[go: up one dir, main page]

WO2016011657A1 - Catalyseurs de réactions d'hydrogénation, leurs procédés de préparation et leurs utilisations - Google Patents

Catalyseurs de réactions d'hydrogénation, leurs procédés de préparation et leurs utilisations Download PDF

Info

Publication number
WO2016011657A1
WO2016011657A1 PCT/CN2014/083009 CN2014083009W WO2016011657A1 WO 2016011657 A1 WO2016011657 A1 WO 2016011657A1 CN 2014083009 W CN2014083009 W CN 2014083009W WO 2016011657 A1 WO2016011657 A1 WO 2016011657A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
silica
hydrogenation reaction
less
oxide
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/CN2014/083009
Other languages
English (en)
Inventor
Xiangang MA
Qingjie Ge
Junguo MA
Xuebin Liu
Zhiqiang Yang
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.)
Dalian Institute of Chemical Physics of CAS
BP China Holdings Ltd
Original Assignee
Dalian Institute of Chemical Physics of CAS
BP China Holdings Ltd
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 Dalian Institute of Chemical Physics of CAS, BP China Holdings Ltd filed Critical Dalian Institute of Chemical Physics of CAS
Priority to PCT/CN2014/083009 priority Critical patent/WO2016011657A1/fr
Publication of WO2016011657A1 publication Critical patent/WO2016011657A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • B01J23/76—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
    • B01J23/83—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 rare earths or actinides
    • 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
    • B01J21/08—Silica
    • 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
    • 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
    • B01J23/80—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 zinc, cadmium or mercury
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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

