CN108642298B - A method for recycling waste liquid used in photovoltaic black silicon wafer production line - Google Patents
A method for recycling waste liquid used in photovoltaic black silicon wafer production line Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 104
- 239000002699 waste material Substances 0.000 title claims abstract description 102
- 229910021418 black silicon Inorganic materials 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title abstract description 25
- 238000004064 recycling Methods 0.000 title description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052709 silver Inorganic materials 0.000 claims abstract description 51
- 239000004332 silver Substances 0.000 claims abstract description 51
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 30
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract description 17
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 abstract description 16
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract description 15
- 238000011084 recovery Methods 0.000 abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 235000012431 wafers Nutrition 0.000 description 17
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 16
- 239000006228 supernatant Substances 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 8
- 239000000920 calcium hydroxide Substances 0.000 description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 8
- 239000001103 potassium chloride Substances 0.000 description 8
- 235000011164 potassium chloride Nutrition 0.000 description 8
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 235000010216 calcium carbonate Nutrition 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- 239000010432 diamond Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000008267 milk Substances 0.000 description 4
- 210000004080 milk Anatomy 0.000 description 4
- 235000013336 milk Nutrition 0.000 description 4
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910017611 Ag(NH3)2 Inorganic materials 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010436 fluorite Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- -1 silver ions Chemical class 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
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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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Analytical Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明公开了一种利用黑硅片扩孔废液对含银废液中金属银的回收方法以及包含这两种废液的光伏黑硅片生产线用废液回收方法，并提供了一种废液电解时使用的旋转电极。本发明的有益效果是：本发明的含银废液和强酸废液的回收方法以及包含这两种废液的光伏黑硅片处理废液回收方法，实现了废液中贵金属银的回收，得到单质银，联产纯度在80‑85%的氟化钙，纯度在90‑95%硝酸钙、浓度在20‑30%的氨水，蒸发出的水、制得的氨水可回用于生产，实现废液中物料的高效利用，能够降低废液处理综合运行成本，避免对环境污染。
The invention discloses a method for recovering metallic silver in silver-containing waste liquid by using black silicon wafer hole reaming waste liquid and a method for recovering waste liquid for photovoltaic black silicon wafer production line comprising the two waste liquids, and provides a waste liquid recovery method. Rotating electrode used in liquid electrolysis. The beneficial effects of the present invention are as follows: the method for recovering silver-containing waste liquid and strong acid waste liquid and the method for recovering photovoltaic black silicon wafer processing waste liquid comprising these two kinds of waste liquids of the present invention realize the recovery of precious metal silver in the waste liquid, and obtain Elemental silver, co-produces calcium fluoride with a purity of 80-85%, calcium nitrate with a purity of 90-95%, and ammonia water with a concentration of 20-30%. The evaporated water and the prepared ammonia water can be reused for production, realizing The efficient utilization of materials in waste liquid can reduce the comprehensive operation cost of waste liquid treatment and avoid environmental pollution.
Description
Technical Field
The invention relates to the technical field of solar photovoltaic power generation, in particular to a waste liquid recovery method for a photovoltaic black silicon wafer production line.
Background
At present, the solar energy conversion material is mainly monocrystalline silicon and polycrystalline silicon material. The monocrystalline silicon has the outstanding advantage of high photoelectric conversion efficiency and continuously occupies the leading position of solar products, but the monocrystalline silicon material has high cost and limited productivity, and further popularization of the monocrystalline silicon material is influenced. Polycrystalline silicon has price and resource advantages, particularly, diamond wire cutting is adopted to replace traditional sand wire cutting, the diamond wire cutting speed is high, the cut silicon slice quality is stable, the silicon slice cost can be obviously reduced, however, the surface of the diamond wire cut polycrystalline silicon slice is too smooth, sunlight is easy to reflect and cannot be absorbed by a battery, the photoelectric conversion efficiency is reduced, and texturing processing must be carried out on the surface of the polycrystalline silicon slice for the purpose, namely, a so-called black silicon processing technology. Polycrystal manufacturers hope to solve the problem that the conversion efficiency of a battery is easily reduced by cutting a diamond wire into silicon wafers through black silicon, so that new market opportunities are found for huge polycrystal productivity, and in recent two years, a lot of manufacturers begin to invest in black silicon research and production.
