JPH0694382B2 - How to protect glass equipment from hydrofluoric acid - Google Patents
How to protect glass equipment from hydrofluoric acidInfo
- Publication number
- JPH0694382B2 JPH0694382B2 JP61075599A JP7559986A JPH0694382B2 JP H0694382 B2 JPH0694382 B2 JP H0694382B2 JP 61075599 A JP61075599 A JP 61075599A JP 7559986 A JP7559986 A JP 7559986A JP H0694382 B2 JPH0694382 B2 JP H0694382B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- hydrofluoric acid
- acid
- test piece
- added
- 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.)
- Expired - Fee Related
Links
- 239000011521 glass Substances 0.000 title claims description 43
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000010936 titanium Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- -1 tantalum Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910007926 ZrCl Inorganic materials 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- PWKNBLFSJAVFAB-UHFFFAOYSA-N 1-fluoro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1F PWKNBLFSJAVFAB-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- SKOWZLGOFVSKLB-UHFFFAOYSA-N hypodiboric acid Chemical compound OB(O)B(O)O SKOWZLGOFVSKLB-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000004812 organic fluorine compounds Chemical class 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- MTBYTWZDRVOMBR-UHFFFAOYSA-N 1,2,3,4-tetrachloro-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=C(Cl)C(Cl)=C1Cl MTBYTWZDRVOMBR-UHFFFAOYSA-N 0.000 description 1
- OWALCRQILZGQDH-UHFFFAOYSA-N 1,3-dichloro-2,4-difluoro-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=C(F)C(Cl)=C1F OWALCRQILZGQDH-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- NNMBNYHMJRJUBC-UHFFFAOYSA-N 1-bromo-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(Br)=C1 NNMBNYHMJRJUBC-UHFFFAOYSA-N 0.000 description 1
- VIPWUFMFHBIKQI-UHFFFAOYSA-N 1-fluoro-4-methoxybenzene Chemical compound COC1=CC=C(F)C=C1 VIPWUFMFHBIKQI-UHFFFAOYSA-N 0.000 description 1
- FBRJYBGLCHWYOE-UHFFFAOYSA-N 2-(trifluoromethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(F)(F)F FBRJYBGLCHWYOE-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 description 1
- ZUGAOYSWHHGDJY-UHFFFAOYSA-K 5-hydroxy-2,8,9-trioxa-1-aluminabicyclo[3.3.2]decane-3,7,10-trione Chemical compound [Al+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZUGAOYSWHHGDJY-UHFFFAOYSA-K 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910016943 AlZn Inorganic materials 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910007880 ZrAl Inorganic materials 0.000 description 1
- 229910006501 ZrSiO Inorganic materials 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- KMJRBSYFFVNPPK-UHFFFAOYSA-K aluminum;dodecanoate Chemical compound [Al+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O KMJRBSYFFVNPPK-UHFFFAOYSA-K 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N benzoic acid ethyl ester Natural products CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 1
- ZCLVNIZJEKLGFA-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxalumolan-2-yl) oxalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZCLVNIZJEKLGFA-UHFFFAOYSA-H 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005796 dehydrofluorination reaction Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- MGNPLIACIXIYJE-UHFFFAOYSA-N n-fluoroaniline Chemical compound FNC1=CC=CC=C1 MGNPLIACIXIYJE-UHFFFAOYSA-N 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- ZZIZZTHXZRDOFM-XFULWGLBSA-N tamsulosin hydrochloride Chemical compound [H+].[Cl-].CCOC1=CC=CC=C1OCCN[C@H](C)CC1=CC=C(OC)C(S(N)(=O)=O)=C1 ZZIZZTHXZRDOFM-XFULWGLBSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はフッ酸が存在若しくは発生する化学反応又は処
理工程でフッ酸の腐食作用からガラス製装置を保護し、
工業的使用を可能とすることにある。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention protects a glass device from the corrosive action of hydrofluoric acid in the chemical reaction or treatment process in which hydrofluoric acid is present or generated,
It is to enable industrial use.
