CN106498167B - A kind of intensified by ultrasonic wave ammonium hydrogen carbonate is the diachylon desulphurization method of desulfurizing agent - Google Patents

A kind of intensified by ultrasonic wave ammonium hydrogen carbonate is the diachylon desulphurization method of desulfurizing agent Download PDF

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Publication number
CN106498167B
CN106498167B CN201610967559.0A CN201610967559A CN106498167B CN 106498167 B CN106498167 B CN 106498167B CN 201610967559 A CN201610967559 A CN 201610967559A CN 106498167 B CN106498167 B CN 106498167B
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digester
hydrogen carbonate
ammonium hydrogen
desulfurizing agent
ultrasonic wave
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CN106498167A (en
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张俊丰
王幸
刘磊
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
    • C22B7/001—Dry 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Abstract

The invention discloses the diachylon desulphurization methods that a kind of intensified by ultrasonic wave ammonium hydrogen carbonate is desulfurizing agent.Lead plaster is configured to the slurries of solid content 30 ~ 70% in digester, digester is added portionwise by 2.02 ~ 2.10 times that the amount of total material is lead sulfate in desulfurizing agent ammonium hydrogen carbonate, the mass concentration overall process for controlling ammonium hydrogen carbonate in digester is not more than 5%, and speed of agitator controls 70 ~ 120 revs/min.In the middle part of digester, 2 or 4 supersonic generator probes are configured, reinforcing desulfuration is used for；Middle part on digester configures 2 or 4 supersonic generator probes, for defoaming；Slurry pump is matched in inverted v-shaped high centered on desulfurization pot bottom, periphery is low, bottom, and the slurries that reaction is completed are transported to subsequent handling.The present invention not only enhances the Surface Renewal of sweetening process reaction mass, but also effectively eliminates the foam that reaction generates, and achieves extraordinary desulfurization effect；And technique and device structure are simple, operation energy consumption is low, and industrial applicability is strong.

