JPS6114136B2 - - Google Patents
Info
- Publication number
- JPS6114136B2 JPS6114136B2 JP58244852A JP24485283A JPS6114136B2 JP S6114136 B2 JPS6114136 B2 JP S6114136B2 JP 58244852 A JP58244852 A JP 58244852A JP 24485283 A JP24485283 A JP 24485283A JP S6114136 B2 JPS6114136 B2 JP S6114136B2
- Authority
- JP
- Japan
- Prior art keywords
- ruthenium
- reaction
- present
- orthonitroanilines
- hydrogen
- 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
Links
- -1 aliphatic alcohols Chemical class 0.000 claims description 9
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002879 Lewis base Substances 0.000 description 3
- 150000007527 lewis bases Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- DLURHXYXQYMPLT-UHFFFAOYSA-N 2-nitro-p-toluidine Chemical compound CC1=CC=C(N)C([N+]([O-])=O)=C1 DLURHXYXQYMPLT-UHFFFAOYSA-N 0.000 description 1
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 description 1
- VDCZKCIEXGXCDJ-UHFFFAOYSA-N 3-methyl-2-nitroaniline Chemical compound CC1=CC=CC(N)=C1[N+]([O-])=O VDCZKCIEXGXCDJ-UHFFFAOYSA-N 0.000 description 1
- HWUFVIKSDPBKKL-UHFFFAOYSA-N C1(C=CC=C1)[Ru](=C=O)=C=O Chemical compound C1(C=CC=C1)[Ru](=C=O)=C=O HWUFVIKSDPBKKL-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021603 Ruthenium iodide Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- STWARMWRDXFBIE-UHFFFAOYSA-L [OH-].[OH-].[Ru++] Chemical compound [OH-].[OH-].[Ru++] STWARMWRDXFBIE-UHFFFAOYSA-L 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- VMDTXBZDEOAFQF-UHFFFAOYSA-N formaldehyde;ruthenium Chemical compound [Ru].O=C VMDTXBZDEOAFQF-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000007975 iminium salts Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- KFBOUJZFFJDYTA-UHFFFAOYSA-N n-methyl-2-nitroaniline Chemical compound CNC1=CC=CC=C1[N+]([O-])=O KFBOUJZFFJDYTA-UHFFFAOYSA-N 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical class [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- BNBKCTCLPAQLAH-UHFFFAOYSA-K ruthenium(3+) triformate Chemical compound [Ru+3].[O-]C=O.[O-]C=O.[O-]C=O BNBKCTCLPAQLAH-UHFFFAOYSA-K 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- FZHCFNGSGGGXEH-UHFFFAOYSA-N ruthenocene Chemical compound [Ru+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 FZHCFNGSGGGXEH-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、液相において一酸化炭素および水素
の混合物（以下、合成ガスと略称する）から、脂
肪族アルコール類を直接製造する方法に関する。
さらに詳しくは、メタノール、エタノール、エチ
レングリコール等の低級脂肪族一価アルコールも
しくは多価アルコールの新規な製造法に関する。
液相において、合成ガスから低級脂肪族アルコ
ール類を直接製造する方法に関しては、従来から
数多くの研究がなされている。その結果、これま
でに周期律表の第族元素、特にロジウムあるい
はルテニウムを含む触媒が脂肪族アルコール類、
特にエチレングリコールの生成に活性を示すこと
が知られている。しかしながら、それらの触媒
は、活性、選択性が未だ不充分であり、また触媒
の循環使用が困難である等の理由のため、工業的
実現をみていない。
本発明者等は、上記合成反応に対して、ルテニ
ウム化合物触媒を使用することを鋭意検討した結
果、オルトニトロアニリン類を添加することによ
り、合成ガスから脂肪族アルコール類、特にエチ
レングリコールが効率良く得られる事実を見出
し、本発明に到達した。
なお、特開昭55−115834号および特開昭57−
82328号公報中に、主触媒の可溶化されたルテニ
ウムカルボニル錯体に、ルイス塩基含有化合物を
助触媒として用いる方法が提案されている。これ
ら公報中にはルイス塩基の例示として各種のアル
カリ金属ハロゲン化物、アルカリ土類金属塩、イ
ミニウム塩、アミン類等が記載されている。しか
しながら、実施例に記されているルイス塩基は前
記三者のみであり、特に有機窒素塩基についての
具体的な例示がない。しかも、上記先行技術に見
られるルテニウム系触媒の性能はエチレングリコ
ール製造のために充分なものであるとは言えな
い。
ところが本発明者等はアミン類の中でオルトニ
トロアニリン類が特異的に有効な働きをするとい
う新規な事実を見い出したものである。
即ち、本発明はルテニウム化合物の存在下に液
相で一酸化炭素および水素の混合物を反応せしめ
て脂肪族アルコール類を製造するにあたり、下式
The present invention relates to a method for producing aliphatic alcohols directly from a mixture of carbon monoxide and hydrogen (hereinafter abbreviated as synthesis gas) in the liquid phase.
