherein the dry distilling temperature is 150 ℃, the dry distilling time is 1.5 hours, the gas generated in the dry distilling process is dry distilling gas, and the residue of the dry distilling is dry distilling slag;
(3) cooling and absorbing: performing gas cooling and spray water cyclic absorption on the dry distillation gas in the step (2), wherein the absorption cyclic end point is that the pH value of absorption liquid reaches-0.8, the obtained acid solution is bromine and chloric acid liquid, and the residual waste gas after absorption is SO2An exhaust gas;
(4) replacement with chlorine gas: introducing circulating chlorine into the bromine and chloric acid solution obtained in the step (3), wherein the introducing speed of the chlorine is 2.5L/(L.min) relative to the chlorine bromine and chloric acid solution, the displacement reaction time of the chlorine is 30min, the displaced bromine simple substance is in a liquid state and is deposited at the bottom, and the aqueous solution at the upper part is hydrochloric acid solution;
(5) lime slurry absorption: SO obtained in the step (3)2Introducing the waste gas into lime slurry to obtain lime slurry precipitate, wherein the concentration of the lime slurry is 45%, and the dosage of the lime slurry is 6L/m3The lime slurry precipitate is calcium sulfite;
(6) dissolving in water: adding water into the dry distillation residues in the step (2) for soluble substance dissolution to obtain a dissolved solution and undissolved residual substances, wherein the mass ratio of the dry distillation residues to the water is 1:4, the undissolved residual substances are crude lead residues mainly containing lead sulfate, and the dissolved solution is acidic polymetallic liquid mainly containing copper, zinc and tin;
(7) zinc oxide neutralization: adding fine-grained zinc oxide into the acidic multi-metal liquid obtained in the step (6) for neutralization, wherein the end point of the neutralization is that the pH of the solution is 5, the obtained nascent precipitate is a tin-containing precipitate mainly containing tin basic sulfate, and the neutralized solution is a copper-zinc solution mainly containing copper sulfate and zinc sulfate;
(8) zinc powder replacement: adding zinc powder into the copper-zinc solution obtained in the step (7) for copper replacement, wherein the replaced simple substance copper forms a precipitate, and the solution after copper replacement is zinc sulfate crude solution mainly containing zinc sulfate;
(9) dissolving ammonium acetate: and (3) dissolving the crude lead slag obtained in the step (6) by using an ammonium acetate solution, wherein the concentration of the ammonium sulfate solution is 10%, and the using amount of the ammonium acetate solution is 7.5L/kg relative to the crude lead slag, so as to obtain a final insoluble substance and an ammonium lead crude liquid, wherein the final insoluble substance is the precious metal slag with highly enriched precious metals such as gold and silver, and lead is mainly added into the ammonium lead crude liquid.
Finally, in the obtained different products, the bromine recovery rate is 93.42 percent, the chlorine recovery rate is 92.47 percent, the tin recovery rate is 95.36 percent, the copper recovery rate is 93.17 percent, the zinc recovery rate is 91.73 percent, the lead recovery rate is 93.33 percent, and the gold and the silver in the noble metal slag can be respectively enriched to 517g/t and 6617 g/t.
Example 3: the soot sample of this example is from environmental protection company of Chongqing city, and the content of bromine, chlorine, copper, lead, zinc and tin is 23.4%, 8.8%, 5.3%, 4.1%, 5.7% and 10.4%, respectively, and the content of noble metal gold and silver is 10g/t and 54g/t, respectively, and the following steps are carried out for recovery:
(1) mixing concentrated sulfuric acid: uniformly mixing the circuit board incineration soot (hereinafter referred to as soot) and concentrated sulfuric acid, wherein the mass ratio of the soot to the concentrated sulfuric acid is 1:1, and uniformly mixing to obtain an ash acid mixture;
(2) heating and dry distillation: heating and dry distilling the ash acid mixture obtained in the step (1), wherein the dry distilling temperature is 150 ℃, the dry distilling time is 1.5 hours, the gas generated in the dry distilling process is dry distilling gas, and the residue of the dry distilling is dry distilling slag;
(3) cooling and absorbing: performing gas cooling and spray water cyclic absorption on the dry distillation gas in the step (2), wherein the absorption cyclic end point is that the pH value of absorption liquid reaches-0.7, the obtained acid solution is bromine and chloric acid liquid, and the residual waste gas after absorption is SO2An exhaust gas;
(4) replacement with chlorine gas: introducing circulating chlorine into the bromine and chloric acid solution obtained in the step (3), wherein the introducing speed of the chlorine is 2.8L/(L.min) relative to the chlorine bromine and chloric acid solution, the replacement reaction time of the chlorine is 35min, the replaced bromine simple substance is in a liquid state and is deposited at the bottom, and the aqueous solution at the upper part is hydrochloric acid solution;
(5) lime slurry absorption: SO obtained in the step (3)2Introducing the waste gas into lime slurry to obtain lime slurry precipitate, wherein the concentration of the lime slurry is 45%, and the dosage of the lime slurry is 6L/m3The lime slurry precipitate is calcium sulfite;
