JPH0518761B2 - - Google Patents
Info
- Publication number
- JPH0518761B2 JPH0518761B2 JP28456887A JP28456887A JPH0518761B2 JP H0518761 B2 JPH0518761 B2 JP H0518761B2 JP 28456887 A JP28456887 A JP 28456887A JP 28456887 A JP28456887 A JP 28456887A JP H0518761 B2 JPH0518761 B2 JP H0518761B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- rhodium
- group
- rhx
- bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 11
- 239000010948 rhodium Substances 0.000 claims description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- 150000003284 rhodium compounds Chemical class 0.000 claims description 5
- 125000005538 phosphinite group Chemical group 0.000 claims description 4
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- 238000000034 method Methods 0.000 description 7
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- -1 p-methylphosphorene Chemical compound 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003283 rhodium Chemical class 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- RJTJVVYSTUQWNI-UHFFFAOYSA-N 2-ethylnaphthalene Chemical compound C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LTEQMZWBSYACLV-UHFFFAOYSA-N Hexylbenzene Chemical compound CCCCCCC1=CC=CC=C1 LTEQMZWBSYACLV-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 2
- 239000004914 cyclooctane Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- QRRVMWPNMMLSGD-UHFFFAOYSA-N (2-dimethylphosphanylphenyl)-dimethylphosphane Chemical compound CP(C)C1=CC=CC=C1P(C)C QRRVMWPNMMLSGD-UHFFFAOYSA-N 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- ZKWQSBFSGZJNFP-UHFFFAOYSA-N 1,2-bis(dimethylphosphino)ethane Chemical compound CP(C)CCP(C)C ZKWQSBFSGZJNFP-UHFFFAOYSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 description 1
- GZDVNUHKYJNVNT-UHFFFAOYSA-N 3-dimethylphosphanylpropyl(dimethyl)phosphane Chemical compound CP(C)CCCP(C)C GZDVNUHKYJNVNT-UHFFFAOYSA-N 0.000 description 1
- FNAYAXPWEKXHQU-UHFFFAOYSA-N 4-dimethylphosphanylbutyl(dimethyl)phosphane Chemical compound CP(C)CCCCP(C)C FNAYAXPWEKXHQU-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- UBLCREXFPCOOSX-UHFFFAOYSA-N cyclopenta-1,4-dien-1-yl(dimethyl)phosphane iron(2+) Chemical compound [Fe++].CP(C)[c-]1cccc1.CP(C)[c-]1cccc1 UBLCREXFPCOOSX-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- ZXMSTCRBSAVFDO-UHFFFAOYSA-N dimethoxy(methyl)phosphane Chemical compound COP(C)OC ZXMSTCRBSAVFDO-UHFFFAOYSA-N 0.000 description 1
- LMZLQYYLELWCCW-UHFFFAOYSA-N dimethoxy(phenyl)phosphane Chemical compound COP(OC)C1=CC=CC=C1 LMZLQYYLELWCCW-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- ODXKYOFRPVSRTK-UHFFFAOYSA-N methoxy(dimethyl)phosphane Chemical compound COP(C)C ODXKYOFRPVSRTK-UHFFFAOYSA-N 0.000 description 1
- OAADXJFIBNEPLY-UHFFFAOYSA-N methoxy(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(OC)C1=CC=CC=C1 OAADXJFIBNEPLY-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002872 norbornadienyl group Chemical group C12=C(C=C(CC1)C2)* 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- SWMBQMGPRYJSCI-UHFFFAOYSA-N octylphosphane Chemical compound CCCCCCCCP SWMBQMGPRYJSCI-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- RAVACSWYIIPFFV-UHFFFAOYSA-N tris[(4-methoxyphenyl)methyl]phosphane Chemical compound C1=CC(OC)=CC=C1CP(CC=1C=CC(OC)=CC=1)CC1=CC=C(OC)C=C1 RAVACSWYIIPFFV-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
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、水素の生成法に関し、より詳しく
は、炭化水素を脱水素させることからなる水素の
製造技術に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing hydrogen, and more particularly to a technology for producing hydrogen comprising dehydrogenating hydrocarbons.