Definitions

  • the present application relates to the field of chemical catalysts, in particular, catalysts for hydrogenation reactions.
  • Ethanol is widely used as a raw material for making acetic acid, beverages, flavors, dyes, fuels, etc. It is also an excellent solvent and disinfectant.
  • the application of ethanol is becoming broader as an important raw material for the production of chemicals and clean fuels.
  • the non-precious metal catalysts for producing ethanol by hydrogenation of acetic ester are mainly copper-based catalysts.
  • catalytic stability is critical for copper-based catalysts because the copper particles intend to aggregate and sinter at high temperature and may thus lose catalytic activity. Therefore, a critical issue for ethanol production by hydrogenation of acetic ester is to develop copper-based catalysts with high activity and stability.
  • the present application relates to catalysts for a hydrogenation reaction and methods for making or using such catalysts.
  • the present application provides a catalyst which comprises metallic copper (Cu) or copper oxide or a mixture thereof, silica and an electron donating oxide, wherein the mass percentage of copper (Cu) element in the catalyst is 10-70%, the mass percentage of silica in the catalyst is 25-89.9%, and the mass percentage of the metal element of the electron donating oxide in the catalyst is 0.1%-5%.
  • the hydrogenation reaction is an ester hydrogenation reaction. In some embodiments, the ester hydrogenation reaction is an acetate ester hydrogenation reaction.
  • the silica is hydrophilic silica. In some embodiments, the hydrophilic silica has less than 50% of its surface hydroxyl group substituted by hydrophobic groups, and still maintains hydrophilic character. In some embodiments, the silica is acidic silica. In some embodiments, the pH value of 4% aqueous solution of the silica is lower than 6.5. In some embodiments, the specific surface area (BET) of the silica is 50-800 m 2 /g.
  • the electron donating oxide comprises an N-type semi-conductive oxide.
  • the N-type semi-conductive oxide is an N-type semi-conductive metal oxide.
  • the N-type semi-conductive metal oxide is ZnO, CdO, TiO 2 , CeO 2 or a mixture thereof.
  • the N-type semi-conductive metal oxide is ZnO.
  • the mass percentage of the metal element of the electron donating oxide in the catalyst is 0.1-5%.
  • the present application provides a method for preparing a catalyst, which method comprises: a) mixing Cu containing salt, metal salt and aqueous ammonia solution, wherein the metal salt can be transformed into electron donating oxide; b) adding silica to the solution of step a) ; c) removing ammonia; d) calcining and grinding the resulting product from step c) .
  • the method further comprises sieving the product of step d) through a mesh screen. In some embodiments, the method further comprises reducing the product of step d) in the presence of hydrogen or other reducing agent.
  • the present application provides the uses of the catalysts in hydrogenation reactions.
  • the present application provides a method of ethanol production by hydrogenation of acetic ester, which comprises: a) contacting acetic ester and hydrogen with a catalyst of the present application; b) carrying out a hydrogenation reaction of the acetic ester and the hydrogen.
  • the catalyst comprises metallic copper (Cu) or copper oxide or a mixture thereof, silica and electron donating oxide, wherein the mass percentage of copper (Cu) element in the catalyst is 10-70%, the mass percentage of silica in the catalyst is 25-89.9%, and the mass percentage of the metal element of the electron donating oxide in the catalyst is 0.1%-5%.
  • the term “catalyst” as used herein means a substance that can initiate or increase the rate of a chemical reaction of one or more reactants whilenot being consumed by the reaction.
  • the catalyst includes metallic copper (Cu) or copper oxide or the mixture thereof as an active ingredient for catalyzing a hydrogenation reaction.
  • the copper oxide included in the catalyst is Cu 2 O.
  • the catalyst uses Cu/Cu + as main active ingredients.
  • the copper (Cu) element in the catalyst of the present application can be contained in the metallic copper or in the copper oxide. If the catalyst of the present application contains a mixture of metallic copper and copper oxide, then the copper element is contained in both the metallic copper and the copper oxide. In some embodiments, the mass percentage of the copper (Cu) element in the catalyst of the present application is 10-70%, or 10-60%, or 10-50%, or 10-40%, or 10-30%, or 10-20%, or 20-70%, or 30-70%, or 40-70%, or 50-70%, or 60-70%.
