CN108046507B - System and method for recycling pickling waste liquid containing heavy metal - Google Patents
System and method for recycling pickling waste liquid containing heavy metal Download PDFInfo
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- CN108046507B CN108046507B CN201810085776.6A CN201810085776A CN108046507B CN 108046507 B CN108046507 B CN 108046507B CN 201810085776 A CN201810085776 A CN 201810085776A CN 108046507 B CN108046507 B CN 108046507B
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- 239000007788 liquid Substances 0.000 title claims abstract description 264
- 239000002699 waste material Substances 0.000 title claims abstract description 90
- 238000004064 recycling Methods 0.000 title claims abstract description 43
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000005554 pickling Methods 0.000 title claims description 31
- 238000000605 extraction Methods 0.000 claims abstract description 124
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 109
- 238000003756 stirring Methods 0.000 claims abstract description 80
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000000926 separation method Methods 0.000 claims abstract description 59
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000011701 zinc Substances 0.000 claims abstract description 58
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 58
- 238000001704 evaporation Methods 0.000 claims abstract description 53
- 229910052742 iron Inorganic materials 0.000 claims abstract description 51
- 239000002253 acid Substances 0.000 claims abstract description 50
- 230000005587 bubbling Effects 0.000 claims abstract description 46
- 230000008020 evaporation Effects 0.000 claims abstract description 44
- 238000005406 washing Methods 0.000 claims abstract description 33
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 235000021110 pickles Nutrition 0.000 claims abstract description 17
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229940007718 zinc hydroxide Drugs 0.000 claims abstract description 17
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims abstract description 17
- 229960004887 ferric hydroxide Drugs 0.000 claims abstract description 16
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 16
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000011084 recovery Methods 0.000 claims abstract description 11
- 150000003751 zinc Chemical class 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims description 55
- 238000003860 storage Methods 0.000 claims description 42
- 239000000498 cooling water Substances 0.000 claims description 33
- 239000003513 alkali Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 230000001590 oxidative effect Effects 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims 1
- 239000011133 lead Substances 0.000 abstract description 28
- 229960000443 hydrochloric acid Drugs 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 28
- 238000011282 treatment Methods 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 11
- 229960002089 ferrous chloride Drugs 0.000 description 10
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- -1 lead and zinc Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 241000197194 Bulla Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000011276 addition treatment Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 208000002352 blister Diseases 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/16—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- 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)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The application discloses a system and a method for recycling acid washing waste liquid containing heavy metals, and belongs to the field of recycling dangerous waste. Aiming at the problem of high recovery difficulty of waste pickle containing three heavy metals of iron, zinc and lead in the prior art, the application provides a recycling system and a recycling method of waste pickle containing heavy metals; the system comprises an extraction device, a bubbling device, a stirring device, a solid-liquid separation device and an evaporation device, wherein the extraction device, the bubbling device, the stirring device and the solid-liquid separation device are sequentially connected, and the extraction device is connected with the evaporation device. The method comprises the following steps: extracting iron and zinc, back-extracting to recover ferric salt, back-extracting to recover zinc salt, recycling extractant, evaporating to recover hydrochloric acid and recovering lead salt. The application can realize the recycling of the acid washing waste liquid containing heavy metals, thereby respectively recovering and obtaining high-purity ferric hydroxide, zinc hydroxide, hydrochloric acid and lead chloride.
Description
Technical Field
The application belongs to the field of recycling of dangerous wastes, and particularly relates to a system and a method for recycling acid washing waste liquid containing heavy metals.
Background
Acid is widely used as a cleaning agent in industries such as metallurgy, machinery and the like, for example, the metal product processing industry, a large amount of acid is needed for surface cleaning or corrosion treatment, most enterprises mainly use hydrochloric acid as a cleaning liquid at present, and when the metal ions in the acid liquid reach a certain concentration, the cleaning effect and the corrosion effect are obviously reduced to form pickling waste liquid. The acid washing waste liquid has strong acidity, high concentration, large production amount and easy formation of acid mist, if the acid washing waste liquid is not properly treated, the acid washing waste liquid not only can seriously pollute the environment, but also can cause great waste of resources.
The main element contents of the pickling waste liquid are as follows: fe (Fe) 2+ The content is 70+ -5 g/L, fe 3+ The content is 30+/-5 g/L, zn 2+ The content is 5+/-1 g/L, pb 2+ The content is 3+/-1 g/L. The traditional treatment method adopts NaOH or Ca (OH) 2 The neutralization treatment is carried out, the pH value after the neutralization can meet the requirement, but other indexes are difficult to reach the standard, and a large amount of produced sludge contains metal salts, is difficult to dehydrate, difficult to dry and high in treatment difficulty, and most of the conditions are that the sludge is piled up to be treated, occupies a large amount of land and wastes a large amount of metal and acid. In addition to this, there are other treatments, such as membrane treatment, high temperature calcination. The membrane treatment method can efficiently recycle the acid and the metal salt, has high acid recovery rate and high purity, but has small treatment capacity, high pretreatment requirement, easy pollution of a membrane component and high treatment cost. The high-temperature roasting method has the advantages of large investment, large equipment occupation area, high requirements on equipment design, management, control and corrosion resistance, high operation cost and consumption of a large amount of cooling water, electricity and fuel, so that the method is only suitable for large enterprises and is not suitable for small and medium-sized enterprises.
