CN101061060A - Process for preparing element halides - Google Patents
Process for preparing element halides Download PDFInfo
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- CN101061060A CN101061060A CN 200580039498 CN200580039498A CN101061060A CN 101061060 A CN101061060 A CN 101061060A CN 200580039498 CN200580039498 CN 200580039498 CN 200580039498 A CN200580039498 A CN 200580039498A CN 101061060 A CN101061060 A CN 101061060A
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- described method
- compound
- carbon
- mixture
- halogen
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- 150000004820 halides Chemical class 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 claims description 93
- 238000006243 chemical reaction Methods 0.000 claims description 73
- 239000000203 mixture Substances 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 41
- 239000003575 carbonaceous material Substances 0.000 claims description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- 229910052799 carbon Inorganic materials 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 28
- 229910052736 halogen Inorganic materials 0.000 claims description 28
- 150000002367 halogens Chemical class 0.000 claims description 25
- 239000000460 chlorine Substances 0.000 claims description 22
- 230000005672 electromagnetic field Effects 0.000 claims description 19
- 239000004576 sand Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 17
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 12
- 150000002366 halogen compounds Chemical class 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 230000005855 radiation Effects 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 150000001722 carbon compounds Chemical class 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 230000005284 excitation Effects 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910052755 nonmetal Inorganic materials 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract 6
- 206010039203 Road traffic accident Diseases 0.000 abstract 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 40
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 description 16
- 229910021485 fumed silica Inorganic materials 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 229910000039 hydrogen halide Inorganic materials 0.000 description 12
- 239000012433 hydrogen halide Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- -1 makeup Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 229910003902 SiCl 4 Inorganic materials 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000005255 carburizing Methods 0.000 description 7
- 238000005660 chlorination reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910001570 bauxite Inorganic materials 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- 239000006004 Quartz sand Substances 0.000 description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000005695 dehalogenation reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000026030 halogenation Effects 0.000 description 3
- 238000005658 halogenation reaction Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000005049 silicon tetrachloride Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 101100232929 Caenorhabditis elegans pat-4 gene Proteins 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 2
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000004607 11B NMR spectroscopy Methods 0.000 description 1
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 1
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 241000588731 Hafnia Species 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000005293 duran Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000006194 liquid suspension Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
To specify vehicles carrying persons who can be eyewitnesses in the event of a traffic accident. This vehicle detection apparatus is for detecting any vehicle located in the vicinity of an accident site at the time of occurrence of an accident and comprises a vehicle information storage part for storing vehicle identifiers; a one's own vehicle impact detection storage part for storing information about witnessing vehicles; a vehicle information reader part for obtaining vehicle identifiers from the vehicle information storage part of another vehicle detection apparatus; and an impact detection part for detecting impact and for obtaining the vehicle identifiers from the vehicle information reader part upon detection of the impact to store the vehicle identifiers as information about the eyewitnessing vehicles in the one's own vehicle impact detection storage part. Thus when detecting impact on a vehicle, the apparatus can obtain the identification numbers of nearby vehicles and specify any vehicles carrying persons who can be eyewitnesses of the traffic accident.
Description
Technical field
The invention describes a kind of method that is used to prepare element halide, it is characterized in that, in the first step, the mixture that manufacturing is made up of the material that contains each element and carbon or carbonaceous material, this mixture is contacted and heats be gasiform halogen, hydrogen halide or their mixture under selected reaction conditions, wherein utilize the alternating electromagnetic field intake.
Background technology
Element halide is the compound of the mixture of element and halogens fluorine, chlorine, bromine, iodine or these halogens.At this, element-halogen compounds can have Ionized characteristic, and for example halogen-basic metal key as NaCl, perhaps is mainly covalant character, and metal-halogen bond for example is as SiCl
4, perhaps nonmetal-halogen bond, as PCl
3
At industrial widely-used element halide.Obtain some elements by element halide, as aluminium, titanium, boron or silicon.Under the situation of some elements, also adopt halogenation oxygenizement and dehalogenation reductive action subsequently to prepare the extra high element of these purity.In the case, element-halogen compounds is optional also can purify by distillation extraly, for example AlCl
3, perhaps purify, for example TiCl by distillation
4For example can utilize hydrogen to BCl
3Implement dehalogenation, perhaps implement dehalogenation, for example on tungsten filament, make BBr by thermolysis
3Decompose.Make element halide become the important initial substance of CVD or similar procedure thus.In addition; element halide is the basal component that for example industry reaches the important catalyst on synthesizing; the Friedel-Crafts catalyzer that for example is used for the replacement of aromatics electrophilic, alkylation, acylations; perhaps be used for polymerization, be used to form element-Ziegler-Natta catalyst of element key; for example pass through the salt metathesis of Wurtz linked reaction, Grignard reaction, generting element-oxygen key, element-phosphorus key, element-nitrogen key, element-boron key, element-sulfide linkage; and intermediate product; and auxiliary, for example AlCl in medicine, makeup, textiles
3Perhaps as the flocculation agent in the water treatment.Element halide as industrial particularly important should be mentioned titanium tetrachloride and tetrachloro silicane, as the intermediate product that is used to make the intermediate product of titanium dioxide and be used to make silicon-dioxide in small, broken bits.
