JPH0262304B2 - - Google Patents
Info
- Publication number
- JPH0262304B2 JPH0262304B2 JP57062374A JP6237482A JPH0262304B2 JP H0262304 B2 JPH0262304 B2 JP H0262304B2 JP 57062374 A JP57062374 A JP 57062374A JP 6237482 A JP6237482 A JP 6237482A JP H0262304 B2 JPH0262304 B2 JP H0262304B2
- Authority
- JP
- Japan
- Prior art keywords
- cobalt
- tertiary phosphine
- catalyst
- phosphine catalyst
- crown
- 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
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 68
- 239000003054 catalyst Substances 0.000 claims description 39
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 34
- 238000004821 distillation Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 19
- 238000009835 boiling Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- 238000007037 hydroformylation reaction Methods 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- -1 400 and 600 Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 5
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 150000002334 glycols Chemical class 0.000 claims 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000006227 byproduct Substances 0.000 description 12
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 10
- AZZXYUVGVTVQHH-UHFFFAOYSA-N cobalt;trioctylphosphane Chemical compound [Co].CCCCCCCCP(CCCCCCCC)CCCCCCCC AZZXYUVGVTVQHH-UHFFFAOYSA-N 0.000 description 8
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- UMYVESYOFCWRIW-UHFFFAOYSA-N cobalt;methanone Chemical compound O=C=[Co] UMYVESYOFCWRIW-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- MQIKJSYMMJWAMP-UHFFFAOYSA-N dicobalt octacarbonyl Chemical group [Co+2].[Co+2].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] MQIKJSYMMJWAMP-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 3
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- SWMBQMGPRYJSCI-UHFFFAOYSA-N octylphosphane Chemical compound CCCCCCCCP SWMBQMGPRYJSCI-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical compound CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- NDFKTBCGKNOHPJ-UHFFFAOYSA-N hex-2-enal Natural products CCCCC=CC=O NDFKTBCGKNOHPJ-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- WHFQAROQMWLMEY-UHFFFAOYSA-N propylene dimer Chemical compound CC=C.CC=C WHFQAROQMWLMEY-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-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
- Y02P20/584—Recycling of catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明はコバルト−第三級ホスフイン触媒の存
在下オレフイン又はオレフインとアルデヒドの混
合物を原料としてヒドロホルミル化及び水素化反
応を同時に行ないアルコールを製造するいわゆる
コバルト・修飾ヒドロホルミル化反応に於いて反
応生成物とコバルト−第三級ホスフイン触媒との
分離法にかかわるものである。オキソアルコール
は近年可塑剤原料、洗剤原料、農薬、医薬並びに
食品添加物等の中間原料及び各種溶剤として消費
され安定した需要を示している。ヒドロホルミル
