WO2010150278A2 - Hydrogenolysis of polyhydroxy alcohols using metal incorporated manganese oxide octahedral molecular sieve as a catalyst - Google Patents

Hydrogenolysis of polyhydroxy alcohols using metal incorporated manganese oxide octahedral molecular sieve as a catalyst Download PDF

Info

Publication number
WO2010150278A2
WO2010150278A2 PCT/IN2010/000406 IN2010000406W WO2010150278A2 WO 2010150278 A2 WO2010150278 A2 WO 2010150278A2 IN 2010000406 W IN2010000406 W IN 2010000406W WO 2010150278 A2 WO2010150278 A2 WO 2010150278A2
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogenolysis
catalyst
oms
polyhydroxy alcohol
reaction
Prior art date
Application number
PCT/IN2010/000406
Other languages
French (fr)
Other versions
WO2010150278A3 (en
Inventor
Ganapati Dadasaheb Yadav;
Payal Arvind Chandan
Devendra Pandurag Tekale
Bhavana Ganesh Motirale
Original Assignee
Ganapati Dadasaheb Yadav;
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 Ganapati Dadasaheb Yadav; filed Critical Ganapati Dadasaheb Yadav;
Publication of WO2010150278A2 publication Critical patent/WO2010150278A2/en
Publication of WO2010150278A3 publication Critical patent/WO2010150278A3/en

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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—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
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J35/58—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration

Definitions

  • This invention claims priority from 1435/Mum/2009 dated 15 th June 2009 and 1775/Mum/2010 dated 11* June 2010 of INDIA.
  • the present invention is related to the process of selective hydrogenolysis of polyhydroxy alcohols to their corresponding lower alcohols.
  • hydrogenolysis of polyhydroxy alcohol is carried out in the presence of a heterogeneous catalyst with at least one metal other than manganese incorporated in octahedral molecular sieve (OMS) tunnel structure.
  • OMS octahedral molecular sieve
  • Hydrogenolysis of glycerol to propylene glycol is performed at temperatures above 50 0 C and hydrogen pressure of at least 10 bar while maintaining high selectivity and good conversion.
  • Manganese nodules have been described as useful catalysts in the oxidation of carbon monoxide, methane and butane in US3214236.
  • US5545393 describes the synthesis of manganese oxide octahedral molecular sieves.
  • WO/1995/25693 patent represents the synthetic method of manganese oxide octahedral molecular sieve incorporated with at least one metal.
  • Patent WO/2006/019560 claims for the preparation of monometallic catalyst of various compositions for oxidation of CO in PEM fuel cell.
  • glycerol is regarded as one of the building blocks in the biorefinery feedstocks. It is expected that glycerol can be supplied abundantly from the process of the biodiesel production from vegetable oils. Attention has been recently paid to the catalytic conversion of glycerol to petrochemicals, such as propanediols, acrolein, glyceric acid, glycerol carbonate and dihydroxy acetone. The conversion of glycerol to 1, 2-propanediol by both heterogeneous and homogeneous catalyst is disclosed in prior art and can be discussed with their merits and demerits.
  • US5616817 patent discloses a process for the preparation of 1, 2-propanediol by catalytic hydrogenation of glycerol at elevated temperature and pressure, comprises using glycerol having a water content of up to 20% by weight and a catalyst comprising the metals cobalt, copper, manganese and molybdenum in amounts of, based on the total weight of the catalyst, from 40 to 70% by weight of cobalt, from 10 to 20% by weight of copper, from 0 to 10% by weight of manganese and from 0 to 10% by weight of molybdenum, where this catalytically active material may additionally contain inorganic polyacids and/or heteropolyacids in an amount of up to 10% by weight, based on the total weight of the catalyst.
  • the disclosed process is gas phase hydrogenation.
  • DE4302464 patent discloses process for catalytic conversion using metal or metal oxides of group VII elements as a catalyst.
  • the catalyst is copper chromite, Cu-Al 2 O 3 , Cu- ZnO, Cu-SiO 2 process uses temperature between 150 0 C to 320 °C and 20 to 300 bar pressure preferably between 100 to 250 bar.
  • 30-40% Cu, 23-30 % Cr with smaller amount of Mn/ Si/ Zr/ Ba are the catalyst compositions used.
  • WO/2007/099161 patent discloses process for preparation of 1,2 -propanediol in the gas phase by hydrogenation of glycerol using the catalyst used is 23-35% wt of Cu in oxide or elemental form, Cu- Ti, Cu- Zr, Cu- Mn 5 Cu-AI, Cu- Ni, Cu-Mn, Cu- Al, with at least one further metal selected from La, W 5 Mo, Mn, Zn, Ti, Sn, Ni, Co, Cu, Cr, Ca, C, Al, Mn optionally Zr are claimed.
  • European patent EP0523014 discloses ruthenium supported on activated carbon catalyst, with a percentage of ruthenium on the substrate of between 0.5 and 7% in the presence of sulphide ions and the ratio of sulphide ions to ruthenium in the catalyst is between 0.2 and 5, preferably between 0.5 and 2. The reaction is being carried out at least at 200 °C temperature.
  • the similar type of catalyst is also been claimed in US4476331 for hydrogenolysis of carbohydrates particularly glycerol.
  • German patent DE-PS-54362 discloses process for the hydrogenation of glycerol with a nickel-based catalyst to form 1, 2-propanediol. With the use of nickel as the catalyst, satisfactory yields of glycerol conversion can be achieved only at higher temperatures of about 270 0 C, at this temperature considerable quantity of unwanted gaseous hydrocarbons, mainly methane is produced.
  • European patent EP-A-72629 discloses a catalytic method of hydrogenating glycerol with the use of Ni, Pd and Pt. According to this document, a key factor for achieving high conversion rates and selectivity towards the formation of diol is the presence of a promoter constituted by one of the basic inorganic hydroxides.
  • US5214219 patent discloses hydrogenation of aqueous glycerol to propanediol using copper- zinc catalyst at a pressure of at least 200 psi and temperature 220 to 280 0 C.
  • Patent WO095536 discloses a reactive-separation process converts glycerin into lower alcohols, having boiling points less than 200 "C, at high yields. Conversion of natural glycerin to propylene glycol through an acetol intermediate is achieved at temperatures from 150 to 250 0 C at a pressure ranging from 1-25 bar.
  • the preferred catalyst for this process is a copper-chromium powder.
  • the heterogeneous catalyst was selected from the group consisting of palladium, nickel, rhodium, copper, zinc, chromium and combinations thereof.
  • US4624394 discloses a process for the production of propanediol which comprises reacting glycerol, carbon monoxide and hydrogen in an aprotic organic amide solvent medium in contact with a soluble catalyst composition containing tungsten and Group VIH metal compounds, at a temperature between about 100 - 200 0 C and a pressure between about 500- 10,000 psi to yield a product mixture comprising 1,2-propanediol and 1,3 -propanediol.
  • EPl 836147 patent discloses process for vapor phase hydrogenation of glycerol in the presence of a catalyst at a temperature from about 160 0 C to 260 0 C, a pressure of about 10 to about 30 bar, hydrogen to glycerol ratio of from 400: 1 to about 600: 1 and a residence time from about 0.01 to about 2.5 hour uses copper/zinc catalyst and cobalt, copper, manganese and molybdenum catalyst supported on carbon, alumina and silica.
