CN113371683B - Electronic grade hydrogen peroxide production method - Google Patents
Electronic grade hydrogen peroxide production method Download PDFInfo
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- CN113371683B CN113371683B CN202011485832.9A CN202011485832A CN113371683B CN 113371683 B CN113371683 B CN 113371683B CN 202011485832 A CN202011485832 A CN 202011485832A CN 113371683 B CN113371683 B CN 113371683B
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- hydrogen peroxide
- grade hydrogen
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- concentration
- electronic grade
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 508
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 68
- 239000011347 resin Substances 0.000 claims abstract description 68
- 150000002500 ions Chemical class 0.000 claims abstract description 42
- 238000001914 filtration Methods 0.000 claims abstract description 39
- 238000001179 sorption measurement Methods 0.000 claims abstract description 32
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 27
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 25
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 25
- 238000005342 ion exchange Methods 0.000 claims abstract description 24
- 229920001429 chelating resin Polymers 0.000 claims abstract description 15
- 239000012528 membrane Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 47
- 239000012535 impurity Substances 0.000 claims description 37
- 239000003381 stabilizer Substances 0.000 claims description 36
- 239000000126 substance Substances 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 25
- 239000002033 PVDF binder Substances 0.000 claims description 22
- 239000013067 intermediate product Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 18
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 15
- 239000004760 aramid Substances 0.000 claims description 13
- 229920003235 aromatic polyamide Polymers 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 12
- LMHAGAHDHRQIMB-UHFFFAOYSA-N 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(Cl)C1(F)Cl LMHAGAHDHRQIMB-UHFFFAOYSA-N 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 8
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 7
- 229940120146 EDTMP Drugs 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 6
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000110 cooling liquid Substances 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004813 Perfluoroalkoxy alkane Substances 0.000 claims description 3
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 3
- 229920006026 co-polymeric resin Polymers 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 claims 1
- 125000000129 anionic group Chemical group 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- 238000005341 cation exchange Methods 0.000 abstract description 12
- 239000012467 final product Substances 0.000 abstract description 5
- 238000005349 anion exchange Methods 0.000 abstract description 4
- 239000012043 crude product Substances 0.000 description 23
- 239000000463 material Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 238000012856 packing Methods 0.000 description 16
- 238000000746 purification Methods 0.000 description 16
- 239000013522 chelant Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 10
- 150000001722 carbon compounds Chemical class 0.000 description 9
- 229920001903 high density polyethylene Polymers 0.000 description 9
- 239000004700 high-density polyethylene Substances 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000009614 chemical analysis method Methods 0.000 description 6
- 238000007689 inspection Methods 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 5
- 239000013065 commercial product Substances 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229920001273 Polyhydroxy acid Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960004365 benzoic acid Drugs 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- HLWRUJAIJJEZDL-UHFFFAOYSA-M sodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O HLWRUJAIJJEZDL-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- USIPWJRLUGPSJM-UHFFFAOYSA-K trisodium 2-(2-aminoethylamino)ethanol triacetate Chemical compound [Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.NCCNCCO USIPWJRLUGPSJM-UHFFFAOYSA-K 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene Substances 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
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/013—Separation; Purification; Concentration
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/013—Separation; Purification; Concentration
- C01B15/0135—Purification by solid ion-exchangers or solid chelating agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a production method of electronic grade hydrogen peroxide, which takes industrial grade hydrogen peroxide with concentration less than or equal to 30% as raw material, and carries out vacuum rectification and concentration to 35-50 wt% under the conditions of temperature of 45-60 ℃ and vacuum degree of minus 0.05-minus 0.1MPa, the concentrated solution is adsorbed and decontaminated by polytetrafluoroethylene membrane and macroporous adsorption resin at the flow rate of 200-250L/h, and high valence ion is removed by chelating resin, and low valence ion is purified step by sequentially passing through an anion exchange column, a cation exchange column and a mixed ion exchange column; and carrying out multistage filtration through a microporous filter to obtain the electronic grade hydrogen peroxide final product. The invention produces the high-purity electronic grade hydrogen peroxide with lower cost, has excellent performance indexes, and fully meets the actual application requirements.
Description
Technical Field
The invention belongs to the field of hydrogen peroxide purification and preparation, and particularly relates to a production method for preparing electronic grade hydrogen peroxide by purifying industrial grade hydrogen peroxide.
Background
In the 90 s of the 20 th century, along with the rapid development of the electronic industry, particularly with the high integration of integrated circuits, the demand for electronic grade hydrogen peroxide has been rapidly increasing. Electronic grade hydrogen peroxide is widely used in the field of electronic industry and is one of electronic chemicals necessary for integrated circuit production. Its purity has a very important impact on the yield, electrical performance and reliability of integrated circuits.
Electronic grade hydrogen peroxide is typically prepared from technical grade hydrogen peroxide. Commercial industrial grade hydrogen peroxide generally has the concentration of below 30wt%, has high impurity content, for example, hydrogen peroxide produced by Guangdong sunshine has the specific indexes that: the hydrogen peroxide content is 27.5-28.5 wt%, free acid content is less than or equal to 800ppm, non-volatile matter content is less than or equal to 1000ppm, total carbon content (TOC) is less than or equal to 800ppm, stability is more than or equal to 97.0 Wt%, wherein the impurity content of organic matters, cations, anions and the like is too high to completely meet the purity requirements of the electronic industry, especially the integrated circuit manufacturing field, and therefore, the electronic grade hydrogen peroxide is required to be prepared by a purification mode. The purification production method of the related hydrogen peroxide is referred at present:
The patent application of the hydrogen peroxide purification production system with the publication number of CN109775665A discloses a hydrogen peroxide purification method, wherein organic substances in the hydrogen peroxide are adsorbed by organic adsorption resin in an organic resin exchange column in the hydrogen peroxide purification process, metal particles such as iron, sodium, magnesium and the like in the hydrogen peroxide are removed by cation resin in a cation resin exchange column in a mixed resin, and acid radical particles such as hydrochloric acid, sulfuric acid and the like in the anion resin exchange column are removed, so that the high-purity hydrogen peroxide meeting international standards is obtained.
The patent application of the invention of a manufacturing process and equipment of ultra-clean high-purity electronic grade hydrogen peroxide with the publication number of CN101249953A discloses a hydrogen peroxide purification process, which comprises the following technical scheme: the hydrogen peroxide aqueous solution containing impurities is made to pass through more than one ion adsorption columns connected in series to adsorb organic carbon, and then pass through more than one anion-cation exchange columns connected in series to carry out ion exchange, so that organic matters, inorganic ions and impurities can be effectively removed, and the ultra-clean high-purity electronic grade hydrogen peroxide is prepared.
The patent of the invention, with publication number CN102757019B, discloses a concentration and purification method of hydrogen peroxide, which is to mix 25-35wt% industrial hydrogen peroxide as a raw material with a stabilizer and then rectify the mixture to obtain a hydrogen peroxide product with concentration not less than 50 wt%. Wherein the stabilizer is one or more of sodium silicate, ethylenediamine tetraacetic acid sodium salt, sodium stannate, sodium pyrophosphate, 8-hydroxyquinoline and benzoic acid.
