CN104125941A - 用于合成醇的方法 - Google Patents

用于合成醇的方法 Download PDF

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CN104125941A
CN104125941A CN201280069706.2A CN201280069706A CN104125941A CN 104125941 A CN104125941 A CN 104125941A CN 201280069706 A CN201280069706 A CN 201280069706A CN 104125941 A CN104125941 A CN 104125941A
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alcohol
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synthetic gas
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CN104125941B (zh
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C·维克斯
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Topsoe AS
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Haldor Topsoe AS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
    • C07C27/04—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by reduction of oxygen-containing compounds
    • C07C27/06—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by reduction of oxygen-containing compounds by hydrogenation of oxides of carbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/02—Formation or introduction of functional groups containing oxygen of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
    • C07C29/90—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound using hydrogen only

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

用于催化生产醇产物的方法，其中用含氢吹洗气体对副产物进行氢化，所述副产物含有包含于醇产物中的酮、醛和酯化合物。

Description

用于合成醇的方法
本发明涉及用于从醇合成气生产醇的方法。特别是，本发明涉及醇的纯化，其通过在一种或多种催化剂的存在下将醇中存在的酮、酯和醛转化为醇，所述一种或多种催化剂具有将酮、酯、醛和氢转化为醇的活性。
在从包括氢和碳氧化物的合成气合成醇的过程中，经常形成副产物如水、醛、酯和酮。具有与所制备醇的沸点接近的沸点的物质如丙酮和甲基乙基酮难以除去，因此这些物质的存在会使得需要用于醇产物的纯化的较大和较昂贵的蒸馏塔。
因此，本发明的总的目的是提供通过催化转化H2、CO和CO2来生产醇产物的方法，其中所产生的醇产物具有显著减少的包括醛和酮杂质的含氧化物含量。
因此，本发明提供了用于生产醇产物的方法，包括以下步骤：
(a)提供含有氢气和一氧化碳的醇合成气；
(b)在一种或多种催化剂的存在下将所述醇合成气转化为粗醇产物流，所述粗醇产物流包含一种或多种醇和未转化的醇合成气，所述一种或多种催化剂具有将醇合成气转化为一种或多种醇的活性；
(c)冷却和分离从步骤(b)中取出的所述粗醇产物为气相和液相，所述气相包含氢、一氧化碳和二氧化碳，所述液相包含一种或多种醇和副产物，所述副产物包括在醇合成气的转化中形成的酮、酯和醛；
(d)吹洗步骤(c)得到的气相的一部分并再循环剩余的气相至步骤(a)；
(e)在将剩余的气相引入至步骤(a)之前，将所述再循环剩余气相产物与新鲜的合成气混合，以形成醇合成气；和
(f)在步骤(c)中的冷却和分离之后，取出液相并使所述液相经受将酮、酯和醛副产物转化为相应的醇的两相催化氢化；
其中所述液相是使用来自步骤(d)的被吹洗的气相的部分来氢化的。
用于醇合成和氢化酮、酯和醛的催化剂在本领域中是已知的。
在Cu基催化剂上，醇是通过下列反应由合成气制备的：
nCO+2nH2＝CnH2n+1OH+(n-1)H2O(1)。
在醇合成中，含氧化合物副产物如丙酮和甲基乙基酮等都以少量形成。
这些副产物的氢化可以在铜、镍和/或贵金属基催化剂上进行，并随后进行下列反应：
甲酸甲酯：C2H4O2+2H2＝2CH3OH
丙酮：C3H6O+H2＝C3H8O
甲基乙基酮：C4H8O+H2＝C3H8O
特别合适的用于氢化的催化剂含有包括铂和钯的贵金属。现有技术已经提到碱金属催化剂如10wt％的镍-铜催化剂。例如美国专利5,243,095公开了一种用于酮氢化的铜、铁、锰、铝基催化剂，美国专利3,925,490请求保护铜、铬催化剂。
在一般情况下，在含Cu氢化催化剂中，Cu的含量是在10-95wt％范围内，优选40-70wt％。
该催化剂可以呈粒料、挤出物或粉末的形式。
附图中的图1示出了根据本发明一个实施方案的方法的简化流程图。
参照图1，通过混合含有一氧化碳和氢气的新鲜合成气1与循环气2形成醇合成气。由此所形成的合成气3被引入到醇合成反应器系统4。
自醇合成反应器系统4形成的粗醇产物5含有甲醇、未转化的醇合成气和痕量的酮、酯和醛。
粗醇产物5被冷却(未示出)。然后，该冷却的产物在分离器中被分别分离成气相7和液相8。一部分气相通过管线9被吹洗，以减少在合成回路中惰性物质(如氩气，氮气和CH4)积聚的量。气体的其余部分形成再循环气流2。
液体流8被送至两相氢化反应器10中。在氢化催化剂的存在下，使用吹洗气9将在液相8中含有的酮、醛和酯氢化为醇。

