WO1996022832A1 - Catalyseur intermetallique ruthenium-etain utile dans la synthese d'aldehydes - Google Patents
Catalyseur intermetallique ruthenium-etain utile dans la synthese d'aldehydes Download PDFInfo
- Publication number
- WO1996022832A1 WO1996022832A1 PCT/FR1996/000101 FR9600101W WO9622832A1 WO 1996022832 A1 WO1996022832 A1 WO 1996022832A1 FR 9600101 W FR9600101 W FR 9600101W WO 9622832 A1 WO9622832 A1 WO 9622832A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- support
- composition according
- equal
- advantageously
- ruthenium
- Prior art date
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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
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/41—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenolysis or reduction of carboxylic groups or functional derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
Definitions
- the present invention relates to a process for preparing aldehydes and their derivatives, by reduction in the vapor phase in the presence of hydrogen, acids, esters or carboxylic anhydrides.
- the present process relates more particularly as substrate the carboxylic compounds carrying halogen and in particular fluorine capable of being hydrogenolysed during the reduction. It is known in the prior art to prepare saturated aromatic or aliphatic aldehydes by reduction of the corresponding acids or esters by means of a catalyst chosen from cerium, zirconium, uranium, praseodymium and yttrium oxides, at a temperature between 350 and 450 ° C (US 4,328,373).
- Another object of the present invention is to provide a composition of the above type which avoids parasitic reactions or reduces their relative importance.
- a composition useful as a reduction catalyst which comprises a support which comprises as constituent material at least one oxide chosen from oxides which are inert or capable of being rendered inert. with respect to the reaction mixture and a metallic phase covering at least in part said support comprising at least in part a ruthenium-tin intermetallic at least partially in the form of the defined compound of RusSn.
- the phase containing ruthenium and tin has an Sn / Ru atomic ratio at least equal to 2/3, advantageously 3/2, preferably 7/3. Furthermore, it is preferable that the Sn / Ru atomic ratio is at most equal to 3, advantageously 5/2.
- said phase covering at least partially said support contains at least 50%, advantageously 80%, preferably at least 90% of said intermetallic phase.
- at least 90%, advantageously at least 95%, preferably 98% of the ruthenium present on the support is in the form of said phase covering said support.
- the invention is more particularly suitable for the preparation of aldehydes of general formula:
- R represents a hydrogen atom or an optionally substituted hydrocarbon radical comprising from 1 to 40 carbon atoms which may be a saturated or unsaturated, linear or branched acyclic aliphatic radical; a saturated, unsaturated or aromatic, monocyclic or polycyclic carbocyclic or heterocyclic radical, by reduction of esters, anhydrides or acids of formula:
- R ' represents:
- the carboxylic acids or derivatives preferably used correspond to formula (II) in which R represents an optionally substituted hydrocarbon radical containing from 1 to 20 carbon atoms.
- the invention is entirely suitable for the preparation of aldehydes from halogenated aliphatic carboxylic acids such as fluorine.
- the invention is very well suited to the synthesis of aldehydes from aromatic carboxylic acids and halobenzoic acids, preferably fluorobenzoic acids.
- aromatic compound means the classic concept of aromaticity as defined in the literature, in particular by Jerry
- benzoic acid is understood to mean any benzene compound carrying at least one COOH function. As indicated above, it is also possible to use the carboxylic acid as defined above in the form of its ester.
- R ′ preferably represents an aliphatic radical containing from 1 to 10 carbon atoms, optionally substituted. More preferably, R 'represents a linear or branched alkyl radical having from 1 to 6 carbon atoms.
- radicals R ′ mention may be made of methyl, ethyl or hexyl radicals.
- the invention is particularly well suited to the synthesis of aldehydes having in their formulas one or more halogens, especially when these halogens are at least partly fluorines.
- aldehydes obtained from perhalogenocarboxylic acids or those which are equivalent to them in terms of reactivity.
- the invention is particularly well suited to the synthesis of aldehydes where the, or rather the two, vicinal carbons are perfluorinated.
- a carboxylic acid in the form of its anhydrides and esters.