Description

A kind of intensified by ultrasonic wave ammonium hydrogen carbonate is the diachylon desulphurization method of desulfurizing agent
Technical field
The present invention relates to the diachylon desulphurization methods that a kind of intensified by ultrasonic wave ammonium hydrogen carbonate is desulfurizing agent, belong to waste and old lead acid storage Battery resource regeneration field, for the lead plaster desulfurization in waste and old lead acid accumulator regenerative process.
Background technology
China is the production and marketing state of the first big lead in the world, lead consumption figure 80% in lead-acid accumulator, China is scrapped every year Lead-acid accumulator have more than 300,000,000, leaded nearly 4,000,000 tons.Containing lead, sulfuric acid in lead-acid accumulator, belong to hazardous waste, it is necessary to Safe disposal.After waste and old lead acid accumulator is pooled to reviver enterprise, first carry out cracking and sorting, obtain plastics, spent acid, lead head, The main material such as lead plaster, wherein lead plaster are most important compositions, and the main component of lead plaster includes：PbSO4（50-60%）、PbO2 （30-35%）、PbO（10-15%）With other substances（0.2-0.7%）.Existing lead cycle industrial policy requires to carry out lead plaster pre- Lead sulfate is changed into the substance of the not sulfur-bearing such as carbonate by desulfurization process, enters back into melting link, not only can be with when such melting Low smelting heat is carried out, the volatilization loss of lead is reduced while substantially reducing energy consumption, and fusion process is not generated or seldom produced Raw sulfur dioxide, makes fusion process become more to clean, more environmentally friendly.The pre- sulfur removal technology of lead plaster that industry uses at present is nearly all carbon Sour sodium sulfur removal technology, desulfurization effect is fine, and operation is also very stable, but the product of pre- desulfurization is sodium sulphate, China's sodium sulphate production capacity It is very very sufficient, and sodium sulphate is inexpensive, thus the pre- desulphurization system of sodium carbonate is although realize the regenerated clean manufacturing of lead plaster, But economic benefit is bad.Explore the pre- desulfurization technical matters of more economical efficient lead plaster and equipment, to lead plaster clean regeneration industry into Step has critically important promotion meaning.
Ammonium carbonate and ammonium hydrogen carbonate are other two kinds of substances that can be used as the pre- desulfurizing agent of lead plaster, the sulfuric acid obtained after desulfurization It can be used for agricultural production, but the selling at exorbitant prices of ammonium carbonate at present after ammonium purification, use it for the pre- desulfurization of lead plaster, final economy Performance ratio is lower using sodium carbonate.The price of ammonium hydrogen carbonate is much lower compared with ammonium carbonate, will compare sodium carbonate as the pre- desulfurization of lead plaster Process efficiency is possible to greatly promote.Ammonium hydrogen carbonate and reacting for lead sulfate are as follows：
PbSO4（S）+2NH4HCO3= PbCO3（S）+(NH4)2SO4+CO2↑
As it can be seen that reaction process needs to pay attention to there are two problem, first, lead sulfate PbSO4Solid and soluble NH4HCO3Instead It answers, generates solid PbCO3With soluble (NH4)2SO4, the PbCO of generation3PbSO will be wrapped in4Surface forms product layer, will Hinder PbSO4With NH4HCO3Further reaction, to make desulphurization reaction carry out it is thorough, it is necessary to take enhancements in time will It is wrapped in PbSO4The PbCO on surface3Product shell is crushed and is removed in time；Second is that desulphurization reaction process generates a large amount of CO2, this Retort will be caused to generate a large amount of foam, it is necessary to take measures the removal of foam in time.
Invention content
Reaction is hindered to carry out and generate in order to solve ammonium hydrogen carbonate lead plaster desulphurization reaction process product covering reaction-ure surface The problem of a large amount of foams, promotes effect of ammonium hydrogen carbonate during lead plaster desulphurization reaction, and it is strong that the present invention provides a kind of ultrasonic wave Change the diachylon desulphurization method that ammonium hydrogen carbonate is desulfurizing agent, is wrapped in instead using ultrasonic wave for the pulverization of solid is immediately broken It is distributed in slurries under the action of stirring immediately after answering the product layer on object surface, product layer broken；Ultrasonic wave is utilized simultaneously Cavitation smash the bubble in foam immediately, release the slurries carried secretly in bubble, prevent froth bed from expanding.
The technical scheme is that：
A kind of intensified by ultrasonic wave ammonium hydrogen carbonate is the diachylon desulphurization method of desulfurizing agent, is included the following steps：After lead plaster is weighed Water or ammonium sulfate is added to be configured to solid content 30 ~ 70% in digester（Mass percent or mass concentration）Slurries, take off Sulphur agent ammonium hydrogen carbonate total amount is 2.02 ~ 2.10 times of the amount of lead sulfate substance in lead plaster, and desulfurizing agent ammonium hydrogen carbonate is added portionwise de- Sulphur tank, the mass concentration overall process for controlling ammonium hydrogen carbonate in digester are not more than 5%；Digester configures the adjustable blender of rotating speed, 70 ~ 120 revs/min of agitator speed makes the slurries good mixing in digester；Digester configures supersonic generator simultaneously, Start supersonic generator when being initially added into desulfurizing agent and starts desulphurization reaction, when solid material sulfur-bearing rate is less than the standard set, Stop supersonic generator, starts slurry pump and the material after reaction is transported to subsequent handling, material stops defeated after conveying Send pump and blender.
