CN114423713A - Method for preparing microspheres containing oxygen zinc compound - Google Patents
Method for preparing microspheres containing oxygen zinc compound Download PDFInfo
- Publication number
- CN114423713A CN114423713A CN202080049549.3A CN202080049549A CN114423713A CN 114423713 A CN114423713 A CN 114423713A CN 202080049549 A CN202080049549 A CN 202080049549A CN 114423713 A CN114423713 A CN 114423713A
- Authority
- CN
- China
- Prior art keywords
- conductivity
- composition
- precipitate
- zinc
- determining
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 124
- 239000004005 microsphere Substances 0.000 title claims abstract description 73
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims description 72
- 239000002244 precipitate Substances 0.000 claims abstract description 191
- 239000000203 mixture Substances 0.000 claims abstract description 152
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 85
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 56
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 53
- 239000000725 suspension Substances 0.000 claims description 43
- 239000011701 zinc Substances 0.000 claims description 40
- -1 zinc oxide compound Chemical class 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 35
- 150000007529 inorganic bases Chemical class 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 31
- 239000003513 alkali Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000001556 precipitation Methods 0.000 claims description 27
- 239000011787 zinc oxide Substances 0.000 claims description 27
- 229910052725 zinc Inorganic materials 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000000889 atomisation Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 150000003841 chloride salts Chemical class 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 10
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 10
- 239000011686 zinc sulphate Substances 0.000 claims description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 9
- 238000004073 vulcanization Methods 0.000 claims description 8
- 238000001033 granulometry Methods 0.000 claims description 7
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 235000016709 nutrition Nutrition 0.000 claims description 5
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 claims description 5
- 150000002823 nitrates Chemical class 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 150000003839 salts Chemical class 0.000 description 24
- 239000006185 dispersion Substances 0.000 description 20
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 16
- 239000011575 calcium Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- 239000000292 calcium oxide Substances 0.000 description 12
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 12
- 239000000395 magnesium oxide Substances 0.000 description 12
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 11
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 11
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 11
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 10
- 229910004878 Na2S2O4 Inorganic materials 0.000 description 10
- 239000007832 Na2SO4 Substances 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 150000001450 anions Chemical class 0.000 description 10
- 239000007900 aqueous suspension Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 7
- 235000021355 Stearic acid Nutrition 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 7
- 239000001103 potassium chloride Substances 0.000 description 7
- 239000008117 stearic acid Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 229910052925 anhydrite Inorganic materials 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- STSDHUBQQWBRBH-UHFFFAOYSA-N n-cyclohexyl-1,3-benzothiazole-2-sulfonamide Chemical compound N=1C2=CC=CC=C2SC=1S(=O)(=O)NC1CCCCC1 STSDHUBQQWBRBH-UHFFFAOYSA-N 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 6
- 229910007511 Li2S2O4 Inorganic materials 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 239000012736 aqueous medium Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 5
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 5
- 239000001095 magnesium carbonate Substances 0.000 description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 5
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- FXBYOMANNHFNQV-UHFFFAOYSA-L magnesium;hydrogen sulfate Chemical compound [Mg+2].OS([O-])(=O)=O.OS([O-])(=O)=O FXBYOMANNHFNQV-UHFFFAOYSA-L 0.000 description 5
- 239000011736 potassium bicarbonate Substances 0.000 description 5
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 5
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 5
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 5
- 238000000518 rheometry Methods 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 239000002775 capsule Substances 0.000 description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 3
- 229940007718 zinc hydroxide Drugs 0.000 description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical group C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 2
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 2
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 2
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000011667 zinc carbonate Substances 0.000 description 2
- 235000004416 zinc carbonate Nutrition 0.000 description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- 229910013868 M2SO4 Inorganic materials 0.000 description 1
- 229910018965 MCl2 Inorganic materials 0.000 description 1
- 229910015853 MSO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000019728 animal nutrition Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000004463 hay Substances 0.000 description 1
- JSRLCNHTWASAJT-UHFFFAOYSA-N helium;molecular nitrogen Chemical compound [He].N#N JSRLCNHTWASAJT-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 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
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004460 silage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- PCHQDTOLHOFHHK-UHFFFAOYSA-L zinc;hydrogen carbonate Chemical compound [Zn+2].OC([O-])=O.OC([O-])=O PCHQDTOLHOFHHK-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/30—Oligoelements
-
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- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
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- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
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Abstract
The invention relates to a method for preparing an oxygen-containing zinc compound microsphere composition, which comprises the following steps: providing a precipitate containing a zinc compound, adjusting the conductivity of the obtained precipitate until the conductivity as determined using the conductivity determination method is less than 3000 μ S/cm, and obtaining a zinc compound-containing microsphere composition from the precipitate. The invention also relates to an oxygen-containing zinc compound microsphere composition and application thereof, wherein the conductivity of the composition is less than 3000 mu S/cm by using a conductivity measuring method.
Description
Technical Field
The present invention relates to the field of inorganic chemistry, and more particularly to a zinc compound-containing microsphere composition which can be easily dispersed in a material and has high dispersion uniformity when dispersed in the material.
Background
Oxygen-containing zinc compounds such as zinc oxide, zinc hydroxide, zinc carbonate and derivatives thereof are commonly used as additives in many fields. For example, zinc oxide can be used in the fields of oil, paint, varistor, ceramics, and the like.
The use of zinc compounds containing oxygen is usually dispersed in materials such as nutritional compositions (as food additives: feed (hay, straw, silage, oilseeds and cereals)) and manufactured or polymeric materials (elastomers or plastic-based compounds/composites) usually consisting of a combination mixture of animal food, possibly containing additives (https:// www.efsa.europa.eu/fr/topics/animal-feed).
In the particular field of elastomers, oxygen-containing zinc compounds are used as activators, in particular in the vulcanization of polymers such as polyisoprene, polybutadiene, styrene-butadiene rubber or EPDM (ethylene-propylene-diene monomer) rubber. Vulcanization is a crosslinking reaction, and generally employs sulfur as a crosslinking agent, an oxygen-containing zinc compound as an activator, and an accelerator such as CBS (N-cyclohexyl-2-benzothiazole sulfonamide) or DPG (diphenyl guanidine), and a fatty acid such as stearic acid and its derivatives. The zinc compounds containing oxygen are not soluble in The polymeric material, while stearic acid will aid in The dissolution of The zinc compounds containing oxygen in The polymeric material (The rubber for laboratory design Library). It is generally accepted that during the vulcanization reaction, an oxygen-containing zinc compound (activator), fatty acid (stearic acid) and a promoter combine in situ in the polymeric material to form a catalyst that will catalyze crosslinking of the polymer by reaction between the double bonds of the polymer and sulfur.
Sometimes, the zinc-containing compounds can also act as a charge, giving the product, like other products (carbon black, chalk, kaolin, talc, etc.), specific properties (electrical conductivity, improved resilience, thermal conductivity, etc.).
When the zinc-oxygen-containing compound is dispersed in a material such as a polymeric material, it is of utmost importance to obtain a final dispersion with good dispersion uniformity. In fact, for example, when ZnO is used as a curing activator, the uneven distribution of ZnO may result in a cured polymer having an uneven crosslink density. Since this inhomogeneous distribution of ZnO is uncontrolled, the distribution of the crosslink density is also uncontrolled. This results in an uncontrolled structure and properties of the vulcanized polymer, which may negatively affect the mechanical properties of the vulcanized polymer, and thus its final quality.
When the zinc-containing compound acts as a charge, the non-uniform dispersion of the latter in materials such as polymeric materials can also have a negative effect on the properties that the zinc-containing compound should bring, and thus on the final quality and properties of the final material.
It is therefore important to have a method of preparing microspheres of zinc oxy-containing compounds that can be easily and uniformly dispersed in materials such as nutritional compositions or polymeric materials.
EP1546039B1 discloses a process for the preparation of microsphere powders of zinc oxide-containing compounds and their use in polymers. This patent is particularly concerned with the drying step of the zinc-containing compound after the "wet" synthesis. In particular, the drying step is carried out by an atomization process in an atomization chamber. The obtained zinc compound containing oxygen is in microsphere form, especially Flodex index is less than 15, D50Is 50-200 μm.
Accordingly, there is a continuing need to develop an improved process for preparing zinc compound containing microsphere compositions that can be readily dispersed in materials, particularly polymeric materials or nutritional compositions, and that allows for improved uniformity of dispersion. Furthermore, such a preparation method should be versatile and economically profitable enough to meet the needs of the industry.
Summary of The Invention
The present inventors have surprisingly found that it is possible to provide an improved process to meet the above needs.
Accordingly, one object of the present invention is a process for the preparation of microsphere compositions (C) containing zinc oxide compounds, comprising the steps of:
a) providing a Precipitate (PR) of an oxygen-containing zinc compound, preferably in the form of a suspension,
b) adjusting the conductivity of the Precipitate (PR) obtained in step a) until the conductivity, determined according to the method for determining the conductivity, is lower than 3000. mu.S/cm,
c) obtaining the zinc compound containing microsphere composition (C) from the Precipitate (PR).
Another object of the present invention is a zinc compound containing microsphere composition (C) having an electrical conductivity of less than 3000 μ S/cm as measured according to the method for measuring electrical conductivity.
