EP2480329A2 - The catalyst and method of catalytic hydrogenation of hydroxycarboxylic acid esters to glycols - Google Patents

The catalyst and method of catalytic hydrogenation of hydroxycarboxylic acid esters to glycols

Info

Publication number
EP2480329A2
EP2480329A2 EP10765981A EP10765981A EP2480329A2 EP 2480329 A2 EP2480329 A2 EP 2480329A2 EP 10765981 A EP10765981 A EP 10765981A EP 10765981 A EP10765981 A EP 10765981A EP 2480329 A2 EP2480329 A2 EP 2480329A2
Authority
EP
European Patent Office
Prior art keywords
catalyst
copper
glycols
esters
hydroxysilicate
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Withdrawn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
EP10765981A
Other languages
German (de)
French (fr)
Inventor
Margarita Petrovna Demeshkina
Alexandr Alexandrovich Khasin
Tatyana Petrovna Minjukova
Valentin Nikolaevich Parmon
Irina Leonidovna Simakova
Mikhail Nikolaevich Simonov
Tamara Mikhailovna Jurieva
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.)
Springhill SA
Original Assignee
Springhill SA
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 Springhill SA filed Critical Springhill SA
Publication of EP2480329A2 publication Critical patent/EP2480329A2/en
Withdrawn legal-status Critical Current

Links

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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J21/16—Clays or other mineral silicates
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

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

Abstract

The invention relates to processes for the low-cost production of glycols from esters of hydroxycarboxylic acids. The esters of hydroxycarboxylic acids and hydrogen in gas phase are contacted with the catalyst which contains hydroxysilicate of copper or reduced hydroxysilicate of copper. The reduced hydrosilicate of copper contains metallic copper nanoparticles decorated by amorphous oxyhydroxide of silicon. Such decorated copper nanoparticles have advantageous activity and selectivity in catalytic hydrogenation of hydroxycarboxylic acid esters to glycols.