The production of the black silicon is mainly divided into a dry method and a wet method, the black silicon prepared by the dry method has high photoelectric conversion efficiency, but expensive equipment and high production cost, the wet method can be basically produced by using the existing equipment, the operation cost is slightly increased, the photoelectric conversion efficiency of the prepared silicon wafer is high, and the silicon wafer is easy to popularize and use, but working waste liquid containing silver nitrate and cleaning water are generated in the production process, so that the pollution of heavy metal silver, concentrated acid and concentrated alkali exists, and under the current environmental protection policy of China, project establishment and popularization are greatly limited, and the problem which needs to be solved in the field is solved.
The black silicon production mainly comprises the working procedures of wool making, silver deposition, silver removal, hole expansion and the like. The wool making adopts 5-10% KOH aqueous solution, the silver deposition adopts the mixed solution of 0.5% HF and 0.02-0.05g/L silver nitrate to treat, and then 5-10% HF and 5-15% H are used2O2Further etching the mixed solution, and removing silver with 1% NH3·H2O and 1.0-2.0% H2O2Mixed solution is used for reaming by adopting 3.0 to 5.0 percent of HF and about 30 percent of HNO3After the mixed solution is treated, 3 to 5 percent of KOH and 1 percent of NH are added3·H2O and 1.0-2.0% H2O2Further treating the mixture, and treating with 8-10% HF and 5-10% HClAnd (6) processing. From the above, the working solution used in the production process of the black silicon is high-concentration strong acid, strong base and silver-containing solution, so that the working solution is frequently scrapped in the continuous production process to ensure the product quality, and a large amount of waste liquid is generated.
The waste liquid from the black silicon production is directly used as hazardous waste, the treatment cost is very high, and enterprises are difficult to bear. Simple neutralization and precipitation treatment, ineffective separation and reuse of materials, large amount of dangerous solid waste, further treatment of water, direct discharge and high treatment cost. At present, no treatment method for effectively treating waste liquid generated in black silicon production, efficiently separating materials and recycling is available at home and abroad.
Disclosure of Invention
The invention provides a waste liquid recovery method for a photovoltaic black silicon wafer production line aiming at waste liquid generated in black silicon production, which is used for classifying and collecting the waste liquid, separating and recovering effective components in the waste liquid to the maximum extent according to the principle of treating waste by waste, and realizing material recycling. Photovoltaic black silicon chip handles waste liquid silver recovery and material coproduction technique utilizes the aqueous ammonia that contains silver waste liquid of nitric acid neutralization in the reaming waste liquid that black silicon production self produced, transfers to strong acid back, recycles noble metal silver through the multilayer cask form metal titanium net rotary electrode electrolysis of taking the arris, coproduction aqueous ammonia, potassium nitrate, potassium chloride, calcium nitrate and calcium fluoride, and aqueous ammonia, water reuse in production realizes treating waste with the waste, and the material is whole high-efficient to be recycled.
The technology realizes the recovery of noble metal silver in the black silicon production waste liquid, obtains simple substance silver, coproduces calcium fluoride with the purity of 80-85%, calcium nitrate with potassium chloride with the purity of 90-95% and ammonia water with the concentration of 20-30%, and can reuse the evaporated water and the prepared ammonia water for production, thereby realizing the efficient utilization of materials in the black silicon production waste liquid, reducing the comprehensive operation cost of waste liquid treatment and avoiding environmental pollution.
In order to achieve the purpose, the invention provides a method for recovering metallic silver in silver-containing waste liquid by using black silicon wafer reaming waste liquid, which comprises the following steps:
step one, collecting and mixing waste liquid: collecting the silver-containing waste liquid, adding the black silicon wafer reaming waste liquid into the silver-containing waste liquid to obtain a mixed solution, and adjusting the pH value of the mixed solution to 1-2 by using the black silicon wafer reaming waste liquid;
step two, electrolyzing and recovering metallic silver: electrolyzing the mixed solution in the first step by using an electrode to obtain metallic silver, wherein the electrolytic reaction is as follows:
Ag++e→Ag。
the silver-containing waste liquid mainly comprises ammonia water and [ Ag (NH)3)2]+。
The hole-expanding waste liquid mainly comprises a mixed liquid of nitric acid with the concentration of 30-35% and hydrofluoric acid with the concentration of 3-3.5%.