(6) dissolving in water: adding water into the dry distillation residues in the step (2) for soluble substance dissolution to obtain a dissolved solution and undissolved residual substances, wherein the mass ratio of the dry distillation residues to the water is 1:3.5, the undissolved residual substances are crude lead residues mainly containing lead sulfate, and the dissolved solution is acidic polymetallic liquid mainly containing copper, zinc and tin;
(7) zinc oxide neutralization: adding fine-grained zinc oxide into the acidic multi-metal liquid obtained in the step (6) for neutralization, wherein the end point of the neutralization is that the pH of the solution is 5, the obtained nascent precipitate is a tin-containing precipitate mainly containing tin basic sulfate, and the neutralized solution is a copper-zinc solution mainly containing copper sulfate and zinc sulfate;
(8) zinc powder replacement: adding zinc powder into the copper-zinc solution obtained in the step (7) for copper replacement, wherein the replaced simple substance copper forms a precipitate, and the solution after copper replacement is zinc sulfate crude solution mainly containing zinc sulfate;
(9) dissolving ammonium acetate: and (3) dissolving the crude lead slag obtained in the step (6) by using an ammonium acetate solution, wherein the concentration of the ammonium sulfate solution is 10%, and the using amount of the ammonium acetate solution is 7L/kg relative to the crude lead slag, so as to obtain a final insoluble substance and an ammonium lead crude liquid, wherein the final insoluble substance is the precious metal slag highly enriched in precious metals such as gold, silver and the like, and lead is mainly added into the ammonium lead crude liquid.
Finally, in the obtained different products, the bromine recovery rate is 95.42%, the chlorine recovery rate is 90.31%, the tin recovery rate is 98.14%, the copper recovery rate is 91.41%, the zinc recovery rate is 92.03%, the lead recovery rate is 91.16%, and gold and silver in the noble metal slag can be respectively enriched to 131g/t and 721 g/t.
Example 4: the soot sample of this example is from environmental protection company of Chongqing city, and the content of bromine, chlorine, copper, lead, zinc and tin is respectively 30.1%, 6.2%, 3.4%, 5.2%, 4.7% and 8.3%, and the content of noble metal gold and silver is respectively 7g/t and 104g/t, and the soot sample is recovered according to the following steps:
(1) mixing concentrated sulfuric acid: uniformly mixing the circuit board incineration soot (hereinafter referred to as soot) and concentrated sulfuric acid, wherein the mass ratio of the soot to the concentrated sulfuric acid is 1:0.9, and uniformly mixing to obtain an ash acid mixture;
(2) heating and dry distillation: heating and dry distilling the ash acid mixture obtained in the step (1), wherein the dry distilling temperature is 200 ℃, the dry distilling time is 1.8 hours, the gas generated in the dry distilling process is dry distilling gas, and the residue of the dry distilling is dry distilling slag;
(3) cooling and absorbing: performing gas cooling and spray water cyclic absorption on the dry distillation gas in the step (2), wherein the absorption cyclic end point is that the pH value of absorption liquid reaches-0.8, the obtained acid solution is bromine and chloric acid liquid, and the residual waste gas after absorption is SO2An exhaust gas;
(4) replacement with chlorine gas: introducing circulating chlorine into the bromine and chloric acid solution obtained in the step (3), wherein the introducing speed of the chlorine is 2.8L/(L.min) relative to the chlorine bromine and chloric acid solution, the replacement reaction time of the chlorine is 40min, the replaced bromine simple substance is in a liquid state and is deposited at the bottom, and the aqueous solution at the upper part is hydrochloric acid solution;
(5) lime slurry absorption: SO obtained in the step (3)2Introducing the waste gas into lime slurry to obtain lime slurry precipitate, wherein the concentration of the lime slurry is 40%, and the dosage of the lime slurry is 5L/m3The lime slurry precipitate is calcium sulfite;
(6) dissolving in water: adding water into the dry distillation residues in the step (2) for soluble substance dissolution to obtain a dissolved solution and undissolved residual substances, wherein the mass ratio of the dry distillation residues to the water is 1:5, the undissolved residual substances are crude lead residues mainly containing lead sulfate, and the dissolved solution is acidic polymetallic liquid mainly containing copper, zinc and tin;
(7) zinc oxide neutralization: adding fine-grained zinc oxide into the acidic multi-metal liquid obtained in the step (6) for neutralization, wherein the end point of the neutralization is that the pH of the solution is 4.8, the obtained nascent precipitate is a tin-containing precipitate mainly containing tin basic sulfate, and the neutralized solution is a copper-zinc solution mainly containing copper sulfate and zinc sulfate;
(8) zinc powder replacement: adding zinc powder into the copper-zinc solution obtained in the step (7) for copper replacement, wherein the replaced simple substance copper forms a precipitate, and the solution after copper replacement is zinc sulfate crude solution mainly containing zinc sulfate;
(9) dissolving ammonium acetate: and (3) dissolving the crude lead slag obtained in the step (6) by using an ammonium acetate solution, wherein the concentration of the ammonium sulfate solution is 12%, and the using amount of the ammonium acetate solution is 7L/kg relative to the crude lead slag, so as to obtain a final insoluble substance and an ammonium lead crude liquid, wherein the final insoluble substance is the precious metal slag highly enriched in precious metals such as gold, silver and the like, and lead is mainly added into the ammonium lead crude liquid.
