CN109136574A - A kind of pre- sulfur method of lead plaster based on the double salt of sodium ammonium - Google Patents

A kind of pre- sulfur method of lead plaster based on the double salt of sodium ammonium Download PDF

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Publication number
CN109136574A
CN109136574A CN201811232194.2A CN201811232194A CN109136574A CN 109136574 A CN109136574 A CN 109136574A CN 201811232194 A CN201811232194 A CN 201811232194A CN 109136574 A CN109136574 A CN 109136574A
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China
Prior art keywords
lead plaster
lead
ammonium
desulfurization
sodium
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CN201811232194.2A
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Chinese (zh)
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张俊丰
麻洋
黄妍
曹靖
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Xiangtan University
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Xiangtan University
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/24—Sulfates of ammonium
    • C01C1/244—Preparation by double decomposition of ammonium salts with sulfates
    • 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
    • C22B1/11—Removing sulfur, phosphorus or arsenic other than by roasting
    • 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
    • C22B13/02—Obtaining lead by dry processes
    • C22B13/025—Recovery from waste materials
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a kind of pre- sulfur methods of lead plaster based on the double salt of sodium ammonium, belong to waste lead storage battery regeneration field.Use sodium bicarbonate as desulfurizing agent first, pre- desulfurization process is carried out to lead plaster, it is separated by solid-liquid separation again after the reaction was completed, desulphurization mother solution decrease temperature crystalline obtains sal glauberi, the regenerative response that ammonium sulfate carries out desulfurizing agent is added after sal glauberi dissolution, the sodium bicarbonate circulation being prepared is for desulfurization.The present invention only consumes the ammonium hydrogen carbonate of low cost, and gained by-product is the ammonium sulfate of high value, and product yield is high, simple process, has played the advantages of lead plaster sodium method desulphurization reaction is convenient for control, it is thus also avoided that the low disadvantage of sodium method desulfurizing byproduct comprehensive utilization value；The high advantage of lead plaster ammonium method desulfurizing byproduct comprehensive utilization value has been played, while having overcome the uncontrollable disadvantage of ammonium method sweetening process, one has been provided for waste lead accumulator regenerative process lead plaster desulfurization while there is the good method of high environmental benefit and high economic benefit.