Through searching, research on extraction recovery and evaporation recovery of pickling waste liquid is disclosed at present, such as Chinese patent application, publication number: CN105696010a, publication date: the technical scheme is that scrap iron or iron pieces are added into zinc-containing acid washing waste liquid, trivalent iron in the waste liquid is reduced into divalent iron, an extractant consisting of N235, isooctanol and sulfonated kerosene is added into the waste liquid to extract zinc, raffinate is ferrous chloride solution, a zinc-containing loaded organic phase is subjected to back extraction to convert zinc into back extraction liquid, the extracted organic phase is recycled, the back extraction liquid is subjected to sectional alkali addition treatment to obtain zinc hydroxide, and the back extraction liquid is recycled. The patent mainly aims at the iron-containing zinc-containing acid washing wastewater, the added extractant consisting of N235, isooctanol and sulfonated kerosene can separate zinc from iron, but extra iron filings or iron sheets are needed to reduce ferric iron in the wastewater to further prepare ferrous chloride, the ferric iron reduction process needs to strictly control the content of oxidizing substances in equipment, the production cost is increased, and the stability of the extracted product ferrous chloride is poor and is extremely easy to oxidize into ferric chloride; in addition, the extractant cannot recover lead ions, and the toxicity of N235 and sulfonated kerosene in the extractant is relatively high; therefore, the patent scheme cannot be adopted to treat and recover the acid washing wastewater containing iron, zinc and lead.
For another example, chinese patent, publication No.: CN106430100a, publication date: the technical scheme is that the iron-containing waste acid liquid to be treated is conveyed to a heat exchanger for heating, the heated iron-containing waste acid liquid is conveyed to a batching tank, ferrous chloride crystals are added into the batching tank to obtain ferrous chloride solution, the ferrous chloride solution is conveyed to an evaporation reaction kettle for heating and evaporation, acid-containing steam generated by evaporation enters an HCl collection tank after heat exchange of an exhaust pipe and the heat exchanger, evaporated concentrated solution is conveyed to a crystallization kettle for cooling and crystallization, and a solid-liquid separation tank separates the ferrous chloride solution and the ferrous chloride crystals formed after crystallization and respectively collects the separated ferrous chloride solution and ferrous chloride crystals. The method is only suitable for the waste acid liquid containing single metal, and if the waste acid liquid contains other metals such as lead and zinc, the residual products after direct evaporation are difficult to further separate, so that the purity of the obtained products is lower and the economical efficiency is also poor.
Disclosure of Invention
1. Problems to be solved
Aiming at the problem of high recovery difficulty of waste pickle containing three heavy metals of iron, zinc and lead in the prior art, the application provides a recycling system and a recycling method of waste pickle containing heavy metals. The method can recycle and prepare ferric hydroxide, zinc hydroxide, hydrochloric acid and lead chloride, thereby realizing the recycling of dangerous wastes.
2. Technical proposal
In order to solve the problems, the application adopts the following technical scheme.
The utility model provides a pickling waste liquid recycling system containing heavy metal, includes extraction device, bubbling device, agitating unit, solid-liquid separation device and evaporation plant, agitating unit includes agitating unit A and agitating unit B, solid-liquid separation device includes solid-liquid separation device A and solid-liquid separation device B; the extraction device, the bubbling device, the stirring device A, the solid-liquid separation device A, the stirring device B and the solid-liquid separation device B are sequentially connected, and the extraction device is connected with the evaporation device.
Preferably, a plurality of fixed rings are longitudinally arranged on the inner wall of the extraction device along the inner wall, a rotary table is arranged between two adjacent fixed rings and is fixed on a central shaft of the extraction device, the rotary table rotates along with the central shaft at a high speed during extraction, the generated shearing force forces the liquid to be dispersed and broken into a plurality of tiny liquid drops, and strong vortex motion is generated in the liquid, so that the contact area and the mass transfer coefficient between the two adjacent fixed rings are increased, and the extraction efficiency is improved; the first feed inlet of the extraction device is connected with the extractant storage tank through a liquid pump, and the second feed inlet of the extraction device is connected with the pickling waste liquid storage tank through a liquid pump.
Preferably, the feed inlet of the bubbling device is connected with the first discharge outlet of the extraction device through a liquid pump; the bubbling device is internally provided with a gas distributor, and the blown oxidizing gas can be fully mixed with the liquid to achieve the aim of complete oxidation; the first air outlet of the bubbling device is connected with a gas buffer tank through a gas pump, and the gas buffer tank is connected with the second air inlet of the bubbling device.
Preferably, the first feeding port of the stirring device A is connected with the discharging port of the bubbling device through a liquid pump, and the second feeding port of the stirring device A is connected with the alkali liquor storage tank A through the liquid pump. The stirring device A adopts an acid and alkali resistant reaction kettle, and the bottom of the kettle adopts an elliptical bottom structure, so that the mixed liquid is discharged, and the U-shaped polytetrafluoroethylene stirring paddle is arranged in the stirring device A, so that the acid and alkali resistant and uniform stirring effects can be achieved.
Preferably, the first feed inlet of the solid-liquid separation device A is connected with the discharge outlet of the stirring device A through a liquid pump, the solid collecting device A is arranged below the discharge outlet of the solid-liquid separation device A, and the liquid collecting tank A is arranged below the solid-liquid separation device A. The solid-liquid separation device A adopts a plate-frame filter pressing method, so that effective separation of solids and liquid can be realized.