  • US6291725 patent discloses the catalyst and process for the preparation of glycerol, propylene glycol, and ethylene glycol from sugar alcohols such as sorbitol or xylitol, with the metal catalyst comprising ruthenium deposited on an alumina, titania, or carbon support. The dispersion of the ruthenium on the support increases during the hydrogenolysis reaction.
  • the objective of the present invention is to provide a method which enables polyhydroxy alcohols, particularly glycerol which is produced as a byproduct of processes for the saponification and transesteification of fats, to be converted with high conversion rate and good overall selectivity towards the production of their respective lower alcohols.
  • One of the objectives of the present invention is to provide new methods of converting poly hydroxyl alcohol, particularly glycerol and related molecules in to variety of desired chemical products.
  • Another objective of the present invention is to develop a method for the production of desired lower alcohol with high selectivity by reacting polyhydroxy alcohol solution under hydrogen atmosphere.
  • Yet another objective of the present invention is to provide a process for efficient conversion of glycerol to propanediols in a heterogeneously catalyzed reaction medium.
  • One another objective of the present invention is to utilize octahedral manganese molecular sieve type-2 having 2*2 tunnel structure (OMS) incorporated with at least one metal (M) other than manganese as a catalyst (M-OMS) for the hydrogenolysis reaction.
  • OMS 2*2 tunnel structure
  • M-OMS metal-OMS
  • Yet another objective of the present invention is to develop process for production of lower alcohols with minimum total reaction time.
  • Another objective of the present invention is to develop process which utilizes minimum energy for the production of desired product with high purity.
  • Yet another objective of the present invention is to develop an economical viable process for the production of lower alcohol.
  • polyhydroxy alcohol is selectively converted to lower alcohol using heterogeneous catalyst M-OMS where OMS is doped with at least one of the following metals (M) preferably silver, palladium, platinum, ruthenium, copper, cobalt,
  • M metals
  • OMS refers to octahedral molecular sieve of manganese oxide with tunnel structure. More particularly this invention specifies the higher conversion of glycerol to produce propanediol which are of greater commercial value, using heterogeneous OMS-2 based catalyst with greater selectivity to the desired 1,2-propanediol.
  • hydrogenolysis of solution of glycerol is carried out at relatively lower temperature and pressure conditions using M-OMS-2 as a heterogeneous catalyst.
  • the hydrogenolysis is carried out in an autoclave reactor at pressure ranging between 1 to 100 bar and temperature of 50 to 300 0 C.
  • the process gives excellent conversion of glycerol and excellent selectivity towards 1,2 -propanediol.
  • Drawing 1 shows Scanning Electron Microsope (SEM) images of monometallic catalyst at different magnifications.
  • Drawing 2 shows Temperature Programmed Reduction (TPR) analysis of monometallic catalysts.
  • Drawing 3 shows Scanning Electron Microsope (SEM) images of bimetallic catalyst at different magnification
  • FIG. 4 shows Temperature programmed desorption (TPR) analysis of bimetallic catalyst STATEMENT OF INVENTION:
  • a process for the hydrogenolysis of polyhydroxy alcohol to lower alcohols using manganese octahedral molecular sieve incorporated with at least one metal (M-OMS) as a catalyst comprises of following steps as: a. mixing polyhydroxy alcohol solution with M-OMS catalyst and promoter to form a reaction mixture; b. heating a reaction mixture to a temperature ranging from 50 °C to 300 °C over a reaction time interval ranging from 0.5 to 100 hours at a hydrogen pressure ranging from 1 to 100 bar and; c. purifying the product by separating the reaction components.
  • polyhydroxy alcohol solution is obtained by diluting polyhydroxy alcohol with solvent comprising: C 1 to C 8 alcohols, sulpholane, water, N-methyl pyrrolidone, dimethylformamide, dimethylsulfoxide and/or mixture thereof. More particularly solvent used is isopropanol.
  • the concentration of polyhydroxy alcohol in the reaction mixture is atleast about 2% to the solution.
  • catalyst used is a heterogeneous catalyst comprising of: manganese oxide tunnel structure, more particularly octahedral molecular sieve doped with at least one metal.
  • catalyst comprises of doping of OMS with at least one metal selected from the group consisting of: silver, palladium, platinum, ruthenium, copper, cobalt, gold, scandium, tungsten, zinc, nickel, chromium, zirconium, vanadium, titanium, iron, cobalt, cerium, tin, rhodium; more particularly with silver, ruthenium and palladium and/or mixture thereof.
  • catalyst has each metal concentration in the range of 0.1% to 50% to the total weight of the catalyst.
  • promoter has been used like hydroxides of alkali metals or alkaline earth metal and/or mixture thereof and has concentration in the range of 0 to 10% of polyhydroxy alcohol weight in the reaction solution.
  • Temperature for the reaction is preferably in the range of 150 to 200 °C by heating of reaction mixture preferably for at least 3 to 20 hours.
  • Other reaction parameters like hydrogen pressure of the reaction is in the range of 10 to 40 bar.
  • M-OMS catalyst used is selected from Ag-OMS-2, Cu- Ag-OMS- 2 and Pd-Ag-OMS-2.
  • Manganese octahedral molecular sieve is an ordered array of MnO 6 " nodules.
  • Literature is available for the synthesis of various tunnel sizes structure of octahedral molecular sieves of manganese.
  • OMS-I having 3x3 structure with pore size of 6.9 A°
  • OMS- 2 having 2x2 structure with 4.6 A°
  • OMS-3 having 1x1 structures with pore size of 2.3 A°
  • OMS-4 having 1x2 structure with pore size of 2.3 x4.6 A°
  • OMS-5 having 2x4 structure with pore size of 4.6 x 9.2 A°. Due to its tunable pore size as per the requirements, this material is utilized for its applications in oxidation reactions mainly.
  • P-MnO 2 is a naturally occurring manganese oxide characterized by single chains OfMnO 6 octahedra which share edges to form 1 times 1 tunnel structures which are about 2.3 A° square.
  • Ramsdellite, MnO 2 is a naturally occurring manganese oxide characterized by single and double chains of MnO 6 octahedra which shares edges to form 2 times 1 tunnel structure which are about 4.6 A 0 by about 2.3 A° square.
  • the hydrothermal method of synthesizing OMS-2 involves autoclaving an aqueous solution of manganese cation and permanganate anion under acidic conditions, i.e. pH ⁇ 3, at temperatures ranging from about 80 0 C to about 150 0 C in the presence of counter cations.
  • the counter cations can serve as templates for the formation of OMS-2 and retains in the tunnel structures thereof. Based on analytical tests, OMS-2 produced via this method is thermally stable up to about 600 0 C.
  • Synthesis of manganese oxide octahedral molecular sieve wherein manganese framework is incorporated with combination of different metals is produced by following method which consists of: a. forming aqueous medium containing manganese salt at a pH not greater than about 4.5, b. adding of metal salt aqueous solutions sequentially or as a mixture in the above medium under vigorous stirring, c. adding aqueous solution of potassium permanganate at a particular temperature, d. refluxing the resulting reaction medium to produce manganese oxide octahedral sieve and, e. recovering the solid crystalline product.
  • this catalytic material can be produced by the refluxing method.
  • the catalyst is found to be nano fibrous, stable up to 400 0 C temperature and useful for the desired reaction without calcinations.
