CN105400959B - Heavy metal and the method and apparatus of resource utilization in a kind of waste acid recovery - Google Patents

Heavy metal and the method and apparatus of resource utilization in a kind of waste acid recovery Download PDF

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CN105400959B
CN105400959B CN201511010972.XA CN201511010972A CN105400959B CN 105400959 B CN105400959 B CN 105400959B CN 201511010972 A CN201511010972 A CN 201511010972A CN 105400959 B CN105400959 B CN 105400959B
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membranous system
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heavy metal
resource utilization
acid
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CN105400959A (en
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陈福泰
付强
褚永前
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Go Higher Environment Group Co ltd
Ningxia Ningdong Qingdaohua Environmental Resources Co ltd
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Ningxia Ningdong Qing Great Power Hua Kai Hong Environmental Resources Co Ltd
Tsingdahua Environment Group Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/006Wet processes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The present invention provides heavy metal in a kind of waste acid recovery and the method and apparatus of resource utilization, solve the problems such as prior art waste residue yield is big, operating cost is high, the rate of recovery is low.The device of heavy metal and resource utilization includes: buffer tank in waste acid recovery;Pre-filtrating equipment is connect with the buffer tank;Level-one membranous system is connect with the pre-filtrating equipment;Intermediate water tank is connect with the level-one membranous system;Second level membranous system is connect with the intermediate water tank;Through liquid case, it is connect with the second level membranous system;Liquid case is concentrated, is connect with the second level membranous system;Electrolysis unit is connect with the concentration liquid case.The invention has the advantages that: the minimizing processing, the waste residue low output that realize spent acid, heavy metal recovery rate is high, processing cost is low.

Description

Heavy metal and the method and apparatus of resource utilization in a kind of waste acid recovery
Technical field
The invention belongs to hazardous waste process field, heavy metal in a kind of waste acid recovery and resource utilization are particularly related to Method and apparatus.
Background technique
With industry and expanding economy, the spent acid that China generates every year is at 100,000,000 tons or more, and according to China Chemical Industry information Center investigation statistics, wherein inorganic spent acid accounts for about 35 %, organic spent acid accounts for about 65 %, and the spent acid of 40 % or more of content accounts for total amount 46 % or so.Industrial waste acid mostlys come from the production of the industrial chemicals such as petroleum refining, sulfuric acid, steel processing washing, bronze life Produce the fields such as pickling, electronic components fabrication.Since spent acid typically contains organic matter and heavy metal ion, directly utilizing will cause two Secondary pollution, and untreated spent acid enters will cause soil acidification in natural environment, and the heavy metal in spent acid is in acid soil Activity is higher in earth is easily absorbed by plants, and then food-safe causes major hidden danger.The environmental protection faced with China and human body Healthy and safe pressure is increasingly serious, therefore the environmental protection of government-to-businesses clean manufacturing, energy-saving and emission-reduction, wastewater pollution prevention etc. It is required that being continuously improved.
Currently, the treatment process that China's spent acid is generally taken is neutralization precipitation method, which not only needs to consume largely Neutralizer can also generate a large amount of solid slag, and operating cost is higher, and the rate of recovery is low, while neutralization precipitation method can not be from Pollution is fundamentally eliminated, and only shifts pollutant in different media, especially poisonous and hazardous substance is from water It is transferred in solid slag, causes secondary pollution, the vicious circle of " control and be unequal to controlling " is formed, as country is to industrial residue problem Attention, the treatment process there are the drawbacks of become increasingly conspicuous.On the other hand, part industrial waste acid also uses pyrohydrolysis and evaporation Method, but the process energy consumption is excessive, is unsuitable for a wide range of industrial applications, is only applicable to the high particular components of added value of product.
Although spent acid can cause serious harm to natural environment and human health, generally comprise in spent acid has simultaneously The sulfuric acid or nitric acid and metal values (such as copper or nickel) of recoverable value.Based on material recycle and circular economy Theory has been increasingly becoming China's spent acid from simple spent acid qualified discharge to recycling valuable metal and the transformation of water resource reuse technology The development trend of processing.Heavy metal recovery technique generally uses electroplating technology by heavy metal ion in traditional spent acid in industry Be reduced to metallic state, but the quality of metal recovery rate and recycling metal can because in spent acid in the process the reduction of tenor due to by It influences, it is therefore desirable to which tenor in timing detection spent acid and supplements spent acid, and it is cumbersome in turn result in technique, needs a large amount of people Power.And the recycling of acid solution uses heating distillation technique generally to recycle the lower acid solution of boiling point, such as recycling low boiling point in spent acid In the nitric acid of sulfuric acid, but recycles the higher sulfuric acid of boiling point and then need additional recycling equipment, cause complex process and return This raising of harvest.