Preferably, the first feed inlet of the stirring device B is connected with the liquid collecting tank A through a liquid pump, and the second feed inlet of the stirring device B is connected with the alkali liquor storage tank B through the liquid pump. The stirring device B adopts an acid and alkali resistant reaction kettle, the kettle bottom adopts an elliptical bottom structure, the mixed liquid is discharged, and the U-shaped polytetrafluoroethylene stirring paddle is arranged in the stirring device B, so that the acid and alkali resistant and uniform stirring effects can be achieved.
Preferably, the first feed inlet of the solid-liquid separation device B is connected with the discharge outlet of the stirring device B through a liquid pump, the solid collecting device B is arranged below the discharge outlet of the solid-liquid separation device B, the liquid collecting tank B is arranged below the solid-liquid separation device B, and the liquid collecting tank B is connected with the first feed inlet of the extraction device through a liquid pump. The solid-liquid separation device B adopts a plate-frame filter pressing method, so that effective separation of solids and liquid can be realized.
Preferably, the feed inlet of the evaporation device is connected with the second discharge outlet of the extraction device through a liquid pump, the air inlet of the condensation device is connected with the air outlet of the evaporation device through a gas pump, the cooling water storage tank is connected with the water inlet of the condensation device through a liquid pump, the condensation device and the cooling water storage tank form circulation, continuously flowing cooling water cools and condenses gas into liquid, and when the cooling water is insufficient, the cooling water can be replenished through the outside; the water outlet of the condensing device is connected with the cooling water storage tank through a liquid pump, the liquid collecting device is connected with the condensing device, and the solid collecting device C is communicated with the discharge port of the evaporating device.
A method for recycling pickling waste liquid containing heavy metals comprises the following steps:
A. extracting iron and zinc: adding an extractant into the extraction device through a liquid pump from an extractant storage tank, simultaneously adding acid washing waste liquid containing heavy metals into the extraction device through the liquid pump from an acid washing waste liquid storage tank, enabling the extractant to flow from top to bottom in the extractant storage tank, enabling the acid washing waste liquid to flow from bottom to top in the extractant storage tank, and reversely contacting the extractant storage tank and the acid washing waste liquid to perform extraction; the extraction layer is an extraction liquid containing iron and zinc, the extraction layer is transferred to a bubbling device by a liquid pump, and the extraction layer is a waste pickle containing lead and is transferred to an evaporation device by the liquid pump;
B. and (3) back extraction and recovery of ferric salt: continuously bubbling the oxidizing gas in the gas buffer tank into a bubbling device by a gas pump to obtain Fe in the extract liquid 2+ Oxidation to Fe 3+ The oxidizing gas flows in the bubbling device from bottom to top to carry out bubbling reaction, and then flows back to the gas buffer tank through the first gas outlet of the bubbling device to form oxidizing gas circulation; transferring the extract after the oxidation reaction to a stirring device A through a liquid pump at a discharge port of a bubbling device, adding alkali liquor into the stirring device A through a liquid pump from an alkali liquor storage tank A, stirring and mixing to obtain a first mixed liquor, transferring the mixed liquor to a solid-liquid separation device A through a liquid pump at a discharge port of the stirring device A, collecting ferric hydroxide solids obtained by separation in a solid collecting device A, and discharging the extract containing zincInto the liquid collection tank a;
C. and (3) back extraction and recovery of zinc salt: transferring the extract in the liquid collecting tank A to a stirring device B through a liquid pump, adding alkali liquor into the stirring device B through a liquid pump from an alkali liquor storage tank B, stirring and mixing to obtain a second mixed liquor, transferring the mixed liquor to a solid-liquid separation device B through a liquid pump from a discharge port of the stirring device B, collecting zinc hydroxide solids obtained by separation in the solid collecting device B, and discharging the extract without iron and zinc into the liquid collecting tank B;
D. recycling the extractant: the extraction liquid which does not contain iron and zinc in the liquid collecting tank B is returned to the extraction device by a liquid pump for recycling;
E. evaporating and recycling hydrochloric acid: heating the lead-containing pickling waste liquid in an evaporation device, evaporating hydrochloric acid gas from the pickling waste liquid, flowing into a condensing device through a gas pump through an air outlet of the evaporation device, flowing cooling water in a cooling water storage tank into the condensing device through a liquid pump, condensing high-temperature hydrochloric acid gas into liquid, collecting the liquid in a liquid collecting device, and flowing cooling water out of a water outlet of the condensing device and flowing back into the cooling water storage tank through the liquid pump to form cooling water circulation;
F. and (3) recovering lead salt: and after the evaporation of the hydrochloric acid gas in the evaporation device is finished, cooling to room temperature, and collecting the residual lead chloride solid in the solid collecting device C.
