CN115340108B - Method for recycling potassium iodide and potassium iodide product - Google Patents
Method for recycling potassium iodide and potassium iodide product Download PDFInfo
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- CN115340108B CN115340108B CN202211132262.4A CN202211132262A CN115340108B CN 115340108 B CN115340108 B CN 115340108B CN 202211132262 A CN202211132262 A CN 202211132262A CN 115340108 B CN115340108 B CN 115340108B
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- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 title claims abstract description 310
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004064 recycling Methods 0.000 title abstract description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000000706 filtrate Substances 0.000 claims abstract description 104
- 239000013078 crystal Substances 0.000 claims abstract description 85
- 239000012535 impurity Substances 0.000 claims abstract description 66
- 239000000047 product Substances 0.000 claims abstract description 63
- 239000002351 wastewater Substances 0.000 claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 53
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052796 boron Inorganic materials 0.000 claims abstract description 39
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011630 iodine Substances 0.000 claims abstract description 37
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 37
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims description 43
- 239000012452 mother liquor Substances 0.000 claims description 20
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 claims description 17
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 15
- 239000004327 boric acid Substances 0.000 claims description 15
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 11
- 239000000920 calcium hydroxide Substances 0.000 claims description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 11
- 238000004094 preconcentration Methods 0.000 claims description 11
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical group [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 9
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 9
- 238000001223 reverse osmosis Methods 0.000 claims description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 28
- 238000000967 suction filtration Methods 0.000 description 24
- 238000003756 stirring Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 18
- 230000001105 regulatory effect Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 235000011116 calcium hydroxide Nutrition 0.000 description 10
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 229910001424 calcium ion Inorganic materials 0.000 description 8
- 230000005484 gravity Effects 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 239000010413 mother solution Substances 0.000 description 7
- NAFOIZPSUNESOU-UHFFFAOYSA-N [B].[I] Chemical compound [B].[I] NAFOIZPSUNESOU-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 238000011085 pressure filtration Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 3
- 229910001626 barium chloride Inorganic materials 0.000 description 3
- 229910001422 barium ion Inorganic materials 0.000 description 3
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 description 3
- 229940094800 barium oxalate Drugs 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- -1 cation salts Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002999 depolarising effect Effects 0.000 description 1
- 238000001599 direct drying Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C01D3/12—Iodides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The application provides a method for recycling potassium iodide and a potassium iodide product, wherein the method comprises the following steps: providing wastewater containing boron and iodine; pre-concentrating the wastewater containing boron and iodine to obtain a pre-concentrated solution; adding a first impurity removing agent into the pre-concentrated solution, and filtering to obtain a first filtrate. Adding a second impurity removing agent and oxalic acid into the first filtrate to enable the pH value of the first filtrate to be 6-8, enabling the second impurity removing agent to react with sulfate radical in wastewater containing boron and iodine to generate precipitated sulfate, and filtering to obtain the second filtrate. Concentrating and crystallizing the second filtrate, and separating to obtain primary crystals. Adding water into the primary crystals, dissolving, and separating to obtain a third filtrate. Concentrating and crystallizing the third filtrate, separating to obtain secondary crystals, and drying to obtain a potassium iodide product. The method provided by the application can recover potassium iodide in the wastewater containing boron and iodine, and the mass fraction of the potassium iodide contained in the potassium iodide product is more than or equal to 98.5%, so that the recovery and utilization of the potassium iodide are realized.
Description
Technical Field
The application relates to the technical field of wastewater recycling, in particular to a method for recycling potassium iodide and a potassium iodide product.
Background
The lcd is one of the flat panel displays widely used at present, and is composed of a liquid crystal cell and two polarizing plates disposed on both sides of the liquid crystal cell. The existing manufacturing process of the polarizing plate generally comprises the following steps: dyeing the PVA film with iodine or dye with dichroism (dyeing process) of the PVA film (Polyvinyl Alcohol, PVA) film;
then, the iodine on the PVA film is absorbed into the film by boric acid aqueous solution (a cross-linking process);
finally, iodine molecules are aligned in a specific direction by stretching the PVA-based film in a specific direction (stretching step) to form a polarizing plate, and simultaneously, polarized light is removed from a partial region of the polarizing plate using potassium thiosulfate or the like as a bleaching agent to improve heat resistance of the polarized light region on the depolarizing plate, and in this process, wastewater containing boron-iodine is generated due to the use of iodine, potassium iodide, boric acid, and potassium thiosulfate.
In order to meet the discharge standard of the wastewater containing boron and iodine, a plurality of filters and adsorption towers are generally adopted to remove the pollution elements in the wastewater containing boron and iodine so as to reach the wastewater discharge standard, and the potassium iodide in the wastewater containing boron and iodine is not effectively extracted. In recent years, from the viewpoints of energy and environment, developers have started to recover potassium iodide from wastewater containing boron-iodine and reuse the recovered potassium iodide, however, the recovered potassium iodide cannot be fully utilized because the purity of the recovered potassium iodide is not high or new impurities are introduced in the recovery process.
