WO2011128367A1 - Catalyseur pour l'hydrogénation de solutions aqueuses d'alcools polyvalents - Google Patents

Catalyseur pour l'hydrogénation de solutions aqueuses d'alcools polyvalents Download PDF

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Publication number
WO2011128367A1
WO2011128367A1 PCT/EP2011/055796 EP2011055796W WO2011128367A1 WO 2011128367 A1 WO2011128367 A1 WO 2011128367A1 EP 2011055796 W EP2011055796 W EP 2011055796W WO 2011128367 A1 WO2011128367 A1 WO 2011128367A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
copper
gallium
glycerol
zinc
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.)
Ceased
Application number
PCT/EP2011/055796
Other languages
German (de)
English (en)
Inventor
Peter Claus
Arne Bienholz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Technische Universitaet Darmstadt
Original Assignee
Technische Universitaet Darmstadt
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Technische Universitaet Darmstadt filed Critical Technische Universitaet Darmstadt
Publication of WO2011128367A1 publication Critical patent/WO2011128367A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
    • 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
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the present invention relates to a water-stable catalyst for the hydrogenation of polyhydric alcohols.
  • DE 4442124 describes the catalytic hydrogenation of glycerol having a water content of up to 20% by weight to give propylene glycol in a yield of 92%, as by-products n-propanol and lower alcohols are obtained.
  • Complete conversion of glycerol is achieved by using a mixed catalyst of the metals cobalt, copper, manganese and molybdenum.
  • the reaction conditions are in a pressure and temperature range of 100 to 700 bar and 180 to 270 ° C.
  • Preferred hydrogenation conditions are 200 to 325 bar and 200 to 250 ° C.
  • the disadvantage is that at lower pressures, the reaction of glycerol is incomplete, and increasingly form lower alcohols at higher pressures.
  • WO 2007/010299 discloses a process for the hydrogenation of glycerol at 160 ° C to 260 ° C and 1 0 to 30 bar in the presence of a catalyst.
  • This catalyst contains manganese, copper and aluminum.
  • US 4642394 describes a process for the catalytic hydrogenation of glycerol with a catalyst consisting of tungsten and a group Vl II metal.
  • the reaction conditions are in the range of 100 psi to 15,000 psi and 75 to 250 ° C.
  • Preferred process conditions are 100 to 200 ° C and 200 to 10,000 psi.
  • the reaction is carried out under basic conditions by the use of amines or amides as solvent. It is also possible to use metal hydroxides, metal carbonates or quaternary ammonium salts.
  • the solvent is added at a concentration of 5 to 100 ml per gram of glycerol. Carbon monoxide is used to stabilize and activate the catalyst.
  • Catalysts based on copper-zinc have the advantage that they can be produced inexpensively.
  • the big disadvantage of the copper-zinc catalysts is that with water-containing educts the catalysts are deactivated very quickly. This makes it necessary to dry the starting materials beforehand, which means an additional process stage. Furthermore, it also comes by the resulting reaction water to a deactivation of the catalyst. This can be prevented by continuous separation of the water of reaction, which means a lot of effort.
  • the object of the present invention is to overcome the disadvantages of the prior art. [Solution of the task]
  • This object is achieved by the use of a catalyst sators, which is not significantly deactivated by water.
  • the invention is not limited to the use of gallium.
  • indium, thallium or lead should also be used in the specified ranges.
  • the listed elements can be used individually or in combinations.
  • the gallium or combination of elements was used in conjunction with a copper catalyst.
  • the copper catalyst is designed as copper or as a copper alloy.
  • the copper alloy is preferably made of a copper-zinc alloy.
  • the ratio of copper to gallium ranges from 3: 1 to 1: 2.
  • the catalyst is made from the metals, metal oxides or metal salts.
  • metal salts include, but are not limited to, nitrates, nitrides, sulfides, sulfates, sulfites, phosphates, phosphites, halogens (e.g., fluoride, chloride, bromide, iodide), perchlorates, or organic anions such as e.g. Acetate or acetylacetonate.
  • the catalyst comprises gallium in a range of 1 to 50%.
  • Copper is added in a range of 10 ... 80% and zinc in a range of 0 ... 70% to the catalyst.
  • the catalyst is preferably used in a prereduced form.
  • the polyhydric alcohol solution preferably comprises a glycerol solution.
  • the glycerol is mainly hydrogenated to 1, 2-propanediol and water. As a further by-product occurs 1, 2-ethanediol.
  • the aqueous polyhydric alcohol solution consists of 50 to 90% alcohol.
  • the use of the catalyst eliminates the drying of the alcohol. Thus, no disadvantageous drying to 95 or 99% alcohol is necessary. Furthermore, the resulting water of reaction no longer leads to a significant deactivation of the catalyst. Accordingly, a separation of the resulting water of reaction is no longer necessary.
  • the gallium-containing, water-stable catalyst is particularly suitable for reprocessing (recycling). While copper-zinc catalysts have a significant loss of activity after recycling (up to 30%), gallium-containing catalysts showed no significant loss of activity (0 to 5%). These catalysts are particularly suitable for continuous processes.
  • a catalyst containing 29% copper, 58% zinc and 13% gallium is obtained.
  • the preparation of the Cu-Zn catalyst without gallium is analogous to the preparation of the Cu-Zn-Ga catalyst.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un catalyseur pour l'hydrogénation de glycérol en 1,2-propanediol. L'utilisation de gallium dans le catalyseur permet d'obtenir une résistance à l'eau. Des solutions aqueuses de glycérol peuvent alors être hydrogénées en 1,2-propanediol sans séchage préalable.
PCT/EP2011/055796 2010-04-14 2011-04-13 Catalyseur pour l'hydrogénation de solutions aqueuses d'alcools polyvalents Ceased WO2011128367A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201010015006 DE102010015006A1 (de) 2010-04-14 2010-04-14 Katalysator zur Hydrierung von wässrigen mehrwertigen Alkohollösungen
DE102010015006.1 2010-04-14

