EP1651586A1 - Procede d'hydrodecomposition de formiates d'ammonium dans des melanges reactionnels contenant du polyol - Google Patents

Procede d'hydrodecomposition de formiates d'ammonium dans des melanges reactionnels contenant du polyol

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Publication number
EP1651586A1
EP1651586A1 EP04740714A EP04740714A EP1651586A1 EP 1651586 A1 EP1651586 A1 EP 1651586A1 EP 04740714 A EP04740714 A EP 04740714A EP 04740714 A EP04740714 A EP 04740714A EP 1651586 A1 EP1651586 A1 EP 1651586A1
Authority
EP
European Patent Office
Prior art keywords
titanium dioxide
catalyst
weight
formate
hydrogenation
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.)
Withdrawn
Application number
EP04740714A
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German (de)
English (en)
Inventor
Michael Koch
Alexander Wartini
Steffen Maas
Tilman Sirch
Matthias Dernbach
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1651586A1 publication Critical patent/EP1651586A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/392—Metal surface area
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J37/06—Washing
    • 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
    • B01J37/12—Oxidising
    • B01J37/14—Oxidising with gases containing free oxygen
    • 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
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen

Definitions

  • the invention relates to the field of industrial organic chemistry. More specifically, the present invention relates to a process for the effective hydrogenative decomposition of trialkylammonium formate contained in methylolalkanes, which is formed from the trialkylamine used as catalyst in the preparation of methylolalkanal and the formic acid formed as a by-product.
  • the polyols mentioned can be prepared by various processes.
  • One method is the so-called Cannizzaro process, which is still subdivided into the inorganic and organic Cannizzaro processes.
  • an excess of formaldehyde is reacted with the corresponding alkanal in the presence of stoichiometric amounts of an inorganic base such as NaOH or Ca (OH) 2 .
  • the methylolalkanal formed in the first stage reacts in the second stage with the excess formaldehyde in a disproportionation reaction to give the corresponding polyol and the formate of the corresponding base, that is to say about sodium or calcium formate.
  • a teritary amine generally a trialkylamine
  • the reaction proceeds as set out above, forming one equivalent of ammonium formate of the corresponding amine.
  • This can be worked up further by appropriate measures, whereby at least the amine can be recovered and returned to the reaction.
  • the crude polyol obtained can be worked up into pure polyol in various ways.
  • a further development is the hydrogenation process, in which a corresponding alkanal and formaldehyde are reacted with one another, not in the presence of at least stoichiometric amounts, but rather in the catalytic amounts of a tertiary amine, generally about 5 to 10 mol%.
  • the reaction remains at the 2,2-dimethylolalkanal stage, which is subsequently converted into trimethylolalkane by hydrogenation.
  • the description of the effective method can be found in WO 98/28253 by the applicant.
  • trialkylammonium formate is nevertheless formed as a product of a crossed Cannizzaro reaction which occurs to a very small extent as a side reaction.
  • Trialkylammonium formates react under certain conditions, for example the dewatering or heating of trimethylolalkane solutions containing them, to give trialkylamine and trimethylolpropane formates. These reduce the yield of trimethylolalkane and can only be split with difficulty without an undesirable degradation reaction. There was therefore interest in the separation of the trialkylammonium formates.
  • DE 19848 569 discloses a process for the decomposition of formates of tertiary amines which are contained as by-products in trimethylolalkane solutions prepared by the organic Cannizzaro process. These formates, preferably in the presence of modified noble metal catalysts and elevated pressure, are decomposed by heating in hydrogen and carbon dioxide and / or water and carbon monoxide and the tertiary amine. The formate sales in this process are unsatisfactory, and the formation of further by-products is observed.
  • DE 101 52 525 discloses the decomposition of trialkylammonium formates over heterogeneous catalysts which contain at least one metal from the 8th to 12th group of the periodic table, with supported copper-nickel and / or cobalt-containing catalysts being particularly preferred.
  • the above-mentioned process is also only suitable to a limited extent for the effective workup of a trimethylolalkane mixture which is contained by the so-called hydrogenation process and in which only catalytic amounts of trialkylamine are used and which therefore also only contains small amounts of trialkylammonium formate. It is therefore the object of the present invention to provide a process which is suitable both for working up mixtures obtained by the hydrogenation process and by the organic Cannizzaro process. This process should also make it possible to decompose trialkylammonium formates with higher conversions than the processes known from the prior art can. Furthermore, this decomposition should lead to decomposition products which are easy to handle on an industrial scale and which do not trigger any side reactions in order to provide a more economical process for the preparation of high-purity trimethylolpropane.