Description

A kind of pre- sulfur method of lead plaster based on the double salt of sodium ammonium
Technical field
The invention belongs to waste and old lead acid accumulator resource regeneration fields, for the lead in waste and old lead acid accumulator regenerative process Cream desulfurization.
Background technique
Lead-acid accumulator (also referred to as lead storage battery, lead-acid battery) is in communication base station, defence equipment, automobile, electric vehicle, motor The fields such as vehicle are widely used.China, with the rapid development of economy, the bases such as automobile, communication, electric power, traffic, railway, computer Plinth industry is in rapid growth period, and the demand to lead-acid accumulator continues to increase, nearly ten years growth rate reached 10%/ A greatly promotes the development of lead-acid accumulator industry, and preliminary industrial upgrading has been done step-by-step, by initially small-scale, technology Backward low side industry has been developed as possessing 2000 enterprises, the gross output value up to 170,000,000,000 yuan of big industry.2016 1~ October, lead-acid accumulator yield in China's reached 177,460,000 kVAh, increased by 6.7% on a year-on-year basis, the lead-acid accumulator scrapped every year has 1.1 More than hundred million, lead tolerance is up to more than 380 ten thousand tons.The regeneration of lead-acid accumulator recycles lead resource significant.
Currently, China has tentatively established the industrial policy and technical equipment body of waste lead accumulator resource green circulatory System, the cleaning procedure of prevalence " Mechanical Crushing sorting-pre- desulfurization-low smelting heat ".Wherein, " Mechanical Crushing sorting " and " low smelting heat " two links had be sufficiently advanced, efficient technical equipment support." the pre- desulfurization of lead plaster " link is generally adopted Technique is sodium method desulfurization, converts dystectic lead sulfate to the ceruse of low melting point, realizes efficient, thorough desulfurization, Its environmental benefit is prominent, but economic benefit and bad, this is because product sodium sulphate value is low, to constrain scrap lead electric power storage The further development of pond regeneration industry.
Summary of the invention
The purpose of the present invention is to provide a kind of pre- doctor treatments of lead plaster based on the double salt of sodium ammonium, using ammonium hydrogen carbonate as raw material, By-product is converted into ammonium sulfate by sodium sulphate, while high-efficiency desulfurization, significantly reduces desulphurization cost, while being obviously improved economy Benefit.
Technical proposal that the invention solves the above-mentioned problems are as follows:
A kind of pre- doctor treatment of lead plaster based on the double salt of sodium ammonium, includes the following steps:
(1) the pre- desulfurization of lead plaster: resulting lead plaster after waste lead accumulator cracking and sorting is made into lead plaster slurries and is pumped into agitator tank In, desulfurizing agent NaHCO is added in agitator tank3Carry out pre- desulphurization reaction；
(2) sodium sulphate decrease temperature crystalline: being pumped into filter press for step (1) products therefrom, and solid carries out low temperature smelting, carries out lead Regeneration recycling, desulphurization mother solution is pumped into decrease temperature crystalline device, ethyl alcohol is added, and Na is precipitated2SO4·10H2O crystal；
(3) desulfurizer regeneration: by Na obtained by step (2)2SO4·10H2O and NH4HCO3It is added in agitator tank and is reacted, Obtain NaHCO3Magma, is pumped into filter press, and obtained solid is pure NaHCO3Crystal is back to step (1)；
(4) ammonium sulfate purifies: being once evaporated in vacuo step (3) is mother liquid obtained, is separated in mother liquor using thermal method Na2SO4(NH4)2SO4, filtered while hot after the completion of evaporation, the Na of precipitation2SO4Return step (3) continues to participate in reaction, and filtrate is cold But continue to filter afterwards, gained secondary salt Na2SO4·(NH4)2SO4·4H2O is returned in flush distillation liquid, carries out secondary vacuum evaporation, Finished product (NH is obtained by filtration while hot4)2SO4。
Further, in step (3), Na2SO4·10H2O and NH4HCO30.8~1:1 of the ratio between amount of substance, reaction temperature It is 32.4~40 DEG C, the reaction time is 30~90min, and mixing speed is 30~100r/min.
Further, in step (4), the primary temperature that is evaporated in vacuo is 60 DEG C or more, preferably 60~90 DEG C, it is cooled to 20~ 30 DEG C are filtered, and secondary vacuum evaporating temperature is also 60 DEG C or more, and preferably 60~90 DEG C.
Specific reaction process is as follows:
PbSO4+NaHCO3→PbCO3+Na2SO4+H2O+CO2
Na2SO4+2NH4HCO3→(NH4)2SO4+2NaHCO3
The beneficial effects of the present invention are:
(1) present invention is using sodium bicarbonate as direct desulfurization agent, and ammonium hydrogen carbonate is as indirect desulfurization agent and direct desulfurization pair Product sodium sulphate reaction regeneration goes out sodium bicarbonate circulation for desulfurization, the ammonium sulfate that regenerative response obtains as final byproduct into Row comprehensive utilization, substantially only consumes cheap ammonium hydrogen carbonate, by-product by low value in the prior art sodium sulphate It is converted into the ammonium sulfate of high value, product yield is high, and simple process, economic benefit highly significant, it is achieved that high environment The unification of benefit and high economic benefit.
(2) present invention has not only given full play to the advantages of lead plaster sodium method desulphurization reaction is convenient for control, it is thus also avoided that sodium method is de- Sulphur byproduct comprehensive utilization is worth low disadvantage；High excellent of lead plaster ammonium method desulfurizing byproduct comprehensive utilization value is not only utilized Point, while the uncontrollable disadvantage of ammonium method sweetening process is also overcomed, technical effect highly significant regenerated for waste lead accumulator Journey lead plaster desulfurization provides one while having the good method of high environmental benefit and high economic benefit.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, and the main component of lead plaster includes: PbSO4(50-60%), PbO2(30-35%), PbO (10-15%) and other substances (0.2-0.7%).
Embodiment 1
Resulting lead plaster is configured to the lead plaster slurries that mass fraction is 40% and is pumped into desulfurization after waste lead accumulator cracking and sorting In agitator tank, by NaHCO3With PbSO4Molar ratio is that desulfurizing agent NaHCO is added in 2.1:13Pre- desulphurization reaction is carried out, after 60min Carry out filters pressing；Filtrate is pumped into decrease temperature crystalline device, the crystal of precipitation, by Na2SO4·10H2O and NH4HCO3Molar ratio 0.8:1 is added Agitator tank is regenerated, reaction temperature is 38 DEG C, is separated by solid-liquid separation after mixing speed 50r/min, 60min；Filtrate carries out a vacuum Evaporation, 60 DEG C or so filterings, filtrate are cooled to 25 DEG C or so and refilter after the completion of evaporation, and filtrate carries out secondary vacuum evaporation again, 60 DEG C or so are obtained by filtration finished product (NH4)2SO4.Lead plaster sulfur-bearing rate 0.42%, ammonium sulfate purity 21.2% after desulfurization.
Embodiment 2
Resulting lead plaster is configured to the lead plaster slurries that mass fraction is 40% and is pumped into desulfurization after waste lead accumulator cracking and sorting In agitator tank, by NaHCO3With PbSO4Molar ratio is that desulfurizing agent NaHCO is added in 2.05:13Pre- desulphurization reaction is carried out, after 60min Carry out filters pressing；Filtrate is pumped into decrease temperature crystalline device, the crystal of precipitation, by Na2SO4·10H2O and NH4HCO3Molar ratio 0.9:1 is added Agitator tank is regenerated, reaction temperature is 38 DEG C, is separated by solid-liquid separation after mixing speed 60r/min, 60min；Filtrate carries out a vacuum Evaporation, 60 DEG C or so filterings, filtrate are cooled to 25 DEG C or so and refilter after the completion of evaporation, and filtrate carries out secondary vacuum evaporation again, 60 DEG C or so are obtained by filtration finished product (NH4)2SO4.Lead plaster sulfur-bearing rate 0.35%, ammonium sulfate purity 21% after desulfurization.
Embodiment 3
Resulting lead plaster is configured to the lead plaster slurries that mass fraction is 40% and is pumped into desulfurization after waste lead accumulator cracking and sorting In agitator tank, by NaHCO3With PbSO4Molar ratio is that desulfurizing agent NaHCO is added in 2.05:13Pre- desulphurization reaction is carried out, after 90min Carry out filters pressing；Filtrate is pumped into decrease temperature crystalline device, the crystal of precipitation, by Na2SO4·10H2O and NH4HCO3Molar ratio 0.8:1 is added Agitator tank is regenerated, reaction temperature is 38 DEG C, is separated by solid-liquid separation after mixing speed 60r/min, 90min；Filtrate carries out a vacuum Evaporation, 60 DEG C or so filterings, filtrate are cooled to 25 DEG C or so and refilter after the completion of evaporation, and filtrate carries out secondary vacuum evaporation again, 60 DEG C or so are obtained by filtration finished product (NH4)2SO4.Lead plaster sulfur-bearing rate 0.32%, ammonium sulfate purity 21.4% after desulfurization.
Above embodiments show to carry out desulfurization using method of the invention, can not only make desulfurization degree be stably held in compared with High level, while desulfurizing agent can be recycled, thus reduce costs, and by-product is by the sodium sulphate of low value in the prior art It is converted into the ammonium sulfate of high value, has been obviously improved economic benefit, and simple process, yield is high, while high-efficiency desulfurization, significantly Desulphurization cost is reduced, the unification of high-environmental benefit and high economic benefit is realized, it is de- for waste lead accumulator regenerative process lead plaster Sulphur provides a new good method.

