CN105400959A - Method and device for performing recovery and resource utilization on heavy metal in waste acid - Google Patents
Method and device for performing recovery and resource utilization on heavy metal in waste acid Download PDFInfo
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- CN105400959A CN105400959A CN201511010972.XA CN201511010972A CN105400959A CN 105400959 A CN105400959 A CN 105400959A CN 201511010972 A CN201511010972 A CN 201511010972A CN 105400959 A CN105400959 A CN 105400959A
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- 239000002253 acid Substances 0.000 title claims abstract description 110
- 238000011084 recovery Methods 0.000 title claims abstract description 62
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000002699 waste material Substances 0.000 title claims abstract description 42
- 239000012528 membrane Substances 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000012466 permeate Substances 0.000 claims abstract description 20
- 238000004064 recycling Methods 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- 239000004698 Polyethylene Substances 0.000 claims description 12
- 229920002492 poly(sulfone) Polymers 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 12
- -1 polyethylene Polymers 0.000 claims description 10
- 238000001728 nano-filtration Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 238000001471 micro-filtration Methods 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 239000013618 particulate matter Substances 0.000 claims description 6
- 238000011045 prefiltration Methods 0.000 claims description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000108 ultra-filtration Methods 0.000 claims description 6
- 238000009776 industrial production Methods 0.000 claims description 5
- 239000002351 wastewater Substances 0.000 claims description 4
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 38
- 150000002500 ions Chemical class 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 229910001338 liquidmetal Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
-
- 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)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a method and a device for performing recovery and resource utilization on heavy metal in waste acid and solves the problems of high waste residue output, high operating expense, low recovery rate and the like. The device for performing recovery and resource utilization on the heavy metal in the waste acid comprises a buffer tank, a pre-filtering device connected with the buffer tank, a first-level membrane system connected with the pre-filtering device, a middle water tank connected with the first-level membrane system, a second-level membrane system connected with the middle water tank, a permeate liquid tank connected with the second-level membrane system, a concentrated liquid tank connected with the second-level membrane system and an electrolysis unit connected with the concentrated liquid tank. The method and the device have the benefits as follows: the reduction treatment of the waste acid is realized, the waste residue output is low, the heavy metal recovery rate is high, and the treatment expanse is low.
Description
Technical field
The invention belongs to Hazardous wastes process field, refer to the method and apparatus of heavy metal in a kind of waste acid recovery recycling especially.
Background technology
Along with industry and expanding economy, the spent acid that China produces every year is more than 100,000,000 tons, and according to China Chemical Information Center's investigation statistics, wherein inorganic spent acid accounts for 35%, and organic spent acid accounts for 65%, and the spent acid of content more than 40% accounts for about 46% of total amount.Industrial waste acid mainly comes from the fields such as the industrial chemicals such as refining of petroleum, sulfuric acid is produced, iron and steel processing washing, bronze production pickling, electronic components fabrication.Because spent acid is generally containing organism and heavy metal ion, direct utilization can cause secondary pollution, and undressed spent acid enters in physical environment can cause soil acidification, heavy metal in spent acid activity in acid soil is higher to be easily absorbed by plants, and then causes major hidden danger to food safety.The environmental protection faced along with China and HUMAN HEALTH safe pressure increasingly serious, the environmental requirement of the aspects such as therefore government-to-businesses cleaner production, energy-saving and emission-reduction, wastewater pollution prevention improves constantly.
At present, the treatment process that China's spent acid is generally taked is moderate water-cut stage, this technique not only needs to consume a large amount of neutralizing agents, also can produce a large amount of solid slags, and working cost is higher, the rate of recovery is low, simultaneously moderate water-cut stage can not fundamentally decontamination, and just pollutent is shifted in different media, particularly poisonous and hazardous material is transferred in solid slag from water, causes secondary pollution, forms the vicious cycle of " control and be unequal to controlling ", along with country is to the attention of industrial residue problem, the drawback that this treatment process exists becomes increasingly conspicuous.On the other hand, part industrial waste acid also adopts pyrohydrolysis and method of evaporation, but this process energy consumption is excessive, is unsuitable for industrial applications on a large scale, is only applicable to the particular components that added value of product is high.