  • This object is achieved by a process for removing trialkylammonium formate from methylolalkanes which has been obtained by condensation of formaldehyde with a higher aldehyde, this process being characterized in that trialkylammonium formate at elevated temperature on a ruthenium-containing catalyst in the presence of hydrogen-containing catalyst Gas is decomposed.
  • Methylolalkanes suitable for purification by the process according to the invention are, for example, neopentyl glycol, pentaerythritol, trimethylolpropane, trimethylolbutane, trimethylolethane, 2-ethyl-1, 3-propanediol, 2-methyl-1, 3-propanediol, glycerol, dimethylolpropane, dipentaerythritol and 1,1-, 1,2-, 1,3- and 1,4-cyclohexanedimethanol.
  • trimethylolalkanes which are prepared by the organic Cannizzarro or the hydrogenation process are preferably purified from trialkylammonium formates under hydrogenation conditions.
  • Trimethylolalkanes prepared by the hydrogenation process particularly preferably trimethylolpropane, hereinafter abbreviated to TMP, are preferably purified.
  • trialkylammonium formate-containing raw TMP by the Cannizzaro process is disclosed, for example, in DE 19848 569.
  • the TMP is obtained by the hydrogenation process by condensation of n-butyraldehyde with formaldehyde in the presence of catalytic amounts of a tertiary amine and subsequent catalytic hydrogenation of the resulting dimethylolbutanal mixture.
  • This raw TMP contains no alkali or alkaline earth formates or other impurities that arise from the inorganic Cannizzaro process.
  • the raw TMP also contains only small amounts, approx. 5 to 10 mol% of trialkylammonium formates or free trialkylamine, unlike in the organic Cannizzaro process.
  • the crude TMP originating from the hydrogenation and to be subjected to the purification process according to the invention also contains methanol, trialkylamine, trialkylammonium formate, longer-chain linear and branched alcohols and diols, for example methylbutanol or ethylpropane diol, addition products of formaldehyde and methanol with trimethylalpropylolethane, acetaldehole-dimethylolpropane, dehyd-TMP acetal and the so-called Di-TMP.
  • the present invention furthermore relates to a catalyst comprising ruthenium supported on titanium dioxide moldings, the titanium dioxide moldings being difficult to dissolve in the titanium dioxide by treating commercially available titanium dioxide before or after molding with 0.1 to 30% by weight of an acid is obtained, which is used in the method according to the invention.
  • Ruthenium can be used both in the form of the pure metal and as its compound, for example oxide or sulfide.
  • the catalytically active ruthenium is applied by methods known per se, preferably onto prefabricated TiO 2 as the carrier material.
  • a titanium dioxide carrier which is preferably suitable for use in the ruthenium-containing catalyst can be prepared according to DE 197 38464 by treating commercially available titanium dioxide before or after molding with 0.1 to 30% by weight of an acid, based on titanium dioxide, in which the titanium dioxide is sparingly soluble. Titanium dioxide is preferably used in the anatase modification. Examples of suitable acids are formic acid, phosphoric acid, nitric acid, acetic acid or stearic acid.
  • the active component ruthenium can be applied in the form of a ruthenium salt solution to the titanium dioxide support thus obtained in one or more impregnation stages.
  • the impregnated carrier is then dried and optionally calcined.
  • volatile ruthenium compounds such as, for example, ruthenium acetylacetonate or ruthenium carbonyl, can be converted into the gas phase and applied to the support in a manner known per se (chemical vapor deposition).
  • the supported catalysts obtained in this way can be present in all known forms of assembly. Examples are strands, tablets or granules.
  • the ruthenium catalyst precursors are reduced by treatment with hydrogen-containing gas, preferably at temperatures above 100 ° C. Before they are used in the process according to the invention, the catalysts are preferably passivated at temperatures from 0 to 50 ° C., preferably at room temperature, with oxygen-containing gas mixtures, preferably with air-nitrogen mixtures. It is also possible to install the catalyst in oxidic form in the hydrogenation reactor and to reduce it under reaction conditions.
  • the catalyst according to the invention has a ruthenium content of 0.1 to 10% by weight, preferably 2 to 6, based on the total weight of the catalyst composed of catalytically active metal and support.
  • the catalyst according to the invention can have a sulfur content of 0.01 to 1% by weight, based on the total weight of the catalyst, the sulfur being determined coulometrically.
  • the ruthenium surface is from 1 to 20 m 2 / g, preferably from 5 to 15 and the BET surface area (determined according to DIN 66 131) from 5 to 500 m 2 / g, preferably from 50 to 200 m z / g.
  • the catalysts of the invention have a pore volume of 0.1 to 1 ml / g. Furthermore, the catalysts are characterized by a cutting hardness of 1 to 100 N.