- carboxylic anhydrides mention may be made more particularly of homo-anhydrides whether they are internal (cyclic anhydrides) or not and heteroanhydrides (or mixed anhydrides).
- Preferred compounds are bicyclic and consist of a benzene ring
- the process of the invention is carried out in the gas phase.
- the reaction is carried out at a temperature between 100 ° C and 500 ° C, and even more preferably between 200 and 400 ° C. It is understood that the temperature is adapted by a person skilled in the art as a function of the starting acid, and of the desired reaction speed.
- the phase containing ruthenium and tin has an atomic ratio Sn / Ru at least equal to 2/3, advantageously equal to 3/2, preferably equal to 7 / 3. Furthermore, it is preferable that the Sn / Ru atomic ratio is at most equal to 3, advantageously 5/2.
- the treatment should be longer as the temperatures are lower. At a temperature of 400 ° C a day is a minimum, while this minimum is only about 5 hours at 450 ° C. At first it seems that ruthenium catalyzes the reduction of tin and that, under these conditions, the excess tin is at least partially eliminated and that the intermetallic phase on the support approaches the composition of RusSn ⁇ . The longer this stage lasts, the closer we get to the optimal composition of the catalyst, provided that we have started with an excess of tin.
- a practical way of practicing the present invention is to introduce a desired amount of catalyst into a reactor. The reactor temperature is then raised under a stream of hydrogen to a determined value, enabling the catalyst to be activated, then brought back to the reaction temperature. The acid is then injected at the desired rate and the aldehyde formed is recovered. Preferably, the acid is injected directly in gaseous form after having been vaporized by heating.
- inert solvent for the reaction.
- inert solvents mention may be made of aliphatic (for example hexane), alicyclic (for example cyclohexane), aromatic (for example toluene), or ethers (for example dimethoxyethane) hydrocarbons.
- the acid thus injected is vaporized.
- the hydrogen can be injected at atmospheric pressure or under a slight pressure compatible with the vapor phase (partial pressure of a few bars, for example from 0.5 to 10 bar, the bar is here deemed to represent 10 5 Pa).
- the hydrogen can also be diluted in an inert gas under operating conditions, such as nitrogen or helium.
- the hydrogen is injected at a flow rate between 0.1 and 10 liters per hour, and the acid at a liquid flow rate at most equal to 10 ml / h, and preferably between 0 , 5 and 5 ml / h.
- the aldehyde is recovered by any suitable means such as distillation or crystallization. In certain cases, in particular in the case of fluorine, the aldehyde can be obtained in a hydrated form.
- the content of foreign element (s) such as boron is generally less than 1% and preferably less than 0.1 mol%.
- the two metals are dissolved in water in the form of salts, optionally in the presence of the support, and the impregnation is allowed to take place over a period of approximately 15 hours. This is then dried (for example under vacuum) before use.
- One of its preparation methods consists, for example, of introducing a support into a solution which is prepared by dissolving at least one appropriate compound from the elements chosen; the active elements are deposited on the support by distilling off the solvent, preferably water, which can be removed by evaporation under reduced pressure, preferably chosen between 5 and 20 mm of mercury. The contact mass thus obtained is subjected to reduction by means of a stream of hydrogen.
- the deposition of the compound or compounds bringing the metallic elements to the support are carried out by means of compounds previously precipitated in a manner known per se and by subjecting the contact mass thus obtained to a reduction by means of 'hydrogen.
- the deposition on the support of several metal elements can of course be carried out successively but preferably simultaneously.
- the deposition of the precursors of the intermetallic phase can be done by repeating one of the processes described above. This reiteration can be carried out either for iterative impregnations or for iterative impregnation-reduction cycles.
- the nature of the compounds providing the metallic elements used for the preparation of the catalysts of the invention is not critical provided that there is no risk of modification of the tin / ruthenium ratio before the vast majority (at least 3/4, advantageously 9/10, preferably 95%) of the ruthenium is not engaged in a metallic phase with the tin. Metals themselves such as ruthenium and tin can be used.