化反応技術は、こゝ10年来各社が競つて技術改良
を加え、多くの新規な触媒が開発されている。
特に近年の石油原料事情の悪化は石油より導か
れる原料の原単位向上、プロセスの省エネルギー
化に拍車をかけている。
コバルトを触媒とするヒドロホルミル化法とし
ては単純コバルト法とコバルト修飾法があり、両
者ともそれぞれの特徴を有している。
コバルト修飾法は単純コバルト（例えばヒドロ
コバルトカルボニル、及びジコバルトオクタカル
ボニル等のコバルトカルボニル化合物）に第三級
ホスフインを添加し、通常オレフインから１段で
アルコールを製造するプロセスである。このコバ
ルト修飾法はアルコールへの選択率が比較的高
く、アルデヒドの水素化工程が省略される為エネ
ルギー的には有利な方法である。
しかしこの方法は高価な第三級ホスフインを大
量に使用する上に高沸点副生物の生成が避けられ
ず、これらがコバルト−第三級ホスフイン触媒を
反応系で循環使用する際徐々に蓄積するといつた
問題がおこる。この為コバルト−第三級ホスフイ
ン触媒を循環使用するに従いコバルト−第三級ホ
スフイン触媒及び高沸点副生物の混合物の一部を
反応系外に抜き出す必要があつた。高価な第三級
ホスフイン、コバルト−第三級ホスフイン触媒の
廃棄は経済的に不利であり、できるだけ避ける必
要がある。
従来、コバルト−第三級ホスフイン触媒の分離
回収法としてはメタノールの様な極性溶媒中、一
酸化炭素の加圧条件下〔Co（CO）3（PR3）2〕＋〔Co
（Co）4〕-の様なイオン錯体にして分離する方法が
あるが、イオン錯体の生成及び分離が困難な上に
多量の溶媒を回収使用しなくてはならず工業的に
有利な方法とは云えない。又コバルト−第三級ホ
スフイン触媒を水素化分解し、コバルト金属と第
三級ホスフインに分解する方法もあるが分解率が
低く第三級ホスフインの分解、コバルト金属の反
応器への付着があり有利な方法ではない。本発明
者らはコバルト−第三級ホスフイン触媒と反応生
成物の分離に関し種々検討を行ない本発明にいた
つた。即ち蒸留による分離法は工業化プロセスに
組込み易い方法ではあるが、コバルト−第三級ホ
スフイン触媒を分解させずに高沸点副生物を分離
するには高真空度に保つ必要があり（例えば0.1
mmHg以下）実装置適用には困難がともなう。工
業的に容易な真空度（例えば１〜10mmHg）で蒸
留を行なうと、蒸留温度を高くせざるを得ずコバ
ルト−第三級ホスフイン触媒の分解を引きおこ
す。本発明者らはこの蒸留によるコバルト−第三
級ホスフイン触媒の回収法を検討するなかでコバ
ルト−第三級ホスフイン触媒の分解は蒸留温度と
蒸留時の残存アルコール量との間に密接な関係が
あり、130℃以上では蒸留缶残中のアルコール濃
度が１％以下になるとコバルト−第三級ホスフイ
ン触媒が分解する事実を発見した。
そこで、ヒドロホルミル化反応生成物の蒸留時
に第三級ホスフインよりも沸点が低く、且つ目的
とするアルコールよりも沸点の高い含酸素化合物
を溶媒として添加し、蒸溜を行つたところ驚くべ
きことに目的とするアルコールを完全に留出させ
てもコバルト−第三級ホスフイン触媒は安定に存
在し、かつ高沸点副生物の大部分も留出してコバ
ルト−第三級ホスフイン触媒との分離が可能であ
ることを見出した。蒸留分離後のコバルト−第三
級ホスフイン触媒を含む缶残の赤外吸収スペクト
ルを測定した所1907cm-1、1957cm-1にそれぞれ
〔Co（CO）3PR3〕2、〔Co（CO）2（PR3）2〕2に対応す
る
カルボニルの吸収が充分な強度をもつて観察され
た。更にこのコバルト−第三級ホスフイン触媒を
含む蒸留缶残をオレフイン及びアルデヒド存在下
の反応系内に所定の触媒濃度になる様にもどして
反応を行なわせた所、新しい触媒と全く同等の活
性を持つと共に反応に何ら悪影響を及ぼさない事
が分つた。
従つて本発明の蒸留法によるヒドロホルミル化
反応生成物中の生成アルコールとコバルト−第三
級ホスフイン触媒の分離及び触媒の回収方法の適
用範囲は広い。
勿論第三級ホスフインは反応に供するオレフイ
ン又はオレフインとアルデヒドの混合物から生成
するアルコールとの沸点の関係で選ばなくてはな
らないが、次の如き一般式
The present invention deals with the so-called cobalt-modified hydroformylation reaction in which alcohol is produced by simultaneously carrying out hydroformylation and hydrogenation reactions using an olefin or a mixture of an olefin and an aldehyde as a raw material in the presence of a cobalt-tertiary phosphine catalyst. This relates to a method for separating cobalt from a tertiary phosphine catalyst. In recent years, oxo alcohol has been consumed as a raw material for plasticizers, raw materials for detergents, intermediate raw materials for agricultural chemicals, medicines, food additives, etc., and various solvents, and has shown stable demand. Over the past 10 years, various companies have competed to improve the hydroformylation reaction technology, and many new catalysts have been developed. In particular, the deterioration of the petroleum raw material situation