ガラス製の材質からなる化学反応装置、処理装置槽等で
フッ酸が存在若しくは発生する場合、フッ酸の腐食作用
からガラスを保護する有効な手段は知られていない。し
かし従来、この種の方法として特公昭57-26247にはトリ
フロロメチルベンゼンの臭素化の際にシリカゲルを添加
すると装置の腐食が防止できるという記載がある。この
方法ではガラスが長期的に使用出来る程確かな効果がな
く使用には問題がある。その原因とも関係するが微量で
も系内に水が存在すると、ガラスの腐食はいっそう激し
くなる。USP.4401623には全く同様の系で塩化カルシウ
ムを添加する事を記述しているが、これも同様であり、
工業的に実施する程満足いく効果を得ることは出来な
い。When hydrofluoric acid is present or generated in a chemical reactor, a processing apparatus tank or the like made of a glass material, an effective means for protecting glass from the corrosive action of hydrofluoric acid is not known. However, conventionally, as a method of this kind, Japanese Patent Publication No. 57-26247 describes that corrosion of the equipment can be prevented by adding silica gel during the bromination of trifluoromethylbenzene. In this method, the glass is not effective enough to be used for a long period of time and there is a problem in using it. Although related to the cause, the presence of water in the system even in a small amount makes the glass more corrosive. USP.4401623 describes adding calcium chloride in a completely similar system, but this is also the same,
It is not possible to obtain a satisfactory effect as industrially implemented.
近年益々フッ素系有機化合物が医薬、農薬、高分子材料
等に用いられるようになった。そして、それら有機化合
物の製造技術の重要性も増大している。ある種の有機フ
ッ素化合物は取り扱う上で一部脱フッ化水素反応を起こ
し、発生したフッ酸は製造設備のガラス部分を腐食する
ことが知られている。例えばフロロアニリン類の酸性ジ
アゾ分解反応、トリフロロメチル基を有するエステル類
の加水分解反応、トリフロロメチル基又はフッ素原子を
有する化合物のニトロ化、ハロゲン化、スルホン化反
応、フッ素含有のアニゾール、フェネトール等の臭化水
素水による脱アルキル化反応等において知られている。
又、不安定なフッ素原子を含むＯ−フロロニトロベンゼ
ン、ポリハロゲン化されたＯ−ニトロフロロベンゼン等
に含まれる水を脱水したり有機溶剤中濃縮したりする工
程においても然りである。In recent years, fluorinated organic compounds have been increasingly used in medicines, agricultural chemicals, polymer materials and the like. And the importance of the manufacturing technology of these organic compounds is also increasing. It is known that some kinds of organic fluorine compounds cause a dehydrofluorination reaction in handling, and the generated hydrofluoric acid corrodes the glass portion of the manufacturing facility. For example, acidic diazo decomposition reaction of fluoroanilines, hydrolysis reaction of esters having trifluoromethyl group, nitration, halogenation, sulfonation reaction of compounds having trifluoromethyl group or fluorine atom, fluorine-containing anisole, phenetole Are known in the dealkylation reaction with hydrobromide water.
This is also the case in the process of dehydrating water contained in O-fluoronitrobenzene containing an unstable fluorine atom, polyhalogenated O-nitrofluorobenzene or the like, or concentrating it in an organic solvent.
ところで化学工業においては耐薬品性の化学装置の材質
として頻繁に用いられるのはガラスである。通常ガラス
はガラスライニングの形で使用されることが多い。しか
しガラスの最も強力な腐食剤はフッ酸である。したがっ
てフッ酸が存在又は発生するような条件下ではガラス材
を使いこなすことは困難である。そのためタンタル、モ
ネル、ハーステロイ系合金などの高価な金属又は合金を
使用しなければならない。したがって、化学工業におい
てフッ酸の腐食作用からガラスを保護し使いこなすこと
は長年の念願であった。本発明者らは検討を重ねた結
果、フッ酸が存在しても何んら問題なくガラス製材料か
らなる製造設備の使用を可能にした。By the way, in the chemical industry, glass is often used as a material for chemical-resistant chemical devices. Usually glass is often used in the form of glass linings. But the most powerful corrosive agent for glass is hydrofluoric acid. Therefore, it is difficult to use the glass material under the condition that hydrofluoric acid exists or is generated. Therefore, expensive metals or alloys such as tantalum, monel, and Hastelloy alloys must be used. Therefore, it has been a long-standing desire in the chemical industry to protect and use glass from the corrosive action of hydrofluoric acid. As a result of repeated studies by the present inventors, it has become possible to use a manufacturing facility made of a glass material without any problem even in the presence of hydrofluoric acid.