Another object of the invention is said composition (C) of the invention, obtained by said process of the invention.
Another object of the present invention is the use of said composition (C) according to the invention or of said process according to the invention in vulcanization processes.
Another object of the present invention consists in the use of said composition (C) of the invention or of the composition obtained by said process of the invention in a material, preferably a material selected from the group consisting of nutritional compositions, polymeric materials and mixtures thereof; more preferably, the material is a polymer.
Brief description of the drawings
Figure 1 shows an atomising device.
Fig. 2 shows the results of the rheometry of a dispersion of a composition (C) of an oxygen-containing zinc compound of one embodiment of the invention dispersed in a polymeric material.
Figure 3 shows the results of a rheometry for dispersions of ZnO compounds dispersed in polymeric materials and having a conductivity above 3000 mus/cm as determined according to the method for determining conductivity.
Detailed Description
Precipitate (PR)
In the context of the present invention, an "oxygen-containing zinc compound" may be defined as a compound comprising a zinc atom and an oxygen atom. In particular, the zinc-containing compound may be selected from zinc oxide, zinc hydroxide, zinc carbonate, basic zinc carbonate, and a mixture thereof or a derivative thereof, and preferably, the zinc-containing compound is a mixture of zinc oxide and zinc hydroxide.
If desired, the zinc-oxygen-containing compound may be obtained by precipitation on a support. In particular, the support may be an amorphous charge, preferably calcium carbonate, silica, wax and mixtures thereof.
In particular, the electrical conductivity of the Precipitate (PR) of the zinc oxo compound provided in step a), preferably the electrical conductivity as determined according to the method for determining the electrical conductivity, is higher than 3000. mu.S/cm, more particularly higher than 4000. mu.S/cm, still more particularly higher than 5000. mu.S/cm, still more particularly higher than 10000. mu.S/cm, still more particularly higher than 20000. mu.S/cm, still more particularly higher than 30000. mu.S/cm.
If desired, the Precipitate (PR) may not be in suspension or may be in a dry form. In particular, the Precipitate (PR) may not be in suspension and may contain less than 50 wt% moisture, preferably less than 20 wt% moisture, more preferably less than 10 wt% moisture, still more preferably less than 1 wt% moisture.
Preferably, the Precipitate (PR) of the zinc-oxygen-containing compound may be in the form of a suspension (S1).
In particular, the suspension (S1) comprises a weight percentage of the precipitates of the zinc-oxygen-containing compound higher than or equal to 1% by weight, preferably higher than or equal to 5% by weight, more preferably higher than or equal to 8% by weight, still more preferably higher than or equal to 10% by weight, relative to the total weight of the suspension (S1).
If desired, the suspension (S1) comprises less than 90 wt. -%, more preferably less than 80 wt. -%, more preferably less than 50 wt. -%, still more preferably less than 30 wt. -%, still more preferably less than 20 wt. -%, still more preferably less than 15 wt. -%, still more preferably less than 12 wt. -% of the precipitate of the zinc-containing compound relative to the total weight of the suspension (S1).
If desired, the suspension (S1) comprises a weight percentage of precipitates of the zinc-oxygen-containing compound of 1% to 90% by weight, preferably 5% to 50% by weight, more preferably 8% to 30% by weight, still more preferably 8% to 20% by weight, still more preferably 8% to 15% by weight, still more preferably 8% to 12% by weight, relative to the total weight of the suspension (S1).
More preferably, the suspension (S1) is a suspension in an aqueous medium. Preferably, the aqueous medium may be selected from the group consisting of a reaction medium, pure water, and brine. Brine is understood to be water comprising at least one salt. The term reaction medium may refer to the aqueous medium resulting directly from the precipitation of the precipitate of the zinc-oxygen-containing compound.
In particular, when the suspension (S1) is a suspension in an aqueous medium, the suspension (S1) may comprise a percentage by weight of water higher than or equal to 50% by weight, preferably higher than or equal to 60% by weight, more preferably higher than or equal to 70% by weight, still more preferably higher than or equal to 80% by weight, still more preferably higher than or equal to 85% by weight, still more preferably higher than or equal to 90% by weight, relative to the total weight of the suspension (S1).
If desired, when the suspension (S1) is an aqueous suspension, the suspension (S1) comprises a percentage by weight of water lower than 99% by weight, preferably lower than 95% by weight, preferably lower than 93% by weight, with respect to the total weight of the suspension (S1).
If desired, when the suspension (S1) is an aqueous suspension, the suspension (S1) comprises water in a weight percentage of 99 to 50% by weight, preferably 95 to 60% by weight, more preferably 95 to 70% by weight, still more preferably 95 to 80% by weight, still more preferably 95 to 85% by weight, still more preferably 93 to 85% by weight, relative to the total weight of the suspension (S1).
The step a) of providing a Precipitate (PR) of an oxygen-containing zinc compound according to the process of the present invention may be carried out by any means known to the person skilled in the art.
Preferably, said step a) of providing a Precipitate (PR) of an oxygen-containing zinc compound comprises a precipitation process in a solvent, preferably in water.
Such precipitation processes are known to those skilled in the art. For example, starting from a precursor (zinc compound), a Precipitate (PR) of the zinc oxygen-containing compound may be formed by adding an acid or a base. The choice of acid or base depends on the zinc compound.
Preferably, the precipitation process comprises step a 1): zinc compounds, preferably selected from ZnS2O4、Zn(NO3)2、ZnCl2、ZnSO4And mixtures thereof with at least one inorganic base.
The reaction between the zinc compound and the at least one inorganic base is in fact a precipitation reaction, which is capable of generating an oxygen-containing zinc compound, such as Zn (OH)2And/or ZnO.
More preferably, the zinc compound is ZnS2O4. Obtaining ZnS2O4Are known in the art, e.g., the ZnS2O4Can be prepared by reacting Zn and SO in the presence of water2Is obtained by the reaction between.
If desired, the at least one inorganic base comprises a base preferably selected from Li+、Na+、K+、Ca2+、Mg2+And combinations thereof, at least one alkali or alkaline earth metal cation M and preferably selected from O2-、OH-、CO3 2-、HCO3 -And combinations thereof.
Preferably, the at least one inorganic base has the formula [ M]x[A]yWherein M is an alkali metal or alkaline earth metal cation M, preferably selected from Li+、Na+、K+、Ca2+、Mg2+And combinations thereof, A is an anion A, preferably selected from O2-、OH-、CO3 2-、HCO3 -And combinations thereof. The coefficients x and y may take values between 1 or 2 or 1-2. The values of the coefficients x and y depend on the cation and anion.
More preferably, the at least one inorganic base is selected from LiOH, NaOH, KOH, Ca (OH)2、Mg(OH)2、MgO、Li2CO3、Na2CO3、K2CO3、CaCO3、CaO、MgCO3、LiHCO3、NaHCO3、KHCO3、Ca(HCO3)2、Mg(HCO3)2MgO & CaO and mixtures and/or combinations thereof. Still more preferably, the at least one base is NaOH or KOH or CaO or MgO or CaO · MgO, still more preferably, the at least one base is NaOH.
In general, the precipitation process may generate inorganic salts as by-products, which may be trapped in and/or crystallized around the Precipitate (PR), especially if the latter is not in suspension, for example in dry form. Alternatively, these inorganic salts are contained in the suspension, in particular when the Precipitate (PR) is in the form of a suspension. In particular, the inorganic salts comprised in the suspension may be at least partially or fully dissolved, e.g. in a dissociated form in the suspension. For example, if the suspension is an aqueous suspension, the inorganic salt may be at least partially or fully dissolved, for example in dissociated form in water.
In particular, in the precipitation process, during step a1), if the zinc compound is ZnS2O4By ZnS2O4The reaction with the at least one inorganic base produces dithionite which can then be at least partially degraded into various other sulfates and/or bisulfates and-Or a sulfite and/or bisulfite and/or thiosulfate.
In particular, in the precipitation process, during step a1), if the zinc compound is ZnNO3Then through ZnNO3And the at least one inorganic base to form a nitrate salt. In particular, in the precipitation process, during step a1), if the zinc compound is ZnCl2Then through ZnCl2The reaction with the at least one inorganic base produces a chloride salt. In particular, in the precipitation process, during step a1), if the zinc compound is ZnSO4Then through ZnSO4The reaction with the at least one inorganic base produces a sulfate salt. In particular, in the precipitation process, during step a1), if the zinc compounds are each independently selected from ZnS2O4、Zn(NO3)2、ZnCl2、ZnSO4And mixtures of at least two compounds of (a), the mixtures of at least two inorganic salts are each independently selected from dithionite, sulfate, bisulfate, sulfite, bisulfite, thiosulfate, nitrate, chloride salts.