in recent years has spurred efforts to improve the basic unit of raw materials derived from petroleum and to save energy in processes. Hydroformylation methods using cobalt as a catalyst include a simple cobalt method and a cobalt modification method, both of which have their own characteristics. The cobalt modification method is a process in which a tertiary phosphine is added to simple cobalt (for example, a cobalt carbonyl compound such as hydrocobalt carbonyl and dicobalt octacarbonyl), and alcohol is usually produced from an olefin in one step. This cobalt modification method has a relatively high selectivity to alcohol, and is an advantageous method in terms of energy since the aldehyde hydrogenation step is omitted. However, this method uses a large amount of expensive tertiary phosphine and inevitably generates high-boiling byproducts, which gradually accumulate when the cobalt-tertiary phosphine catalyst is recycled in the reaction system. A problem arises. For this reason, as the cobalt-tertiary phosphine catalyst is recycled, it is necessary to extract a portion of the mixture of the cobalt-tertiary phosphine catalyst and high-boiling by-products from the reaction system. Disposal of expensive tertiary phosphine and cobalt-tertiary phosphine catalysts is economically disadvantageous and should be avoided as much as possible. Conventionally, the separation and recovery method for cobalt-tertiary phosphine catalysts has been carried out under pressurized conditions of carbon monoxide in a polar solvent such as methanol [Co(CO) 3 (PR 3 ) 2 ] + [Co
There is a method to separate it by forming an ion complex such as (Co) 4 ] - , but it is difficult to generate and separate the ion complex, and a large amount of solvent must be recovered and used, making it an industrially advantageous method. I can't say that. There is also a method of hydrogenolyzing a cobalt-tertiary phosphine catalyst to decompose it into cobalt metal and tertiary phosphine, but this method is advantageous because the decomposition rate is low and the tertiary phosphine decomposes and cobalt metal adheres to the reactor. Not in a good way. The present inventors conducted various studies regarding the separation of a cobalt-tertiary phosphine catalyst and a reaction product, and arrived at the present invention. That is, although the separation method by distillation is a method that is easy to incorporate into industrial processes, it is necessary to maintain a high degree of vacuum in order to separate high-boiling point byproducts without decomposing the cobalt-tertiary phosphine catalyst (for example,