The Chinese patent with publication number CN1101334C, which is a refining and concentrating method of anthraquinone process hydrogen peroxide, discloses a refining and concentrating method of industrial grade hydrogen peroxide, which has the technical proposal that: the crude hydrogen peroxide is treated by an alumina column, an ion exchange column, a filter and a perforated adsorption resin column to obtain a refined dilute hydrogen peroxide product, and then the refined dilute hydrogen peroxide product is decompressed, preheated and partially evaporated in a rising film evaporator, so that the chemically pure concentrated hydrogen peroxide is obtained from the bottom of a gas-liquid separator, and the analytically pure concentrated hydrogen peroxide is obtained from the bottom of a rectifying tower.
The invention discloses a hydrogen peroxide rectification process disclosed in the patent application with publication number CN111099562A, which comprises the following technical scheme: firstly, obtaining 55-75% high-concentration crude hydrogen peroxide through cyclone separation, wherein the TOC content is 600-700ppm, and the heavy metal ion content is as follows: 10-40ppm of Si ions and 10-56ppm of Hg ions; and rectifying the high-concentration hydrogen peroxide, wherein the pressure at the top of the rectifying tower is-0.1 to-0.05 Mpa, the temperature at the lower part of the rectifying tower is 35-45 ℃, the temperature at the upper part of the rectifying tower is 10-25 ℃, and 35% nitric acid is added as a stabilizer in the rectifying process, so that the high-concentration high-purity hydrogen peroxide is obtained.
The invention patent with the publication number of CN103896217B discloses a hydrogen peroxide stabilizer, which is a composition formed by organic phosphonic acid and other assistants, wherein the weight percentage of the organic phosphonic acid or the salt thereof in the composition is 5-15%, the stabilizer is mainly used for hydrogen peroxide disinfectant, and the adding amount of the stabilizer is 2-10% of the weight percentage of hydrogen peroxide.
The invention discloses a hydrogen peroxide non-phosphorus non-silicon stabilizer composition with the publication number of CN107541926A, and the disclosed stabilizer comprises dithiocarbamic acid based polyethyleneimine, magnesium salt, N-hydroxyethyl ethylenediamine sodium triacetate, amino acid salt, polyhydroxy acid salt, ethylenediamine di-o-phenyl sodium acetate and the like.
The invention discloses a hydrogen peroxide decomposition inhibitor and a preparation method thereof, which are disclosed in the patent of CN107892278A, wherein the mass percentages of the disclosed inhibitor are as follows: 10-20% of sodium gluconate, 2-4% of diethylenetriamine pentamethylene phosphoric acid, 1-2% of sodium hydroxide, 0.4-0.6% of sodium benzoate and the balance of water.
The related technology disclosed above uses industrial grade hydrogen peroxide to purify directly, one is that the method used mainly is that the adsorption resin and anion-cation exchange resin are purified in multistage series connection, but the impurity removal effect is not good in practice, and the index requirement of electronic grade hydrogen peroxide used in the preparation process of an integrated circuit is not easy to be met; secondly, when the hydrogen peroxide with higher concentration is produced by rectification and concentration, the yield is lower due to the decomposition problem, or the types of the stabilizing agents are selected differently, new impurities are introduced, and the purity of the final hydrogen peroxide is additionally influenced.
Disclosure of Invention
In order to overcome or solve the problems existing in the preparation of the electronic grade hydrogen peroxide, the invention provides a production method of the electronic grade hydrogen peroxide, which sequentially comprises the following production steps:
s1: vacuum rectification concentration specifically includes:
Taking industrial grade hydrogen peroxide with concentration less than or equal to 30wt% as a raw material, and concentrating and pre-extracting;
The concentration pretreatment is to carry out rectification concentration on the industrial grade hydrogen peroxide at the temperature of 45-60 ℃ and the vacuum degree of minus 0.05-minus 0.1MPa to 35-50 wt percent, preferably 40-50 percent by weight, so as to obtain a concentrated industrial grade hydrogen peroxide primary product.
The concentration of the rectification concentrate is controlled to be 35-50 wt% through sampling test, and the concentration is tested by adopting a high-precision hydrogen peroxide concentration tester (Kox AU-120 HP).
Preferably, a stabilizer is added into the industrial grade hydrogen peroxide, and the stabilizer has the effects of reducing the decomposition rate of the hydrogen peroxide during vacuum concentration and improving the final yield. The stabilizer is organic phosphines, and the addition amount is 50-100 ppm, and is one or more selected from hydroxyethylidene diphosphonic acid (HEDP), amino trimethylene phosphonic Acid (ATMP), ethylenediamine tetramethylene phosphonic acid (sodium), phosphonic acid butylamine-1, 2,4 tricarboxylic acid (PBTC), diethylenetriamine pentamethylene phosphonic acid (DTPMP) and 2-hydroxyphosphonoacetic acid. The stabilizers mentioned above are commercially available, and the commercial product types are: diethylene triamine penta (methylene phosphonic acid) (DTPMP) produced by Nantong Runfeng petrochemical Co Ltd, and amino methylene phosphonic Acid (ATMP) produced by Zaozhuang municipal and winter waves chemical technology Co Ltd.
Optionally, in step S1, unlike the prior art, the stabilizer selected in the invention is an organic phosphine, the organic component and the component are single, and the dosage is controlled to be 50-100 ppm, so that the decomposition rate of hydrogen peroxide in the concentration process is ensured to be very low, and the exceeding of the TOC of the final product is avoided. Compared with an organic stabilizer, the inorganic phosphorus stabilizer has low hydrogen peroxide yield, because the inorganic stabilizer contains metal ions and plays a role in promoting the decomposition of hydrogen peroxide. The organic stabilizer is mostly complex, has the effect of the radical adsorption to metal ions, and can form chelate with the heavy metal ions, thereby reducing or eliminating the hydrogen peroxide decomposition of the heavy metal ions.
The stability of hydrogen peroxide and the preparation process temperature are too high and the pressure is too high to influence the yield and the cost, and the preferred rectification concentration condition is 45-60 ℃ and the vacuum degree is-0.05 to-0.1 MPa.
In the step S1, the inventor finds that the concentration of the hydrogen peroxide is firstly increased to 35-50 wt% through vacuum rectification concentration, and then the impurities are removed through resin, so that the effect of removing the impurities is better compared with the method that the hydrogen peroxide with the concentration of less than 30wt% is directly removed through resin; when the concentration is higher than 50wt%, the hydrogen peroxide decomposition rate is remarkably increased, and the final yield is affected.