Description

The catalyst and method of catalytic hydrogenation of hydroxycarboxylic acid esters to glycols
BACKGROUND OF THE INVENTION Field of the Invention
The present invention relates to processes for the production of diols with high yield and selectivity by hydrogenation of hydroxycarboxylic acid esters in gas phase over copper containing catalysts. In particular, the present invention relates to a process for the production of ethylene and propylene glycols.
Description of Related Art
The ethylene and propylene glycols are used in a wide variety of applications such as monomers in polyester resins; in antifreeze and de-icing fluids; in the manufacture of food, drugs and cosmetic products; and in liquid detergents. At present, commercial production of glycols is petroleum-based and involves hydrolysis of alkylene oxides at high pressure and high temperature.
Since this process starts with ethylene and propylene, the price of the resulting 1,2-diols depends on the price of oil and other hydrocarbon. The new method is required for production glycols from renewable resources such as plants.
It is well known that plants produce carbohydrates from atmospheric carbon dioxide and sunlight in the process of photosynthesis. Furthermore, as carbon dioxide is a greenhouse gas, so any additional removal of the gas from the atmosphere helps to offset the increase in this gas by industrial emissions. The method based on hydroxycarboxylic acids obtained by fermentation of crude biomass is promising way for glycols production (WO 2000030744, US 6455742, US 6479713).
It is known that liquid-phase hydrogenation of carboxyl groups occurs under high hydrogen pressure. To perform the hydrogenation process under milder conditions carboxylic acids are usually converted into more readily reducible esters. Various patents and articles disclose the reduction of hydroxycarboxylic acid esters. For example, the hydrogenation of organic esters to alcohols and glycols in a liquid phase was reported by Adkins and co-workers who were able to achieve 80% yields of propylene glycol from methyl lactate over copper/chromium oxide and Raney nickel catalysts at temperature from 150 to 250 °C and extremely high hydrogen pressures from 20 to 30 MPa (Bowden and Adkins, J. Am. Chem. Soc. 56: 689 (1934); Adkins and Billica, J. Am. Chem. Soc. 70: 3118 (1948); Adkins and Billica, J. Am. Chem Soc. 70: 3121 (1948)). In addition to high pressure high catalyst loading is necessary to achieve these relatively high yields. Broadbent et al. (J. Org. Chem. 24: 1847 (1959)) was able to obtain propylene glycol from ethyl lactate over rhenium black catalysts with yield as high as 80% at 150°C but at very high hydrogen pressure of about 25 MPa.
The hydrogenation of organic esters to glycols in a liquid phase was reported by Luo and coworkers who have achieved 83% yield of propylene glycol from ethyl lactate over Ru-Sn/γ- A1203 at 150D C and 5.5 MPa. (Luo, G., Yan, S., Qiao, M., Zhuang, J., Fan, K. Appl. Catal. A. 275: 95 (2004)).
The serious disadvantage of all mentioned above hydrogenation processes in liquid phase is necessity to use a high hydrogen pressure.
Carrying out the process of hydrogenation in a vapor phase allows lowering hydrogen pressure. For example, the hydrogenation of organic esters to alcohols and glycols in a vapor phase over the reduced mixture of copper and zinc oxides at 234°C, 1.6 MPa and LHSV=1.06 IT1 was reported by Bradley and co-workers (Pat. WO8203854, 1982 to Davy McKee Ltd.) who have achieved 97.7% selectivity to propylene glycol and 34.7 % conversion of ethyl lactate. The yield of propylene glycol is 0.038 g of propylene glycol /(ml of catalyst *h). Similar approach was claimed by the patent [GB2150860, 1983 to Davy McKee Ltd.] Reduced mixture of CuO and ZnO oxides was used for hydrogenation of carboxylic acid esters. Carbon dioxide is added to the gaseous mixture in the latter invention.
Copper containing catalysts attracted more efforts to find a process for production of 1,2- propanediol from biomass-derived stuff. R.D. Cortright, M. Sanchez-Castillo, J.A. Dumesic in [Applied Catalysis B: Environmental 39 (2002) 353-359] reported high selectivity and activity of Cu/Si02 impregnated catalyst, which comprises copper nitrate over silica surface. Authors achieved 88 % selectivity to 1,2-propanediol at 7 bar and 100 % conversion of lactic acid.
The invention [US Pat. 4628129; to Union Carbide Corporation, 1986] claims Cu/Si02 supported catalysts (prepared by impregnation method, as it follows from the text) to be useful for conversion of alkyl oxalates and alkyl glycolates to ethylene glycol.
Despite these efforts, a need for new methods of production of glycols remains that can be performed under relatively mild conditions and which results in high conversion of esters, selectivity to glycols and glycol yield. Summary of the invention