Disclosure of Invention
In view of the above, the present application provides a method for recovering potassium iodide and a potassium iodide product.
To achieve the above object, the present application provides a method for recovering potassium iodide, comprising: providing wastewater containing boron and iodine; pre-concentrating the wastewater containing boron and iodine to obtain a pre-concentrated solution; adding a first impurity removing agent into the pre-concentrated solution, reacting the first impurity removing agent with boric acid in the wastewater containing boron and iodine to generate precipitated borate, and filtering to obtain a first filtrate. Adding a second impurity removing agent and oxalic acid into the first filtrate to enable the pH value of the first filtrate to be 6-8, enabling the second impurity removing agent to react with sulfate radicals in the wastewater containing boron and iodine to generate precipitated sulfate, and filtering to obtain the second filtrate, wherein the solubility product of cations in the second impurity removing agent and the sulfate radicals generated by the sulfate radicals is smaller than that of cations in the first impurity removing agent and the sulfate radicals generated by the sulfate radicals. Concentrating and crystallizing the second filtrate, and separating to obtain primary crystals. Adding water into the primary crystal, dissolving, and separating to obtain a third filtrate. Concentrating and crystallizing the third filtrate, separating to obtain secondary crystals, and drying to obtain a potassium iodide product.
In some embodiments, the first impurity removing agent is any one or more of calcium hydroxide, calcium oxide, and calcium chloride.
In some embodiments, the second impurity removing agent is barium hydroxide.
In some embodiments, the pre-concentration is any one of high temperature evaporative concentration, reverse osmosis concentration, reduced pressure distillative concentration, or reduced pressure distillative concentration performed after reverse osmosis concentration.
In some embodiments, the temperature at which the second filtrate is concentrated to crystallize is 80-100 ℃.
In some embodiments, the mass of the water added during dissolution of the primary crystals is 0.65-0.75 times the mass of the primary crystals.
In some embodiments, after concentrating and crystallizing the second filtrate, a mother liquor and the primary crystals are obtained, wherein the volume ratio of the mother liquor to the primary crystals is 1:0.8-1:2.
in some embodiments, the pH of the first filtrate is 7-8 after adding the oxalic acid.
The application also provides a potassium iodide product which is prepared according to the method for recycling potassium iodide, wherein the mass fraction of potassium iodide contained in the potassium iodide product is more than or equal to 98.5%, and the mass fraction of sulfate radical contained in the potassium iodide product is less than or equal to 0.01%.
The method for recycling potassium iodide provided by the application can effectively remove boric acid and sulfuric acid in the wastewater containing boron and iodine by adding the first impurity removing agent, the second impurity removing agent and oxalic acid into the wastewater containing boron and iodine, and obtain a potassium iodide product with the purity of more than 98.5% by concentrating, filtering and drying. The method provided by the application is simple, the potassium iodide product can be obtained by using the first impurity removing agent, the second impurity removing agent and oxalic acid, quality guarantee is provided for reutilization of the potassium iodide product, and recycling of resources is realized.
Detailed Description
Embodiments of the present invention are described in detail below. The examples described below are illustrative only and are not to be construed as limiting the invention.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The present application provides a method for recovering potassium iodide, wherein the wastewater containing boron and iodine may be wastewater generated in a process for manufacturing a polarizing plate of a liquid crystal display, such as, but not limited to, wastewater containing boric acid and potassium iodide. In practice, the wastewater containing boron and iodine may also contain sulfuric acid, potassium thiosulfate, other trace organic or inorganic substances.
The method comprises the following steps:
s1, providing wastewater containing boron and iodine.
In some embodiments, the wastewater containing boron and iodine comprises 1-5% boric acid, 1-3% potassium thiosulfate, 0.1-0.5% sulfuric acid, 20-40% potassium iodide, and water and trace amounts of organic matters (polyvinyl alcohol) and inorganic matters.
S2, pre-concentrating the wastewater containing the boron and iodine to obtain a pre-concentrated solution.
In this step, by concentrating the wastewater containing boron-iodine, water in the wastewater containing boron-iodine can be removed to reduce energy consumption in the subsequent treatment process.
In some embodiments, the manner of pre-concentration may be any of high temperature evaporative concentration, reverse osmosis concentration, reduced pressure distillative concentration, or reduced pressure distillative concentration performed after reverse osmosis concentration.
High temperature evaporative concentration may refer to heating the wastewater above 70 ℃ to evaporate water from the wastewater.
Reverse osmosis concentration may refer to a system in which after wastewater is transferred from a wastewater storage tank to a wastewater auxiliary storage tank by a feed pump, the wastewater is allowed to pass through a reverse osmosis membrane from the wastewater auxiliary storage tank by a high pressure pump.
Reduced pressure distillation concentration may mean that distillation may be performed under a certain pressure.