S2: impurity adsorption, specifically comprising:
cooling the concentrated industrial grade hydrogen peroxide primary product to 0-15 ℃ to obtain industrial grade hydrogen peroxide cooling liquid;
And (3) passing the industrial grade hydrogen peroxide cooling liquid flow through an adsorption device formed by combining a polytetrafluoroethylene membrane and macroporous adsorption resin in a series connection mode, filtering impurities, and removing insoluble impurities and organic matters in the hydrogen peroxide to obtain a chemical grade hydrogen peroxide intermediate product (I).
Wherein, the preferable flow rate is controlled between 200 and 250L/h;
wherein, the macroporous adsorption resin is preferably one of halogen-containing aromatic polyamide or polysulfone.
In the step S2, after the hydrogen peroxide cooling liquid flows through the polytetrafluoroethylene membrane, the TOC of organic matters can be reduced to 20ppm besides effectively filtering insoluble matters; after passing through the adsorption resin, the TOC of the organic matters can be further reduced to below 10 ppm.
The preferable flow rate of the step and the subsequent steps is controlled to be 200-250L/h; the flow rate is lower than 200L/h, and the efficiency is reduced although the organic matter filtering efficiency is higher; the flow rate is higher than 250L/h, and the efficiency is improved, but the organic matter filtering efficiency is reduced.
The macroporous adsorption resin is used for separating and purifying organic matters from solution through physical adsorption, has stable physicochemical property, is insoluble in acid, alkali and organic solvent, has good selectivity to the organic matters, is not influenced by inorganic salts, strong ions and low molecular compounds, and can adsorb the solvent in water and the organic solvent to expand. The common macroporous adsorption resin takes styrene and propionate as monomers, vinylbenzene as a cross-linking agent and toluene and xylene as pore-forming agents, and the styrene and the propionate are cross-linked and polymerized with each other to form a porous framework structure. The preferred halogen-containing aromatic polyamide or polysulfone macroporous adsorption resin of the invention has the following commercial product types: AMBERLITE XAD-2, manufactured by Robin Hasi (USA), AB-8, manufactured by Tianjin Siemens gold environmental protection materials science, inc.
S3: the method for removing the high valence ion specifically comprises the following steps:
And (3) allowing the chemical grade hydrogen peroxide intermediate product (I) to flow through a chelate resin device combined in a series connection mode, and removing high valence ions such as Ca2+, fe3+, A13+ and the like in the hydrogen peroxide to obtain a chemical grade hydrogen peroxide intermediate product (II).
Among them, the chelating resin is preferably one of PVDF, PTFE, PFA.
In the prior art, a specific technical scheme for removing high-valence cations from the preparation of electronic grade hydrogen peroxide from industrial grade hydrogen peroxide to chelating resin is not disclosed, and the chelating resin is selected to selectively remove high-valence metal ions, because accumulation of transition metal ions such as Fe < 3+ > and the like on the resin can cause certain potential safety hazards such as hydrogen peroxide decomposition heat release and the like, thereby creating safe and efficient conditions for purifying low-valence ions in the next step.
Chelating resins are polymeric compounds that can selectively chelate specific metal ions in the form of ionic or coordination bonds from solutions containing the metal ions. The resin takes crosslinked polymer (such as styrene/divinylbenzene resin) as a framework and is formed by connecting special functional groups. It belongs to functional polymer. The preferred chelating resin of the invention is one of PVDF, PTFE, PFA, and the commercial product types are as follows: produced by Temeis Co (THERMAX)MonoPlus TP produced by T-IRR, lanxess, cheng Jituan (LANXESS).
S4: the low valence ion removal specifically comprises:
and (3) sequentially flowing the chemical grade hydrogen peroxide intermediate product (II) through an anion resin exchange column, a cation resin exchange column and a mixed ion resin exchange column, and purifying low-valence ions step by step to obtain a chemical grade hydrogen peroxide intermediate product (III).
Wherein the anion exchange resin is preferably styrene resin containing quaternary ammonium salt, and the commercial product types are as follows: d201 manufactured by Tianjin Laided biosciences Co., ltd., manufactured by Japanese company (THERMAX)A-853E。
The cation exchange resin is preferably a sulfonic acid group-containing copolymer resin of styrene and divinylbenzene. The commercial product types are as follows: 001x7 by Tianjin Laider Biotechnology Co., ltd., 001x8 by West An Ji Yue Biotechnology Co., ltd.
S5: insoluble matter filtration, specifically comprising:
And (3) enabling the chemical grade hydrogen peroxide intermediate product (III) to flow through a microporous filter for multistage filtration so as to remove granular insoluble matters possibly carried out in an ion exchange process and obtain electronic grade hydrogen peroxide.
The microporous filter is made of PVDF, the pore diameter is 0.2-0.1 micron, the pore diameters are combined from large to small in multiple stages, namely, the chemical grade hydrogen peroxide intermediate product (III) flows through the pore diameter larger than 0.2 micron and then flows through the pore diameter smaller than 0.1 micron, and the pore diameters are filtered from large to small in multiple stages, so that the optimal filtering effect is achieved. Commercially available microporous filters are manufactured by PVDF in the following product types: HE-1000 manufactured by Hangzhou Huihe mechanical equipments Co., ltd, sc01-3-20 manufactured by Hangzhou Xinkai Water treatment equipments Co., ltd.
Preferably, a post-step is added: a dilution step, and a packaging step, comprising:
Diluting the electronic grade hydrogen peroxide to a required concentration by using ultrapure water; the use concentration of the electronic grade hydrogen peroxide is preferably about 30wt%, the stability of the hydrogen peroxide with too high concentration is relatively low, the transportation and the storage are not facilitated, and the production cost is obviously increased.
Filling the diluted electronic grade hydrogen peroxide in a purifying environment of which the grade is not lower than 1000. The containers used for packaging are typically selected from clean HDPE packaging barrels to prevent contamination during packaging.
Compared with the prior art, the invention has the following advantages:
1. Through S1 vacuum rectification concentration, the impurity removing effect in the steps S2, S3 and S4 is obviously improved, and the yield is improved.
2. In the vacuum rectification concentration step of S1, the inventor prefers to use organic phosphonic acid stabilizers, the types of the stabilizers are single, and the stabilizers are mainly organic matters, so that compared with the method without using or using other stabilizers, the yield of the hydrogen peroxide final product is ensured, and the purity influence caused by introducing excessive impurities in the preparation process is reduced or the cost of the purification process is increased. The inorganic phosphorus stabilizer has lower hydrogen peroxide yield than the organic stabilizer, probably because the inorganic stabilizer contains metal ions and plays a role in promoting hydrogen peroxide decomposition, while the organic stabilizer is mostly complex, has the effect of drastic adsorption on the metal ions and can form chelates with heavy metal ions, thereby reducing or eliminating the hydrogen peroxide decomposition of the heavy metal ions.
3. Unlike available technology, which adopts anion-cation exchange resin, the present invention has S3 to eliminate high valence ion, and the selected chelating resin can eliminate high valence metal ion selectively, and this can avoid the potential safety hazard caused by accumulation of Fe3+ and other transition metal ion, and create safe and efficient condition for the next purification of low valence ion.
