CN108642298A - A kind of black silicon wafer production line method for recovering waste liquid of photovoltaic - Google Patents
A kind of black silicon wafer production line method for recovering waste liquid of photovoltaic Download PDFInfo
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- CN108642298A CN108642298A CN201810382780.9A CN201810382780A CN108642298A CN 108642298 A CN108642298 A CN 108642298A CN 201810382780 A CN201810382780 A CN 201810382780A CN 108642298 A CN108642298 A CN 108642298A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/022—Preparation of aqueous ammonia solutions, i.e. ammonia water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/36—Nitrates
- C01F11/38—Preparation with nitric acid or nitrogen oxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a kind of using black recovery method of the silicon chip reaming waste liquid to metallic silver in silver-containing liquid waste and the black silicon wafer production line method for recovering waste liquid of the photovoltaic comprising both waste liquids, and provides the rotation electrode used when a kind of waste liquid electrolysis.The beneficial effects of the invention are as follows：The silver-containing liquid waste of the present invention and the recovery method of strong acid waste liquid and the black silicon chip of photovoltaic comprising both waste liquids dispose waste liquid recovery method, realize the recycling of noble silver in waste liquid, obtain elemental silver, calcirm-fluoride of the coproduction purity 80 85%, for purity in 90 95% calcium nitrate, ammonium hydroxide of the concentration 20 30%, the water evaporated, ammonium hydroxide obtained can be back to production, realize the efficient utilization of material in waste liquid, liquid waste processing integrated operation cost can be reduced, environmental pollution is avoided.
Description
Technical field
The present invention relates to solar photovoltaic technology field, more particularly to a kind of black silicon wafer production line of photovoltaic is returned with waste liquid
Receiving method.
Background technology
Solar energy converting material is at present still based on monocrystalline silicon, polycrystalline silicon material.Monocrystalline silicon has photoelectric conversion efficiency high
Outstanding advantage, persistently account for the leading position of solar product, but single crystal silicon material own cost is high, production capacity is limited, influences it
Further genralrlization.Polysilicon has price and resources advantage, cuts especially with diamond wire and is cut instead of traditional husky line, diamond wire is cut
Speed, the silicon chip quality that cuts out relatively stablize, silicon chip cost can significantly reduce, however diamond wire cuts the surface of polysilicon chip
It is excessively smooth, so that daylight is easy reflection and can not be absorbed by battery, reduces photoelectric conversion efficiency, it thus must be to polysilicon chip table
Face carries out making herbs into wool processing, i.e., so-called black silicon treatment technology.Polycrystalline manufacturer wishes that cut silicon chip easy to improve diamond wire by black silicon
The problem of making battery conversion efficiency reduce, looks for the new market opportunity for huge polycrystalline production capacity, nearly 2 years, has many manufacturers
Start to put into black silicon research and production.
Black silicon production is broadly divided into two kinds of dry method and wet method, and black silicon chip photoelectric conversion efficiency made from dry method is high, but equipment
Costliness, production cost is high, and wet method can utilize existing equipment to produce substantially, and operating cost is increased slightly, silicon chip photoelectricity obtained
Transfer efficiency is higher, is easy to promote the use of, but work waste liquid and ejected wash water containing silver nitrate are generated in production process, there is weight
The pollution of metallic silver, concentrated acid, concentrated base is approved and initiate a project and is extremely restricted with popularization under the current environmental protection policy in China, is the neck
The problem that domain must solve.
Black silicon production includes mainly that the heavy silver-of making herbs into wool-goes the processes such as silver-reaming.Making herbs into wool uses 5-10%KOH aqueous solutions, sinks
After silver is using the mixed liquor processing of 0.5%HF and 0.02-0.05g/L silver nitrates, then with 5-10%HF and 5-15%H2O2Mixed liquor
Processing is further corroded, silver-colored process is gone to use about 1%NH3·H2O and 1.0-2.0%H2O2Mixed liquor carries out, and reaming uses 3.0-
5.0%HF and about 30%HNO3Mixed liquor processing after, with 3-5%KOH, 1%NH3·H2O and 1.0-2.0%H2O2Mixed liquor into
The processing of one step, finally uses 8-10%HF to be handled with 5-10%HCl mixed liquors.From this, work used in black silicon production process
Liquid is high concentration strong acid, highly basic and Ag-containing solution, and to ensure product quality, working solution is scrapped frequently in continuous production process, production
Raw a large amount of waste liquids.
