JP3729236B2 - Method for producing alkylhalosilane - Google Patents
Method for producing alkylhalosilane Download PDFInfo
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- JP3729236B2 JP3729236B2 JP19506698A JP19506698A JP3729236B2 JP 3729236 B2 JP3729236 B2 JP 3729236B2 JP 19506698 A JP19506698 A JP 19506698A JP 19506698 A JP19506698 A JP 19506698A JP 3729236 B2 JP3729236 B2 JP 3729236B2
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- boron
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- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 229910052796 boron Inorganic materials 0.000 claims description 74
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 72
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 62
- 229910052751 metal Inorganic materials 0.000 claims description 55
- 239000002184 metal Substances 0.000 claims description 55
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 38
- 239000010703 silicon Substances 0.000 claims description 33
- 229910052710 silicon Inorganic materials 0.000 claims description 32
- 239000011863 silicon-based powder Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 24
- 150000001639 boron compounds Chemical class 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 150000001350 alkyl halides Chemical class 0.000 claims description 12
- 238000007670 refining Methods 0.000 claims description 9
- 229910052582 BN Inorganic materials 0.000 claims description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052580 B4C Inorganic materials 0.000 claims description 4
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- FFBGYFUYJVKRNV-UHFFFAOYSA-N boranylidynephosphane Chemical compound P#B FFBGYFUYJVKRNV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 claims description 3
- 229910000149 boron phosphate Inorganic materials 0.000 claims description 3
- 239000003426 co-catalyst Substances 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- FZQBLSFKFKIKJI-UHFFFAOYSA-N boron copper Chemical compound [B].[Cu] FZQBLSFKFKIKJI-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 81
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 36
- 230000001186 cumulative effect Effects 0.000 description 18
- 229940050176 methyl chloride Drugs 0.000 description 18
- 229910000975 Carbon steel Inorganic materials 0.000 description 17
- 239000010962 carbon steel Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 239000011261 inert gas Substances 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 229910052785 arsenic Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 5
- 239000007809 chemical reaction catalyst Substances 0.000 description 5
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical group C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 5
- -1 phosphorus compound Chemical class 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 2
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OFEAOSSMQHGXMM-UHFFFAOYSA-N 12007-10-2 Chemical compound [W].[W]=[B] OFEAOSSMQHGXMM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017755 Cu-Sn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017927 Cu—Sn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 229910007610 Zn—Sn Inorganic materials 0.000 description 1
- MKOYQDCOZXHZSO-UHFFFAOYSA-N [Cu].[Cu].[Cu].[As] Chemical compound [Cu].[Cu].[Cu].[As] MKOYQDCOZXHZSO-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- VDZMENNHPJNJPP-UHFFFAOYSA-N boranylidyneniobium Chemical compound [Nb]#B VDZMENNHPJNJPP-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910021540 colemanite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940108928 copper Drugs 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 239000005048 methyldichlorosilane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Description