The present invention relates to processes for the low-cost production of glycols from esters of hydroxycarboxylic acids under relatively mild conditions with high conversion of esters, selectivity to glycols and glycol yield. In particular, the present invention provides a catalyst for conversion of hydroxycarboxylic acid esters to 1,2-propanediol, which contains the phase of hydroxysilicate of copper with chrysocolla structure or reduced copper hydroxysilicate. The present invention provides also a process for the production of glycols, which comprises a stage of contacting a mixture of esters of hydroxycarboxylic acid and hydrogen in gas phase with the catalyst, which contains the copper hydroxysilicate or reduced copper hydroxysilicate.
The said copper hydroxysilicate (CuH)4Si40io(OH)8 nH20 can be prepared by deposition precipitation method using highly dispersed silica, aqueous soluble copper salt and urea as the raw materials. The said copper hydroxysilicate can also be got from natural deposits of chrysocolla mineral, however in this case mineral admixtures can worsen the catalyst selectivity and/or activity. The said copper hydrosilicate can be prepared also by hydrothermal treatment. The structure of chrysocolla is discriminated from other copper-containing oxides and oxyhydroxides by FTIR method, showing four bands at ca. 470, 670, 1040 and 3620 cm"1, which are only characteristic of this hydroxysilicate [T.M.Yurieva, G.N.Kustova, T.P. Minyukova, E.K. Poels, A. Bliek, M.P.Demeshkina, L.M.Plyasova, T.A.Kriger, V.I. Zaikovskii. Mater. Res. Innov., 5 (1) (2001) 3-11].
Reduced copper hydroxysilicate can be prepared by treating of copper hydrosilicate with the gas, which contains hydrogen, CO or another reducing agent at elevated temperatures from 100 to 500°C. The reduced copper hydroxysilicate comprises metallic copper nanoparticles decorated with amorphous silicon oxyhydroxide clusters. This system differs a lot from the system "metallic copper particles supported by silica" by its physical, spectral, catalytic and adsorptive properties (including its catalytic activity and selectivity in hydroxycarboxylic acid esters hydro genation). The decoration of metallic copper particles can be unambigously monitored by UV-Vis spectroscopy, since decorated metallic copper particles have much lower energy of surface plasmon resonance (below 16500 cm"1 , while 17000-18000 cm"1 is observed for the supported Cu/Si02 having no decoration by the support [see e.g. E. Cattaruzza, G. Battaglin, P. Canton, T. Finotto and C. Sada, Mater.Sci. and Eng.: C, 26(5-7) (2006) 1092-1096]. Lowering in energy of surface plasmon resonance energy is caused by changes in the properties of the metallic copper nanoparticle surface due to decoration of the said particles by Si-oxyhydroxide shell, having high dielectric constant. Examples of the impact of Cu nanoparticles decoration by an oxide shell on their optical properties are reported in literature (see e.g. data for Cu-ZnO system [A.A. Khassin, S.F. Ruzankin, V.F. Anufrienko, A.A. Altynnikov, T.V. Larina, J.C. van den Heuvel, T.M. Yurieva and V.N. Parmon. Doklady Phys. Chem. 409 (1) (2006) 193-197.] and for Cu-Cu20 [T Ghodselahi, M A Vesaghi and A Shafiekhani, J. Phys. D: Appl. Phys. 42 (2009) 015308]).
The reduction of the hydroxysilicate of copper within the catalyst may be performed after loading the catalyst in the reactor by contacting the catalyst with hydrogen of the hydrogen- containing gas mixture at elevated temperatures, including contacting the catalyst with the mixture of hydrogen and hydro xycarboxylic acid esters.
The catalyst may contain other constituents, which improve its rheological properties, pore structure or mechanical strength, like graphite, zinc oxide etc. Preferably, the content of copper in the catalyst should be more than 10 % wt. It is also preferable that the catalyst doesn't contain other copper-containing oxyhydroxide or oxide compounds, except copper hydroxysilicate, since it may worsen the selectivity of the catalyst. However, minor impurities of such oxides may be present in the catalyst composition and don't affect the catalytic properties significantly.
The catalytic properties of the said catalyst in hydrogenation of hydro xycarboxylic acid esters are significantly advantageous with respect to the known supported Cu/Si02 catalysts or with respect the catalysts obtained by the reduction of the copper-containing oxide mixtures (e.g. CuO and ZnO mixture) as it is illustrated by the Examples below.
For the illustration of the method, the esters of aliphatic alcohols and lactic and glycolic acids were used as esters of hydroxycarboxylic acid resulting in formation of propylene and ethylene glycols correspondingly.
Examples
Three catalysts were prepared: two according to the present invention and one according to [R.D. Cortright, M. Sanchez-Castillo, J.A. Dumesic Applied Catalysis B: Environmental 39 (2002) 353-359] as a comparative. The data on these samples are summarized in Table 1.