  • OMS-2 material The general procedure for the synthesis of OMS-2 material is as follows. Aqueous EGVInO 4 solution was added to an aqueous solution of manganese salt and concentrated nitric acid. The resulting black precipitate was refluxed for a particular time. The initial pH of the solution is highly acidic. The precipitate obtained is washed with distilled water until neutral pH, filtered and then dried to obtain OMS-2 material.
  • M-OMS metal incorporated octahedral molecular sieve
  • M-OMS metal incorporated octahedral molecular sieve
  • M-OMS catalyst is designed and developed comprising at least 0.1 to 50 percent of each metal and at least 2 to 95 percent of manganese oxide.
  • Metal can be selected from the group consisting of Co, Fe 5 Ni, Cu, Pd, W 5 Ti 5 Sc, Sn 5 Zn 5 Zr 5 Ce 5 Pt 5 Ru 5 Rh 5 V 5 Ag 5 Au 5 Cr
  • metals are selected from Cu 5 Ag, Pd and/or mixture thereof.
  • One another embodiments of the present invention specifies the application of OMS based catalytic material for the high conversion of polyhydroxy alcohol to produce lower alcohols which have greater commercial value with greater selectivity to the desired product.
  • catalytic process is related to the hydrogenolysis of polyhydroxy alcohols like ethylene glycol, glycerol, sorbitol, glucose, fructose, xylose, sucrose etc. to their corresponding lower alcohols with high selectivity.
  • 1,2-propanediol also known as propylene glycol or 1,2-dihydroxy propane is a valuable and market demanding molecule for its applications as an antifreeze, deicing compound, monomer in polymer industry, synthetic intermediate and a solvent.
  • the traditional hydrogenolysis catalyst generally results in a wide range of products.
  • Typical reaction products of glycerol include: ethane, methane, ethanol, methanol, ethylene glycol, 1,2-propanediol, 1,3 -propanediol, acetol, acrolein.
  • the selectivity to the required 1,2- propanediol can be tuned by choosing the appropriate catalyst for the reaction at proper reaction conditions.
  • Glycerol used in the reaction may be from any source. It may be pure glycerol or it may contain other components like organic compounds, water and/or other impurities. The other components present largely depend on the source of glycerol. Since the process of the present invention may be carried out in the presence of such components there is no requirement to purify the glycerol prior to it being used as a feedstock.
  • polyhydroxy alcohols are converted to lower alcohols using heterogeneous manganese octahedral molecular sieve catalyst (M-OMS) where OMS is doped with one of the following metals (M) preferably silver, palladium, platinum, ruthenium, copper, zinc, nickel, chromium, zirconium, cobalt, vanadium, titanium, iron, cobalt, gold, tungsten, scandium, cerium, tin, rhodium at pressure ranging between 1 to 100 bar and temperature between 50 to 300 0 C.
  • M manganese octahedral molecular sieve catalyst
  • This invention specifies the higher conversion of glycerol to produce diols using heterogeneous catalysts, with greater selectivity to the desired l 5 2-propanediol.
  • the method of preparing the catalyst comprises of the main step of addition of potassium permanganate solution to the acidic solution of mixture of metal salt with manganese salt followed by refluxing the solution and finally filtration, washing till neutral pH and drying.
  • manganese precursor and doping metal precursor can be in the form of nitrate, oxide, chloride, carbonate, acetate isopropoxide, sulphate, hydroxide and/or mixture thereof.
  • hydrogenolysis of polyhydroxyl alcohol in a solvent is carried out at relatively lower temperature and pressure conditions using M-OMS-2 as a heterogeneous catalyst.
  • the hydrogenolysis is carried out in an autoclave reactor at pressure ranging between 1 to 100 bar and temperature of 50 to 300 °C.
  • the present catalytic process is related to the selective hydrogenolysis of polyhydroxy alcohols such as glucose, fructose, sucrose, glycerol, ethylene glycol, xylose to their corresponding lower alcohols. More particularly, the process converts glycerol to propylene glycol, ethylene glycol and/or acetol, more selectively to propylene glycol.
  • polyhydroxy alcohols such as glucose, fructose, sucrose, glycerol, ethylene glycol, xylose
  • the process converts glycerol to propylene glycol, ethylene glycol and/or acetol, more selectively to propylene glycol.
  • propylene glycol that is derived from natural glycerol is a renewable alternative to the petroleum-derived propylene glycol.
  • One of embodiment of the present invention is that the present process utilizes manganese oxide octahedral molecular sieve type-2 doped with at least metal as a catalyst for the desired reaction.
  • the catalyst compositions are expressed as: concentration of metal in the catalyst ranging from 0.1% to 50% to the total catalyst weight.
  • catalytic process is carried out in reactor which is equipped with a four blade pitched turbine impeller under the hydrogen pressure using heterogeneous catalyst. Reaction is carried out in any suitable type of apparatus which enables intimate contact of the reactants and control of the operating conditions and which is suitable for high pressure involved.
  • the process may be carried out in batch, semi- continuous and continuous operation. Batch operation in conventional high pressure autoclave gives excellent results.
  • batch reactor is preferred, other suitable reactor types include slurry batch reactors, trickle bed reactors, fix bed reactor and teabag reactors.
  • the hydrogenolysis reaction is carried out under an atmosphere of hydrogen gas or any mixture of hydrogen gas with other gases which do not interfere with the desired reaction, such as nitrogen, helium, neon or argon gas.
  • the partial pressure of hydrogen gas is about 1 to 100 bar, preferably about 10-40 bar.
  • reaction temperature is in the range of 50 to 300 0 C, more preferably between 150 to 200 0 C.
  • glycerol solution is obtained by diluting glycerol with solvent comprising: C 1 -C 8 alcohol, sulpholane, water, N-methyl pyrrolidone, dimethylformamide, dimethylsulfoxide and/or mixture thereof. More particularly solvent used is isopropanol.
  • One of embodiment of present invention is that in present catalytic process one or more alkali or alkaline earth metal hydroxide and/ or mixtures thereof may be added as a promoter to the reaction mixture to attain basic conditions which improves the conversion.
  • the quantity of the promoter can be from 0% to 10% of the glycerol weight in the reaction mixture.
  • the concentration of polyhydroxy alcohol is generally between 2 to 50 weight % in a solvent and reactions are performed at 150 0 C to 300 °C and hydrogen pressure in the range of 10 to 40 bar. Under these conditions, the conversion to the desired product occurs with high selectivity.
  • Various embodiments of the inventive methods have been found to provide numerous unexpected results that are superior over prior technologies, including: high conversion, mild reaction conditions and high selectivity along with the process controls. Surprisingly, the process of invention offers excellent conversion. However in the process of incomplete conversion, separation of the product from reaction mixture is readily achieved. The invention is further illustrated by means of the following non-limiting examples.
  • Ag-OMS catalyst is characterized by the following methods.
  • Drawing 1 shows Scanning Electron Microscope (SEM) images of the catalysts at different magnifications. From the SEM images of Ag-OMS catalyst, nano-crystalline fibrous structure of the catalyst can be easily depicted.
  • Drawing 2 shows Temperature Programmed Reduction (TPR) analysis of catalyst.
  • TPR data shows sharp peak at 144 0 C showing the reducing property of the catalyst. This shows the applicability of the catalyst for the redox type reactions.