From the viewpoints of economic efficiency and practical existing equipment, the application preferably adopts high-temperature evaporation concentration.
S3, adding a first impurity removing agent into the pre-concentrated solution obtained in the step S2, stirring, and carrying out suction filtration to obtain a first filtrate.
In this step, the first impurity removing agent is mainly used for removing boric acid in the pre-concentrated solution, and the first impurity removing agent reacts with boric acid to generate precipitated borate, and the precipitated borate and the filtrate are separated through suction filtration.
In some embodiments, the first impurity removing agent may be one or more of calcium hydroxide, calcium oxide, and calcium chloride. From the economical point of view, calcium hydroxide is preferably used in the present application. And (3) reacting the calcium hydroxide with boric acid in the pre-concentrated solution to generate precipitated calcium borate, and carrying out suction filtration to obtain a first filtrate which does not contain boric acid.
In this step, the content of B element in boric acid in the pre-concentrated solution is measured by an ICP emission spectrometer, and whether the first impurity removing agent is completely reacted with the pre-concentrated solution is determined according to the decrease amount of boric acid in the pre-concentrated solution.
Suction filtration may be carried out using a filter or a separation device, such as pressure filtration, vacuum filtration or centrifugal filtration, to separate the precipitate from the solution.
S4, adding a second impurity removing agent and oxalic acid into the first filtrate obtained in the step S3 simultaneously to enable the pH value to be 6-8, stirring, enabling the second impurity removing agent to react with sulfate radicals in wastewater containing boron and iodine to generate precipitated sulfate, and carrying out suction filtration to obtain a second filtrate, wherein the solubility product of sulfate radicals generated by cations and sulfate radicals in the second impurity removing agent is smaller than that of sulfate radicals generated by cations and sulfate radicals in the first impurity removing agent.
In this step, the excess cations introduced in step S3 of the first filtrate, as well as sulfate in the first filtrate, are removed by the second impurity removing agent and oxalic acid to obtain precipitated sulfate and cation salts.
In some embodiments, the second impurity removing agent is barium hydroxide.
In this step, the solubility product of the sulfate generated by the cation and sulfate in the second impurity removing agent is smaller than the solubility product of the sulfate generated by the cation and sulfate in the first impurity removing agent, for example, the solubility product constant of barium sulfate is smaller than the solubility product constant of calcium sulfate. The second impurity removing agent is added, so that barium ions contained in the second impurity removing agent react with sulfate radicals in the first filtrate to generate precipitated barium sulfate, and sulfuric acid in the first filtrate is removed conveniently. Wherein the solubility product constant of barium sulfate is 1.08X10 -10 The solubility product constant of barium oxalate is 1.2X10 -7 The solubility product constant of barium sulfate is much smaller than that of barium oxalate, that is, barium ions react first with sulfate ions to form barium sulfate, so that sulfate ions can form precipitates to be removed.
In this application, the addition of oxalic acid to the first filtrate has several effects: in the first aspect, the pH value of the first filtrate can be adjusted by adding oxalic acid, so that the pH value of the first filtrate is in a range of 6-8, and barium sulfate generated by the second impurity removing agent and sulfate radical in the first filtrate forms a precipitate from suspension and is precipitated; in a second aspect, oxalic acid reacts with calcium ions in the first filtrate to produce precipitated calcium oxalate to facilitate removal of excess calcium ions in the first filtrate; in a third aspect, oxalic acid may also react with a portion of the excess barium ions to form precipitated barium oxalate.
Meanwhile, it should be noted that in this step, if the pH value of the solution is less than 6, the amount of oxalic acid added is excessive, and under the condition of adding too much oxalic acid, waste of oxalic acid is caused; meanwhile, part of oxalic acid can be separated out of solution in the subsequent concentrated crystallization, and the separated oxalic acid can be mixed in a potassium iodide product, so that the purity of the potassium iodide is reduced. If the pH value of the solution is more than 8, barium sulfate in the first filtrate cannot be completely precipitated, and part of the barium sulfate can be remained, so that the purity of the prepared potassium iodide is reduced. The pH value of 7-8 is preferably adopted, and the use amount of oxalic acid can be reduced under the condition of ensuring the precipitation of barium sulfate.
In addition, in this step, the addition of oxalic acid can remove not only impurities but also in step S6, compared with the adjustment of the pH of the first filtrate with nitric acid or other acids such as hydrochloric acid. Meanwhile, new impurities can be introduced by adding other acids, so that the steps and the cost for removing the impurities are increased.
In step S3, the mass (g) of the first impurity removing agent is about 2.5% -7% of the volume (mL) of the pre-concentrate, such as by adding 2.5g-7g of the first impurity removing agent to 100mL of the pre-concentrate. In step S4, the mass (g) of the second impurity removing agent is about 2% -4% of the volume (mL) of the first filtrate, such as adding 2g-4g of the first impurity removing agent to 100mL of the first filtrate. According to production experience, the first impurity removing agent and the second impurity removing agent are in the range, and boric acid or sulfate radical can be effectively removed.