mmHg or less) is difficult to apply to actual equipment. If distillation is carried out at an industrially easy degree of vacuum (for example, 1 to 10 mmHg), the distillation temperature must be raised, which causes decomposition of the cobalt-tertiary phosphine catalyst. The present inventors investigated a method for recovering the cobalt-tertiary phosphine catalyst by distillation, and found that the decomposition of the cobalt-tertiary phosphine catalyst has a close relationship between the distillation temperature and the amount of alcohol remaining during distillation. We have discovered that at temperatures above 130°C, the cobalt-tertiary phosphine catalyst decomposes when the alcohol concentration in the still residue falls below 1%. Therefore, when distilling the hydroformylation reaction product, an oxygen-containing compound with a boiling point lower than that of tertiary phosphine and higher than that of the target alcohol was added as a solvent, and the target alcohol was distilled. The cobalt-tertiary phosphine catalyst remains stable even when the alcohol is completely distilled off, and most of the high-boiling by-products can also be distilled off and separated from the cobalt-tertiary phosphine catalyst. I found out. The infrared absorption spectrum of the residue containing the cobalt-tertiary phosphine catalyst after distillation separation was measured at 1907 cm -1 and 1957 cm -1 , respectively [Co(CO) 3 PR 3 ] 2 and [Co(CO) 2 (PR 3 ) 2 ] Carbonyl absorption corresponding to 2 was observed with sufficient intensity. Furthermore, when the residue of the distillation tank containing this cobalt-tertiary phosphine catalyst was returned to the reaction system in the presence of olefin and aldehyde to a predetermined catalyst concentration and the reaction was carried out, it showed exactly the same activity as the new catalyst. It was found that it did not have any negative effect on the reaction. Therefore, the scope of application of the method of separating the alcohol produced in the hydroformylation reaction product and the cobalt-tertiary phosphine catalyst and recovering the catalyst by the distillation method of the present invention is wide. Of course, the tertiary phosphine must be selected in relation to the boiling point of the olefin to be subjected to the reaction or the alcohol produced from the mixture of olefin and aldehyde, but the following general formula
【式】（R1＝R2＝
R3又はR1≠R2≠R3で良くR1、R2、R3の一つ又は
全部が炭素数４以上のアルキル基、シクロアルキ
ル基、芳香族）で表わされる第三級ホスフインを
用いることができる。又一般式[Formula] (R 1 = R 2 = R 3 or R 1 ≠ R 2 ≠ R 3 , and one or all of R 1 , R 2 , and R 3 may be an alkyl group, a cycloalkyl group, or an aromatic group having 4 or more carbon atoms. A tertiary phosphine represented by the following group can be used. Also general formula