  • Manganese acetate (21 g) was dissolved in 67.5 ml deionized distilled water. Concentrated HNO 3 was added in manganese acetate solution to adjust a pH of 1.0. A solution of silver nitrate (2.72 g) in 25 ml deionized distilled water was added drop wise into manganese acetate solution followed by 25 ml (6.08 g) copper nitrate solution. This is solution (A). Solution of potassium permanganate (13.3 g) in 225 ml deionized distilled water was added to the above solution (A). The mixture was refluxed at 100 0 C for 24 hours. Resulting precipitate was washed several times with deionized distilled water until neutral pH, filtered and dried in oven at 120 0 C for 10 hours. The catalyst was then characterized by various techniques as follows.
  • Drawing 3 shows Scanning Electron Microscope (SEM) images of the catalysts at different magnifications.
  • Drawing 4 shows Temperature Programmed Reduction (TPR) analysis of catalyst.
  • Example 3- Preparation of Pd-Ag-OMS-2
  • Manganese acetate (10.5 g) was dissolved in 50 ml deionized distilled water. Concentrated HNO 3 was added in manganese acetate solution to adjust a pH of 1.0.
  • a solution of silver nitrate (1.87 g) and palladium nitrate (0.81 g) in 75 ml deionized distilled water was added drop wise into manganese acetate solution. This is solution (A).
  • Solution of potassium permanganate (6.65 g) in 125 ml deionized distilled water was added to the above solution (A) at 70 0 C temperature. The mixture was refluxed at 100 0 C for 24 hours. Resulting precipitate was washed several times with deionized distilled water until neutral pH, filtered and dried in oven at 120 0 C for 10 hours to get 5% Pd- 10% Ag-OMS-2.
  • Example 4-11 The tests are carried out in a 100 cc autoclave with stirrer system having a stirrer with pitch blades.
  • the reactor is loaded with 20% glycerol solution in 2-propanol of a predetermined concentration and with the desired quantity of 10%Ag-Cu-OMS catalyst.
  • the autoclave is then closed and flushed with nitrogen followed by hydrogen several times to eliminate the air present.
  • There after autoclave is heated to desired temperature and pressurized with hydrogen to 30 bar and kept under these conditions for 8 hours with stirring.
  • Table 1 Table 1
  • Example 12-14 The tests are carried out in a 100 cc autoclave with stirrer system having a stirrer with pitch blades.
  • the reactor is loaded with glycerol solution in 2-propanol of a predetermined concentration (20 wt % of glycerol) and with the desired quantity of 15% Ag-Cu-OMS catalyst.
  • the autoclave is then closed and flushed with nitrogen followed by hydrogen several times to eliminate the air present.
  • There after autoclave is heated to desired temperature and pressurized with hydrogen to 30 bar and kept under these conditions for 8 hours with stirring.
  • the autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis.
  • Reaction is carried out in a 100 cc autoclave with stirrer system having a stirrer with pitch blades.
  • the reactor is loaded with 20% glycerol solution in 2-propanol and with the 5% Pd- 10% Ag-OMS catalyst.
  • the autoclave is heated to 200 0 C temperature and pressurized with hydrogen to 30 bar and kept under these conditions for 8 hours to give 65% conversion of glycerol with 75% selectivity towards 1,2-propanediol.
  • a 100 ml autoclave with pitch bladed stirrer system is loaded with 10.0 g glycerol in 51.0 ml 2-propanol, 0.5 g desired Ag-OMS-2 catalyst and the 0.1 g Of Ca(OH) 2 as a promoter.
  • autoclave is heated to 200 0 C, pressurized with 30 bar hydrogen and kept under these conditions for 8 hours.
  • the autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis.
  • a 100 ml autoclave with pitch bladed stirrer system is loaded with 10.0 g glycerol in 51.0 ml 2-propanol, 0.5 g 30% Ag-OMS-2 catalyst and the desired quantity of Ca(OH) 2 as a promoter.
  • autoclave is heated to 200 °C, pressurized with 30 bar hydrogen and kept under these conditions for 8 hours.
  • the autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis.
  • a 100 ml autoclave with pitch bladed stirrer system is loaded with 10.0 g glycerol in 51.0 ml 2-propanol, 0.5 g of 30% Ag-OMS-2 catalyst and of 0.1 g Ca(OH) 2 as a promoter.
  • autoclave is heated to 200 0 C, pressurized with hydrogen to desired level and kept under these conditions for 8 hours.
  • the autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis.
  • a 100 ml autoclave with pitch bladed stirrer system is loaded with 10.0 g glycerol in 51.0 ml 2-propanol, 0.5 g of 30% Ag-OMS-2 catalyst and of 0.1 g Ca(OH) 2 as a promoter. There after autoclave is heated to the desired temperature, pressurized with 30 bar hydrogen and kept under these conditions for 8 hours. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis.

Abstract

The invention relates to the hydrogenolysis of polyhydroxy alcohols in the presence of metal incorporated manganese oxide octahedral molecular sieve catalyst (M-OMS) to produce their corresponding lower alcohols. Hydrogenolysis of glycerol is performed above 50 °C temperature and hydrogen pressure of at least 10 bar while maintaining good conversions and high selectivity towards desired products.

Description

This invention claims priority from 1435/Mum/2009 dated 15th June 2009 and 1775/Mum/2010 dated 11* June 2010 of INDIA.
TITLE OF INVENTION:
HYDROGENOLYSIS OF POLYHYDROXY ALCOHOLS USING METAL INCARPORATED MANGANESE OXIDE OCTAHEDRAL MOLECULAR SIEVE AS A CATALYST
FIELD OF THE INVENTION:
The present invention is related to the process of selective hydrogenolysis of polyhydroxy alcohols to their corresponding lower alcohols. In the present process, hydrogenolysis of polyhydroxy alcohol is carried out in the presence of a heterogeneous catalyst with at least one metal other than manganese incorporated in octahedral molecular sieve (OMS) tunnel structure. Hydrogenolysis of glycerol to propylene glycol is performed at temperatures above 50 0C and hydrogen pressure of at least 10 bar while maintaining high selectivity and good conversion.
BACKGROUND OF INVENTION:
Manganese nodules have been described as useful catalysts in the oxidation of carbon monoxide, methane and butane in US3214236.
US5545393 describes the synthesis of manganese oxide octahedral molecular sieves. WO/1995/25693 patent represents the synthetic method of manganese oxide octahedral molecular sieve incorporated with at least one metal.
Patent WO/2006/019560 claims for the preparation of monometallic catalyst of various compositions for oxidation of CO in PEM fuel cell.
There is continuing increasing interest in the development of novel and improved materials and processes for efficient conversion of renewable resources to value added chemicals. The above cited references mention variety of manganese oxide octahedral molecular sieve (OMS) based material, but none of the above references describe their utilization for the process of hydrogenolysis. The present invention is intended to utilize this material as a catalyst for the conversion of glycerol to propylene glycol with greater conversion and selectivity.