Example 1
The catalyst was prepared by reductive thermal treatment of a stoichiometric copper hyroxysilicate with Cu:Si ratio of 1 :2 at. with chrysocolla structure under flow of hydrogen and temperature 300°C during 1 hour. The chrysocolla structure of the catalyst before reduction is proved by the presence of bands at 480, 670, 1035 and 3624 cm"1, catalyst doesn't contain phases of Cu nitrate, CuO, Cu20 phases, as it is proved by XRD. After the reduction the catalyst is characterized by the resonant absorption of light at 14600 cm"1, which shows high extent of decoration of metallic copper particles.
Liquid butyl lactate (a flow rate 0.5 ml/min) evaporated and mixed with a stream of hydrogen (a flow rate 300 ml/min). The gaseous mixture of hydrogen and butyl lactate fed into a tubular quartz reactor packed with 5 g of a catalyst (Table 1, Catalyst number 1). Temperature in the reactor was maintained at about 190±2°C. The pressure - 10 bar. Process was carried out within 24 hours. Mole ration of butyl lactate : hydrogen was 1 : 3.97.
The vaporous mixture exiting the reactor was passed through a water cooled condenser and then through a second refrigerated condenser through which coolant at 0°C was passed. The resulting condensate was analyzed. The condensate has the following composition, %wt : butyl lactate - 28.5; propylene glycol - 33.9; butanol - 34.9; l-hydroxy-2-propanone - 1.9; unidentified by-products - 0.8. The conversion of butyl lactate was 71.5 %mol, selectivity to propylene glycol was 91.3 %mol. The propylene glycol yield (g glycol/g catalyst/hour) was 2.01.
Examples 2-12
Processes of hydrogenation were repeated similarly to an example 1, but under various conditions.
Conditions and results of hydrogenation butyl lactate are shown in Table 2. Examples 13-15 Processes of hydrogenation were performed similarly to an example 1, but methyl lactate was used as ester of hydro xycarboxylic acid.
Conditions and results of hydrogenation of methyl lactate under various conditions are shown in Table 2.
Examples 16-18 Processes of hydrogenation were performed similarly to an example 1, but ethyl lactate was used as ester of hydro xycarboxylic acid.
Conditions and results of hydrogenation ethyl lactate under various conditions are shown in Table 2.
Examples 19-20 Processes of hydro genation were performed similarly to an example 1, but methyl glycolate was used as ester of hydro xycarboxylic acid.
Conditions and results of hydrogenation methyl glycolate to ethylene glycol under various conditions are shown in Table 2.
Examples 21-22 (low copper content)
The catalyst was prepared similarly to Example 1 , but the Cu:Si atomic ratio in the catalyst was 1 :8. The catalyst before reduction contains hydro xysilicate with chrysocolla structure which is proved by the presence of bands at 470, 668, 1040 and 3620 cm"1, catalyst doesn't contain phases of Cu nitrate, CuO, Cu20 phases, as it is proved by XRD, some poorly- crystallized Si02 is present in the sample, as follows from XRD and FT-IR data. After the reduction the catalyst is characterized by the resonant absorption of light at 14300 cm"1, which shows high extent of decoration of metallic copper particles.
Processes of hydrogenation were performed similarly to the examples 7 and 9, but with lower content of copper in the catalyst as described above.
Examples 23-24 (comparative)
The catalyst was prepared by the incipient wetness impregnation of highly dispersed silica (aerosil A- 180) with copper nitrate, as it is proposed by R.D. Cortright, M. Sanchez-Castillo, J. A. Dumesic in [Applied Catalysis B : Environmental 39 (2002) 353-359]. After the reductive treatment the catalyst contains 10 % wt. of metallic copper and Si02. The surface plasmon resonance absorption by the reduced catalyst is registered at 17200 cm"1, which shows the typical supported metallic copper over silica with low extent of copper decoration. Processes of hydrogenation were performed similarly to the examples 7 and 9.
Conditions and results of hydrogenation methyl glycolate to ethylene glycol under various conditions are summarized in Table 2. It can be seen from the data that the proposed by this invention copper hydroxysilicate catalyst is advantageous with respect to the supported Cu/Si02 catalyst, having no decoration of the metallic copper.
Table 1. The characteristics of the catalysts
Surface Plasmon
Cu:Si
Phase composition of the resonance band Phase composition of at.
catalyst catalyst maximum for the the reduced catalyst ratio
reduced catalyst
Cuu decorated by
Copper hydrosilicate
1 1 14600 cm"1 amorphous
(CuH)4Si40io(OH)8 nH20
hydroxyoxide of silicon
Cu° decorated by
Copper hydrosilicate l amorphous (CuH)4Si40io(OH)8 nH20 0.14 14300 cm" hydroxyoxide of and Si02 silicon and
amorphous silica
Cu(N03)2 and Si02 0.1 17200 cm"1 Cu° and Si02
Table 1. Conditions and results of hydro genation of esters of hydro xycarboxylic acids.