  • the ruthenium-containing supported catalyst on titanium dioxide used according to the invention for the decomposition of the trialkylammonium formate contained in the crude TMP is also suitable for the hydrogenation of the precursor of the TMP (2,2-dimethylolbutanal).
  • the use of the same catalyst for the hydrogenation of the dimethylol butanal and for the decomposition of the trialkylammonium formate is particularly economical since the In this case, the trialkylammonium formate can be decomposed in the hydrogenation reactor of the hydrogenation process according to WO 98/28253 and no additional reactor is required.
  • the decomposition of the trialkylammonium formates by the process according to the invention can also be carried out in a separate reactor.
  • the decomposition of the trialkylammonium formates is generally carried out at a temperature of 100 to 250 ° C., preferably 120 to 180 ° C.
  • the pressures used are generally above 1 10 6 Pa, preferably 210 6 to 1510 6 Pa.
  • the process according to the invention can be carried out either continuously or batchwise, with continuous process execution being preferred.
  • the amount of the crude trimethylol alkane from the hydrogenation process or the organic Cannizzaro process is preferably about 0.05 to about 3 kg per liter of catalyst per hour, more preferably about 0.1 to about 1 kg per liter Catalyst per hour.
  • the process according to the invention is carried out under hydrogenation conditions, i.e. with an added hydrogenation gas from an external source.
  • reformer exhaust gases can be used. Pure hydrogen is preferably used.
  • An apparatus consisting of two heatable stirred tanks connected by overflow pipes with a total capacity of 72 l was mixed with fresh, aqueous formaldehyde solution (4300 g / l in the form of the 40% aqueous solution and n-butyraldehyde (1800 g / h)) fresh trimethylamine as a catalyst (130 g / h) in the form of the 45% strength aqueous solution, the reactors being heated to 40 ° C.
  • the discharge was passed directly into the upper part of a falling film evaporator with a column attached (11 bar heating steam) and there at normal pressure by distillation into a low-boiling overhead product, essentially comprising n-butyraldehyde, ethyl acetaldehyde, formaldehyde, water and trimethylamine, and a high-boiling product Bottom product separated.
  • a low-boiling overhead product essentially comprising n-butyraldehyde, ethyl acetaldehyde, formaldehyde, water and trimethylamine
  • the top product was continuously condensed and returned to the reactors described above.
  • the high-boiling bottom product from the evaporator (approx. 33.5 kg / h) was continuously mixed with fresh trimethylamine catalyst (50 g / h, in the form of the 45% strength aqueous solution) and into a heatable tubular reactor provided with fillers with an empty volume led by 12 I.
  • the reactor was tempered to 40 ° C.
  • the discharge from the post-reactor was continuously fed into the upper part of a further distillation device, the formaldehyde removal (11 bar heating steam), where it was separated by distillation into a low-boiling top product, essentially comprising ethyl acrolein, formaldehyde, water and trimethylamine, and a high-boiling bottom product.
  • the low-boiling top product (27 kg / h) was continuously condensed and returned to the first stirred tank, whereas the high-boiling bottom product was collected.
  • the bottom product thus obtained essentially contained dimethylol butyraldehyde, formaldehyde and traces of monomethylol butyraldehyde. It was then subjected to continuous hydrogenation.
  • the reaction solution was hydrogenated at 90 bar and 115 ° C. in a main reactor in a cycle / trickle mode and a downstream post-reactor in a cycle mode.
  • the catalyst was prepared in accordance with J of DE 198 09418. It contained 40% CuO, 20% Cu and 40% TiO 2 .
  • the apparatus used consisted of a 10 m long heated main reactor (inside diameter: 27 mm) and a 5.3 m long heated post reactor (inside diameter: 25 mm).
  • the circulation throughput was 25 l / h of liquid, the reactor feed was set to 4 kg / h. Accordingly, 4 kg / h of hydrogenation discharge were obtained.
  • the hydrogenation had the following composition 22.6% by weight of TMP, 1.93% by weight of dimethylolbutanal, 1.4% by weight of methanol, 1.1% by weight of methylbutanol, 0.7% by weight.
  • the porosity of the catalysts was determined using the HG intrusion method in accordance with DIN 66 133.
  • the BET surface area of the catalysts was determined in accordance with DIN 66 131.
  • the formate content is determined by means of ion chromatography in accordance with DEV ISO 10304-2.
  • Example 1 Catalyst production Ru / TiO 2
  • the finished catalyst strands had an Ru content of 4.2% by weight, a BET surface area of 103 m 2 / g, a pore volume of 0.26 ml / g, a ruthenium surface area of 12 m / g and a cutting hardness of 21 , 2 N.
  • Examples 1 to 4
  • the TMP used has the composition 22.6% by weight of TMP, 1.93% by weight of dimethylol butanal, 1.4% by weight of methanol, 1.1% by weight of methyl butanol, 0.7 % By weight of ethyl propanediol, 1.2% by weight of adducts of TMP with formaldehyde and methanol, ⁇ 0.1% by weight of TMP formate, 1.2% by weight of TMP-dimethylbutanal acetals, 2.9% by weight % High boilers, 0.57% by weight trimethylammonium formate and 66.2% by weight water. 180 ml of this crude solution were treated with hydrogen at 180 ° C.