Catalytic conversion of renewable feedstocks and chemicals has increased interest of green technologist. Such catalytic conversion can promote the utilization of renewable energy sources and can facilitate the replacement of petroleum by renewable resources. Recently, it has been proposed that glycerol is regarded as one of the building blocks in the biorefinery feedstocks. It is expected that glycerol can be supplied abundantly from the process of the biodiesel production from vegetable oils. Attention has been recently paid to the catalytic conversion of glycerol to petrochemicals, such as propanediols, acrolein, glyceric acid, glycerol carbonate and dihydroxy acetone. The conversion of glycerol to 1, 2-propanediol by both heterogeneous and homogeneous catalyst is disclosed in prior art and can be discussed with their merits and demerits.
US5616817 patent discloses a process for the preparation of 1, 2-propanediol by catalytic hydrogenation of glycerol at elevated temperature and pressure, comprises using glycerol having a water content of up to 20% by weight and a catalyst comprising the metals cobalt, copper, manganese and molybdenum in amounts of, based on the total weight of the catalyst, from 40 to 70% by weight of cobalt, from 10 to 20% by weight of copper, from 0 to 10% by weight of manganese and from 0 to 10% by weight of molybdenum, where this catalytically active material may additionally contain inorganic polyacids and/or heteropolyacids in an amount of up to 10% by weight, based on the total weight of the catalyst. The disclosed process is gas phase hydrogenation.
DE4302464 patent discloses process for catalytic conversion using metal or metal oxides of group VII elements as a catalyst. Preferably the catalyst is copper chromite, Cu-Al2O3, Cu- ZnO, Cu-SiO2 process uses temperature between 150 0C to 320 °C and 20 to 300 bar pressure preferably between 100 to 250 bar. 30-40% Cu, 23-30 % Cr with smaller amount of Mn/ Si/ Zr/ Ba are the catalyst compositions used. WO/2007/099161 patent discloses process for preparation of 1,2 -propanediol in the gas phase by hydrogenation of glycerol using the catalyst used is 23-35% wt of Cu in oxide or elemental form, Cu- Ti, Cu- Zr, Cu- Mn5 Cu-AI, Cu- Ni, Cu-Mn, Cu- Al, with at least one further metal selected from La, W5 Mo, Mn, Zn, Ti, Sn, Ni, Co, Cu, Cr, Ca, C, Al, Mn optionally Zr are claimed.
European patent EP0523014 discloses ruthenium supported on activated carbon catalyst, with a percentage of ruthenium on the substrate of between 0.5 and 7% in the presence of sulphide ions and the ratio of sulphide ions to ruthenium in the catalyst is between 0.2 and 5, preferably between 0.5 and 2. The reaction is being carried out at least at 200 °C temperature. The similar type of catalyst is also been claimed in US4476331 for hydrogenolysis of carbohydrates particularly glycerol.
German patent DE-PS-54362 discloses process for the hydrogenation of glycerol with a nickel-based catalyst to form 1, 2-propanediol. With the use of nickel as the catalyst, satisfactory yields of glycerol conversion can be achieved only at higher temperatures of about 270 0C, at this temperature considerable quantity of unwanted gaseous hydrocarbons, mainly methane is produced.
European patent EP-A-72629 discloses a catalytic method of hydrogenating glycerol with the use of Ni, Pd and Pt. According to this document, a key factor for achieving high conversion rates and selectivity towards the formation of diol is the presence of a promoter constituted by one of the basic inorganic hydroxides.
US5214219 patent discloses hydrogenation of aqueous glycerol to propanediol using copper- zinc catalyst at a pressure of at least 200 psi and temperature 220 to 280 0C.
Patent WO095536 discloses a reactive-separation process converts glycerin into lower alcohols, having boiling points less than 200 "C, at high yields. Conversion of natural glycerin to propylene glycol through an acetol intermediate is achieved at temperatures from 150 to 250 0C at a pressure ranging from 1-25 bar. The preferred catalyst for this process is a copper-chromium powder. The heterogeneous catalyst was selected from the group consisting of palladium, nickel, rhodium, copper, zinc, chromium and combinations thereof. US4624394 discloses a process for the production of propanediol which comprises reacting glycerol, carbon monoxide and hydrogen in an aprotic organic amide solvent medium in contact with a soluble catalyst composition containing tungsten and Group VIH metal compounds, at a temperature between about 100 - 200 0C and a pressure between about 500- 10,000 psi to yield a product mixture comprising 1,2-propanediol and 1,3 -propanediol.
EPl 836147 patent discloses process for vapor phase hydrogenation of glycerol in the presence of a catalyst at a temperature from about 160 0C to 260 0C, a pressure of about 10 to about 30 bar, hydrogen to glycerol ratio of from 400: 1 to about 600: 1 and a residence time from about 0.01 to about 2.5 hour uses copper/zinc catalyst and cobalt, copper, manganese and molybdenum catalyst supported on carbon, alumina and silica.
US6291725 patent discloses the catalyst and process for the preparation of glycerol, propylene glycol, and ethylene glycol from sugar alcohols such as sorbitol or xylitol, with the metal catalyst comprising ruthenium deposited on an alumina, titania, or carbon support. The dispersion of the ruthenium on the support increases during the hydrogenolysis reaction.
Existing process for the hydrogenolysis of polyhydroxy alcohols to form other products offers means of obtaining desirable products but they suffers from various drawbacks and disadvantages in terms of conversion, reaction conditions, rate and/or economics. For example excessively high temperature and pressure may degrade the reaction products, also working pressure of several hundred bar create safety concerns and increase the capital cost of implementing these processes. Most of these reactions generate substantial impurities which require costly purification step to isolate the desired reaction product. Presently disclosed process advances the art and overcomes the problems outlined above for the hydrogenolysis reaction. Also, the above cited references mentions wide variety of catalysts for the hydrogenolysis of polyhydroxyalcohols such as glucose, fructose, sucrose, sorbitol, glycerol, ethylene glycol, xylose, more particularly glycerol; but none of the above references describes the use of octahedral molecular sieve doped with metal for the desired conversion. Particularly, octahedral manganese molecular sieves, more specifically OMS-2 having 2x2 tunnel structure doped with at least metal other than manganese is not reported for the process of hydrogenolysis of glycerol to propanediol. The present invention is intended to improve the conversion of polyhydroxy alcohols by a heterogeneous catalytic route to the desired lower alcohols with greater selectivity.
OBJECTIVE OF THE INVENTION:
The objective of the present invention is to provide a method which enables polyhydroxy alcohols, particularly glycerol which is produced as a byproduct of processes for the saponification and transesteification of fats, to be converted with high conversion rate and good overall selectivity towards the production of their respective lower alcohols.
One of the objectives of the present invention is to provide new methods of converting poly hydroxyl alcohol, particularly glycerol and related molecules in to variety of desired chemical products.
Another objective of the present invention is to develop a method for the production of desired lower alcohol with high selectivity by reacting polyhydroxy alcohol solution under hydrogen atmosphere.
Yet another objective of the present invention is to provide a process for efficient conversion of glycerol to propanediols in a heterogeneously catalyzed reaction medium.
One another objective of the present invention is to utilize octahedral manganese molecular sieve type-2 having 2*2 tunnel structure (OMS) incorporated with at least one metal (M) other than manganese as a catalyst (M-OMS) for the hydrogenolysis reaction.
Yet another objective of the present invention is to develop process for production of lower alcohols with minimum total reaction time.
Another objective of the present invention is to develop process which utilizes minimum energy for the production of desired product with high purity.