More specifically, the present invention relates to a novel method for producing lower aliphatic monohydric alcohols or polyhydric alcohols such as methanol, ethanol, and ethylene glycol. Many studies have been conducted on methods for directly producing lower aliphatic alcohols from synthesis gas in the liquid phase. As a result, catalysts containing Group Group elements of the periodic table, especially rhodium or ruthenium, have been used for aliphatic alcohols,
It is known to be particularly active in the production of ethylene glycol. However, these catalysts have not been commercially realized because their activity and selectivity are still insufficient, and it is difficult to recycle them. As a result of intensive studies on the use of ruthenium compound catalysts for the above synthesis reaction, the present inventors found that by adding orthonitroanilines, aliphatic alcohols, especially ethylene glycol, can be efficiently removed from synthesis gas. The present invention was achieved based on these findings. In addition, JP-A-55-115834 and JP-A-57-
No. 82328 proposes a method in which a Lewis base-containing compound is used as a co-catalyst in a solubilized ruthenium carbonyl complex as a main catalyst. These publications describe various alkali metal halides, alkaline earth metal salts, iminium salts, amines, etc. as examples of Lewis bases. However, the Lewis bases described in the examples are only the above three, and there are no specific examples of organic nitrogen bases. Moreover, the performance of the ruthenium-based catalysts found in the above-mentioned prior art cannot be said to be sufficient for the production of ethylene glycol. However, the present inventors have discovered a novel fact that among amines, orthonitroanilines have a specifically effective function. That is, in the present invention, in producing aliphatic alcohols by reacting a mixture of carbon monoxide and hydrogen in a liquid phase in the presence of a ruthenium compound, the following formula is used.
【式】
（式中、R1、R2、R3、R4、R5はそれぞれ水素もし
くは低級アルキル基を示す。）
で示されるオルトニトロアニリン類を反応系中に
添加することを特徴とする工業的に優れた脂肪族
アルコール類の製造法を提供するものである。
本発明において使用するルテニウム化合物とし
ては、酸化物、水酸化物、無機酸塩、ハロゲン化
物、カルボン酸塩あるいは窒素、リン、酸素、原
子等を含む種々の配位子を有する錯化合物等が挙
げられる。
それらの具体例は、二酸化ルテニウム、四酸化
ルテニウム、二水酸化ルテニウム、硝酸ルテニウ
ム、塩化ルテニウム、臭化ルテニウム、ヨウ化ル
テニウム、ギ酸ルテニウム、酢酸ルテニウム、ト
リス（アセチルアセトナート）ルテニウム、ドデ
カカルボニルトリルテニウム、ペンタカルボニル
ルテニウム、ビス（トリ−ｎ−ブチルホスフイ
ン）トリカルボニルルテニウム、ジブロモトリカ
ルボニルルテニウム、ウンデカカルボニルヒドリ
ドトリルテニウムテトラフエニルホスフオニウ
ム、テトラカルボニルルテニウム酸ジポタシウ
ム、オクタデカカルボニルヘキサルテニウム酸セ
シウム、シクロペンタジエニルジカルボニルルテ
ニウム、ルテノセン等である。
これらのルテニウム化合物の中では、カルボニ
ル化合物または反応系中で、カルボニル化合物に
転化しうる化合物が特に好ましい。
これらのルテニウム化合物は液相において均一
系触媒あるいは不均一系触媒のいずれの形でも使
用することができる。不均一系の形で使用する場
合には、通常適当な担体に担持させ反応に供す
る。
本発明の方法においては上記のルテニウム化合
物からなる触媒に、オルトニトロアニリン類を添
加することによつて、触媒性能、特にエチレング
リコールの生成活性を著しく高めることができ
る。
本発明に使用されるオルトニトロアニリン類と
しては、下式[Formula] (In the formula, R 1 , R 2 , R 3 , R 4 , and R 5 each represent hydrogen or a lower alkyl group.) It is characterized by adding orthonitroanilines represented by the following into the reaction system. The present invention provides an industrially excellent method for producing aliphatic alcohols. Examples of the ruthenium compound used in the present invention include oxides, hydroxides, inorganic acid salts, halides, carboxylic acid salts, and complex compounds having various ligands containing nitrogen, phosphorus, oxygen, atoms, etc. It will be done. Specific examples thereof are ruthenium dioxide, ruthenium tetroxide, ruthenium dihydroxide, ruthenium nitrate, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium formate, ruthenium