Finally, in the obtained different products, the bromine recovery rate is 96.18%, the chlorine recovery rate is 92.71%, the tin recovery rate is 94.17%, the copper recovery rate is 90.58%, the zinc recovery rate is 89.88%, the lead recovery rate is 91.16%, and gold and silver in the noble metal slag can be respectively enriched to 92g/t and 1357 g/t.
The embodiments of the present invention are described in detail with reference to the drawings, and the scope of the present invention is not limited to the embodiments, and all technical solutions belonging to the idea of the present invention belong to the scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention.

Claims (6)

1. A method for comprehensively recycling circuit board incineration ash is characterized by comprising the following specific steps:
(1) mixing concentrated sulfuric acid: uniformly mixing the circuit board incineration ash and concentrated sulfuric acid, wherein the mass ratio of the circuit board incineration ash to the concentrated sulfuric acid is 1: 0.8-1: 1.2, and obtaining an ash acid mixture;
(2) heating and dry distillation: heating and dry distilling the ash acid mixture obtained in the step (1), wherein gas generated in the dry distilling process is dry distilling gas, the residue of the dry distilling is dry distilling slag, the dry distilling temperature of the heating and dry distilling is 150-250 ℃, and the dry distilling time is 1.5-2.0 h;
(3) cooling and absorbing: performing gas cooling and spray water cyclic absorption on the dry distillation gas in the step (2) to obtain an acid solution, namely bromine and chloric acidThe residual waste gas after the cyclic absorption of the liquid and the spray water is SO2An exhaust gas;
(4) replacement with chlorine gas: introducing circulating chlorine gas into the bromine and chloric acid solution obtained in the step (3) to carry out a chlorine gas displacement reaction, wherein the displaced bromine is precipitated at the bottom in a liquid state, and the aqueous solution at the upper part is a hydrochloric acid solution;
(5) lime slurry absorption: SO obtained in the step (3)2Introducing the waste gas into lime slurry to obtain lime slurry precipitate, wherein the lime slurry precipitate is calcium sulfite;
(6) dissolving in water: adding water into the dry distillation residues in the step (2) to dissolve soluble substances to obtain a dissolved solution and undissolved residual substances, wherein the undissolved residual substances are crude lead residues mainly containing lead sulfate, and the dissolved solution is acidic polymetallic liquid containing copper, zinc and tin;
(7) zinc oxide neutralization: adding zinc oxide into the acidic multi-metal liquid obtained in the step (6) for neutralization, wherein the obtained nascent precipitate is a tin-containing precipitate mainly containing tin basic sulfate, and the neutralized solution is a copper-zinc solution mainly containing copper sulfate and zinc sulfate;
(8) zinc powder replacement: adding zinc powder into the copper-zinc solution obtained in the step (7) for copper replacement, wherein the replaced simple substance copper forms a precipitate, and the solution after copper replacement is zinc sulfate crude solution mainly containing zinc sulfate;
(9) dissolving ammonium acetate: and (3) dissolving the crude lead slag obtained in the step (6) by using an ammonium acetate solution to obtain a final insoluble substance and an ammonium lead crude liquid, wherein the final insoluble substance is the precious metal slag with highly enriched precious metals, lead is mainly added into the ammonium lead crude liquid, the concentration of the ammonium acetate solution is 10-15%, and the using amount of the ammonium acetate solution is 7-8L/kg relative to the crude lead slag.
2. The method for comprehensively recycling circuit board incineration ash according to claim 1, characterized in that: and (4) circularly absorbing by using the spray water in the step (3) until the pH of the absorption liquid reaches-0.6 to-0.8.
3. The method for comprehensively recycling circuit board incineration ash according to claim 1, characterized in that: in the step (4), the chlorine gas introducing speed is 2.5-3L/(L.min), and the chlorine gas replacement reaction time is 30-45 min.
4. The method for comprehensively recycling circuit board incineration ash according to claim 1, characterized in that: in the step (5), the concentration of the lime slurry is 40-50%, and the dosage of the lime slurry is 5-7L/m3。
5. The method for comprehensively recycling circuit board incineration ash according to claim 1, characterized in that: in the step (6), the mass ratio of the dry distillation residues to the water is 1: 3-1: 5.
6. The method for comprehensively recycling circuit board incineration ash according to claim 1, characterized in that: and (4) adding zinc sulfate to neutralize in the step (7), wherein the pH value of the solution is 4.5-5 at the end point of neutralization.
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