  • the mass percentage of the copper (Cu) element in the catalyst of the present application is at least 10%, or at least 15%, or at least 20%, or at least 25%, or at least 30%, or at least 35%, or at least 40%, or at least 45%, or at least 50%. In some embodiments, the mass percentage of the copper (Cu) element in the catalyst of present application is no more than 70%, or no more than 65%, or no more than 60%,or no more than 55%, or no more than 50%.
  • the catalyst further includes electron donating oxides as a promoter which can provide electrons to the active ingredient of the catalyst to facilitate the hydrogenation reaction.
  • electron donating oxide as used herein means an oxide that can provide electrons to the metal copper or copper oxide of the catalyst in the presence of hydrogen or other reducing agent under the reaction condition of hydrogenation reaction.
  • the electron donating oxide comprises an N-type semi-conductive oxide that can provide electrons to the metal copper or copper oxide of the catalyst in the presence of hydrogen or other reducing agent under the reaction condition of hydrogenation reaction.
  • the electron donating oxide is an N-type semi-conductive oxide or a mixture of two or more N-type semi-conductive oxides.
  • the N-type semi-conductive oxide is an N-type semi-conductive metal oxide.
  • the N-type semi-conductive metal oxide is ZnO, CdO, TiO 2 , CeO 2 or a mixture thereof.
  • the N-type semi-conductive metal oxide is ZnO.
  • the N-type semi-conductive metal oxide can facilitate the formation of the oxidation-reduction cycle of the copper and copper oxide (e. g. Cu + /Cu 0 ) .
  • the mass percentage of the metal element of the electron donating oxide in the catalyst of the present application is 0.1-5%, or 0.2-3%, or 0.2-1.5%, or 0.5-1%, or 0.5-2%, or 1.5-3%, or 1.5-2.5%. In some embodiments, the mass percentage of the metal element of the electron donating oxide in the catalyst of the present application is at least 0.1%, or at least 0.2%, or at least 0.3%, or at least 0.4%, or at least 0.5%, or at least 0.6%, or at least 0.7%, or at least 0.8%, or at least 0.9%, or at least 1%, or at least 1.5%, or at least 2%, or at least 2.5%.
  • the mass percentage of the metal element of the electron donating oxide in the catalyst of the present application is no more than 5%, or no more than 4.5%, or no more than 4%, or no more than 3.5%, or no more than 3%, or no more than 2.5%, or no more than 2%.
  • the electron donating oxide is ZnO
  • the metal element of the electron donating oxide is Zn
  • the mass percentage of the Zn element in the catalyst is 0.1-5%, or 0.2-3%, or 0.2-1.5%, or 0.5-1%, or 0.5-2%, or 1.5-3%, or 1.5-2.5%, or wherein the mass percentage of the Zn element in the catalyst is at least 2%, or wherein the mass percentage of the Zn element in the catalyst is at least 0.5%.
  • the catalyst of the present application includes silica as a carrier for holding and supporting the active ingredient and the promoter of the catalyst.
  • silica as used herein, is a substance that consists of silicon (Si) and oxygen (O) atoms.
  • the catalyst of the present application contains silica in the form of solid particle or sol or aerosol or other suitable forms.
  • the silica of the present application contains SiO 2 .
  • the mass percentage of the silica in the catalyst of the present application is 25-89.9%, or 25-85%, or 25-80%, or 25-75%, or 25-70%, or 25-65%, or 25-60%, or 25-55%, or 25-50%, .
  • the mass percentage of the silica in the catalyst of the present application is at least 25%, or at least 30%, or at least 35%, or at least 40%, or at least 45%, or at least 50%, or at least 55%, or at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%. In some embodiments, the mass percentage of the silica in the catalyst of the present application is no more than 85%, or no more than 80%, or no more than 75%, or no more than 70%, or no more than 65%, or no more than 60%, or no more than 55%.
  • the catalyst of the present application may further include one or more other materials that are not silica as carriers to hold and support the active ingredient and the promoter of the catalyst.
  • examples of such other materials are pure silica mesoporous molecular sieves SBA-15, MCM-41, et al.
  • the mass percentage of each component of the catalyst is calculated as follows:
  • Cu% W Cu / (W Cu +W X +W silica ) *100%
  • Cu% refers to the mass percentage of the copper (Cu) element in the catalyst
  • X% refers to the mass percentage of the metal element of the electron donating oxides in the catalyst
  • Silica% refers to the mass percentage of the silica in the catalyst