Black silicon produces waste liquid directly as hazardous waste, and the processing cost is high, and enterprise is difficult to bear.It is simple to neutralize, precipitate
Processing, material cannot be efficiently separated, be recycled, and equally generate a large amount of hazardous solid wastes, water also needs to be further processed, Bu Nengzhi
Outer row is met, processing cost is equally very high.Currently, being effectively treated not yet about generation waste liquid in the production of black silicon both at home and abroad, material
It efficiently separates, recycle processing method.
Invention content
The present invention provides a kind of black silicon wafer production line devil liquor recovery side of photovoltaic for the waste liquid generated in the production of black silicon
Method, in line with treatment of wastes with processes of wastes against one another principle, detaches to waste liquid categorised collection, recycles active ingredient therein, realize material again to greatest extent
It utilizes.The black silicon chip of photovoltaic disposes waste liquid silver recovery and material co-production technology, in the reaming waste liquid that itself generation is produced using black silicon
Nitric acid in and silver-containing liquid waste ammonium hydroxide, after being adjusted to highly acid, pass through the barrel-shaped ti-alloy mesh rotation electrode electricity of the multilayer with rib
Solution recycling noble silver, coproduction ammonium hydroxide, potassium nitrate, potassium chloride, calcium nitrate and calcirm-fluoride, ammonium hydroxide, water are back to production, realization with
It is useless to control useless, the whole efficiently recyclings of material.
The black silicon chip of photovoltaic disposes waste liquid silver recovery and material co-production technology, realizes noble silver in black silicon production waste liquid
Recycling, obtains elemental silver, and in the calcirm-fluoride of 80-85%, purity exists coproduction purity in 90-95% calcium nitrate and potassium chloride, concentration
The ammonium hydroxide of 20-30%, the water evaporated, ammonium hydroxide obtained can be back to production, realize the efficient of material in black silicon production waste liquid
It utilizes, reduces liquid waste processing integrated operation cost, avoid environmental pollution.
In order to achieve the above-mentioned object of the invention, the present invention provides a kind of using black silicon chip reaming waste liquid to golden in silver-containing liquid waste
Belong to the recovery method of silver, the recovery method includes the following steps：
Step 1: waste collection mixes：Silver-containing liquid waste is collected, and black silicon chip reaming waste liquid is added into silver-containing liquid waste and obtains
The pH value of mixed solution is adjusted to 1-2 by mixed solution using black silicon chip reaming waste liquid；
Step 2: reclaiming metals are silver-colored：Mixed solution in the first step is electrolysed using electrode to obtain metallic silver,
Cell reaction is as follows：
Ag++e→Ag。
The silver-containing liquid waste main component is ammonium hydroxide and [Ag (NH3)2]+。
The reaming waste liquid mainly includes the mixed liquor of a concentration of 30-35% nitric acid and a concentration of 3-3.5% hydrofluoric acid.
Electrode in the step 2 is a rotation electrode, and the rotation electrode includes a central electrode column, the center
Electrode column upper end is fixedly connected with a motor, if the central electrode column is provided with dried layer electrode network close to end portion periphery
Circle, every layer of electrode net circle are surrounded by porous metal mesh, and the porous metal mesh radial direction convolution is at several corner angle；
Connect if being fixed by the dried layer supporting beam being arranged from bottom to top between the central electrode column and the electrode net circle
It connects, every layer of supporting beam is made of several supporting ribs being radially arranged, and described supporting rib one end and the electrode net circle are close
Property at parts of edges and corners is fixedly connected, and the supporting rib other end is fixedly connected with the central electrode column lateral wall.