Further, the configuration of supersonic generator by the middle part of digester configure reaction supersonic generator probe and Defoaming supersonic generator probe is configured in digester middle and upper part to realize；In the middle part of digester, it is super to configure 2 or 4 reactions Sonic generator is popped one's head in, and release ultrasonic wave is used for reinforcing desulfuration, and probe is inserted into outside digester wall surface, is immersed in desulfurization slurry In；The middle part on digester, 2 or 4 defoaming supersonic generator probes of configuration, probe are inserted outside digester wall surface Enter, be immersed in the froth bed of sweetening process, realizes defoaming.
Further, the low inverted v-shaped in height, periphery centered on desulfurization pot bottom has both been convenient for the lead head enrichment that proportion is larger Without precipitating, slurry pump imbibition is also allowed for, and desulfurization pot bottom matches slurry pump.
The beneficial effects of the present invention are：
（1）The present invention uses intensified by ultrasonic wave ammonium hydrogen carbonate for the lead plaster desulphurization reaction of desulfurizing agent, on the one hand enhances de- On the other hand the Surface Renewal of sulphur process reaction material effectively eliminates the foam that reaction generates, achieves extraordinary desulfurization Effect.
（2）The method and process of the present invention is simple, and device structure is simple, and operation energy consumption is low, and industrial applicability is strong.
Description of the drawings
Fig. 1 is the equipment flowsheet of present invention process, wherein 1, digester, 2, agitating paddle, 3, defoaming ultrasonic probe, 4, ultrasonic probe is reacted, 5, slurry pump.
Specific implementation mode
The present invention is described in further details below in conjunction with specific embodiment, but the present invention is not limited thereto.
The slurries that lead plaster adds water or ammonium sulfate to be configured to solid content 30 ~ 70% after weighing in digester, desulfurizing agent Ammonium hydrogen carbonate total amount is 2.02 ~ 2.10 times of the amount of lead sulfate substance in lead plaster, and digester 1 is added portionwise, and is controlled in digester The concentration overall process of ammonium hydrogen carbonate is not more than 5%.70 ~ 120 revs/min of 2 rotating speed of blender for adjusting digester 1, makes digester 1 In slurries good mixing.Start reaction supersonic generator 4 and defoaming supersonic generator 3 after being initially added into ammonium hydrogen carbonate. Stop supersonic generator 3,4 after the completion of desulphurization reaction and start slurry pump 5 that the slurries after reaction are delivered to follow-up press filtration etc. Process, material stop blender 2 and slurry pump 5 after conveying.
Embodiment 1
By the broken rear gained 400 kilograms of input digesters of lead plaster of waste lead acid battery, 900 kilograms of water is added to be made into mass percent For 30.8% 1 m of slurries3, start blender, for adjustment speed of agitator to 80 revs/min, stirring after five minutes, it is public to weigh total amount 107 Jin desulfurizing agent NH4HCO3, start supersonic generator, be added three times NH4HCO3, it is spaced 10min, the amount of sequentially adding is 50 public Jin, 40 kilograms, 27 kilograms.Original lead plaster sulfur-bearing rate is 5.3%, through this sulfur removal technology desulfurization 40min, lead plaster sulfur-bearing rate after desulfurization It is 0.32%.
Embodiment 2
By the broken rear gained 600 kilograms of input digesters of lead plaster of waste lead acid battery, 900 kilograms of water is added to be made into mass percent For 40% 1.2 m of slurries3, start blender, for adjustment speed of agitator to 100 revs/min, stirring after five minutes, it is public to weigh total amount 162 Jin desulfurizing agent NH4HCO3, start supersonic generator, be added three times NH4HCO3, it is spaced 10min, the amount of sequentially adding is 80 public Jin, 60 kilograms, 22 kilograms.Original lead plaster sulfur-bearing rate is 5.3%, through this sulfur removal technology desulfurization 40min, lead plaster sulfur-bearing rate after desulfurization It is 0.34%.
Embodiment 3
By the broken rear gained 1200 kilograms of input digesters of lead plaster of waste lead acid battery, 900 kilograms of water is added to be made into quality percentage The slurries 1.5m that number is 57%3, start blender, for adjustment speed of agitator to 120 revs/min, stirring after five minutes, weighs total amount 330 Kilogram desulfurizing agent NH4HCO3, start supersonic generator, point 4 addition NH4HCO3, it is spaced 10min, the amount of sequentially adding is 400 Kilogram, 300 kilograms, 300 kilograms, 200 kilograms.Original lead plaster sulfur-bearing rate is 5.3%, through this sulfur removal technology desulfurization 60min, desulfurization Lead plaster sulfur-bearing rate is 0.28% afterwards.