In the prior art, the various method that is used to prepare element halide is known, and they can be divided into many groups.
All known element halides can choose that the reaction by element and various halogens produces under the situation of heating wantonly.Under the situation of some elements, the reaction of also known and hydrogen halide, the wherein extra usually hydrogen that discharges.In this reducing atmosphere, obtain the element halide under comparable suboxide state usually.In order to obtain the element halide under the higher state of oxidation, can make in some cases the reaction of element and halogen rather than with hydrogen halide reaction, perhaps use halogen, especially chlorine subsequently, the element halide that oxidation is lower.Also available hydrogen or the reductibility reagent of similarly removing halogen are converted into the lower state of oxidation with the element halide of high oxidation state.
The example of this type of reaction is:
Fe+2HCl→FeCl
2+H
2，
2Fe+3Cl
2→2FeCl
3，
PCl
3+Cl
2→PCl
5，
2BCl
3+ " removing the reagent of chlorine " → B
2Cl
4
Wherein, in the end in equation, the reagent of removing chlorine can be copper or mercury.
Another known method is a carburizing chlorination.Term " carburizing chlorination " is meant the reaction under the situation of input heat energy of preferred elements oxide compound and carbon and chlorine.For some elements, the also known carburizing chlorination that utilizes hydrogenchloride.
This type of reaction has for example been described in JP 62-143813 A2 and U.S. Pat 4,576,812:
TiO
2+2Cl
2+2C→TiCl
4+2CO，
Al
2O
3+3Cl
2+3C→2AlCl
3+3CO，
BaSO
4+C+Cl
2→BaCl
2+CO
2+SO
2。
A kind of method that is similar to carburizing chlorination is chloridizing roasting.In the chloridizing roasting process, choose wantonly under the situation that has carbon or carbon compound, element compound is mixed with chlorine-containing compound and heat.Used chlorine-containing compound for example is tetrachloro silicane or tetrachloromethane, sodium-chlor or chloride sulphur compound, as thionyl chloride and SULPHURYL CHLORIDE.
Therefore, according to people's such as H.F.Johnstone Ind.engg.Chem.34 (1942) 280, the mixture of chromite and sodium-chlor or Repone K can with sulfurous gas/air mixture water generation reaction dissolubility muriate and vitriol.Rauter (Liebigs Ann.270,1892,236) has described the reaction of Cadmium oxide and silicon tetrachloride generation Cadmium chloride fine powder:
2CdO+SiCl
4→2CdCl
2+SiO
2。
Can utilize the method described in the J.Am.Chem.Soc.35 (1913) 2088 of North and Hagemann to obtain Cadmium chloride fine powder according to following equation equally by Cadmium oxide:
FeS
2+SCl
2→FeCl
2+3S。
U.S. Pat 2,895,796 and US 3,652,219 for example a kind of method that is used for being made by iron sulphide according to following equation iron(ic) chloride (II) is disclosed:
FeS
2+SCl
2→FeCl
2+3S。
In addition, for example in U.S. Pat 4,209,501 and US 4,576,812 in described according to the following equational method of making iron(ic) chloride (II) by iron(ic) chloride (III):
ZnS+2FeCl
3→ZnCl
2+2FeCl
2+S。
At last, the direct reaction of the following example of basis that can mention element compound and hydrogen halide is with forming element halogenide and discharge hydrogen compound:
SiO
2+4HF→SiF
4+2H
2O，
As
2O
3+ HCl → AsCl
3+ H
2O, and
SnS+2HCl→SnCl
2+H
2S。
In the prior art, become known for preparing the various embodiment of element halide.For example in U.S. Pat 4,083, the method of usually using in comparable mode described in 923 makes being solid-state initial compounds under the reaction conditions and changes into be the gasiform element halide under reaction conditions, for example in U.S. Pat 4, disclosed method obtains to be solid state elements halogenide from the solid parent material in 576,812 under reaction conditions.Also known additive method, wherein initial compounds reacts in liquid phase or suspension, for example in salt melt.In the case, for example in U.S. Pat 4,039, disclosed method is created on and is the gasiform element halide under the reaction conditions in 648, and for example in U.S. Pat 4,209,501 or US 4,597, the method described in 840 produces the product that is dissolved in the liquid phase.
The reaction of the mixture of various element compound has also been described in the prior art, for example aluminum oxide or bauxite, with the halid mixture of forming element, it can be purified by fractional condensation, filtration or distillation subsequently.In addition, for example in U.S. Pat 3,935,297, US4,083,923 and WO 2004/063096 in disclosed method the possibility of removing the impurity in desired target product by reaction optionally is provided.
In the case, more described in the prior art is not partly to have following shortcoming by the initial method of element, and contained element only has small part to change into element halide.Usually use catalyzer to improve productive rate or to improve speed of reaction, for example in U.S. Pat 1,565, described in 220 by when the carburizing chlorination aluminum oxide, adding sulphur to promote reaction, and in U.S. Pat 4, described in 083,927 by when carburizing chlorination contains kaolinic raw material, adding BCl
3With with form SiCl
4Reacting phase than and promote to form AlCl
3Reaction.In addition, in these methods of a part, be formed on the by product that labour hygiene and environmental toxicity aspect need take in.Therefore, for example available chlorine carburizing chlorination element oxide and produce dichloro ketone (phosgene).Must make used chlorine as far as possible fully at the reactor internal reaction so that the release of phosgene minimize, for example described in JP60-112610 A2 and the JP 60-118623 A2:
SiO
2+2C+2Cl
2→SiCl
4+2CO，
CO+Cl
2→COCl
2。
Summary of the invention
The object of the present invention is to provide a kind of method that is used to make element halide, this method has extra high versatility aspect the used initial substance, and this method is implemented under the situation of not adding catalyzer.