In conclusion waste acid treatment and recovery process traditional in industry exist in actual application it is some not Foot, such as easily caused, secondary pollution, technique are cumbersome, the rate of recovery is low, cost recovery is high, therefore explore and develop weight in new spent acid The method and apparatus of metal recovery and resource utilization has important meaning to Industrial-Enterprises in China clean manufacturing, energy-saving and emission-reduction Justice.
Summary of the invention
The present invention provides heavy metal in a kind of waste acid recovery and the method and apparatus of resource utilization, solve existing work The waste residue that skill technology generates easily causes the problems such as secondary pollution, technique are cumbersome, the rate of recovery is low, cost recovery is high.
The technical scheme of the present invention is realized as follows:
Heavy metal and the device of resource utilization in a kind of waste acid recovery, comprising:
Buffer tank guarantees subsequent treatment process stable operation for carrying out the adjusting of water quality and quantity to spent acid;
Pre-filtrating equipment, for removing the particulate matters such as suspended matter, colloidal substance in spent acid waste water, with the buffer tank Connection;
Level-one membranous system, for removing the suspended matter and colloidal substance that fail retention in pre-filtration system, with the pre- mistake Filter device connection;
Intermediate water tank is connect for collecting the water outlet of level-one membranous system with the level-one membranous system;
Second level membranous system is connect for separating the acid solution in spent acid, anion and metal ion with the intermediate water tank;
Through liquid case, for collecting in the second level membranous system containing most of monovalent ion (such as F-、Cl-) permeate, with The second level membranous system connection;
Liquid case is concentrated, for collecting in the second level membranous system containing a small amount of F-And Cl-Concentrate, with the second level membrane system System connection;
Electrolysis unit is connect for recycling the precious metal in concentrate with the concentration liquid case.
Further, the pre-filtrating equipment is more medium filter, sand filtering device, active carbon filter or bag type filtering One of device is a variety of.
Further, the level-one membranous system includes several ultrafiltration or microfiltration membranes, and the ultrafiltration or microfiltration membranes are tubular membrane Or one of rolled film.
Further, the membrane component material of the level-one membranous system is polytetrafluoroethylene (PTFE) (PTFE), polyether sulfone (PES), gathers One of ethylene (PE) or polysulfones (PSF).
Further, the second level membranous system be include several acidproof nanofiltration membranes of special type, the acidproof nanofiltration membrane of special type is One of tubular membrane or rolled film.
Further, the membrane material of extraordinary acidproof nanofiltration membrane is polysulfones (PSF), polytetrafluoroethylene (PTFE) in the second level membranous system (PTFE) or one of polyethylene (PE).
Further, the electrolysis unit is reverse-flow type electrolysis unit, rotary electrolysis unit or tumble type electrolysis unit One of.
Further, the electrode of the electrolysis unit is one of graphite electrode or lead electrode.
A kind of method of heavy metal and resource utilization in waste acid recovery, comprising the following steps:
A. spent acid is lifted into buffer tank through pump, carries out the adjusting of water quality and quantity, to guarantee that subsequent treatment process is stablized Operation;
B. the particulate matters such as suspended matter, colloidal substance in pre-filtrating equipment filtering removal buffer tank water outlet;
C. pre-filtrating equipment water outlet enters level-one membranous system, removes the suspended matter and colloid for failing retention in pre-filtration system Substance;
D. intermediate water tank collects the water outlet of level-one membranous system;
E. intermediate water tank water outlet enters second level membranous system, separates acid solution, anion and metal ion in spent acid, and discharge contains The permeate of most of monovalent ion and the concentrate containing a small amount of monovalent ion;
F. the permeate containing most of monovalent ion of second level membranous system discharge is after through liquid case by after neutralisation treatment It can be used for industrial reuse;
G. enter electrolysis dress after most of concentrated liquid case of concentrate containing a small amount of monovalent ion of second level membranous system discharge Setting progress acid solution and expensive, heavy metal recycling, acid solution after the recovery and heavy metal can be back in industrial production, realize Resource utilization, another part concentrate are back to intermediate water tank.
Further, handled spent acid is the mixed acid containing heavy metal.
Further, concentration sour in concentrate caused by the second level membranous system is the % of 10 % ~ 20.