Yet another objective of the present invention is to develop an economical viable process for the production of lower alcohol. SUMMARY OF INVENTION:
In the process of present invention polyhydroxy alcohol is selectively converted to lower alcohol using heterogeneous catalyst M-OMS where OMS is doped with at least one of the following metals (M) preferably silver, palladium, platinum, ruthenium, copper, cobalt,
Scandium, gold, tungsten, zinc, nickel, chromium, zirconium, vanadium, titanium, iron, cerium, tin, rhodium at pressure ranging between 1 to 100 bar and temperature between 50 to
300 0C. Here OMS refers to octahedral molecular sieve of manganese oxide with tunnel structure. More particularly this invention specifies the higher conversion of glycerol to produce propanediol which are of greater commercial value, using heterogeneous OMS-2 based catalyst with greater selectivity to the desired 1,2-propanediol.
In the present invention hydrogenolysis of solution of glycerol, is carried out at relatively lower temperature and pressure conditions using M-OMS-2 as a heterogeneous catalyst. The hydrogenolysis is carried out in an autoclave reactor at pressure ranging between 1 to 100 bar and temperature of 50 to 300 0C. The process gives excellent conversion of glycerol and excellent selectivity towards 1,2 -propanediol.
BRIEF DESCRIPTION OF DRAWINGS:
Drawing 1 shows Scanning Electron Microsope (SEM) images of monometallic catalyst at different magnifications.
Drawing 2 shows Temperature Programmed Reduction (TPR) analysis of monometallic catalysts.
Drawing 3 shows Scanning Electron Microsope (SEM) images of bimetallic catalyst at different magnification
Drawing 4 shows Temperature programmed desorption (TPR) analysis of bimetallic catalyst STATEMENT OF INVENTION:
In the present claims of invention, a process for the hydrogenolysis of polyhydroxy alcohol to lower alcohols using manganese octahedral molecular sieve incorporated with at least one metal (M-OMS) as a catalyst has been claimed. The invented process comprises of following steps as: a. mixing polyhydroxy alcohol solution with M-OMS catalyst and promoter to form a reaction mixture; b. heating a reaction mixture to a temperature ranging from 50 °C to 300 °C over a reaction time interval ranging from 0.5 to 100 hours at a hydrogen pressure ranging from 1 to 100 bar and; c. purifying the product by separating the reaction components.
In the present process, polyhydroxy alcohol solution is obtained by diluting polyhydroxy alcohol with solvent comprising: C1 to C8 alcohols, sulpholane, water, N-methyl pyrrolidone, dimethylformamide, dimethylsulfoxide and/or mixture thereof. More particularly solvent used is isopropanol.
The concentration of polyhydroxy alcohol in the reaction mixture is atleast about 2% to the solution.
For present invented process, catalyst used is a heterogeneous catalyst comprising of: manganese oxide tunnel structure, more particularly octahedral molecular sieve doped with at least one metal.
Thus catalyst comprises of doping of OMS with at least one metal selected from the group consisting of: silver, palladium, platinum, ruthenium, copper, cobalt, gold, scandium, tungsten, zinc, nickel, chromium, zirconium, vanadium, titanium, iron, cobalt, cerium, tin, rhodium; more particularly with silver, ruthenium and palladium and/or mixture thereof.
In the invented process, catalyst has each metal concentration in the range of 0.1% to 50% to the total weight of the catalyst. In the process of invention, promoter has been used like hydroxides of alkali metals or alkaline earth metal and/or mixture thereof and has concentration in the range of 0 to 10% of polyhydroxy alcohol weight in the reaction solution.
Temperature for the reaction is preferably in the range of 150 to 200 °C by heating of reaction mixture preferably for at least 3 to 20 hours. Other reaction parameters like hydrogen pressure of the reaction is in the range of 10 to 40 bar.
With the current invented process, equivalent process has been developed with different polyhydroxy alcohol to the knowledge of person skilled in art. Hydrogenolysis of polyhydroxy alcohol is carried out and glycerol can be used as polyhydroxy alcohol.
In the process of invention M-OMS catalyst used is selected from Ag-OMS-2, Cu- Ag-OMS- 2 and Pd-Ag-OMS-2.
DESCRIPTION OF INVENTION:
Manganese octahedral molecular sieve (OMS) is an ordered array of MnO6 " nodules. Literature is available for the synthesis of various tunnel sizes structure of octahedral molecular sieves of manganese. OMS-I having 3x3 structure with pore size of 6.9 A°, OMS- 2 having 2x2 structure with 4.6 A°, OMS-3 having 1x1 structures with pore size of 2.3 A°, OMS-4 having 1x2 structure with pore size of 2.3 x4.6 A°, OMS-5 having 2x4 structure with pore size of 4.6 x 9.2 A°. Due to its tunable pore size as per the requirements, this material is utilized for its applications in oxidation reactions mainly.
Pyrolusite, P-MnO2 is a naturally occurring manganese oxide characterized by single chains OfMnO6 octahedra which share edges to form 1 times 1 tunnel structures which are about 2.3 A° square. Ramsdellite, MnO2, is a naturally occurring manganese oxide characterized by single and double chains of MnO6 octahedra which shares edges to form 2 times 1 tunnel structure which are about 4.6 A0 by about 2.3 A° square.
The hydrothermal method of synthesizing OMS-2 involves autoclaving an aqueous solution of manganese cation and permanganate anion under acidic conditions, i.e. pH< 3, at temperatures ranging from about 80 0C to about 150 0C in the presence of counter cations. The counter cations can serve as templates for the formation of OMS-2 and retains in the tunnel structures thereof. Based on analytical tests, OMS-2 produced via this method is thermally stable up to about 600 0C.
Synthesis of manganese oxide octahedral molecular sieve wherein manganese framework is incorporated with combination of different metals is produced by following method which consists of: a. forming aqueous medium containing manganese salt at a pH not greater than about 4.5, b. adding of metal salt aqueous solutions sequentially or as a mixture in the above medium under vigorous stirring, c. adding aqueous solution of potassium permanganate at a particular temperature, d. refluxing the resulting reaction medium to produce manganese oxide octahedral sieve and, e. recovering the solid crystalline product.
Unlike the hydrothermal method of synthesis of OMS which involves the use of closed system reactor, i.e. an autoclave under pressure, this catalytic material (M-OMS) can be produced by the refluxing method. The catalyst is found to be nano fibrous, stable up to 400 0C temperature and useful for the desired reaction without calcinations.
The general procedure for the synthesis of OMS-2 material is as follows. Aqueous EGVInO4 solution was added to an aqueous solution of manganese salt and concentrated nitric acid. The resulting black precipitate was refluxed for a particular time. The initial pH of the solution is highly acidic. The precipitate obtained is washed with distilled water until neutral pH, filtered and then dried to obtain OMS-2 material.
For the present invention, metal incorporated octahedral molecular sieve (M-OMS) is prepared by the following general process. Manganese salt is dissolved in distilled water; concentrated nitric acid is added to maintain the pH about 1. Aqueous solutions of metal salts are added sequentially or as a mixture to the acidic manganese salt solution. To this solution, aqueous solution of potassium permanganate is added drop wise at a particular temperature. After addition, the resultant solution is refluxed for 12-24 hours. The resulting precipitate is washed several times with distilled water till neutral pH, filtered to obtain solid brown-black material which is further dried in oven and can be used as a catalyst without calcination.