This purpose is to realize by the method that is used to make element halide according to the present invention, it is characterized in that, the mixture that will form by the material that contains described element and carbon or carbonaceous material under the situation that the effect that utilizes alternating electromagnetic field is heated with contain the air-flow that under reaction conditions, is gasiform halogen or gasiform halogen compounds or their mixture and contact.
Find using alternating electromagnetic field according to the present invention, preferred microwave radiation, as energy source when implementing the method according to this invention, can use any compound that contains described element, wherein the method according to this invention aspect the kind of the used material that contains described element or aspect the specific surface area of this material all without any restriction.Also there is any restriction hardly aspect the kind of used carbon or carbonaceous material and the specific surface area.At this, used carbon or carbonaceous material must promptly can be existed by the form of alternating electromagnetic field thermal excitation to be suitable for hertzian wave is converted into the form of heat energy.
Need not catalyzer with enforcement the method according to this invention, and need catalyzer in the prior art usually.
Method of the present invention never improves for the used material that contains described element and the demand of carbonaceous material.But preferably use the mixture of element oxide or element sulfide and these oxide compounds or sulfide and impurity compound, especially have high as far as possible described constituent content person.As the non-limiting example of spendable mixture, can mention the titaniferous waste material of making from titanium dioxide, contain scrap silicon, as rice hull ash, and from the carbonaceous residue of combustion processes or pyrolytic process.These materials are the problem material that must pile up at the landfill yard that relates to all associated problem and cost at present.Glass also capable of circulation, contain the degradation production of aluminosilicate or the mixture of forming by aluminum oxide and Si oxide and ferriferous oxide, for example bauxite.
Some suitable parent materials are listed in the table 1.
Table 1
| Element | The source |
| Fe | Fe 2O 3、FeO、Fe 3O 4, iron ore |
| Ti | TiO 2, ilmenite |
| Si | Desert sand, quartz, mica, rice hull ash, pyrogenic silica, window glass, Beer Bottle, silicon-dioxide in small, broken bits, quartz sand, Duran glass, silicon carbide, silicon nitride |
| Al | Al 2O 3, bauxite |
| P | Ca 3(PO 4) 2 |
| B | B 2O 3 |
| Hf | HfO 2 |
| C | Gac, hard coal, brown coal, petroleum coke |
Element halide can be chosen wantonly after making the mixture halogenation and be separated by known physics or chemical process, for example by distillation liquid state or elementary gas halogenide, by distillation solid element halogenide, perhaps filter so that liquid state or elementary gas halogenide separate with solid element halogenide.
Also can make parent material or its mixture reaction of the described element that contains specified proportion.Thus, for example can be follow-up deposition process and regulate the ratio of adding in advance in metering.
In the method according to the invention, can prepare under reaction conditions be in a liquid state, gaseous state or solid state elements halogenide.Therefore, the inventive method is characterised in that and has extra high versatility.
The inventive method can utilize hydrogen to combine with the sediment-filled phase of element halide.Can use the hydrogen that is produced when implementing halogenation with hydrogen halide for this reason.
The hydrogen that is discharged can optionally be used to obtain the required part energy of this method.With wherein described element is carried out halogenated method and compares, adopt the single stage method described herein can save energy and manufacturing cost.Omitted the manufacturing of described element.The inventive method is implemented under the situation of the state of oxidation that does not change described element usually in form.
Used carbon or used carbonaceous material can not only be brought into play its conduct in the method according to the invention and be used for being undertaken by alternating electromagnetic field such as microwave radiation the effect of the heating element of thermal excitation, and play the effect as reductibility reagent.
In a particularly preferred embodiment of the present invention, use hydrogenchloride as the compound that contains halogen.Except avoiding phosgene, hydrogenchloride also since its compare with chlorine and have significantly lower boiling point and can be more easily separate with desired element halide, so industrial be preferred.Hydrogenchloride has advantage equally aspect reactor structure, because compare hydrogenchloride with chlorine reactor material is had lower oxidisability.
Use hydrogen halide to have following shortcoming for the conversion of element oxide especially, owing to during reaction form water with the hydrogen of halogen bond, and water can make the element halide hydrolysis once more of the facile hydrolysis that is produced.In an embodiment of the method according to this invention, can when element halide for preparing facile hydrolysis such as titanium tetrachloride,, preferably surpass 800 ℃ by selecting suitable temperature, following aqueous vapor balance is shifted to the direction of carbon monoxide and hydrogen:
Water is taken out from this balance, hydrolysis does not take place.The carbon monoxide/hydrogen mixture of this generation can energy or chemical aspect be used.
The method according to this invention aspect the kind of the used material that contains described element or aspect the specific surface area of this material all without any restriction.Also there is any restriction hardly aspect the kind of used carbon or carbonaceous material and the specific surface area.