Claims (3)

1. a kind of pre- doctor treatment of lead plaster based on the double salt of sodium ammonium, which comprises the steps of:
(1) the pre- desulfurization of lead plaster: being made into lead plaster slurries for resulting lead plaster after waste lead accumulator cracking and sorting and be pumped into agitator tank, Desulfurizing agent NaHCO is added in agitator tank3Carry out pre- desulphurization reaction；
(2) sodium sulphate decrease temperature crystalline: step (1) products therefrom is pumped into filter press, solid carries out the regeneration recycling of lead, and desulfurization is female Liquid pump enters decrease temperature crystalline device, and Na is precipitated in decrease temperature crystalline2SO4·10H2O crystal；
(3) desulfurizer regeneration: by Na obtained by step (2)2SO4·10H2O and NH4HCO3It is added in agitator tank and is reacted, obtained NaHCO3Magma, is pumped into filter press, and obtained solid is pure NaHCO3Crystal is back to step (1)；
(4) ammonium sulfate purifies: being once evaporated in vacuo step (3) is mother liquid obtained, thermal method is utilized to separate the Na in mother liquor2SO4 (NH4)2SO4, filtered while hot after the completion of evaporation, the Na of precipitation2SO4Return step (3) continues to participate in reaction, and filtrate cooling is subsequent Continuous filtering, gained secondary salt Na2SO4·(NH4)2SO4·4H2O is returned in flush distillation liquid, carries out secondary vacuum evaporation, while hot mistake Filter obtains finished product (NH4)2SO4。
2. the sodium ammonium double salt according to claim 1 that are based on are to the pre- sulfur method of lead plaster, which is characterized in that in step (3), Na2SO4·10H2O and NH4HCO30.8~1:1 of the ratio between amount of substance, reaction temperature be 32.4~40 DEG C, the reaction time be 30~ 90min, mixing speed are 30~100r/min.
3. the lead plaster pre- sulfur method according to claim 1 based on the double salt of sodium ammonium, which is characterized in that in step (4), one Secondary vacuum evaporation temperature is 60 DEG C or more, is cooled to 20~30 DEG C and is filtered, and secondary vacuum evaporating temperature is 60 DEG C or more.
CN201811232194.2A 2018-10-22 2018-10-22 A kind of pre- sulfur method of lead plaster based on the double salt of sodium ammonium Pending CN109136574A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109811140A (en) * 2019-02-20 2019-05-28 湘潭大学 A kind of lead plaster ammonium sulfur method of product purity height guarantee
CN112591788A (en) * 2020-10-09 2021-04-02 超威电源集团有限公司 Method for circularly desulfurizing lead waste

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105645514A (en) * 2016-01-20 2016-06-08 西北大学 Method for separating and purifying ammonium sulfate and sodium sulfate mixed solution during flue gas desulfurizer regeneration
CN105655661A (en) * 2016-01-06 2016-06-08 湘潭大学 Lead plaster pre-desulphurization method based on limestone

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105655661A (en) * 2016-01-06 2016-06-08 湘潭大学 Lead plaster pre-desulphurization method based on limestone
CN105645514A (en) * 2016-01-20 2016-06-08 西北大学 Method for separating and purifying ammonium sulfate and sodium sulfate mixed solution during flue gas desulfurizer regeneration

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109811140A (en) * 2019-02-20 2019-05-28 湘潭大学 A kind of lead plaster ammonium sulfur method of product purity height guarantee
CN112591788A (en) * 2020-10-09 2021-04-02 超威电源集团有限公司 Method for circularly desulfurizing lead waste

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