acetate, tris(acetylacetonate)ruthenium, dodecacarbonyltriruthenium. , pentacarbonylruthenium, bis(tri-n-butylphosphine)tricarbonylruthenium, dibromotricarbonylruthenium, undecacarbonylhydridotriruthenium tetraphenylphosphonium, dipotassium tetracarbonylruthenate, cesium octadecacarbonylhexarthenate, Cyclopentadienyldicarbonylruthenium, ruthenocene, etc. Among these ruthenium compounds, carbonyl compounds or compounds that can be converted into carbonyl compounds in the reaction system are particularly preferred. These ruthenium compounds can be used in the form of either homogeneous or heterogeneous catalysts in the liquid phase. When used in a heterogeneous form, it is usually supported on a suitable carrier and subjected to the reaction. In the method of the present invention, by adding orthonitroanilines to the catalyst made of the above-mentioned ruthenium compound, the catalyst performance, particularly the ethylene glycol production activity, can be significantly improved. The orthonitroanilines used in the present invention include the following formula:
【式】
で示される化合物が含まれる。ここで、R1、
R2、R3、R4、R5としてはそれぞれ水素もしくは
炭素数１〜４の低級アルキル基があげられる。
好ましいオルトニトロアニリン類の具体例とし
ては、ｏ−ニトロアニリン、２−ニトロ−ｍ−ト
ルイジン、２−ニトロ−ｐ−トルイジン、ｏ−ニ
トロ−Ｎ−メチルアニリン等があげられる。
本発明の方法において用いられる溶媒の種類に
特に制限はないが、好ましい溶媒はケトン類、ア
ルコール類、エーテル類、カルボン酸、カルボン
酸無水物、エステル類、ラクトン類、アミド類、
スルホン類、スルホキシド類、脂肪族または芳香
族の炭化水素類あるいは反応温度以下において融
解する固体塩およびこれらの混合物である。
本発明方法において、反応系中のルテニウム化
合物の濃度は、通常0.001〜１mol/の範囲であ
る。
オルトニトロアニリン類の添加量は、オルトニ
トロアニリン類のモル数とルテニウム化合物中に
含まれるルテニウムのｇ原子数との比（Ａ／Ru
比）で表わすと、通常１／1000ないし10000／１
の範囲であり、好ましくは、１／100ないし
1000／１である。
反応圧力は、一酸化炭素の分圧と水素の分圧と
の合計で表わすと、通常50ないし3000Kg/cm2の範
囲であり、好ましくは、100ないし1500Kg/cm2であ
る。
一酸化炭素と水素のモル比は１／10ないし10／
１の範囲内にあるのが適当である。また、窒素、
アルゴン、メタン、二酸化炭素等の当該反応に不
活性なガスが存在していてもよい。
反応温度は、100ないし450℃の範囲が好まし
く、さらに好ましくは、200ないし350℃である。
本発明による反応は連続式、回分式のいずれの
方式によつても実施できる。
本発明の方法に従つて得られるメタノール、エ
タノール、エチレングリコール等の生成物は、反
応液から公知の分離操作（例えば、蒸留、抽出
等）によつて容易に分離できる。使用した触媒
は、不均一系触媒の場合には、例えば、別等に
より容易に分離できる。また、均一系触媒の場合
には、所望の生成物を分離した残液をそのまま、
反応系へ循環し再使用することもできる。
以下、実施例により、さらに詳細に説明する
が、本発明はこれらによつて限定されるものでは
ない。
実施例１〜５および比較例１
内容積30mlの振盪式ハステロイＣ製オートクレ
ーブの内部を窒素で置換した後、0.1mg−atomの
ルテニウムを含むRu3（CO）12と助触媒として所
定量のオルトニトロアニリン類および所定の溶媒
7.5mlとを移し入れ、内容物をよく混合し、オー
トクレーブを閉じた。オートクレーブ内にCO／
H2のモル比が１／１の合成ガスを所定の圧力に
なるまで圧入した後、オートクレーブを振盪させ
ながら、所定温度で３時間加熱して反応を行なわ
せた。
反応終了後、オートクレーブを室温まで冷却
し、大部分のガスをゆつくりと放出し、常圧まで
戻した後、反応液を取り出し、ガスクロマトグラ
フにより生成物の分析を行なつた。結果を表１に
示す。表中の「反応圧力」の値は、反応時の最高
到達圧力および反応終了時の圧力を示す。EGは
エチレングリコール、MeOHはメタノール、
EtOHはエタノールを表わす。THF、TGMはそ
れぞれテトラヒドロフラン、テトラエチレングリ
コールジメチルエーテルを表わす。Compounds represented by the following formula are included. Here, R 1 ,
R 2 , R 3 , R 4 and R 5 each include hydrogen or a lower alkyl group having 1 to 4 carbon atoms. Specific examples of preferred orthonitroanilines include o-nitroaniline, 2-nitro-m-toluidine, 2-nitro-p-toluidine, o-nitro-N-methylaniline, and the like. There is no particular restriction on the type of solvent used in the method of the present invention, but preferred solvents are ketones, alcohols, ethers, carboxylic acids, carboxylic acid anhydrides, esters, lactones, amides,
These include sulfones, sulfoxides, aliphatic or aromatic hydrocarbons, solid salts that melt below the reaction temperature, and mixtures thereof. In the method of the present invention, the concentration of the ruthenium compound in the reaction system is usually in the range of 0.001 to 1 mol/. The amount of orthonitroanilines added is determined by the ratio of the number of moles of orthonitroanilines to the number of g atoms of ruthenium contained in the ruthenium compound (A/Ru
Usually expressed as a ratio of 1/1000 to 10000/1
, preferably from 1/100 to