【０００１】
【発明の属する技術分野】
本発明は、アルキルハロシランの直接法による製造方法に関し、特に金属珪素とアルキルハライドを銅触媒存在下で気−固接触反応させてアルキルハロシランを連続的に製造するアルキルハロシランの製造方法に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
アルキルハロシランの合成法に関しては、米国特許第２，３８０，９９５号においてロコーが銅触媒による金属珪素とアルキルハライドとの直接法を開示して以来、銅触媒の存在下で用いる種々の助触媒に関するもの、銅触媒とその処理に関するもの、反応装置に関するもの、反応時の添加物に関するものなど、数多くの研究者によって、その成果が報告されてきた。
【０００３】
この直接法は、金属珪素に銅触媒を添加した触体を活性化した後、これにアルキルハライドを導入して金属珪素とアルキルハライドとを直接気−固接触させることにより、アルキルハロシランを得る方法である。アルキルハロシランの工業的合成においては、シリコーン樹脂に最も多用されるジアルキルジハロシランの選択性、及びシランの生成速度が重要とされる。ジアルキルジハロシランの選択性は生成シラン中の重量比（あるいはモル比）、及びＴ／Ｄ比により評価される。生成アルキルハロシラン中に含まれる物質としては、ジアルキルジハロシラン（Ｄ）、トリアルキルハロシラン（Ｍ）、アルキルトリハロシラン（Ｔ）などが挙げられ、アルキルヒドロジハロシラン（Ｈ）やアルキルハロジシラン類も生成する。特に、シラン製造業者において残渣と呼ばれるジシラン類は有効な利用方法が少なくほとんどが廃棄されているものである。Ｔ／Ｄ比とは全生成アルキルハロシラン中のアルキルトリハロシランとジアルキルジハロシランの組成比でありＴ／Ｄ比が小さいほど好ましい。一方、アルキルハロシランの生成速度は、ＳＴＹ（Ｓｐａｃｅ Ｔｉｍｅ Ｙｉｅｌｄ）値を用いる。ＳＴＹ値は反応器内に保持される金属珪素重量に対する単位時間当たりの生成粗アルキルハロシランの重量である。これら生成ジアルキルジハロシラン組成の向上あるいはＴ／Ｄ比の低下及びＳＴＹ値を向上させるため、触媒、促進剤を中心とした種々の研究がなされてきた。
【０００４】
１９５９年１月２４日付のソヴィエト出願明細書第６１７，５６９号（発明者証第１２２，７４９号）では、金属珪素−銅合金にアンチモンを２０〜４０ｐｐｍ添加した反応が開示されている。このときジメチルジクロロシランの組成は４０％から６０％へ向上したことが示されている。また、米国特許第４，５００，７２４号においては、２００〜３０００ｐｐｍの錫を含有する銅／亜鉛／錫系触媒を用いることによりＴ／Ｄが０．０３７に向上したことが示されている。更に、特公平６−９２４２１号公報においては、砒素濃度にして５０ｐｐｍ以上のヒ化銅を用いた反応が開示されている。これら錫、アンチモン、砒素助触媒は、金属珪素−銅からなる反応触体に添加することで反応活性を高め、従って金属珪素の反応率を向上させ得ることが述べられている。
【０００５】
１９６４年６月２日付のソヴィエト出願明細書第９０３，３６９号（発明者証第１７８，８１７号）では、亜鉛、ビスマス、リン（２００ｐｐｍ）、砒素、錫、鉄から選択された助触媒を用いてジメチルジクロロシランの組成が前述の出願明細書第６１７，５６９号（発明者証第１２２，７４９号）から７２．１％まで向上している。また、１９６９年１１月２０日付のソヴィエト出願明細書第１，１５２，９４３号（発明者証第２３７，８９２号）において、リン、銅、珪素の合金の形態で触体に対して２５００〜３００００ｐｐｍのリンを添加することが示されており、ジメチルジクロロシラン組成は８２．３％と改善されている。また、米国特許第４，６０２，１０１号（特公平５−５１５９６号公報）においては、反応器内で元素状のリンが発生するリン化合物を触体に対して２５〜２５００ｐｐｍ添加することが示されている。
【０００６】
以上のようにこれまで多くの研究者がアルキルハロシランの直接法の改良を目指して種々の金属の助触媒効果を検討してきたが、更に有効な助触媒が望まれている。
【０００７】
本発明は、上記事情に鑑みなされたもので、所望のＳＴＹにおいてジアルキルジハロシランの生産量を高め、かつ不必要なジシラン類を減少させるアルキルハロシランの直接法による製造方法を提供することを目的とする。
【０００８】
【課題を解決するための手段及び発明の実施の形態】
本発明者らは、工業的に有効な直接法によるアルキルハロシランの製造方法、特に、所望のＳＴＹにおいてジアルキルジハロシランの生産量を高め、かつ不必要なジシラン類を減少させるアルキルハロシランの直接法について鋭意検討を行った結果、硼素を含有した反応触体を使用することによって反応活性を維持しながらハイドロシラン類、ジシラン類の生成を減少せしめ、従ってジアルキルジハロシランの生産量を高めることを見出した。
【０００９】
即ち、上述したように、従来より種々の助触媒について検討されてきたが、本発明に係る硼素化合物に関してはこれまで殆んど検討されておらず、例えばＴｕｓｅｔ，Ｊ．Ｋ．，Ｉｎｔ．Ｓｅｍ．ｏｎ Ｒｅｆｉｎｉｎｇ ａｎｄ Ａｌｌｏｙｉｎｇ ｏｆ Ｌｉｑｕｉｄ Ａｌ ＆ Ｆｅｒｒｏａｌｌｏｙｓ（１９８５）Ｔｒｏｎｄｈｅｉｍには標準的な金属珪素中の硼素濃度は多くても５０ｐｐｍであり、直接法反応に使用される精製された金属珪素では多くても４０ｐｐｍであることが示されているが、多くの総説において直接法の反応活性は殆んどないか、あるいは多量に使用する場合には触媒毒となると示されているのみである。しかしながら、実際に使用する金属珪素中の硼素含有濃度は原料となる硅石の生産諸国により著しく異なる。硼素含有濃度は元来少ない上に、通常は金属珪素の精錬工程で一層低減され、触体中には実質的に硼素は殆ど含まれていないものである。本発明者の分析によれば、ブラジル等南米産、中国産、オーストラリア産の精錬金属粉末中の硼素濃度は、１０ｐｐｍ以下、フランス、ノルウェー等の欧州産の精錬金属珪素粉末中の硼素濃度は、１０ｐｐｍ以上３０ｐｐｍ以下のものが多数をしめている。
【００１０】
ところが、本発明者は、従来はむしろ触媒毒となると考えられていた硼素が助触媒として優れた効果を有し、触体中に硼素を含有させることにより、反応活性を維持しながらハイドロシラン類、ジシラン類の生成を減少させ、ジアルキルジハロシランの生産量を高めることができることを知見し、本発明をなすに至った。
【００１１】
以下、本発明を更に詳しく説明すると、本発明のアルキルハロシランの製造方法は、金属珪素粉末と銅触媒とを含む触体を反応器に仕込み、該反応器にアルキルハライドを含むガスを導入して直接合成法により、下記一般式
ＲnＳｉＸ4-n
（但し、式中Ｒは炭素数１〜４のアルキル基、Ｘはハロゲン原子を示し、ｎは０〜４の整数である。）
で示されるシラン類を製造する方法において、珪素精錬工程を含む工程における溶融状態の金属珪素に硼素化合物を添加することによって得られる硼素を含有する金属珪素粉末及び／又は硼素もしくは硼素化合物を添加することにより助触媒として上記触体に５０〜１００００ｐｐｍの硼素元素を含有させたことを特徴とするものである。
【００１２】
ここで、金属珪素は、通常、珪素の純度が９７重量％以上、特に純度が９８重量％以上のものを用いることが好ましい。また、金属珪素は粉砕し、適当な粒度を持った粉末として使用することが好ましく、反応器として流動層反応器又は撹拌型反応器を用いる場合は、金属珪素粉末に良好な流動性を持たせるため、金属珪素粉末の粒子径は篩分による重量基準累積分布曲線の５０％に相当する粒径として５〜１５０μｍの範囲とすることが好ましい。
【００１３】