  • W Cu refers to the total mass of the copper (Cu) element of the metallic Cu or copper oxide or a mixture thereof in the catalyst
  • W X refers to the total mass of the metal element of the electron donating oxides in the catalyst
  • W silica refers to the total mass of silica in the catalyst.
  • hydrogenation reaction means any reaction in which hydrogen or an isotope of hydrogen (e. g. deuterium) or a hydrogen transfer agent (e. g. formic acid) is an active reactant and hydrogen is added to a substrate as another reactant of the reaction.
  • hydrogen transfer agent e. g. formic acid
  • Such reactions include hydrogenolysis, saturation reactions, reductive alkylation/amination and also hydroformylation.
  • the substrate or the reactant to be hydrogenated is typically, but not exclusively, selected from: ketone, aldehyde, hydroxy acid, ester, alkene, alkyne, lactone, anhydride, cyclic anhydride, amide, lactam, Schiffs base, alcohol, nitro, hydroxylamine, nitrile, oxime, imine, azine, hydrazone, azide, cyanate, isocyanate, thiocyanate, isothiocyanate, diazonium, azo, nitroso, phenol, ether, furan, epoxide, hydroperoxide, ozonide, peroxide, arene, unsaturated heterocyclic, acetal and ketal.
  • the hydrogenation reaction is an ester hydrogenation reaction. In some embodiments, the hydrogenation reaction is a ketone hydrogenation reaction. In some embodiments, the hydrogenation reaction is an aldehyde hydrogenation reaction. In some embodiments, the hydrogenation reaction is a hydroxy acid hydrogenation reaction. In some embodiments, the ester hydrogenation reaction is an acetic ester hydrogenation reaction. In some embodiments, the acetic ester hydrogenation reaction is an ethyl acetate hydrogenation reaction. In some embodiments, the acetic ester hydrogenation reaction is a methyl acetate hydrogenation reaction. In some embodiments, the acetic ester hydrogenation reaction is a butyl acetate hydrogenation reaction. In some embodiments, the ester hydrogenation reaction is an aliphatic ester hydrogenation reaction. In some embodiments, the aliphatic ester is an aliphatic ester with 1-6carbon atoms.
  • the present application provides the uses of the catalysts in hydrogenation reactions.
  • the use of the catalyst of present application is the use thereof in acetic ester hydrogenation reactions.
  • the acetic ester hydrogenation reaction is conducted at the temperature of 200-240°C, or 210-230°C, or 215-225°C. In some embodiments, the acetic ester hydrogenation reaction is conducted at the temperature of 220°C. In some embodiments, the acetic ester hydrogenation reaction is conducted at the pressure of 0.5-7 MPa, or 0.5-2 MPa, or 1-4 MPa, or 1.5-2.5 MPa. In some embodiments, the acetic ester hydrogenation reaction is conducted at the pressure of 2.0 MPa.
  • the molar ratio between hydrogen and acetic ester of the acetic ester hydrogenation reaction is 5:1-100:1, or 10:1-100:1, or 30:1-80:1, or 30:1-50:1, or 50:1-80:1.
  • the conversion rate of the acetic ester hydrogenation reaction is no less than 70%, or no less than 75%, or no less than 80%, or no less than 85%, or no less than 90%.
  • the main product selectivity of the acetic ester hydrogenation reaction is no less than 90%, or no less than 95%, or no less than 98%.
  • the catalyst of the present application contains silica with a specific surface area (BET) of 50-800 m 2 /g.
  • BET specific surface area
  • the term"specific surface area (BET) "as used herein is calculated with reference to the nitrogen desorption isotherm (assuming cylindrical pores) by the B. E. T. technique as described by S. Brunauer, P. Emmett, and E. Teller in the Journal of American Chemical Society, 60, pp 209-319 (1939) .
  • the silica of the present application has a specific surface area (BET) of 100-800 m 2 /g, or 200-800 m 2 /g, or 300-800 m 2 /g, or 400-800 m 2 /g, or 500-800 m 2 /g, or 600-800 m 2 /g, or 700-800 m 2 /g.
  • the silica of the present application has a specific surface area (BET) of 100-200 m 2 /g.or 100-300 m 2 /g. or 100-400 m 2 /g, or 100-500 m 2 /g, or 100-600 m 2 /g, or 100-700 m 2 /g.
  • the silica of the present application has a specific surface area (BET) of at least 100 m 2 /g, or at least 200 m 2 /g, or at least 300 m 2 /g, or at least 400 m 2 /g, or at least 500 m 2 /g, or at least 600 m 2 /g, or at least 700 m 2 /g.
  • BET specific surface area
  • the silica of the present application has a specific surface area (BET) of no more than 800 m 2 /g, or no more than 700 m 2 /g, or no more than 600 m 2 /g, or no more than 500 m 2 /g, or no more than 400 m 2 /g.
  • the silica of the present application is hydrophilic silica.
  • the hydrophilic silica of the present application has none of its surface hydroxyl group substituted by hydrophobic groups.