The electrode in the second step is a rotating electrode which comprises a central electrode column, the upper end of the central electrode column is fixedly connected with a motor, a plurality of layers of electrode mesh rings are arranged on the periphery of the central electrode column, which is close to the lower end part of the central electrode column, each layer of electrode mesh ring is surrounded by a porous metal mesh, and the porous metal mesh is radially rolled and folded into a plurality of edges;
the center electrode post with through a plurality of layers of a supporting beam fixed connection that set up from bottom to top, every layer between the electrode net circle the supporting beam comprises a plurality of radial support bars that set up, support bar one end with the electrode net circle is close to angular position fixed connection, the support bar other end with center electrode post lateral wall fixed connection.
In order to realize the purpose, the invention also provides a method for recovering the waste liquid for the photovoltaic black silicon wafer production line, wherein the waste liquid comprises silver-containing waste liquid generated in a silver precipitation process and hole expansion waste liquid generated in a hole expansion process; the recovery method specifically comprises the following steps:
step one, waste liquid collection and mixing: will contain silver-colored waste liquid with a mixing tank is collected to reaming waste liquid, wherein, contain silver-colored waste liquid with the volume ratio of reaming waste liquid is: 1: (1-1.2); the pH value of the mixed solution is adjusted to 1-2 by using the reaming waste liquid, free silver ions are released, and the main reaction after mixing is as follows:
[Ag(NH3)2]++2H+→Ag++2NH4 +
NH3+H+→NH4 +；
step two, electrolyzing and recovering metallic silver: electrolyzing the mixed solution in the first step by using an electrode to recover noble metal silver with current density of 0.1-0.3A/dm2, and electrolyzing to Ag+Less than 0.2mg/L, the electrolysis reaction is as follows:
Ag++e→Ag；
thirdly, adding the electrolyte into the electrolyte after the electrolysis in the second step according to the formula F-Lime milk is added in an amount which is 1.2-1.5 times of the mass of the calcium fluoride, the mixture is mechanically stirred, produced gas is collected by a purified water absorption tower to obtain ammonia water, supernatant and precipitate which are formed by standing after mechanical stirring are separated, the precipitate is washed by water to obtain calcium fluoride (fluorite), the supernatant is sequentially subjected to evaporation and crystallization to obtain calcium nitrate solid, and the main reaction is as follows:
2HF+Ca(OH)2→CaF2↓+H2O
2HNO3+Ca(OH)2→Ca(NO3)2+H2O
NH4 ++OH-→NH3↑+H2O。
the photovoltaic black silicon wafer waste liquid for production line still includes other acid-base waste liquids, other acid-base waste liquids main component is: hydrofluoric acid, hydrochloric acid, potassium hydroxide and ammonia water, other acid-base waste liquids are retrieved through the following steps:
separately collecting the other acid-base waste liquid into a mixing tank, and then performing treatment according to the formula F-Adding lime milk in an amount which is 1.2-1.5 times of the mass of the mixture, mechanically stirring, collecting generated gas by using a purified water absorption tower to obtain ammonia water, separating supernatant and precipitate which are formed by standing after mechanical stirring, obtaining calcium fluoride after washing the precipitate, introducing air into the supernatant, standing to obtain precipitate calcium carbonate and supernatant potassium chloride solution, and sequentially evaporating and crystallizing the supernatant to obtain potassium chloride solid; the main reaction is as follows:
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 electrode in the second step is a rotating electrode which comprises a central electrode column, the upper end of the central electrode column is fixedly connected with a motor, a plurality of layers of electrode mesh rings are arranged on the periphery of the central electrode column close to the lower end part, each layer of electrode mesh ring is formed by surrounding a porous metal mesh, and the porous metal mesh is radially rolled and folded into a plurality of edges and corners;
the center electrode post with through a plurality of layers of a supporting beam fixed connection that set up from bottom to top, every layer between the electrode net circle the supporting beam comprises a plurality of radial support bars that set up, support bar one end with the electrode net circle is close to angular position fixed connection, the support bar other end with center electrode post lateral wall fixed connection.
The central electrode column, the electrode mesh ring and the supporting beam are all made of titanium.
The aperture of the porous metal net is 0.1-1mm, and the angle of the edge angle of the porous metal net is 60-120 degrees.