In the present invention M-OMS catalyst is designed and developed comprising at least 0.1 to 50 percent of each metal and at least 2 to 95 percent of manganese oxide. Metal can be selected from the group consisting of Co, Fe5 Ni, Cu, Pd, W5 Ti5 Sc, Sn5 Zn5 Zr5 Ce5 Pt5 Ru5 Rh5 V5 Ag5 Au5 Cr Preferably for hydrogenolysis reaction, metals are selected from Cu5 Ag, Pd and/or mixture thereof.
One another embodiments of the present invention specifies the application of OMS based catalytic material for the high conversion of polyhydroxy alcohol to produce lower alcohols which have greater commercial value with greater selectivity to the desired product. In the present invention, catalytic process is related to the hydrogenolysis of polyhydroxy alcohols like ethylene glycol, glycerol, sorbitol, glucose, fructose, xylose, sucrose etc. to their corresponding lower alcohols with high selectivity.
1,2-propanediol also known as propylene glycol or 1,2-dihydroxy propane is a valuable and market demanding molecule for its applications as an antifreeze, deicing compound, monomer in polymer industry, synthetic intermediate and a solvent.
The traditional hydrogenolysis catalyst generally results in a wide range of products. Typical reaction products of glycerol include: ethane, methane, ethanol, methanol, ethylene glycol, 1,2-propanediol, 1,3 -propanediol, acetol, acrolein. The selectivity to the required 1,2- propanediol can be tuned by choosing the appropriate catalyst for the reaction at proper reaction conditions.
The processes and procedures described in this text are generally applicable to polyhydroxyl alcohols, particularly to refined as well as crude glycerol. Glycerol used in the reaction may be from any source. It may be pure glycerol or it may contain other components like organic compounds, water and/or other impurities. The other components present largely depend on the source of glycerol. Since the process of the present invention may be carried out in the presence of such components there is no requirement to purify the glycerol prior to it being used as a feedstock. In the present invention polyhydroxy alcohols are converted to lower alcohols using heterogeneous manganese octahedral molecular sieve catalyst (M-OMS) where OMS is doped with one of the following metals (M) preferably silver, palladium, platinum, ruthenium, copper, zinc, nickel, chromium, zirconium, cobalt, vanadium, titanium, iron, cobalt, gold, tungsten, scandium, cerium, tin, rhodium at pressure ranging between 1 to 100 bar and temperature between 50 to 300 0C. Here OMS refers to OMS-2 with octahedral molecular sieve of manganese having 2x2 tunnel structure. More particularly this invention specifies the higher conversion of glycerol to produce diols using heterogeneous catalysts, with greater selectivity to the desired l52-propanediol.
The method of preparing the catalyst comprises of the main step of addition of potassium permanganate solution to the acidic solution of mixture of metal salt with manganese salt followed by refluxing the solution and finally filtration, washing till neutral pH and drying.
One of embodiments of the invention is that in the M-OMS catalyst, manganese precursor and doping metal precursor can be in the form of nitrate, oxide, chloride, carbonate, acetate isopropoxide, sulphate, hydroxide and/or mixture thereof.
hi the present process, hydrogenolysis of polyhydroxyl alcohol in a solvent is carried out at relatively lower temperature and pressure conditions using M-OMS-2 as a heterogeneous catalyst. The hydrogenolysis is carried out in an autoclave reactor at pressure ranging between 1 to 100 bar and temperature of 50 to 300 °C.
One of embodiment of the present invention is that the present catalytic process is related to the selective hydrogenolysis of polyhydroxy alcohols such as glucose, fructose, sucrose, glycerol, ethylene glycol, xylose to their corresponding lower alcohols. More particularly, the process converts glycerol to propylene glycol, ethylene glycol and/or acetol, more selectively to propylene glycol. In this regard, use of propylene glycol that is derived from natural glycerol is a renewable alternative to the petroleum-derived propylene glycol.
One of embodiment of the present invention is that the present process utilizes manganese oxide octahedral molecular sieve type-2 doped with at least metal as a catalyst for the desired reaction. The catalyst compositions are expressed as: concentration of metal in the catalyst ranging from 0.1% to 50% to the total catalyst weight. One of embodiment of present invention is that catalytic process is carried out in reactor which is equipped with a four blade pitched turbine impeller under the hydrogen pressure using heterogeneous catalyst. Reaction is carried out in any suitable type of apparatus which enables intimate contact of the reactants and control of the operating conditions and which is suitable for high pressure involved. The process may be carried out in batch, semi- continuous and continuous operation. Batch operation in conventional high pressure autoclave gives excellent results. Although batch reactor is preferred, other suitable reactor types include slurry batch reactors, trickle bed reactors, fix bed reactor and teabag reactors.
The hydrogenolysis reaction is carried out under an atmosphere of hydrogen gas or any mixture of hydrogen gas with other gases which do not interfere with the desired reaction, such as nitrogen, helium, neon or argon gas. The partial pressure of hydrogen gas is about 1 to 100 bar, preferably about 10-40 bar.
One of embodiment of present invention is that reaction temperature is in the range of 50 to 300 0C, more preferably between 150 to 200 0C.
One another embodiment of the present invention is that glycerol solution is obtained by diluting glycerol with solvent comprising: C1-C8 alcohol, sulpholane, water, N-methyl pyrrolidone, dimethylformamide, dimethylsulfoxide and/or mixture thereof. More particularly solvent used is isopropanol.
One of embodiment of present invention is that in present catalytic process one or more alkali or alkaline earth metal hydroxide and/ or mixtures thereof may be added as a promoter to the reaction mixture to attain basic conditions which improves the conversion. The quantity of the promoter can be from 0% to 10% of the glycerol weight in the reaction mixture.
Another embodiment of the present invention is that the concentration of polyhydroxy alcohol is generally between 2 to 50 weight % in a solvent and reactions are performed at 150 0C to 300 °C and hydrogen pressure in the range of 10 to 40 bar. Under these conditions, the conversion to the desired product occurs with high selectivity. Various embodiments of the inventive methods have been found to provide numerous unexpected results that are superior over prior technologies, including: high conversion, mild reaction conditions and high selectivity along with the process controls. Surprisingly, the process of invention offers excellent conversion. However in the process of incomplete conversion, separation of the product from reaction mixture is readily achieved. The invention is further illustrated by means of the following non-limiting examples.
Example 1 Preparation of M-OMS-2 catalyst
21.0 g manganese acetate is dissolved in 67.5 ml distilled water; 9.8 ml of concentrated nitric acid was added to it. 9.97 g silver nitrate is dissolved in 50 ml distilled water and added to acidic manganese acetate solution at room temperature. 13.3 g KMnO4 Ui 275 ml distilled water is added to the above solution dropwise at 70 0C. The resulting black precipitate is refluxed at 100 0C for 24 h under stirring. The precipitate is washed several times with distilled water to attain neutral pH, filtered and dried at 120 °C for 12 h to obtain about 15.8 g 30% Ag-OMS-2.
Ag-OMS catalyst is characterized by the following methods.
Drawing 1 shows Scanning Electron Microscope (SEM) images of the catalysts at different magnifications. From the SEM images of Ag-OMS catalyst, nano-crystalline fibrous structure of the catalyst can be easily depicted.
Drawing 2 shows Temperature Programmed Reduction (TPR) analysis of catalyst. TPR data shows sharp peak at 144 0C showing the reducing property of the catalyst. This shows the applicability of the catalyst for the redox type reactions.