  • the hydrophilic silica of the present application has some of its surface hydroxyl group substituted by hydrophobic groups but still maintains its hydrophilic characteristics.
  • the hydrophilic silica has less than 5%, or less than 10%, or less than 20%, or less than 30%, or less than 40%, or less than 50%, or less than 60%, or less than 70% of its surface hydroxyl group substituted by hydrophobic groups.
  • the number of silica surface hydroxyl groups can be determined by the titrimetric method.
  • the titrimetric method includes the following steps: firstly, measure 2.0 g of dry silica and soak it in 25 mL of ethanol, followed by adding 75 mL of 20% NaCl solution, mix well; secondly, adjust the solution to a pH of 4.0 by adding 0.1 mol/L HCl solution; finally adjust the solution to a pH 9.0 by adding 0.1 mol/L NaOH solution, waiting until the pH remains stable for at least 3 minutes.
  • the number of surface hydroxyl groups of silica is then represented by the volume of NaOH used to adjust 2.0 g of silica from pH 4.0to pH 9.0.
  • the BET surface area of the silica is defined as S (m 2 /g)
  • the volume of NaOH used is defined as V (mL)
  • the calculation formula of the number of surface hydroxyl groups of silica (/nm 2 ) is as follows:
  • the surface hydroxyl group substitution of silica can be calculated by dividing the result of the number of surface hydroxyl groups of standard silica (silica with no substitution of hydroxyl groups by hydrophobic groups) minus the number of surface hydroxyl groups of treated silica by the number of surface hydroxyl groups of the standard silica.
  • Any silica whose surface is treated with silylating agents for example halogenated silanes such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes such as hexamethyldisiloxane, or silazanes, will have its surface hydroxyl groups substituted by hydrophobic groups.
  • the silica of the present application is acidic silica wherein a 4% aqueous solution of the silica has a pH value below 7.0.
  • the pH value of silica can be determined by thoroughly mixing 4 grams of dry silica with 100 milliliters of distilled water and then measure the pH of the solution.
  • the 4% aqueous solution of the silica has a pH value of lower than 6.5, or lower than 6.0, or lower than 5.0, or lower than 4.0, or lower than 3.0, or lower than 2.0, or lower than 1.0.
  • the 4%aqueous solution of the silica has a pH value of 2.0-6.0.
  • the 4%aqueous solution of the silica has a pH value of 3.0-5.0.
  • the catalyst is reduced before use e. g. by the conventional method of heating prepared catalyst in the presence of a reducing agent such as hydrogen, carbon monoxide, or any other suitable reducing agent. In some embodiments, the catalyst is reduced by heating it in the presence of hydrogen and/or carbon monoxide.
  • a reducing agent such as hydrogen, carbon monoxide, or any other suitable reducing agent.
  • the catalyst is reduced by heating it in the presence of hydrogen and/or carbon monoxide.
  • the reactivity of a catalyst can be tested by any known method in the field.
  • the following schemes are used to test the reactivity of a catalyst.
  • the test on the catalyst for producing ethanol by hydrogenation of acetic ester was carried out in a continuous flow fixed-bed reactor, wherein the weight of the catalyst loaded was 1.0 g. Pure hydrogen was used to reduce the catalyst under atmospheric pressure at 350°C at a gas speed of 100 mL/min, wherein the temperature was raised from room temperature to 350°C at the rate of 1 ⁇ 2°C/min and maintained for 3 hrs. After the temperature was lowered to the reaction temperature at the rate of 2°C/min, the raw materials were introduced to start the reaction. The reaction products were analyzed by gas chromatography, wherein the chromatography column was 30m FFAP-type polar capillary column, and hydrogen flame ionization detector (FID) was used to detect the raw materials and reaction products.
  • FID hydrogen flame ionization detector
  • the quantity of A or M was calculated based on carbon moles included in A or M.
  • the “M” in the formula above refers to the reaction product, which can be main product ethanol, or side-products ethane, diethyl ether, acetaldehyde, methanol, etc.
  • the catalyst of the present application can achieve a conversion rate of no less than 95% in a hydrogenation reaction. In some embodiments, the catalyst of the present application can achieve a conversion rate of no less than 90%, or no less than 85%, or no less than 80%, or no less than 75%, in a hydrogenation reaction.