The invention has the benefit that
1. heavy metal and the method and apparatus of resource utilization in waste acid recovery of the present invention, by UF membrane, chemistry Neutralization combines with electrolysis tech, avoids traditional neutralization precipitation technique and generates the deficiency that waste residue causes secondary pollution, realizes The minimizing processing of spent acid, waste residue, and the recycling of acid solution and heavy metal can be carried out, and then increase certain economy for enterprise Benefit.
2. heavy metal and the method and apparatus of resource utilization, second level membranous system penetrate in waste acid recovery of the present invention SO in liquid4 2-Low with the above heavy metal concentration of divalent, waste residue yield reduces during subsequent neutralisation treatment, and spent acid minimizing journey Degree is high, can reach the % of 30 % ~ 50.
3. the method and apparatus of heavy metal and resource utilization, waste acid treatment are at low cost in waste acid recovery of the present invention.
4. heavy metal and the method and apparatus of resource utilization in waste acid recovery of the present invention, the rate of recovery is high, recycling Acid solution and heavy metal can be back in industrial production, realize resource utilization.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this Some embodiments of invention for those of ordinary skill in the art, can be under the precursor not made the creative labor Other attached drawings are obtained according to these attached drawings.
Fig. 1 is the structural block diagram of heavy metal and resource utilization device in a kind of waste acid recovery of the present invention;
Fig. 2 is heavy metal and the step flow chart of resource utilization method in a kind of waste acid recovery of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts all other Embodiment shall fall within the protection scope of the present invention.
As shown in Figure 1, heavy metal and the device of resource utilization in a kind of waste acid recovery of the present invention, comprising:
Buffer tank guarantees subsequent treatment process stable operation for carrying out the adjusting of water quality and quantity to spent acid;
Pre-filtrating equipment, for removing the particulate matters such as suspended matter, colloidal substance in spent acid waste water, with the buffer tank Connection;
Level-one membranous system, for removing the suspended matter and colloidal substance that fail retention in pre-filtration system, with the pre- mistake Filter device connection;
Intermediate water tank is connect for collecting the water outlet of level-one membranous system with the level-one membranous system;
Second level membranous system is connect for separating the acid solution in spent acid, anion and metal ion with the intermediate water tank;
Through liquid case, for collecting in the second level membranous system containing most of monovalent ion (such as F-、Cl-) permeate, with The second level membranous system connection;
Liquid case is concentrated, for collecting in the second level membranous system containing a small amount of F-And Cl-Concentrate, with the second level membrane system System connection;
Electrolysis unit is connect for recycling the precious metal in concentrate with the concentration liquid case.
Preferably, the pre-filtrating equipment is more medium filter, sand filtering device, active carbon filter or bag filter One of or it is a variety of.Wherein, more medium filter is to make water logical under certain pressure conditions using one or more media Certain thickness granular or on-granulated filtrate is crossed, so that the suspended matter and colloid that are effectively removed in water make the device of clarification of water, Common filtrate has quartz sand, anthracite, gravel, magnetic iron ore or anthracite etc..
Preferably, the level-one membranous system includes several ultrafiltration or microfiltration membranes, the ultrafiltration or microfiltration membranes be tubular membrane or One of rolled film.
Preferably, the membrane component material of the level-one membranous system is polytetrafluoroethylene (PTFE) (PTFE), polyether sulfone (PES), poly- second One of alkene (PE) or polysulfones (PSF).
Preferably, the second level membranous system be include several acidproof nanofiltration membranes of special type, the acidproof nanofiltration membrane of special type is pipe One of formula film or rolled film.
Preferably, the membrane material of extraordinary acidproof nanofiltration membrane is polysulfones (PSF), polytetrafluoroethylene (PTFE) in the second level membranous system (PTFE) or one of polyethylene (PE).
Preferably, the electrolysis unit is in reverse-flow type electrolysis unit, rotary electrolysis unit or tumble type electrolysis unit One kind, electrolysis unit carries out electrolysis processing using electric power provided by power supply, and the heavy metal ion in concentrate is filled in electrolysis Cathodic reduction is set into metallic state to realize recycling, and remaining electrolysis waste solution contains acid solution ingredient and can carry out acid solution in electrolysis unit Recycling.
Preferably, the electrode of the electrolysis unit is one of graphite electrode or lead electrode.
