CN116873870B - Method for recovering and refining hydrofluoric acid from solution containing hydrofluoric acid - Google Patents
Method for recovering and refining hydrofluoric acid from solution containing hydrofluoric acid Download PDFInfo
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- CN116873870B CN116873870B CN202311154086.9A CN202311154086A CN116873870B CN 116873870 B CN116873870 B CN 116873870B CN 202311154086 A CN202311154086 A CN 202311154086A CN 116873870 B CN116873870 B CN 116873870B
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000007670 refining Methods 0.000 title claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 91
- -1 fluoride ions Chemical class 0.000 claims abstract description 67
- 239000002699 waste material Substances 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 20
- 239000000706 filtrate Substances 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004064 recycling Methods 0.000 claims abstract description 10
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003463 adsorbent Substances 0.000 claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
- 229910021532 Calcite Inorganic materials 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 5
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 56
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 55
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 55
- 238000003756 stirring Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 230000005855 radiation Effects 0.000 claims description 26
- 239000010812 mixed waste Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 19
- 238000010992 reflux Methods 0.000 claims description 18
- 238000012545 processing Methods 0.000 claims description 13
- 230000005251 gamma ray Effects 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- 239000013049 sediment Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- QFVGCVZHAQQIMT-UHFFFAOYSA-L nickel(2+);prop-2-enoate Chemical compound [Ni+2].[O-]C(=O)C=C.[O-]C(=O)C=C QFVGCVZHAQQIMT-UHFFFAOYSA-L 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 6
- 150000002221 fluorine Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 17
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 11
- 229910021645 metal ion Inorganic materials 0.000 abstract description 8
- 238000001556 precipitation Methods 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 6
- 239000012141 concentrate Substances 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 16
- 150000003254 radicals Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 230000001502 supplementing effect Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 3
- 229940031826 phenolate Drugs 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PMHOLXNNEPPFNZ-UHFFFAOYSA-N n-(3-hydroxyphenyl)prop-2-enamide Chemical compound OC1=CC=CC(NC(=O)C=C)=C1 PMHOLXNNEPPFNZ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical class FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- WELLGRANCAVMDP-UHFFFAOYSA-N isocyanatoethane;prop-2-enoic acid Chemical compound CCN=C=O.OC(=O)C=C WELLGRANCAVMDP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LSUGARZMXSJAAI-UHFFFAOYSA-N nitric acid hydrate hydrofluoride Chemical compound O.F.O[N+]([O-])=O LSUGARZMXSJAAI-UHFFFAOYSA-N 0.000 description 1
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
- C01B7/197—Separation; Purification by adsorption
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
Abstract
The invention relates to the technical field of treatment of hydrofluoric acid-containing waste liquid, in particular to a method for recycling and refining hydrofluoric acid from a solution containing hydrofluoric acid; the method comprises the steps of carrying out precipitation and filtration on hydrofluoric acid-containing waste liquid by a pretreatment system, allowing filtrate to enter a rectification system, carrying out refining and concentration, and then sending the filtrate into a post-treatment system, and carrying out adsorption filtration and purification to obtain hydrofluoric acid with different purities; the invention uses the additive nitrate to lead fluosilicic acid to generate precipitate and separate out, and the filtrate is further rectified to obtain mixed acid of hydrofluoric acid and nitric acid; the invention adopts a rectification process, can concentrate mixed acid, and can remove metal ions and COD in waste acid at the same time, so as to further improve the concentration of the mixed acid; the invention adopts an adsorbent: activated carbon, calcite, activated alumina, hydroxyapatite and the like to adsorb fluoride ions so as to prepare hydrofluoric acid with different purities.
Description
Technical Field
The invention relates to the technical field of treatment of waste liquid containing hydrofluoric acid, in particular to a method for recycling and refining hydrofluoric acid from solution containing hydrofluoric acid.
Background
In the texturing and etching process of the solar cell, a large amount of mixed acid is consumed each year, and the mixed acid consists of electronic-grade hydrofluoric acid, hydrochloric acid, nitric acid, fluosilicic acid and the like. In addition, the process produces a large amount of aqueous mixed waste acid, and also produces a large amount of waste water during the waste acid treatment. The existing acid-containing wastewater treatment process comprises the steps of mixing and then carrying out stepwise treatment, wherein the concentration of the acid in the mixed acid aqueous solution is high, and a large amount of alkali liquor is consumed by alkali neutralization at the present stage. Because hydrofluoric acid is used, the content of fluoride ions in the mixed acid aqueous solution is very high, and calcium chloride precipitation is needed to be added to remove the fluoride ions; in addition, the mixed acid aqueous solution has high nitrogen content, and the emission index can be reached by adopting anaerobic and aerobic treatment. Therefore, the treatment of the mixed acid aqueous solution not only has complex process and causes the waste of mixed acid resources, but also consumes chemical reagents such as alkali and CaCl 2 And the like, the processing cost is high. Therefore, development of a new mixed acid treatment process, reduction of new water consumption and realization of water recycling are urgent.