（従来の技術）
現下の化学工業の原料体系に於ては、基礎原料
である水素の製造は大部分炭化水素類の熱分解反
応によつている。(Prior Art) In the current raw material system of the chemical industry, hydrogen, which is a basic raw material, is mostly produced by thermal decomposition reactions of hydrocarbons.
（発明が解決しようとする問題点）
しかし、この熱分解には700〜900℃もの高温を
要するのが普通であり、必ずしも工業的に有利な
ものではなく、解決すべき技術的問題点をかかえ
ている。(Problem to be solved by the invention) However, this thermal decomposition usually requires a high temperature of 700 to 900°C, which is not necessarily industrially advantageous, and there are technical problems that need to be solved. ing.
このような状況に鑑み、本発明者らは、炭化水
素類を原料として水素を温和な条件下で効率的に
製造しうる新規方法について、鋭意探索・研究を
行つた。 In view of this situation, the present inventors have earnestly searched and researched a new method that can efficiently produce hydrogen under mild conditions using hydrocarbons as raw materials.
（目的を解決するための手段）
本発明は、ホスフイン、ホスホナイト、ホスフ
イナイトおよびホスフアイトから成る群から選ば
れる少なくとも一種の有機リン化合物のロジウム
錯体の存在下、または少なくとも一種の該有機リ
ン化合物とロジウム化合物との共存下に、炭化水
素に光照射することを特徴とする炭化水素類の脱
水素法を要旨とするものであり、これにより、水
素の効率的な製造法が提供される。(Means for Solving the Objects) The present invention provides a method for combining rhodium complexes of at least one organophosphorus compound selected from the group consisting of phosphine, phosphonite, phosphinite, and phosphite, or in the presence of a rhodium complex of at least one organophosphorus compound and a rhodium compound. The gist of this method is a method for dehydrogenating hydrocarbons, which is characterized by irradiating the hydrocarbons with light in the coexistence with light, thereby providing an efficient method for producing hydrogen.
本発明の水素の製造方法は、ホスフイン、ホス
ホナイト、ホスフイナイトおよびホスフアイトか
らなる群から選ばれた少なくとも一種の有機リン
化合物のロジウム錯体の存在下に行われる。 The method for producing hydrogen of the present invention is carried out in the presence of a rhodium complex of at least one organic phosphorus compound selected from the group consisting of phosphine, phosphonite, phosphinite, and phosphite.
これらの有機リン化合物におけるリンは、すべ
て３価であり、具体的には、単座配位性の有機リ
ン化合物（PR′3で示す）として例えばトリメチ
ルホスフイン、トリエチルホスフイン、トリブチ
ルホスフイン、トリオクチルホスフイン、トリフ
エニルホスフイン、トリ（ｐ−トリル）ホスフイ
ン、トリ（ｐ−アニシル）ホスフイン等の鎖状ホ
スフイン、ｐ−メチルホスホレン、ｐ−メチルホ
スホール等の環状ホスフイン、ジメチル メチル
ホスホナイト、ジメチル フエニルホスホナイト
等のホスホナイト、メチル ジメチルホスフイナ
イト、メチル ジフエニルホスフイナイト等のホ
スフイナイト、およびトリエチルホスフアイト、
トリフエニルホスフアイト、トリメチロールプロ
パンホスフアイト等のホスフアイトを挙げること
ができ、また２座配位性の有機リン化合物
（R2 2P−PR2 2で示す）として、例えば１，２−ビ
ス（ジメチルホスフイノ）エタン、１，３−ビス
（ジメチルホスフイノ）プロパン、１，４−ビス
（ジメチルホスフイノ）ブタン、１，２−ビス
（ジフエニルホスフイノ）エタン、１，４−ビス
（ジフエニルホスフイノ）ブタン、１，1′−ビス
（ジメチルホスフイノ）フエロセン、１，1′−ビ
ス（ジフエニルホスフイノ）フエロセン、α，
α′−ビス（ジメチルホスフイノ）−ｏ−キシレン、
１，２−ビス（ジメチルホスフイノ）ベンゼン等