3. Advantageous effects
Compared with the prior art, the application has the beneficial effects that:
(1) The system for recycling the pickling waste liquid containing heavy metals comprises an extraction device, a bubbling device, a stirring device, a solid-liquid separation device and an evaporation device, wherein the devices are connected through a liquid pump, so that the production efficiency can be improved, the maximization of enterprise benefits is realized, and meanwhile, metal salt with higher added value is recovered and obtained, and the recycling of dangerous waste is realized;
(2) According to the extraction device of the acid washing waste liquid recycling system containing heavy metals, the fixed rings are arranged on the inner wall of the extraction device, the tray is arranged between two adjacent fixed rings, the rotary table is fixed on the central shaft, the mutual contact area and the mass transfer coefficient can be increased during extraction, and the extraction efficiency is improved;
(3) The solid-liquid separation device of the acid washing waste liquid recycling system containing heavy metals can realize further separation of solids and liquids in the mixed liquid, and is favorable for obtaining ferric hydroxide and zinc hydroxide products with higher purity; the solid-liquid separation device adopts a plate-frame filter pressing method, so that the effective separation of solids and liquid can be realized;
(4) According to the reaction kettle of the stirring device of the pickling waste liquid recycling system containing heavy metals, the longitudinal section of the bottom of the reaction kettle is elliptical, and the structure is favorable for discharging mixed liquid; meanwhile, the U-shaped polytetrafluoroethylene stirring paddle is arranged in the stirring device, so that the effects of acid and alkali resistance and uniform stirring can be achieved;
(5) According to the bubbling device of the pickling waste liquid recycling system containing heavy metals, the gas distributor can fully mix the blown oxidizing gas with the liquid, so that the purpose of complete oxidation is achieved;
(6) According to the recycling method of the acid washing waste liquid containing heavy metals, the effective separation of the acid washing waste liquid containing iron, zinc and lead is realized by combining an extraction method and an evaporation method, so that high-purity ferric hydroxide, zinc hydroxide, hydrochloric acid and lead chloride are recovered; the method adopts the modes of oxidizing gas reflux, cooling water reflux and extractant recycling, thereby greatly reducing the production cost and improving the benefit.
Drawings
FIG. 1 is a schematic structural diagram of a system for recycling waste pickle containing heavy metals;
FIG. 2 is a flow chart of a method for recycling waste pickle containing heavy metals.
In the figure: 1. an extractant storage tank; 2. a pickling waste liquid storage tank; 3. a liquid pump; 4. an extraction device; 5. a bubbling device; 6. a gas pump; 7. a gas buffer tank; 8. a stirring device A; 9. an alkali liquor storage tank A; 10. a solid-liquid separation device A; 11. a solid collection device A; 12. a liquid collection tank A; 13. a stirring device B; 14. an alkali liquor storage tank B; 15. a solid-liquid separation device B; 16. a solid collecting device B; 17. a liquid collection tank B; 18. an evaporation device; 19. a condensing device; 20. a cooling water storage tank; 21. a solid collecting device C; 22. a liquid collection device.
Detailed Description
The application is further described below in connection with specific embodiments.
The utility model provides a pickling waste liquid recycling system containing heavy metal, includes extraction device 4, bubbling device 5, agitating unit, solid-liquid separation device and evaporation plant 18, agitating unit includes agitating unit A8 and agitating unit B13, solid-liquid separation device includes solid-liquid separation device A10 and solid-liquid separation device B15; the extraction device 4, the bubbling device 5, the stirring device A8, the solid-liquid separation device A10, the stirring device B13 and the solid-liquid separation device B15 are sequentially connected, and the extraction device 4 is connected with the evaporation device 18.
A plurality of fixing rings are longitudinally arranged on the inner wall of the extraction device 4 along the inner wall, a rotary table is arranged between two adjacent fixing rings, and the rotary table is fixed on a central shaft of the extraction device; the first feed inlet of the extraction device 4 is connected with the extractant storage tank 1 through the liquid pump 3, and the second feed inlet of the extraction device 4 is connected with the pickling waste liquid storage tank 2 through the liquid pump 3.
The feed inlet of the bubbling device 5 is connected with the first discharge outlet of the extraction device 4 through a liquid pump 3; the bubbling device 5 is internally provided with a gas distributor, a first gas outlet of the bubbling device 5 is connected with a gas buffer tank 7 through a gas pump 6, and the gas buffer tank 7 is connected with a second gas inlet of the bubbling device 5.
The first feed inlet of agitating unit A8 pass through liquid pump 3 with the discharge gate of tympanic bulla device 5 links to each other, agitating unit A8's second feed inlet passes through liquid pump 3 and links to each other with alkali lye storage tank A9, agitating unit A8 inside is equipped with U type stirring rake.
The first feed inlet of the solid-liquid separation device A10 is connected with the discharge outlet of the stirring device A8 through a liquid pump 3, the solid collecting device A11 is arranged below the discharge outlet of the solid-liquid separation device A10, and the liquid collecting tank A12 is arranged below the solid-liquid separation device A10.
The first feed inlet of agitating unit B13 passes through liquid pump 3 and links to each other with liquid collecting vat A12, agitating unit B13's second feed inlet passes through liquid pump 3 and links to each other with alkali lye storage tank B14, agitating unit B13 inside is equipped with U type stirring rake.
The first feed inlet of the solid-liquid separation device B15 is connected with the discharge port of the stirring device B13 through the liquid pump 3, the solid collecting device B16 is arranged below the discharge port of the solid-liquid separation device B15, the liquid collecting tank B17 is arranged below the solid-liquid separation device B15, and the liquid collecting tank B17 is connected with the first feed inlet of the extraction device 4 through the liquid pump 3.