In order to achieve the above-mentioned object of the invention, the present invention also provides a kind of black silicon wafer production line devil liquor recovery sides of photovoltaic
Method, the waste liquid include the silver-containing liquid waste that heavy silver-colored process generates and the reaming waste liquid that reaming process generates；The recovery method tool
Body is：
The first step, waste collection mixing：By the silver-containing liquid waste and the reaming waste collection to a mixing channel, wherein
The volume ratio of the silver-containing liquid waste and the reaming waste liquid is：1：(1~1.2)；Using reaming waste liquid by mixed pH value of solution
Value is adjusted to 1-2, releases free silver ion, and mixed key reaction is：
[Ag(NH3)2]++2H+→Ag++2NH4 +
NH3+H+→NH4 +；
Second step, reclaiming metals silver：Electrolytic recovery noble metal is carried out using electrode to the mixed solution in the first step
Silver-colored current density is in 0.1-0.3A/dm2, electrolysis to Ag+Less than 0.2mg/L, cell reaction is as follows：
Ag++e→Ag；
Third step presses F into the electrolyte after the completion of the second one-step electrolysis-Milk of lime is added simultaneously in 1.2-1.5 times of amount of substance
And mechanical agitation is carried out, ammonium hydroxide is obtained after the gas pure water absorption tower collection of production, formation will be stood after mechanical agitation
Supernatant and sediment are detached, and sediment washing obtains calcirm-fluoride (fluorite), and supernatant is obtained through pervaporation, crystallization successively
Calcium nitrate solid, key reaction are as follows：
2HF+Ca(OH)2→CaF2↓+H2O
2HNO3+Ca(OH)2→Ca(NO3)2+H2O
NH4 ++OH-→NH3↑+H2O。
The black silicon wafer production line waste liquid of photovoltaic further includes other acid-base waste fluids, other described acid-base waste fluid main components
For：Hydrofluoric acid, hydrochloric acid, potassium hydroxide and ammonium hydroxide, other described acid-base waste fluids are recycled by following steps：
Other described acid-base waste fluids are collected separately to a mixing channel, F is then pressed-Stone is added in 1.2-1.5 times of amount of substance
Ash is newborn and carries out mechanical agitation, obtains ammonium hydroxide after the gas pure water absorption tower collection of generation, will be stood after mechanical agitation
The supernatant and sediment of formation are detached, and are obtained calcirm-fluoride after sediment washing, are stood after air is passed through into supernatant,
Sediment calcium carbonate and supernatant Klorvess Liquid are obtained, supernatant is obtained into solid potassium chloride through pervaporation, crystallization successively；It is main
It reacts and is：
2F-+Ca2+→CaF2↓
2HF+Ca(OH)2→CaF2↓+H2O
NH4 ++OH-→NH3↑+H2O
Ca(OH)2+CO2+H2O→CaCO3↓+H2O
HCl+KOH→KCl+H2O。
Electrode in the second step is a rotation electrode, and the rotation electrode includes a central electrode column, the center
Electrode column upper end is fixedly connected with a motor, if the central electrode column is provided with dried layer electrode network close to end portion periphery
Circle, every layer of electrode net circle are surrounded by porous metal mesh, and the porous metal mesh radial direction convolution is at several corner angle；
Connect if being fixed by the dried layer supporting beam being arranged from bottom to top between the central electrode column and the electrode net circle
It connects, every layer of supporting beam is made of several supporting ribs being radially arranged, and described supporting rib one end and the electrode net circle are close
Property at parts of edges and corners is fixedly connected, and the supporting rib other end is fixedly connected with the central electrode column lateral wall.
The central electrode column, the electrode net circle, the supporting beam are made of titanium.
The porous metals screen distance is 0.1-1mm, and the angle of the porous metal mesh corner angle is 60-120 degree.
In order to preferably realize foregoing invention purpose, the present invention also provides a kind of electrolysis rotation electrode, the rotations
Electrode includes a central electrode column, and central electrode column upper end is fixedly connected with a motor, and the central electrode column is under
If end part periphery is provided with dried layer electrode network circle, every layer of electrode net circle is surrounded by porous metal mesh, the porous metals
The radial convolution of net is at several corner angle；
Connect if being fixed by the dried layer supporting beam being arranged from bottom to top between the central electrode column and the electrode net circle
It connects, every layer of supporting beam is made of several supporting ribs being radially arranged, and described supporting rib one end and the electrode net circle are close
Property at parts of edges and corners is fixedly connected, and the supporting rib other end is fixedly connected with the central electrode column lateral wall.
The central electrode column, the electrode net circle, the supporting beam are made of titanium.
The porous metals screen distance is 0.1-1mm, and the angle of the porous metal mesh corner angle is 60-120 degree.
The spacing of two layers adjacent of electrode net circle is 10-100mm.The number of plies is by silver-containing liquid waste and reaming waste liquid mixed liquor
The volume of slot determines, is formed by 10-100 layers.
The rotation electrode is under motor drive with the speed uniform rotation of 10-60r/min；Average current when electrolysis
Density is 0.05-0.20A/dm2.