Although spent acid can cause serious harm to physical environment and HUMAN HEALTH, generally comprise in spent acid simultaneously and there is the sulfuric acid or nitric acid and metal values (as copper or nickel) that recoverable is worth.Based on the theory of material recycle and recycling economy, changing from simple spent acid qualified discharge to recovery valuable metal and water resources reuse technology becomes China gradually and to give up acid-treated development trend.In spent acid traditional in industry, heavy metal recovery technique is generally and adopts electroplating technology that heavy metal ion is reduced to metallic state, but the quality of metal recovery rate and Footwall drift can be affected because of the reduction of metal content in spent acid in process, therefore timing is needed to detect metal content in spent acid, and supplement spent acid, and then cause technique loaded down with trivial details, need a large amount of manpowers.And the recovery of acid solution generally adopts heating distil process to reclaim the lower acid solution of boiling point in spent acid, such as reclaim the nitric acid of boiling point lower than sulfuric acid, but the sulfuric acid reclaiming boiling point higher then needs extra recycling equipment, complex process and cost recovery is caused to improve.
In sum, spent acid process traditional in industry and recovery process all come with some shortcomings in actual application, as easily caused secondary pollution, technique is loaded down with trivial details, the rate of recovery is low, cost recovery is high, therefore explores to develop heavy metal recovery in the spent acid that makes new advances and the method and apparatus of recycling has great importance to Industrial-Enterprises in China cleaner production, energy-saving and emission-reduction.
Summary of the invention
The invention provides the method and apparatus of heavy metal in a kind of waste acid recovery recycling, the waste residue solving the generation of existing Technology easily causes the problems such as secondary pollution, technique is loaded down with trivial details, the rate of recovery is low, cost recovery is high.
Technical scheme of the present invention is achieved in that
Heavy metal in waste acid recovery a device for recycling, comprising:
Buffer tank, for carrying out the adjustment of water quality and quantity to spent acid, ensures subsequent treatment process steady running;
Pre-filtrating equipment, for removing the particulate matter such as suspended substance, colloidalmaterial in spent acid waste water, is connected with described buffer tank;
One-level membranous system, for removing in pre-filtration system the suspended substance and colloidalmaterial failing to retain, is connected with described pre-filtrating equipment;
Intermediate water tank, for collecting the water outlet of one-level membranous system, is connected with described one-level membranous system;
Secondary membrane system, for separating of the acid solution in spent acid, negatively charged ion and metal ion, is connected with described intermediate water tank;
Permeate case, contains most of monovalent ion (as F for collecting in described secondary membrane system
-, Cl
-) permeate, be connected with described secondary membrane system;
Concentrated solution case, for collecting in described secondary membrane system containing a small amount of F
-and Cl
-concentrated solution, be connected with described secondary membrane system;
Electrolyzer, for reclaiming the noble metal in concentrated solution, is connected with described concentrated solution case.
Further, described pre-filtrating equipment is one or more in more medium filter, sand filtering device, activated charcoal filter or deep bed filter.
Further, described one-level membranous system comprises some ultrafiltration or microfiltration membrane, and described ultrafiltration or microfiltration membrane are the one in tubular membrane or rolled film.
Further, the membrane element material of described one-level membranous system is the one in tetrafluoroethylene (PTFE), polyethersulfone (PES), polyethylene (PE) or polysulfones (PSF).
Further, described secondary membrane system is for comprising the acidproof nanofiltration membrane of some special types, and the acidproof nanofiltration membrane of described special type is the one in tubular membrane or rolled film.
Further, in described secondary membrane system, the mould material of extraordinary acidproof nanofiltration membrane is the one in polysulfones (PSF), tetrafluoroethylene (PTFE) or polyethylene (PE).
Further, described electrolyzer is the one in return-flow type electrolyzer, rotary type electrolyzer or tumble type electrolyzer.
Further, the electrode of described electrolyzer is the one in Graphite Electrodes or lead electrode.
Heavy metal in waste acid recovery a method for recycling, comprise the following steps:
A. spent acid promotes through pump and enters buffer tank, carries out the adjustment of water quality and quantity, to ensure subsequent treatment process steady running;
B. pre-filtrating equipment filters the particulate matter such as suspended substance, colloidalmaterial removed in buffer tank water outlet;
C. pre-filtrating equipment water outlet enters one-level membranous system, removes in pre-filtration system the suspended substance and colloidalmaterial failing to retain;
D. intermediate water tank collects the water outlet of one-level membranous system;
E. intermediate water tank water outlet enters secondary membrane system, is separated acid solution, negatively charged ion and metal ion in spent acid, discharges the permeate containing most of monovalent ion and the concentrated solution containing a small amount of monovalent ion;
F. secondary membrane system discharge containing the permeate of most of monovalent ion after permeate case by can be used for industrial reuse after neutralizing treatment;
G. the major part that secondary membrane system is discharged enters electrolyzer containing the concentrated solution of a small amount of monovalent ion and carries out acid solution and recovery that is expensive, heavy metal after concentrated solution case, acid solution after recovery and heavy metal all can be back in industrial production, realize recycling, a part of concentrated solution is back to intermediate water tank in addition.