S5, concentrating and crystallizing the second filtrate obtained in the step S4, and carrying out suction filtration to obtain primary crystals.
Specifically, evaporating and concentrating the second filtrate at a high temperature (for example, 90 ℃) to reduce the water content in the second filtrate, and concentrating the second filtrate to obtain mother liquor and primary crystals, wherein the volume ratio of the mother liquor to the primary crystals is 1:1, under the condition, most potassium iodide in the second filtrate is separated out, and the primary crystal is obtained by suction filtration.
Meanwhile, in this step, since potassium iodide and potassium thiosulfate have different solubilities at different temperatures, when the temperature is more than 20 ℃, the solubility of potassium thiosulfate is more than that of potassium iodide, that is, potassium iodide is preferentially precipitated during high-temperature evaporation. In addition, the concentration of potassium iodide in the wastewater (or the second filtrate) containing boron and iodine is far greater than that of potassium thiosulfate, so that in the concentration and crystallization process, potassium iodide is gradually separated out, and most of potassium thiosulfate remains in the mother liquor. The concentration and crystallization in this step can reduce potassium thiosulfate in the primary crystals. The solubility of potassium iodide and potassium thiosulfate is as follows in table 1:
table 1 solubility units of potassium iodide and potassium thiosulfate at different temperatures: g/100g water
0℃ | 10℃ | 20℃ | 30℃ | 40℃ | 50℃ | 60℃ | |
Potassium iodide KI | 128 | 136 | 144 | 153 | 162 | 168 | 176 |
Potassium thiosulfate K 2 S 2 O 3 | 96 | / | 155 | 175 | 205 | / | 238 |
Meanwhile, in the step, the trace organic matters in the second filtrate are carbonized at high temperature through high-temperature concentration, and trace organic matters (such as polyvinyl alcohol) in the wastewater containing boron and iodine are removed through suction filtration.
In some embodiments, the volume ratio of mother liquor to primary crystals is 1:0.8-1:2. if the volume ratio of the mother solution to the primary crystals is too large, more potassium iodide remains in the mother solution, so that the recovery rate of the primary crystals is low, and the production cost is increased. If the volume ratio of the mother solution to the primary crystals is too small, i.e. the content of the mother solution is smaller than that of the primary crystals, the potassium thiosulfate in the mother solution is crystallized, so that the primary crystals contain more potassium thiosulfate crystals, and the purity of the potassium iodide in the potassium iodide product is reduced.
In some embodiments, the temperature at which the second filtrate is concentrated to crystallize is 80-100 ℃. If the temperature of the second filtrate for evaporative crystallization is too high, the energy consumption required for the precipitated primary crystals is large. If the temperature of the second filtrate for evaporative crystallization is too low, the concentration crystallization time is longer.
S6, adding water into the primary crystal obtained in the step S5, dissolving and stirring, filtering to obtain a third filtrate, concentrating and crystallizing the third filtrate, filtering to obtain a secondary crystal, and drying to obtain a potassium iodide product, wherein the potassium iodide product contains more than or equal to 98.5% by mass of potassium iodide and less than or equal to 0.01% by mass of sulfate radical.
By dissolving the primary crystals to obtain the third filtrate to obtain the secondary crystals, impurities in the primary crystals can be further reduced, and a potassium iodide product with higher purity can be obtained.
In some embodiments, the mass of water added during dissolution of the primary crystals is 0.65-0.75 times the mass of the primary crystals. The quality of the added water is controlled, so that a theoretical saturated solution of potassium iodide is obtained after the primary crystal is dissolved, and the secondary crystal is prevented from containing excessive oxalic acid to be dissolved again in the step S4. Under the same temperature condition, the solubility of oxalic acid is smaller than that of potassium iodide, so that the content of oxalic acid crystals in secondary crystals can be reduced by controlling the adding amount of water in the step S6, and the purity of potassium iodide in a potassium iodide product can be improved.
Meanwhile, in the process of concentrating and crystallizing the third filtrate, potassium thiosulfate in the secondary crystal can be reduced.
After the third filtrate is concentrated and crystallized, the volume ratio of the mother solution to the secondary crystals precipitated in the mother solution is 1: and 1, carrying out suction filtration and separation to obtain secondary crystals.
The application also provides a potassium iodide product which is prepared according to the method for recycling potassium iodide, wherein the mass fraction of potassium iodide contained in the potassium iodide product is more than or equal to 98.5%, and the mass fraction of sulfate radical contained in the potassium iodide product is less than or equal to 0.01%.
The method for recycling potassium iodide provided by the application can effectively remove boric acid and sulfuric acid in the wastewater containing boron and iodine by adding the first impurity removing agent, the second impurity removing agent and oxalic acid into the wastewater containing boron and iodine, and obtain a potassium iodide product with the purity of more than 98.5% by concentrating, filtering and drying. The method provided by the application is simple, the potassium iodide product can be obtained by using the first impurity removing agent, the second impurity removing agent and oxalic acid, quality guarantee is provided for reutilization of the potassium iodide product, and recycling of resources is realized.