のビスホスフインが挙げられる。 Phosphorus in these organic phosphorus compounds is all trivalent, and specifically, monodentate organic phosphorus compounds (indicated by PR' 3 ) such as trimethylphosphine, triethylphosphine, tributylphosphine, trivalent Chain phosphine such as octylphosphine, triphenylphosphine, tri(p-tolyl)phosphine, tri(p-anisyl)phosphine, cyclic phosphine such as p-methylphosphorene, p-methylphosphole, dimethyl methylphosphonite , phosphonites such as dimethyl phenylphosphonite, phosphinites such as methyl dimethylphosphinite, methyl diphenylphosphinite, and triethylphosphite,
Phosphites such as triphenyl phosphite and trimethylolpropane phosphite can be mentioned, and examples of bidentate organic phosphorus compounds (represented by R 2 2 P-PR 2 2 ) include 1,2-bis( dimethylphosphino)ethane, 1,3-bis(dimethylphosphino)propane, 1,4-bis(dimethylphosphino)butane, 1,2-bis(diphenylphosphino)ethane, 1,4-bis(diphenylphosphino)ethane enylphosphino)butane, 1,1'-bis(dimethylphosphino)ferrocene, 1,1'-bis(diphenylphosphino)ferrocene, α,
α′-bis(dimethylphosphino)-o-xylene,
Examples include bisphosphine such as 1,2-bis(dimethylphosphino)benzene.
これら有機リン化合物のロジウム錯体として
は、種々の構造のものを用いることがてきるが、
一価のロジウム錯体が好ましい。 Rhodium complexes of these organophosphorus compounds can have various structures, but
Monovalent rhodium complexes are preferred.
具体的には例えばRhX（PR′3）3（PR′3は前記内
容を示す。またＸは水素、ハロゲン原子、水酸
基、シアノ基、アルコキシ基、カルボキシラト基
およびチオシアナト基からなる群から選ばれる基
を示す。以下同様）、RhX（CO）（PR′3）2、RhX
（CO）2（PR′3）、RhX（CO）2（PR′3）2、RhX
（PR′3）4、〔Rh（PR′3）4〕Ｙ（ＹはPF6、Ｂ
（C6H5）4、BF4、C104および前記Ｘからなる群か
ら選ばれる基を示す。以下同様）、〔Rh（PR′3）2
（CNR2）2〕Ｙ（CNR2はイソニトリルを、R2はア
ルキルまたはアリール基を示す。以下同様）、
〔Rh（PR′3）2（CNR2）3〕Ｙ、RhX（CO）（R2 2P−
PR2 2）などを挙げることができる。 Specifically, for example, RhX (PR' 3 ) 3 (PR' 3 indicates the above content, and X is selected from the group consisting of hydrogen, a halogen atom, a hydroxyl group, a cyano group, an alkoxy group, a carboxylate group, and a thiocyanato group) (hereinafter the same), RhX (CO) (PR′ 3 ) 2 , RhX
(CO) 2 (PR′ 3 ), RhX (CO) 2 (PR′ 3 ) 2 , RhX
(PR′ 3 ) 4 , [Rh(PR′ 3 ) 4 ]Y (Y is PF 6 , B
It represents a group selected from the group consisting of (C 6 H 5 ) 4 , BF 4 , C10 4 and the above X. (Similarly below), [Rh (PR′ 3 ) 2
(CNR 2 ) 2 ]Y (CNR 2 represents isonitrile, R 2 represents an alkyl or aryl group. The same applies hereinafter),
[Rh(PR′ 3 ) 2 (CNR 2 ) 3 ]Y, RhX(CO)(R 2 2 P−
PR 2 2 ), etc.
本発明の水素製造法においては、必ずしも上記
した有機リン化合物のロジウム錯体を予め調整し
て用いる必要はなく、上記有機リン化合物と適当
なロジウム化合物とを反応系に共存させ、系中に
おいてロジウム錯体を形成させる方法によつて
も、好ましく実施することができる。 In the hydrogen production method of the present invention, it is not necessary to prepare the rhodium complex of the above-mentioned organophosphorus compound in advance and use it, but the above-mentioned organophosphorus compound and a suitable rhodium compound are allowed to coexist in the reaction system, and the rhodium complex is formed in the system. It can also be preferably carried out by a method of forming.