Further, handled spent acid is the mixing acid containing heavy metal.
Further, in the concentrated solution that produces of described secondary membrane system, the concentration of acid is 10% ~ 20%.
Beneficial effect of the present invention is:
1. heavy metal the method and apparatus of recycling in waste acid recovery of the present invention, membrane sepn, chemical neutralization are combined with electrolysis tech, avoid traditional neutralization precipitation technique and produce the deficiency that waste residue causes secondary pollution, achieve the minimizing process of spent acid, waste residue, and the recovery of acid solution and heavy metal can be carried out, and then increase certain economic benefit for enterprise.
2. heavy metal the method and apparatus of recycling in waste acid recovery of the present invention, SO in secondary membrane system permeate
4 2-low with the above heavy metal concentration of divalence, in follow-up neutralizing treatment process, waste residue output reduces, and spent acid minimizing degree is high, can reach 30% ~ 50%.
3. heavy metal the method and apparatus of recycling in waste acid recovery of the present invention, spent acid processing cost is low.
4. heavy metal the method and apparatus of recycling in waste acid recovery of the present invention, the rate of recovery is high, and restored acid liquid and heavy metal all can be back in industrial production, realize recycling.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the precursor not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is heavy metal the structured flowchart of resource utilization device in a kind of waste acid recovery of the present invention;
Fig. 2 is heavy metal the flow chart of steps of resource utilization method in a kind of waste acid recovery of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making other embodiments all obtained under creative work prerequisite, belong to the scope of protection of the invention.
As shown in Figure 1, heavy metal in a kind of waste acid recovery of the present invention the device of recycling, comprising:
Buffer tank, for carrying out the adjustment of water quality and quantity to spent acid, ensures subsequent treatment process steady running;
Pre-filtrating equipment, for removing the particulate matter such as suspended substance, colloidalmaterial in spent acid waste water, is connected with described buffer tank;
One-level membranous system, for removing in pre-filtration system the suspended substance and colloidalmaterial failing to retain, is connected with described pre-filtrating equipment;
Intermediate water tank, for collecting the water outlet of one-level membranous system, is connected with described one-level membranous system;
Secondary membrane system, for separating of the acid solution in spent acid, negatively charged ion and metal ion, is connected with described intermediate water tank;
Permeate case, contains most of monovalent ion (as F for collecting in described secondary membrane system
-, Cl
-) permeate, be connected with described secondary membrane system;
Concentrated solution case, for collecting in described secondary membrane system containing a small amount of F
-and Cl
-concentrated solution, be connected with described secondary membrane system;
Electrolyzer, for reclaiming the noble metal in concentrated solution, is connected with described concentrated solution case.
Preferably, described pre-filtrating equipment is one or more in more medium filter, sand filtering device, activated charcoal filter or deep bed filter.Wherein, more medium filter utilizes one or more media, make water by certain thickness granular or on-granulated filtrate under certain pressure conditions, thus the suspended substance effectively removed in water and colloid make the device of clarification of water, conventional filtrate has quartz sand, hard coal, gravel, magnetite or hard coal etc.
Preferably, described one-level membranous system comprises some ultrafiltration or microfiltration membrane, and described ultrafiltration or microfiltration membrane are the one in tubular membrane or rolled film.
Preferably, the membrane element material of described one-level membranous system is the one in tetrafluoroethylene (PTFE), polyethersulfone (PES), polyethylene (PE) or polysulfones (PSF).
Preferably, described secondary membrane system is for comprising the acidproof nanofiltration membrane of some special types, and the acidproof nanofiltration membrane of described special type is the one in tubular membrane or rolled film.
Preferably, in described secondary membrane system, the mould material of extraordinary acidproof nanofiltration membrane is the one in polysulfones (PSF), tetrafluoroethylene (PTFE) or polyethylene (PE).
Preferably, described electrolyzer is the one in return-flow type electrolyzer, rotary type electrolyzer or tumble type electrolyzer, the electric power that electrolyzer utilizes power supply to provide carries out electrolysis treatment, heavy metal ion in concentrated solution becomes metallic state to realize reclaiming at electrolyzer cathodic reduction, and electrolysis waste solution residual in electrolyzer contains the recovery that acid solution composition can carry out acid solution.