The feed inlet of evaporation plant 18 pass through liquid pump 3 with extraction plant 4's second discharge gate links to each other, and condensing equipment 19's air inlet pass through gas pump 6 with evaporation plant 18's gas outlet links to each other, and cooling water storage tank 20 passes through liquid pump 3 and condensing equipment 19's water inlet links to each other, cooling water storage tank 20 passes through liquid pump 3 with condensing equipment 19's water inlet links to each other, condensing equipment 19's delivery port pass through liquid pump 3 with cooling water storage tank 20 links to each other, liquid collection device 22 with condensing equipment 19 links to each other, and solid collection device C21 with evaporation plant 18's discharge gate intercommunication.
A method for recycling pickling waste liquid containing heavy metals comprises the following steps:
A. extracting iron and zinc: an extractant is added into an extraction device 4 through a liquid pump 3 from an extractant storage tank 1, meanwhile, acid washing waste liquid containing heavy metal is added into the extraction device 4 through the liquid pump 3 from an acid washing waste liquid storage tank 2, the extractant flows from top to bottom in the extractant storage tank 1, and the acid washing waste liquid flows from bottom to top in the extractant storage tank 1, and the two are reversely contacted for extraction; the extraction is divided into an extraction layer and a raffinate layer, wherein the extraction layer is an extraction liquid containing iron and zinc, the extraction liquid is transferred to a bubbling device 5 by a liquid pump 3, and the raffinate layer is a lead-containing pickling waste liquid and is transferred to an evaporation device 18 by the liquid pump 3; the extractant in the step A is TBP, the adding volume of the TBP is 1/3-1/2 of the adding volume of the extracting device 4, the adding volume of the pickling waste liquid is 0.5-1 times of the adding volume of the TBP (the numerical values of 0.5, 0.6, 0.7, 0.8, 0.9, 1 and the like can be selected in specific application), and the extracting time is 1-2h (the numerical values of 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h and the like can be selected in specific application).
B. And (3) back extraction and recovery of ferric salt: the oxidizing gas in the gas buffer tank 7 is continuously blown into the bubbling device 5 by the gas pump 6, and Fe in the extract liquid is discharged 2+ Oxidation to Fe 3+ The oxidizing gas flows from bottom to top in the bubbling device 5 to carry out the bubbling reaction, wherein the oxidizing gas in the step B is oxygen and/or ozone, the bubbling reaction time is 2-3h (when the bubbling device is used, the values of 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h, 3h and the like can be selected), the selected oxidizing gas is common gas, the cost can be saved, and the bubbling time is selected for the completion of the reaction; then flows back to the gas buffer tank 7 through the first air outlet of the bubbling device 5 to form an oxidizing gas circulation; transferring the extract after the oxidation reaction to a stirring device A8 through a liquid pump 3 at a discharge port of a bubbling device 5, adding alkali liquor into the stirring device A8 through the liquid pump 3 by an alkali liquor storage tank A9, stirring and mixing to obtain a first mixed liquor, wherein the alkali liquor in the step B is sodium hydroxide solution and/or potassium hydroxide solution, and adding the alkali liquor to adjust the pH of the first mixed liquor to 1-3 (when the pH is specifically applied, values such as 1, 2, 3 and the like can be selected); the stirring rotation speed in the stirring and mixing reaction is 200-400r/min (the values of 200r/min, 220r/min, 240r/min, 260r/min, 280r/min, 300r/min, 320r/min, 340r/min, 360r/min, 380r/min, 400r/min and the like can be selected in specific application), and the stirring time is 1-2h (the values of 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h and the like can be selected in specific application); transferring the mixed solution to a solid-liquid separation device A10 through a discharge port of a stirring device A8 by a liquid pump 3, collecting ferric hydroxide solids obtained by separation in a solid collecting device A11, and discharging an extraction solution containing zinc to a liquid collecting tank A12;
C. and (3) back extraction and recovery of zinc salt: transferring the extract in the liquid collecting tank A12 to a stirring device B13 through a liquid pump 3, adding alkali liquor into the stirring device B13 through the liquid pump 3 from an alkali liquor storage tank B14, stirring and mixing to obtain a second mixed liquor, wherein the alkali liquor in the step C is sodium hydroxide and/or potassium hydroxide solution, and the pH of the second mixed liquor is adjusted to 5-8 by adding the alkali liquor (when the pH is specifically applied, the values of 5, 6, 7, 8 and the like can be selected); the stirring rotation speed in the stirring and mixing reaction is 200-400r/min (values of 200r/min, 220r/min, 240r/min, 260r/min, 280r/min, 300r/min, 320r/min, 340r/min, 360r/min, 380r/min, 400r/min and the like can be selected in specific application), and the time is 1-2h (values of 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h and the like can be selected in specific application); transferring the mixed solution to a solid-liquid separation device B15 through a liquid pump 3 at a discharge port of a stirring device B13, collecting zinc hydroxide solids obtained by separation in a solid collecting device B16, and discharging an extracting solution without iron and zinc into a liquid collecting tank B17;
D. recycling the extractant: the extraction liquid which does not contain iron and zinc in the liquid collecting tank B17 flows back to the extraction device 4 through the liquid pump 3 for recycling;
E. evaporating and recycling hydrochloric acid: heating the lead-containing pickling waste liquid in an evaporation device 18, evaporating hydrochloric acid gas from the pickling waste liquid, flowing the hydrochloric acid gas into a condensing device 19 through a gas pump 6 at a gas outlet of the evaporation device 18, flowing cooling water in a cooling water storage tank 20 into the condensing device 19 through a liquid pump 3, condensing the high-temperature hydrochloric acid gas into liquid, collecting the liquid in a liquid collecting device 22, and flowing the cooling water out of a water outlet of the condensing device 19 and flowing the cooling water back into the cooling water storage tank 20 through the liquid pump 3 to form cooling water circulation;
F. and (3) recovering lead salt: after the hydrochloric acid gas in the evaporation device 18 is evaporated, the temperature is reduced to room temperature, and the remaining lead chloride solid is collected in the solid collecting device C21.