本発明は周期律長IIIA、IVB族の元素又はそれらの化合
物（フッ化物を除く）を媒体中に室温〜190℃の温度範
囲で存在させることを特徴とするフッ酸の腐食作用から
ガラス製装置を保護する方法に関するものである。さら
に詳しく述べるならば、例えばアルコール、エステル、
ハロゲン化炭化水素、エーテル、脂肪族炭化水素、ケト
ン、芳香族炭化水素、脂肪族アミン、芳香族アミン、脂
肪族カルボン酸、芳香族カルボン酸、フェノール類、非
プロトン性極性溶媒といった有機媒体中或いは水、硫
酸、塩酸、臭化水素酸、ヨウ化水素酸、硝酸、クロルス
ルホン酸、リン酸といった無機媒体或いはそれらの混合
媒体中でフッ酸が存在又は発生する化学反応又は処理工
程でフッ酸からガラス製装置を保護するために周期律表
IIIA、IVB例えばＢ、Al、Ga、In、Tl、Ti、Zrといった
元素又はそれらの化合物を媒体中に存在させることから
なる。それらの化合物とは有機、無機のいずれの化合物
でも良く、媒体中で水、酸、塩基等と接触して分解して
もかまわない。具体例としてはBO、B4O5、B2O3、次ホウ
酸、次ホウ酸塩、ホウ酸、ホウ酸塩、ペルオキソホウ酸
塩、ホウ酸エステル、BPO4、BAsO4、BCl3、BBr3、BI3、B2C
l4、B2Br4、B2I4、B(OCOCH3)3、H3BO3、(CH3)3B、(CH3)2BrB、C
H3B(OH)2、CH3BBr2、phBCl2、phB(OH)2、BFe、MBR4、MBH4、B
HR2、BH2R（Ｒはアルキル基又はアリール基、Ｍは１価の
金属原子）Al(OCH2CH2CH2CH3)3、〔AlH3〕x、MgH2・2AlH3、
LiAlH4、Al2O3、リン酸アルミニウム、Al(OH)3、アルミ
ン酸塩、AlCl3、AlBr3、シュウ酸アルミニウム、AlI3、Al
2(SO4)3、クエン酸アルミニウム、KAl(SO4)2・12H2O、Al2
O3・3SiO2、Al(NO3)3、Al2O3・B2O3、Al(SCN)3、Al(CH3CO
O)3、ラウリル酸アルミニウム、塩基性酢酸アルミニウ
ム、AlCl3・NH4Cl、AlNH4(SO4)2・12H2O、AlNa(SO4)2・12H
2O、AlZn(SO4)4・24H2O、Al2S3、AlR3、AlR2X、AlRX2（Ｒ＝ア
ルキル基又はアリール基 Ｘ＝Cl、Br、Ｉ）TiH2、Ti
H4、TiO、Ti(OH)2、Ti2O3、Ti(OH)3、TiO2、TiCl2、TiBr2、Ti
I2、TiCl3、〔Ti(OH)6〕Cl3、TiBr3、TiI3、TiCl4、TiBr4、TiI
4、TiS、Ti2S3、TiS2、Ti2(SO4)3、TiP2O7、Ti(SO4)2、Ti(OC
H3)4、TiCaO3、Ti(COO)3、Ti(COO)4、TiMgO3、TiS、TiS2、M2
TiO3、M〔TiCl5(OH2)〕、MTiCl6、MTiBr6（Ｍは１価の金属
原子）ZrO2、ZrO2・XH2O、ZrO3・2H2O、ZrCl2、K4ZrO4・4H2O2・
2H2O、ZrBr4、ZrI2、ZrBr2、ZrCl3、ZrBr3、ZrI3、ZrCl4、ZrI4、
ZrOCl2・8H2O、Zr2O3Cl2、Zr(NO3)4・5H2O、ZrO(NO3)2・2H2O、
Zr(SO4)2、Zr(SO4)2・4H2O、ZrO(SO4)、ZrO(H2PO4)2、ZrP
2O7、ZrSiO4、Zr(CH3COO)4、ZrO(CH3COO)2、Zr（IV）アセ
チルアセトネート、ZrAl2、ZrB2、ZrCl2O、ZrCl2O9、ZrH2、M
ZrO3、（Ｍは１価の金属原子）であるが、それらに限定
されるものではない。又それらは単独、あるいは混合系
で用いても良い。効果を発揮する使用量はフッ酸の量に
関係する。通常、フッ酸のモル数に対して0.5〜10倍で
使用するのが良いが、効果を高めるためにさらに多量に
使用してもよい。添加に際しては、媒体に溶解性のある
ものを選ぶのが望ましいが、溶解性が悪い場合は、粉砕
して比表面積を大きくし、系内を激しく攪拌し、フッ酸
との接触効率を上げるとよい。又水、アルコール、ベン
ゼン等の溶媒に溶解して加えてもよい。本発明が使用さ
れる媒体は前記々載の媒体の如くであるが、工業上特別
価値の高いものは、酸性媒体中又はそれらの水溶液中で
の反応又は取り扱いである。酸としては、前記々載した
もの等である。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is characterized by allowing elements of Group IIIA and IVB of periodicity control or compounds thereof (excluding fluorides) to exist in a medium in the temperature range of room temperature to 190 ° C. It is about how to protect. More specifically, for example, alcohols, esters,
In organic media such as halogenated hydrocarbons, ethers, aliphatic hydrocarbons, ketones, aromatic hydrocarbons, aliphatic amines, aromatic amines, aliphatic carboxylic acids, aromatic carboxylic acids, phenols, aprotic polar solvents or When hydrofluoric acid is present or generated in an inorganic medium such as water, sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, chlorosulfonic acid, phosphoric acid, or a mixed medium thereof, hydrofluoric acid is used in a chemical reaction or treatment process. Periodic table to protect glass equipment