Preferably, the electrode of described electrolyzer is the one in Graphite Electrodes or lead electrode.
As shown in Figure 2, present invention also offers the method for heavy metal in a kind of waste acid recovery recycling, comprise the following steps:
A. spent acid promotes through pump and enters buffer tank, carries out the adjustment of water quality and quantity, to ensure subsequent treatment process steady running;
B. pre-filtrating equipment filters the particulate matter such as suspended substance, colloidalmaterial removed in buffer tank water outlet;
C. pre-filtrating equipment water outlet enters one-level membranous system, removes in pre-filtration system the suspended substance and colloidalmaterial failing to retain;
D. intermediate water tank collects the water outlet of one-level membranous system;
E. intermediate water tank water outlet enters secondary membrane system, is separated acid solution, negatively charged ion and metal ion in spent acid, discharges the permeate containing most of monovalent ion and the concentrated solution containing a small amount of monovalent ion;
F. secondary membrane system discharge containing the permeate of most of monovalent ion after permeate case by can be used for industrial reuse after neutralizing treatment;
G. the major part that secondary membrane system is discharged enters electrolyzer containing the concentrated solution of a small amount of monovalent ion and carries out acid solution and recovery that is expensive, heavy metal after concentrated solution case, acid solution after recovery and heavy metal all can be back in industrial production, realize recycling, a part of concentrated solution is back to intermediate water tank in addition.
Preferably, handled spent acid is the mixing acid containing heavy metal.
Preferably, in the concentrated solution that produces of described secondary membrane system, the concentration of acid is 10% ~ 20%.
Heavy metal in waste acid recovery of the present invention the method and apparatus of recycling, have the following advantages:
1. heavy metal the method and apparatus of recycling in waste acid recovery of the present invention, membrane sepn, chemical neutralization are combined with electrolysis tech, avoid traditional neutralization precipitation technique and produce the deficiency that waste residue causes secondary pollution, achieve the minimizing process of spent acid, waste residue, and the recovery of acid solution and heavy metal can be carried out, and then increase certain economic benefit for enterprise.
2. heavy metal the method and apparatus of recycling in waste acid recovery of the present invention, SO in secondary membrane system permeate
4 2-low with the above heavy metal concentration of divalence, in follow-up neutralizing treatment process, waste residue output reduces, and spent acid minimizing degree is high, can reach 30% ~ 50%.
3. heavy metal the method and apparatus of recycling in waste acid recovery of the present invention, spent acid processing cost is low.
4. heavy metal the method and apparatus of recycling in waste acid recovery of the present invention, the rate of recovery is high, and restored acid liquid and heavy metal all can be back in industrial production, realize recycling.
Below enumerate several example so that effect of the present invention to be described, but the right of invention is not limited only to this.
Embodiment 1 is certain Copper making spent acid, wherein sour massfraction (with sulphur acid meter) is 7.2%, fluorinion concentration is 153mg/L, chlorine ion concentration is 1080mg/L, copper ion concentration is 510mg/L, plumbum ion concentration is 60mg/L, by pre-filtrating equipment and one-level membranous system, suspended substance in spent acid and colloid are removed, in secondary membrane system permeate, sour massfraction is 0.8%, chlorine ion concentration is 1030mg/L, fluorinion concentration is 140mg/L, in concentrated solution, sour massfraction is 13.8%, copper ion concentration is 503mg/L, plumbum ion concentration is 58.87mg/L, concentrated solution after electrolyzer electrolysis in electrolytic solution sour massfraction be about 14%, the rate of recovery of copper is 97.9%, the plumbous rate of recovery is 95%.
Embodiment 2 is the spent acid of certain Electroplate Factory, wherein sour massfraction (with sulphur acid meter) is 6.2%, zinc ion concentration is 33.2mg/L, copper ion concentration is 118mg/L, plumbum ion concentration is 12.5mg/L, nickel ion concentration is 20mg/L, by pre-filtrating equipment and one-level membranous system, suspended substance in spent acid and colloid are removed, in secondary membrane system permeate, sour massfraction is 0.68%, in concentrated solution, sour massfraction is 11.9%, zinc ion concentration is 32.8mg/L, copper ion concentration is 116.3mg/L, plumbum ion concentration is 11.6mg/L, nickel ion concentration is 19.3mg/L, concentrated solution after electrolyzer electrolysis in electrolytic solution sour massfraction be about 12%, the rate of recovery of zinc is 96.6%, the rate of recovery 975% of copper, the plumbous rate of recovery is 96%, the rate of recovery of nickel is 98.6%.