プロピレンダイマー（組成：２−メチルベンテ
ン−１ 92％、ｎ−ヘキセン５％、２，３−ジメ
チルブテン２％、４−メチルペンテン−１，１
％）をジコバルトオクタカルボニルを触媒として
ヒドロホルミル化反応を行なわせ生成物（組成：
ヘキサン1.5％、未反応ヘキセン10％、ヘプタナ
ール83.5％、ヘプタノール３％、高沸点副生物２
％）を得た。以下の実施例ではこの反応生成物を
原料という。
実施例 １
原料１Kgを５ステンレス製上下撹拌式オート
クレープに仕込み、ジコバルトオクタカルボニル
11.6ｇを溶解させた後トリ−ｎ−オクチルホスフ
イン50ｇを添加し充分に撹拌した後に水素／一酸
化炭素＝２なるガスを仕込み70Kg/cm2（ゲージ）
190〜200℃で２時間反応を行なつた。反応生成物
の組成はヘキサン3.2％、ヘキセントレース、ヘ
プタナール0.2％、ヘプタノール89.2％、トリｎ
−オクチルホスフインとコバルト−トリｎ−オク
チルホスフイン触媒合計量5.6％、高沸点副生物
1.8％であり、ヘキセン転化率99.9％、水添率
（アルコール／アルデヒド＋アルコール）99.8％であつ
た。
実施例 ２
実施例１で得た反応生成物100grを蒸留フラス
コにとり、テトラエチレングリコール3.5ｇを添
加する。
全系を300mmHgに減圧して、ヘキサン、ヘキセ
ン類を除去した後全系を５mmHgまで減圧後加熱
を開始した。
蒸留缶温度が70℃付近からヘプタノールが留出
し始め180℃になるまで蒸留を行なつた。留出液
は94.2ｇであり、その組成はヘキサン3.4％、ヘ
プタナール0.2％、ヘプタノール94.7％、高沸点
副生物1.7％、蒸留缶残は9.3ｇであり組成はテト
ラエチレングリコール37.6％、トリｎ−オクチル
ホスフインとコバルト−トリｎ−オクチルホスフ
イン触媒合計量60.2％、高沸点副生物は2.2％で
あつた。
蒸留中におけるコバルト−トリｎ−オクチルホ
スフイン触媒の分解はなく蒸留缶残の一部をとり
赤外吸収スペクトルを測定したところ1902cm-1、
1950cm-1に〔Co（CO）3PR3〕2〔Co（CO）2（PR3）2〕2
に由来する吸収が認められた。回収したコバルト
−トリｎ−オクチルホスフイン触媒を含む蒸留缶
残9.3ｇをとり原料90ｇに混合し実施例１と同様
な操作を行なつた所２時間後にオレフイン転化率
99.0％、水添率99.8％となり実施例１と同様な反
応活性を示した。
実施例 ３
実施例１で得た反応生成物100ｇを蒸留フラス
コにとり、ポリエチレングリコール400、10.7ｇ
を添加した。以後の操作は実施例２と同様に行な
つた。留出液は95.9ｇであつた。留出液の組成は
ヘキサン3.3％、ヘキセン0.8％、ヘプタナール0.2
％、ヘプタノール93.6％、ポリエチレングリコー
ル400 2.1％、高沸点副生物1.4％であつた。
蒸留缶残は14.8ｇであつた。蒸留缶残の組成は
トリｎ−オクチルホスフインとコバルト−トリｎ
−オクチルホスフイン触媒合計量37.8％ポリエチ
レングリコール400、58.7％、高沸点副生成3.4％
となつた。蒸留中でのコバルト−トリｎ−オクチ
ルホスフイン触媒の分解はなく、蒸留缶残の赤外
吸収スペクトルも1902cm-1、1950cm-1に強い吸収
を示した。回収したコバルト−トリｎ−オクチル
ホスフイン触媒を含む蒸留缶残14.8ｇをとり、原
料85ｇに混合し実施例１と同様な操作を行つた
所、２時間後にヘキセン転化率99.5％、水添率
99.8％となり実施例１と同様な反応活性を示し
た。
比較例
実施例１で得た反応生成物100ｇを蒸留フラス
コにとり、溶媒を加えずに実施例２と同様な条件
で蒸留した。
蒸留缶温度が160℃を越えたあたりからコバル
ト−トリｎ−オクチルホスフイン触媒の分解が認
められ、液が紫色から緑色に変色した。
留出液は92.7ｇでその組成はヘキサン3.5％ヘ
プタナール0.2％、ヘプタノール96.2％、高沸点
副生物0.1％であつた。蒸留缶残は7.3ｇであり組
成は析出金属コバルト、トリｎ−オクチルホスフ
イン及びコバルト−トリｎ−オクチルホスフイン
触媒の合計量76.7％、高沸点副生物23.3％であつ
た。
蒸留缶残の一部をとり赤外吸収スペクトルを測
定したところ実施例２、３と異なり1900〜2000cm
-1付近のカルボニル基の吸収は殆んど認められな
かつた。
蒸留缶残7.3ｇをとり、原料100ｇに溶解し実施
例１と同様の条件で反応させた所２時間後のヘキ
セン転化率85％、水添率90％であつた。
Propylene dimer (composition: 2-methylbentene-1 92%, n-hexene 5%, 2,3-dimethylbutene 2%, 4-methylpentene-1,1
%) was subjected to a hydroformylation reaction using dicobalt octacarbonyl as a catalyst to produce a product (composition:
Hexane 1.5%, unreacted hexene 10%, heptanal 83.5%, heptanol 3%, high boiling point by-product 2
%) was obtained. In the following examples, this reaction product is referred to as a raw material. Example 1 1 kg of raw material was charged into a stainless steel autoclave with vertical stirring, and dicobalt octacarbonyl was prepared.
After dissolving 11.6g, add 50g of tri-n-octylphosphine, stir thoroughly, and then add hydrogen/carbon monoxide = 2 gas to 70Kg/cm 2 (gauge).