このような目的のために好ましく用いられるロ
ジウム化合物としては、Rh（acac）（CO）2（acac
はアセチルアセトナート基を示す）、〔RhX
（CO）2〕2、〔RhX（DE）〕2（DEはノルボルナジエ
ン、１，５−シクロオクタジエン、または１，５
−ヘキサジエンを示す）、〔RhX（EN2〕2（ENはエ
チレンまたはシクロオクテンを示す）、RhX
（CO）（PR′3）2などが挙げられる。 Rhodium compounds preferably used for this purpose include Rh(acac)(CO) 2 (acac
represents an acetylacetonato group), [RhX
(CO) 2 ] 2 , [RhX(DE)] 2 (DE is norbornadiene, 1,5-cyclooctadiene, or 1,5
-hexadiene), [RhX (EN 2 ) 2 (EN indicates ethylene or cyclooctene), RhX
Examples include (CO)(PR′ 3 ) 2 .
本発明の方法に用いられる炭化水素は少なくと
も１つの水素原子を結合した炭素原子が隣接して
単結合で結合した部分構造を有するものである。
その具体例としては、エタン、プロパン、ブタ
ン、ペンタン、ヘキサン、オクタン、イソペンタ
ン、イソオクタン、デカン、エイコサン、エチル
ベンゼン、ｎ−ヘキシルベンゼン、イソプロピル
ベンゼン、ドデシルベンゼン、α−又はβ−エチ
ルナフタレン、シクロペンタン、シクロヘキサ
ン、シクロオクタン、シクロデドカン、デカリ
ン、テトラリン等を挙げることができるが、前記
の部分構造を有する炭化水素誘導体であれば、こ
れらに限定されることなく好適に用いることが出
来、置換基を有する化合物を用いることも可能で
ある。 The hydrocarbon used in the method of the present invention has a partial structure in which carbon atoms bonded to at least one hydrogen atom are bonded adjacently through single bonds.
Specific examples include ethane, propane, butane, pentane, hexane, octane, isopentane, isooctane, decane, eicosane, ethylbenzene, n-hexylbenzene, isopropylbenzene, dodecylbenzene, α- or β-ethylnaphthalene, cyclopentane, Examples include cyclohexane, cyclooctane, cyclodedocane, decalin, tetralin, etc., but any hydrocarbon derivatives having the above-mentioned partial structures can be suitably used without being limited to these. Compounds having substituents It is also possible to use
これらの炭化水素類のロジウム錯体またはロジ
ウム化合物に対する使用量は、任意に選ぶことが
でき、これら炭化水素類が液体である場合には、
この炭化水素類自体を溶媒量用いることも有利な
方法である。 The amount of these hydrocarbons to be used relative to the rhodium complex or rhodium compound can be arbitrarily selected. When these hydrocarbons are liquid,
It is also advantageous to use the hydrocarbons themselves in solvent quantities.
本発明における反応は、光照射下に進行する
が、光の波長領域はいわゆる紫外・可視光領域で
あれば良く、水銀燈、タングステンランプ、ハロ
ゲンランプ、キセノンランプ、太陽光などの照射
が好ましく用いられる。 The reaction in the present invention proceeds under light irradiation, but the wavelength range of light may be in the so-called ultraviolet/visible light range, and irradiation with mercury lamps, tungsten lamps, halogen lamps, xenon lamps, sunlight, etc. is preferably used. .
反応は０℃以下でも進行するが、好ましい反応
速度を達成するために250℃まで加熱することも
できる。 Although the reaction proceeds below 0°C, it can also be heated to 250°C to achieve favorable reaction rates.
（発明の効果）
本発明の炭化水素類の脱水素法によれば、入手
容易な炭化水素を用いて、温和な条件下に水素を
製造することが出来る。(Effects of the Invention) According to the hydrocarbon dehydrogenation method of the present invention, hydrogen can be produced under mild conditions using easily available hydrocarbons.