Thus, the Precipitate (PR) provided in step a) may comprise at least one inorganic salt, in particular at least one inorganic salt originating from the precipitation process, in particular when the Precipitate (PR) is not in a suspension form, or in a dry form. Preferably, if the Precipitate (PR) is in the form of a suspension (S1), the suspension (S1) may further comprise at least one inorganic salt, in particular at least one inorganic salt originating from the precipitation process. In particular, when the Precipitate (PR) is not in the form of a suspension or in a dry form, the precipitate may comprise the at least one inorganic salt in a concentration such that the conductivity of the Precipitate (PR) determined according to the method for determining the conductivity is higher than 3000. mu.S/cm, more particularly higher than 4000. mu.S/cm, still more particularly higher than 5000. mu.S/cm, still more particularly higher than 10000. mu.S/cm, still more particularly higher than 20000. mu.S/cm, still more particularly higher than 30000. mu.S/cm. In particular, if the Precipitate (PR) is in the form of a suspension (S1), the suspension (S1) may further comprise the at least one inorganic salt in a concentration such that the conductivity of the Precipitate (PR), as determined according to the method for determining conductivity, is higher than 3000 μ S/cm, more particularly higher than 4000 μ S/cm, still more particularly higher than 5000 μ S/cm, still more particularly higher than 10000 μ S/cm, still more particularly higher than 20000 μ S/cm, and still more particularly higher than 30000 μ S/cm.
In particular, the at least one inorganic salt is selected from the group consisting of nitrates, chloride salts, sulfates, dithionites, bisulfates, sulfites, bisulfites, thiosulfates and mixtures thereof. More particularly, the at least one inorganic salt is selected from the group consisting of sulfates, dithionites, bisulfates, sulfites, bisulfites, thiosulfates, and mixtures thereof.
If desired, the at least one inorganic salt may be selected from alkali or alkaline earth metal nitrates, alkali or alkaline earth metal chloride salts, alkali or alkaline earth metal sulfates, alkali or alkaline earth metal dithionites, alkali or alkaline earth metal bisulfates, alkali or alkaline earth metal sulfites, alkali or alkaline earth metal bisulfites, alkali or alkaline earth metal thiosulfates, and mixtures thereof. Preferably, the at least one inorganic salt may be selected from alkali or alkaline earth metal sulfates, alkali or alkaline earth metal dithionites, alkali or alkaline earth metal bisulfates, alkali or alkaline earth metal sulfites, alkali or alkaline earth metal bisulfites, alkali or alkaline earth metal thiosulfates, and mixtures thereof.
In particular, the at least one inorganic salt may comprise Li, preferably selected from Li+、Na+、K+、Ca2+、Mg2+And combinations thereof and preferably selected from HSO4 -、HSO3 -、SO3 2-、S2O3 2-、S2O4 2-、NO3 -、Cl-And SO4 2-And combinations thereof.
Preferably, the at least one inorganic salt is selected from LiHSO4、LiHSO3、Li2SO3、Li2S2O3、Li2S2O4、LiNO3、LiCl、Li2SO4、NaHSO4、NaHSO3、Na2SO3、Na2S2O3、Na2S2O4、NaNO3、NaCl、NaSO4、KHSO4、KHSO3、K2SO3、K2S2O3、K2S2O4、KNO3、KCl、KSO4、Ca(HSO4)2、Ca(HSO3)2、CaSO3、CaS2O3、CaS2O4、Ca(NO3)2、CaCl2、CaSO4、Mg(HSO4)2、Mg(HSO3)2、MgSO3、MgS2O3、MgS2O4、Mg(NO3)2、MgCl2、MgSO4And mixtures thereof, preferably, the at least one inorganic salt may be selected from Li2S2O4、LiHSO4、LiHSO3、Li2SO4、Li2SO3、Li2S2O3、Na2S2O4、NaHSO4、NaHSO3、Na2SO4、Na2SO3、Na2S2O3、K2S2O4、KHSO4、KHSO3、K2SO4、K2SO3、K2S2O3、CaS2O4、Ca(HSO4)2、Ca(HSO3)2、CaSO4、CaSO3、CaS2O3、MgS2O4、Mg(HSO4)2、Mg(HSO3)2、MgSO4、MgSO3、MgS2O3And mixtures thereof, more preferably, the at least oneThe inorganic salt may be selected from Na2S2O4、NaHSO4、NaHSO3、Na2SO4、Na2SO3、Na2S2O3And mixtures thereof.
In particular, in the precipitation process, during step a1), if the zinc compound is ZnNO3Then the at least one inorganic salt is a nitrate salt.
In particular, in the precipitation process, during step a1), if the zinc compound is ZnCl2Then the at least one inorganic salt is a chloride salt.
In particular, in the precipitation process, during step a1), if the zinc compound is ZnSO4Then the at least one inorganic salt is a sulfate salt. In particular, in the precipitation process, during step a1), if the zinc compound is ZnS2O4Then the at least one inorganic salt is selected from the group consisting of dithionite, sulfate, bisulfate, sulfite, bisulfite, thiosulfate, and mixtures thereof.
In particular, in said precipitation process, during step a1), if the zinc compounds are each independently selected from ZnS2O4、Zn(NO3)2、ZnCl2、ZnSO4Of said Precipitate (PR) provided in step a) may comprise at least two inorganic salts, each independently selected from the group consisting of dithionite, sulphate, bisulphate, sulphite, bisulphite, thiosulphate, nitrate, chloride salts.
More particularly, in said step a1), if the zinc compound is ZnS2O4And if the at least one inorganic base has the formula [ M]x[A]yWherein M is selected from Li+、Na+、K+、Ca2+、Mg2+And combinations thereof, A is selected from O2-、OH-、CO3 2-、HCO3 -And combinations thereof, the coefficients x and y may take values between 1 or 2 or 1 and 2, the values of the coefficients x and y depending on the cationAnd an anion, or when the at least one inorganic base is selected from LiOH, NaOH, KOH, Ca (OH)2、Mg(OH)2、Li2CO3、Na2CO3、K2CO3、CaCO3、MgCO3、LiHCO3、NaHCO3、KHCO3、Ca(HCO3)2、Mg(HCO3)2CaO, MgO, CaO & MgO, and mixtures thereof, the at least one inorganic salt may be selected from Li2S2O4、LiHSO4、LiHSO3、Li2SO4、Li2SO3、Li2S2O3、Na2S2O4、NaHSO4、NaHSO3、Na2SO4、Na2SO3、Na2S2O3、K2S2O4、KHSO4、KHSO3、K2SO4、K2SO3、K2S2O3、CaS2O4、Ca(HSO4)2、Ca(HSO3)2、CaSO4、CaSO3、CaS2O3、MgS2O4、Mg(HSO4)2、Mg(HSO3)2、MgSO4、MgSO3、MgS2O3And mixtures thereof.
Still more particularly, in said step a1), if the zinc compound is ZnS2O4And if the at least one inorganic base is NaOH, the at least one inorganic salt may be selected from Na2S2O4、NaHSO4、NaHSO3、Na2SO4、Na2SO3、Na2S2O3And mixtures thereof.
More particularly, in the step a1), if the zinc compound is Zn (NO)3)2And if the at least one inorganic base has the formula [ M]x[A]yWherein M is selected from Li+、Na+、K+、Ca2+、Mg2+And combinations thereof, A is selected from O2-、OH-、CO3 2-、HCO3 -And combinations thereof, the coefficients x and y may take values between 1 or 2 or 1 and 2, the values of the coefficients x and y depending on the cation and anion, then the at least one inorganic salt may have the formula MNO3(if M is Li)+Or Na+Or K+) Or M (NO)3)2(if M is Ca2+Or Mg2+)。
Still more particularly, in said step a1), if the zinc compound is Zn (NO)3)2And if the at least one inorganic base has the formula [ M]x[A]yWherein M is selected from Li+、Na+、K+、Ca2+、Mg2+And combinations thereof, A is selected from O2-、OH-、CO3 2-、HCO3 -And combinations thereof, the coefficients x and y may take values between 1 or 2 or 1 and 2, the values of the coefficients x and y depending on the cation and anion, or when the at least one inorganic base is selected from CaO, MgO, CaO MgO, LiOH, NaOH, KOH, Ca (OH)2、Mg(OH)2、Li2CO3、Na2CO3、K2CO3、CaCO3、MgCO3、LiHCO3、NaHCO3、KHCO3、Ca(HCO3)2、Mg(HCO3)2And mixtures thereof, the at least one inorganic salt may be selected from LiNO3、NaNO3、KNO3、Ca(NO3)2、Mg(NO3)2And mixtures thereof.
Still more particularly, in said step a1), if the zinc compound is Zn (NO)3)2And if the at least one inorganic base is NaOH, the at least one inorganic salt may be NaNO3。
More particularly, in said step a1), if the zinc compound is ZnCl2And if the at least one inorganic base has the formula [ M]x[A]yWherein M is selected from Li+、Na+、K+、Ca2+、Mg2+And combinations thereof, A is selected from O2-、OH-、CO3 2-、HCO3 -And combinations thereof, the coefficients x and y may take values of 1 or 2 or between 1 and 2, the values of the coefficients x and y depending on the cation and anion, the at least one inorganic salt may have the formula MCl (if M is Li)+Or Na+Or K+) Or MCl2(if M is Ca2+Or Mg2+)。
Still more particularly, in said step a1), if the zinc compound is ZnCl2And if the at least one inorganic base has the formula [ M]x[A]yWherein M is selected from Li+、Na+、K+、Ca2+、Mg2+And combinations thereof, A is selected from O2-、OH-、CO3 2-、HCO3 -And combinations thereof, the coefficients x and y may take values between 1 or 2 or 1 and 2, the values of the coefficients x and y depending on the cation and anion, or when the at least one inorganic base is selected from CaO, MgO, CaO MgO, LiOH, NaOH, KOH, Ca (OH)2、Mg(OH)2、Li2CO3、Na2CO3、K2CO3、CaCO3、MgCO3、LiHCO3、NaHCO3、KHCO3、Ca(HCO3)2、Mg(HCO3)2And mixtures thereof, the at least one inorganic salt is selected from the group consisting of LiCl, NaCl, KCl, CaCl2、MgCl2And mixtures thereof.