In summary, to realize the recycling of water, the recycling of mixed concentrated acid in the etching and texturing processes is a key step for realizing the water circulation of the whole factory.
Chinese patent CN116081575a: a process for preparing electronic-class inorganic acid from waste hydrofluoric acid liquid includes such steps as adding alkali metal fluoride and alkali metal nitrate to the waste hydrofluoric acid liquid containing hydrofluoric acid, water and water, breaking the azeotropic phenomenon of hydrofluoric acid and water, and rectifying to obtain hydrogen fluoride vapour. And evaporating the nitric acid and water from the mixed solution to form a nitric acid-water mixed solution, adding alkaline earth metal nitrate into the nitric acid/water mixed solution, breaking the azeotropic phenomenon of the nitric acid and water, and rectifying and separating the nitric acid. And respectively removing mist drops containing impurities from the separated hydrogen fluoride vapor and nitric acid vapor in sequence, condensing, adding ultrapure water, and concentrating to prepare the electronic grade hydrofluoric acid and the electronic grade nitric acid which meet the purity standard required by the semiconductor industry.
Chinese patent CN116477577a: relates to a method for preparing anhydrous hydrogen fluoride by recycling low-concentration hydrofluoric acid, which comprises the following steps: (1) Adding a certain amount of sodium fluoride and other sodium salt powder into waste acid containing hydrofluoric acid to carry out fluorination reaction; (2) Filtering after the fluorination reaction, drying a sodium bifluoride filter cake to remove surface water, and then introducing the sodium bifluoride filter cake into a sodium bifluoride decomposing furnace for decomposition; (3) The sodium hydrogen fluoride filtrate is partially used for preparing sodium fluoride slurry, and is partially neutralized; (4) And (3) refining the hydrogen fluoride gas generated by decomposing the sodium hydrogen fluoride through a condensation and refining process to obtain an anhydrous hydrogen fluoride product. The treatment method is simple, low in cost, high in recovery efficiency and suitable for industrial popularization and application; the invention converts the fluorine-containing waste acid into the fluorine product with high added value and market demand, thereby not only solving the problem of enterprise expansion, but also realizing the recycling of fluorine resources.
Chinese patent CN116477696a: the invention discloses a device for separating a mixture of hydrofluoric acid and hydrochloric acid, which specifically comprises a stripping tower, a stripping reboiler, a gas-liquid separation tank and a hydrofluoric acid recovery tower, wherein hydrofluoric acid/hydrochloric acid raw material liquid is stripped in the stripping tower through high-temperature nitrogen, and separated liquid is secondarily recovered through the separation effect of the gas-liquid separation tank, so that the effective recycling of the hydrofluoric acid is realized.
In the above solutions, the acid recovery process is mostly to recover the acid in a single acid aqueous solution, but an azeotropic mixture is formed in a three-component system of nitric acid-hydrofluoric acid-water, and each acid cannot be concentrated to an electronic grade concentration; in addition, due to the texturing and etching process, the monocrystalline silicon reacts with hydrofluoric acid to produce fluosilicic acid (H 2 SiF 6 ) The hydrofluoric acid, the nitric acid and the fluosilicic acid are mutually interfered to form a complex vapor-liquid equilibrium state so as to separate distillationBecome more difficult; in addition, nitric acid is easily thermally decomposed at a relatively high temperature, and it is difficult to obtain hydrofluoric acid and nitric acid as pure components.
Disclosure of Invention
In order to solve the problems, the invention provides a method for recycling and refining hydrofluoric acid from a solution containing hydrofluoric acid, and belongs to the technical field of treatment of waste liquid containing hydrofluoric acid.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for recovering and refining hydrofluoric acid from a solution containing hydrofluoric acid:
the mixed waste acid is subjected to pretreatment system, precipitation and filtration, filtrate enters a rectification system, is refined and concentrated, and is sent to a post-treatment system, and hydrofluoric acid is obtained after adsorption, filtration and purification.