- ruthenium compounds of ruthenium chloride III, ruthenium chloride IV, pentafluoride ruthenium, ruthenium oxide II, ruthenium oxide IV, ammonia ruthenium oxychloride Ru2 (OH) 2Cl4, 7NH3, 5H2O, ruthenium acetate and, as tin compounds, the oxides , chlorides, nitrates, carboxylates, tin alcoholates or organometallic compounds in which the tin is linked to a hydrogen atom and / or alkyl radicals preferably having from 1 to 4 carbon atoms.
- the preferred salts are as follows: ruthenium compounds such as ruthenium III chloride, tin compounds such as tin chloride II, tin chloride IV, tin acetate II, l octoate II, tin ethylhexanoate.
- the aldehydes in the form of their derivatives such as their acetals, their hemiacetals or their bisulfitic combinations
- reaction of the aldehyde and of the reagent [alcohol in the case of (hemi) acait] which is introduced either jointly with the acid, when the reagent is volatile; either at the end of the reaction.
- reagent such as their acetals, their hemiacetals or their bisulfitic combinations
- the support must be chosen so as to maximize the resistance to industrial conditions, and in particular the resistance to mechanical or quasi-mechanical abrasion; especially resistance to attrition.
- the support must be chosen so as to avoid significant pressure drops, while allowing good contact between the gases and the catalyst.
- the support must be chosen from inert oxides (that is to say having good chemical resistance with respect to) or capable of being rendered inert with respect to the reaction mixture.
- inert oxides that is to say having good chemical resistance with respect to
- the problem is particularly acute in the case where one chooses as substrate carboxylic acids having halogen atoms and in particular fluorine.
- the support it is preferable for the support to show significant resistance to humid hydrohalic acids and in particular with respect to humid gaseous hydrofluoric acid (reduction to an aldehyde of an acid gives water).
- Said support is advantageously a support capable of being made inert by the action of gaseous hydrofluoric acid without losing its external geometry and its mechanical strength.
- charcoal-type supports are particularly to be avoided since they promote parasitic reactions and give rise to intense coking of the substrates.
- oxides such as aluminum or zirconium oxides.
- Mixed oxides are also suitable, more particularly those containing at least 1/4 advantageously 1/3, preferably 2/5 by mass of aluminum expressed as Al2O3.
- Said support advantageously has a silicon content which, expressed as SiO2, is at most equal to 2/3 of the total weight. Advantageously at most 1/4.
- the ceramics obtained by firing, at approximately 1000 ° C. at least, clays containing as main elements the aluminum and silicon oxides have been tested and have given particularly interesting results.
- silico-aluminous clay which gives good results, mention may be made of Provins clays, in particular those sold by Denain Anzin Minéraux under the trade name of chamotte 40/42.
- Said support advantageously has a particle size such that its dso is at least equal to 0.1 millimeter, advantageously to 0.5 millimeter, preferably to one millimeter.
- a good arbitration consists in choosing little porous balls from 1mm to 1cm giving good results.
- a specific surface area of the support which is advantageously small, less than 10 m 2 per gram, preferably at most equal to 1 m 2 per gram.
- the mass ratio between the support and the surface phase is between 1% and
- Another object of the present invention is to provide a process which makes it possible to prepare the composition according to the present invention.
- Another object of the present invention is to provide a process of the above type which makes it possible to reach a covering phase as close as possible to the ruthenium-tin intermetallic of composition Ru3Sn7.
- stanniferous (rutheniferous) species is such that this minimizes volatilization during the reduction step.
- Example 1 Manufacture of a batch of 9 liters of 3.5% Ru / ex-clay catalyst with an Sn / Ru ratio of 2.3
- Tin hydroxide is obtained by neutralization with ammonia of SnC.4, 5H2O. 5 kg of SnC.4, 5H2O are dissolved in 3.1 liters of water.
- this solution is diluted with 8.6 liters of water to reach a tin salt concentration of 1.25 M.
- the precipitation under steady conditions and continuous is carried out in a one liter reactor equipped with agitation, temperature regulation, continuous pH regulation, level regulation and two feed pumps.
- the tin chloride solution is fed at a constant flow rate of 2.5 l / h.
- the supply of the ammonia solution depends on the set pH setpoint and the deviation from this setpoint.