Example 1
The system and method for recycling the waste pickle containing heavy metal in this embodiment are as follows, referring to fig. 1 and 2, adding an extractant TBP into an extraction device 4, wherein the adding amount of TBP is 1/3 of the volume of the extraction device, and meanwhile, adding the waste pickle containing heavy metal into the extraction device 4, wherein the adding amount of the waste pickle is V (waste pickle): v (TBP) =0.5: 1, extracting for 1h. After extraction, the extract is transferred to the bubbling device 5, and the raffinate layer is transferred to the evaporation device 18. Oxygen was continuously bubbled into the bubbler 5 for 2 hours. After the reaction, the extract was transferred to a stirring apparatus A8, to which a sodium hydroxide solution was added, ph=1 was adjusted, and the stirring speed was 200r/min for 1 hour. The mixed solution after the completion of the reaction is transferred to a solid-liquid separator a10, the separated ferric hydroxide solid is collected in a solid collecting device a11, and the zinc-containing extract is transferred to a stirring device B13. Sodium hydroxide solution was added to stirring apparatus B13, ph=5 was adjusted, stirring speed was 200r/min, and time was 1h. The mixed solution after the reaction is transferred to a solid-liquid separation device B15, the zinc hydroxide solid obtained by separation is collected in a solid collection device B16, and the extraction liquid without iron and zinc is refluxed to an extraction device 4. The waste pickle containing lead is heated in the evaporator 18 at 200 ℃ for 1 hour. The hydrochloric acid gas enters the condensing device 19, and the continuously flowing cooling water condenses the high-temperature hydrochloric acid gas into liquid, and the liquid is collected in the liquid collecting device 22. After the hydrochloric acid gas in the evaporation device 18 is evaporated, the temperature is reduced to room temperature, and the remaining lead chloride solid is collected in the solid collecting device C21.
In this embodiment, the pickling waste liquid is treated by the extraction device 4 to extract iron and zinc, and lead-containing intermediate products of the raffinate layer are evaporated by the evaporation device 18 to recover hydrochloric acid and lead salt, meanwhile, the extraction liquid containing iron and zinc of the extraction layer is treated by back-extracted iron to precipitate and recover ferric salt and back-extracted zinc to treat and precipitate and recover zinc salt, the extraction liquid after back-extracted zinc treatment is returned to the extraction device 4 to re-extract iron and zinc, so as to realize recycling of extractant, and the purity of ferric hydroxide is 81%, the purity of zinc hydroxide is 85%, the concentration of hydrochloric acid is 29% and the purity of lead chloride is 88% in various products recovered by detection.
Example 2
Referring to fig. 1 and 2, an extractant TBP is added into an extraction device 4, the adding amount of TBP is 1/4 of the volume of the extraction device, meanwhile, the acid washing waste liquid containing heavy metals is added into the extraction device 4, and the adding amount of the acid washing waste liquid is V (acid washing waste liquid): v (TBP) =0.7: 1, extracting for 1.5h. After extraction, the extract is transferred to the bubbling device 5, and the raffinate layer is transferred to the evaporation device 18. Ozone was continuously bubbled into the bubbler 5 for 3 hours. After the reaction, the extract was transferred to a stirring apparatus A8, to which a potassium hydroxide solution was added, ph=3 was adjusted, and the stirring speed was 400r/min for 2 hours. The mixed solution after the completion of the reaction is transferred to a solid-liquid separator a10, the separated ferric hydroxide solid is collected in a solid collecting device a11, and the zinc-containing extract is transferred to a stirring device B13. Potassium hydroxide solution was added to stirring apparatus B13, ph=6 was adjusted, and stirring speed was 300r/min for 1.5 hours. The mixed solution after the reaction is transferred to a solid-liquid separation device B15, the zinc hydroxide solid obtained by separation is collected in a solid collection device B16, and the extraction liquid without iron and zinc is refluxed to an extraction device 4. The waste pickle containing lead is heated in the evaporator 18 at 300 ℃ for 2 hours. The hydrochloric acid gas enters the condensing device 19, and the continuously flowing cooling water condenses the high-temperature hydrochloric acid gas into liquid, and the liquid is collected in the liquid collecting device 22. After the hydrochloric acid gas in the evaporation device 18 is evaporated, the temperature is reduced to room temperature, and the remaining lead chloride solid is collected in the solid collecting device C21.