Still more particularly, in said step a1), if the zinc compound is ZnCl2And if the at least one inorganic base is NaOH, the at least one inorganic salt may be NaCl.
More particularly, in the step a1), if the zinc compound is ZnSO4And if the at least one inorganic base has the formula [ M]x[A]yWherein M is selected from Li+、Na+、K+、Ca2+、Mg2+And combinations thereof, A is selected from O2-、OH-、CO3 2-、HCO3 -And combinations thereof, the coefficients x and y may take values between 1 or 2 or 1 and 2, the values of the coefficients x and y depending on the cation and anion, then the at least one inorganic salt may have the formula M2SO4(if M is Li)+Or Na+Or K+) Or MSO4(if M is Ca2+Or Mg2+)。
Still more particularly, in said step a1), if the zinc compound is ZnSO4And if the at least one inorganic base has the formula [ M]x[A]yWherein M is selected from Li+、Na+、K+、Ca2+、Mg2+And combinations thereof, A is selected from O2-、OH-、CO3 2-、HCO3 -And combinations thereof, the coefficients x and y may take values between 1 or 2 or 1 and 2, the values of the coefficients x and y depending on the cation and anion, or when the at least one inorganic base is selected from CaO, MgO, CaO MgO, LiOH, NaOH, KOH, Ca (OH)2、Mg(OH)2、Li2CO3、Na2CO3、K2CO3、CaCO3、MgCO3、LiHCO3、NaHCO3、KHCO3、Ca(HCO3)2、Mg(HCO3)2And mixtures thereof, the at least one inorganic salt may be chosen from Li2SO4、Na2SO4、K2SO4、CaSO4、MgSO4And mixtures thereof.
Still more particularly, in said step a1), if the zinc compound is ZnSO4And if the at least one inorganic base is NaOH, the at least one inorganic salt may be NaSO4。
In particular, the at least one inorganic salt will depend on the at least one inorganic base and the zinc compound. For example, if Li is used+、Na+、K+、Ca2+Or Mg2+Of at least one inorganic base, then the at least one inorganic salt produced accordingly comprises Li+、Na+、K+、Ca2+Or Mg2+. In another example, if the zinc compound contains an anion S2O4 2-、Cl-、SO4 2-Or NO3 -The at least one inorganic salt produced accordingly then comprises S2O4 2-(can be at least partially decomposed to HSO4 -、HSO3 -、SO4 2-、SO3 2-、S2O3 2-)、Cl-、SO4 2-Or NO3 -。
In the present invention, the at least one inorganic salt may be dissolved, for example in dissociated form, if it is comprised in the suspension.
In another particular embodiment, the precipitation process may comprise step a 1): zinc compound (preferably selected from Zn (NH)3)4(OH)2、Zn(NH3)4CO3、Zn(NH3)4Cl2And mixtures thereof) with at least one mineral acid (preferably selected from HCl, H2SO4、CO2And mixtures thereof).
Adjustment of the conductivity
The inventors have found that when the conductivity of the Precipitate (PR) is below 3000 mus/cm, microsphere compositions containing zinc compounds which are easily dispersed in the material can be obtained. Furthermore, the dispersions obtained have an improved uniformity of dispersion compared to the prior art. Furthermore, it was observed that the materials obtained by means of these dispersions have improved, in particular reproducible, properties compared with the prior art.
If necessary, adjusting the conductivity of the Precipitate (PR) of the zinc-containing compound obtained in step a) until the conductivity, determined according to the method for determining the conductivity, is below 2500. mu.S/cm, preferably below 2000. mu.S/cm.
The conductivity of the Precipitate (PR) of the zinc oxo compound obtained in step a) can be adjusted, if desired, until the conductivity, determined according to the method for determining the conductivity, is below 1500 μ S/cm, in particular below 1000 μ S/cm, still more in particular below 700 μ S/cm.
Advantageously, the conductivity of the Precipitate (PR) of the zinc-containing compound obtained in step a) is adjusted until the conductivity, determined according to the method for determining the conductivity, is higher than 100. mu.S/cm, preferably higher than 200. mu.S/cm, preferably higher than 300. mu.S/cm, more preferably higher than 400. mu.S/cm. Surprisingly, it was observed that such an adjustment of the conductivity of the Precipitate (PR) makes it possible to obtain a composition of microspheres containing zinc compounds having the advantages described above, while ensuring the economic profitability of the process of the invention. The conductivity of the Precipitate (PR) of the zinc-oxygen-containing compound obtained in step a) may, if desired, be adjusted until the conductivity as determined according to the method for determining the conductivity is 3000-.
In the present invention, said step b) of adjusting the conductivity of said Precipitate (PR) of said zinc-oxygen-containing compound can be carried out by any technique known to the skilled person that is capable of adjusting said conductivity of said Precipitate (PR).
Said step b) of adjusting the conductivity of said Precipitate (PR) can be carried out by washing, dialysis, or by a centrifugation or filtration process or a combination of these techniques.
If desired, said step b) of adjusting the conductivity of said Precipitate (PR) can be carried out by filtration and washing, preferably by simultaneous filtration and washing, more preferably by simultaneous filtration and washing in a filter press.
Advantageously, said step b) of adjusting the conductivity of said Precipitate (PR) is carried out by simultaneous filtration and washing, said washing being carried out with a solvent. Advantageously, the solvent is an organic solvent, an aqueous solution or a mixture thereof. Preferably, the organic solvent may be selected from the group consisting of methanol, ethanol, acetonitrile, DMF, DMSO, and combinations thereof. Preferably, the aqueous solution may be a demineralized aqueous solution or a saline solution.
Advantageously, the temperature of the washing solvent is higher than 20 ℃, preferably higher than 25 ℃, more preferably higher than 30 ℃. It will be appreciated that preferably the temperature of the solvent may be below 50 ℃, more preferably below 45 ℃, still more preferably below 40 ℃.
Advantageously, the temperature of the solvent is from 20 ℃ to 50 ℃, preferably from 30 ℃ to 40 ℃.
Surprisingly, it was observed that if a solvent is added to the Precipitate (PR) at a temperature of 20-50 ℃, preferably 30-40 ℃, the temperature is sufficiently high to enable a rapid and efficient dissolution (compatible with industrial processes) of the inorganic salt contained in the Precipitate (PR) of the zinc-oxygen containing compound and is sufficiently short that the process of the invention is economically profitable. Furthermore, in case the salt is soluble, washing at this temperature is optimal, which avoids precipitation of inorganic salts.
Advantageously, the pH of the solvent is between 6 and 12, preferably between 7 and 11.
In the present invention, the washing may be performed by any technique known to those skilled in the art.
Advantageously, the washing is carried out by filtration, by reflux or dilution, preferably by filtration in a filter press.
In particular, the washing step may comprise adding said solvent and removing said added solvent, in particular in order to reduce the conductivity of said Precipitate (PR); the solvent thus removed comprises the at least one inorganic salt.
Method for determining electrical conductivity
In the present invention, the method of determining electrical conductivity comprises:
step m 1): forming a mixture M1 consisting of the Precipitate (PR) and demineralized water, having a conductivity lower than or equal to 3.5. mu.S/cm, the concentration of the Precipitate (PR) being 100g/L, the total weight of the mixture (M1) being P1,
step m 2): heating to boiling for a sufficient period of time, preferably 10 minutes, to at least partially dissolve the inorganic salts contained in the Precipitate (PR) in the demineralized water of the mixture (M1).
Generally, the heating step M2) results in the evaporation of part of the water in the mixture (M1). In this case, step M3) is carried out, adding a sufficient amount of demineralized water to the mixture (M1) to obtain the total weight P1.
After said step m3), said method of determining electrical conductivity further comprises:
step m 4): decanting the mixture (M1) to obtain a decanted mixture (M2),
step m 5): the conductivity of the decanted mixture (M2) was measured. Said step m5) is repeated five times and is performed using a conductivity meter with internal temperature compensation. The conductivity, expressed at 25 ℃, is the average of five measurements.
The method of determining conductivity further comprises the step of calibrating with a KCl solution of known concentration and conductivity. The method of measuring the conductivity will be described in detail in the examples.