IIIA, IVB, for example, B, Al, Ga, In, Tl, Ti, Zr, or a compound thereof is allowed to exist in the medium. These compounds may be organic or inorganic compounds and may be decomposed by contact with water, acid, base or the like in a medium. Specific examples are BO, B 4 O 5 , B 2 O 3 , hypoboric acid, hypoboric acid, boric acid, borate, peroxoborate, borate ester, BPO 4 , BAsO 4 , BCl 3 , BBr 3 , BI 3 , B 2 C
l 4 , B 2 Br 4 , B 2 I 4 , B (OCOCH 3 ) 3 , H 3 BO 3 , (CH 3 ) 3 B, (CH 3 ) 2 BrB, C
H 3 B (OH) 2 , CH 3 BBr 2 , phBCl 2 , phB (OH) 2 , BFe, MBR 4 , MBH 4 , B
HR 2 , BH 2 R (R is an alkyl group or an aryl group, M is a monovalent metal atom) Al (OCH 2 CH 2 CH 2 CH 3 ) 3 , [AlH 3 ] x , MgH 2 .2AlH 3 ,
LiAlH 4 , Al 2 O 3 , aluminum phosphate, Al (OH) 3 , aluminate, AlCl 3 , AlBr 3 , aluminum oxalate, AlI 3 , Al
2 (SO 4 ) 3 , aluminum citrate, KAl (SO 4 ) 2・ 12H 2 O, Al 2
O 3 · 3SiO 2, Al ( NO 3) 3, Al 2 O 3 · B 2 O 3, Al (SCN) 3, Al (CH 3 CO
O) 3 , aluminum laurate, basic aluminum acetate, AlCl 3 · NH 4 Cl, AlNH 4 (SO 4 ) 2 · 12H 2 O, AlNa (SO 4 ) 2 · 12H
2 O, AlZn (SO 4 ) 4 · 24H 2 O, Al 2 S 3 , AlR 3 , AlR 2 X, AlRX 2 (R = alkyl group or aryl group X = Cl, Br, I) TiH 2 , Ti
H 4 , TiO, Ti (OH) 2 , Ti 2 O 3 , Ti (OH) 3 , TiO 2 , TiCl 2 , TiBr 2 , Ti
I 2 , TiCl 3 , [Ti (OH) 6 ] Cl 3 , TiBr 3 , TiI 3 , TiCl 4 , TiBr 4 , TiI
4 , TiS, Ti 2 S 3 , TiS 2 , Ti 2 (SO 4 ) 3 , TiP 2 O 7 , Ti (SO 4 ) 2 , Ti (OC
H 3 ) 4 , TiCaO 3 , Ti (COO) 3 , Ti (COO) 4 , TiMgO 3 , TiS, TiS 2 , M 2
TiO 3 , M [TiCl 5 (OH 2 )], MTiCl 6 , MTiBr 6 (M is a monovalent metal atom) ZrO 2 , ZrO 2 · XH 2 O, ZrO 3 · 2H 2 O, ZrCl 2 , K 4 ZrO 4・ 4H 2 O 2・
2H 2 O, ZrBr 4 , ZrI 2 , ZrBr 2 , ZrCl 3 , ZrBr 3 , ZrI 3 , ZrCl 4 , ZrI 4 ,
ZrOCl 2 , 8H 2 O, Zr 2 O 3 Cl 2 , Zr (NO 3 ) 4 , 5H 2 O, ZrO (NO 3 ) 2 , 2H 2 O,
Zr (SO 4) 2, Zr (SO 4) 2 · 4H 2 O, ZrO (SO 4), ZrO (H 2 PO 4) 2, ZrP
2 O 7 , ZrSiO 4 , Zr (CH 3 COO) 4 , ZrO (CH 3 COO) 2 , Zr (IV) acetylacetonate, ZrAl 2 , ZrB 2 , ZrCl 2 O, ZrCl 2 O 9 , ZrH 2 , M