  • the catalyst of the present application can achieve a product selectivity of no less than 95% in a hydrogenation reaction. In some embodiments, the catalyst of the present application can achieve a product selectivity of no less than 90%, or no less than 85%, or no less than 80%, or no less than 75%, in a hydrogenation reaction.
  • the present application provides a catalyst containing copper and copper oxide as active ingredients and an N-type semi-conductive metal oxide as promoter (e. g. ZnO or CeO 2 ) , wherein the promoter can facilitate the formation of the oxidation-reduction cycle (Cu + /Cu 0 , Zn 2+ /Zn (2- ⁇ )+ or Ce 4+ /Ce (4- ⁇ )+ ) in the atmosphere of feed gas (ester/hydrogen) as well as improve and maintain the ratio of Cu + /Cu 0 in the copper-based catalyst so as to improve the activity and stability of the catalyst in the acetic ester hydrogenation reaction.
  • promoter e. g. ZnO or CeO 2
  • the promoter can facilitate the formation of the oxidation-reduction cycle (Cu + /Cu 0 , Zn 2+ /Zn (2- ⁇ )+ or Ce 4+ /Ce (4- ⁇ )+ ) in the atmosphere of feed gas (ester/hydrogen) as well as improve and maintain the ratio of
  • Catalyst A contains a mixture of copper, copper oxides such as Cu 2 O, and SiO 2 .
  • SiO 2 % W SiO2 / (W Cu +W SiO2 ) *100%
  • the nominal mass percentage of each component is approximately equal to the mass percentage calculated based on ICP-MS (inductively coupled plasma mass spectrometry) measurements.
  • the mass percentage of each component of catalyst B is calculated as follows:
  • Cu% W Cu / (W Cu +W Zn +W SiO2 ) *100%
  • Zn% W Zn / (W Cu +W Zn +W SiO2 ) *100%
  • SiO 2 % W SiO2 / (W Cu +W Zn +W SiO2 ) *100%
  • the nominal mass percentage of each component is approximately equal to the weight percentage calculated based on ICP-MS measurements.
  • Catalyst B containing a mixture of copper, copper oxides such as Cu 2 O, NiO and SiO 2 was obtained.
  • Ni% W Ni / (W Cu +W Ni +W SiO2 ) *100%
  • SiO 2 % W SiO2 / (W Cu +W Ni +W SiO2 ) *100%
  • the nominal mass percentage of each component is approximately equal to the mass percentage calculated based on ICP-MS measurements.
  • Catalyst C containing a mixture of copper, copper oxides such as Cu 2 O, CeO 2 and SiO 2 was obtained.
  • the mass percentage of each component of catalyst C is calculated as follows:
  • SiO 2 % W SiO2 / (W Cu +W Ce +W SiO2 ) *100%
  • the nominal mass percentage of each component is approximately equal to the mass percentage calculated based on ICP-MS measurements.
  • Catalyst C containing a mixture of copper, copper oxides such as Cu 2 O, CoO and SiO 2 was obtained.
  • Co% W Co / (W Cu +W Co +W SiO2 ) *100%
  • SiO 2 % W SiO2 / (W Cu +W Co +W SiO2 ) *100%
  • the nominal mass percentage of each component is approximately equal to the mass percentage calculated based on ICP-MS measurements.
  • Catalyst D containing a mixture of copper, copper oxides such as Cu 2 O, ZnO and SiO 2 was obtained.
  • Cu% W Cu / (W Cu +W Zn +W SiO2 ) *100%
  • Zn% W Zn / (W Cu +W Zn +W SiO2 ) *100%
  • SiO 2 % W SiO2 / (W Cu +W Zn +W SiO2 ) *100%
  • the nominal mass percentage of each component is approximately equal to the weight percentage calculated based on ICP-MS measurements.
  • Example2 Catalytic characteristics of catalysts for ethyl acetate (EA) hydrogenation
  • the catalytic characteristics of the catalysts A and A’for the hydrogenation of ethyl acetate is listed in Table 2.
  • Example 4 Catalytic characteristics of catalysts for ethyl acetate hydrogenation under different reaction condition
  • Table 5 shows the catalytic characteristics of the catalyst A for the hydrogenation of ethyl acetate at 2 hrs after each reaction was conducted under different conditions.
  • Table 5 shows that, the reaction condition obviously affect the catalytic characteristics of Catalyst A.
  • the increase of reaction temperature promoted EA conversion, with no apparent effects on ethanol selectivity. At 220°C, ethanol selectivity reached up to above 98%. When increasing temperature beyond that, the change in EA conversion was not apparent but the selectivity slightly decreased.
  • High reaction pressure was beneficial to EA conversion. EA conversion increased from 46% to 87% as the pressure rose from 0.1 MPa to 0.5 MPa. A gradual increase of EA conversion rate to 98%was observed when the pressure was raised from 0.5MPa to 2.0 MPa, while the ethanol selectivity was not apparently affected.
  • the increase of H 2 /EA ratio lifted the EA conversion but the effect of H 2 /EA ratio on ethanol selectivity was not apparent.
  • Example 5 Catalytic characteristics of catalysts for methyl acetate (MA) hydrogenation
  • the catalytic characteristics of the catalysts A/B/B’/Dfor the hydrogenation of methyl acetate is listed in Table 6.