The scheme of the present invention will be explained below with reference to examples. It will be appreciated by those skilled in the art that the following examples are for illustrative purposes only and are not to be construed as limiting the invention. Unless otherwise indicated, the reagents, software and instrumentation involved in the examples below are all conventional commercial products or open source.
Example 1
2L of wastewater containing boron and iodine (the composition is shown in Table 2) was subjected to evaporation pre-concentration treatment at normal pressure and 80 ℃, the raw liquid gravity of the wastewater containing boron and iodine was 1.16, and discharging was performed when the evaporation pre-concentration treatment was carried out until the concentrated liquid gravity was 1.5, to obtain 830ml of pre-concentrated liquid (the composition is shown in Table 3).
41.5g of slaked lime powder was slowly added to the preconcentrate to remove impurities, the reaction pH was about 12, and the reaction was pressure-filtered for 1h to obtain 710ml of a first filtrate (see Table 4 for ingredients). To the first filtrate, 23.4g of barium hydroxide powder and 14g of oxalic acid were added in this order to remove impurities of sulfate radical and free calcium ion, and at this time, the pH was about 8, and press filtration was carried out to obtain a second filtrate (composition shown in Table 5).
Transferring the second filtrate into a rotary evaporator, regulating the pressure to-0.095 Mpa, evaporating, concentrating and crystallizing at 90 ℃, stopping heating when the volume ratio of the crystal in the evaporating liquid to the mother liquor is about 1:1, transferring the evaporating liquid into a beaker for stirring and cooling, and carrying out suction filtration when the temperature is reduced to below 50 ℃ to obtain 242.5g of primary crystal.
And returning the primary crystal to the regulating tank, adding pure water, stirring and dissolving, wherein the water adding amount is 0.65 time of the weight of the crystal, dissolving for about 30min, and performing suction filtration to obtain a third filtrate.
Transferring the third filtrate into a rotary evaporator, regulating the pressure to-0.095 Mpa, evaporating, concentrating and crystallizing at 90 ℃, stopping heating when the volume ratio of the crystal in the evaporating liquid to the mother liquor is about 1:1, transferring the evaporating liquid into a beaker for stirring and cooling, filtering when the temperature is reduced to below 50 ℃, obtaining secondary crystals, and drying the product to finally obtain 125g of potassium iodide product.
Table 2 constituent units of wastewater containing boron-iodine in example 1: mg/l
KI | Ca | Mg | Na | B | Pb | As | Fe | TN | P | Ba | S | Cl |
256.91g/l | 27.9 | 5.7 | 1050 | 6860 | <0.2 | <0.5 | 6.73 | 4.01 | 39.8 | 0.08 | 4910 | 20-40 |
Table 3 composition units of preconcentrate in example 1: mg/l
KI | Ca | Mg | Na | B | Pb | As | Fe | TN | P | Ba | S | Cl |
673.82g/l | 24.6 | 14.7 | 1220 | 10160 | <0.2 | 0.7 | 9.16 | 2.24 | 73.8 | 0.1 | 8730 | 50-100 |
Table 4 composition unit of the first filtrate in example 1: mg/l
Table 5 constituent units of the second filtrate in example 1: mg/l
KI | B | S | As | Ca | Pb | Ba | P | Fe |
679.8g/l | 1890 | 2310 | 0.6 | 7.87 | <0.2 | 4.59 | <0.2 | 1.06 |
Example 2
2L of wastewater containing boron and iodine (the composition is shown in Table 6) was subjected to evaporation pre-concentration treatment at normal pressure and 80 ℃, the raw liquid gravity of the wastewater containing boron and iodine was 1.23, and discharging was performed when the evaporation pre-concentration treatment was carried out until the concentrated liquid gravity was 1.5, to obtain 922ml of pre-concentrated liquid (the composition is shown in Table 7).
65g of slaked lime powder was slowly added to the preconcentrate to remove impurities, the reaction pH was about 12, and the reaction was pressure-filtered for 2 hours to obtain 800ml of a first filtrate (the composition is shown in Table 8). 28g of barium hydroxide powder and 19g of oxalic acid are sequentially added into the first filtrate to remove sulfate radical and free calcium ions, the pH value is about 7, the reaction is carried out for 2 hours at normal temperature, and the filter pressing is carried out, so that a second filtrate (the composition is shown in Table 9) is obtained.
Transferring the second filtrate into a beaker, heating by adopting an electric furnace to evaporate at normal pressure, stopping heating when the volume ratio of the crystal to the mother liquor in the evaporated liquid is about 1:1.5, stirring and cooling the beaker, and carrying out suction filtration when the temperature is reduced to below 50 ℃ to obtain 290g of primary crystal.