In this embodiment, the pickling waste liquid is treated by the extraction device 4 to extract iron and zinc, and lead-containing intermediate products of the raffinate layer are evaporated by the evaporation device 18 to recover hydrochloric acid and lead salt, meanwhile, the extraction liquid containing iron and zinc of the extraction layer is treated by back-extracted iron to precipitate and recover ferric salt and back-extracted zinc to treat and precipitate and recover zinc salt, the extraction liquid after back-extracted zinc treatment is returned to the extraction device 4 to re-extract iron and zinc, so as to realize recycling of extractant, and the purity of ferric hydroxide is 83%, the purity of zinc hydroxide is 79%, the concentration of hydrochloric acid is 31% and the purity of lead chloride is 85% in various products recovered by detection.
Example 3
Referring to fig. 1 and 2, an extractant TBP is added into an extraction device 4, the adding amount of TBP is 1/2 of the volume of the extraction device, meanwhile, the acid washing waste liquid containing heavy metals is added into the extraction device 4, and the adding amount of the acid washing waste liquid is V (acid washing waste liquid): v (TBP) =0.8: 1, extracting for 2h. After extraction, the extract is transferred to the bubbling device 5, and the raffinate layer is transferred to the evaporation device 18. The bubbling device 5 was continuously bubbled with a mixed gas of oxygen and ozone for 2.5 hours. After the reaction, the extract was transferred to a stirring apparatus A8, to which a mixed solution of sodium hydroxide and potassium hydroxide was added, ph=2 was adjusted, and the stirring speed was 300r/min for 1.5 hours. The mixed solution after the completion of the reaction is transferred to a solid-liquid separator a10, the separated ferric hydroxide solid is collected in a solid collecting device a11, and the zinc-containing extract is transferred to a stirring device B13. Sodium hydroxide solution was added to stirring apparatus B13, ph=8 was adjusted, stirring speed was 400r/min, and time was 2h. The mixed solution after the reaction is transferred to a solid-liquid separation device B15, the zinc hydroxide solid obtained by separation is collected in a solid collection device B16, and the extraction liquid without iron and zinc is refluxed to an extraction device 4. The waste pickle containing lead is heated in the evaporator 18 at 270 ℃ for 1.5 hours. The hydrochloric acid gas enters the condensing device 19, and the continuously flowing cooling water condenses the high-temperature hydrochloric acid gas into liquid, and the liquid is collected in the liquid collecting device 22. After the hydrochloric acid gas in the evaporation device 18 is evaporated, the temperature is reduced to room temperature, and the remaining lead chloride solid is collected in the solid collecting device C21.
In this embodiment, the pickling waste liquid is treated by the extraction device 4 to extract iron and zinc, and lead-containing intermediate products of the raffinate layer are evaporated by the evaporation device 18 to recover hydrochloric acid and lead salt, meanwhile, the extraction liquid containing iron and zinc of the extraction layer is treated by back-extracted iron to precipitate and recover ferric salt and back-extracted zinc to precipitate and recover zinc salt, the extraction liquid after back-extracted zinc treatment is returned to the extraction device 4 to re-extract iron and zinc, so as to realize recycling of extractant, and the purity of ferric hydroxide is 84%, the purity of zinc hydroxide is 82%, the concentration of hydrochloric acid is 30% and the purity of lead chloride is 86% in various products recovered by detection.
Example 4
Referring to fig. 1 and 2, an extractant TBP is added into an extraction device 4, the adding amount of TBP is 1/3 of the volume of the extraction device, meanwhile, the acid washing waste liquid containing heavy metals is added into the extraction device 4, and the adding amount of the acid washing waste liquid is V (acid washing waste liquid): v (TBP) =1: 1, extracting for 2h. After extraction, the extract is transferred to the bubbling device 5, and the raffinate layer is transferred to the evaporation device 18. Ozone was continuously bubbled into the bubbler 5 for 3 hours. After the reaction, the extract was transferred to a stirring apparatus A8, to which a potassium hydroxide solution was added, ph=2 was adjusted, and the stirring speed was 300r/min for 2 hours. The mixed solution after the completion of the reaction is transferred to a solid-liquid separator a10, the separated ferric hydroxide solid is collected in a solid collecting device a11, and the zinc-containing extract is transferred to a stirring device B13. The mixed solution of sodium hydroxide and potassium hydroxide was added to stirring apparatus B13, ph=7 was adjusted, and the stirring speed was 300r/min for 1.5 hours. The mixed solution after the reaction is transferred to a solid-liquid separation device B15, the zinc hydroxide solid obtained by separation is collected in a solid collection device B16, and the extraction liquid without iron and zinc is refluxed to an extraction device 4. The lead-containing pickle liquor was heated in the evaporator 18 at 280℃for 2 hours. The hydrochloric acid gas enters the condensing device 19, and the continuously flowing cooling water condenses the high-temperature hydrochloric acid gas into liquid, and the liquid is collected in the liquid collecting device 22. After the hydrochloric acid gas in the evaporation device 18 is evaporated, the temperature is reduced to room temperature, and the remaining lead chloride solid is collected in the solid collecting device C21.
The scheme of the application utilizes a combined method of extraction and evaporation to completely separate iron, zinc, lead and hydrochloric acid, so that high-purity ferric hydroxide, zinc hydroxide, hydrochloric acid and lead chloride are obtained, and the economy is good; meanwhile, the pickling waste liquid contains lead, the metal elements are different, the extraction method is different, TBP is firstly added as an extractant to extract iron and zinc, the iron and zinc are separated from the lead-containing pickling waste liquid, and then alkaline solution is added to adjust the pH value to separate the iron and the zinc.