The reaction was carried out at 190-200°C for 2 hours. The composition of the reaction product is hexane 3.2%, hexentrace, heptanal 0.2%, heptanol 89.2%, trin
-Octylphosphine and cobalt-tri-n-octylphosphine catalyst total amount 5.6%, high boiling point by-product
The hexene conversion rate was 99.9%, and the hydrogenation rate (alcohol/aldehyde + alcohol) was 99.8%. Example 2 100g of the reaction product obtained in Example 1 is placed in a distillation flask, and 3.5g of tetraethylene glycol is added thereto. The pressure of the entire system was reduced to 300 mmHg to remove hexane and hexenes, and then the pressure of the entire system was reduced to 5 mmHg and heating was started. Distillation was continued until the distillation vessel temperature reached 180°C, when heptanol began to be distilled out from around 70°C. The distillate weighs 94.2g, and its composition is 3.4% hexane, 0.2% heptanal, 94.7% heptanol, and 1.7% high-boiling byproducts.The distillate residue is 9.3g, and its composition is 37.6% tetraethylene glycol, tri-n- The total amount of octylphosphine and cobalt-tri-n-octylphosphine catalysts was 60.2%, and the high boiling point by-product was 2.2%. There was no decomposition of the cobalt-tri-n-octylphosphine catalyst during distillation, and an infrared absorption spectrum of a part of the residue of the distillation tank was measured, and the result was 1902 cm -1 .
At 1950cm -1 [Co(CO) 3 PR 3 ] 2 [Co(CO) 2 (PR 3 ) 2 ] 2
Absorption originating from was observed. 9.3 g of the residue from the distillation tank containing the recovered cobalt-tri-n-octylphosphine catalyst was taken and mixed with 90 g of the raw material, and the same operation as in Example 1 was performed. After 2 hours, the olefin conversion rate increased.
The hydrogenation rate was 99.0% and the hydrogenation rate was 99.8%, showing the same reaction activity as in Example 1. Example 3 100g of the reaction product obtained in Example 1 was placed in a distillation flask, and 10.7g of polyethylene glycol 400 was added.
was added. The subsequent operations were performed in the same manner as in Example 2. The distillate weighed 95.9 g. The composition of the distillate is 3.3% hexane, 0.8% hexene, and 0.2 heptanal.
%, heptanol 93.6%, polyethylene glycol 400 2.1%, and high boiling point by-products 1.4%. The residue in the still was 14.8 g. The composition of the still residue is tri-n-octylphosphine and cobalt-tri-n.
- Total amount of octylphosphine catalyst: 37.8% Polyethylene glycol 400, 58.7%, high boiling point by-product 3.4%
It became. There was no decomposition of the cobalt-tri-n-octylphosphine catalyst during distillation, and the infrared absorption spectrum of the residue from the distillation tank showed strong absorption at 1902 cm -1 and 1950 cm -1 . 14.8 g of the distillation tank residue containing the recovered cobalt-tri-n-octylphosphine catalyst was taken, mixed with 85 g of raw material, and the same operation as in Example 1 was performed. After 2 hours, the hexene conversion rate was 99.5% and the hydrogenation rate was 99.5%.
The reaction activity was 99.8%, indicating the same reaction activity as in Example 1. Comparative Example 100 g of the reaction product obtained in Example 1 was placed in a distillation flask and distilled under the same conditions as in Example 2 without adding a solvent. When the temperature of the distillation vessel exceeded 160°C, decomposition of the cobalt-tri-n-octylphosphine catalyst was observed, and the color of the liquid changed from purple to green. The distillate weighed 92.7 g, and its composition was 3.5% hexane, 0.2% heptanal, 96.2% heptanol, and 0.1% high-boiling byproducts. The residue in the distillation tank was 7.3 g, and its composition was 76.7% in total of precipitated metal cobalt, tri-n-octylphosphine and cobalt-tri-n-octylphosphine catalyst, and 23.3% of high boiling point by-products. When we measured the infrared absorption spectrum of a part of the still residue, it was found to be 1900 to 2000 cm, unlike in Examples 2 and 3.
Almost no absorption of the carbonyl group near -1 was observed. 7.3 g of the residue from the distillation tank was taken, dissolved in 100 g of raw material, and reacted under the same conditions as in Example 1. After 2 hours, the hexene conversion rate was 85% and the hydrogenation rate was 90%.