- the precipitation pH chosen is 5. Agitation is adjusted to
- the tin hydroxide gel thus obtained has a variable water content according to the efficiency of the filtration measured by a loss on ignition at 1000 ° C. of between 55 and 70%.
- the water content of the hydroxide gel measured by loss on ignition at 1000 ° C. is 57% in this example.
- Degussa-OX-50 silica are therefore added as thickener, in order to obtain the viscosity suitable for coating.
- a variant consists in mixing the tin hydroxide gel and the Ru salt by long-term mechanical stirring (24 h) without additional addition of water or silica.
- T375 balls 11, 25 kg are placed in a bezel, whose volume, angle of the axis of rotation and speed of rotation are chosen so as to avoid loss of ball by expulsion from the bezel and to get an eye in the rotating bed.
- the active phase precursor prepared previously is then gradually poured into the rotating bezel.
- the coating of the beads with the active phase precursor is perfectly homogeneous.
- the addition of precursor is stopped at the appearance of a shiny, slightly damp appearance on the beads.
- the catalyst thus obtained is put to dry in a vacuum oven of 540 mm Hg at 80 ° C.
- the height of the catalytic bed in the nacelle is limited to 2 cm.
- the drying lasts between 5 hours and 16 hours.
- the catalyst After drying, the catalyst is returned to the bezel to practice the second coating of precursor. The desired percentage of Ru is reached after 6 coatings of active phase precursor.
- the sequence of coatings of active phase precursor and silica for the preparation of catalyst I is summarized in the table in annex I.
- the catalyst is ready for loading into the catalytic reactor, where it will be activated by reduction under hydrogen.
- Example 2 Manufacture of a batch of 9 liters of catalyst 3.1% Ru / Ex-clay ball with an Sn / Ru ratio of 3
- the tin hydroxide gel in this case after filtration has a water content measured by its loss on ignition at 1000 ° C. of 65%.
- the aluminum beads were treated in 2 batches, as described above.
- Example 3 Example of preparation of hydrofluorine CF CH (OH) by selective reduction of the trifluoroacdov ⁇ ue acid CF3COH TFA by hydrogen gas in the presence of catalyst, whose active phase RU3SN7 is deposited on alumina beads.
- reaction crude is trapped in a cooled pot then, after usual treatment, is analyzed by gas chromatography:
- CATALYST II Manufacture of a 9-liter batch of 3.1% Ru / T375 ex-clay catalyst with an Sn / Ru ratio of 3
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP52266796A JP3946763B2 (ja) | 1995-01-23 | 1996-01-22 | アルデヒド及びその誘導体の合成方法 |
HU9602571A HU225172B1 (en) | 1995-01-23 | 1996-01-22 | Reduction catalyst composition, uses thereof and process for producing aldehydes and aldehyde-derivatives |
AU46254/96A AU4625496A (en) | 1995-01-23 | 1996-01-22 | Intermetallic ruthenium-tin catalyst for use in aldehyde synthesis |
AT96901829T ATE191157T1 (de) | 1995-01-23 | 1996-01-22 | Intermetallischer ruthenium-zinn-katalysator zur synthese von aldehyden |
DE69607431T DE69607431T2 (de) | 1995-01-23 | 1996-01-22 | Intermetallischer ruthenium-zinn-katalysator zur synthese von aldehyden |
US08/716,399 US5973210A (en) | 1995-01-23 | 1996-01-22 | Intermetallic ruthenium tin-catalyst for use in aldehyde synthesis |
EP96901829A EP0765192B1 (fr) | 1995-01-23 | 1996-01-22 | Catalyseur intermetallique ruthenium-etain utile dans la synthese d'aldehydes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR95/00699 | 1995-01-23 | ||