Further supplementing, the mixed waste acid contains 4-11wt% of HF,3-7wt% of fluosilicic acid and 6-32wt% of HNO 3 Is a mixed acid aqueous solution of (a).
When the mixed waste acid passes through the pretreatment system, additives are added to enable fluosilicic acid to generate sediment and separate out, a sediment technology is adopted to filter and remove fluosilicic acid, and meanwhile, entrained solid suspended matters are filtered and removed, so that filtrate is obtained.
Further supplementing, the additive is nitrate, preferably potassium nitrate or sodium nitrate or calcium nitrate or barium nitrate, and the adding proportion is that the mass ratio of the mixed waste acid to the additive is 40-70:1.
the rectification system comprises a feed pump, a rectification tower, a reboiler, a condenser, a reflux tank and a noncondensable gas treatment system; the specific operation steps are as follows:
a1: the waste acid after pretreatment is pumped into a rectifying tower by a charging pump, the waste acid at the tower bottom is heated by a reboiler and self-circulated, and condensate liquid enters a reflux tank after gas phase is condensed by a tower top condenser;
a2: one part of the reflux tank is refluxed to the rectifying tower, and the other part is sent to the post-treatment system;
a3: the non-condensable gas in the condenser is absorbed and washed by water and then is emptied.
Further supplementing, the temperature of the rectifying tower is 60-80 ℃, the temperature of the condenser is 0-10 ℃, and the pressure of the condenser is 0.01-0.06MPa.
Further supplementing, the adsorbent adopted in the post-treatment system is one or more of activated carbon, calcite, activated alumina and hydroxyapatite.
Further supplementing, the filter device is a fine filter with a modified polytetrafluoroethylene membrane, a modified polytetrafluoroethylene membrane filter core is arranged in the fine filter, and the preparation method of the modified polytetrafluoroethylene membrane filter core comprises the following steps:
s1: and (3) radiation activation: placing the polytetrafluoroethylene membrane filter core in a gamma ray radiation field for irradiation processing to obtain a polytetrafluoroethylene membrane with a surface activated and containing fluorine free radicals for later use;
s2: adding 0.3-3 parts of isocyanate ethyl acrylate, 0.02-0.6 part of 1-hydroxyethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and 0.2-0.5 part of dibutyltin dilaurate into a stirring kettle according to parts by weight, and stirring and reacting for 25-55 minutes at 55-75 ℃;
s3: adding 3-8 parts of 3-acrylamide-phenol, 0.04-0.5 part of nickel acrylate, 2-8 parts of initiator, 200-300 parts of deionized water, stirring and reacting for 25-55 minutes at 55-75 ℃, immersing 50-70 parts of polytetrafluoroethylene membrane filter core with surface activated fluorine free radicals in the materials, stirring and reacting for 4-8 hours at 80-90 ℃, taking out the polytetrafluoroethylene membrane filter core, washing with water, drying, and then placing in a gamma-ray radiation field for irradiation processing, wherein the irradiation conditions are the same as those of the step S1, thus obtaining the modified polytetrafluoroethylene membrane filter core.
Further supplementing, the irradiation conditions in the steps S1 and S3 are that the irradiation dose rate is 33Gy/min, the irradiation time is 6-24 h, the irradiation dose is 5-25 Gy, the irradiation non-uniformity is less than 1.0, and the irradiation environment temperature is 18-28 ℃.
Further supplementing, the initiator is at least one of tert-butyl hydroperoxide, tert-butyl peroxybenzoate and persulfate.
The reaction mechanism involves the following processes:
1: reacting isocyanate ethyl acrylate with 1-hydroxyethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt to obtain an intermediate 1;
2: 3-acrylamido-phenol, nickel acrylate, intermediate 1, and polytetrafluoroethylene with free radical,
3. reacting bis (trifluoromethanesulfonyl) imide salt with hydrofluoric acid to form insoluble salt and trifluoromethanesulfonic acid; reacting phenol with nitric acid to form insoluble phenolate and nitrate; the generated phenolate and trifluoromethanesulfonic acid can form a protective layer on the surface of the filtering membrane, and the protective layer cooperates with organic nickel, performs barrier adsorption on metal ions, and slows down the corrosion of hydrofluoric acid.