And returning the primary crystal to the regulating tank, adding pure water, stirring and dissolving, wherein the water adding amount is 0.65 time of the weight of the crystal, dissolving for about 30min, and performing suction filtration to obtain a third filtrate.
Transferring the third filtrate into a beaker, heating by adopting an electric furnace to evaporate at normal pressure, stopping heating when the volume ratio of crystals to mother liquor in the evaporating liquid is about 1:0.8, stirring and cooling the beaker, and carrying out suction filtration when the temperature is reduced to below 50 ℃ to obtain secondary crystals, and drying the secondary crystals to finally obtain 149g of potassium iodide product.
Table 6 composition unit of wastewater containing boron-iodine in example 2: mg/l
KI | Ca | Mg | Na | B | Pb | As | Fe | TN | P | Ba | S | Cl |
372g/l | 25.2 | 4.9 | 1080 | 7650 | <0.2 | 0.7 | 5.3 | 2.32 | <0.2 | 0.05 | 4066 | 20-40 |
Table 7 compositional units of pre-concentrate in example 2: mg/l
Table 8 composition unit of the first filtrate in example 2: mg/l
KI | B | S | As | Ca | Pb | Ba | P | Fe |
700g/l | 1330 | 10430 | <0.4 | 611 | <0.4 | 0.7 | 1.5 | 0.8 |
Table 9 constituent units of the second filtrate in example 2: mg/l
KI | B | S | As | Ca | Pb | Ba | P | Fe |
708.7g/l | 1250 | 3810 | <0.5 | 3.55 | <0.2 | 18.1 | <0.2 | 1.22 |
Comparative example 1
Comparative example 2 differs from example 1 in that the potassium iodide product of example 2 was obtained by direct drying of primary crystals, yielding 242.5g of potassium iodide product.
Comparative example 2
1L of wastewater containing boron and iodine (wastewater containing boron and iodine as in example 1) was subjected to evaporation and preconcentration treatment at normal pressure and 80℃and discharged when the specific gravity of the concentrate was 1.5, to obtain 408ml of preconcentrate.
20.4g of slaked lime powder was slowly added to the preconcentrate to remove impurities, the reaction pH was about 12, and press filtration was performed to obtain 366ml of a first filtrate. Adding 4g of oxalic acid into the first filtrate to remove free calcium ions, wherein the pH is about 6.5, and performing filter pressing to obtain a second filtrate.
Transferring the second filtrate into a rotary evaporator, regulating the pressure to-0.095 Mpa, evaporating, concentrating and crystallizing at 90 ℃, stopping heating when the volume ratio of crystal to mother liquor in the evaporating liquid is about 1:1, transferring the evaporating liquid into a beaker for stirring and cooling, and carrying out suction filtration when the temperature is reduced to below 50 ℃ to obtain 134g of primary crystal.
And returning the primary crystal to the regulating tank, adding pure water, stirring and dissolving, wherein the water adding amount is 0.65 time of the weight of the crystal, dissolving for about 30min, and performing suction filtration to obtain a third filtrate.
Transferring the third filtrate into a rotary evaporator, regulating the pressure to-0.095 Mpa, evaporating, concentrating and crystallizing at 90 ℃, stopping heating when the volume ratio of the crystal to the mother liquor in the evaporating liquid is about 1:1, transferring the evaporating liquid into a beaker for stirring and cooling, and performing suction filtration when the temperature is reduced to below 50 ℃ to obtain the secondary crystal. And drying the secondary crystal to obtain 72g of potassium iodide product.
Comparative example 3
1L of wastewater containing boron and iodine (wastewater containing boron and iodine, which is the same as in example 1) was subjected to evaporation pre-concentration treatment at normal pressure and 80 ℃, and discharging was performed when the specific gravity of the concentrated solution was 1.5, to obtain 400ml of pre-concentrated solution;
20g of slaked lime powder is slowly added into the pre-concentrated solution for impurity removal, the reaction pH is about 12, and after 1h of reaction, the mixture is subjected to pressure filtration to obtain 350ml of first filtrate. 12g of barium hydroxide powder and 9g of oxalic acid are sequentially added into the first filtrate to remove sulfate radical and free calcium ions, the pH value is about 5, and after 2 hours of reaction, the second filtrate is obtained by pressure filtration.
Transferring the second filtrate into a rotary evaporator, regulating the pressure to-0.095 Mpa, evaporating, concentrating and crystallizing at 90 ℃, stopping heating when the volume ratio of the crystal in the evaporating liquid to the mother liquor is about 1:1, transferring the evaporating liquid into a beaker for stirring and cooling, and carrying out suction filtration when the temperature is reduced to below 50 ℃ to obtain 128g of primary crystal.
And returning the primary crystal to the regulating tank, adding pure water, stirring and dissolving, wherein the water adding amount is 0.65 time of the weight of the crystal, dissolving for about 30min, and performing suction filtration to obtain a third filtrate.