Landscapes

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

Abstract

L'invention concerne des catalyseurs de réactions d'hydrogénation, en particulier des réactions d'hydrogénation d'ester acétique. Ces catalyseurs utilisent du cuivre ou ses oxydes ou leur mélange comme ingrédient actif et SiO2 comme support, et comprennent en outre certains oxydes métalliques appropriés comme promoteur. Les catalyseurs de l'invention présentent une activité et une stabilité élevées.
PCT/CN2014/083009 2014-07-25 2014-07-25 Catalyseurs de réactions d'hydrogénation, leurs procédés de préparation et leurs utilisations Ceased WO2016011657A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2014/083009 WO2016011657A1 (fr) 2014-07-25 2014-07-25 Catalyseurs de réactions d'hydrogénation, leurs procédés de préparation et leurs utilisations

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2014/083009 WO2016011657A1 (fr) 2014-07-25 2014-07-25 Catalyseurs de réactions d'hydrogénation, leurs procédés de préparation et leurs utilisations

Publications (1)

Publication Number Publication Date
WO2016011657A1 true WO2016011657A1 (fr) 2016-01-28

Family

ID=55162454

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/083009 Ceased WO2016011657A1 (fr) 2014-07-25 2014-07-25 Catalyseurs de réactions d'hydrogénation, leurs procédés de préparation et leurs utilisations

Country Status (1)