The beneficial effects of the invention are as follows：The present invention silver-containing liquid waste and strong acid waste liquid recovery method and include both
The black silicon chip of photovoltaic of waste liquid disposes waste liquid recovery method, realizes the recycling of noble silver in waste liquid, obtains elemental silver, coproducing pure
Spend the calcirm-fluoride in 80-85%, purity 90-95% calcium nitrate, concentration 20-30% ammonium hydroxide, it is the water evaporated, obtained
Ammonium hydroxide can be back to production, realize the efficient utilization of material in waste liquid, can reduce liquid waste processing integrated operation cost, avoid pair
Environmental pollution.
Description of the drawings
Fig. 1 is rotation electrode schematic diagram of the embodiment of the present invention.
Wherein, reference numeral is：1, central electrode column；2, electrode net circle；3, supporting rib.
Specific implementation mode
In order to clarify the technical characteristics of the invention, below by specific implementation mode, this programme is illustrated.
Embodiment 1
Referring to Fig. 1, an embodiment of the present invention provides be electrolysed the rotation electrode used, electric rotating in a kind of method for recovering waste liquid
Pole includes a central electrode column 1, and 1 upper end of central electrode column is fixedly connected with a motor, and central electrode column 1 is outside end portion
It is provided with dried layer electrode network circle 2 if enclosing, every layer of electrode net circle 2 is surrounded by porous metal mesh, porous metal mesh radial direction convolution Cheng Ruo
Dry corner angle；
If being fixedly connected by the dried layer supporting beam being arranged from bottom to top between central electrode column 1 and electrode net circle 2, every layer
Supporting beam is made of several supporting ribs 3 being radially arranged, and 3 one end of supporting rib is fixedly connected with electrode net circle 2 close to property at parts of edges and corners,
3 other end of supporting rib is fixedly connected with 1 lateral wall of central electrode column.
Central electrode column 1, electrode net circle 2, supporting beam are made of titanium.
Porous metals screen distance is 0.1-1mm, and the angle of porous metal mesh corner angle is 60-120 degree.
The spacing of two layers adjacent of electrode net circle 2 is 10-100mm.The number of plies is by silver-containing liquid waste and reaming waste liquid mixing liquid bath
Volume determine, formed by 10-100 layers.
Rotation electrode is under motor drive with the speed uniform rotation of 10-60r/min；Average current density is when electrolysis
0.05-0.20A/dm2。
Embodiment 2
An embodiment of the present invention provides a kind of using black silicon chip reaming waste liquid to the recovery method of metallic silver in silver-containing liquid waste,
The recovery method includes the following steps：
Step 1: waste collection mixes：Silver-containing liquid waste is collected, and black silicon chip reaming waste liquid is added into silver-containing liquid waste and obtains
The pH value of mixed solution is adjusted to 1-2 by mixed solution using black silicon chip reaming waste liquid；
Step 2: reclaiming metals are silver-colored：Electricity is carried out using the electrode that embodiment 1 provides to the mixed solution in the first step
Solution obtains metallic silver, and cell reaction is as follows：
Ag++e→Ag。
The silver-containing liquid waste main component is ammonium hydroxide and [Ag (NH3)2]+。
The reaming waste liquid mainly includes the mixed liquor of a concentration of 30-35% nitric acid and a concentration of 3-3.5% hydrofluoric acid.
