• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Process for the catalytic production of alcohol products, wherein by-products comprising ketone, aldehyde and ester compounds contained in the alcohol product are subjected to hydrogenation with a hydrogen-containing purge gas.
    公开号:AU2012370043A1
    申请号:U2012370043
    申请日:2012-10-18
    公开日:2014-08-28
    发明作者:Christian Wix
    申请人:Haldor Topsoe AS；
    IPC主号:C07C29-149
    专利说明:
    WO 2013/120548 PCT/EP2012/070674 1 Title: Process for synthesis of alcohols The invention relates to a process for production of alco hols from alcohol synthesis gas. In particular the inven 5 tion concerns purification of alcohols by conversion of ke tones, aldehydes and esters present in the alcohols in presence of one or more catalysts being active in the con version of ketones, esters, aldehydes and hydrogen to alco hols. 10 During alcohol synthesis from hydrogen and carbon oxides comprising synthesis gas, by-products such as water, alde hydes, esters and ketones are formed frequently. Species like acetone and methyl ethyl ketone with a boiling point 15 close to that of the prepared alcohol are difficult to re move and consequently the presence of these species will contribute to the demand for a larger and more costly dis tillation column for the purification of the alcohol prod uct. 20 It is thus a general object of the invention to provide a process for the production of an alcohol product by cata lytic conversion of H 2 , CO and C02, wherein the produced alcohol product has a substantially reduced content of oxo 25 compounds including aldehyde and ketone impurities. Thus, the present invention provides a process for produc tion of alcohol product, comprising the steps of 30 (a) providing an alcohol synthesis gas comprising hydrogen and carbon monoxide; WO 2013/120548 PCT/EP2012/070674 2 (b) converting the alcohol synthesis gas into a crude al cohol product stream comprising one or more alcohols and unconverted alcohol synthesis gas in presence of one or more catalysts active in converting the alcohol synthesis 5 gas into the one or more alcohols; (c) cooling and separating the crude alcohol product with drawn from step (b) into a gas phase comprising hydrogen, carbon monoxide and carbon dioxide and into a liquid prod 10 uct comprising the one or more alcohols and by-products comprising ketones, esters and aldehydes formed in the con version of the alcohol synthesis gas; (d) purging a part of the gas phase obtained in step (c) 15 and recycling the remaining gas phase to step (a); (e) prior to introduction of the remaining gas phase into step (a) mixing the recycled remaining gas phase product with fresh synthesis gas to form the alcohol synthesis gas; 20 and (f) subsequent to the cooling and separation in step (c) withdrawing the liquid phase and subjecting the liquid phase to a two phase catalytic hydrogenation of the ke 25 tones, esters and aldehydes by-products to corresponding alcohols, wherein the liquid phase is hydrogenated with the part of the gas phase being purged from step (d). 30 WO 2013/120548 PCT/EP2012/070674 3 Catalysts for use in the alcohol synthesis and hydrogena tion ketones, esters and aldehydes are known per se in the art. 5 On a Cu-based catalyst, alcohol is produced from synthesis gas via the following reactions n CO + 2n H 2 = CnH 2 nnOH + (n-1) H 2 0 (1) . 10 The oxo -compound by-products such as acetone and methyl ethyl ketone etc are formed in small quantities during al cohol synthesis. Hydrogenation of these by-products is possible on copper, 15 nickel and/or noble metal based catalysts and follows e.g the reactions: Methyl formate: C 2
    H
    4 0 2 + 2H 2 = 2CH 3 0H Acetone: C3H 6 0 + H 2 = C3H 8 O 20 Methyl ethyl ketone: C 4
    H
    8 O + H 2 = C3H 8 O Particular suitable catalysts for the hydrogenation contain noble metal including Pt and Pd. Base metal catalysts like a 10 wt% Ni-Cu catalyst have been mentioned in the art. 25 E.g. US-patent No. 5,243,095 discloses a Cu, Fe, Mn, Al based catalyst for ketone hydrogenation and US Patent No. 3,925,490 claims a Cu, Cr catalyst. In general, the Cu content in the Cu-containing hydrogena 30 tion catalysts is in the range of 10-95% by weight, pref erably 40-70% by weight.