Transferring the third filtrate into a rotary evaporator, regulating the pressure to-0.095 Mpa, evaporating, concentrating and crystallizing at 90 ℃, stopping heating when the volume ratio of the crystal in the evaporating liquid to the mother liquor is about 1:1, transferring the evaporating liquid into a beaker for stirring and cooling, filtering when the temperature is reduced to below 50 ℃, obtaining secondary crystals, drying the secondary crystals, and finally obtaining 66.6g of potassium iodide products.
Comparative example 4
1L of wastewater containing boron and iodine (wastewater containing boron and iodine as in example 1) was subjected to evaporation and preconcentration treatment at normal pressure and 80℃and discharged when the specific gravity of the concentrate was 1.5, to obtain 408ml of preconcentrate.
20.5g of slaked lime powder is slowly added into the pre-concentrated solution for impurity removal, the reaction pH is about 12, and after 1h of reaction, the first filtrate of 348ml is obtained by pressure filtration. And adding 10.5g of barium hydroxide powder and 5.3g of oxalic acid into the first filtrate in sequence to remove sulfate radical and free calcium ions, wherein the pH is about 9, and performing pressure filtration after reacting for 2 hours to obtain a second filtrate.
Transferring the second filtrate into a rotary evaporator, regulating the pressure to-0.095 Mpa, evaporating and crystallizing at 90 ℃, stopping heating when the volume ratio of the crystal in the evaporating liquid to the mother liquor is about 1:1, transferring the evaporating liquid into a beaker for stirring and cooling, and carrying out suction filtration when the temperature is reduced to below 50 ℃ to obtain 125.3g of primary crystal.
And returning the primary crystal to the regulating tank, adding pure water, stirring and dissolving, wherein the water adding amount is 0.65 time of the weight of the crystal, dissolving for about 30min, and performing suction filtration to obtain a third filtrate.
Transferring the third filtrate into a rotary evaporator, regulating the pressure to-0.095 Mpa, evaporating and crystallizing at 90 ℃, stopping heating when the volume ratio of the crystal in the evaporating liquid to the mother liquor is about 1:1, transferring the evaporating liquid into a beaker for stirring and cooling, filtering to obtain secondary crystals when the temperature is reduced to below 50 ℃, and drying the secondary crystals to finally obtain 67.7g of potassium iodide product.
Comparative example 5
1L of wastewater containing boron and iodine (wastewater containing boron and iodine as in example 1) was subjected to evaporation and preconcentration treatment at normal pressure and 80℃and discharged when the specific gravity of the concentrate was 1.5, to obtain 410ml of a preconcentrate.
20.7g of slaked lime powder was slowly added to the preconcentrate to remove impurities, the reaction pH was about 12, and press filtration was performed to obtain 367ml of a first filtrate. 9g of barium chloride powder and 3g of oxalic acid are sequentially added into the first filtrate to remove sulfate radical and free calcium ions, the pH value is about 8, and the second filtrate is obtained through filter pressing.
Transferring the second filtrate into a rotary evaporator, regulating the pressure to-0.095 Mpa, evaporating, concentrating and crystallizing at 90 ℃, stopping heating when the volume ratio of the crystal in the evaporating liquid to the mother liquor is about 1:1, transferring the evaporating liquid into a beaker for stirring and cooling, and carrying out suction filtration when the temperature is reduced to below 50 ℃ to obtain 136g of primary crystal.
And returning the primary crystal to the regulating tank, adding pure water, stirring and dissolving, wherein the water adding amount is 0.65 time of the weight of the crystal, dissolving for about 30min, and performing suction filtration to obtain a third filtrate.
Transferring the third filtrate into a rotary evaporator, regulating the pressure to-0.095 Mpa, evaporating, concentrating and crystallizing at 90 ℃, stopping heating when the volume ratio of the crystal to the mother liquor in the evaporating liquid is about 1:1, transferring the evaporating liquid into a beaker for stirring and cooling, and performing suction filtration when the temperature is reduced to below 50 ℃ to obtain secondary crystals. Drying and crystallizing for the second time to finally obtain 74g of potassium iodide product.
In tables 5 and 9, most of the S element contained in the second filtrate was present in the second filtrate as thiosulfate.
The content of each component is tested by an inductively coupled plasma spectrometer (ICP emission spectrometer for short). The content of the components of the potassium iodide products of examples 1-2 and comparative examples 1-5, respectively, was also determined and compared with the GB/T1272-2007 standard applicable potassium iodide. Such as tables 10 and 11.
TABLE 10 reagents or procedures for the corresponding procedures in examples 1-2 and comparative examples 1-5
Table 11 specification of Potassium iodide in GB/T1272-2007 Standard, and component content of Potassium iodide products in examples 1-2 and comparative examples 1-5
As is clear from tables 10 and 11, the mass fraction of potassium iodide in the potassium iodide products prepared in examples 1-2 was 99.2% or more, and the mass fraction of sulfate radical was less than 0.01%. The potassium iodide product prepared in the examples 1-2 meets the chemical purity requirement of potassium iodide in GB/T1272-2007 standard, so that the potassium iodide product prepared in the examples 1-2 has more application fields.