The method for recovering and refining hydrofluoric acid from a solution containing hydrofluoric acid of the present invention has the following remarkable effects compared with the prior art:
1. the invention uses the additive nitrate to lead fluosilicic acid to generate precipitate and separate out, and the filtrate is further rectified to obtain mixed acid of hydrofluoric acid and nitric acid;
2. the invention adopts a rectification process, can concentrate mixed acid, and can remove metal ions and COD in waste acid at the same time, so as to further improve the concentration of the mixed acid; the recovery rate of hydrofluoric acid is 95.7 percent, and the recovery rate of nitric acid is 97.6 percent;
3. the invention adopts an adsorbent: activated carbon, calcite, activated alumina, hydroxyapatite, etc., to adsorb fluoride ions to prepare hydrofluoric acid;
4. the modified polytetrafluoroethylene membrane fine filter adopted by the invention is internally provided with the phenolate and the trifluoromethane sulfonic acid in the modified polytetrafluoroethylene membrane filter core, so that a protective layer can be formed on the surface of the filter membrane to prevent the corrosion of hydrofluoric acid and block and adsorb metal ions.
Detailed Description
The present invention will be further described with reference to the following examples in order to better understand the technical solutions of the present invention and to make the above features, objects and advantages of the present invention more clearly understood. The examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
The metal ion content of the refined hydrofluoric acid is detected by adopting an X-ray fluorescence spectrometry.
Example 1
A method for recovering and refining hydrofluoric acid from a solution containing hydrofluoric acid, comprising:
the mixed waste acid is subjected to pretreatment system, precipitation and filtration, filtrate enters a rectification system, is refined and concentrated, and is sent to a post-treatment system, and hydrofluoric acid is obtained after adsorption, filtration and purification.
The mixed waste acid contains 4wt% of HF, 3wt% of fluosilicic acid and 32wt% of HNO 3 Is a mixed acid aqueous solution of (a).
When the mixed waste acid passes through the pretreatment system, additives are added to enable fluosilicic acid to generate sediment and separate out, a sediment technology is adopted to filter and remove fluosilicic acid, and meanwhile, entrained solid suspended matters are filtered and removed, so that filtrate is obtained.
The additive is nitrate, preferably potassium nitrate, and the adding proportion is that the mass ratio of the mixed waste acid to the additive is 40:1.
the rectification system comprises a feed pump, a rectification tower, a reboiler, a condenser, a reflux tank and a noncondensable gas treatment system; the specific operation steps are as follows:
a1: the waste acid after pretreatment is pumped into a rectifying tower by a charging pump, the waste acid at the tower bottom is heated by a reboiler and self-circulated, and condensate liquid enters a reflux tank after gas phase is condensed by a tower top condenser;
a2: one part of the reflux tank is refluxed to the rectifying tower, and the other part is sent to the post-treatment system;
a3: the non-condensable gas in the condenser is absorbed and washed by water and then is emptied.
The temperature of the rectifying tower is 60 ℃, the temperature of the condenser is 10 ℃, and the pressure of the condenser is 0.01MPa.
The adsorbent adopted in the post-treatment system is activated carbon.
The filter device is a fine filter with a modified polytetrafluoroethylene membrane, a modified polytetrafluoroethylene membrane filter core is arranged in the fine filter, and the preparation method of the modified polytetrafluoroethylene membrane filter core is as follows:
s1: and (3) radiation activation: placing the polytetrafluoroethylene membrane filter core in a gamma ray radiation field for irradiation processing to obtain a polytetrafluoroethylene membrane with a surface activated and containing fluorine free radicals for later use;
s2: adding 0.3kg of isocyanate ethyl acrylate, 0.02kg of 1-hydroxyethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and 0.2kg of dibutyltin dilaurate into a stirring kettle, and stirring and reacting for 25 minutes at 55 ℃;
s3: 3kg of 3-acrylamide-phenol, 0.04kg of nickel acrylate, 2kg of initiator, 200kg of deionized water and stirring for reaction at 55 ℃ for 25 minutes are added into a stirring kettle in the step S2, then 50kg of polytetrafluoroethylene membrane filter core with surface activated and fluorine free radicals is immersed into the materials, stirring for reaction at 80 ℃ for 4 hours, the polytetrafluoroethylene membrane filter core is taken out, washed, dried and then placed in a gamma-ray radiation field for radiation processing, and the radiation conditions are the same as those in the step S1, so that the modified polytetrafluoroethylene membrane filter core is obtained.