Claims

Claims
1. A catalyst for catalytic hydrogenation of esters of hydroxycarboxylic acids to glycols, wherein the catalyst contains hydroxysilicate of copper.
2. The catalyst according to claim 1, wherein the catalyst contains 10-55 % wt. of copper.
3. The catalyst for catalytic hydrogenation of esters of hydroxycarboxylic acids to glycols, wherein the catalyst contains the reduced hydroxysilicate of copper and its UV-Vis spectrum contains light absorption band having maximum in the range from 11000 to 16000 cm"1.
4. The catalyst according to claim 3, wherein the catalyst contains 10-55 % wt. of copper.
5. A method for preparation of catalyst according to claim 3, wherein the catalyst is prepared by treatment of the composition, which contains hydroxysilicate of copper, with the hydrogen-containing gas mixture.
6. The method of catalytic hydrogenation of esters of hydroxycarboxylic acids to glycols, which comprises contacting the mixture containing ester of hydroxycarboxylic acid and hydrogen in gas phase with the catalyst wherein the catalyst used is the catalyst according to claims 1-4.
7. The method according to claim 6, wherein the processes is carried out at pressure from 1 to 15 bar and temperature between 140 and 220 °C.
8. The method according to claim 6, wherein the processes is carried out at temperature between 180 and 200 °C.
EP10765981A 2009-09-22 2010-09-22 The catalyst and method of catalytic hydrogenation of hydroxycarboxylic acid esters to glycols Withdrawn EP2480329A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EEP200900073A EE200900073A (en) 2009-09-22 2009-09-22 Catalyst and Method for the Catalytic Hydrogenation of Carboxylic Acid Esters to Gl Schools
PCT/EP2010/064001 WO2011036189A2 (en) 2009-09-22 2010-09-22 The catalyst and method of catalytic hydrogenation of hydroxycarboxylic acid esters to glycols

Publications (1)

Publication Number Publication Date
EP2480329A2 true EP2480329A2 (en) 2012-08-01

Family

ID=43707761

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10765981A Withdrawn EP2480329A2 (en) 2009-09-22 2010-09-22 The catalyst and method of catalytic hydrogenation of hydroxycarboxylic acid esters to glycols

Country Status (4)

Country Link
EP (1) EP2480329A2 (en)
EA (1) EA021350B1 (en)
EE (1) EE200900073A (en)
WO (1) WO2011036189A2 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011107959A1 (en) 2011-07-20 2013-01-24 Thyssenkrupp Uhde Gmbh Preparation of optically pure propane-1,2-diol
GB201617698D0 (en) * 2016-10-19 2016-11-30 Johnson Matthey Davy Technologies Limited Process
RU2734237C1 (en) * 2020-01-27 2020-10-13 Андрей Владиславович Курочкин Apparatus for complex gas treatment by low-temperature condensation
CN112517017B (en) * 2020-11-30 2023-05-05 陕西延长石油（集团）有限责任公司 Doped copper silicate nanotube catalyst for methyl acetate hydrogenation and preparation method and application thereof
CN116459846B (en) * 2023-05-09 2024-03-26 中国科学院兰州化学物理研究所 Hydroxy ester hydrogenation nano Cu-based catalyst and preparation method and application thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1190783B (en) 1981-04-29 1988-02-24 Davy Mckee Oil & Chem PROCESS FOR HYDROGENOLYSIS OF ESTERS OF CARBOXYLIC ACIDS
JPS60109028A (en) 1983-11-17 1985-06-14 Hitachi Maxell Ltd Magnetic recording medium
US4628129A (en) * 1985-02-04 1986-12-09 Union Carbide Corporation Process for the preparation of ethylene glycol
SU1594138A1 (en) * 1988-03-17 1990-09-23 Карагандинский Государственный Университет Method of producing synthetic chrysocolla
WO2000030744A1 (en) 1998-11-24 2000-06-02 Michigan State University Condensed phase catalytic hydrogenation of lactic acid to propylene glycol
US6455742B1 (en) * 1999-09-02 2002-09-24 Wisconsin Alumni Research Foundation Method for catalytically reducing carboxylic acid groups to hydroxyl groups in hydroxycarboxylic acids
US6479713B1 (en) 2001-10-23 2002-11-12 Battelle Memorial Institute Hydrogenolysis of 5-carbon sugars, sugar alcohols, and other methods and compositions for reactions involving hydrogen
RU2290994C1 (en) * 2005-12-21 2007-01-10 Институт Катализа Им. Г.К. Борескова Сибирского Отделения Российской Академии Наук Catalyst, method for preparation thereof, and dihydroxyalkane production process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011036189A2 *