In order to better achieve the purpose of the invention, the invention also provides a rotary electrode for electrolysis, which comprises a central electrode column, wherein the upper end of the central electrode column is fixedly connected with a motor, a plurality of layers of electrode net rings are arranged on the periphery of the central electrode column, which is close to the lower end part of the central electrode column, each layer of electrode net ring is enclosed by a porous metal net, and the porous metal net is radially rolled and folded into a plurality of edges and corners;
the center electrode post with through a plurality of layers of a supporting beam fixed connection that set up from bottom to top, every layer between the electrode net circle the supporting beam comprises a plurality of radial support bars that set up, support bar one end with the electrode net circle is close to angular position fixed connection, the support bar other end with center electrode post lateral wall fixed connection.
The central electrode column, the electrode mesh ring and the supporting beam are all made of titanium.
The aperture of the porous metal net is 0.1-1mm, and the angle of the edge angle of the porous metal net is 60-120 degrees.
The distance between two adjacent layers of the electrode net rings is 10-100 mm. The number of layers is determined by the volume of the mixed liquid tank of the silver-containing waste liquid and the hole-expanding waste liquid, and the mixed liquid tank consists of 10-100 layers.
The rotating electrode is driven by the motor to uniformly rotate at the speed of 10-60 r/min; the average current density during electrolysis is 0.05-0.20A/dm 2.
The invention has the beneficial effects that: according to the method for recovering the silver-containing waste liquid and the strong acid waste liquid and the method for recovering the photovoltaic black silicon wafer treatment waste liquid containing the silver-containing waste liquid and the strong acid waste liquid, disclosed by the invention, the recovery of precious metal silver in the waste liquid is realized, the simple substance silver is obtained, the calcium fluoride with the purity of 80-85% is co-produced, the calcium nitrate with the purity of 90-95% and the ammonia water with the concentration of 20-30% are co-produced, the evaporated water and the prepared ammonia water can be recycled for production, the efficient utilization of materials in the waste liquid is realized, the comprehensive operation cost of waste liquid treatment can be reduced, and.
Drawings
FIG. 1 is a schematic view of a rotating electrode according to an embodiment of the present invention.
Wherein the reference numerals are: 1. a central electrode column; 2. an electrode mesh ring; 3. and (7) supporting ribs.
Detailed Description
In order to clearly illustrate the technical features of the present solution, the present solution is explained below by way of specific embodiments.
Example 1
Referring to fig. 1, an embodiment of the present invention provides a rotary electrode for electrolysis in a waste liquid recovery method, where the rotary electrode includes a central electrode column 1, an upper end of the central electrode column 1 is fixedly connected to a motor, a plurality of electrode mesh rings 2 are disposed on an outer periphery of the central electrode column 1 near a lower end portion, each electrode mesh ring 2 is surrounded by a porous metal mesh, and the porous metal mesh is radially rolled and folded into a plurality of edges;
the central electrode column 1 and the electrode mesh ring 2 are fixedly connected through a plurality of layers of supporting beams arranged from bottom to top, each layer of supporting beam is composed of a plurality of supporting ribs 3 arranged in the radial direction, one ends of the supporting ribs 3 are fixedly connected with the electrode mesh ring 2 close to the edge part, and the other ends of the supporting ribs 3 are fixedly connected with the outer side wall of the central electrode column 1.
The central electrode column 1, the electrode mesh ring 2 and the supporting beam are all made of titanium.
The aperture of the porous metal net is 0.1-1mm, and the angle of the edge angle of the porous metal net is 60-120 degrees.
The distance between two adjacent layers of electrode net rings 2 is 10-100 mm. The number of layers is determined by the volume of the mixed liquid tank of the silver-containing waste liquid and the hole-expanding waste liquid, and the mixed liquid tank consists of 10-100 layers.
The rotating electrode is driven by a motor to uniformly rotate at the speed of 10-60 r/min; the average current density during electrolysis is 0.05-0.20A/dm 2.
Example 2
The embodiment of the invention provides a method for recovering metallic silver in silver-containing waste liquid by using black silicon wafer reaming waste liquid, which comprises the following steps:
step one, collecting and mixing waste liquid: collecting the silver-containing waste liquid, adding the black silicon wafer reaming waste liquid into the silver-containing waste liquid to obtain a mixed solution, and adjusting the pH value of the mixed solution to 1-2 by using the black silicon wafer reaming waste liquid;
step two, electrolyzing and recovering metallic silver: the mixed solution in the first step was electrolyzed using the electrode provided in example 1 to obtain metallic silver, and the electrolytic reaction was as follows:
Ag++e→Ag。
the silver-containing waste liquid mainly comprises ammonia water and [ Ag (NH)3)2]+。
The hole-expanding waste liquid mainly comprises a mixed liquid of nitric acid with the concentration of 30-35% and hydrofluoric acid with the concentration of 3-3.5%.