また銅触媒としては、銅粉末、スタンピング銅などの単体銅あるいは酸化第一銅、酸化第二銅、ハロゲン化銅などの銅化合物など種々の形態のものを用いることができる。また助触媒として、亜鉛、錫、アンチモン、砒素などの種々の促進剤を用いてもよく、これらは単独で用いても銅との合金として用いてもよい。例示すると金属亜鉛、金属錫、金属アンチモン、金属砒素粉及びこれらの塩化物あるいは酸化物、Ｃｕ−Ｚｎ，Ｃｕ−Ｓｎ，Ｃｕ−Ｚｎ−ＳｎあるいはＺｎやＳｎの代わりにＳｂ，Ａｓを用いた銅合金が一般に製造可能である。またこれらの銅触媒は反応器中に単独で仕込んでもよいし、金属珪素粉末と共に合金として仕込んでもよい。これら銅触媒の配合量は、金属珪素粉末１００部（重量部、以下同じ）に対して銅量に換算して０．１〜１０部、特に２〜８部とすることが好ましい。また亜鉛の配合量は、金属珪素粉末１００部に対して０．０５〜１部、錫、アンチモン及び砒素の配合量は、金属珪素粉末に対していずれか一種あるいは合計で０．００１〜０．０５部、好ましくは０．００５〜０．０１部とするのがよい。
【００１４】
本発明においては、上記触体として、硼素元素を５０〜８０００ｐｐｍ、更に好ましくは５５〜６０００ｐｐｍ、最も好ましくは２００〜５０００ｐｐｍ含むものを使用する。
【００１５】
この場合、触体中の硼素を上記濃度にする方法としては、触体を構成する金属珪素として硼素濃度の高い金属珪素を用いる方法、金属珪素の製造において、金属珪素の溶融温度で揮発性の少ない硼素化合物を添加し、硼素濃度の高い金属珪素を使用する方法、更に直接法反応器中の反応触体に硼素化合物を添加する方法が挙げられる。
【００１６】
ここで、硼素を含む金属珪素は、原料珪素の精製工程を含むプロセスの中で硼素化合物を珪素に供給することによって得ることができ、この場合、不揮発性の化合物を珪素精錬工程を含む工程における溶融状態の金属珪素に加えることができる。この際に用いられる硼素化合物としては、ほう砂（Ｎａ2Ｂ4Ｏ7・１０Ｈ2Ｏ）、カーン石（Ｎａ2Ｂ4Ｏ7・１４Ｈ2Ｏ）、コールマン石（Ｃａ2Ｂ6Ｏ11・５Ｈ2Ｏ）等の硼素を含有する天然鉱物や、Ｍ1 2Ｂ（但し、Ｍ1はＦｅ，Ｃｏ，Ｎｉ，Ｍｎ，Ｍｏ，Ｗ，Ｔａ等を示す）、Ｍ2 3Ｂ2（但し、Ｍ2はＭｇ等を示す）、Ｍ3Ｂ（但し、Ｍ3はＦｅ，Ｃｏ，Ｎｉ，Ｍｎ，Ｃｒ，Ｍｏ，Ｗ，Ｎｂ，Ｔａ等を示す）、Ｍ4 3Ｂ4（但し、Ｍ4はＴａ，Ｎｂ，Ｍｎ，Ｃｒ等を示す）、Ｍ5Ｂ2（但し、Ｍ5はＴｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａ，Ｃｒ等を示す）、Ｍ6 2Ｂ5（但し、Ｍ6はＭｏ，Ｗ等を示す）で示される硼化物、窒化硼素、炭化硼素、燐化硼素、硼素リン酸塩などを挙げることができる。また、珪素精錬条件下に硼素化合物を加えた際、この硼素化合物が還元されて硼素が含有された珪素を用いることも好ましいが、このような硼素化合物としては、硼酸、硼酸金属塩、酸化硼素を挙げることができる。
【００１７】
また、硼素化合物は、気相状あるいは直ちに揮発するものを用いることができる。
【００１８】
更に、珪素に硼素を含有させる方法としては、珪素精錬の原料として、硼素を含有する石英、硼素を含有する石炭、硼素を含有するコークス、硼素を含有する木炭、硼素を含有するユーカリを使用する方法を挙げることもできる。また、珪素精錬の電極として硼素を含有するカーボン電極を用いる方法を採用してもよい。
【００１９】
一方、反応触体に硼素化合物を添加する場合、硼素は、例えば酸化物を還元して得られる無定形硼素等の元素硼素、硼素−銅合金、上記と同様のＭ1 2Ｂ、Ｍ2 3Ｂ2、Ｍ3Ｂ、Ｍ4 3Ｂ4、Ｍ5Ｂ2、Ｍ6 2Ｂ5で示される硼化物、窒化硼素、炭化硼素、燐化硼素、硼素リン酸塩等を挙げることができる。これらを直接法反応器に添加する場合には、微量の水分を除去するために予め２００℃程度で加熱脱水処理を施すことが更に好ましい。また、添加する硼素化合物として、気相状あるいは直ちに揮発するハロゲン化硼素等を用いることができる。
【００２０】
金属珪素と反応させてアルキルハロシランを得るためのアルキルハライドとしては、塩化メチル、塩化エチル、塩化プロピル、臭化メチル、臭化エチルなどを例示することができる。この中で工業的に最も有用なものは塩化メチルであり、これを用いて製造されるジメチルジクロロシランは多くのシリコーン樹脂の原料として幅広い用途がある。アルキルハライドは予め昇温し、ガス化した後、反応器へ送入する。この場合、アルキルハライドガスを単独で送入してもよいし、不活性ガスとの混合ガスとしてもよい。このアルキルハライドガスの送入量は、不活性ガスと合わせて触体が流動化する量として算出され、用いる反応器の直径と空塔速度から適宜決定される。
【００２１】
触体の加熱又は触体への触媒活性付与工程において、反応器内の触体の流動化に用いる不活性ガスは、窒素ガス、アルゴンガス等が例示されるが、経済性の点から、窒素ガスを用いることが好ましい。これらの工程における不活性ガスの流速は触体の流動化開始速度以上であればよいが、特に流動化開始速度の５倍程度が好ましい。不活性ガスの流速をこの範囲より小さくすると触体の均一な流動化が困難となり、一方、不活性ガスの流速をこの範囲より大きくすると、金属珪素粉の飛散が増加し、また不活性ガスのロスや熱のロスが増加するため不利となる場合が生じる。また、不活性ガスを循環使用することがより好ましい。
【００２２】
上述のようにして触体への触媒活性付与を行った後、反応器にアルキルハライドを導入し、常法に従い、アルキルハライドと金属珪素とを気−固接触反応させることによりアルキルハロシランを得ることができる。この場合、反応温度は２８０〜３００℃とすることができる。なお、反応方法としては、流動層内で連続条件の下に反応を行う方法、撹拌層で反応を行う方法、固定層で反応を行う方法などを挙げることができる。
【００２３】
【実施例】
以下、実施例を示し、本発明を具体的に説明するが、本発明は下記の実施例に限定されるものではない。なお、下記の例において部は重量部を示す。
【００２４】
〔実施例１，２〕
直径５０ｍｍ、高さ３００ｍｍのカーボンスチール製の流動層反応器に、金属珪素粉を１００部、金属銅粉よりなる触媒混合物４部を仕込んだ。また表１に示す硼素化合物を種々の添加量で仕込んだ。
【００２５】
その後、塩化メチルを流速１．３ｃｍ／ｓｅｃで反応器に導入し、反応器内温度を３３０℃まで上げ、反応を継続し、６時間後反応を停止した。反応開始から反応終了時までの累積のＳＴＹを表１に示す。また、生成した全メチルクロロシラン量に対するジメチルジクロロシランの割合、メチルジクロロシランの割合、高沸点生成物（生成メチルクロロシラン中のジシランなどの常圧における沸点が７０℃より高い生成物）の割合も表１にそれぞれＤ、Ｈ、Ｒとして併記する。なお、上記ＳＴＹは以下の意味を示す。
【００２６】
【数１】
【表１】
〔実施例３〕
直径５０ｍｍ、高さ３００ｍｍのカーボンスチール製の流動層反応器に、硼素を７４ｐｐｍ含有する金属珪素粉を１００部、金属銅粉よりなる触媒混合物４部を仕込んだ。触体中の硼素濃度を表２に示す。
【００３１】
その後、塩化メチルを流速１．３ｃｍ／ｓｅｃで反応器に導入し、反応器内温度を３３０℃まで上げ、反応を継続し、６時間後反応を停止した。反応開始から反応終了時までの累積のＳＴＹ、Ｄ、Ｈ、Ｒを表２に示す。
【００３２】
〔実施例４〕
直径５０ｍｍ、高さ３００ｍｍのカーボンスチール製の流動層反応器に、硼素を１４８ｐｐｍ含有する金属珪素粉を１００部、金属銅粉よりなる触媒混合物４部を仕込んだ。触体中の硼素濃度を表２に示す。
【００３３】
その後、塩化メチルを流速１．３ｃｍ／ｓｅｃで反応器に導入し、反応器内温度を３３０℃まで上げ、反応を継続し、６時間後反応を停止した。反応開始から反応終了時までの累積のＳＴＹ、Ｄ、Ｈ、Ｒを表２に示す。
【００３４】
〔実施例５〕
直径５０ｍｍ、高さ３００ｍｍのカーボンスチール製の流動層反応器に、硼素を２２００ｐｐｍ含有する金属珪素粉を１００部、金属銅粉よりなる触媒混合物４部を仕込んだ。触体中の硼素濃度を表２に示す。
【００３５】
その後、塩化メチルを流速１．３ｃｍ／ｓｅｃで反応器に導入し、反応器内温度を３３０℃まで上げ、反応を継続し、６時間後反応を停止した。反応開始から反応終了時までの累積のＳＴＹ、Ｄ、Ｈ、Ｒを表２に示す。
【００３６】
〔比較例１〕
直径５０ｍｍ、高さ３００ｍｍのカーボンスチール製の流動層反応器に、硼素を０．０３２ｐｐｍ含有する金属珪素粉を１００部、金属銅粉よりなる触媒混合物４部を仕込んだ。触体中の硼素濃度を表２に示す。
【００３７】