Electronic grade hydrogen peroxide is applied to the field of integrated circuit manufacturing, and the following technical indexes are generally required to be met:
1. The concentration is 30-35 wt%;
2. The particle size (more than or equal to 0.03 um) is lower than 200 pcs/ml;
3. The cations include specifically: sn, fe, ca, al, na, ni, etc., all at levels below 10ppt.
4. The anions include in particular: cl -、NO3-、PO4 3-、SO4 2-, etc., the contents of which are all lower than 10ppb.
5. The TOC of the organic matters is lower than 10ppm, and the total nitrogen TN is lower than 20ppb.
The invention takes the medium-low concentration industrial grade hydrogen peroxide with the concentration less than or equal to 30wt% as the raw material, and the electronic grade hydrogen peroxide is obtained through impurity removal and purification by the method, so that the yield is high, and all technical indexes meet the requirements and are even more excellent.
Drawings
FIG. 1 is a flow chart of an electronic grade hydrogen peroxide production process.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to fig. 1 and the embodiment. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The electronic grade hydrogen peroxide production method is shown in figure 1, and the specific process is as follows:
Firstly, adding 50g of ethylenediamine tetramethylene phosphonic acid into 1.0 ton of industrial grade hydrogen peroxide with the mass percentage concentration of 27.5wt%, and then carrying out vacuum rectification concentration and purification at a low temperature of 60 ℃ to 50wt% to obtain a concentrated industrial grade hydrogen peroxide crude product with the mass percentage concentration of 50 wt%.
And cooling the crude product to 0 ℃, flowing through a Polytetrafluoroethylene (PTFE) membrane at a flow rate of 200L/h, filtering out particulate impurities in the hydrogen peroxide, flowing through a halogen-containing aromatic polyamide-based macroporous adsorption resin at a flow rate of 200L/h, removing organic carbon compounds in the hydrogen peroxide, treating to obtain chemical grade hydrogen peroxide (I), and cooling and delivering.
And then the chemical grade hydrogen peroxide (I) flows through PVDF-based chelate resin at the flow rate of 200L/h, so that the content of high valence ions such as Ca 2+、Fe3+、A13+ in the hydrogen peroxide is effectively reduced, the chemical grade hydrogen peroxide (II) is obtained after treatment, and the chemical grade hydrogen peroxide (II) is cooled and then sent out.
The chemical grade hydrogen peroxide (II) flows through a styrene-based resin anion exchange column containing quaternary ammonium salt at the flow rate of 200L/h, then flows through a styrene and divinylbenzene copolymer-based resin cation exchange column containing sulfonic acid group and a mixed ion exchange column at the flow rate of 200L/h, low-valence ions in the hydrogen peroxide are purified step by step, the chemical grade hydrogen peroxide (III) is obtained after treatment, and the chemical grade hydrogen peroxide (III) is cooled and then sent out.
And (3) sequentially flowing chemical grade hydrogen peroxide (III) through a combined microporous filter with PVDF, pore size of 0.2 micron and pore size of 0.1 micron at the flow rate of 200L/h for multistage filtration so as to remove granular insoluble matters possibly carried out in the ion exchange process, so that the optimal filtration effect is achieved, and the granular impurities in the product meet the requirements.
The electronic grade hydrogen peroxide is prepared into a 30wt% product by ultrapure water, and the electronic grade hydrogen peroxide product with the concentration of 30.1wt% is actually obtained by 0.85 ton, and the yield is 93 percent relative to 1.0 ton of feeding calculation.
Filling in 1000-level purifying environment, and packing with clean HDPE packing barrel.
The key process conditions of example 1 are:
1. Stabilizer selection: 50ppm ethylenediamine tetramethylene phosphonic acid;
2. and (3) selecting the rectification temperature: 60 ℃;
3. concentration degree selection: concentrating the crude product of industrial hydrogen peroxide by 50 wt%;
4. And (3) cooling temperature selection: 0 ℃;
5. and (3) flow rate selection: 200L/h;
6. selecting a Polytetrafluoroethylene (PTFE) film;
7. Selecting halogen-containing aromatic polyamide-based macroporous adsorption resin;
8. Selecting PVDF-based chelating resin;
9. Selecting styrene-based resin containing quaternary ammonium salt by an anion exchange column;
10. The cation exchange column selects styrene and divinylbenzene copolymer based resin containing sulfonic acid groups;
11. Selecting the above-mentioned anion-cation mixed ion exchange column;
12. The material is PVDF, and the pore size is 0.2 micron and 0.1 micron.
Product inspection
In this example 1, the electronic grade hydrogen peroxide as the final product after microporous filtration was detected by using a conventional chemical analysis method, and the comprehensive detection data were obtained as follows:
| Technical index | Content of | Yield rate | Sn | Fe | Ca | Al | Na |
| Unit (B) | Wt％ | Wt％ | ppt | ppt | ppt | ppt | ppt |
| Numerical value | 30.0-32.0 | ≥90 | ≤10 | ≤10 | ≤10 | ≤10 | ≤10 |
| Example 1 | 30.1 | 93 | 0.89 | 0.48 | 0.24 | 0.37 | 0.35 |
Example 2
According to the production steps of reference example 1, 80g of butylamine-1, 2, 4-tricarboxylic acid phosphonate is added into 27.5wt% industrial grade hydrogen peroxide, and then the concentrated industrial grade 50wt% hydrogen peroxide crude product is obtained through vacuum rectification concentration and purification to 50wt% at a low temperature of 55 ℃.
Cooling the crude product to 5 ℃, flowing through a polytetrafluoroethylene membrane at a flow rate of 220L/h, filtering out particulate impurities in the hydrogen peroxide, flowing through a halogen-containing aromatic polyamide-based macroporous adsorption resin at a flow rate of 220L/h, removing organic carbon compounds in the hydrogen peroxide, treating to obtain chemical grade hydrogen peroxide (I), and cooling and delivering.
And then the chemical grade hydrogen peroxide (I) flows through PVDF-based chelate resin at the flow rate of 220L/h to effectively reduce the content of high valence ions such as Ca 2+、Fe3+、A13+ and the like in the hydrogen peroxide, and the chemical grade hydrogen peroxide (II) is obtained after treatment and is sent out after cooling.
The chemical grade hydrogen peroxide (II) flows through a styrene-based resin anion exchange column containing quaternary ammonium salt at the flow rate of 220L/h, then flows through a styrene and divinylbenzene copolymer-based resin cation exchange column containing sulfonic acid groups and a mixed ion exchange column at the flow rate of 220L/h, low-valence ions in the hydrogen peroxide are purified step by step, the chemical grade hydrogen peroxide (III) is obtained after treatment, and the chemical grade hydrogen peroxide (III) is cooled and then sent out.