FR9500699A FR2729586B1 (fr) | 1995-01-23 | 1995-01-23 | Procede de synthese d'aldehydes et de leurs derives et catalyseur de reduction selective de derives carboxyliques en aldehydes |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996022832A1 true WO1996022832A1 (fr) | 1996-08-01 |
Family
ID=9475380
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1996/000101 WO1996022832A1 (fr) | 1995-01-23 | 1996-01-22 | Catalyseur intermetallique ruthenium-etain utile dans la synthese d'aldehydes |
Country Status (11)
Country | Link |
---|---|
US (1) | US5973210A (fr) |
EP (1) | EP0765192B1 (fr) |
JP (1) | JP3946763B2 (fr) |
CN (1) | CN1119204C (fr) |
AT (1) | ATE191157T1 (fr) |
AU (1) | AU4625496A (fr) |
DE (1) | DE69607431T2 (fr) |
ES (1) | ES2143749T3 (fr) |
FR (1) | FR2729586B1 (fr) |
HU (1) | HU225172B1 (fr) |
WO (1) | WO1996022832A1 (fr) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5985789A (en) * | 1997-03-27 | 1999-11-16 | E. I. Du Pont De Nemours And Company | Ru, Sn/oxide catalyst and process for hydrogenation in acidic aqueous solution |
US6180830B1 (en) | 1995-11-08 | 2001-01-30 | Rhodia Chimie | Method for preparing a bimetallic ruthenium/tin catalyst and a process for the synthesis of aldehydes |
WO2011124578A1 (fr) * | 2010-04-07 | 2011-10-13 | Rhodia Operations | Procede de preparation d'une lactone |
US10737956B1 (en) | 2019-12-12 | 2020-08-11 | Brian Rudy Parisien | Method and system for changing a property of a polar liquid |
US10763021B1 (en) | 2019-10-31 | 2020-09-01 | Brian Rudy Parisien | Method of changing a property of a polar liquid |
US10875794B1 (en) | 2019-10-31 | 2020-12-29 | Brian Rudy Parisien | Method of changing a property of a polar liquid |
US10934186B1 (en) | 2019-12-12 | 2021-03-02 | Brian Rudy Parisien | Method and system for changing a property of a polar liquid |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7030053B2 (en) * | 2002-11-06 | 2006-04-18 | Conocophillips Company | Catalyst composition comprising ruthenium and a treated silica support component and processes therefor and therewith for preparing high molecular weight hydrocarbons such as polymethylene |
US20040127584A1 (en) * | 2002-12-31 | 2004-07-01 | Phillips Petroleum Company | Chemical vapor deposition synthesis of polymerization catalyst composition |
DE102010039734A1 (de) * | 2010-08-25 | 2012-03-01 | Bayer Materialscience Aktiengesellschaft | Katalysator und Verfahren zur Herstellung von Chlor durch Gasphasenoxidation |
US9108895B2 (en) | 2012-10-26 | 2015-08-18 | Eastman Chemical Company | Promoted ruthenium catalyst for the improved hydrogenation of carboxylic acids to the corresponding alcohols |
WO2015163020A1 (fr) * | 2014-04-22 | 2015-10-29 | 株式会社ダイセル | Catalyseur solide pour production d'aldéhyde, et procédé de production d'aldéhyde |
EP3539657A1 (fr) | 2018-03-14 | 2019-09-18 | Basf Se | Catalyseurs améliorés comprenant des composés intermétalliques à base d'argent |
CN109763023A (zh) * | 2019-04-01 | 2019-05-17 | 杭州辰卓科技有限公司 | 一种包覆型120-160度散热用锡基液态金属材料 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0539274A1 (fr) * | 1991-10-24 | 1993-04-28 | Rhone-Poulenc Chimie | Procédé de synthèse d'aldéhydes et de leurs dérivés |
EP0626201A1 (fr) * | 1992-09-10 | 1994-11-30 | Daicel Chemical Industries, Ltd. | Procede de production de l'acide acetique ou de l'acetate de methyle et catalyseur |
-
1995
- 1995-01-23 FR FR9500699A patent/FR2729586B1/fr not_active Expired - Fee Related
-
1996