ZrO 3 , (M is a monovalent metal atom), but is not limited thereto. Further, they may be used alone or in a mixed system. The effective amount used is related to the amount of hydrofluoric acid. Usually, it is preferable to use 0.5 to 10 times the molar number of hydrofluoric acid, but a larger amount may be used to enhance the effect. At the time of addition, it is desirable to select one that is soluble in the medium, but if the solubility is poor, crush it to increase the specific surface area and vigorously stir the system to increase the contact efficiency with hydrofluoric acid. Good. Alternatively, it may be added after being dissolved in a solvent such as water, alcohol or benzene. The medium in which the present invention is used is the same as the above-mentioned mediums, but one having a special industrial value is a reaction or handling in an acidic medium or an aqueous solution thereof. Examples of the acid include those listed above.
ガラスについて述べると、本発明の方法で特に効果のあ
るガラスは、工業用として多用されている酸化物ガラス
（SiO2、B2O3、GeO2、As2O5、Na2O、Sb2O3、BaO、Bi2O3、V
2O5、Sb2O5、ZrO2、ZnO、TiO2など）である。その中でも
ケイ酸又はケイ酸を含むガラス（ケイ酸アルカリガラ
ス、ソーダ石灰ガラス、カリ石灰ガラス、バリウムガラ
ス、ホウケイ酸など）である。しかし硝酸塩ガラス、塩
化物ガラス、炭酸塩ガラスなど上記以外のものでもよ
い。例としては、パイレックス、テレックス（商品名
ホウケイ酸ガラス）Vycor（商品名石英ガラス）や金属
表面にガラス層を焼き付けたホウロウ、グラスライニン
グ材（池袋琺瑯工業株式会社 GL-400等）などである。As for the glass, the glass that is particularly effective in the method of the present invention is an oxide glass (SiO 2 , B 2 O 3 , GeO 2 , As 2 O 5 , Na 2 O, Sb 2) that is widely used for industrial purposes. O 3 , BaO, Bi 2 O 3 , V
2 O 5 , Sb 2 O 5 , ZrO 2 , ZnO, TiO 2, etc.). Among them, silicic acid or glass containing silicic acid (alkali silicate glass, soda lime glass, potassium lime glass, barium glass, borosilicate, etc.). However, other glass such as nitrate glass, chloride glass, and carbonate glass may be used. Examples include Pyrex, Telex (brand name
Borosilicate glass) Vycor (trade name: quartz glass), enamel that has a glass layer baked on the metal surface, glass lining material (GL-400 etc., Ikebukuro Enamel Co., Ltd.).
以下実施例を示す。尚実施例中のガラス試験片は、顕微
鏡スライドガラス〔マツナミガラス工業（株）製 JIS
R3703〕を用いて行った。又％はすべて重量％を示す。Examples will be shown below. The glass test pieces in the examples are microscope slide glass [Matsunami Glass Industry Co., Ltd. JIS
R3703]. Moreover, all% are% by weight.
実施例１ フッ化水素0.28gを含む25％硫酸20gを120mlテフロン製
のビンに加え、さらに粉末状のホウ酸1.8gを加える。次
にガラスの試験片を入れ、栓をし、同温で１時間攪拌し
た後ガラス試験片を取り、水洗、乾燥後、腐食状況を観
察したところ、試験片は変化が認められなかった。Example 1 20 g of 25% sulfuric acid containing 0.28 g of hydrogen fluoride was added to a 120 ml Teflon bottle, and 1.8 g of boric acid powder was added. Next, a glass test piece was put thereinto, the stopper was put thereinto, the mixture was stirred at the same temperature for 1 hour, the glass test piece was taken out, washed with water, dried, and then observed for corrosion. No change was observed in the test piece.