その後、塩化メチルを流速１．３ｃｍ／ｓｅｃで反応器に導入し、反応器内温度を３３０℃まで上げ、反応を継続し、６時間後反応を停止した。反応開始から反応終了時までの累積のＳＴＹ、Ｄ、Ｈ、Ｒを表２に示す。
【００３８】
〔比較例２〕
直径５０ｍｍ、高さ３００ｍｍのカーボンスチール製の流動層反応器に、硼素を０．５０ｐｐｍ含有する金属珪素粉を１００部、金属銅粉よりなる触媒混合物４部を仕込んだ。触体中の硼素濃度を表２に示す。
【００３９】
その後、塩化メチルを流速１．３ｃｍ／ｓｅｃで反応器に導入し、反応器内温度を３３０℃まで上げ、反応を継続し、６時間後反応を停止した。反応開始から反応終了時までの累積のＳＴＹ、Ｄ、Ｈ、Ｒを表２に示す。
【００４０】
なお、上記実施例３〜５、比較例１、２において、硼素は硼酸、硼酸金属塩（金属はナトリウムあるいはカリウム）、酸化硼素を用いて所定量を含有させた。この場合、これら硼素化合物は、原料珪素の精錬工程において、還元反応前に、原料硅石、木炭、木片等と共に電炉釜に添加し、１５００℃以上でアークを発生させ、還元反応を行った。その後、容器を移し換え、窒素、空気によるバブリングを１時間以上２０時間以下行い、酸化物スラグと分別し、冷却するという方法で処理した。
【００４１】
【表２】
〔実施例６〕
直径５０ｍｍ、高さ３００ｍｍのカーボンスチール製の流動層反応器に、硼素を７．０ｐｐｍ含有する金属珪素粉を１００部、金属銅粉３．７部、硼素を２．０重量％含有する金属銅粉０．３部を仕込んだ。触体中の硼素濃度を表３に示す。
【００４３】
その後、塩化メチルを流速１．３ｃｍ／ｓｅｃで反応器に導入し、反応器内温度を３３０℃まで上げ、反応を継続し、６時間後反応を停止した。反応開始から反応終了時までの累積のＳＴＹ、Ｄ、Ｈ、Ｒを表３に示す。
【００４４】
〔実施例７〕
直径５０ｍｍ、高さ３００ｍｍのカーボンスチール製の流動層反応器に、硼素を５５０ｐｐｍ含有する金属珪素粉を１００部、金属銅粉３．５部、硼素を２．０重量％含有する金属銅粉０．５部を仕込んだ。触体中の硼素濃度を表３に示す。
【００４５】
その後、塩化メチルを流速１．３ｃｍ／ｓｅｃで反応器に導入し、反応器内温度を３３０℃まで上げ、反応を継続し、６時間後反応を停止した。反応開始から反応終了時までの累積のＳＴＹ、Ｄ、Ｈ、Ｒを表３に示す。
【００４６】
〔実施例８〕
直径５０ｍｍ、高さ３００ｍｍのカーボンスチール製の流動層反応器に、硼素を１４８ｐｐｍ含有する金属珪素粉を１００部、金属銅粉４．０部、硼化チタン１．２部を仕込んだ。触体中の硼素濃度を表３に示す。
【００４７】
その後、塩化メチルを流速１．３ｃｍ／ｓｅｃで反応器に導入し、反応器内温度を３３０℃まで上げ、反応を継続し、６時間後反応を停止した。反応開始から反応終了時までの累積のＳＴＹ、Ｄ、Ｈ、Ｒを表３に示す。
【００４８】
〔実施例９〕
直径５０ｍｍ、高さ３００ｍｍのカーボンスチール製の流動層反応器に、硼素を５５０ｐｐｍ含有する金属珪素粉を１００部、金属銅粉４．０部、硼化ジルコニウム０．５部を仕込んだ。触体中の硼素濃度を表３に示す。
【００４９】
その後、塩化メチルを流速１．３ｃｍ／ｓｅｃで反応器に導入し、反応器内温度を３３０℃まで上げ、反応を継続し、６時間後反応を停止した。反応開始から反応終了時までの累積のＳＴＹ、Ｄ、Ｈ、Ｒを表３に示す。
【００５０】
〔実施例１０〕
直径５０ｍｍ、高さ３００ｍｍのカーボンスチール製の流動層反応器に、硼素を７４ｐｐｍ含有する金属珪素粉を１００部、金属銅粉４．０部、硼化ニオブ０．５部を仕込んだ。触体中の硼素濃度を表３に示す。
【００５１】
その後、塩化メチルを流速１．３ｃｍ／ｓｅｃで反応器に導入し、反応器内温度を３３０℃まで上げ、反応を継続し、６時間後反応を停止した。反応開始から反応終了時までの累積のＳＴＹ、Ｄ、Ｈ、Ｒを表３に示す。
【００５２】
〔実施例１１〕
直径５０ｍｍ、高さ３００ｍｍのカーボンスチール製の流動層反応器に、硼素を１４８ｐｐｍ含有する金属珪素粉を１００部、金属銅粉３．５部、硼化タングステン１．０部を仕込んだ。触体中の硼素濃度を表３に示す。
【００５３】
その後、塩化メチルを流速１．３ｃｍ／ｓｅｃで反応器に導入し、反応器内温度を３３０℃まで上げ、反応を継続し、６時間後反応を停止した。反応開始から反応終了時までの累積のＳＴＹ、Ｄ、Ｈ、Ｒを表３に示す。
【００５４】
なお、上記実施例６〜１１において、硼素を７〜５５０ｐｐｍ含有する金属珪素粉は、実施例３〜５と同様にして製造した。また、硼素を２．０重量％含有する金属銅粉は、硼素と銅粉末とを混合し、窒素雰囲気下において室温から２時間かけて１８００〜２２００℃に加熱して１時間保持した後、溶融体を冷却させることにより製造した。
【００５５】
【表３】
〔実施例１２〕
直径５０ｍｍ、高さ３００ｍｍのカーボンスチール製の流動層反応器に、硼素を７．０ｐｐｍ含有する金属珪素粉を１００部、金属銅粉よりなる触媒混合物４部、窒化硼素０．２部を仕込んだ。触体中の硼素濃度を表４に示す。
【００５７】
その後、塩化メチルを流速１．３ｃｍ／ｓｅｃで反応器に導入し、反応器内温度を３３０℃まで上げ、反応を継続し、６時間後反応を停止した。反応開始から反応終了時までの累積のＳＴＹ、Ｄ、Ｈ、Ｒを表４に示す。
【００５８】
〔実施例１３〕
直径５０ｍｍ、高さ３００ｍｍのカーボンスチール製の流動層反応器に、硼素を７．０ｐｐｍ含有する金属珪素粉を１００部、金属銅粉よりなる触媒混合物４部、窒化硼素０．７部を仕込んだ。触体中の硼素濃度を表４に示す。
【００５９】
その後、塩化メチルを流速１．３ｃｍ／ｓｅｃで反応器に導入し、反応器内温度を３３０℃まで上げ、反応を継続し、６時間後反応を停止した。反応開始から反応終了時までの累積のＳＴＹ、Ｄ、Ｈ、Ｒを表４に示す。
【００６０】
〔実施例１４〕
直径５０ｍｍ、高さ３００ｍｍのカーボンスチール製の流動層反応器に、硼素を７．０ｐｐｍ含有する金属珪素粉を１００部、金属銅粉よりなる触媒混合物４部、窒化硼素１．４部を仕込んだ。触体中の硼素濃度を表４に示す。
【００６１】
その後、塩化メチルを流速１．３ｃｍ／ｓｅｃで反応器に導入し、反応器内温度を３３０℃まで上げ、反応を継続し、６時間後反応を停止した。反応開始から反応終了時までの累積のＳＴＹ、Ｄ、Ｈ、Ｒを表４に示す。
【００６２】
〔実施例１５〕
直径５０ｍｍ、高さ３００ｍｍのカーボンスチール製の流動層反応器に、硼素を７．０ｐｐｍ含有する金属珪素粉を１００部、金属銅粉よりなる触媒混合物４部、炭化硼素０．５部を仕込んだ。触体中の硼素濃度を表４に示す。
【００６３】
その後、塩化メチルを流速１．３ｃｍ／ｓｅｃで反応器に導入し、反応器内温度を３３０℃まで上げ、反応を継続し、６時間後反応を停止した。反応開始から反応終了時までの累積のＳＴＹ、Ｄ、Ｈ、Ｒを表４に示す。
【００６４】
〔実施例１６〕
直径５０ｍｍ、高さ３００ｍｍのカーボンスチール製の流動層反応器に、硼素を７８ｐｐｍ含有する金属珪素粉を１００部、金属銅粉よりなる触媒混合物４部、メタ燐酸硼素３．０部を仕込んだ。触体中の硼素濃度を表４に示す。
【００６５】
その後、塩化メチルを流速１．３ｃｍ／ｓｅｃで反応器に導入し、反応器内温度を３３０℃まで上げ、反応を継続し、６時間後反応を停止した。反応開始から反応終了時までの累積のＳＴＹ、Ｄ、Ｈ、Ｒを表４に示す。
【００６６】
【表４】
【発明の効果】
本発明に基づいて硼素を従来の反応触体に添加すれば、従来に比較してより安価な方法で所望のＳＴＹにおいてジアルキルジハロシランの生産量を高め、かつ不必要なハイドロシラン類、ジシラン類を減少させることによってアルキルハロシランの直接法による製造方法の生産性を向上させることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an alkylhalosilane by a direct method, and more particularly to a method for producing an alkylhalosilane by continuously producing an alkylhalosilane by subjecting metal silicon and an alkyl halide to a gas-solid contact reaction in the presence of a copper catalyst. .