Example 3
The embodiment of the invention provides a method for recovering waste liquid for a photovoltaic black silicon wafer production line, wherein the waste liquid comprises silver-containing waste liquid generated in a silver removing process and reaming waste liquid generated in a reaming process; the recovery method specifically comprises the following steps:
step one, waste liquid collection and mixing: will contain silver-colored waste liquid with a mixing tank is collected to reaming waste liquid, wherein, contain silver-colored waste liquid with the volume ratio of reaming waste liquid is: 1, (1-1.2); the pH value of the mixed solution is adjusted to 1-2 by using the reaming waste liquid, free silver ions are released, and the main reaction after mixing is as follows:
[Ag(NH3)2]++2H+→Ag++2NH4 +
NH3+H+→NH4 +；
step two, electrolyzing and recovering metallic silver: the mixed solution in the first step was electrolyzed using the electrode provided in example 1 at a current density of 0.1-0.3A/dm2 to obtain Ag+Less than 0.2mg/L, the electrolysis reaction is as follows:
Ag++e→Ag；
thirdly, adding lime milk into the electrolyte after the electrolysis in the second step according to 1.2-1.5 times of the mass of the F & lt- & gt, mechanically stirring, collecting the produced gas by using a purified water absorption tower to obtain ammonia water, separating the supernatant and the precipitate formed by standing after mechanical stirring, washing the precipitate with water to obtain calcium fluoride (fluorite), and sequentially evaporating and crystallizing the supernatant to obtain a calcium nitrate solid, wherein the main reaction is as follows:
2HF+Ca(OH)2→CaF2↓+H2O
2HNO3+Ca(OH)2→Ca(NO3)2+H2O
NH4 ++OH-→NH3↑+H2O。
the photovoltaic black silicon wafer waste liquid for production line still includes other acid-base waste liquids, other acid-base waste liquids main component is: hydrofluoric acid, hydrochloric acid, potassium hydroxide and ammonia water, other acid-base waste liquids are retrieved through the following steps:
separately collecting the other acid-base waste liquid into a mixing tank, adding lime milk according to 1.2-1.5 times of the mass of F & lt- & gt, mechanically stirring, collecting the generated gas by using a purified water absorption tower to obtain ammonia water, separating the supernatant and the precipitate formed by standing after mechanical stirring, obtaining calcium fluoride after washing the precipitate, introducing air into the supernatant, standing to obtain precipitate calcium carbonate and a supernatant potassium chloride solution, and sequentially evaporating and crystallizing the supernatant to obtain a potassium chloride solid; the main reaction is as follows:
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 present invention is not limited to the above preferred embodiments, and any modifications, equivalent replacements, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (2)
1. A method for recovering metallic silver in silver-containing waste liquid by using black silicon wafer reaming waste liquid is characterized by comprising the following steps:
step one, collecting and mixing waste liquid: collecting the silver-containing waste liquid, adding the black silicon wafer reaming waste liquid into the silver-containing waste liquid to obtain a mixed solution, and adjusting the pH value of the mixed solution to 1-2 by using the black silicon wafer reaming waste liquid;
step two, electrolyzing and recovering metallic silver: electrolyzing the mixed solution in the first step by using an electrode to obtain metallic silver, wherein the electrolytic reaction is as follows:
Ag++e→Ag；
the electrode in the second step is a rotating electrode which comprises a central electrode column, the upper end of the central electrode column is fixedly connected with a motor, a plurality of layers of electrode mesh rings are arranged on the periphery of the central electrode column, which is close to the lower end part of the central electrode column, each layer of electrode mesh ring is surrounded by a porous metal mesh, and the porous metal mesh is radially rolled and folded into a plurality of edges;
the center electrode post with through a plurality of layers of a supporting beam fixed connection that set up from bottom to top, every layer between the electrode net circle the supporting beam comprises a plurality of radial support bars that set up, support bar one end with the electrode net circle is close to angular position fixed connection, the support bar other end with center electrode post lateral wall fixed connection.
2. The method according to claim 1, wherein the silver-containing waste liquid contains ammonia water and [ Ag (NH) as main components3)2]+。
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| 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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