And (3) sequentially flowing chemical grade hydrogen peroxide (III) through microporous filters with the material of PVDF and the pore size of 0.2 micron and 0.1 micron at the flow rate of 220L/h for multistage filtration so as to remove granular insoluble matters possibly carried out in the ion exchange process, so that the optimal filtration effect is achieved, and the granular impurities in the product meet the requirements.
The electronic grade hydrogen peroxide is prepared into a 30wt% product by using ultrapure water, and the electronic grade hydrogen peroxide product with the concentration of 30.2wt% is actually obtained by 0.859 ton, and the yield is 94 percent compared with 1.0 ton of feeding material.
Filling in 1000-level purifying environment, and packing with clean HDPE packing barrel.
This example 2 is achieved by changing the relevant materials and process conditions of each step, and specifically differs from example 1 in that:
1. stabilizer selection: 80ppm of butylamine-1, 2, 4-tricarboxylic acid phosphonate;
2. and (3) selecting the rectification temperature: 55 ℃;
3. concentration degree selection: concentrating the crude product of industrial hydrogen peroxide by 50 wt%;
4. and (3) cooling temperature selection: 5 ℃;
5. And (3) flow rate selection: 220L/h.
Product inspection
The electronic grade hydrogen peroxide prepared in example 2 was detected using conventional chemical analysis methods, resulting in comprehensive detection data as follows:
| Technical index | Content of | Yield rate | Sn | Fe | Ca | Al | Na |
| Unit (B) | Wt％ | Wt％ | ppt | ppt | ppt | ppt | ppt |
| Numerical value | 30.0-32.0 | ≥90 | ≤10 | ≤10 | ≤10 | ≤10 | ≤10 |
| Example 2 | 30.2 | 94 | 0.00 | 0.00 | 0.07 | 0.00 | 0.00 |
Example 3
According to the production steps of reference example 1, firstly, 100g of 2-hydroxyphosphonoacetic acid is added into 27.5wt% industrial grade hydrogen peroxide, and the industrial grade hydrogen peroxide is concentrated and purified to 50wt% by vacuum rectification at a low temperature of 60 ℃ to obtain a concentrated industrial grade 40wt% hydrogen peroxide crude product.
Cooling the crude product to 10 ℃, flowing through a polytetrafluoroethylene membrane at a flow rate of 250L/h, filtering out particulate impurities in the hydrogen peroxide, flowing through a halogen-containing aromatic polyamide-based macroporous adsorption resin at a flow rate of 250L/h, removing organic carbon compounds in the hydrogen peroxide, and cooling the treated hydrogen peroxide and delivering the cooled hydrogen peroxide.
Then the mixture flows through PVDF-based chelate resin at the flow rate of 250L/h, so that the content of high valence ions such as Ca 2+、Fe3+、A13+ in the hydrogen peroxide is effectively reduced, and the treated hydrogen peroxide is cooled and then sent out.
And the mixture flows through a styrene-divinylbenzene copolymer based resin cation exchange column containing sulfonic acid groups and a mixed ion exchange column at the flow rate of 250L/h, and low-valence ions in the hydrogen peroxide are purified step by step.
The hydrogen peroxide obtained after the treatment by the steps flows through PVDF (polyvinylidene fluoride) with the material of 250L/h flow rate, and different microporous filters with the pore size of 0.2 micron and 0.1 micron are subjected to multistage filtration so as to remove granular insoluble matters possibly carried out in an ion exchange process, so that the optimal filtration effect is achieved, and the granular impurities in the product meet the requirements.
The electronic grade hydrogen peroxide is prepared into a 30wt% product by using ultrapure water, and the electronic grade hydrogen peroxide product with the concentration of 30.01wt% is actually obtained by 0.87 ton, and the yield is approximately 95% compared with 1.0 ton of feeding calculation.
Filling in 1000-level purifying environment, and packing with clean HDPE packing barrel.
This example 3 is achieved by changing the relevant materials and process conditions of each step, and specifically differs from example 1 in that:
1. stabilizer selection: 100ppm of 2-hydroxyphosphonoacetic acid;
2. and (3) selecting the rectification temperature: 60 ℃;
3. concentration degree selection: concentrating the crude product of industrial hydrogen peroxide by 50 wt%;
4. And (3) cooling temperature selection: 10 ℃;
5. and (3) flow rate selection: 250L/h.
Product inspection
The electronic grade hydrogen peroxide prepared in example 3 was detected using conventional chemical analysis methods, resulting in comprehensive detection data as follows:
| Technical index | Content of | Yield rate | Sn | Fe | Ca | Al | Na |
| Unit (B) | Wt％ | Wt％ | ppt | ppt | ppt | ppt | ppt |
| Numerical value | 30.0-32.0 | ≥90 | ≤10 | ≤10 | ≤10 | ≤10 | ≤10 |
| Example 3 | 30.01 | 95 | 0.00 | 0.02 | 0.00 | 0.22 | 0.42 |
Example 4
According to the production steps of reference example 1, firstly, 30g of ethylenediamine tetramethylene phosphonic acid and 30g of 2-hydroxyphosphonoacetic acid are added into 1 ton of industrial grade hydrogen peroxide with the mass percentage concentration of 27.5wt%, and then the industrial grade hydrogen peroxide is concentrated and purified to 35wt% through vacuum rectification at the low temperature of 50 ℃ to obtain a concentrated industrial grade 35wt% hydrogen peroxide crude product.
Cooling the crude product to 15 ℃, flowing through a polytetrafluoroethylene membrane at a flow rate of 250L/h, filtering out particulate impurities in the hydrogen peroxide, flowing through a 1-grade halogen-containing aromatic polyamide-based macroporous adsorption resin at a flow rate of 250L/h, removing organic carbon compounds in the hydrogen peroxide, and cooling the treated hydrogen peroxide and delivering.
Then the mixture flows through PVDF-based chelate resin at the flow rate of 250L/h, so that the content of high valence ions such as Ca 2+、Fe3+、A13+ in the hydrogen peroxide is effectively reduced, and the treated hydrogen peroxide is cooled and then sent out.
And the mixture flows through a styrene-divinylbenzene copolymer based resin cation exchange column containing sulfonic acid groups and a mixed ion exchange column at the flow rate of 250L/h, and low-valence ions in the hydrogen peroxide are purified step by step.
The hydrogen peroxide obtained after the treatment by the steps flows through PVDF (polyvinylidene fluoride) with the material of 250L/h flow rate, and different microporous filters with the pore size of 0.2 micron and 0.1 micron are subjected to multistage filtration so as to remove granular insoluble matters possibly carried out in an ion exchange process, so that the optimal filtration effect is achieved, and the granular impurities in the product meet the requirements.
The electronic grade hydrogen peroxide is prepared into a 30wt% product by ultrapure water, and the electronic grade hydrogen peroxide product with the concentration of 30.05wt% is actually obtained by 0.87 ton, and the yield is 95 percent relative to 1.0 ton of feeding calculation.
Filling in 1000-level purifying environment, and packing with clean HDPE packing barrel.