Therefore, in the present invention, it is understood that "the conductivity of the Precipitate (PR)" actually means "the conductivity of the Precipitate (PR) measured according to the method for measuring the conductivity". In fact, the step m2) of heating to boiling enables at least partial dissolution of the inorganic salts contained in the Precipitate (PR). Thus, at least a portion of the inorganic salt is dissolved in the water of the mixture (M1). During step M5), the conductivity is actually measured in the solution in the decanted mixture (M2), and therefore it represents the concentration of the inorganic salts dissolved in the water of the decanted mixture (M2). In particular, in said step a1), when said at least one inorganic base is NaOH, the step of adjusting the conductivity of said Precipitate (PR) of said zinc oxo compound obtained in step a) until the conductivity determined according to the method for determining the conductivity is lower than 3000 μ S/cm may correspond to adjusting the salt concentration of said Precipitate (PR) obtained in step a) until the salt concentration is lower than 2.95% by weight with respect to the total weight of said Precipitate (PR).
In another example, in said step a1), when said at least one inorganic base is NaOH, the step of adjusting the conductivity of said Precipitate (PR) obtained in step a) until the conductivity determined according to the method for determining the conductivity is lower than 2500 μ S/cm, in particular lower than 2000 μ S/cm, more in particular lower than 1500 μ S/cm, still more in particular lower than 1000 μ S/cm, still more in particular lower than 700 μ S/cm may correspond respectively to the step of adjusting the salt concentration of said Precipitate (PR) obtained in step a) until the salt concentration is lower than 2.4%, in particular lower than 1.85%, in particular lower than 1.3%, more in particular lower than 0.75%, still more in particular lower than 0.42% by weight relative to the total weight of said Precipitate (PR).
Alternatively, the step of adjusting the conductivity of the Precipitate (PR) of the zinc oxo compound obtained in step a) until the conductivity measured according to the method for determining the conductivity is higher than 100 μ S/cm, preferably higher than 200 μ S/cm, preferably higher than 300 μ S/cm, more preferably higher than 400 μ S/cm may correspond respectively to the step of adjusting the salt concentration of the Precipitate (PR) obtained in step a) until the salt concentration is higher than 0.1 wt% relative to the total weight of the precipitate.
Microsphere composition containing zinc compound(C)
The zinc compound containing microspheres composition (C) is obtained from the precipitate, the conductivity of which has been adjusted in step b).
In the present invention, the zinc compound containing microsphere composition (C) obtained from the precipitate may be obtained by any technique known in the art. For example, the zinc compound containing microsphere composition (C) obtained from the precipitate may be obtained by drying and/or calcining step C1).
Therefore, advantageously, said step of obtaining said zinc oxo compound microsphere composition (C) may comprise step C1): drying and/or calcining the zinc oxo compound Precipitate (PR).
Preferably, said drying and/or calcining step c1) is carried out by:
an atomization process, or
Heating in a rotary kiln, or
Filtering, forming a filter cake with said Precipitate (PR) of the zinc-oxygen-containing compound, and pumping said filter cake in a hot gas stream, preferably at a temperature of 20 ℃ to 100 ℃, still more preferably 30 ℃ to 70 ℃.
More preferably, said drying and/or calcining step c1) is carried out by an atomization process.
If desired, the drying step c1) is carried out until a Precipitate (PR) is obtained comprising less than 5% by weight of water, preferably less than 2% by weight of water, more preferably less than 1% by weight of water, relative to the total weight of the Precipitate (PR).
Still more preferably, said step b) of adjusting the electrical conductivity of said Precipitate (PR) is performed before said step c) of obtaining said zinc compound containing microsphere composition comprising a drying and/or calcining step c 1).
This has the advantage that if step b) is performed after step c1), an additional drying step is required after step b) of adjusting the conductivity of the Precipitate (PR), which would result in costs. It is therefore economically more advantageous to have said step b) of adjusting the conductivity take place before said drying and/or calcining step c 1).
Still more advantageously, said atomization process comprises injecting the aqueous suspension of said Precipitate (PR) containing zinc compounds obtained in step b) through a nozzle by means of a gas flow, the solid matter content of which is 25-70% by weight relative to the total weight of said aqueous suspension, the pressure inside the atomization chamber being 10-100 bar, preferably 10-50 bar, the entry temperature being 150-800 ℃, the exit temperature being 50-300 ℃. It was observed that when using such an atomisation process, the process of the present invention enables to obtain a zinc compound containing microsphere composition which has, inter alia, improved flowability and which has an improved dispersion homogeneity in the material compared to zinc compound containing powders which are not in the form of microspheres.
Since the zinc compound containing microsphere composition (C) is obtained from the precipitate, the electrical conductivity thereof has been adjusted in step b), the electrical conductivity of the zinc compound containing microsphere composition (C) is below 3000 μ S/cm as determined according to the method for determining electrical conductivity.
Advantageously, said zinc compound containing microsphere composition (C) has an electrical conductivity, measured according to the method for determining electrical conductivity, lower than 2500. mu.S/cm, preferably lower than 2000. mu.S/cm.
If desired, the conductivity of the zinc oxide compound containing microsphere composition (C) as determined according to the method for determining conductivity may preferably be below 1500. mu.S/cm, more preferably below 1400. mu.S/cm, more preferably below 1300. mu.S/cm, still more preferably below 1250. mu.S/cm, still more preferably below 1000. mu.S/cm, still more preferably below 900. mu.S/cm, still more preferably below 800. mu.S/cm, still more particularly below 700. mu.S/cm.
Advantageously, the conductivity of said zinc compound containing microspheres composition (C) as determined according to the method for determining conductivity may be higher than 100. mu.S/cm, preferably higher than 200. mu.S/cm, preferably higher than 300. mu.S/cm, more preferably higher than 400. mu.S/cm.
Advantageously, the conductivity of the zinc oxide compound-containing microsphere composition (C) determined according to the method for determining the conductivity may be 3000-100. mu.S/cm, preferably 2500-400. mu.S/cm, more preferably 2000-400. mu.S/cm, still more preferably 1500-400. mu.S/cm, still more preferably 1000-400. mu.S/cm, still more preferably 700-400. mu.S/cm.
If desired, the zinc compound-containing microsphere composition (C) may comprise at least one inorganic salt, preferably, the at least one inorganic salt is selected from the group consisting of nitrate, chloride salt, sulfate, dithionite, bisulfate, sulfite, bisulfite, thiosulfate, and mixtures thereof. More particularly, the at least one inorganic salt is selected from the group consisting of sulfates, dithionites, bisulfates, sulfites, bisulfites, thiosulfates, and mixtures thereof.
If desired, the at least one inorganic salt may be selected from alkali or alkaline earth metal nitrates, alkali or alkaline earth metal chloride salts, alkali or alkaline earth metal sulfates, alkali or alkaline earth metal dithionites, alkali or alkaline earth metal bisulfates, alkali or alkaline earth metal sulfites, alkali or alkaline earth metal bisulfites, alkali or alkaline earth metal thiosulfates, and mixtures thereof. Preferably, the at least one inorganic salt may be selected from alkali or alkaline earth metal sulfates, alkali or alkaline earth metal dithionites, alkali or alkaline earth metal bisulfates, alkali or alkaline earth metal sulfites, alkali or alkaline earth metal bisulfites, alkali or alkaline earth metal thiosulfates, and mixtures thereof.
In particular, the at least one inorganic salt may comprise Li, preferably selected from Li+、Na+、K+、Ca2+、Mg2+And combinations thereof and preferably selected from HSO4 -、HSO3 -、SO3 2-、S2O3 2-、S2O4 2-、NO3 -、Cl-And SO4 2-And combinations thereof.
Preferably, the at least one inorganic salt is selected from LiHSO4、LiHSO3、Li2SO3、Li2S2O3、Li2S2O4、LiNO3、LiCl、Li2SO4、NaHSO4、NaHSO3、Na2SO3、Na2S2O3、Na2S2O4、NaNO3、NaCl、NaSO4、KHSO4、KHSO3、K2SO3、K2S2O3、K2S2O4、KNO3、KCl、KSO4、Ca(HSO4)2、Ca(HSO3)2、CaSO3、CaS2O3、CaS2O4、Ca(NO3)2、CaCl2、CaSO4、Mg(HSO4)2、Mg(HSO3)2、MgSO3、MgS2O3、MgS2O4、Mg(NO3)2、MgCl2、MgSO4And mixtures thereof, preferably, the at least one inorganic salt may be selected from Li2S2O4、LiHSO4、LiHSO3、Li2SO4、Li2SO3、Li2S2O3、Na2S2O4、NaHSO4、NaHSO3、Na2SO4、Na2SO3、Na2S2O3、K2S2O4、KHSO4、KHSO3、K2SO4、K2SO3、K2S2O3、CaS2O4、Ca(HSO4)2、Ca(HSO3)2、CaSO4、CaSO3、CaS2O3、MgS2O4、Mg(HSO4)2、Mg(HSO3)2、MgSO4、MgSO3、MgS2O3And mixtures thereof, more preferably, the at least one inorganic salt may be selected from Na2S2O4、NaHSO4、NaHSO3、Na2SO4、Na2SO3、Na2S2O3And mixtures thereof.