Country Link
WO (1) WO2016011657A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109364923A (zh) * 2018-11-07 2019-02-22 江苏索普（集团）有限公司 铜基耐水催化剂M-Cu/SiO2制备方法及使用方法
CN111389461A (zh) * 2020-04-13 2020-07-10 天津大学 一种经含氮硅烷偶联剂硅烷化改性的铜硅催化剂及其制备方法和用途
CN116351416A (zh) * 2023-01-17 2023-06-30 郑州大学 一种糠醛醚化制糠醚用非贵金属催化剂及其制备方法和使用方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050051463A1 (en) * 2003-09-09 2005-03-10 Chevron U.S.A. Inc. Production of high quality lubricant bright stock
US20100197486A1 (en) * 2008-07-31 2010-08-05 Celanese International Corporation Catalysts for making ethyl acetate from acetic acid
CN102962071A (zh) * 2012-11-26 2013-03-13 江苏索普（集团）有限公司 一种用于醋酸酯加氢制乙醇的催化剂、其制备方法及其应用
CN103333059A (zh) * 2013-06-09 2013-10-02 北京东方红升新能源应用技术研究院有限公司 一种固定床催化加氢精制聚甲醛二烷基醚的方法
CN104174407A (zh) * 2013-05-23 2014-12-03 中国科学院大连化学物理研究所 一种草酸酯加氢制乙二醇的催化剂及其应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050051463A1 (en) * 2003-09-09 2005-03-10 Chevron U.S.A. Inc. Production of high quality lubricant bright stock
US20100197486A1 (en) * 2008-07-31 2010-08-05 Celanese International Corporation Catalysts for making ethyl acetate from acetic acid
CN102962071A (zh) * 2012-11-26 2013-03-13 江苏索普（集团）有限公司 一种用于醋酸酯加氢制乙醇的催化剂、其制备方法及其应用
CN104174407A (zh) * 2013-05-23 2014-12-03 中国科学院大连化学物理研究所 一种草酸酯加氢制乙二醇的催化剂及其应用
CN103333059A (zh) * 2013-06-09 2013-10-02 北京东方红升新能源应用技术研究院有限公司 一种固定床催化加氢精制聚甲醛二烷基醚的方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109364923A (zh) * 2018-11-07 2019-02-22 江苏索普（集团）有限公司 铜基耐水催化剂M-Cu/SiO2制备方法及使用方法
CN111389461A (zh) * 2020-04-13 2020-07-10 天津大学 一种经含氮硅烷偶联剂硅烷化改性的铜硅催化剂及其制备方法和用途
CN116351416A (zh) * 2023-01-17 2023-06-30 郑州大学 一种糠醛醚化制糠醚用非贵金属催化剂及其制备方法和使用方法

Similar Documents

Publication Publication Date Title
Qi et al. Switching of reactions between hydrogenation and epoxidation of propene over Au/Ti-based oxides in the presence of H2 and O2
Sagar et al. Dispersion and reactivity of copper catalysts supported on Al2O3− ZrO2
US9539567B2 (en) Catalysts
US8618182B2 (en) Process for synthesizing C5+ hydrocarbons in the presence of a catalyst prepared using at least one cyclic oligosaccharide
US9433932B2 (en) Hydrogenation catalyst and method of manufacturing the same
CN106622327A (zh) 一种氮掺杂多孔碳负载金属的催化剂及其制备方法和用途
KR20110138221A (ko) 피셔­트롭쉬 촉매의 제조 방법 및 이의 용도
EP3496856B1 (fr) Une composition contenant de coablt
US9327273B2 (en) Catalysts
CN103691442B (zh) 一种合成气制异丁醇催化剂及其制备方法
SA519402398B1 (ar) إجراء بدء تشغيل لعملية فيشر – تروبش
WO2016011657A1 (fr) Catalyseurs de réactions d'hydrogénation, leurs procédés de préparation et leurs utilisations
EP3580307A1 (fr) Procédé de production d'un catalyseur de synthèse de fischer-tropsch
CN111545239B (zh) 一种用于甘油氧化的固体催化剂及其制备方法
US11865513B2 (en) Extruded titania-based materials comprising quaternary ammonium compounds and/or prepared using quaternary ammonium compounds
AU2012311175B2 (en) Process for preparing a cobalt - containing Fischer Tropsch catalyst
CN107427816B (zh) 氢化和乙炔化催化剂
CN105268439B (zh) 用于加氢反应的催化剂及其制备方法和用途
CN113272407A (zh) 费-托方法
US10675610B2 (en) Extruded titania-based materials comprising one or more acids or prepared using one or more acids
US20130289145A1 (en) Catalyst for fischer-tropsch synthesis, production method therefor, and production method using fischer-tropsch synthesis catalyst
EP3181543B1 (fr) Procédé de préparation de 4-methyl-3-decen-5-one
KR101564404B1 (ko) 백금／Ａｌ-ＳＢＡ-15 촉매를 이용한 피셔-트롭쉬 왁스의 수소첨가 분해방법
Xiao et al. Controllable modification for adjacent circumstance controls cellulose conversion to ketols on Ni CCCs at particle levels
EP3722287B1 (fr) Procédé de fabrication d'éther cyclique

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14898277

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14898277

Country of ref document: EP

Kind code of ref document: A1