- 1996-01-22 AU AU46254/96A patent/AU4625496A/en not_active Abandoned
- 1996-01-22 EP EP96901829A patent/EP0765192B1/fr not_active Expired - Lifetime
- 1996-01-22 HU HU9602571A patent/HU225172B1/hu not_active IP Right Cessation
- 1996-01-22 JP JP52266796A patent/JP3946763B2/ja not_active Expired - Fee Related
- 1996-01-22 US US08/716,399 patent/US5973210A/en not_active Expired - Lifetime
- 1996-01-22 WO PCT/FR1996/000101 patent/WO1996022832A1/fr active IP Right Grant
- 1996-01-22 CN CN96190054A patent/CN1119204C/zh not_active Expired - Fee Related
- 1996-01-22 ES ES96901829T patent/ES2143749T3/es not_active Expired - Lifetime
- 1996-01-22 AT AT96901829T patent/ATE191157T1/de active
- 1996-01-22 DE DE69607431T patent/DE69607431T2/de not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0539274A1 (fr) * | 1991-10-24 | 1993-04-28 | Rhone-Poulenc Chimie | Procédé de synthèse d'aldéhydes et de leurs dérivés |
EP0626201A1 (fr) * | 1992-09-10 | 1994-11-30 | Daicel Chemical Industries, Ltd. | Procede de production de l'acide acetique ou de l'acetate de methyle et catalyseur |
Non-Patent Citations (3)
Title |
---|
CHEMICAL ABSTRACTS, vol. 86, no. 26, 27 June 1977, Columbus, Ohio, US; abstract no. 198283m, HEINRICH: "Bonding in iron-tin and ruthenium-tin mixtures" page 565; XP002003086 * |
J. LESS-COMMON METALS, vol. 52, no. 1, GER, pages 87 - 91 * |
V.M. DESPHANDE ET.AL.: "Studies on ruthenium-tin boride catalysts", JOURNAL OF CATALYSIS, vol. 121, no. 1, DULUTH, MN, US, pages 174 - 182, XP002003085 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6180830B1 (en) | 1995-11-08 | 2001-01-30 | Rhodia Chimie | Method for preparing a bimetallic ruthenium/tin catalyst and a process for the synthesis of aldehydes |
EP0874687B1 (fr) * | 1995-11-08 | 2002-07-03 | Rhone-Poulenc Chimie | Procede de preparation d'un catalyseur bi-metallique ruthenium/etain |
US5985789A (en) * | 1997-03-27 | 1999-11-16 | E. I. Du Pont De Nemours And Company | Ru, Sn/oxide catalyst and process for hydrogenation in acidic aqueous solution |
WO2011124578A1 (fr) * | 2010-04-07 | 2011-10-13 | Rhodia Operations | Procede de preparation d'une lactone |
FR2958642A1 (fr) * | 2010-04-07 | 2011-10-14 | Rhodia Operations | Procede d'une preparation d'une lactone. |
CN102834172A (zh) * | 2010-04-07 | 2012-12-19 | 罗地亚经营管理公司 | 用于制备内酯的方法 |
US10763021B1 (en) | 2019-10-31 | 2020-09-01 | Brian Rudy Parisien | Method of changing a property of a polar liquid |
US10875794B1 (en) | 2019-10-31 | 2020-12-29 | Brian Rudy Parisien | Method of changing a property of a polar liquid |
US10737956B1 (en) | 2019-12-12 | 2020-08-11 | Brian Rudy Parisien | Method and system for changing a property of a polar liquid |
US10934186B1 (en) | 2019-12-12 | 2021-03-02 | Brian Rudy Parisien | Method and system for changing a property of a polar liquid |
Also Published As
Publication number | Publication date |
---|---|
HU9602571D0 (en) | 1996-11-28 |
FR2729586A1 (fr) | 1996-07-26 |
JPH09511181A (ja) | 1997-11-11 |
CN1145594A (zh) | 1997-03-19 |
HUP9602571A1 (en) | 1997-04-28 |
CN1119204C (zh) | 2003-08-27 |
DE69607431D1 (de) | 2000-05-04 |
EP0765192B1 (fr) | 2000-03-29 |
ATE191157T1 (de) | 2000-04-15 |
EP0765192A1 (fr) | 1997-04-02 |
HU225172B1 (en) | 2006-07-28 |
AU4625496A (en) | 1996-08-14 |
HUP9602571A3 (en) | 1998-04-28 |
FR2729586B1 (fr) | 1997-04-04 |
DE69607431T2 (de) | 2000-11-23 |
JP3946763B2 (ja) | 2007-07-18 |
US5973210A (en) | 1999-10-26 |
ES2143749T3 (es) | 2000-05-16 |
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