[0002]
[Prior art and problems to be solved by the invention]
With respect to the synthesis of alkylhalosilanes, various cocatalysts used in the presence of copper catalysts since Locoh disclosed a direct method of copper-catalyzed metal silicon and alkyl halides in US Pat. No. 2,380,995. The results have been reported by many researchers, such as those related to copper catalysts and their treatment, reactors, and additives in the reaction.
[0003]
In this direct method, after activating a contact body obtained by adding a copper catalyst to metal silicon, an alkyl halide is introduced into the contact body to bring the metal silicon and alkyl halide into direct gas-solid contact, thereby obtaining an alkylhalosilane. Is the method. In the industrial synthesis of alkylhalosilanes, the selectivity of dialkyldihalosilanes most frequently used in silicone resins and the rate of silane formation are important. The selectivity of dialkyldihalosilane is evaluated by the weight ratio (or molar ratio) in the produced silane and the T / D ratio. Examples of substances contained in the generated alkylhalosilane include dialkyldihalosilane (D), trialkylhalosilane (M), and alkyltrihalosilane (T), and alkylhydrodihalosilane (H) and alkylhalosilane. Disilanes are also produced. In particular, disilanes called residues in silane manufacturers have few effective uses and are mostly discarded. The T / D ratio is the composition ratio of the alkyltrihalosilane and the dialkyldihalosilane in the total generated alkylhalosilane, and the T / D ratio is preferably as small as possible. On the other hand, STY (Space Time Yield) value is used for the production rate of alkylhalosilane. The STY value is the weight of the resulting crude alkylhalosilane per unit time relative to the weight of metal silicon held in the reactor. In order to improve the composition of these produced dialkyldihalosilanes or lower the T / D ratio and improve the STY value, various studies have been conducted focusing on catalysts and accelerators.
[0004]
Soviet application specification No. 617,569 (inventor's certificate No. 122,749) dated January 24, 1959 discloses a reaction in which 20-40 ppm of antimony is added to a metal silicon-copper alloy. At this time, it is shown that the composition of dimethyldichlorosilane was improved from 40% to 60%. U.S. Pat. No. 4,500,724 shows that T / D is improved to 0.037 by using a copper / zinc / tin-based catalyst containing 200 to 3000 ppm of tin. Further, Japanese Patent Publication No. 6-92421 discloses a reaction using copper arsenide having an arsenic concentration of 50 ppm or more. It is stated that these tin, antimony, and arsenic cocatalysts can be added to a reaction catalyst made of metal silicon-copper to increase the reaction activity and thus improve the reaction rate of metal silicon.
[0005]
Soviet application specification No. 903,369 dated June 2, 1964 (Inventor ID No. 178,817) uses a promoter selected from zinc, bismuth, phosphorus (200 ppm), arsenic, tin, iron Thus, the composition of dimethyldichlorosilane is improved to 72.1% from the above-mentioned application specification No. 617,569 (Inventor ID No. 122,749). Further, in Soviet application specification No. 1,152,943 (inventor's certificate No. 237,892) dated November 20, 1969, 2500 to 30000 ppm with respect to the contact body in the form of an alloy of phosphorus, copper and silicon. Of phosphorus has been shown to improve the dimethyldichlorosilane composition to 82.3%. Further, US Pat. No. 4,602,101 (Japanese Patent Publication No. 5-51596) shows that 25 to 2500 ppm of a phosphorus compound generating elemental phosphorus in the reactor is added to the contact body. Has been.
[0006]
As described above, many researchers have so far studied the cocatalyst effect of various metals with the aim of improving the direct method of alkylhalosilane, but more effective cocatalysts are desired.
[0007]
The present invention has been made in view of the above circumstances, and provides a production method of an alkylhalosilane by a direct method that increases the production amount of dialkyldihalosilane and reduces unnecessary disilanes in a desired STY. Objective.
[0008]
Means for Solving the Problem and Embodiment of the Invention
The inventors of the present invention have provided an industrially effective direct method for producing alkylhalosilanes, particularly alkylhalosilanes that increase dialkyldihalosilane production and reduce unnecessary disilanes in a desired STY. As a result of diligent studies on the direct method, the use of a reaction catalyst containing boron reduced the production of hydrosilanes and disilanes while maintaining the reaction activity, thus increasing the production of dialkyldihalosilanes. I found out.
[0009]
That is, as described above, various cocatalysts have been conventionally studied, but the boron compound according to the present invention has not been studied so far. For example, Tuset, J. et al. K. , Int. Sem. on Refining and Alloying of Liquid Al & Ferroalloys (1985) Trondheim has a boron concentration of at most 50 ppm in standard metallic silicon, and at most 40 ppm for purified metallic silicon used in direct process reactions. Although it has been shown, there are few direct reaction activities in many reviews, or only a catalyst poison when used in large amounts. However, the boron-containing concentration in the silicon metal actually used varies significantly depending on the country where the meteorite used as a raw material is produced. The boron-containing concentration is originally low and is usually further reduced by the refining process of metallic silicon, and the contact body is substantially free of boron. According to the inventor's analysis, the boron concentration in refined metal powders from South America such as Brazil, China and Australia is 10 ppm or less, and the boron concentration in refined metal silicon powders from Europe such as France and Norway is Many are 10 ppm or more and 30 ppm or less.