As shown in Fig. 2, the present invention also provides heavy metal in a kind of waste acid recovery and the methods of resource utilization, including with Lower step:
A. spent acid is lifted into buffer tank through pump, carries out the adjusting of water quality and quantity, to guarantee that subsequent treatment process is stablized Operation;
B. the particulate matters such as suspended matter, colloidal substance in pre-filtrating equipment filtering removal buffer tank water outlet;
C. pre-filtrating equipment water outlet enters level-one membranous system, removes the suspended matter and colloid for failing retention in pre-filtration system Substance;
D. intermediate water tank collects the water outlet of level-one membranous system;
E. intermediate water tank water outlet enters second level membranous system, separates acid solution, anion and metal ion in spent acid, and discharge contains The permeate of most of monovalent ion and the concentrate containing a small amount of monovalent ion;
F. the permeate containing most of monovalent ion of second level membranous system discharge is after through liquid case by after neutralisation treatment It can be used for industrial reuse;
G. enter electrolysis dress after most of concentrated liquid case of concentrate containing a small amount of monovalent ion of second level membranous system discharge Setting progress acid solution and expensive, heavy metal recycling, acid solution after the recovery and heavy metal can be back in industrial production, realize Resource utilization, another part concentrate are back to intermediate water tank.
Preferably, handled spent acid is the mixed acid containing heavy metal.
Preferably, concentration sour in concentrate caused by the second level membranous system is the % of 10 % ~ 20.
Heavy metal and the method and apparatus of resource utilization, have the advantage that in waste acid recovery of the present invention
1. heavy metal and the method and apparatus of resource utilization in waste acid recovery of the present invention, by UF membrane, chemistry Neutralization combines with electrolysis tech, avoids traditional neutralization precipitation technique and generates the deficiency that waste residue causes secondary pollution, realizes The minimizing processing of spent acid, waste residue, and the recycling of acid solution and heavy metal can be carried out, and then increase certain economy for enterprise Benefit.
2. heavy metal and the method and apparatus of resource utilization, second level membranous system penetrate in waste acid recovery of the present invention SO in liquid4 2-Low with the above heavy metal concentration of divalent, waste residue yield reduces during subsequent neutralisation treatment, and spent acid minimizing journey Degree is high, can reach the % of 30 % ~ 50.
3. the method and apparatus of heavy metal and resource utilization, waste acid treatment are at low cost in waste acid recovery of the present invention.
4. heavy metal and the method and apparatus of resource utilization in waste acid recovery of the present invention, the rate of recovery is high, recycling Acid solution and heavy metal can be back in industrial production, realize resource utilization.
Several examples are exemplified below to illustrate effect of the invention, but the scope of the claims invented is not limited only to this.
Embodiment 1 is certain Copper making spent acid, and wherein acid mass fraction (with sulphur acid meter) is 7.2 %, fluorinion concentration 153 Mg/L, chlorine ion concentration are 1080 mg/L, and copper ion concentration is 510 mg/L, and plumbum ion concentration is 60 mg/L, pass through pre- mistake Device and level-one membranous system are filtered, the suspended matter and colloid in spent acid are removed, and acid mass fraction is in second level membranous system permeate 0.8 %, chlorine ion concentration are 1030 mg/L, and fluorinion concentration is 140 mg/L, and acid mass fraction is 13.8 % in concentrate, Copper ion concentration is 503 mg/L, and plumbum ion concentration is 58.87 mg/L, and concentrate is after electrolysis unit is electrolysed in electrolyte Acid mass fraction is about 14 %, and the rate of recovery of copper is 97.9 %, and the rate of recovery of lead is 95 %.
Embodiment 2 is the spent acid of certain electroplate factory, and wherein acid mass fraction (with sulphur acid meter) is 6.2 %, and zinc ion concentration is 33.2 mg/L, copper ion concentration are 118 mg/L, and plumbum ion concentration is 12.5 mg/L, and nickel ion concentration is 20 mg/L, are passed through Pre-filtrating equipment and level-one membranous system, suspended matter and colloid in spent acid are removed, sour quality point in second level membranous system permeate Number is 0.68 %, and acid mass fraction is 11.9 % in concentrate, and zinc ion concentration is 32.8 mg/L, copper ion concentration 116.3 Mg/L, plumbum ion concentration are 11.6 mg/L, and nickel ion concentration is 19.3 mg/L, and concentrate is electrolysed after electrolysis unit is electrolysed Acid mass fraction is about 12 % in liquid, and the rate of recovery of zinc is 96.6 %, and 97 5 % of the rate of recovery of copper, the rate of recovery of lead is 96 %, The rate of recovery of nickel is 98.6 %.
It is described above to be not intended to limit the invention because of presently preferred embodiments of the present invention, it is all in essence of the invention Within mind and principle, made any modification, substitute equivalents, improvement etc. be should be included within protection scope of the present invention.