Advantageously, said at least one inorganic salt may be comprised by said zinc compound containing microsphere composition (C) in a concentration lower than 2.95%, in particular lower than 2.4%, in particular lower than 1.85%, in particular lower than 1.3%, more in particular lower than 0.75%, still more in particular lower than 0.42% by weight relative to the total weight of said composition (C). Advantageously, said at least one inorganic salt may be comprised by said zinc compound containing microsphere composition (C) in a concentration higher than 0.01% by weight with respect to the total weight of said composition (C), preferably in a concentration higher than 0.05% by weight with respect to the total weight of said composition (C), more preferably in a concentration higher than 0.1% by weight with respect to the total weight of said composition (C). Advantageously, said at least one inorganic salt may be comprised by said zinc compound containing microsphere composition (C) in a concentration ranging from 0.01% to 2.95% by weight relative to the total weight of said composition (C), preferably ranging from 0.1% to 2.4% by weight relative to the total weight of said composition (C), more preferably ranging from 0.1% to 1.85% by weight relative to the total weight of said composition (C), more preferably ranging from 0.1% to 1.3% by weight relative to the total weight of said composition (C), more preferably ranging from 0.1% to 0.75% by weight relative to the total weight of said composition (C), more preferably ranging from 0.1% to 0.42% by weight relative to the total weight of said composition (C).
If desired, the zinc compound containing microsphere composition (C) may comprise less than 5% by weight of water, preferably less than 2% by weight of water, more preferably less than 1% by weight of water, relative to the total weight of the composition (C).
In the present invention, the term "microsphere" may be defined as a particle consisting of aggregated particles. It has been observed that when the microspheres are composed of smaller aggregated particles, the microspheres may disintegrate as they are dispersed in the material or in the powder or in an aqueous suspension.
Advantageously, the microspheres have a D as determined by laser granulometry in aqueous solution50Is 50 μm to 200. mu.m, preferably 80 to 170. mu.m. Advantageously, the microspheres have a D as determined by laser granulometry in aqueous solution10Is 1 μm to 80 μm, preferably 8 to 70 μm. Advantageously, the microspheres have a D as determined by laser granulometry in aqueous solution90Is 200 μm to 300 μm, preferably 210 μm to 260 μm. In the present invention, symbol DXRepresents the diameter, expressed in μm, wherein X volume% of the total volume of the particles determined consists of the smaller particles. It was observed that when the microspheres had D as described above50、D10And D90When the size distribution of the microspheres is narrow. This allows for a better control of the properties of the zinc compound containing microsphere composition, which also allows for a better control of the distribution properties of the composition in a material, e.g. in a polymeric material or an animal nutrition composition.
Advantageously, the microspheres are each composed of aggregated particles, D thereof50All of them are 1 to 20 μm, more preferably1-10 μm, still more preferably 1-5 μm or even 1-3 μm.
Advantageously, the Flodex index of the microspheres is below 15, preferably below 10. The Flodex index is a test that enables determination of powder flowability. The instrument used is a container into which the powder to be tested is placed, the bottom of which consists of a septum with a calibrated opening through which it is observed whether the powder has flowed. By successive tests, the minimum diameter of the free flow of the powder can be determined. This diameter (in millimeters) corresponds to the Flodex index.
In general, D10And/or D50And/or D90And/or the characteristics of the Flodex index can be obtained by any means known to the person skilled in the art, for example by said step of drying and/or calcining said Precipitate (PR).
The microspheres may also have a specific surface area BET of less than 150m2G, advantageously less than 100m2A/g, preferably less than 50m2(ii) in terms of/g. The specific surface area BET is determined by the adsorption pressure method using a helium/nitrogen (70/30) mixture after degassing at 150 ℃ for at least 1 hour and is calculated according to the BET (Brunauer-Emmett-Taylor) method.
In a particular embodiment, the electrical conductivity of the zinc oxo compound Precipitate (PR) provided in step a), preferably the electrical conductivity as determined according to the method for determining electrical conductivity, is higher than 3000 μ S/cm. In this particular embodiment, the zinc oxo compound Precipitate (PR) is in the form of a suspension (S1) in an aqueous medium, comprising a weight percentage of zinc oxo compound precipitate comprised between 8% and 15% by weight with respect to the total weight of the suspension (S1).
In this particular embodiment, said step a) of providing a Precipitate (PR) of an oxygen-containing zinc compound comprises a precipitation process in water, said precipitation process comprising step a 1): ZnS2O4Reaction between a compound and the inorganic base NaOH. The precipitation process can produce a precipitate consisting of Zn (OH)2And ZnO.
Inorganic salts are produced during this precipitation process, and the suspension (S1) therefore also contains at least one inorganic salt, which may optionally beFrom Na2S2O4、NaHSO4、NaHSO3、Na2SO4、Na2SO3、Na2S2O3And mixtures thereof. The conductivity of the Precipitate (PR) determined according to the method for determining the conductivity is higher than 3000. mu.S/cm.
In this embodiment, the conductivity of the Precipitate (PR) obtained in step a) is adjusted in step b) until the conductivity, determined according to the method for determining the conductivity, is below 3000 μ S/cm. Said step b) of adjusting the conductivity of said Precipitate (PR) is carried out by simultaneous washing and filtration with an aqueous solution in a filter press.
In this embodiment, thereafter, the method comprises the step of obtaining the zinc compound containing microsphere composition (C) comprising step C1): drying and calcining the zinc oxo compound Precipitate (PR) by an atomization process. In this embodiment, the atomization process comprises injecting the aqueous suspension of the Precipitate (PR) containing zinc compounds obtained in step b) through a nozzle with a gas flow having a solid matter content of 25 to 70% by weight relative to the total weight of the aqueous suspension, a pressure in the atomization chamber of 10 to 100 bar, preferably 10 to 50 bar, an entry temperature of 150 ℃ to 800 ℃ and an exit temperature of 50 ℃ to 300 ℃. After the atomization process, a zinc compound-containing microsphere composition (C) was obtained, which had an electrical conductivity of 3000 and 100. mu.S/cm as determined according to the method for determining electrical conductivity. In this embodiment, the zinc compound containing microsphere composition (C) comprises less than 1% by weight of water relative to the total weight of the composition (C). In this embodiment, the composition (C) comprises Na2S2O4、NaHSO4、NaHSO3、Na2SO4、Na2SO3、Na2S2O3And mixtures thereof. The concentration of said inorganic salt is between 0.01% and 2.95% by weight relative to the total weight of the composition (C). In this embodiment, it is observed that the microspheres of composition (C) are composed of smaller aggregated particles, which will disintegrate when they are dispersed in a material or in a powder or in an aqueous suspension.
Advantageously, the microspheres have a D as determined by laser granulometry in aqueous solution50Is 80-170 μm. Further, the microspheres have a D value determined by a laser particle sizer in an aqueous solution10D, measured in aqueous solution by means of a laser particle sizer, of between 8 and 70 μm90Is 200-300 μm. Furthermore, the microspheres are each composed of aggregated particles, D thereof50Is 1-5 μm. The Flodex index of the microspheres is below 10. Further, the microspheres have a specific surface area BET of less than 50m2/g。
The respective preferred, advantageous or particular variants of the individual embodiments can be combined with the respective preferred, advantageous or particular variants of the individual embodiments.
It will be understood that the present invention is by no means limited to the embodiments described above, but that many modifications may be made thereto without departing from the scope of the appended claims.
Examples1
Synthesis of ZnO
In the presence of water, SO2Reacting with metallic zinc in a vessel to produce ZnS2O4. Metallic zinc and SO2The addition is carried out in stoichiometric amounts.
Thereafter, NaOH was added to the vessel to prepare a solution containing ZnO and Zn (OH)2The Precipitate (PR) of (1). Na is also formed as a by-product2S2O4It remains in the aqueous phase. Na (Na)2S2O4It can also degrade and form other substances, such as: NaHSO4、NaHSO3、Na2SO4、Na2SO3、Na2S2O3。
Thereafter, the Precipitate (PR) is filtered in a filter press to form a filter cake and recovered.
After the filtration, water was added to wash the filter cake, and the filter cake was filtered in a filter press, thereby obtaining a Precipitate (PR) in the filter cake, which has an electric conductivity of 1130. mu.S/cm as measured by the method for measuring an electric conductivity.
The method for determining the conductivity is as follows: 10g of a mixture comprising ZnO and Zn (OH)2And form a filterCake Precipitate (PR) was mixed with 90g of demineralized water and the resulting mixture was stirred. At the same time, the obtained mixture was boiled for 10 minutes, after which it was cooled. To the obtained mixture was added demineralized water to make it 100g in weight. The mixture obtained in this way is then decanted.
Thereafter, the temperature of the mixture was measured, and the conductivity meter was set to this temperature. The measured conductivity is expressed in 25 ℃ and the average is calculated in five measurements.
Each series of conductivity measurements is preceded by a calibration to prevent deviations due to, for example, electrode aging.
For calibration, the conductivity of the KCl solution was determined at 25 deg.C (0.1N or 1N, depending on the measurement range to be used). If necessary, a potentiometer of the battery parameters is set to adjust the conductivity values to:
KCl 0.1N: 12.88 microsiemens/cm,
KCl 1N: 111.8 microsiemens/cm.
The conductivity meter used for the conductivity measurement was a conductivity meter with internal temperature compensation (compensation factor 2.2%/deg.c).