The preferred parent material of selecting the method according to this invention can easily be mixed them industrial.For example can be to contain the material of described element and the grinding product of carbonaceous material, they are implemented process of lapping in the mode of separating or be pre-mixed.In another embodiment, composition part of this mixture or this mixture itself can be porous.This mixture especially preferably should have enough big pore volume, thereby can make gaseous halogen or gaseous halogen compound by wherein passing through, and promotes the reaction that is taken place in this way.Utilize the method according to this invention also can use and have the long-pending compact material of small specific surface, for example rough natural materials of pulverizing is as bauxite, ilmenite, quartz or sand.
Carbon of Shi Yonging or corresponding carbonaceous material are brought into play the effect of the heating element in the mixture on the one hand in the method according to the invention, the optional effect as reductive agent of performance on the other hand.In addition, used carbon is removed water by water is reduced into hydrogen, and has for example avoided the negative impact for the element halide of making facile hydrolysis of the water that can bring into by parent material or the water that discharges in reaction in this way.
Can obtain element halide basically quantitatively.In the method according to the invention, can use the various compounds that contain described element arbitrarily.
In all embodiments of the method according to this invention, can add catalyzer to reaction mixture, to improve speed of reaction or to improve the selectivity of desired element halide, use impure when containing the compound of described element especially in the method according to the invention.Catalyzer is introduced in the reaction mixture before can be in entering reactor, during reaction send into individually as solid, liquid or gas, perhaps as with the mixture of hydrogen halide in gas introduce in the reaction compartment.
In first embodiment of the method according to this invention, the material that contains described element preferably with particle for example the form of powder, particulate, ball or particulate used, thereby gaseous halogen or gaseous halogen compound are passed through easily.
The mol ratio of preferred element and carbon can't be limited in blanket mode, because the embodiment that the inventive method can be divided into the various minimum carbon content of many needs is with the desired element halide of quantitative generation:
1, reaction, wherein carbon is not brought into play the effect of reductive agent to the compound that contains described element; Carbon or carbonaceous material be only by being consumed with the reaction of impurity or with the reaction of the by product of halogenating reaction, and mainly bring into play the effect of filler and heating element.Therefore, must mix to produce uniform reaction mixture with the parent material that contains described element of being filled repeatedly always.In the case, the mol ratio of element and carbon is preferably 100: 1 to 1: 2.
2, carbon is as the reductive agent of pure element compound; In the case, must exist enough carbon to guarantee that described element is by stoichiometric reaction.Therefore, the heat that can continue to produce is excessive on stoichiometry is favourable.In the case, the molar ratio of element and carbon is preferably 1: 1 to 1: 10.
3, use carbon to contain the element compound of impurity with reduction.In the case, must exist enough carbon producing desired element halide, and must quantitative reaction impurity when desired parent material complete reaction; Selective reaction obviously is conceivable equally, especially for example according to U.S. Pat 4,083,927 when implementing to use catalyzer in the method according to this invention.Under this third situation, the mol ratio of the halide compound of carbon and all generations is preferably 10: 1 to 1: 1.
The temperature of reaction that is used to prepare the element halide of facile hydrolysis is preferably greater than 700 ℃, is preferably greater than 800 ℃ especially.
Used halogen gas is preferably chlorine.In another embodiment of the method according to this invention, use hydrogen halide, preferred hydrogen chloride gas (HCl) is as the gaseous halogen compound.Can use hydrogen fluoride (HF) equally.Containing the gas of halogen can purified form or use with vector gas.Vector gas is preferably CO
2Or be selected from rare gas element in following group: helium, nitrogen, argon gas and composition thereof.
In a preferred embodiment, obtain silicon tetrahalogen basically quantitatively.In the method according to the invention, can use various SiO arbitrarily basically
xThe source, wherein x represents 1 to 2 number.Use SiO
2Be favourable, but also can use SiO and/or both mixtures.Suitable SiO
xThe source for example is a sand, as desert sand or quartz sand, glass, rice hull ash and silicate.Therefore can use by SiO
xThat form or contain SiO
xAll material, comprise corresponding silicate.
In a particularly preferred embodiment of the method according to this invention, for example use desert sand as suitable SiO
xThe source is because it can supply use in a large number.This type of desert sand has the SiO greater than 80% usually
2Content.
The exemplary composition of desert sand is listed in (in %) in the following table 2:
Table 2: the per-cent of desert sand is formed
| Desert sand from Abu Dhabi | ||
| White sand | Red sand | |
| Fe 2O 3 | 0.32 | 1.21 |
| TiO 2 | 0.05 | 0.06 |
| CaO | 11.6 | 9.8 |
| K 2O | 0.91 | 1.12 |
| MgO | 1.08 | 3.40 |
| Na 2O | 0.59 | 0.51 |
| P 2O 5 | 0.05 | 0.02 |
| Al 2O 3 | 1.62 | 2.12 |
| SiO 2 | 83.8 | 81.8 |
SiO
xOr contain SiO
xMaterial preferably with particle for example the form of powder, particulate, ball or particulate used, thereby gaseous halogen or gaseous halogen compound are mixed easily and pass through easily.
SiO
xBe preferably 1: 1 to 1: 10 with the mol ratio of carbon, be preferably 1: 2 to 1: 7 especially.Because therefore the effect of carbon performance reductive agent and heating element is favourable to add above stoichiometry.