The irradiation conditions in the steps S1 and S3 are that the irradiation dose rate is 33Gy/min, the irradiation time is 6 hours, the irradiation dose is 5Gy, the irradiation unevenness is less than 1.0, and the irradiation environment temperature is 18 ℃.
The initiator is tert-butyl hydroperoxide.
Example 2
A method for recovering and refining hydrofluoric acid from a solution containing hydrofluoric acid, comprising:
the mixed waste acid is subjected to pretreatment system, precipitation and filtration, filtrate enters a rectification system, is refined and concentrated, and is sent to a post-treatment system, and hydrofluoric acid is obtained after adsorption, filtration and purification.
The mixed waste acid contains 6wt% of HF, 5wt% of fluosilicic acid and 15wt% of HNO 3 Is a mixed acid aqueous solution of (a).
When the mixed waste acid passes through the pretreatment system, additives are added to enable fluosilicic acid to generate sediment and separate out, a sediment technology is adopted to filter and remove fluosilicic acid, and meanwhile, entrained solid suspended matters are filtered and removed, so that filtrate is obtained.
The additive is nitrate, preferably sodium nitrate, and the adding proportion is that the mass ratio of the mixed waste acid to the additive is 50:1.
the rectification system comprises a feed pump, a rectification tower, a reboiler, a condenser, a reflux tank and a noncondensable gas treatment system; the specific operation steps are as follows:
a1: the waste acid after pretreatment is pumped into a rectifying tower by a charging pump, the waste acid at the tower bottom is heated by a reboiler and self-circulated, and condensate liquid enters a reflux tank after gas phase is condensed by a tower top condenser;
a2: one part of the reflux tank is refluxed to the rectifying tower, and the other part is sent to the post-treatment system;
a3: the non-condensable gas in the condenser is absorbed and washed by water and then is emptied.
The temperature of the rectifying tower is 65 ℃, the temperature of the condenser is 5 ℃, and the pressure of the condenser is 0.03MPa.
The adsorbent used in the post-treatment system is calcite.
The filter device is a fine filter with a modified polytetrafluoroethylene membrane, a modified polytetrafluoroethylene membrane filter core is arranged in the fine filter, and the preparation method of the modified polytetrafluoroethylene membrane filter core is as follows:
s1: and (3) radiation activation: placing the polytetrafluoroethylene membrane filter core in a gamma ray radiation field for irradiation processing to obtain a polytetrafluoroethylene membrane with a surface activated and containing fluorine free radicals for later use;
s2: 1kg of isocyanate ethyl acrylate, 0.08kg of 1-hydroxyethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and 0.3kg of dibutyltin dilaurate are added into a stirring kettle, and stirring and reacting for 30 minutes at 60 ℃;
s3: adding 5kg of 3-acrylamide-phenol, 0.1kg of nickel acrylate, 3kg of initiator and 220kg of deionized water into a stirring kettle in the step S2, stirring and reacting for 30 minutes at 60 ℃, immersing 60kg of polytetrafluoroethylene membrane filter core with surface activated fluorine free radicals into the materials, stirring and reacting for 5 hours at 82 ℃, taking out the polytetrafluoroethylene membrane filter core, washing with water, drying, and then placing in a gamma-ray radiation field for radiation processing under the same radiation conditions as in the step S1 to obtain the modified polytetrafluoroethylene membrane filter core.
The irradiation conditions in the steps S1 and S3 are that the irradiation dose rate is 33Gy/min, the irradiation time is 12h, the irradiation dose is 10Gy, the irradiation unevenness is less than 1.0, and the irradiation environment temperature is 22 ℃.
The initiator is tert-butyl peroxybenzoate.
Example 3
A method for recovering and refining hydrofluoric acid from a solution containing hydrofluoric acid, comprising:
the mixed waste acid is subjected to pretreatment system, precipitation and filtration, filtrate enters a rectification system, is refined and concentrated, and is sent to a post-treatment system, and hydrofluoric acid is obtained after adsorption, filtration and purification.
The mixed waste acid contains 8wt% of HF, 6wt% of fluosilicic acid and 19wt% of HNO 3 Is a mixed acid aqueous solution of (a).
When the mixed waste acid passes through the pretreatment system, additives are added to enable fluosilicic acid to generate sediment and separate out, a sediment technology is adopted to filter and remove fluosilicic acid, and meanwhile, entrained solid suspended matters are filtered and removed, so that filtrate is obtained.