Comprising ZnO and Zn (OH)2The percentage of salt in the cake Precipitate (PR) of (a) was 0.42 wt% with respect to the total weight of the cake Precipitate (PR), after which it was determined by the method of determining the weight percentage of salt as follows: 10.00g of a solution containing ZnO and Zn (OH)2The cake Precipitate (PR) of (1) was mixed with 100ml of demineralized water and the mixture obtained was heated to boiling for 10 minutes. After cooling, demineralised water at 20 ℃ was added to bring the volume of the mixture to 200 ml. The mixture obtained in this way was homogenized and filtered through 2 dry-pleated filters.
Filtration was repeated as many times as necessary until a clear filtrate was obtained. After this time, 50ml of clear filtrate was transferred to tared capsules. The whole was evaporated to dryness at 105 ℃ until a dry residue was obtained in the capsules, cooled until constant weight.
Thereafter, the capsules were reweighed with a 1mg balance. Salts that are soluble at elevated temperatures are represented by the formula: salt (%) -400R/P, where P (g) is the test sample and R (g) is the weight of the dry residue contained in the capsules.
Then, ZnO and Zn (OH) are added2And the washed cake Precipitate (PR) was injected into the atomization apparatus shown in fig. 1.
The atomising device comprises a cylindrical atomising chamber 1 having a conical bottom in which a hot gas stream flows. The inflow air passes through the filter 2 and the burner 3 in advance to be preheated and enters the upper portion of the atomizing chamber 1 through the fin distributor 4 at a temperature of 550 c. The air flow rate range is 700N m3/h。
Comprising ZnO and Zn (OH)2Is supplied by a pump and through the duct 5, in the form of an aqueous suspension comprising 40-45% by weight of Precipitate (PR) relative to the total weight of the suspension, prepared in a mixing disperser 12. The suspension is introduced through a nozzle 6 arranged in the centre of the chamber 1 at a pressure of 20-30 bar at a flow rate of about 80-100 litres per hour. The suspension is sprayed (atomized) in a hot gas stream and allowed to dry within a few seconds.
The ZnO particles obtained fall to the lower part of the chamber where they are collected and emptied through a valve 7, for example immediately bagged. At this level, 85-90% of the zinc oxide (free flowing) was collected in microsphere form, which included less than 0.5% residual water. Under the suction of the fan 9, the finest particles are drawn away in the air flowing out of the room through the duct 8. They are then separated from the outflowing air, for example in a vortex 10, and recovered through a valve 11 so as to be able to be recovered for the preparation of a suspension in a disperser 12. Therefore, about 10 to 15% by weight of fine powder (non-aggregated powder in the form of microspheres) is separated from the microspheres containing an oxygen zinc compound of the present invention and recovered. The obtained oxygen-containing zinc compound is ZnO and Zn (OH)2A mixture of (a).
The air is filtered through a bag filter 13 before leaving the circuit. Particles that may be recovered on the rod are collected at valve 14, which may also be recovered to disperser 12 (along the dashed line).
The nozzles 6 used may be sprinklers (Delavan SDX type), which in the present example have a swirl chamber with an outlet diameter of 1.62mm, or two-fluid nozzles, in which the energy is provided by compressed air, a very high degree of spray mist being obtained, and thus a finer powder being obtained.
The obtained microspheres containing the zinc compound with oxygen are characterized.
TABLE 1
The microspheres actually consist of smaller aggregated particles. In order to be able to collapse the microspheres, they were subjected to sonication. D of the smaller particles forming the microspheres50It was 2.6 μm.
The electrical conductivity is measured by a method for measuring electrical conductivity.
Salt concentration is determined by measuring the weight percent salt.
D10、D50And D90Measured in the aqueous phase by a laser particle sizer.
The specific surface area of the invention is determined by degassing at 150 ℃ under vacuum for at least 1 hour before subjecting to He-N2(70/30) the adsorption pressure of the mixture is measured and calculated according to the BET method.
The Flodex index is a test that enables determination of powder flowability. The instrument used is a container into which the powder to be tested is placed, the bottom of which consists of a septum with a calibrated opening through which it is observed whether the powder has flowed. By successive tests, the minimum diameter of the free flow of the powder can be determined. This diameter (in millimeters) corresponds to the Flodex index.
Dispersion in polymers
In the drum mixer, the natural rubber-based compound was first heated for 2 minutes, after which the zinc oxide compound of the present invention having the characteristics of table 1 and stearic acid were simultaneously introduced. Stirring was carried out for 5 minutes during which time the other ingredients shown in table 2 were added.
The compositions and amounts implemented are as follows:
| components | Portions are |
| |
80 |
| BR1220L | 20 |
| N347 | 55 |
| |
7 |
| |
2 |
| TMQ | 1 |
| CBS | 0.8 |
| Sulfur | 2.3 |
| Stearic acid | 2.5 |
| ZnO of the invention | 2.5 |
Wherein the content of the first and second substances,
TSR10 technical grade rubber (TSR) (natural rubber),
BR 1220L ═ high cis polybutadiene rubber,
n347 ═ carbon black N347,
s Napht oil is naphthenic oil,
6ppd ═ N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine (antioxidant and antiozonant),
TMQ ═ 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer (antioxidant),
CBS ═ N-cyclohexyl-2-benzothiazole sulfonamide (accelerator).
The dispersions obtained have a very high homogeneity. The homogeneity of the dispersion means that the zinc density in the final mixture is uniform. In the case of vulcanization, this is reflected in a flow control curve that is fairly close to or overlapping or nearly overlapping.
The dispersion obtained was controlled on an MDR2000 rheometer at 150 ℃ according to ASTM D2084-17 Standard test method for rubber Properties-vulcanization Using an Oscillating disc curometer ". Rheological measurements were carried out under the same conditions for the dispersions obtained according to the method of "example 1". The results of the three measurements are shown in FIG. 2, and represent the measured torque S' (dNm) as a function of time (minutes). The rheological curves are quite close to each other, showing the same or very close characteristics for each measurement. Therefore, the zinc compound composition (C) containing oxygen of the present invention can be easily dispersed in a polymer material, thereby obtaining improved dispersion uniformity.
Comparative example 1
In the drum mixer, the natural rubber-based compound is first heated for 2 minutes, after which a zinc oxide compound having an electrical conductivity higher than 3000. mu.S/cm, as measured according to the method for measuring electrical conductivity, and stearic acid are simultaneously introduced. Stirring was carried out for 5 minutes during which time the other ingredients shown in table 2 were added.
The compositions and amounts implemented are as follows:
| components | Portions are |
| |
80 |
| BR1220L | 20 |
| N347 | 55 |
| |
7 |
| |
2 |
| TMQ | 1 |
| CBS | 0.8 |
| Sulfur | 2.3 |
| Stearic acid | 2.5 |
| ZnO with conductivity higher than 3000 mu S/cm | 2.5 |
The dispersions obtained have a very low homogeneity, which is reflected on the rheology control curves, which are far apart from each other.
The dispersion obtained was controlled on an MDR2000 rheometer at 150 ℃ according to ASTM D2084-17 Standard test method for rubber Properties-vulcanization Using an Oscillating disc curometer ". Rheological measurements were carried out under the same conditions for the dispersions obtained according to the method of "comparative example 1". The results of the three measurements are shown in FIG. 3, which shows the relationship between the measured torque S' (dNm) and the time (minutes). The rheological curves are far apart from each other, showing that different properties are obtained for each measurement. This is a result of the rather low uniformity.
Claims (34)
1. A method of preparing a microsphere composition (C) comprising a zinc oxide compound, comprising the steps of:
a) providing a Precipitate (PR) of an oxygen-containing zinc compound, preferably in the form of a suspension,
b) adjusting the conductivity of the Precipitate (PR) obtained in step a) until the conductivity, determined according to the method for determining the conductivity, is lower than 3000. mu.S/cm,
c) obtaining the zinc compound containing microsphere composition (C) from the Precipitate (PR); the microspheres are particles, which are composed of smaller aggregated particles.
2. The method according to claim 1, wherein the conductivity of the Precipitate (PR) of the zinc-oxygen-containing compound obtained in step a) is adjusted until the conductivity, as determined according to the method for determining the conductivity, is below 2500 μ S/cm.
3. The method of any of the preceding claims, wherein the conductivity of the Precipitate (PR) of the zinc-oxygen-containing compound obtained in step a) is adjusted until the conductivity, as determined according to the method for determining the conductivity, is below 2000 μ S/cm.
4. The method of any of the preceding claims, wherein the conductivity of the Precipitate (PR) of the zinc-oxygen-containing compound obtained in step a) is adjusted until the conductivity, as determined according to the method for determining the conductivity, is below 1500 μ S/cm.
5. The method of any of the preceding claims, wherein the conductivity of the Precipitate (PR) of the zinc-oxygen-containing compound obtained in step a) is adjusted until the conductivity, as determined according to the method for determining the conductivity, is below 1000 μ S/cm.
6. The method of any of the preceding claims, wherein the conductivity of the Precipitate (PR) of the zinc-oxygen-containing compound obtained in step a) is adjusted until the conductivity, as determined according to the method for determining the conductivity, is below 700 μ S/cm.
7. The method of any of the preceding claims, wherein the conductivity of the Precipitate (PR) of the zinc-oxygen-containing compound obtained in step a) is adjusted until the conductivity, as determined according to the method for determining the conductivity, is below 400 μ S/cm.