When making silicon halide, the preferred halogen gas that uses is a chlorine.Preferred fluorine in addition.In the case, can purified form or use gaseous halogen, gaseous state hydrogen halide or its mixture with vector gas.Vector gas is preferably the rare gas element that is selected from following group: helium, nitrogen, argon gas and composition thereof.
In another preferred embodiment, hydrogen is fed halogen, hydrogen halide or its mixture and optional vector gas, produce halogenated silanes H
aSiX
4-a, wherein a represents 0 to 3 integer, and X represents halogen.
In another embodiment that is used for making the method for silicon tetrahalogen according to the present invention, use hydrogen halide, preferred hydrogen chloride gas (HCl) as the gaseous halogen compound.Can use hydrogen fluoride (HF) equally.
At the SiO that contains according to the present invention
xMaterial and halogen gas (X
2) in the reaction under the situation that has carbon granule or carbonaceous particles, generate silicon tetrahalogen (SiX
4) and carbon monoxide (CO), carbon monoxide and carbonic acid gas (CO
2) be in the thermodynamic(al)equilibrium.
At the SiO that contains according to the present invention
xMaterial and the reaction of hydrogen halide under the situation that has carbon material or carbonaceous material in, generate halogenated silanes H
aSiX
4-a, wherein a represents 0 to 3 integer, and X represents halogen, and possible hydrogen and carbon monoxide CO, carbon monoxide and carbonic acid gas CO
2Be in the thermodynamic(al)equilibrium.
As heat-conduction medium and optional as reductive agent be used to prepare the carbon of element halide or corresponding carbonaceous material preferred equally with particle for example the form of powder, particulate, ball or particulate used, thereby can make halogen gas or halogen compounds mix easily and pass through easily.The kind of material therefor is not crucial.
The granulation of the mixture of being made up of element compound and carbonaceous material or granulating make contact especially intimately between two kinds of components; owing to can reach higher gas stream flux, compare higher speed of reaction simultaneously thereby observe with the situation of blended powder by the porosity of bead or little bed that forms.Can to the situation of the mixture of forming by element compound and carbonaceous material, implement to granulate or granulating at the binding agent that adds maximum 20%.Suitable binding agent is the carbon compound of using always, for example polyvinyl alcohol, polyvinyl acetate, Mierocrystalline cellulose, starch or molasses and the compound that contains element.
In another embodiment of the method according to this invention, the material that will contain described element is chosen wantonly with liquid form or as gas and feed solid-state carbon or the carbonaceous material that applies alternating electromagnetic field under the temperature that improves.
In another embodiment of the method according to this invention, the carbonaceous material of available alternating electromagnetic field heating chosen wantonly under the temperature that improves with liquid form or as gas introduce in the reaction compartment.
In another embodiment of the method according to this invention, choose wantonly under the temperature that improves with liquid form or as gas as the carbonaceous material of reductive agent part to the major general and to introduce in the reaction compartment.If in this reaction compartment, contained the carbon or the carbonaceous material of available alternating electromagnetic field heating, then need not equally with the liquid state or the gaseous state carbonaceous material of alternating electromagnetic field heating as reductive agent.
In another embodiment of the method according to this invention, used carbon or used carbonaceous material change into the form that available alternating electromagnetic field heats by alternating electromagnetic field such as microwave to the effect of substance mixture contained in this reaction compartment in reaction compartment.
In the embodiment of the method according to this invention, the effect of carbon or carbonaceous material performance heating element and reductive agent, thereby during reaction be consumed, so excessive interpolation is favourable on stoichiometry.
Reaction mixture is applied alternating electromagnetic field can cause lighting and stabilization of plasma body in the reaction compartment.
The method according to this invention can also be implemented in having the reactor that shakes bed of reaction mixture except can implementing in the fixed-bed reactor described in the enforcement scheme, for example agitated bed or shake bed or use fluidized bed process by vibration.For continuous operation, it is particularly advantageous that moving-bed is arranged.
In the method according to the invention, by the preferred microwave radiation intake of alternating electromagnetic field.Radiating power depends on the geometrical shape of reactor and content and the kind and the desired temperature of initial reactant.Under the situation of the element halide of facile hydrolysis, the preferred employing is higher than 800 ℃ temperature.
Another advantage of the method according to this invention especially is, can use element compound arbitrarily, because the input microwave energy is with the carbon of reacting by heating mixture, thereby reach a high temperature, almost can not or only reach this high temperature in the mode of quite high reactor material thermal stresses and use such as the traditional heat source of radiation heating.Equally, can't reach by the input rapid heating speed that microwave energy reached by traditional heat source such as radiation heating.Therefore, utilize microwave to heat and be considered to effective especially.
In the method that is used for making silicon tetrahalogen according to the present invention, utilize the alternating electromagnetic field intake.In the case, preferably utilize the microwave intake, especially power is 100W or higher microwave.Especially preferably import 400 to 900W microwave energy.Radiating power depends on the geometrical shape of reactor and the content of initial reactant.Find that shockingly observed spark discharge can cause very fast and active and enduringly between carbon granule or carbonaceous particles thus.The preferred employing is higher than 800 ℃ temperature.