In comparison with example 1, the crystallization process of the potassium iodide product of comparative example 1 was performed only once, and the purity of the obtained potassium iodide was lower than that of the potassium iodide product obtained in example 1. This also means that oxalic acid crystals and potassium thiosulfate contained in the primary crystals and which affect the purity of the potassium iodide product.
When the second impurity removing agent is not added in comparative example 2, the sulfate radical element content in the prepared potassium iodide product is far more than 0.01%, which shows the sulfate radical removing effect of the second impurity removing agent.
In comparative example 3, when the pH after oxalic acid is added to the first filtrate is less than 6, the purity of the prepared potassium iodide product is lower, which means that the oxalic acid is excessively added when the pH is lower, so that part of oxalic acid is mixed in the potassium iodide product, and the purity of the potassium iodide product is reduced. In comparative example 4, when the pH after adding oxalic acid to the first filtrate was greater than 8, the sulfate content in the potassium iodide product increased, indicating that a portion of the sulfate did not form a precipitate with barium hydroxide.
Compared with example 1, the barium chloride is used in comparative example 5 to replace the barium hydroxide in example 1, so that new impurity chlorine element is introduced into the potassium iodide product, the obtained potassium iodide product contains excessive chlorine element, and in the process, the sulfate radical content in the potassium iodide product is higher. The chlorine content in the product prepared in comparative example 5 far exceeds the GB/T1272-2007 standard, which shows that the removal of sulfate ions by barium chloride in the present application cannot meet the requirements.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (4)
1. A method for recovering potassium iodide comprising:
providing wastewater containing boron and iodine;
pre-concentrating the wastewater containing boron and iodine to obtain a pre-concentrated solution;
adding a first impurity removing agent into the pre-concentrated solution, reacting the first impurity removing agent with boric acid in the wastewater containing boron and iodine to generate precipitated borate, wherein the first impurity removing agent is any one or more of calcium hydroxide, calcium oxide and calcium chloride, and filtering to obtain a first filtrate;
adding a second impurity removing agent and oxalic acid into the first filtrate, wherein the second impurity removing agent is barium hydroxide, so that the pH value of the first filtrate is 6-8, the second impurity removing agent reacts with sulfate radical in the wastewater containing boron and iodine to generate precipitated sulfate, the oxalic acid is also used for reacting with cation in the first impurity removing agent to produce precipitated oxalate and removing superfluous cation in the second impurity removing agent, and the second filtrate is obtained after filtration, wherein the solubility product of the cation in the second impurity removing agent and the sulfate radical is smaller than that of the sulfate generated by the cation in the first impurity removing agent and the sulfate radical;
concentrating and crystallizing the second filtrate, wherein the temperature of the second filtrate is 80-100 ℃, and separating to obtain primary crystals containing potassium iodide and mother liquor containing potassium thiosulfate;
adding water into the primary crystal, dissolving, wherein the mass of the water is 0.65-0.75 times of that of the primary crystal, and separating to obtain a third filtrate;
concentrating and crystallizing the third filtrate, separating to obtain secondary crystals, and drying to obtain a potassium iodide product.
2. The method for recovering potassium iodide according to claim 1, wherein the pre-concentration is any one of high-temperature evaporation concentration, reverse osmosis concentration, reduced pressure distillation concentration, and reduced pressure distillation concentration performed after reverse osmosis concentration.
3. The method for recovering potassium iodide of claim 1, wherein the volume ratio of the mother liquor to the primary crystals is 1:0.8-1:2.
4. the method of recovering potassium iodide of claim 1, wherein the first filtrate has a pH of from 7 to 8 after the oxalic acid is added.
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JP2002210475A (en) * | 2001-01-23 | 2002-07-30 | Japan Organo Co Ltd | Treating method of waste water containing boron |
CN109553116A (en) * | 2017-09-26 | 2019-04-02 | 黄载昌 | The purification process of the potassium iodide waste liquid of boronic acid containing |
CN113443762A (en) * | 2020-03-27 | 2021-09-28 | 日东电工株式会社 | Method for treating waste liquid from manufacture of polarizing plate |
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JP2002210475A (en) * | 2001-01-23 | 2002-07-30 | Japan Organo Co Ltd | Treating method of waste water containing boron |
CN109553116A (en) * | 2017-09-26 | 2019-04-02 | 黄载昌 | The purification process of the potassium iodide waste liquid of boronic acid containing |
CN113443762A (en) * | 2020-03-27 | 2021-09-28 | 日东电工株式会社 | Method for treating waste liquid from manufacture of polarizing plate |
Non-Patent Citations (1)
Title |
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GB/T1272-2007,化学试剂碘化钾;中华人民共和国国家质量监督检验检疫总局 中国国家标准化管理委员会;《中华人民共和国国家标准》;第1-5页 * |
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