This example 4 was achieved by changing the relevant materials, process conditions of each step, and specifically differs from example 1 in that:
1. stabilizer selection: 30ppm ethylenediamine tetramethylene phosphonic acid +30ppm 2-hydroxyphosphonoacetic acid;
2. And (3) selecting the rectification temperature: 50 ℃;
3. concentration degree selection: concentrating the crude product of industrial hydrogen peroxide in the concentration of 35 wt%;
4. And (3) cooling temperature selection: 15 ℃;
5. and (3) flow rate selection: 250L/h;
8. PFA-based chelating resins were selected.
Product inspection
The electronic grade hydrogen peroxide prepared in example 4 was detected using conventional chemical analysis methods, resulting in comprehensive detection data as follows:
| Technical index | Content of | Yield rate | Sn | Fe | Ca | Al | Na |
| Unit (B) | Wt％ | Wt％ | ppt | ppt | ppt | ppt | ppt |
| Numerical value | 30.0-32.0 | ≥90 | ≤10 | ≤10 | ≤10 | ≤10 | ≤10 |
| Example 4 | 30.05 | 95 | 0.21 | 0.00 | 0.07 | 0.00 | 0.00 |
Example 5
According to the production steps of reference example 1, 40g of butylamine-1, 2,4 tricarboxylic acid phosphonate and 30g of 2-hydroxyphosphonoacetic acid are added into 27.5wt% industrial grade hydrogen peroxide, and the concentrated industrial grade 35wt% hydrogen peroxide crude product is obtained through vacuum rectification concentration and purification to 35wt% at a low temperature of 50 ℃.
Cooling the crude product to 10 ℃, flowing through a polytetrafluoroethylene membrane at a flow rate of 250L/h, filtering out particulate impurities in the hydrogen peroxide, flowing through a 1-grade halogen-containing aromatic polyamide-based macroporous adsorption resin at a flow rate of 250L/h, removing organic carbon compounds in the hydrogen peroxide, and cooling the treated hydrogen peroxide and delivering.
Then the mixture flows through PTFE-based chelate resin at the flow rate of 250L/h, so that the content of high valence ions such as Ca 2+、Fe3+、A13+ in the hydrogen peroxide is effectively reduced, and the treated hydrogen peroxide is cooled and then sent out.
And the mixture flows through a styrene-divinylbenzene copolymer based resin cation exchange column containing sulfonic acid groups and a mixed ion exchange column at the flow rate of 250L/h, and low-valence ions in the hydrogen peroxide are purified step by step.
The hydrogen peroxide obtained after the treatment by the steps flows through PVDF (polyvinylidene fluoride) with the material of 250L/h flow rate, and different microporous filters with the pore size of 0.2 micron and 0.1 micron are subjected to multistage filtration so as to remove granular insoluble matters possibly carried out in an ion exchange process, so that the optimal filtration effect is achieved, and the granular impurities in the product meet the requirements.
The electronic grade hydrogen peroxide is prepared into a 30wt% product by ultrapure water, and the electronic grade hydrogen peroxide product with the concentration of 30.12wt% is actually obtained by 0.858 ton, and the yield is 94 percent relative to 1.0 ton of feeding material.
Filling in 1000-level purifying environment, and packing with clean HDPE packing barrel.
This example 5 is achieved by changing the relevant materials and process conditions of each step, and specifically differs from example 1 in that:
1. stabilizer selection: 40ppm butylamine-1, 2,4 tricarboxylic acid+30 ppm 2-hydroxyphosphonoacetic acid;
2. And (3) selecting the rectification temperature: 50 ℃;
3. concentration degree selection: concentrating the crude product of industrial hydrogen peroxide in the concentration of 35 wt%;
4. And (3) cooling temperature selection: 10 ℃;
5. and (3) flow rate selection: 250L/h;
8. PTFE-based chelating resins were chosen.
Example 6
According to the production steps of reference example 1, 90g of 2-hydroxyphosphonoacetic acid is added into 1 ton of industrial grade hydrogen peroxide with the mass percentage concentration of 27.5wt%, and the industrial grade hydrogen peroxide is concentrated and purified to 40wt% by vacuum rectification at the low temperature of 45 ℃ to obtain a concentrated industrial grade 40wt% hydrogen peroxide crude product.
Cooling the crude product to 10 ℃, flowing through a polytetrafluoroethylene membrane at a flow rate of 250L/h, filtering out particulate impurities in the hydrogen peroxide, flowing through a 1-grade halogen-containing aromatic polyamide-based macroporous adsorption resin at a flow rate of 250L/h, removing organic carbon compounds in the hydrogen peroxide, and cooling the treated hydrogen peroxide and delivering.
Then the mixture flows through PTFE-based chelate resin at the flow rate of 250L/h, so that the content of high valence ions such as Ca2+, fe3+, A13+ and the like in the hydrogen peroxide is effectively reduced, and the treated hydrogen peroxide is cooled and then sent out.
And the mixture flows through a styrene-divinylbenzene copolymer based resin cation exchange column containing sulfonic acid groups and a mixed ion exchange column at the flow rate of 250L/h, and low-valence ions in the hydrogen peroxide are purified step by step.
The hydrogen peroxide obtained after the treatment by the steps flows through PVDF (polyvinylidene fluoride) with the material of 250L/h flow rate, and different microporous filters with the pore size of 0.2 micron and 0.1 micron are subjected to multistage filtration so as to remove granular insoluble matters possibly carried out in an ion exchange process, so that the optimal filtration effect is achieved, and the granular impurities in the product meet the requirements.
The electronic grade hydrogen peroxide is prepared into a 30wt% product by ultrapure water, 0.817 tons of electronic grade hydrogen peroxide product with the concentration of 30.3wt% is actually obtained, and the yield is 90 percent relative to 1.0 ton of feeding material.
Filling in 1000-level purifying environment, and packing with clean HDPE packing barrel.
This example 6 was achieved by changing the relevant materials and process conditions for each step, and differs from example 1 in particular in that:
1. Stabilizer selection: 90ppm of 2-hydroxyphosphonoacetic acid;
2. And (3) selecting the rectification temperature: 45 ℃;
3. concentration degree selection: concentrating the crude product of industrial hydrogen peroxide by 40 wt%;
4. And (3) cooling temperature selection: 10 ℃;
5. and (3) flow rate selection: 250L/h;
8. PTFE-based chelating resins were chosen.
Product inspection
The electronic grade hydrogen peroxide prepared in example 6 was detected using conventional chemical analysis methods, resulting in comprehensive detection data as follows:
| Technical index | Content of | Yield rate | Sn | Fe | Ca | Al | Na |
| Unit (B) | Wt％ | Wt％ | ppt | ppt | ppt | ppt | ppt |
| Numerical value | 30.0-32.0 | ≥90 | ≤10 | ≤10 | ≤10 | ≤10 | ≤10 |
| Example 6 | 30.3 | 90 | 0.00 | 0.08 | 0.00 | 0.00 | 0.41 |
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The electronic grade hydrogen peroxide produced in the above examples 1-6 has various indexes superior to the conventional standard, and the yield is more than 90wt%.