    WO 2013/120548 PCT/EP2012/070674 4 The catalyst can be in form of pellets, extrudates or pow der. 5 Fig.1 of the drawings shows a simplified flow sheet of a process according to an embodiment of the invention. Referring to Fig. 1, alcohol synthesis gas is formed by mixing fresh synthesis gas 1 comprising carbon monoxide and hydrogen with recycle gas 2. Thus the formed synthesis gas 10 3 is introduced into alcohol synthesis reactor system 4. The crude alcohol product from 5 from the alcohol synthesis reactor system 4 contains methanol, unconverted alcohol synthesis gas and traces of ketones, esters and aldehydes. 15 The crude alcohol product 5 is cooled (not shown). The cooled product is then separated in the separator into a vapour and liquid phase, 7 and 8 respectively. A part of the gas phase is purged through line 9 to reduce the amount 20 of inerts accumulating in the synthesis loop (eg. Ar, N2 and CH4). The remainder of the gas forms recycle gas stream 2. The liquid stream 8 is passed into two phase hydrogenation 25 reactor 10. Ketones, aldehydes and esters contained in the liquid phase 8, are hydrogenated with purge gas 9 into al cohol in presence of a hydrogenation catalyst.
    权利要求:
    Claims (3)
    [1] 1. A process for production of alcohol product, compris ing the steps of 5 (a) providing an alcohol synthesis gas comprising hydrogen and carbon monoxide; (b) converting the alcohol synthesis gas into a crude al 10 cohol product stream comprising one or more alcohols and unconverted alcohol synthesis gas in presence of one or more catalysts active in converting the alcohol synthesis gas into the one or more alcohols; 15 (c) cooling and separating the crude alcohol product with drawn from step (b) into a gas phase comprising hydrogen, carbon monoxide and carbon dioxide and into a liquid prod uct comprising the one or more alcohols and by-products comprising ketones, esters and/or aldehydes formed in the 20 conversion of the alcohol synthesis gas; (d) purging a part of the gas phase obtained in step (c) and recycling the remaining gas phase to step (a) 25 (e) prior to introduction of the remaining gas phase into step (a) mixing the recycled remaining gas phase product with fresh synthesis gas to form the alcohol synthesis gas; and 30 (f) subsequent to the cooling and separation in step (c) withdrawing the liquid phase and subjecting the liquid phase to a two phase catalytic hydrogenation of the ke- WO 2013/120548 PCT/EP2012/070674 6 tones, esters and/or aldehydes in the by-products to corre sponding alcohols, wherein the liquid phase is hydrogenated with the part of 5 the gas phase being purged from step (d).
    [2] 2. Process according to claim 1, wherein the hydro genation catalyst is a Cu based catalyst. 10 3. Process according to claim 2, wherein the Cu con tent of the hydrogenation catalyst is in the range of
    [3] 10-95% by weight, preferably 40-70% by weight. 4. Process according to claim 1, wherein the hydro 15 genation catalyst is a noble metal based catalyst. 5. Process according to anyone of the preceding claims, wherein the hydrogenation of the crude alcohol is performed at a pressure of between 2 and 15 MPa and a tem 20 perature between 200C and 1200C.
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    同族专利:
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB694962A|1949-06-29|1953-07-29|Stanolind Oil & Gas Co|Improvements in or relating to production of alcohols and organic acids from oxygenated organic compounds|
    DE1935900C3|1969-07-15|1975-03-13|Chemische Werke Huels Ag, 4370 Marl|Process for the removal of aldehydes and ketones from gas streams containing carbon monoxide|
    US5243095A|1992-04-24|1993-09-07|Engelhard Corporation|Hydrogenation catalyst, process for preparing and process for using said catalyst|
    KR101137818B1|2002-12-21|2012-04-18|할도르 토프쉐 에이/에스|Process for synthesis of methanol|
    EP1741692A1|2005-07-06|2007-01-10|BP Chemicals Limited|Process for the conversion of hydrocarbons to C2-oxygenates|
    FR2894251B1|2005-12-05|2008-01-04|Air Liquide|METHANOL SYNTHESIS METHOD FOR RECYCLING RESIDUAL GAS|
    PL2215041T3|2007-11-14|2014-04-30|Bp Plc|Process for the production of alcohol from a carbonaceous feedstock|
    法律状态:
    2017-10-12| FGA| Letters patent sealed or granted (standard patent)|
    2020-05-14| MK14| Patent ceased section 143(a) (annual fees not paid) or expired|
    优先权:
    申请号 | 申请日 | 专利标题
    DKPA201200112||2012-02-13||
    DKPA201200112||2012-02-13||
    PCT/EP2012/070674|WO2013120548A1|2012-02-13|2012-10-18|Process for synthesis of alcohols|
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