Claims (2)

1. a kind of intensified by ultrasonic wave ammonium hydrogen carbonate is the diachylon desulphurization method of desulfurizing agent, it is characterised in that include the following steps：Lead Cream adds water or ammonium sulfate to be configured to the slurries that solid content is 30 ~ 70% in digester, and desulfurizing agent ammonium hydrogen carbonate adds in batches Enter digester；So that lead plaster slurries is uniformly dispersed by adjusting digester speed of agitator, starts ultrasonic wave when being initially added into desulfurizing agent Generator stops supersonic generator when solid material sulfur-bearing rate is less than the standard set, starts slurry pump by the object after reaction Material is transported to subsequent handling, and material stops delivery pump and blender after conveying；
The configuration of supersonic generator by the middle part of digester configure reaction supersonic generator probe and in digester on Portion's configuration defoaming supersonic generator probe is realized；In the middle part of digester, 2 or 4 reaction supersonic generators of configuration are visited Head, release ultrasonic wave are used for reinforcing desulfuration, and probe is inserted into outside digester wall surface, is immersed in desulfurization slurry；In digester Upper middle part, 2 or 4 defoaming supersonic generator probes of configuration, probe are inserted into outside digester wall surface, are immersed in desulfurization In the froth bed of process, defoaming is realized.
2. intensified by ultrasonic wave ammonium hydrogen carbonate according to claim 1 is the diachylon desulphurization method of desulfurizing agent, which is characterized in that Inverted v-shaped high centered on desulfurization pot bottom, periphery is low, and desulfurization pot bottom matches slurry pump.
CN201610967559.0A 2016-10-31 2016-10-31 A kind of intensified by ultrasonic wave ammonium hydrogen carbonate is the diachylon desulphurization method of desulfurizing agent Active CN106498167B (en)

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Publication number Priority date Publication date Assignee Title
CN107394300A (en) * 2017-06-30 2017-11-24 湖北楚凯冶金有限公司 A kind of sulfur method of waste lead acid battery lead cream
CN111170351A (en) * 2018-11-13 2020-05-19 湖南省金翼有色金属综合回收有限公司 Lead sulfate waste material desulfurization device and process thereof
CN112442603A (en) * 2020-10-09 2021-03-05 超威电源集团有限公司 Method for desulfurizing lead waste

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WO2014125266A1 (en) * 2013-02-12 2014-08-21 Ultromex Ltd Apparatus and method for recovery of lead
CN204365272U (en) * 2014-12-17 2015-06-03 安徽超威电源有限公司 A kind of colloid electrolyte for lead-acid battery ultrasonic machining device
CN105734274A (en) * 2016-03-24 2016-07-06 湖南江冶机电科技股份有限公司 Lead plaster desulfurization method based on gas-liquid mixed flow
CN105950870A (en) * 2016-06-30 2016-09-21 中南大学 Hydrothermal deep conversion desulfurization method for waste lead plaster of lead-acid storage battery

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
CN101518711A (en) * 2009-04-03 2009-09-02 武汉工程大学 Process and device for continuous ultrasound desulfurization of scrapped lead paste
WO2014125266A1 (en) * 2013-02-12 2014-08-21 Ultromex Ltd Apparatus and method for recovery of lead
CN204365272U (en) * 2014-12-17 2015-06-03 安徽超威电源有限公司 A kind of colloid electrolyte for lead-acid battery ultrasonic machining device
CN105734274A (en) * 2016-03-24 2016-07-06 湖南江冶机电科技股份有限公司 Lead plaster desulfurization method based on gas-liquid mixed flow
CN105950870A (en) * 2016-06-30 2016-09-21 中南大学 Hydrothermal deep conversion desulfurization method for waste lead plaster of lead-acid storage battery

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