（実施例）
次に実施例により、本発明をさらに詳細に説明
する。(Example) Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
Pyrex製、内部照射型光反応容器にクロロカル
ボニルビス（トリメチルホスフイン）ロジウム
6.7mg（0.021mmol）のシクロヘキサン溶液（30ml）
をしこみ、凍結脱気を２回行つた後、一気圧の窒
素を導入し、容器を密閉した。100Wの高圧水銀
灯を用いて光照射しながら16.5時間撹拌した後、
気相をガスクロマトグラフイーで分析したとこ
ろ、2.94mmolの水素が検出された。Example 1 Chlorocarbonylbis(trimethylphosphine)rhodium in an internally irradiated photoreaction vessel manufactured by Pyrex
6.7 mg (0.021 mmol) in cyclohexane solution (30 ml)
After freezing and degassing twice, one atmosphere of nitrogen was introduced and the container was sealed. After stirring for 16.5 hours while irradiating with light using a 100W high-pressure mercury lamp,
When the gas phase was analyzed by gas chromatography, 2.94 mmol of hydrogen was detected.
実施例 ２
溶媒としてネオヘキサンを用いる以外は、実施
例１と同様にして反応を行い、0.05mmolの水素
を得た。Example 2 A reaction was carried out in the same manner as in Example 1 except that neohexane was used as a solvent, and 0.05 mmol of hydrogen was obtained.
実施例 ３
気相部を水素吸蔵合金の入つたフラスコに連結
したPyrex製、内部照射型光反応容器にクロロカ
ルボニルビス（トリメチルホスフイン）ロジウム
6.7mg（0.021mmol）のシクロオクタン溶液（30
ml）をしこみ、凍結脱気を二回行つた後、一気圧
の窒素を導入した。液相部を95℃に加熱しながら
100Wの高圧水銀灯照射下に70時間攪拌した。Example 3 Chlorocarbonylbis(trimethylphosphine)rhodium was placed in a Pyrex internally illuminated photoreaction vessel whose gas phase was connected to a flask containing a hydrogen storage alloy.
6.7 mg (0.021 mmol) of cyclooctane solution (30
After freezing and degassing twice, one atmosphere of nitrogen was introduced. While heating the liquid phase to 95℃
The mixture was stirred for 70 hours under irradiation with a 100W high-pressure mercury lamp.
水素吸蔵合金の入つたフラスコをガスビユレツ
トにつなぎかえた後、水素吸蔵合金を加熱して水
素を放出させたところ、54.6mmolの水素が得ら
れた。 After connecting the flask containing the hydrogen storage alloy to a gas bottle, the hydrogen storage alloy was heated to release hydrogen, yielding 54.6 mmol of hydrogen.
Claims (1)
およびホスフアイトから成る群から選ばれる少な
くとも一種の有機リン化合物のロジウム錯体の存
在下、または少なくとも一種の該有機リン化合物
とロジウム化合物との共存下に、置換又は未置換
の炭化水素に光照射することを特徴とする水素の
製造方法。1 Substituted or unsubstituted carbonization in the presence of a rhodium complex of at least one organic phosphorus compound selected from the group consisting of phosphine, phosphonite, phosphinite, and phosphite, or in the coexistence of at least one organic phosphorus compound and a rhodium compound. A method for producing hydrogen, characterized by irradiating hydrogen with light.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28456887A JPH01126201A (en) | 1987-11-11 | 1987-11-11 | Production of hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28456887A JPH01126201A (en) | 1987-11-11 | 1987-11-11 | Production of hydrogen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01126201A JPH01126201A (en) | 1989-05-18 |
| JPH0518761B2 true JPH0518761B2 (en) | 1993-03-12 |
Family
ID=17680148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28456887A Granted JPH01126201A (en) | 1987-11-11 | 1987-11-11 | Production of hydrogen |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01126201A (en) |
-
1987
- 1987-11-11 JP JP28456887A patent/JPH01126201A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01126201A (en) | 1989-05-18 |
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