[0010]
However, the present inventor has found that boron, which was conventionally considered to be rather a catalyst poison, has an excellent effect as a co-catalyst, and hydrosilanes while maintaining reaction activity by containing boron in the contact body. The inventors have found that production of disilanes can be reduced and the production amount of dialkyldihalosilanes can be increased, and the present invention has been made.
[0011]
Hereinafter, the present invention will be described in more detail. In the method for producing an alkylhalosilane of the present invention, a contact body containing a metal silicon powder and a copper catalyst is charged into a reactor, and a gas containing an alkyl halide is introduced into the reactor. The following general formula R n SiX 4-n
(In the formula, R represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, and n is an integer of 0 to 4.)
In the method for producing silanes represented by the above, boron-containing metal silicon powder and / or boron or a boron compound obtained by adding a boron compound to molten metal silicon in a process including a silicon refining process is added. Thus, the contact body contains 50 to 10,000 ppm of boron element as a promoter .
[0012]
Here, it is preferable to use metal silicon having a purity of silicon of 97% by weight or more, particularly 98% by weight or more. Metal silicon is preferably pulverized and used as a powder having an appropriate particle size. When a fluidized bed reactor or a stirred reactor is used as a reactor, the metal silicon powder has good fluidity. Therefore, the particle size of the metal silicon powder is preferably in the range of 5 to 150 μm as the particle size corresponding to 50% of the weight-based cumulative distribution curve by sieving.
[0013]
As the copper catalyst, various forms such as copper powder, single copper such as stamping copper, or copper compounds such as cuprous oxide, cupric oxide, and copper halide can be used. Various promoters such as zinc, tin, antimony, and arsenic may be used as a co-catalyst, and these may be used alone or as an alloy with copper. For example, metallic zinc, metallic tin, metallic antimony, metallic arsenic powder and their chlorides or oxides, Cu—Zn, Cu—Sn, Cu—Zn—Sn, or copper using Sb, As instead of Zn or Sn Alloys are generally manufacturable. These copper catalysts may be charged alone in the reactor or may be charged as an alloy together with the metal silicon powder. The blending amount of these copper catalysts is preferably 0.1 to 10 parts, particularly 2 to 8 parts in terms of copper amount with respect to 100 parts of metal silicon powder (parts by weight, the same applies hereinafter). Moreover, the compounding quantity of zinc is 0.05-1 part with respect to 100 parts of metal silicon powder, and the compounding quantity of tin, antimony and arsenic is 0.001-0. 05 parts, preferably 0.005 to 0.01 parts.
[0014]
In the present invention, the contact body contains boron element in an amount of 50 to 8000 ppm, more preferably 55 to 6000 ppm, and most preferably 200 to 5000 ppm.
[0015]
In this case, the boron in the contact body is made to have the above concentration by using a metal silicon having a high boron concentration as the metal silicon constituting the contact body. Examples include a method of adding a small amount of boron compound and using metal silicon having a high boron concentration, and a method of adding a boron compound to the reaction catalyst in the direct method reactor.
[0016]
Here, the metal silicon containing boron can be obtained by supplying a boron compound to silicon in a process including a purification step of raw material silicon. In this case, a nonvolatile compound in a step including a silicon refining step is obtained. It can be added to molten metallic silicon. Examples of the boron compound used in this, borax (Na 2 B 4 O 7 · 10H 2 O), (2 O Na 2 B 4 O 7 · 14H) Kahn stone, colemanite (Ca 2 B 6 O 11 · Natural minerals containing boron such as 5H 2 O), M 1 2 B (where M 1 represents Fe, Co, Ni, Mn, Mo, W, Ta, etc.), M 2 3 B 2 (where, M 2 represents Mg, etc.), M 3 B (provided that M 3 represents Fe, Co, Ni, Mn, Cr, Mo, W, Nb, Ta, etc.), M 4 3 B 4 (provided that M 4 Represents Ta, Nb, Mn, Cr, etc.), M 5 B 2 (where M 5 represents Ti, Zr, Hf, V, Nb, Ta, Cr, etc.), M 6 2 B 5 (where M 6 represents Mo, W, etc.), boride, boron nitride, boron carbide, boron phosphide, boron phosphate and the like. In addition, when a boron compound is added under silicon refining conditions, it is also preferable to use silicon containing boron by reduction of the boron compound. Examples of such a boron compound include boric acid, metal borate, boron oxide. Can be mentioned.
[0017]
The boron compound can be used in the vapor phase or immediately volatilizing.
[0018]
Furthermore, as a method of adding boron to silicon, as a raw material for silicon refining, quartz containing boron, coal containing boron, coke containing boron, charcoal containing boron, and eucalyptus containing boron are used. A method can also be mentioned. Alternatively, a method of using a carbon electrode containing boron as an electrode for silicon refining may be employed.
[0019]
On the other hand, when a boron compound is added to the reaction catalyst, boron is, for example, elemental boron such as amorphous boron obtained by reducing an oxide, boron-copper alloy, M 1 2 B, M 2 3 similar to the above. Examples thereof include borides, boron nitride, boron carbide, boron phosphide, and boron phosphate represented by B 2 , M 3 B, M 4 3 B 4 , M 5 B 2 , and M 6 2 B 5 . When these are directly added to the method reactor, it is more preferable to perform a heat dehydration treatment at about 200 ° C. in advance in order to remove a trace amount of water. Further, as the boron compound to be added, vapor-phase or immediately volatile boron halide or the like can be used.
[0020]
Examples of the alkyl halide for reacting with metal silicon to obtain an alkylhalosilane include methyl chloride, ethyl chloride, propyl chloride, methyl bromide, and ethyl bromide. Of these, methyl chloride is industrially most useful, and dimethyldichlorosilane produced using this is widely used as a raw material for many silicone resins. The alkyl halide is heated in advance and gasified, and then sent to the reactor. In this case, the alkyl halide gas may be sent alone or a mixed gas with an inert gas. The amount of the alkyl halide gas fed in is calculated as the amount of fluidization of the contact body together with the inert gas, and is appropriately determined from the diameter of the reactor used and the superficial velocity.
[0021]
In the step of heating the contactor or imparting catalytic activity to the contactor, examples of the inert gas used for fluidizing the contactor in the reactor include nitrogen gas and argon gas. It is preferable to use a gas. The flow rate of the inert gas in these steps may be equal to or higher than the fluidization start speed of the contact body, but is preferably about 5 times the fluidization start speed. If the flow rate of the inert gas is lower than this range, it is difficult to uniformly fluidize the contact body. On the other hand, if the flow rate of the inert gas is higher than this range, the scattering of the metal silicon powder increases, and the inert gas flows. It may be disadvantageous because loss and heat loss increase. Further, it is more preferable to circulate and use an inert gas.
[0022]
After the catalytic activity is imparted to the contact body as described above, an alkyl halide is introduced into the reactor, and an alkyl halosilane is obtained by subjecting the alkyl halide and metal silicon to gas-solid contact reaction according to a conventional method. be able to. In this case, the reaction temperature can be 280 to 300 ° C. In addition, as a reaction method, the method of reacting on a continuous condition in a fluidized bed, the method of reacting with a stirring layer, the method of reacting with a fixed bed, etc. can be mentioned.
[0023]
【Example】
EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited to the following Example. In the following examples, parts indicate parts by weight.