The additive is nitrate, preferably calcium nitrate, and the adding proportion is that the mass ratio of the mixed waste acid to the additive is 60:1.
the rectification system comprises a feed pump, a rectification tower, a reboiler, a condenser, a reflux tank and a noncondensable gas treatment system; the specific operation steps are as follows:
a1: the waste acid after pretreatment is pumped into a rectifying tower by a charging pump, the waste acid at the tower bottom is heated by a reboiler and self-circulated, and condensate liquid enters a reflux tank after gas phase is condensed by a tower top condenser;
a2: one part of the reflux tank is refluxed to the rectifying tower, and the other part is sent to the post-treatment system;
a3: the non-condensable gas in the condenser is absorbed and washed by water and then is emptied.
The temperature of the rectifying tower is 75 ℃, the temperature of the condenser is 5 ℃, and the pressure of the condenser is 0.05MPa.
The adsorbent used in the post-treatment system is activated alumina.
The filter device is a fine filter with a modified polytetrafluoroethylene membrane, a modified polytetrafluoroethylene membrane filter core is arranged in the fine filter, and the preparation method of the modified polytetrafluoroethylene membrane filter core is as follows:
s1: and (3) radiation activation: placing the polytetrafluoroethylene membrane filter core in a gamma ray radiation field for irradiation processing to obtain a polytetrafluoroethylene membrane with a surface activated and containing fluorine free radicals for later use;
s2: 2kg of isocyanate ethyl acrylate, 0.3kg of 1-hydroxyethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and 0.4kg of dibutyltin dilaurate are added into a stirring kettle, and stirring and reacting for 50 minutes at 70 ℃;
s3: adding 7kg of 3-acrylamide-phenol, 0.4kg of nickel acrylate, 6kg of initiator and 280kg of deionized water into a stirring kettle in the step S2, stirring and reacting for 50 minutes at 70 ℃, immersing 60kg of polytetrafluoroethylene membrane filter core with surface activated fluorine free radicals into the materials, stirring and reacting for 7 hours at 87 ℃, taking out the polytetrafluoroethylene membrane filter core, washing with water, drying, and then placing in a gamma-ray radiation field for radiation processing under the same radiation conditions as in the step S1 to obtain the modified polytetrafluoroethylene membrane filter core.
The irradiation conditions in the steps S1 and S3 are that the irradiation dose rate is 33Gy/min, the irradiation time is 18h, the irradiation dose is 20Gy, the irradiation unevenness is less than 1.0, and the irradiation environment temperature is 25 ℃.
The initiator is tert-butyl peroxybenzoate.
Example 4
A method for recovering and refining hydrofluoric acid from a solution containing hydrofluoric acid, comprising:
the mixed waste acid is subjected to pretreatment system, precipitation and filtration, filtrate enters a rectification system, is refined and concentrated, and is sent to a post-treatment system, and hydrofluoric acid is obtained after adsorption, filtration and purification.
The mixed waste acid contains 11wt% of HF, 7wt% of fluosilicic acid and 6wt% of HNO 3 Is a mixed acid aqueous solution of (a).
When the mixed waste acid passes through the pretreatment system, additives are added to enable fluosilicic acid to generate sediment and separate out, a sediment technology is adopted to filter and remove fluosilicic acid, and meanwhile, entrained solid suspended matters are filtered and removed, so that filtrate is obtained.
The additive is nitrate, preferably barium nitrate, and the adding proportion is that the mass ratio of the mixed waste acid to the additive is 70:1.
the rectification system comprises a feed pump, a rectification tower, a reboiler, a condenser, a reflux tank and a noncondensable gas treatment system; the specific operation steps are as follows:
a1: the waste acid after pretreatment is pumped into a rectifying tower by a charging pump, the waste acid at the tower bottom is heated by a reboiler and self-circulated, and condensate liquid enters a reflux tank after gas phase is condensed by a tower top condenser;
a2: one part of the reflux tank is refluxed to the rectifying tower, and the other part is sent to the post-treatment system;
a3: the non-condensable gas in the condenser is absorbed and washed by water and then is emptied.
The temperature of the rectifying tower is 80 ℃, the temperature of the condenser is 0 ℃, and the pressure of the condenser is 0.06MPa.
The adsorbent adopted in the post-treatment system is hydroxyapatite.