Embodiment 3
An embodiment of the present invention provides a kind of black silicon wafer production line method for recovering waste liquid of photovoltaic, the waste liquid includes removing silver
The reaming waste liquid that the silver-containing liquid waste and reaming process that process generates generate；The recovery method is specially：
The first step, waste collection mixing：By the silver-containing liquid waste and the reaming waste collection to a mixing channel, wherein
The volume ratio of the silver-containing liquid waste and the reaming waste liquid is：1:(1~1.2)；Using reaming waste liquid by mixed pH value of solution
Value is adjusted to 1-2, releases free silver ion, and mixed key reaction is：
[Ag(NH3)2]++2H+→Ag++2NH4 +
NH3+H+→NH4 +；
Second step, reclaiming metals silver：Electricity is carried out using the electrode that embodiment 1 provides to the mixed solution in the first step
Solution recycling noble silver, current density is in 0.1-0.3A/dm2, electrolysis to Ag+Less than 0.2mg/L, cell reaction is as follows：
Ag++e→Ag；
Into the electrolyte after the completion of the second one-step electrolysis by 1.2-1.5 times of F- amount of substance milk of lime is added simultaneously in third step
And mechanical agitation is carried out, ammonium hydroxide is obtained after the gas pure water absorption tower collection of production, formation will be stood after mechanical agitation
Supernatant and sediment are detached, and sediment washing obtains calcirm-fluoride (fluorite), and supernatant is obtained through pervaporation, crystallization successively
Calcium nitrate solid, key reaction are as follows：
2HF+Ca(OH)2→CaF2↓+H2O
2HNO3+Ca(OH)2→Ca(NO3)2+H2O
NH4 ++OH-→NH3↑+H2O。
The black silicon wafer production line waste liquid of photovoltaic further includes other acid-base waste fluids, other described acid-base waste fluid main components
For：Hydrofluoric acid, hydrochloric acid, potassium hydroxide and ammonium hydroxide, other described acid-base waste fluids are recycled by following steps：
Other described acid-base waste fluids are collected separately to a mixing channel, stone then is added by 1.2-1.5 times of F- amount of substance
Ash is newborn and carries out mechanical agitation, obtains ammonium hydroxide after the gas pure water absorption tower collection of generation, will be stood after mechanical agitation
The supernatant and sediment of formation are detached, and are obtained calcirm-fluoride after sediment washing, are stood after air is passed through into supernatant,
Sediment calcium carbonate and supernatant Klorvess Liquid are obtained, supernatant is obtained into solid potassium chloride through pervaporation, crystallization successively；It is main
It reacts and is：
2F-+Ca2+→CaF2↓
2HF+Ca(OH)2→CaF2↓+H2O
NH4 ++OH-→NH3↑+H2O
Ca(OH)2+CO2+H2O→CaCO3↓+H2O
HCl+KOH→KCl+H2O。
The foregoing is merely a prefered embodiment of the invention, is not intended to limit the invention, all in the spirit and principles in the present invention
Within, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (10)
1. it is a kind of using black silicon chip reaming waste liquid to the recovery method of metallic silver in silver-containing liquid waste, which is characterized in that the recycling
Method includes the following steps：
Step 1: waste collection mixes：Silver-containing liquid waste is collected, and black silicon chip reaming waste liquid is added into silver-containing liquid waste and is mixed
The pH value of mixed solution is adjusted to 1-2 by solution using black silicon chip reaming waste liquid；
Step 2: reclaiming metals are silver-colored：Mixed solution in the first step is electrolysed using electrode to obtain metallic silver, is electrolysed
Reaction is as follows：
Ag++e→Ag。
2. the method according to claim 1 recycled to silver-containing liquid waste using black silicon chip reaming waste liquid, which is characterized in that institute
It is ammonium hydroxide and [Ag (NH to state silver-containing liquid waste main component3)2]+。
3. the method according to claim 1 recycled to silver-containing liquid waste using black silicon chip reaming waste liquid, which is characterized in that institute
State the mixed liquor that reaming waste liquid mainly includes a concentration of 30-35% nitric acid and a concentration of 3-3.5% hydrofluoric acid.
4. being returned to metallic silver in silver-containing liquid waste using black silicon chip reaming waste liquid according to claim 1-3 any one of them is a kind of
Receiving method, which is characterized in that the electrode in the step 2 is a rotation electrode, and the rotation electrode includes a central electrode
Column, central electrode column upper end are fixedly connected with a motor, if the central electrode column is provided with close to end portion periphery
Dried layer electrode net circle, every layer of electrode net circle are surrounded by porous metal mesh, and the porous metal mesh radial direction convolution is at several ribs
Angle；
If being fixedly connected by the dried layer supporting beam being arranged from bottom to top between the central electrode column and the electrode net circle, often
The layer supporting beam is made of several supporting ribs being radially arranged, and described supporting rib one end is with the electrode net circle close to corners
Position is fixedly connected, and the supporting rib other end is fixedly connected with the central electrode column lateral wall.