Claims (10)

1. heavy metal and the device of resource utilization in a kind of waste acid recovery characterized by comprising
Buffer tank guarantees subsequent treatment process stable operation for carrying out the adjusting of water quality and quantity to spent acid;
Pre-filtrating equipment, for removing suspended matter, colloidal substance in spent acid waste water, the pre-filtrating equipment is multi-medium filtering One of device, sand filtering device, active carbon filter or bag filter are a variety of, connect with the buffer tank;
Level-one membranous system, for removing the suspended matter and colloidal substance that fail retention in pre-filtration system, the level-one membranous system Including several ultrafiltration or microfiltration membranes, it is connect with the pre-filtrating equipment;
Intermediate water tank is connect for collecting the water outlet of level-one membranous system with the level-one membranous system;
Second level membranous system, for separating the acid solution in spent acid, anion and metal ion, the second level membranous system be include several Extraordinary acidproof nanofiltration membrane, connect with the intermediate water tank;
Through liquid case, for collecting in the second level membranous system containing most of monovalent ion F-And Cl-Permeate, with described two Grade membranous system connection;
Liquid case is concentrated, for collecting in the second level membranous system containing a small amount of F-And Cl-Concentrate, with the second level membranous system connect It connects;
Electrolysis unit is connect for recycling the precious metal in concentrate with the concentration liquid case.
2. heavy metal and the device of resource utilization in waste acid recovery according to claim 1, which is characterized in that described one The ultrafiltration of grade membranous system or microfiltration membranes are one of tubular membrane or rolled film.
3. heavy metal and the device of resource utilization in waste acid recovery according to claim 1, which is characterized in that described one The membrane component material of grade membranous system is polytetrafluoroethylene (PTFE) (PTFE), polyether sulfone (PES), in polyethylene (PE) or polysulfones (PSF) It is a kind of.
4. heavy metal and the device of resource utilization in waste acid recovery according to claim 1, which is characterized in that described two The acidproof nanofiltration membrane of special type of grade membranous system is one of tubular membrane or rolled film.
5. heavy metal and the device of resource utilization in waste acid recovery according to claim 1, which is characterized in that described two The membrane material of extraordinary acidproof nanofiltration membrane is polysulfones (PSF), in polytetrafluoroethylene (PTFE) (PTFE) or polyethylene (PE) in grade membranous system It is a kind of.
6. heavy metal and the device of resource utilization in waste acid recovery according to claim 1, which is characterized in that the electricity Solution device is one of reverse-flow type electrolysis unit, rotary electrolysis unit or tumble type electrolysis unit.
7. heavy metal and the device of resource utilization in waste acid recovery according to claim 1, which is characterized in that the electricity The electrode for solving device is one of graphite electrode or lead electrode.
8. a kind of method of heavy metal and resource utilization in waste acid recovery, which comprises the following steps:
A, spent acid is lifted into buffer tank through pump, the adjusting of water quality and quantity is carried out, to guarantee subsequent treatment process stable operation;
B, the suspended matter in pre-filtrating equipment filtering removal buffer tank water outlet, colloidal substance;
C, pre-filtrating equipment water outlet enters level-one membranous system, removes the suspended matter and colloid substances for failing retention in pre-filtration system Matter;
D, intermediate water tank collects the water outlet of level-one membranous system;
E, intermediate water tank water outlet enters second level membranous system, separates acid solution, anion and metal ion in spent acid, and discharge contains big portion The permeate for dividing monovalent ion and the concentrate containing a small amount of monovalent ion;
F, the permeate containing most of monovalent ion of second level membranous system discharge is after through liquid case by that can use after neutralisation treatment In industrial reuse;
G, enter after most of concentrated liquid case of concentrate containing a small amount of monovalent ion of second level membranous system discharge electrolysis unit into Row acid solution and expensive, heavy metal recycling, acid solution after the recovery and heavy metal can be back in industrial production, realize resource Change and utilize, another part concentrate is back to intermediate water tank.
9. the method for heavy metal and resource utilization in waste acid recovery according to claim 8, which is characterized in that handled Spent acid be the mixed acid containing heavy metal.
10. the method for heavy metal and resource utilization in waste acid recovery according to claim 8, which is characterized in that described Sour concentration is 10%~20% in concentrate caused by second level membranous system.
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CN106544528B (en) * 2016-10-27 2018-07-03 环境保护部华南环境科学研究所 A kind of method that metallic nickel is recycled from pickling waste waters
CN108675502A (en) * 2018-06-13 2018-10-19 武汉飞博乐环保工程有限公司 A kind of waste acid resource method
CN109824128B (en) * 2019-04-03 2021-09-24 东北师范大学 Method for removing heavy metal ions in waste acid
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