Comparative example 1
In the production step of reference example 1, 1 ton of industrial grade hydrogen peroxide with the mass percentage concentration of 27.5wt% is firstly subjected to vacuum rectification concentration and purification at the low temperature of 50 ℃ to 33wt%, so as to obtain a concentrated industrial grade 33wt% hydrogen peroxide crude product.
Cooling the crude product to 5 ℃, allowing the crude product to flow through a polytetrafluoroethylene membrane at a flow rate of 250L/h, filtering out particulate impurities in the hydrogen peroxide, allowing the hydrogen peroxide to flow through a halogen-containing aromatic polyamide-based macroporous adsorption resin at a flow rate of 250L/h, removing organic carbon compounds in the hydrogen peroxide, and cooling the treated hydrogen peroxide and then delivering the treated hydrogen peroxide.
Then the mixture flows through PFA-based chelate resin at the flow rate of 250L/h, so that the content of high valence ions such as Ca2+, fe3+, A13+ and the like in the hydrogen peroxide is effectively reduced, and the treated hydrogen peroxide is cooled and then sent out.
And the mixture flows through a styrene-divinylbenzene copolymer based resin cation exchange column containing sulfonic acid groups and a mixed ion exchange column at the flow rate of 250L/h, and low-valence ions in the hydrogen peroxide are purified step by step.
The hydrogen peroxide obtained after the treatment by the steps flows through PVDF (polyvinylidene fluoride) with the material of 250L/h flow rate, and different microporous filters with the pore size of 0.2 micron and 0.1 micron are subjected to multistage filtration so as to remove granular insoluble matters possibly carried out in an ion exchange process, so that the optimal filtration effect is achieved, and the granular impurities in the product meet the requirements.
The electronic grade hydrogen peroxide product is obtained by 0.75 ton, the detection concentration is 31.02 weight percent, and the yield is 85 percent relative to 1.0 ton feeding calculation.
Filling in 1000-level purifying environment, and packing with clean HDPE packing barrel.
Comparative example 1 is different from example 1 in particular in that:
1. No stabilizer is added;
2. The rectification temperature is 50 ℃;
3. Concentrating the crude product of the industrial hydrogen peroxide at 33 wt%;
4. the cooling temperature is 5 ℃;
5. the flow rate is 250L/h;
8. PVDF-based chelate resins.
Product inspection
The electronic grade hydrogen peroxide prepared in comparative example 1 was detected by using a conventional chemical analysis method, and comprehensive detection data were obtained as follows:
| Technical index | Content of | Yield rate | Sn | Fe | Ca | Al | Na |
| Unit (B) | Wt％ | Wt％ | ppt | ppt | ppt | ppt | ppt |
| Numerical value | 30.0-32.0 | ≥90 | ≤10 | ≤10 | ≤10 | ≤10 | ≤10 |
| Comparative example 1 | 31.02 | 85 | 2.21 | 1.03 | 1.07 | 0.64 | 0.00 |
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Comparative example 2
According to the production steps of reference example 1, 20g of butylamine-1, 2, 4-tricarboxylic acid phosphonate is added into 27.5wt% industrial grade hydrogen peroxide, and then concentrated and purified to 50% by vacuum distillation at a low temperature of 55 ℃ to obtain a concentrated industrial grade 50wt% product.
Cooling the product to 5 ℃, enabling 200L/h flow rate to flow through a polytetrafluoroethylene membrane, filtering out particulate impurities in the hydrogen peroxide, enabling the filtered hydrogen peroxide to flow through a halogen-containing aromatic polyamide-based macroporous adsorption resin at 200L/h flow rate, removing organic carbon compounds in the hydrogen peroxide, and cooling the treated hydrogen peroxide and then delivering the cooled hydrogen peroxide.
And then the solution flows through the PFA-based chelate resin at the flow rate of 200L/h to effectively reduce the content of high valence ions such as Ca2+, fe3+, A13+ and the like in the hydrogen peroxide, and the treated hydrogen peroxide is cooled and then sent out.
And the mixture flows through a styrene-divinylbenzene copolymer based resin cation exchange column containing sulfonic acid groups and a mixed ion exchange column at a flow rate of 200L/h, and low-valence ions in the hydrogen peroxide are purified step by step.
The hydrogen peroxide obtained after the treatment by the steps flows through PVDF (polyvinylidene fluoride) with the material of 200L/h flow rate, and different microporous filters with the pore size of 0.2 micron and 0.1 micron are subjected to multistage filtration so as to remove granular insoluble matters possibly carried out in the ion exchange process, so that the optimal filtration effect is achieved, and the granular impurities in the product meet the requirements.
The electronic grade hydrogen peroxide is prepared into a 30wt% product by ultrapure water, and the electronic grade hydrogen peroxide product with the concentration of 30.8wt% is actually obtained by 0.768 ton, and the yield is 86 percent relative to 1.0 ton of feeding calculation.
Filling in 1000-level purifying environment, and packing with clean HDPE packing barrel.
Comparative example 2 is different from example 1 in particular in that:
1. 20ppm butylamine-1, 2, 4-tricarboxylic acid phosphonate;
2. the rectification temperature is 55 ℃;
3. concentrating the crude industrial hydrogen peroxide product by 50wt% and cooling to 5 ℃;
4. The flow rate is 200L/h;
8. PTFE-based chelating resins.
Comparative example 3
According to the production steps of reference example 1, 50g of sodium tripolyphosphate is added into 27.5wt% industrial grade hydrogen peroxide with a mass percentage concentration of 1 ton, and then the concentrated industrial grade 40wt% hydrogen peroxide product is obtained through vacuum rectification concentration and purification to 40wt% at a low temperature of 60 ℃.
Cooling the product to 5 ℃, allowing the product to flow through a polytetrafluoroethylene membrane at a flow rate of 230L/h, filtering out particulate impurities in the hydrogen peroxide, allowing the product to flow through a halogen-containing aromatic polyamide-based macroporous adsorption resin at a flow rate of 230L/h, removing organic carbon compounds in the hydrogen peroxide, and cooling the treated hydrogen peroxide and then delivering the treated hydrogen peroxide.
Then the mixture flows through PFA-based chelate resin at the flow rate of 230L/h, so that the content of high valence ions such as Ca2+, fe3+, A13+ and the like in the hydrogen peroxide is effectively reduced, and the treated hydrogen peroxide is cooled and then sent out.
And the mixture flows through a styrene-divinylbenzene copolymer based resin cation exchange column containing sulfonic acid groups and a mixed ion exchange column at a flow rate of 230L/h, and low-valence ions in the hydrogen peroxide are purified step by step.