It is 1000/1. The reaction pressure, expressed as the sum of the partial pressures of carbon monoxide and hydrogen, is usually in the range of 50 to 3000 Kg/cm 2 , preferably 100 to 1500 Kg/cm 2 . The molar ratio of carbon monoxide and hydrogen is 1/10 to 10/
It is appropriate that the value be within the range of 1. Also, nitrogen,
Gases inert to the reaction may be present, such as argon, methane, carbon dioxide, etc. The reaction temperature is preferably in the range of 100 to 450°C, more preferably 200 to 350°C. The reaction according to the present invention can be carried out either continuously or batchwise. Products such as methanol, ethanol, and ethylene glycol obtained according to the method of the present invention can be easily separated from the reaction solution by known separation operations (eg, distillation, extraction, etc.). If the catalyst used is a heterogeneous catalyst, it can be easily separated, for example, by separation. In addition, in the case of a homogeneous catalyst, the residual liquid after separating the desired product can be used as is.
It can also be recycled to the reaction system and reused. Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Examples 1 to 5 and Comparative Example 1 After purging the inside of a shaking type Hastelloy C autoclave with an internal volume of 30 ml with nitrogen, Ru 3 (CO) 12 containing 0.1 mg-atom of ruthenium and a predetermined amount of ortho as a promoter were added. Nitroanilines and specified solvents
7.5 ml, the contents were mixed well, and the autoclave was closed. CO in the autoclave/
Synthesis gas having a H 2 molar ratio of 1/1 was injected under pressure until a predetermined pressure was reached, and the autoclave was heated at a predetermined temperature for 3 hours while shaking to carry out a reaction. After the reaction was completed, the autoclave was cooled to room temperature, most of the gas was slowly released, the pressure was returned to normal pressure, the reaction solution was taken out, and the product was analyzed by gas chromatography. The results are shown in Table 1. The value of "reaction pressure" in the table indicates the maximum pressure reached during the reaction and the pressure at the end of the reaction. EG is ethylene glycol, MeOH is methanol,
EtOH stands for ethanol. THF and TGM represent tetrahydrofuran and tetraethylene glycol dimethyl ether, respectively.
Claims (1)
素および水素の混合物を反応せしめて脂肪族アル
コール類を製造するにあたり、下式 【式】 （式中、R1、R2、R3、R4、R5はそれぞれ水素もし
くは低級アルキル基を示す。） で示されるオルトニトロアニリン類を反応系中に
添加することを特徴とする脂肪族アルコール類の
製造法。[Claims] 1. In producing aliphatic alcohols by reacting a mixture of carbon monoxide and hydrogen in a liquid phase in the presence of a ruthenium compound, the following formula [formula] (where R 1 , R 2 , R 3 , R 4 and R 5 each represent hydrogen or a lower alkyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58244852A JPS60139632A (en) | 1983-12-27 | 1983-12-27 | Production of aliphatic alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58244852A JPS60139632A (en) | 1983-12-27 | 1983-12-27 | Production of aliphatic alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60139632A JPS60139632A (en) | 1985-07-24 |
| JPS6114136B2 true JPS6114136B2 (en) | 1986-04-17 |
Family
ID=17124933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58244852A Granted JPS60139632A (en) | 1983-12-27 | 1983-12-27 | Production of aliphatic alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60139632A (en) |
-
1983
- 1983-12-27 JP JP58244852A patent/JPS60139632A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60139632A (en) | 1985-07-24 |
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| EXPY | Cancellation because of completion of term |