Claims (1)
レフイン又はオレフインとアルデヒドの混合物を
原料にしてヒドロホルミル化及び水素化反応を同
時に行なわせた該反応生成物から目的とするアル
コールとコバルト・第三級ホスフイン触媒との分
離に際し、目的アルコールよりも高沸点であり、
かつ第三級ホスフインよりも低沸点の溶媒を添加
し蒸留分離する事を特徴とするコバルト−第三級
ホスフイン触媒の回収方法。 ２ 溶媒としてエチレングリコール、ジエチレン
グリコール、トリエチレングリコール、テトラエ
チレングリコール、ポリエチレングリコール200、
400、600等のグリコール類、エチレングリコール
アルキルエーテル、ジエチレングリコールアルキ
ルエーテル、テトラエチレングリコールアルキル
エーテル等のモノ及びジエーテル化合物、炭素数
16以上の直鎖もしくは分岐の高級アルコール、又
は18−クラウン−６、ジシクロヘキシル−18−ク
ラウン−６、ジベンゾ−18−クラウン−６等のク
ラウンエーテル化合物を使用することを特徴とす
る特許請求の範囲第１項記載のコバルト−第三級
ホスフイン触媒の回収方法。 ３ 一般式【式】（R1＝R2＝R3又はR1≠R2≠ R3でR1、R2、R3の一つ又は全部が炭素数４以上
のアルキル基、シクロアルキル基、芳香族）で表
わわされる第三級ホスフイン及び一般式
【式】（Ｒは炭素数１〜20のアルキル基） で表わされる８員環ホスフインを使用することを
特徴とする特許請求の範囲第１項記載のコバルト
−第三級ホスフイン触媒の回収方法。[Scope of Claims] 1. The desired alcohol and cobalt are obtained from the reaction product obtained by simultaneously carrying out hydroformylation and hydrogenation reactions using an olefin or a mixture of an olefin and an aldehyde as a raw material in the presence of a cobalt/tertiary phosphine catalyst.・When separated from the tertiary phosphine catalyst, it has a higher boiling point than the target alcohol,
A method for recovering a cobalt-tertiary phosphine catalyst, which comprises adding a solvent having a boiling point lower than that of the tertiary phosphine and separating it by distillation. 2 As a solvent, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol 200,
Glycols such as 400 and 600, mono- and diether compounds such as ethylene glycol alkyl ether, diethylene glycol alkyl ether, and tetraethylene glycol alkyl ether, carbon number
Claims characterized in that a linear or branched higher alcohol of 16 or more or a crown ether compound such as 18-crown-6, dicyclohexyl-18-crown-6, or dibenzo-18-crown-6 is used. A method for recovering a cobalt-tertiary phosphine catalyst according to item 1. 3 General formula [Formula] (R 1 = R 2 = R 3 or R 1 ≠ R 2 ≠ R 3 and one or all of R 1 , R 2 , and R 3 is an alkyl group or cycloalkyl group having 4 or more carbon atoms , aromatic) and an 8-membered ring phosphine represented by the general formula [Formula] (R is an alkyl group having 1 to 20 carbon atoms). A method for recovering a cobalt-tertiary phosphine catalyst according to Scope 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57062374A JPS58180236A (en) | 1982-04-16 | 1982-04-16 | Method for recovering hydroformylation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57062374A JPS58180236A (en) | 1982-04-16 | 1982-04-16 | Method for recovering hydroformylation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58180236A JPS58180236A (en) | 1983-10-21 |
| JPH0262304B2 true JPH0262304B2 (en) | 1990-12-25 |
Family
ID=13198273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57062374A Granted JPS58180236A (en) | 1982-04-16 | 1982-04-16 | Method for recovering hydroformylation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58180236A (en) |
-
1982
- 1982-04-16 JP JP57062374A patent/JPS58180236A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58180236A (en) | 1983-10-21 |
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