[0024]
Examples 1 and 2
A fluidized bed reactor made of carbon steel having a diameter of 50 mm and a height of 300 mm was charged with 100 parts of metal silicon powder and 4 parts of a catalyst mixture made of metal copper powder. Further, boron compounds shown in Table 1 were charged in various addition amounts.
[0025]
Thereafter, methyl chloride was introduced into the reactor at a flow rate of 1.3 cm / sec, the temperature in the reactor was raised to 330 ° C., the reaction was continued, and the reaction was stopped after 6 hours. Table 1 shows cumulative STY from the start of the reaction to the end of the reaction. In addition, the ratio of dimethyldichlorosilane, the ratio of methyldichlorosilane, and the ratio of high-boiling products (products having a boiling point higher than 70 ° C. at normal pressure such as disilane in the generated methylchlorosilane) are also shown in the table. 1 are also written as D, H, and R respectively. The above STY has the following meaning.
[0026]
[Expression 1]
[Table 1]
[Example 3 ]
A carbon steel fluidized bed reactor having a diameter of 50 mm and a height of 300 mm was charged with 100 parts of metal silicon powder containing 74 ppm of boron and 4 parts of a catalyst mixture made of metal copper powder. Table 2 shows the boron concentration in the contact body.
[0031]
Thereafter, methyl chloride was introduced into the reactor at a flow rate of 1.3 cm / sec, the temperature in the reactor was raised to 330 ° C., the reaction was continued, and the reaction was stopped after 6 hours. Table 2 shows cumulative STY, D, H, and R from the start of the reaction to the end of the reaction.
[0032]
[Example 4 ]
A fluidized bed reactor made of carbon steel having a diameter of 50 mm and a height of 300 mm was charged with 100 parts of metal silicon powder containing 148 ppm of boron and 4 parts of a catalyst mixture made of metal copper powder. Table 2 shows the boron concentration in the contact body.
[0033]
Thereafter, methyl chloride was introduced into the reactor at a flow rate of 1.3 cm / sec, the temperature in the reactor was raised to 330 ° C., the reaction was continued, and the reaction was stopped after 6 hours. Table 2 shows cumulative STY, D, H, and R from the start of the reaction to the end of the reaction.
[0034]
[Example 5 ]
A fluidized bed reactor made of carbon steel having a diameter of 50 mm and a height of 300 mm was charged with 100 parts of metal silicon powder containing 2200 ppm of boron and 4 parts of a catalyst mixture made of metal copper powder. Table 2 shows the boron concentration in the contact body.
[0035]
Thereafter, methyl chloride was introduced into the reactor at a flow rate of 1.3 cm / sec, the temperature in the reactor was raised to 330 ° C., the reaction was continued, and the reaction was stopped after 6 hours. Table 2 shows cumulative STY, D, H, and R from the start of the reaction to the end of the reaction.
[0036]
[Comparative Example 1]
A carbon steel fluidized bed reactor having a diameter of 50 mm and a height of 300 mm was charged with 100 parts of metal silicon powder containing 0.032 ppm of boron and 4 parts of a catalyst mixture made of metal copper powder. Table 2 shows the boron concentration in the contact body.
[0037]
Thereafter, methyl chloride was introduced into the reactor at a flow rate of 1.3 cm / sec, the temperature in the reactor was raised to 330 ° C., the reaction was continued, and the reaction was stopped after 6 hours. Table 2 shows cumulative STY, D, H, and R from the start of the reaction to the end of the reaction.
[0038]
[Comparative Example 2]
A carbon steel fluidized bed reactor having a diameter of 50 mm and a height of 300 mm was charged with 100 parts of metallic silicon powder containing 0.50 ppm of boron and 4 parts of a catalyst mixture made of metallic copper powder. Table 2 shows the boron concentration in the contact body.
[0039]
Thereafter, methyl chloride was introduced into the reactor at a flow rate of 1.3 cm / sec, the temperature in the reactor was raised to 330 ° C., the reaction was continued, and the reaction was stopped after 6 hours. Table 2 shows cumulative STY, D, H, and R from the start of the reaction to the end of the reaction.
[0040]
In Examples 3 to 5 and Comparative Examples 1 and 2, boron was added in a predetermined amount using boric acid, a boric acid metal salt (metal is sodium or potassium), and boron oxide. In this case, these boron compounds were added to the electric furnace together with the raw material meteorite, charcoal, wood chips and the like in the refining process of the raw material silicon, and an arc was generated at 1500 ° C. or higher to perform the reduction reaction. Thereafter, the container was transferred, and bubbling with nitrogen and air was performed for 1 hour to 20 hours, separated from oxide slag, and cooled.
[0041]
[Table 2]
[Example 6 ]
Metallic copper containing 100 parts of metallic silicon powder containing 7.0 ppm of boron, 3.7 parts of metallic copper powder and 2.0% by weight of boron in a fluidized bed reactor made of carbon steel having a diameter of 50 mm and a height of 300 mm 0.3 parts of powder was charged. Table 3 shows the boron concentration in the contact body.
[0043]
Thereafter, methyl chloride was introduced into the reactor at a flow rate of 1.3 cm / sec, the temperature in the reactor was raised to 330 ° C., the reaction was continued, and the reaction was stopped after 6 hours. Table 3 shows cumulative STY, D, H, and R from the start of the reaction to the end of the reaction.
[0044]
[Example 7 ]
Metallic copper powder containing 100 parts of metallic silicon powder containing 550 ppm of boron, 3.5 parts of metallic copper powder and 2.0% by weight of boron in a fluidized bed reactor made of carbon steel having a diameter of 50 mm and a height of 300 mm 0 .5 parts were charged. Table 3 shows the boron concentration in the contact body.
[0045]
Thereafter, methyl chloride was introduced into the reactor at a flow rate of 1.3 cm / sec, the temperature in the reactor was raised to 330 ° C., the reaction was continued, and the reaction was stopped after 6 hours. Table 3 shows cumulative STY, D, H, and R from the start of the reaction to the end of the reaction.
[0046]
[Example 8 ]
A fluidized bed reactor made of carbon steel having a diameter of 50 mm and a height of 300 mm was charged with 100 parts of metal silicon powder containing 148 ppm of boron, 4.0 parts of metal copper powder, and 1.2 parts of titanium boride. Table 3 shows the boron concentration in the contact body.
[0047]
Thereafter, methyl chloride was introduced into the reactor at a flow rate of 1.3 cm / sec, the temperature in the reactor was raised to 330 ° C., the reaction was continued, and the reaction was stopped after 6 hours. Table 3 shows cumulative STY, D, H, and R from the start of the reaction to the end of the reaction.
[0048]
[Example 9 ]
A fluidized bed reactor made of carbon steel having a diameter of 50 mm and a height of 300 mm was charged with 100 parts of metallic silicon powder containing 550 ppm of boron, 4.0 parts of metallic copper powder, and 0.5 part of zirconium boride. Table 3 shows the boron concentration in the contact body.
[0049]
Thereafter, methyl chloride was introduced into the reactor at a flow rate of 1.3 cm / sec, the temperature in the reactor was raised to 330 ° C., the reaction was continued, and the reaction was stopped after 6 hours. Table 3 shows cumulative STY, D, H, and R from the start of the reaction to the end of the reaction.