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

Abstract

La présente invention concerne des procédés pour extraire du formiate de trialkylammonium de méthylolalcanes obtenus par condensation de formaldéhyde avec un aldéhyde supérieur. Cette invention est caractérisée en ce que le formiate de trialkylammonium est décomposé à température élevée, sur un catalyseur contenant du ruthénium supporté sur du dioxyde de titane, en présence de gaz contenant de l'hydrogène. Ce procédé permet de séparer le formiate de trialkylammonium de méthylolalcanes produits selon le procédé un Cannizzaro organique et selon un procédé d'hydrogénation.
EP04740714A 2003-07-29 2004-07-07 Procede d'hydrodecomposition de formiates d'ammonium dans des melanges reactionnels contenant du polyol Withdrawn EP1651586A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10334489A DE10334489A1 (de) 2003-07-29 2003-07-29 Verfahren zur hydrierenden Zersetzung von Ammoniumformiaten in polyolhaltigen Reaktionsgemischen
PCT/EP2004/007396 WO2005019145A1 (fr) 2003-07-29 2004-07-07 Procede d'hydrodecomposition de formiates d'ammonium dans des melanges reactionnels contenant du polyol

Publications (1)

Publication Number Publication Date
EP1651586A1 true EP1651586A1 (fr) 2006-05-03

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP04740714A Withdrawn EP1651586A1 (fr) 2003-07-29 2004-07-07 Procede d'hydrodecomposition de formiates d'ammonium dans des melanges reactionnels contenant du polyol

Country Status (8)

Country Link
EP (1) EP1651586A1 (fr)
JP (1) JP2007500138A (fr)
KR (1) KR20060054364A (fr)
CN (1) CN100383097C (fr)
BR (1) BRPI0412987A (fr)
DE (1) DE10334489A1 (fr)
MX (1) MXPA06000481A (fr)
WO (1) WO2005019145A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2010115798A2 (fr) * 2009-04-07 2010-10-14 Basf Se Procédé de production de 1,6-hexanediol et de caprolactone

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DE1952738A1 (de) * 1968-12-17 1970-07-09 Leuna Werke Veb Verfahren zur Herstellung von Trimethylolpropan
DE3217751A1 (de) * 1982-05-12 1983-11-17 Degussa Ag, 6000 Frankfurt Presslinge aus pyrogen hergestelltem titandioxid, verfahren zu ihrer herstellung sowie ihre verwendung
US4647592A (en) * 1984-01-05 1987-03-03 Exxon Research & Engineering Company Start-up with ruthenium catalysts
DE3715035A1 (de) * 1987-05-06 1988-11-17 Basf Ag Verfahren zur gewinnung von trialkylaminen und methylformiat bei der herstellung von trimethylolalkanen
US5484757A (en) * 1994-06-02 1996-01-16 Norton Chemical Process Products Corp. Titania-based catalyst carriers
JPH11504255A (ja) * 1995-04-17 1999-04-20 エンゲルハード・コーポレーシヨン 成形組成物
DE19530528C2 (de) * 1995-08-19 1998-12-10 Dornier Gmbh Verwendung eines Ru/TiO¶2¶-Metall-Trägerkatalysators für die Methanisierung von Kohlendioxid
KR20010023544A (ko) * 1997-09-03 2001-03-26 스타르크, 카르크 촉매로 사용될 수 있는 성형 재료
JPH11124348A (ja) * 1997-10-22 1999-05-11 Koei Chem Co Ltd トリメチロールアルカンを製造する方法
US6235797B1 (en) * 1999-09-03 2001-05-22 Battelle Memorial Institute Ruthenium on rutile catalyst, catalytic system, and method for aqueous phase hydrogenations
DE10152525A1 (de) * 2001-10-24 2003-05-08 Basf Ag Verfahren zur Zersetzung von Ammoniumformiaten in polyolhaltigen Reaktionsgemischen

Non-Patent Citations (1)

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Title
See references of WO2005019145A1 *

Also Published As

Publication number Publication date
BRPI0412987A (pt) 2006-10-03
DE10334489A1 (de) 2005-02-24
JP2007500138A (ja) 2007-01-11
CN1829674A (zh) 2006-09-06
WO2005019145A1 (fr) 2005-03-03
CN100383097C (zh) 2008-04-23
KR20060054364A (ko) 2006-05-22
MXPA06000481A (es) 2006-04-05

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