実施例２ フッ化水素0.14gを含むエタノール40gを120mlテフロン
製のビンに加え、さらに粉末状の水酸化アルミニウム1.
0gを加える。そして60℃で３分攪拌処理する。これにガ
ラス試験片を入れて栓をし、同温度で１時間攪拌した
後、以下実施例１と同様に操作したところ、試験片は変
化が認められなかった。Example 2 40 g of ethanol containing 0.14 g of hydrogen fluoride was added to a 120 ml Teflon bottle, and powdered aluminum hydroxide was added.
Add 0g. Then, the mixture is stirred at 60 ° C. for 3 minutes. When a glass test piece was placed in this and capped and stirred at the same temperature for 1 hour and then operated in the same manner as in Example 1, no change was observed in the test piece.
実施例３ フッ化水素0.06g含むキシレン30gを120mlテフロン製の
ビンに加え、粉末状のZr（IV）アセチルアセトネート1.
0gを加える。そして室温で10分攪拌処理する。これにガ
ラス試験片を入れて栓をし、100℃で１時間攪拌した
後、以下実施例１と同様に操作したところ、試験片は変
化が認められなかった。Example 3 30 g of xylene containing 0.06 g of hydrogen fluoride was added to a 120 ml Teflon bottle, and powdered Zr (IV) acetylacetonate 1.
Add 0g. Then, the mixture is stirred at room temperature for 10 minutes. When a glass test piece was placed in this and capped and stirred at 100 ° C. for 1 hour and then operated in the same manner as in Example 1, no change was observed in the test piece.
実施例４ 実施例１でホウ酸の代わりに20％三塩化チタン10.8gを
加え、同様に操作したところ、試験片は変化が認められ
なかった。Example 4 When 10.8 g of 20% titanium trichloride was added in place of boric acid in Example 1 and the same operation was performed, no change was observed in the test piece.
以下に酸の種類、温度、ガラス保護剤を変えた実施例５
から21までを表に示す。但し、ガラス保護剤は完溶又は
懸濁させて用いた。Example 5 in which the kind of acid, temperature and glass protective agent were changed to
Tables 21 to 21 are shown. However, the glass protective agent was completely dissolved or suspended before use.
以下同様に実施例22から25までを示す。但し、ガラス試
験片の代わりに池袋琺瑯工業株式会社製ガラスライニン
グ（GL-400）試験棒を用いて行った。 Similarly, Examples 22 to 25 will be shown below. However, a glass lining (GL-400) test rod manufactured by Ikebukuro Enamel Industry Co., Ltd. was used instead of the glass test piece.
実施例27 47％臭化水素酸250gとＰ−メトキシフロロベンゼン60g
と水酸化アルミニウム1gをフラスコに入れ、グラスライ
ニングテストピースGL-400（池袋琺瑯工業株式会社製）
を付した後、加熱還流下に11時間攪拌した。反応終了後
室温まで冷却し、ジクロロメタン50gで３回抽出した。
濃縮してＰ−クロロフェノール41.6gを得た。テストピ
ースは全く変化が認められなかった。同様に水酸化アル
ミニウムを加えず行った場合は、テストピースに激しい
腐食が認められた。 Example 27 47% hydrobromic acid 250 g and P-methoxyfluorobenzene 60 g
Glass lining test piece GL-400 (made by Ikebukuro Enamel Industry Co., Ltd.)
After adding, the mixture was stirred for 11 hours while heating under reflux. After completion of the reaction, the mixture was cooled to room temperature and extracted with 50 g of dichloromethane three times.
Concentration gave 41.6 g of P-chlorophenol. No change was observed in the test piece. Similarly, when the test was performed without adding aluminum hydroxide, severe corrosion was observed in the test piece.
実施例28 （１）95％Ｐ−フロロアニリン100gを濃硫酸100gと水80
0mlからなる酸性水溶液中に氷を加えながら滴加し、Ｐ
−フロロアニリン硫酸塩のスラリーとした。これに30.7
％の亜硝酸ナトリウム水溶液を氷を加え液温を７℃以下
に保ち、約２時間で滴下した。その後同温で２時間攪拌
することで、ジアゾ化は完結した。スルファミン酸1.0g
を加え過剰の亜硝酸ソーダを分解し、約1.2lのＰ−フロ
ロアニリンジアゾニウム塩を得た。Example 28 (1) 100% of 95% P-fluoroaniline, 100 g of concentrated sulfuric acid and 80% of water
While adding ice, add dropwise to an acidic aqueous solution of 0 ml.