[0050]
Example 10
A fluidized bed reactor made of carbon steel having a diameter of 50 mm and a height of 300 mm was charged with 100 parts of metallic silicon powder containing 74 ppm of boron, 4.0 parts of metallic copper powder, and 0.5 part of niobium boride. Table 3 shows the boron concentration in the contact body.
[0051]
Thereafter, methyl chloride was introduced into the reactor at a flow rate of 1.3 cm / sec, the temperature in the reactor was raised to 330 ° C., the reaction was continued, and the reaction was stopped after 6 hours. Table 3 shows cumulative STY, D, H, and R from the start of the reaction to the end of the reaction.
[0052]
Example 11
A fluidized bed reactor made of carbon steel having a diameter of 50 mm and a height of 300 mm was charged with 100 parts of metallic silicon powder containing 148 ppm of boron, 3.5 parts of metallic copper powder, and 1.0 part of tungsten boride. Table 3 shows the boron concentration in the contact body.
[0053]
Thereafter, methyl chloride was introduced into the reactor at a flow rate of 1.3 cm / sec, the temperature in the reactor was raised to 330 ° C., the reaction was continued, and the reaction was stopped after 6 hours. Table 3 shows cumulative STY, D, H, and R from the start of the reaction to the end of the reaction.
[0054]
In Examples 6 to 11 , the metal silicon powder containing 7 to 550 ppm of boron was produced in the same manner as in Examples 3 to 5 . Moreover, the metallic copper powder containing 2.0 wt% boron is mixed with boron and copper powder, heated from room temperature to 1800 to 2200 ° C. over 2 hours in a nitrogen atmosphere, held for 1 hour, and then melted. Manufactured by cooling the body.
[0055]
[Table 3]
[Example 12 ]
A carbon steel fluidized bed reactor having a diameter of 50 mm and a height of 300 mm was charged with 100 parts of metal silicon powder containing 7.0 ppm of boron, 4 parts of a catalyst mixture made of metal copper powder, and 0.2 part of boron nitride. . Table 4 shows the boron concentration in the contact body.
[0057]
Thereafter, methyl chloride was introduced into the reactor at a flow rate of 1.3 cm / sec, the temperature in the reactor was raised to 330 ° C., the reaction was continued, and the reaction was stopped after 6 hours. Table 4 shows cumulative STY, D, H, and R from the start of the reaction to the end of the reaction.
[0058]
[Example 13 ]
A carbon steel fluidized bed reactor having a diameter of 50 mm and a height of 300 mm was charged with 100 parts of metal silicon powder containing 7.0 ppm of boron, 4 parts of a catalyst mixture made of metal copper powder, and 0.7 part of boron nitride. . Table 4 shows the boron concentration in the contact body.
[0059]
Thereafter, methyl chloride was introduced into the reactor at a flow rate of 1.3 cm / sec, the temperature in the reactor was raised to 330 ° C., the reaction was continued, and the reaction was stopped after 6 hours. Table 4 shows cumulative STY, D, H, and R from the start of the reaction to the end of the reaction.
[0060]
[Example 14 ]
A carbon steel fluidized bed reactor having a diameter of 50 mm and a height of 300 mm was charged with 100 parts of metal silicon powder containing 7.0 ppm of boron, 4 parts of a catalyst mixture made of metal copper powder, and 1.4 parts of boron nitride. . Table 4 shows the boron concentration in the contact body.
[0061]
Thereafter, methyl chloride was introduced into the reactor at a flow rate of 1.3 cm / sec, the temperature in the reactor was raised to 330 ° C., the reaction was continued, and the reaction was stopped after 6 hours. Table 4 shows cumulative STY, D, H, and R from the start of the reaction to the end of the reaction.
[0062]
Example 15
A carbon steel fluidized bed reactor having a diameter of 50 mm and a height of 300 mm was charged with 100 parts of metallic silicon powder containing 7.0 ppm of boron, 4 parts of a catalyst mixture made of metallic copper powder, and 0.5 part of boron carbide. . Table 4 shows the boron concentration in the contact body.
[0063]
Thereafter, methyl chloride was introduced into the reactor at a flow rate of 1.3 cm / sec, the temperature in the reactor was raised to 330 ° C., the reaction was continued, and the reaction was stopped after 6 hours. Table 4 shows cumulative STY, D, H, and R from the start of the reaction to the end of the reaction.
[0064]
Example 16
A carbon steel fluidized bed reactor having a diameter of 50 mm and a height of 300 mm was charged with 100 parts of metallic silicon powder containing 78 ppm of boron, 4 parts of a catalyst mixture made of metallic copper powder, and 3.0 parts of boron metaphosphate. Table 4 shows the boron concentration in the contact body.
[0065]
Thereafter, methyl chloride was introduced into the reactor at a flow rate of 1.3 cm / sec, the temperature in the reactor was raised to 330 ° C., the reaction was continued, and the reaction was stopped after 6 hours. Table 4 shows cumulative STY, D, H, and R from the start of the reaction to the end of the reaction.
[0066]
[Table 4]
【The invention's effect】
If boron is added to the conventional reaction catalyst according to the present invention, the production amount of dialkyldihalosilane is increased in a desired STY by a cheaper method compared to the conventional method, and unnecessary hydrosilanes, disilane It is possible to improve the productivity of the production method of the alkylhalosilane by the direct method by reducing the number of the kinds.
Claims (2)
ＲnＳｉＸ4-n
（但し、式中Ｒは炭素数１〜４のアルキル基、Ｘはハロゲン原子を示し、ｎは０〜４の整数である。）
で示されるシラン類を製造する方法において、珪素精錬工程を含む工程における溶融状態の金属珪素に硼素化合物を添加することによって得られる硼素を含有する金属珪素粉末及び／又は硼素もしくは硼素化合物を添加することにより助触媒として上記触体に５０〜１００００ｐｐｍの硼素元素を含有させたことを特徴とするアルキルハロシランの製造方法。A contact body containing a metal silicon powder and a copper catalyst is charged into a reactor, a gas containing an alkyl halide is introduced into the reactor, and the following general formula R n SiX 4-n is obtained by a direct synthesis method.
(In the formula, R represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, and n is an integer of 0 to 4).
In the method for producing silanes represented by the above, boron-containing metal silicon powder and / or boron or boron compound obtained by adding a boron compound to molten metal silicon in a process including a silicon refining process is added. Thus, 50 to 10,000 ppm of boron element is contained in the contact body as a co-catalyst .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19506698A JP3729236B2 (en) | 1997-06-27 | 1998-06-25 | Method for producing alkylhalosilane |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-187574 | 1997-06-27 | ||
| JP18757497 | 1997-06-27 | ||
| JP19506698A JP3729236B2 (en) | 1997-06-27 | 1998-06-25 | Method for producing alkylhalosilane |
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| Publication Number | Publication Date |
|---|---|
| JPH1171384A JPH1171384A (en) | 1999-03-16 |
| JP3729236B2 true JP3729236B2 (en) | 2005-12-21 |
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| KR100839938B1 (en) * | 2001-11-09 | 2008-06-20 | 주식회사 케이씨씨 | Catalyst composition for methylchlorosilane synthesis and production of methylchlorosilane using said catalyst |
| DE102006044372A1 (en) * | 2006-09-20 | 2008-04-03 | Wacker Chemie Ag | Process for the preparation of methylchlorosilanes |
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