Therefore, the method according to this invention can shockingly make SiO arbitrarily in a preferred embodiment
xThe source changes into silicon halide under the situation of not using catalyzer.In addition, the final product silicon tetrahalogen of gained is preferably not moisture.
The method according to this invention is preferred for using chlorine or hydrogenchloride to make the element muriate under as the situation of reactant gases.Utilize the method according to this invention, especially can use naturally occurring starting material, as desert sand or bauxite, and need not complicated pretreatment, except having its versatility, also have the simple and feature with low cost of processing thereby make the method according to this invention.
The method according to this invention is used for using Cl in an especially preferred embodiment
2Or make silicon tetrachloride under the situation of HCl as reactant gases.Utilize the method according to this invention, especially can use the naturally occurring SiO of containing
xMaterial (desert sand etc.), and need not complicated pretreatment, handle simple and feature with low cost thereby make the method according to this invention and except having its versatility, also have.
According to the present invention, can use the SiO that is selected from following group
xThe source: silicon-dioxide in small, broken bits is preferably the surface-area that utilizes the BET method to record and is at least 50m
2/ g more preferably is at least 250m
2The silicon-dioxide of/g; Meticulous silica powder is preferably median size and is at least 0.1 μ m, and more preferably at least 1 μ m and theoretical specific surface area are preferably 0.1m at least
2/ g, more preferably 0.5m
2The silica powder of/g; Quartz sand, its median size is at least 0.005mm, is preferably 0.1mm, and theoretical specific surface area is at least 10cm
2/ g, more preferably 50cm
2/ g; Desert sand, its particle diameter is preferably 0.001 to 1mm; Vial as lime soda glass, is preferably through pulverizing or the grinder; Pyrogenic silica, mica and SiO powder, its particle diameter are preferably 0.01 μ m to 0.1mm.
Set forth the present invention by means of the relevant embodiment of industry below.Special element-the oxygen with high element-oxygen bond enthalpy that uses makes up.They are listed in the table 3.
Table 3
| Element | Bond enthalpy [kJ/mol] |
| Al | 512 |
| B | 808 |
| Si | 800 |
| Ti | 672 |
| Hf | 802 |
| P | 600 |
Embodiment
Embodiment
Embodiment 1
Because the operability and the thermotolerance of pyrogenic silica are used the device and the reaction carriers that comprise this material.It is unaffected under reaction conditions.For the protective glass device is not reacted and the influence of thermal stresses, reactant to be introduced on the pyrogenic silica carrier in the reactor, it comprises and has the sufficient pyrogenic silica pipe that vertically is cut into half.Therefore, owing to have little surface-area and the significantly lower temperature of comparing with powdered or particulate state reaction mixture, the speed of reaction of reactor outer wall obviously reduces, and does not observe breaking of reactor outer wall between the reaction period at single.
The mixture that 1 to 1.5 gram is made up of listed material and same listed carbonaceous material places (be cut into the pyrogenic silica pipe of half, diameter is 13mm, and length is about 100mm, the sufficient 5mm of pyrogenic silica) on the pyrogenic silica carrier.This pyrogenic silica carrier is introduced in the reaction tubes (pyrogenic silica pipe, diameter are 30mm, and length is 550mm), and this reaction tubes is packed into, and (MX 4000 for microwave reactor; MUEGGE Electronics Co., Ltd.) in the focus.By activating microwave reactor to make Cl under the situation that heats (550 to 1300 ℃)
2Or HCl air-flow (1 to 5 liter/minute) passes through reaction tubes.To be in a liquid state under the usual conditions or the gasiform reaction product is equipped with in the cold-trap of pentane to go out with the ethanol cryostat condensation that is lower than-30 ℃ therein.Reaction times is about 10 minutes.
In this testing apparatus, make the following compound and the carbon compound reaction that is selected from following group that contains element: gac (high purity, about 2.5mm), gac (high purity, powder), graphite (high purity), hard coal (German hard coal), brown coal (RWE powder) and petroleum coke (OMV).
The compound that contains element:
Aluminum oxide (III);＜150 μ m, 99%
Boron oxide (III); High purity, 〉=99.98%
Ferric oxide (III); 5 μ m, 〉=99%
Hafnia (IV); 98%
Mica sheet
Silicon carbide; 37 μ m
Silicon-dioxide (380m in small, broken bits
2/ g)
Meticulous silica powder (median size 3 μ m, theoretical specific surface area 0.75m
2/ g)
Quartz sand (median size 0.32mm, theoretical specific surface area 75cm
2/ g)
Desert sand; (Sahara Desert, coordinate N23 ° 27.419; 009 ° 01.489 of E, particle diameter＜0.5mm)
The callable brown beverage bottle of pulverizing (amber glass)
The Pasteur suction pipe of pulverizing (lime soda glass)
Japan's rice hull ash
Catalyzer based on zeolite
Silicon nitride; Si
3N
4, 44 μ m
Silicon monoxide; ≤ 44 μ m
Titanium dioxide; 〉=99.8%;
Tricalcium phosphate; 35 to 40%Ca.
Compare with the n-compound that can buy, utilize GCMS to reach
29Si NMR is to detect silicon tetrachloride.