The filter device is a fine filter with a modified polytetrafluoroethylene membrane, a modified polytetrafluoroethylene membrane filter core is arranged in the fine filter, and the preparation method of the modified polytetrafluoroethylene membrane filter core is as follows:
s1: and (3) radiation activation: placing the polytetrafluoroethylene membrane filter core in a gamma ray radiation field for irradiation processing to obtain a polytetrafluoroethylene membrane with a surface activated and containing fluorine free radicals for later use;
s2: 3kg of isocyanate ethyl acrylate, 0.6kg of 1-hydroxyethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and 0.5kg of dibutyltin dilaurate are added into a stirring kettle, and stirring and reacting for 55 minutes at 75 ℃;
s3: adding 8kg of 3-acrylamide-phenol, 0.5kg of nickel acrylate, 8kg of initiator and 300kg of deionized water into a stirring kettle in the step S2, stirring and reacting for 55 minutes at 75 ℃, then immersing 70kg of polytetrafluoroethylene membrane filter core with surface activated fluorine free radicals into the materials, stirring and reacting for 8 hours at 90 ℃, taking out the polytetrafluoroethylene membrane filter core, washing with water, drying, and then placing in a gamma-ray radiation field for radiation processing under the same radiation conditions as in the step S1 to obtain the modified polytetrafluoroethylene membrane filter core.
The irradiation conditions in the steps S1 and S3 are that the irradiation dose rate is 33Gy/min, the irradiation time is 24 hours, the irradiation dose is 25Gy, the irradiation unevenness is less than 1.0, and the irradiation environment temperature is 28 ℃.
The initiator is ammonium persulfate.
Comparative example 1
In this example, the modified polytetrafluoroethylene membrane filter element was prepared without adding ethyl isocyanate acrylate, and otherwise the same as in example 1.
Comparative example 2
In this example, 1-hydroxyethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt was not added in the preparation of the modified polytetrafluoroethylene membrane cartridge, and the same procedure as in example 1 was followed.
Comparative example 3
In this example, 3-acrylamido-phenol was not added to prepare the modified polytetrafluoroethylene membrane filter element, and the same procedure as in example 1 was followed.
Comparative example 4
In this example, nickel acrylate was not added in the preparation of the modified polytetrafluoroethylene membrane cartridge, and the procedure of example 1 was followed.
Table 1 example test data
| Recovery of nitric acid% | Recovery rate of hydrofluoric acid% | Metal ion content wt% of refined hydrofluoric acid | |
| Example 1 | 91.6 | 90.5 | 2.7 |
| Example 2 | 92.9 | 93.1 | 2.1 |
| Example 3 | 95.1 | 93.7 | 1.7 |
| Example 4 | 97.6 | 95.7 | 1.3 |
| Comparative example 1 | 80.7 | 76.3 | 13.1 |
| Comparative example 2 | 85.5 | 80.2 | 8.8 |
| Comparative example 3 | 86.3 | 82.4 | 6.9 |
| Comparative example 4 | 89.7 | 87.6 | 3.5 |
From the data analysis of the above examples and comparative examples, it can be seen that most of nitric acid and hydrofluoric acid can be recovered by the invention, the recovery rate of hydrofluoric acid is 95.7%, and the recovery rate of nitric acid is 97.6%; the metal ion content of the refined hydrofluoric acid is 1.3%, so that the metal ions in the waste acid can be removed.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. The method for recycling and refining hydrofluoric acid from solution containing hydrofluoric acid is characterized by comprising the steps of enabling mixed waste acid to pass through a pretreatment system, precipitating and filtering, enabling filtrate to enter a rectification system, enabling filtrate to enter a post-treatment system after refining and concentrating, and obtaining hydrofluoric acid after adsorption, filtering and purifying;
wherein, the filtering device in the two filtering procedures is a fine filter with a modified polytetrafluoroethylene membrane, a modified polytetrafluoroethylene membrane filter element is arranged in the fine filter, and the preparation method of the modified polytetrafluoroethylene membrane filter element is as follows:
s1: and (3) radiation activation: placing the polytetrafluoroethylene membrane filter core in a gamma ray radiation field for irradiation processing to obtain a polytetrafluoroethylene membrane with a surface activated and containing fluorine free radicals for later use;
s2: adding 0.3-3 parts of isocyanate ethyl acrylate, 0.02-0.6 part of 1-hydroxyethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt and 0.2-0.5 part of dibutyltin dilaurate into a stirring kettle according to parts by weight, and stirring and reacting for 25-55 minutes at 55-75 ℃;
s3: adding 3-8 parts of 3-acrylamide-phenol, 0.04-0.5 part of nickel acrylate, 2-8 parts of initiator, 200-300 parts of deionized water, stirring and reacting for 25-55 minutes at 55-75 ℃, immersing 50-70 parts of polytetrafluoroethylene membrane filter core with surface activated fluorine free radicals in the materials, stirring and reacting for 4-8 hours at 80-90 ℃, taking out the polytetrafluoroethylene membrane filter core, washing with water, drying, and then placing in a gamma-ray radiation field for irradiation processing, wherein the irradiation conditions are the same as those of the step S1, thus obtaining the modified polytetrafluoroethylene membrane filter core;
the rectification system comprises a feed pump, a rectification tower, a reboiler, a condenser, a reflux tank and a noncondensable gas treatment system; the specific operation steps are as follows:
a1: the waste acid after pretreatment is pumped into a rectifying tower by a charging pump, the waste acid at the tower bottom is heated by a reboiler and self-circulated, and condensate liquid enters a reflux tank after gas phase is condensed by a tower top condenser;
a2: one part of the reflux tank is refluxed to the rectifying tower, and the other part is sent to the post-treatment system;
a3: the non-condensable gas in the condenser is absorbed and washed by water and then is emptied.