5. a kind of black silicon wafer production line method for recovering waste liquid of photovoltaic, which is characterized in that the waste liquid includes that heavy silver-colored process generates
Silver-containing liquid waste and reaming process generate reaming waste liquid；The recovery method is specially：
The first step, waste collection mixing：By the silver-containing liquid waste and the reaming waste collection to a mixing channel, wherein described
The volume ratio of silver-containing liquid waste and the reaming waste liquid is：1:(1~1.2)；Using reaming waste liquid by mixed solution ph tune
To 1-2, free silver ion is released, mixed key reaction is：
[Ag(NH3)2]++2H+→Ag++2NH4 +
NH3+H+→NH4 +；
Second step, reclaiming metals silver：Electrolytic recovery noble silver, electricity are carried out using electrode to the mixed solution in the first step
Current density is in 0.1-0.3A/dm2, electrolysis to Ag+Less than 0.2mg/L, cell reaction is as follows：
Ag++e→Ag；
Third step presses F into the electrolyte after the completion of the second one-step electrolysis-1.2-1.5 times of amount of substance is added milk of lime and carries out
Mechanical agitation obtains ammonium hydroxide after the gas pure water absorption tower collection of production, the supernatant of formation will be stood after mechanical agitation
It is detached with sediment, sediment washing obtains calcirm-fluoride (fluorite), and supernatant obtains calcium nitrate through pervaporation, crystallization successively
Solid, key reaction are as follows：
2HF+Ca(OH)2→CaF2↓+H2O
2HNO3+Ca(OH)2→Ca(NO3)2+H2O
NH4 ++OH-→NH3↑+H2O。
6. the black silicon wafer production line method for recovering waste liquid of photovoltaic according to claim 5, which is characterized in that the waste liquid is also
Including other acid-base waste fluids, other described acid-base waste fluid main components are：Hydrofluoric acid, hydrochloric acid, potassium hydroxide and ammonium hydroxide, it is described its
He is recycled acid-base waste fluid by following steps：
Other described acid-base waste fluids are collected separately to a mixing channel, F is then pressed-Milk of lime is added simultaneously in 1.2-1.5 times of amount of substance
And mechanical agitation is carried out, ammonium hydroxide is obtained after the gas pure water absorption tower collection of generation, formation will be stood after mechanical agitation
Supernatant and sediment are detached, and are obtained calcirm-fluoride after sediment washing, are stood, sunk after air is passed through into supernatant
Supernatant is obtained solid potassium chloride by starch calcium carbonate and supernatant Klorvess Liquid through pervaporation, crystallization successively；Key reaction
For：
2F-+Ca2+→CaF2↓
2HF+Ca(OH)2→CaF2↓+H2O
NH4 ++OH-→NH3↑+H2O
Ca(OH)2+CO2+H2O→CaCO3↓+H2O
HCl+KOH→KCl+H2O。
7. the black silicon wafer production line method for recovering waste liquid of photovoltaic according to claim 5 or 6, which is characterized in that described
Electrode in two steps is a rotation electrode, and the rotation electrode includes a central electrode column, central electrode column upper end and one
Motor is fixedly connected, if the central electrode column is provided with dried layer electrode network circle, every layer of electrode close to end portion periphery
Net circle is surrounded by porous metal mesh, and the porous metal mesh radial direction convolution is at several corner angle；
If being fixedly connected by the dried layer supporting beam being arranged from bottom to top between the central electrode column and the electrode net circle, often
The layer supporting beam is made of several supporting ribs being radially arranged, and described supporting rib one end is with the electrode net circle close to corners
Position is fixedly connected, and the supporting rib other end is fixedly connected with the central electrode column lateral wall.
8. rotation electrode according to claim 7, which is characterized in that the central electrode column, the electrode net circle, described
Supporting beam is made of titanium.
9. rotation electrode according to claim 7, which is characterized in that the porous metals screen distance is 0.1-1mm, described
The angle of porous metal mesh corner angle is 60-120 degree.
10. a kind of electrolysis rotation electrode, which is characterized in that the rotation electrode includes a central electrode column, the middle electrocardio
Pole upper end is fixedly connected with a motor, if the central electrode column is provided with dried layer electrode network circle close to end portion periphery,
Every layer of electrode net circle is surrounded by porous metal mesh, and the porous metal mesh radial direction convolution is at several corner angle；
If being fixedly connected by the dried layer supporting beam being arranged from bottom to top between the central electrode column and the electrode net circle, often
The layer supporting beam is made of several supporting ribs being radially arranged, and described supporting rib one end is with the electrode net circle close to corners
Position is fixedly connected, and the supporting rib other end is fixedly connected with the central electrode column lateral wall.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111154983A (en) * | 2020-02-26 | 2020-05-15 | 苏州晶洲装备科技有限公司 | Method and device for recovering silver and mixed acid from silver-containing waste acid liquid in photovoltaic waste liquid |
| CN112520776A (en) * | 2020-11-26 | 2021-03-19 | 广沣金源（北京）科技有限公司 | Combined treatment method for fluorine-containing nitric acid waste liquid and hydrofluoric acid waste liquid |
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