Compare with the n-compound that can buy, utilize
11B NMR reaches
31P NMR is to detect boron trichloride and the phosphorus trichloride as the diethyl ether adducts.Utilize EDX and X-ray powder diffraction to detect ferrous chloride, aluminum chloride and hafnium tetrachloride.
Can't directly detect titanium tetrachloride with the current experiments chamber device.The pentane solution of being fuming strongly is transferred in the GC bottle.After the precipitate that forms, take out the upper strata settled solution by barrier film, and be transferred in the new bottle by barrier film.By barrier film water is sneaked into this settled solution.Produce the white depositions of large volume immediately.It is carried out drying, and be accredited as titanium oxide with EDX.
Embodiment 2
(be cut into the pyrogenic silica pipe of half at the pyrogenic silica carrier, diameter is 13mm, length is about 100mm, the sufficient 5mm of pyrogenic silica) go up to place by maximum particle diameter be that the desert sand of 0.5mm and particle diameter are the SiO that 2 to 2.5mm gac is formed with 1: 4 ratio
2/ C mixture 1 to 1.5 gram.The pyrogenic silica carrier is packed in the reaction tubes (Glass tubing, diameter is 30mm, has two chimneys, overflow pipe and upper conduits, mean distance is 100mm), this reaction tubes is packed in the focus of microwave reactor (Panasonic's household electrical appliance).Make cl gas flow (40 liters/hour in chlorine, 10 liters/hour of argon gas) pass through this reaction tubes by argon-dilution.After heating by the activation of microwave device, in being housed, the cold-trap of pentane goes out reaction product with the ethanol cryostat condensation that is lower than-30 ℃.Quantitatively reach qualitative analysis.The reaction product of gained is SiCl
4
In 15 to 20 minutes reaction times, make 50 to 60% husky conversion the in desert, wherein at reaction SiO
2+ 2C+2Cl
2→ SiCl
4Deviation of weight by sample after the+2CO calculates.Further do not reduce if the continuation radiation was observed weight after 5 minutes, then stop experiment.At the SiO that has considered in used sand
2Content is about 80% and wherein form CO by CO
2And under the situation of the Boudouard equilibrated of C influence, correspondingly improved SiO
2Actual conversion.Therefore, based on SiO
xThe source can obtain quantitative basically productive rate.
Embodiment 3
Make the mixture of forming by hydrogenchloride (60 liters/hour) and nitrogen (40 liters/hour) by the testing apparatus described in the embodiment 1.In 15 to 20 minutes reaction times, make 50 to 60% husky conversion the in desert, wherein at reaction SiO
2+ 2C+2Cl
2→ SiCl
4Deviation of weight by sample after the+2CO calculates.Further do not reduce if the continuation radiation was observed weight after 5 minutes, then stop experiment.Considering the SiO in the sand
2Content is about 80% and wherein form CO by CO
2And under the situation of the Boudouard equilibrated of C influence, correspondingly improved SiO
2Actual conversion.Therefore, based on SiO
xThe source can obtain quantitative basically productive rate.
Embodiment 4
Make the mixture of forming by hydrogenchloride (20 liters/hour) and hydrogen (20 liters/hour) by the testing apparatus described in the embodiment 1.Isolating product contains SiCl
4And HSiCl
3
Claims (25)
1, is used to make the method for element halide, it is characterized in that, the mixture that will form by the material that contains described element and carbon or carbonaceous material under the situation that the effect that utilizes alternating electromagnetic field is heated with contain the air-flow that under reaction conditions, is gasiform halogen or gasiform halogen compounds or their mixture and contact.
2, method according to claim 1 is characterized in that, uses the dusty material that contains respective element.
3, method according to claim 1 and 2 is characterized in that, uses microgranular or pulverous carbon or carbonaceous material.
4, according to claim 1 or 3 described methods, it is characterized in that, introduce in the reaction compartment with liquid form or as the material that contains described element of gas.
5, according to claim 1,2 or 4 described methods, it is characterized in that, introduce in the reaction compartment with liquid form or as the described carbonaceous material of gas.
6, according to the described method of one of claim 1 to 5, it is characterized in that, produce used alternating electromagnetic field by microwave radiation.
7, according to the described method of one of claim 1 to 6, it is characterized in that, by used carbon or the carbonaceous material of described alternating electromagnetic field heating.
According to the described method of one of claim 1 to 7, it is characterized in that 8, described carbon or carbonaceous material are converted to the form that available this alternating electromagnetic field heats by alternating electromagnetic field to the effect of the substance mixture that exists in the reaction compartment.
9, according to the described method of one of claim 1 to 8, it is characterized in that, under reaction conditions, be gasiform halogen, gasiform halogen compounds or its mixture and use with vector gas.
10, according to the described method of one of claim 1 to 9, it is characterized in that, use fluorine-containing or chloride compound as the compound that contains halogen.
11, according to the described method of one of claim 1 to 10, it is characterized in that, use chlorine, perhaps use hydrogenchloride as the gaseous halogen compound as gaseous halogen.
12, according to the described method of one of claim 1 to 11, it is characterized in that, use any compound that contains corresponding element.
According to the described method of one of claim 1 to 12, it is characterized in that 13, contained element is a metal or nonmetal in used element compound.
According to the described method of one of claim 1 to 13, it is characterized in that 14, the compound that contains described element exists with the form with the mixture of other materials.