2. A method for recovering and refining hydrofluoric acid from a solution containing hydrofluoric acid as claimed in claim 1, wherein: the mixed waste acid is a mixed acid aqueous solution containing 4-11wt% of HF,3-7wt% of fluosilicic acid and 6-32wt% of HNO 3.
3. A method for recovering and refining hydrofluoric acid from a solution containing hydrofluoric acid as claimed in claim 2, wherein: when the mixed waste acid passes through the pretreatment system, additives are added to enable fluosilicic acid to generate sediment and separate out, a sediment technology is adopted to filter and remove fluosilicic acid, and meanwhile, entrained solid suspended matters are filtered and removed, so that filtrate is obtained.
4. A method for recovering and refining hydrofluoric acid from a solution containing hydrofluoric acid as claimed in claim 3, wherein: the additive is nitrate, the adding proportion is that the mass ratio of the mixed waste acid to the additive is 40-70:1.
5. a method for recovering and refining hydrofluoric acid from a solution containing hydrofluoric acid as claimed in claim 1, wherein: the temperature of the rectifying tower is 60-80 ℃, the temperature of the condenser is 0-10 ℃, and the pressure of the condenser is 0.01-0.06MPa.
6. A method for recovering and refining hydrofluoric acid from a solution containing hydrofluoric acid as claimed in claim 1, wherein: the adsorbent used in the post-treatment system is one or more of activated carbon, calcite, activated alumina and hydroxyapatite.
7. A method for recovering and refining hydrofluoric acid from a solution containing hydrofluoric acid as claimed in claim 1, wherein: the irradiation conditions in the steps S1 and S3 are that the irradiation dose rate is 33Gy/min, the irradiation time is 6-24 h, the irradiation dose is 5-25 Gy, the irradiation non-uniformity is less than 1.0, and the irradiation environment temperature is 18-28 ℃.
8. A method for recovering and refining hydrofluoric acid from a solution containing hydrofluoric acid as claimed in claim 1, wherein: the initiator is at least one of tert-butyl hydroperoxide, tert-butyl peroxybenzoate and persulfate.
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| WO2002073718A1 (en) * | 2001-03-14 | 2002-09-19 | Yuasa Corporation | Positive electrode active material and nonaqueous electrolyte secondary cell comprising the same |
| CN101528682A (en) * | 2006-12-27 | 2009-09-09 | 株式会社艾迪科 | Oxime ester compound and photopolymerization initiator comprising the compound |
| CN102009957A (en) * | 2010-11-20 | 2011-04-13 | 江阴市润玛电子材料有限公司 | Method for purifying high-yield superclean high-purity hydrofluoric acid |
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| WO2002073718A1 (en) * | 2001-03-14 | 2002-09-19 | Yuasa Corporation | Positive electrode active material and nonaqueous electrolyte secondary cell comprising the same |
| CN101528682A (en) * | 2006-12-27 | 2009-09-09 | 株式会社艾迪科 | Oxime ester compound and photopolymerization initiator comprising the compound |
| CN102009957A (en) * | 2010-11-20 | 2011-04-13 | 江阴市润玛电子材料有限公司 | Method for purifying high-yield superclean high-purity hydrofluoric acid |
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