-A slurry of fluoroaniline sulfate. To this 30.7
% Aqueous sodium nitrite solution was added with ice to keep the liquid temperature at 7 ° C. or lower, and the solution was added dropwise in about 2 hours. Then, the mixture was stirred at the same temperature for 2 hours to complete the diazotization. Sulfamic acid 1.0 g
Was added to decompose excess sodium nitrite, and about 1.2 l of P-fluoroaniline diazonium salt was obtained.
（２）コンデンサーを付した１四ツ口フラスコに硫酸
銅・５水和物150g水150g水酸化アルミニウム4.0gを加
え、さらに実施例27と同じガラステストピースを付し、
加熱攪拌した。（１）記載のジアゾニウム塩を沸点下に
一定速度で滴下し、約３時間で全量を加えた。滴下とと
もにコンデンサーよりＰ−フロロフェノールを含む水が
留出した。留出水を約1.3l得た。これに塩化ナトリウム
260gを加え完溶させた後、トルエン200mlで３回抽出
し、Ｐ−フロロフェノール分を分析したところ、収率93
％を得た。同反応を20回行った後、テストピースを取り
出し観察したところ、変化は認められなかった。参考と
して、水酸化アルミニウムを加えずに同数回行った実験
は、テストピースに激しい腐食が認められた。(2) To a 1-necked flask equipped with a condenser, copper sulfate pentahydrate 150 g, water 150 g, aluminum hydroxide 4.0 g were added, and the same glass test piece as in Example 27 was attached.
Heated and stirred. The diazonium salt described in (1) was added dropwise at a constant rate at the boiling point, and the total amount was added in about 3 hours. Water containing P-fluorophenol was distilled out from the condenser with the dropping. About 1.3 l of distilled water was obtained. Sodium chloride
After adding 260 g to dissolve completely, it was extracted 3 times with 200 ml of toluene and the P-fluorophenol content was analyzed.
Earned%. After carrying out the same reaction 20 times, the test piece was taken out and observed, and no change was observed. As a reference, in the experiment conducted the same number of times without adding aluminum hydroxide, severe corrosion was observed in the test piece.
実施例29 実施例28で得たＰ−フロロフェノールトルエン溶液に20
0メッシュ水酸化アルミニウム2.0gを加え、さらに実施
例27と同じガラステストピースを付したフラスコで精留
した。精留は、塔頂温度60〜110℃で減圧下に10時間を
要した。精留後テストピースを取り出し観察したとこ
ろ、変化は全々認められなかった。Example 29 To the P-fluorophenoltoluene solution obtained in Example 28, 20
2.0 g of 0-mesh aluminum hydroxide was added, and rectification was further carried out in a flask equipped with the same glass test piece as in Example 27. The rectification took 10 hours under reduced pressure at a column top temperature of 60 to 110 ° C. After rectification, the test piece was taken out and observed, and no change was observed.
実施例30 ベンゾトリフルオライド70g、AlBr325gを2lフラスコに
入れ、さらに実施例27と同じガラステストピースを付し
た。40〜60℃の反応温度で攪拌下に臭素70gを約20時間
にわたって滴下反応させた。反応生成物は荷性ソーダ水
溶液で中和した後水蒸気蒸留、ジクロルエタンで抽出、
濃縮、蒸留し、ｍ−ブロモベンゾトリフルオライド27g
を得た。反応終了後テストピースを取り出し観察したと
ころ、変化が認められなかった。Example 30 70 g of benzotrifluoride and 25 g of AlBr 3 were placed in a 2 liter flask, and the same glass test piece as in Example 27 was attached. 70 g of bromine was reacted dropwise with stirring at a reaction temperature of 40 to 60 ° C. over about 20 hours. The reaction product is neutralized with an aqueous solution of soda, then steam distilled, extracted with dichloroethane,
Concentrated and distilled to give 27 g of m-bromobenzotrifluoride
Got After the reaction was completed, the test piece was taken out and observed, and no change was observed.