Also Published As

Publication number Publication date
EA021350B1 (en) 2015-05-29
EE200900073A (en) 2011-06-15
EA201200528A1 (en) 2012-09-28
WO2011036189A2 (en) 2011-03-31
WO2011036189A3 (en) 2012-02-23

Similar Documents

Publication Publication Date Title
CN108236955B (en) Preparation method of catalyst for synthesizing ethanol by dimethyl oxalate hydrogenation, catalyst obtained by preparation method and application of catalyst
CN108144643B (en) Catalyst and method for preparing low-carbon olefin by directly converting synthesis gas
Wu et al. Aqueous phase reforming of biodiesel byproduct glycerol over mesoporous Ni-Cu/CeO2 for renewable hydrogen production
RU2450043C2 (en) Hydrocarbon synthesis method
CN108970638B (en) Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas
CN107774302B (en) Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas
WO2011036189A2 (en) The catalyst and method of catalytic hydrogenation of hydroxycarboxylic acid esters to glycols
WO2017074582A1 (en) Catalysts prepared from nanostructures of mno2 and wo3 for oxidative coupling of methane
CN109745965B (en) Catalyst containing CeZr oxide and method for preparing low-carbon olefin by directly converting carbon monoxide through hydrogenation
López et al. Study of hydrotalcite-supported transition metals as catalysts for crude glycerol hydrogenolysis
Ashokraju et al. Formic acid assisted hydrogenation of levulinic acid to\upgamma γ-valerolactone over ordered mesoporous Cu/Fe _ 2 O _ 3 Cu/Fe 2 O 3 catalyst prepared by hard template method
US20120203040A1 (en) Process for the Production of Paraffinic Hydrocarbons
Ahmad et al. Synthesis of oxymethylene dimethyl ethers (OMEn) via methanol mediated COx hydrogenation over Ru/BEA catalysts
Díaz et al. Carbon nanofibers and nanospheres-supported bimetallic (Co and Fe) catalysts for the Fischer–Tropsch synthesis
CN108927132B (en) Bifunctional catalyst and method for preparing ethylene by carbon monoxide hydrogenation
Liao et al. New approach for bio-jet fuels production by hydrodeoxygenation of higher alcohols derived from CC coupling of bio-ethanol
WO2009103682A1 (en) The catalyst and method of catalytic reduction of esters of hydroxycarboxylic acid to glycols
CN108970637B (en) Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas
CN108970635B (en) Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas
CN107661773B (en) Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas
Yin et al. The influence mechanism of solvent on the hydrogenation of dimethyl oxalate
CN111569894A (en) Supported Cu-Fe-based catalyst and preparation method and application thereof
CN111346666A (en) Catalyst and method for preparing liquid fuel with high aromatic hydrocarbon content by directly converting synthesis gas
Zhang et al. Waste alkaline Mn–Zn batteries as efficient catalysts applied in ketonization of fatty acids
Pulungan et al. The stabilization of bio-oil as an alternative energy source through hydrodeoxygenation using Co and Co-Mo supported on active natural zeolite

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20120423

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20130312

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20140401