The above is because preferred embodiment of the present invention, and not in order to limit the present invention, all within the spirit and principles in the present invention, any amendment, substitute equivalents, improvement etc. done, within all should being included in protection scope of the present invention.
Claims (10)
1. heavy metal a device for recycling in waste acid recovery, is characterized in that, comprising:
Buffer tank, for carrying out the adjustment of water quality and quantity to spent acid, ensures subsequent treatment process steady running;
Pre-filtrating equipment, for removing the particulate matter such as suspended substance, colloidalmaterial in spent acid waste water, is connected with described buffer tank;
One-level membranous system, for removing in pre-filtration system the suspended substance and colloidalmaterial failing to retain, is connected with described pre-filtrating equipment;
Intermediate water tank, for collecting the water outlet of one-level membranous system, is connected with described one-level membranous system;
Secondary membrane system, for separating of the acid solution in spent acid, negatively charged ion and metal ion, is connected with described intermediate water tank;
Permeate case, contains most of monovalent ion (as F for collecting in described secondary membrane system
-, Cl
-) permeate, be connected with described secondary membrane system;
Concentrated solution case, for collecting in described secondary membrane system containing a small amount of F
-and Cl
-concentrated solution, be connected with described secondary membrane system;
Electrolyzer, for reclaiming the noble metal in concentrated solution, is connected with described concentrated solution case.
2. heavy metal the device of recycling in waste acid recovery according to claim 1, it is characterized in that, described one-level membranous system comprises some ultrafiltration or microfiltration membrane, and described ultrafiltration or microfiltration membrane are the one in tubular membrane or rolled film.
3. heavy metal the device of recycling in waste acid recovery according to claim 1, it is characterized in that, the membrane element material of described one-level membranous system is the one in tetrafluoroethylene (PTFE), polyethersulfone (PES), polyethylene (PE) or polysulfones (PSF).
4. heavy metal the device of recycling in waste acid recovery according to claim 1, is characterized in that, described secondary membrane system is for comprising the acidproof nanofiltration membrane of some special types, and the acidproof nanofiltration membrane of described special type is the one in tubular membrane or rolled film.
5. heavy metal the device of recycling in waste acid recovery according to claim 1, it is characterized in that, in described secondary membrane system, the mould material of extraordinary acidproof nanofiltration membrane is the one in polysulfones (PSF), tetrafluoroethylene (PTFE) or polyethylene (PE).
6. heavy metal the device of recycling in waste acid recovery according to claim 1, it is characterized in that, described electrolyzer is the one in return-flow type electrolyzer, rotary type electrolyzer or tumble type electrolyzer.
7. heavy metal the device of recycling in waste acid recovery according to claim 1, is characterized in that, the electrode of described electrolyzer is the one in Graphite Electrodes or lead electrode.
8. heavy metal a method for recycling in waste acid recovery, is characterized in that, comprise the following steps:
A, spent acid promote through pump and enter buffer tank, carry out the adjustment of water quality and quantity, to ensure subsequent treatment process steady running;
B, pre-filtrating equipment filter the particulate matter such as suspended substance, colloidalmaterial removed in buffer tank water outlet;
C, pre-filtrating equipment water outlet enter one-level membranous system, remove in pre-filtration system the suspended substance and colloidalmaterial failing to retain;
D, intermediate water tank collect the water outlet of one-level membranous system;
E, intermediate water tank water outlet enter secondary membrane system, are separated acid solution, negatively charged ion and metal ion in spent acid, discharge the permeate containing most of monovalent ion and the concentrated solution containing a small amount of monovalent ion;
F, secondary membrane system discharge containing the permeate of most of monovalent ion after permeate case by can be used for industrial reuse after neutralizing treatment;
The major part that G, secondary membrane system are discharged enters electrolyzer containing the concentrated solution of a small amount of monovalent ion and carries out acid solution and recovery that is expensive, heavy metal after concentrated solution case, acid solution after recovery and heavy metal all can be back in industrial production, realize recycling, a part of concentrated solution is back to intermediate water tank in addition.
9. heavy metal the method for recycling in waste acid recovery according to claim 8, it is characterized in that, handled spent acid is the mixing acid containing heavy metal.
10. heavy metal the method for recycling in waste acid recovery according to claim 8, is characterized in that, in the concentrated solution that described secondary membrane system produces, the concentration of acid is 10% ~ 20%.
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