実施例31 １フラスコにボールミルで24時間粉砕したフッ化カリ
ウム148g、スルホラン500ml、２、３、４、５−テトラ
クロルニトロベンゼン168gを加え、190℃×６時間還流
した後、冷却、過した。液は2lフラスコに移し、水
500ml、オキシ塩化ジルコニウム2.0gを加え、さらに実
施例27と同じテストピースを付した。その後水蒸気蒸留
を行い、３、５−ジクロル−２、４−ジフロロニトロベ
ンゼン110gを含む留出水約2lを得た。テストピースは変
化が認められなかった。Example 31 To a flask, 148 g of potassium fluoride crushed for 24 hours by a ball mill and 500 ml of sulfolane, 168 g of 2,3,4,5-tetrachloronitrobenzene were added, and the mixture was refluxed at 190 ° C for 6 hours, then cooled and passed. Transfer the liquid to a 2 l flask and add water.
500 ml and 2.0 g of zirconium oxychloride were added, and the same test piece as in Example 27 was attached. After that, steam distillation was performed to obtain about 2 liters of distilled water containing 110 g of 3,5-dichloro-2,4-difluoronitrobenzene. No change was observed in the test piece.
実施例32 500mlフラスコにＰ−トリフロロメチル安息香酸エチル1
00g、20％硫酸300mlを加え、さらに実施例27と同様にテ
ストピースを付した。副生エタノールを留去しながら10
時間加熱攪拌した。このとき、留出量にみあう水を反応
系に補給した。冷却後析出した結晶を別、乾燥しＰ−
トリフロロメチル安息香酸81.9gが得られた。テストピ
ースは変化が認められなかった。Example 32 P-trifluoromethyl ethyl benzoate 1 in a 500 ml flask
00 g and 300 ml of 20% sulfuric acid were added, and a test piece was added as in Example 27. While distilling off by-product ethanol 10
The mixture was heated and stirred for an hour. At this time, water matching the amount of distillate was supplied to the reaction system. After cooling, the precipitated crystals are separated and dried to form P-
81.9 g of trifluoromethylbenzoic acid was obtained. No change was observed in the test piece.
フッ酸が存在又は発生する反応、処理工程において、ガ
ラス製装置を使用してもガラスには全く変化がないか、
極く僅かしか変化がなかった。In the reaction or treatment process in which hydrofluoric acid is present or generated, there is no change in the glass even if a glass device is used,
There was very little change.
Claims (1)
合媒体中でフッ酸が存在又は発生する化学反応又は処理
工程において、該媒体中に周期律表IIIA、IVB族の元素
又はそれらの化合物（フッ化物を除く）を室温〜190℃
の温度範囲で存在させることを特徴とするフッ酸の腐食
作用からガラス製装置を保護する方法1. A chemical reaction or treatment step in which hydrofluoric acid is present or generated in an organic medium, an inorganic medium, or a mixed medium thereof, in the medium, an element of Group IIIA or IVB of the periodic table or a compound thereof (fluorine). (Excluding compounds) at room temperature to 190 ° C
For protecting glass equipment from corrosive effects of hydrofluoric acid characterized by being present in the temperature range of
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61075599A JPH0694382B2 (en) | 1986-04-03 | 1986-04-03 | How to protect glass equipment from hydrofluoric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61075599A JPH0694382B2 (en) | 1986-04-03 | 1986-04-03 | How to protect glass equipment from hydrofluoric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62235235A JPS62235235A (en) | 1987-10-15 |
| JPH0694382B2 true JPH0694382B2 (en) | 1994-11-24 |
Family
ID=13580828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61075599A Expired - Fee Related JPH0694382B2 (en) | 1986-04-03 | 1986-04-03 | How to protect glass equipment from hydrofluoric acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0694382B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117699742B (en) * | 2024-02-05 | 2024-07-12 | 上海联风气体有限公司 | Hydrofluoric acid regeneration method for photovoltaic waste acid |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5855346A (en) * | 1981-09-25 | 1983-04-01 | Nippon Sheet Glass Co Ltd | Treatment of surface of glass containing alkali metal |
| US4434191A (en) * | 1981-10-06 | 1984-02-28 | Schott Glass Technologies, Inc. | Integral anti-reflective surfaces of silicate glasses |
| JPS5888142A (en) * | 1981-11-20 | 1983-05-26 | Nissha Printing Co Ltd | Glass etchant for high temperature use and etching of glass using said etchant |
| JPS58145674A (en) * | 1982-02-17 | 1983-08-30 | 日本写真印刷株式会社 | Manufacture of ceramic products with relief surface |
| JPS6191042A (en) * | 1984-10-08 | 1986-05-09 | Toyota Motor Corp | Anti-fogging glass and its production |
-
1986
- 1986-04-03 JP JP61075599A patent/JPH0694382B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62235235A (en) | 1987-10-15 |
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