Claims (5)

1.用于生产醇产物的方法，包括以下步骤：
(a)提供含有氢气和一氧化碳的醇合成气；
(b)在一种或多种催化剂的存在下，将所述醇合成气转化为粗醇产物流，所述粗醇产物流包含一种或多种醇和未转化的醇合成气，所述一种或多种催化剂具有将醇合成气转化为一种或多种醇的活性；
(c)冷却和分离从步骤(b)中取出的所述粗醇产物为气相和液相，所述气相包含氢、一氧化碳和二氧化碳，所述液相包含一种或多种醇和副产物，所述副产物包括在醇合成气的转化中形成的酮、酯和/或醛；
(d)吹洗步骤(c)得到的气相的一部分并再循环剩余的气相至步骤(a)；
(e)在将剩余的气相引入至步骤(a)之前，将所述再循环剩余气相产物与新鲜的合成气混合，以形成醇合成气；和
(f)在步骤(c)中的冷却和分离之后，取出液相并使所述液相经受将副产物中的酮、酯和/或醛转化为相应的醇的两相催化氢化；
其中所述液相是使用来自步骤(d)的被吹洗的气相的部分来氢化的。
2.根据权利要求1的方法，其中所述氢化催化剂是Cu基催化剂。
3.根据权利要求2的方法，其中所述氢化催化剂的Cu含量是在10-95wt％范围内，优选40-70wt％。
4.根据权利要求1的方法，其中所述氢化催化剂是贵金属基催化剂。
5.根据前述任一项权利要求的方法，其中粗醇的氢化在2至15MPa的压力和20℃至120℃的温度下进行。
CN201280069706.2A 2012-02-13 2012-10-18 用于合成醇的方法 Expired - Fee Related CN104125941B (zh)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB694962A (en) * 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
CN1747918A (zh) * 2002-12-21 2006-03-15 赫多特普索化工设备公司 合成甲醇的方法
WO2007066036A2 (fr) * 2005-12-05 2007-06-14 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede de synthese de methanol ou d'oxo alcools permettant un recyclage du gaz residuaire
CN101218197A (zh) * 2005-07-06 2008-07-09 英国石油化学品有限公司 用于烃类转化到c2-氧合物的工艺

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Publication number Priority date Publication date Assignee Title
DE1935900C3 (de) 1969-07-15 1975-03-13 Chemische Werke Huels Ag, 4370 Marl Verfahren zur Entfernung von Aldehyden und Ketonen aus Kohlenmonoxid enthaltenden Gasströmen
US5243095A (en) 1992-04-24 1993-09-07 Engelhard Corporation Hydrogenation catalyst, process for preparing and process for using said catalyst
WO2009063176A1 (en) * 2007-11-14 2009-05-22 Bp P.L.C. Process for the production of alcohol from a carbonaceous feedstock

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB694962A (en) * 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
CN1747918A (zh) * 2002-12-21 2006-03-15 赫多特普索化工设备公司 合成甲醇的方法
CN101218197A (zh) * 2005-07-06 2008-07-09 英国石油化学品有限公司 用于烃类转化到c2-氧合物的工艺
WO2007066036A2 (fr) * 2005-12-05 2007-06-14 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede de synthese de methanol ou d'oxo alcools permettant un recyclage du gaz residuaire

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EA201491516A1 (ru) 2015-01-30
EA024691B1 (ru) 2016-10-31
CN104125941B (zh) 2016-08-17
WO2013120548A1 (en) 2013-08-22
AU2012370043B2 (en) 2017-06-15
US20150045460A1 (en) 2015-02-12
MX2014009401A (es) 2014-11-10
AR089946A1 (es) 2014-10-01
EA024691B9 (ru) 2018-02-28
AU2012370043A1 (en) 2014-08-28
EP2814799A1 (en) 2014-12-24
KR20140129008A (ko) 2014-11-06
US9181155B2 (en) 2015-11-10
MX355458B (es) 2018-04-19

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