According to the described method of one of claim 1 to 14, it is characterized in that 15, during producing element halide, used carbon or carbonaceous material change at least in part can not be by the carbon compound of alternating electromagnetism field excitation.
16, according to the described method of one of claim 1 to 15, it is characterized in that, the preparation facile hydrolysis element halide the time with described mixture heating up to being higher than 700 ℃.
17, according to the described method of one of claim 1 to 16, it is characterized in that, use naturally occurring starting material as the material that contains element.
18, according to the described method of one of claim 1 to 17, it is characterized in that, use the by product of Industrial processes or the material that the refuse conduct contains described element.
19, according to the described method of one of claim 1 to 18, it is characterized in that, before being used for the method according to this invention, the material that contains described element is implemented purification step or is used to improve the step of the concentration of this element.
20, according to the described method of one of claim 1 to 19, it is characterized in that, use and contain SiO
xMaterial as containing the material of element, wherein x can be 1 to 2 number.
21, method according to claim 20 is characterized in that, defeated 100 to 900W microwave energy.
22, according to claim 20 or 21 described methods, it is characterized in that, additionally hydrogen is fed in the reactant gases.
23, according to the described method of one of claim 20 to 22, it is characterized in that, use hydrogenchloride as the gaseous halogen compound.
24, according to the described method of one of claim 20 to 23, it is characterized in that, use Si oxide source conduct arbitrarily to contain Si oxide SiO
xMaterial.
25, method according to claim 24 is characterized in that, uses desert sand as described Si oxide source.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004055687.3 | 2004-11-18 | ||
| DE102004055687 | 2004-11-18 | ||
| DE102005024104.2 | 2005-05-25 |
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| CN101061060A true CN101061060A (en) | 2007-10-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200580039498 Pending CN101061060A (en) | 2004-11-18 | 2005-11-10 | Process for preparing element halides |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863502A (en) * | 2010-06-24 | 2010-10-20 | 浙江师范大学 | Preparation method of beta-aluminum fluoride with high specific surface area |
| CN103708470A (en) * | 2013-12-20 | 2014-04-09 | 贵州万方铝化科技开发有限公司 | Preparation method of SiF4 |
| CN104169217A (en) * | 2011-10-27 | 2014-11-26 | 斯帕恩特私人有限公司 | Method for producing tetrahalosilanes |
| CN105753029A (en) * | 2016-05-19 | 2016-07-13 | 东北大学 | Method for preparing anhydrous aluminum chloride by performing microwave chlorination on bauxite |
| CN106006692A (en) * | 2016-05-19 | 2016-10-12 | 东北大学 | Method for preparing anhydrous aluminum chloride by microwave chlorination of fly ash |
| CN106011498A (en) * | 2016-05-19 | 2016-10-12 | 东北大学 | Method for preparing metal aluminum from bauxite through microwave chlorination |
| CN106048226A (en) * | 2016-05-19 | 2016-10-26 | 东北大学 | Method for preparing metal aluminum through microwave chlorination of coal ash |
| CN108584992A (en) * | 2018-07-12 | 2018-09-28 | 赣州有色冶金研究所 | A kind of method that vapor phase method prepares anhydrous lithium chloride |
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2005
- 2005-11-10 CN CN 200580039498 patent/CN101061060A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863502A (en) * | 2010-06-24 | 2010-10-20 | 浙江师范大学 | Preparation method of beta-aluminum fluoride with high specific surface area |
| CN104169217A (en) * | 2011-10-27 | 2014-11-26 | 斯帕恩特私人有限公司 | Method for producing tetrahalosilanes |
| CN103708470A (en) * | 2013-12-20 | 2014-04-09 | 贵州万方铝化科技开发有限公司 | Preparation method of SiF4 |
| CN103708470B (en) * | 2013-12-20 | 2016-02-03 | 贵州天合国润高新材料科技有限公司 | SiF 4preparation method |
| CN105753029A (en) * | 2016-05-19 | 2016-07-13 | 东北大学 | Method for preparing anhydrous aluminum chloride by performing microwave chlorination on bauxite |
| CN106006692A (en) * | 2016-05-19 | 2016-10-12 | 东北大学 | Method for preparing anhydrous aluminum chloride by microwave chlorination of fly ash |
| CN106011498A (en) * | 2016-05-19 | 2016-10-12 | 东北大学 | Method for preparing metal aluminum from bauxite through microwave chlorination |
| CN106048226A (en) * | 2016-05-19 | 2016-10-26 | 东北大学 | Method for preparing metal aluminum through microwave chlorination of coal ash |
| CN106011498B (en) * | 2016-05-19 | 2018-05-04 | 东北大学 | A kind of method that bauxite microwave chlorination prepares metallic aluminium |
| CN106048226B (en) * | 2016-05-19 | 2018-10-23 | 东北大学 | A kind of method that the chlorination of flyash microwave prepares metallic aluminium |
| CN108584992A (en) * | 2018-07-12 | 2018-09-28 | 赣州有色冶金研究所 | A kind of method that vapor phase method prepares anhydrous lithium chloride |
| CN108584992B (en) * | 2018-07-12 | 2020-07-10 | 赣州有色冶金研究所 | Method for preparing anhydrous lithium chloride by gas phase method |
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