In this embodiment, the pickling waste liquid is treated by the extraction device 4 to extract iron and zinc, and lead-containing intermediate products of the raffinate layer are evaporated by the evaporation device 18 to recover hydrochloric acid and lead salt, meanwhile, the extraction liquid containing iron and zinc of the extraction layer is treated by back-extracted iron to precipitate and recover ferric salt and back-extracted zinc to treat and precipitate and recover zinc salt, the extraction liquid after back-extracted zinc treatment is returned to the extraction device 4 to re-extract iron and zinc, so as to realize recycling of extractant, and the purity of ferric hydroxide is 82%, the purity of zinc hydroxide is 84%, the concentration of hydrochloric acid is 28% and the purity of lead chloride is 87% in various products recovered by detection.
The application and its embodiments have been described above by way of illustration and not limitation, and the application is illustrated in the accompanying drawings and described in the drawings in which the actual structure is not limited thereto. Therefore, if one of ordinary skill in the art is informed by this disclosure, the structural mode and the embodiments similar to the technical scheme are not creatively designed without departing from the gist of the present application.
Claims (2)
1. A method for recycling pickling waste liquid containing heavy metals comprises the following steps:
A. extracting iron and zinc: an extractant is added into an extraction device (4) from an extractant storage tank (1), meanwhile, acid washing waste liquid containing heavy metal is added into the extraction device (4) from an acid washing waste liquid storage tank (2), the extractant flows from top to bottom in the extraction device (4), and the acid washing waste liquid flows from bottom to top in the extraction device (4) and is reversely contacted with the acid washing waste liquid for extraction; the extraction is divided into an extraction layer and a raffinate layer, wherein the extraction layer is an extraction liquid containing iron and zinc, the extraction liquid is transferred to a bubbling device (5) by a liquid pump (3), and the raffinate layer is a waste pickle containing lead and is transferred to an evaporation device (18) by the liquid pump (3);
B. and (3) back extraction and recovery of ferric salt: continuously bubbling the oxidizing gas in the gas buffer tank (7) into the bubbling device (5) by the gas pump (6) to discharge Fe in the extract liquid 2+ Oxidation to Fe 3+ Oxidizing gas flows in the bubbling device (5) from bottom to top to carry out bubbling reaction, and then flows back to the gas buffer tank (7) through a first gas outlet of the bubbling device (5) to form oxidizing gas circulation; transferring the extract after the oxidation reaction to a stirring device A (8) through a discharge hole of a bubbling device (5), adding alkali liquor into the stirring device A (8) through an alkali liquor storage tank A (9), stirring and mixing to obtain a first mixed liquor, and discharging the mixed liquor from the stirring device A (8)Transferring the material port into a solid-liquid separation device A (10), collecting ferric hydroxide solids obtained by separation in a solid collecting device A (11), and discharging an extraction liquid containing zinc into a liquid collecting tank A (12);
C. and (3) back extraction and recovery of zinc salt: transferring the extract in the liquid collecting tank A (12) to a stirring device B (13), adding alkali liquor into the stirring device B (13) from an alkali liquor storage tank B (14), stirring and mixing to obtain a second mixed liquor, transferring the mixed liquor to a solid-liquid separation device B (15) through a discharge port of the stirring device B (13), collecting zinc hydroxide solids obtained by separation in a solid collecting device B (16), and discharging the extract without iron and zinc into a liquid collecting tank B (17);
D. recycling the extractant: the extraction liquid which does not contain iron and zinc in the liquid collecting tank B (17) flows back to the extraction device (4) through the liquid pump (3) for recycling;
E. evaporating and recycling hydrochloric acid: heating the lead-containing pickling waste liquid in an evaporation device (18), evaporating hydrochloric acid gas from the pickling waste liquid, flowing the hydrochloric acid gas into a condensing device (19) through a gas pump (6) at a gas outlet of the evaporation device (18), flowing cooling water in a cooling water storage tank (20) into the condensing device (19), condensing the high-temperature hydrochloric acid gas into liquid, collecting the liquid in a liquid collecting device (22), and flowing the cooling water out of a water outlet of the condensing device (19) and flowing the cooling water back into the cooling water storage tank (20) through a liquid pump (3) to form cooling water circulation;
F. and (3) recovering lead salt: after the hydrochloric acid gas in the evaporation device (18) is evaporated, the temperature is reduced to room temperature, and the residual lead chloride solid is collected in the solid collecting device C (21).
2. The method for recycling the waste pickle containing heavy metal according to claim 1, which is characterized by comprising the following steps: the extractant in the step A is TBP, the adding volume of the TBP is 1/3-1/2 of the volume of the extraction device (4), the adding volume of the pickling waste liquid is 0.5-1 times of the adding volume of the TBP, and the extraction time is 1-2h.
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| JPS54119331A (en) * | 1978-03-09 | 1979-09-17 | Agency Of Ind Science & Technol | Separating method of zinc and/or iron |
| CN102264925A (en) * | 2008-11-24 | 2011-11-30 | Bhp比利顿奥林匹克坝有限公司 | Process for controlled oxidation of a ferrous solution |
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| CN105696010A (en) * | 2016-01-12 | 2016-06-22 | 惠州市斯瑞尔环境化工有限公司 | Method for recycling iron and zinc containing waste hydrochloric acid solution |
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