Publications (1)

Publication Number Publication Date
WO2011128367A1 true WO2011128367A1 (fr) 2011-10-20

Family

ID=44066918

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/055796 Ceased WO2011128367A1 (fr) 2010-04-14 2011-04-13 Catalyseur pour l'hydrogénation de solutions aqueuses d'alcools polyvalents

Country Status (2)

Country Link
DE (1) DE102010015006A1 (fr)
WO (1) WO2011128367A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4642394A (en) 1985-07-16 1987-02-10 Celanese Corporation Production of propanediols
EP0523015A2 (fr) 1991-07-10 1993-01-13 NOVAMONT S.p.A. Méthode d'hydrogénation du glycérol
DE4302464A1 (de) 1993-01-29 1994-08-04 Henkel Kgaa Herstellung von 1,2-Propandiol aus Glycerin
DE4442124A1 (de) 1994-11-26 1996-05-30 Basf Ag Verfahren zur Herstellung von Propandiol-1,2
WO2007010299A1 (fr) 2005-07-15 2007-01-25 Davy Process Technology Ltd Procede
CN101085719A (zh) * 2007-06-29 2007-12-12 上海华谊丙烯酸有限公司 一种甘油加氢制备1,2－丙二醇的方法
DE102007003188B3 (de) 2007-01-22 2008-06-05 Clariant International Ltd. Verfahren zur Herstellung von 1,2-Propandiol durch Hydrogenolyse von Glycerin

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4642394A (en) 1985-07-16 1987-02-10 Celanese Corporation Production of propanediols
EP0523015A2 (fr) 1991-07-10 1993-01-13 NOVAMONT S.p.A. Méthode d'hydrogénation du glycérol
DE4302464A1 (de) 1993-01-29 1994-08-04 Henkel Kgaa Herstellung von 1,2-Propandiol aus Glycerin
DE4442124A1 (de) 1994-11-26 1996-05-30 Basf Ag Verfahren zur Herstellung von Propandiol-1,2
WO2007010299A1 (fr) 2005-07-15 2007-01-25 Davy Process Technology Ltd Procede
DE102007003188B3 (de) 2007-01-22 2008-06-05 Clariant International Ltd. Verfahren zur Herstellung von 1,2-Propandiol durch Hydrogenolyse von Glycerin
CN101085719A (zh) * 2007-06-29 2007-12-12 上海华谊丙烯酸有限公司 一种甘油加氢制备1,2－丙二醇的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MARIA LACHOWSKA, JERZY SKRZYPEK: "Ga, Mn and Mg promoted copper/zinc/zirconia - catalysts for hydrogenation of carbon dioxide to methanol", STUDIES IN SURFACE SCIENCE AND CATALYSIS, vol. 153, 2004 - 2004, pages 173 - 176, XP001525586, DOI: 10.1016/S0167-2991(04)80241-6 *

Also Published As

Publication number Publication date
DE102010015006A1 (de) 2011-11-24

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