The hydrogen peroxide obtained after the treatment by the steps flows through PVDF (polyvinylidene fluoride) with a material of 230L/h flow rate, and different microporous filters with pore sizes of 0.2 micron and 0.1 micron are subjected to multistage filtration so as to remove granular insoluble matters possibly carried out in an ion exchange process, so that the optimal filtration effect is achieved, and the granular impurities in the product meet the requirements.
The electronic grade hydrogen peroxide is prepared into a 30wt% product by ultrapure water, and the electronic grade hydrogen peroxide product with the concentration of 30.22wt% is actually obtained by 0.78 ton, and the yield is 86 percent relative to 1.0 ton of feeding.
Comparative example 3 is different from example 1 in particular in that:
1. 50ppm sodium tripolyphosphate;
2. The rectification temperature is 60 ℃;
3. concentrating the crude product of industrial hydrogen peroxide by 40 wt%;
4. the cooling temperature is 5 ℃;
5. the flow rate is 230L/h;
8. PFA-based chelate resins.
The yield of the final product is lower than 90wt% in the comparative examples 1-3, and the content index of each impurity in the comparative example 1 meets the requirements of electronic grade hydrogen peroxide, but is obviously higher than that in the examples.
Preliminary experiments
The effect of the flow rate of the impurity adsorption step on removal of organic TOC in example 1 was shown in the following table, in which the organic TOC was reduced to 20ppm after passing through the PTFE membrane and the organic TOC was reduced to 10ppm or less after adsorption into the resin:
| Sequence number | Flow rate L/h | Cation ppb | Ppb of anions | TOC |
| 1 | 150 | ≤30 | ≤2000 | ≤6 |
| 2 | 200 | ≤30 | ≤2000 | ≤8 |
| 3 | 230 | ≤40 | ≤3000 | ≤9 |
| 4 | 250 | ≤50 | ≤5000 | ≤10 |
| 5 | 280 | ≤60 | ≤6000 | ≤12 |
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (7)
1. The electronic grade hydrogen peroxide production method is characterized by comprising the following production steps in sequence:
s1: vacuum rectification concentration specifically includes:
Taking industrial grade hydrogen peroxide with concentration less than or equal to 30wt% as a raw material, and concentrating and pre-extracting;
The concentration pretreatment is to carry out rectification concentration on the industrial grade hydrogen peroxide to 35-50 wt% under the conditions that the temperature is 45-60 ℃ and the vacuum degree is minus 0.05-minus 0.1MPa, so as to obtain a concentrated industrial grade hydrogen peroxide primary product;
S2: impurity adsorption, specifically comprising:
cooling the concentrated industrial grade hydrogen peroxide primary product to 0-15 ℃ to obtain industrial grade hydrogen peroxide cooling liquid;
filtering impurities from the industrial grade hydrogen peroxide cooling liquid flow through an adsorption device formed by combining a polytetrafluoroethylene membrane and macroporous adsorption resin in a serial mode, and removing insoluble impurities and organic matters in the hydrogen peroxide to obtain a chemical grade hydrogen peroxide intermediate product (I);
s3: the method for removing the high valence ion specifically comprises the following steps:
the chemical grade hydrogen peroxide intermediate product (I) flows through chelating resin devices combined in a series connection mode, and high valence ions in the hydrogen peroxide are removed, so that the chemical grade hydrogen peroxide intermediate product (II) is obtained;
S4: the low valence ion removal specifically comprises:
Sequentially flowing the chemical grade hydrogen peroxide intermediate product (II) through an anion resin exchange column, a cation resin exchange column and a mixed ion resin exchange column, and purifying low-valence ions step by step to obtain a chemical grade hydrogen peroxide intermediate product (III);
s5: insoluble matter filtration, specifically comprising:
Allowing the chemical grade hydrogen peroxide intermediate product (III) to flow through a microporous filter for multistage filtration to remove granular insoluble matters carried out in an ion exchange process, so as to obtain electronic grade hydrogen peroxide;
In the vacuum rectification concentration, a stabilizer is added into the industrial grade hydrogen peroxide, wherein the stabilizer is organic phosphines, and the addition amount is 50-100 ppm;
The flow rate of the production steps S2-S5 is controlled to be 200-250L/h.
2. The method of producing electronic grade hydrogen peroxide according to claim 1, wherein a dilution step is post-positioned at step S5, and a packaging step, the dilution step comprising:
Diluting the electronic grade hydrogen peroxide to a required concentration by using ultrapure water;
the packaging step comprises the following steps:
filling the diluted electronic grade hydrogen peroxide in a purifying environment of which the grade is not lower than 1000.
3. The method for producing electronic grade hydrogen peroxide according to claim 1, wherein the organic phosphine stabilizer is one or more selected from hydroxyethylidene diphosphonic acid (HEDP), aminotrimethylene phosphonic Acid (ATMP), ethylenediamine tetramethylene phosphonic acid, butyl phosphonic acid-1, 2,4 tricarboxylic acid (PBTC), diethylenetriamine pentamethylene phosphonic acid (DTPMP), and 2-hydroxyphosphonoacetic acid.
4. The method for producing electronic grade hydrogen peroxide according to claim 1, wherein the macroporous adsorption resin is one selected from halogen-containing aromatic polyamide and polysulfone.
5. The method for producing electronic grade hydrogen peroxide according to claim 1, wherein the chelating resin is one selected from PVDF, PTFE, PFA.
6. The method for producing electronic grade hydrogen peroxide according to claim 1, wherein the cationic resin is a quaternary ammonium salt-containing styrene resin, and the anionic resin is a sulfonic acid group-containing styrene and divinylbenzene copolymer resin.
7. The method for producing electronic grade hydrogen peroxide according to claim 1, wherein the microporous filter is made of PVDF, the pore diameter is 0.2-0.1 micron, and the pore diameters are combined in multiple stages from large to small.
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| CN114084872A (en) * | 2021-12-03 | 2022-02-25 | 杭州精欣化工有限公司 | Stabilizer for electronic grade hydrogen peroxide solution and application |
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| CN101239704A (en) * | 2008-03-14 | 2008-08-13 | 华南理工大学 | Method for purifying hydrogen peroxide solution |
| CN102556976A (en) * | 2010-12-08 | 2012-07-11 | 上海华谊微电子材料有限公司 | Method for continuous production of ultrapure hydrogen peroxide |
| CN102701158A (en) * | 2012-06-21 | 2012-10-03 | 苏州晶瑞化学有限公司 | Continuous preparation method for high-purity hydrogen peroxide |
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| CN101239704A (en) * | 2008-03-14 | 2008-08-13 | 华南理工大学 | Method for purifying hydrogen peroxide solution |
| CN102556976A (en) * | 2010-12-08 | 2012-07-11 | 上海华谊微电子材料有限公司 | Method for continuous production of ultrapure hydrogen peroxide |
| CN102701158A (en) * | 2012-06-21 | 2012-10-03 | 苏州晶瑞化学有限公司 | Continuous preparation method for high-purity hydrogen peroxide |
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