8. The method according to any one of the preceding claims, wherein the Precipitate (PR) provided in step a) comprises at least one inorganic salt.
9. The method of claim 8, wherein the at least one inorganic salt is selected from the group consisting of nitrates, chloride salts, sulfates, dithionites, bisulfates, sulfites, bisulfites, thiosulfates, and mixtures thereof.
10. The method according to any one of the preceding claims, wherein the step b) of adjusting the conductivity of the Precipitate (PR) is carried out by washing, dialysis, or by a centrifugation or filtration process or a combination of these techniques.
11. The method of any one of the preceding claims, wherein said step a) of providing a Precipitate (PR) of an oxygen-containing zinc compound comprises a precipitation process in a solvent, preferably in water.
12. The method of claim 11, wherein the precipitation process comprises step a 1): zinc compounds, preferably selected from ZnS2O4、Zn(NO3)2、ZnCl2、ZnSO4And mixtures thereof with at least one inorganic base.
13. The method of claim 12, wherein the at least one inorganic base comprises at least one member selected from the group consisting of Li+、Na+、K+、Ca2+、Mg2+And combinations thereof, at least one alkali or alkaline earth metal cation M and at least one metal selected from O2-、OH-、CO3 2-、HCO3 -And combinations thereof.
14. The method of any of the preceding claims, wherein the step of obtaining the zinc compound containing microsphere composition (C) may comprise step C1): drying and/or calcining the zinc oxo compound Precipitate (PR).
15. The process according to claim 14, wherein the drying and/or calcining step c1) is carried out by:
an atomization process, or
Heating in a rotary kiln, or
Filtering, forming a filter cake with said Precipitate (PR) of the zinc-oxygen-containing compound, and pumping said filter cake in a hot gas stream, preferably at a temperature of 20 ℃ to 100 ℃, still more preferably 30 ℃ to 70 ℃.
16. A zinc compound-containing microsphere composition (C) having an electrical conductivity of less than 3000 μ S/cm as measured according to the method for measuring electrical conductivity; the microspheres are particles, which are composed of smaller aggregated particles.
17. Composition (C) according to claim 16, having a conductivity lower than 2500 μ S/cm, measured according to the method for measuring conductivity.
18. A composition (C) according to claim 16 or claim 17, having an electrical conductivity, measured according to the method for measuring electrical conductivity, lower than 2000 μ S/cm.
19. Composition (C) according to any one of claims 16 to 18, having a conductivity lower than 1500 μ S/cm, determined according to the method for determining the conductivity.
20. Composition (C) according to any one of claims 16 to 19, having a conductivity lower than 1000 μ S/cm, determined according to the method for determining the conductivity.
21. Composition (C) according to any one of claims 16 to 20, having a conductivity lower than 700 μ S/cm, determined according to the method for determining the conductivity.
22. Composition (C) according to any one of claims 16 to 21, having a conductivity higher than 100 μ S/cm, preferably higher than 200 μ S/cm, more preferably higher than 300 μ S/cm, more preferably higher than 400 μ S/cm, determined according to the method for determining conductivity.
23. Composition (C) according to any one of claims 16 to 22, having a conductivity higher than 100 μ S/cm, determined according to the method for determining the conductivity.
24. The composition (C) according to any one of claims 16 to 23, comprising at least one inorganic salt.
25. The composition (C) according to claim 24, wherein said at least one inorganic salt is chosen from nitrates, chloride salts, sulfates, dithionites, bisulfates, sulfites, bisulfites, thiosulfates and mixtures thereof.
26. Composition (C) according to any one of claims 16 to 25, comprising said at least one inorganic salt in a concentration lower than 2.95%, in particular lower than 2.4%, in particular lower than 1.85%, in particular lower than 1.3%, more in particular lower than 0.75%, still more in particular lower than 0.42% by weight relative to the total weight of the composition (C).
27. Composition (C) according to any one of claims 16 to 26, wherein the microspheres have a D determined by laser granulometry in aqueous solution50Is 50 μm to 200. mu.m, preferably 80 to 170. mu.m.
28. Composition (C) according to any one of claims 16 to 27, wherein the microspheres have a D determined by laser granulometry in aqueous solution10Is 1 μm to 80 μm, preferably 8 to 70 μm.
29. Composition (C) according to any one of claims 16 to 28, said microspheres having a D determined by laser granulometry in aqueous solution90Is 200 μm to 300 μm, preferably 210 μm to 260 μm.
30. Composition (C) according to any one of claims 16 to 29, wherein the microspheres each consist of aggregated particles, D thereof50Each 1-20 μm, more preferably 1-10 μm, still more preferably 1-5 μm or even 1-3 μm.
31. Composition (C) according to any one of claims 16 to 30, wherein the microspheres have a specific surface area BET of less than 150m2G, advantageously less than 100m2A/g, preferably less than 50m2/g。
32. The composition (C) according to any one of claims 16 to 31, obtained by the process according to any one of claims 1 to 15.
33. Use of the composition (C) according to any one of claims 16 to 31 or obtained by the process according to any one of claims 1 to 15 in a vulcanization process.
34. Use of the composition (C) according to any one of claims 16 to 31 or obtained by the process according to any one of claims 1 to 15 in a material selected from the group consisting of a nutritional composition, a polymeric material, and mixtures thereof.
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| BEBE2019/5499 | 2019-07-31 | ||
| BE20195499A BE1027472B1 (en) | 2019-07-31 | 2019-07-31 | Process for preparing microspherules of an oxygenated zinc compound |
| PCT/EP2020/071486 WO2021019002A1 (en) | 2019-07-31 | 2020-07-30 | Method for preparing microspherules of an oxygenated zinc compound |
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|---|---|
| EP (1) | EP4003914A1 (en) |
| CN (1) | CN114423713A (en) |
| BE (1) | BE1027472B1 (en) |
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|---|---|---|---|---|
| US5312614A (en) * | 1989-06-21 | 1994-05-17 | Metallgesellschaft Aktiengesellschaft | Method for producing white electrically conductive zinc oxide |
| WO1994025397A1 (en) * | 1993-04-28 | 1994-11-10 | Mamoun Muhammed | Elongate zinc oxide particles and a method for the production thereof |
| CN1684909A (en) * | 2002-09-25 | 2005-10-19 | 列日氧化物工业股份有限公司 | Zinc oxide in the form of an improved flow powder, method for the production and use thereof in polymers |
| US20110152433A1 (en) * | 2008-08-13 | 2011-06-23 | Basf Se | Process for the preparation of nanoparticulate zinc oxide |
| CN102603285A (en) * | 2012-02-23 | 2012-07-25 | 西北稀有金属材料研究院 | Preparation method of zinc oxide-based tubular rotary target material |
| CN103193262A (en) * | 2013-04-09 | 2013-07-10 | 桂林电子科技大学 | Indium-gallium-zinc oxide powder and preparation method of ceramic target thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU6627394A (en) * | 1993-04-28 | 1994-11-21 | Mark Mitchnick | Conductive polymers |
| GB9616978D0 (en) * | 1996-08-13 | 1996-09-25 | Tioxide Specialties Ltd | Zinc oxide dispersions |
| KR101645056B1 (en) * | 2009-04-22 | 2016-08-02 | 교와 가가꾸고교 가부시키가이샤 | Columnar zinc oxide particles and method for producing same |
-
2019
- 2019-07-31 BE BE20195499A patent/BE1027472B1/en active IP Right Grant
-
2020
- 2020-07-30 EP EP20746222.7A patent/EP4003914A1/en active Pending
- 2020-07-30 CA CA3145847A patent/CA3145847A1/en active Pending
- 2020-07-30 WO PCT/EP2020/071486 patent/WO2021019002A1/en unknown
- 2020-07-30 CN CN202080049549.3A patent/CN114423713A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5312614A (en) * | 1989-06-21 | 1994-05-17 | Metallgesellschaft Aktiengesellschaft | Method for producing white electrically conductive zinc oxide |
| WO1994025397A1 (en) * | 1993-04-28 | 1994-11-10 | Mamoun Muhammed | Elongate zinc oxide particles and a method for the production thereof |
| CN1684909A (en) * | 2002-09-25 | 2005-10-19 | 列日氧化物工业股份有限公司 | Zinc oxide in the form of an improved flow powder, method for the production and use thereof in polymers |
| US20110152433A1 (en) * | 2008-08-13 | 2011-06-23 | Basf Se | Process for the preparation of nanoparticulate zinc oxide |
| CN102603285A (en) * | 2012-02-23 | 2012-07-25 | 西北稀有金属材料研究院 | Preparation method of zinc oxide-based tubular rotary target material |
| CN103193262A (en) * | 2013-04-09 | 2013-07-10 | 桂林电子科技大学 | Indium-gallium-zinc oxide powder and preparation method of ceramic target thereof |
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| BE1027472A1 (en) | 2021-02-25 |
| EP4003914A1 (en) | 2022-06-01 |
| WO2021019002A1 (en) | 2021-02-04 |
| CA3145847A1 (en) | 2021-02-04 |
| BE1027472B1 (en) | 2021-03-03 |
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