ASAP (surface area) results of the catalysts:
Figure imgf000014_0001
Example 2- Preparation of Cu-Ag-OMS-2
Manganese acetate (21 g) was dissolved in 67.5 ml deionized distilled water. Concentrated HNO3 was added in manganese acetate solution to adjust a pH of 1.0. A solution of silver nitrate (2.72 g) in 25 ml deionized distilled water was added drop wise into manganese acetate solution followed by 25 ml (6.08 g) copper nitrate solution. This is solution (A). Solution of potassium permanganate (13.3 g) in 225 ml deionized distilled water was added to the above solution (A). The mixture was refluxed at 100 0C for 24 hours. Resulting precipitate was washed several times with deionized distilled water until neutral pH, filtered and dried in oven at 120 0C for 10 hours. The catalyst was then characterized by various techniques as follows.
Drawing 3 shows Scanning Electron Microscope (SEM) images of the catalysts at different magnifications.
Drawing 4 shows Temperature Programmed Reduction (TPR) analysis of catalyst.
Example 3- Preparation of Pd-Ag-OMS-2 Manganese acetate (10.5 g) was dissolved in 50 ml deionized distilled water. Concentrated HNO3 was added in manganese acetate solution to adjust a pH of 1.0. A solution of silver nitrate (1.87 g) and palladium nitrate (0.81 g) in 75 ml deionized distilled water was added drop wise into manganese acetate solution. This is solution (A). Solution of potassium permanganate (6.65 g) in 125 ml deionized distilled water was added to the above solution (A) at 70 0C temperature. The mixture was refluxed at 100 0C for 24 hours. Resulting precipitate was washed several times with deionized distilled water until neutral pH, filtered and dried in oven at 120 0C for 10 hours to get 5% Pd- 10% Ag-OMS-2.
Example 4-11 The tests are carried out in a 100 cc autoclave with stirrer system having a stirrer with pitch blades. The reactor is loaded with 20% glycerol solution in 2-propanol of a predetermined concentration and with the desired quantity of 10%Ag-Cu-OMS catalyst. The autoclave is then closed and flushed with nitrogen followed by hydrogen several times to eliminate the air present. There after autoclave is heated to desired temperature and pressurized with hydrogen to 30 bar and kept under these conditions for 8 hours with stirring. The results obtained are described in Table- 1. Table 1
Example Temp Catalyst Hydrogen Conversion Selectivity
No. (K) loading Pressure (%) (%)
(wt% of (psi) 1,2-PDO Acetol Others glycerol)
4 473 3.5 425 30 83 2 15
5 473 5.0 425 43 79 4.2 16.8
6 473 6.5 425 65 87 3 10
7 453 6.5 425 32 100 0 0
8 463 6.5 425 54 88 3 9
9 493 6.5 425 71 54 12 34
10 473 5.0 285 18 78 4 18
11 513 5.0 425 49 71 04 24
Example 12-14 The tests are carried out in a 100 cc autoclave with stirrer system having a stirrer with pitch blades. The reactor is loaded with glycerol solution in 2-propanol of a predetermined concentration (20 wt % of glycerol) and with the desired quantity of 15% Ag-Cu-OMS catalyst. The autoclave is then closed and flushed with nitrogen followed by hydrogen several times to eliminate the air present. There after autoclave is heated to desired temperature and pressurized with hydrogen to 30 bar and kept under these conditions for 8 hours with stirring. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis.
Table 2
Example Catalyst Temp Hydrogen Conversion Selectivity
No. loading (K) Pressure (%) (%)
(wt% of (psi) 1,2-PDO Acetol Others glycerol)
12 3.5 473 425 13 86 03 11
13 5.0 473 425 23 87 04 09
14 6.5 473 425 43 88 01 11
Example 15
Reaction is carried out in a 100 cc autoclave with stirrer system having a stirrer with pitch blades. The reactor is loaded with 20% glycerol solution in 2-propanol and with the 5% Pd- 10% Ag-OMS catalyst. The autoclave is heated to 200 0C temperature and pressurized with hydrogen to 30 bar and kept under these conditions for 8 hours to give 65% conversion of glycerol with 75% selectivity towards 1,2-propanediol.
Example 16-18
A 100 ml autoclave with pitch bladed stirrer system, is loaded with 10.0 g glycerol in 51.0 ml 2-propanol, 0.5 g desired Ag-OMS-2 catalyst and the 0.1 g Of Ca(OH)2 as a promoter. There after autoclave is heated to 200 0C, pressurized with 30 bar hydrogen and kept under these conditions for 8 hours. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis.
Table 3
Catalyst Selectivity
% Ag Promoter
Example loading Conversion in Quantity No. (wt % of (%) catalyst (wt %) 1,2-PDO Acetol EG Others glycerol)
16. 10 5 1 47.81 89.51 3.81 3.65 3.03
17. 15 5 1 56.89 90.41 2.66 4.81 2.12
18. 30 5 1 69.27 91.59 2.20 3.78 2.43
The symbols used in table 3 have the following meanings: 1, 2-PDO: I5 2-propanediol; EG: ethylene glycol Others: This includes propan-1-ol, methanol and some unidentified byproducts.
Example 19-21
A 100 ml autoclave with pitch bladed stirrer system, is loaded with 10.0 g glycerol in 51.0 ml 2-propanol, 0.5 g 30% Ag-OMS-2 catalyst and the desired quantity of Ca(OH)2 as a promoter. There after autoclave is heated to 200 °C, pressurized with 30 bar hydrogen and kept under these conditions for 8 hours. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis. Table 4
Catalyst Selectivity
% Ag Promoter
Example loading Conversion in Quantity No. (wt % of catalyst (wt %) 1,2-PDO Acetol EG Others glycerol)
19. 30 5 0 63 84.6 3.9 8.96 2.54
20. 30 5 0.5 64.19 80.62 2.11 14.98 2.29
21. 30 5 1.5 69.16 92.54 1.45 4.01 2.00
The symbols used in table 4 have the following meanings: 1, 2-PDO: 1, 2-propanediol; EG: ethylene glycol Others: This includes propan-1-ol, methanol and some unidentified byproducts.
Example 22-25
A 100 ml autoclave with pitch bladed stirrer system, is loaded with 10.0 g glycerol in 51.0 ml 2-propanol, 0.5 g of 30% Ag-OMS-2 catalyst and of 0.1 g Ca(OH)2 as a promoter. There after autoclave is heated to 200 0C, pressurized with hydrogen to desired level and kept under these conditions for 8 hours. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis.
Table 5
% Ag Hydrogen Promoter Selectivity
Example Conversion in Pressure Quantity (%) No. (%) catalyst (bar) - (wt %) 1,2-PDO Acetol EG Others
22. 30 10 1 44.4 69.85 2.59 3.66 23.90
23. 30 20 1 55.39 88.05 2.49 5.80 3.66
24. 30 30 1 69.27 91.59 2.20 3.78 2.43
25. 30 40 1 59.81 91.92 0.90 6.27 0.91
The symbols used in table 5 have the following meanings:
1, 2-PDO: 1, 2-propanediol; EG: ethylene glycol
Others: This includes propan-1-ol, methanol and some unidentified by-products .
Example 26-29
A 100 ml autoclave with pitch bladed stirrer system, is loaded with 10.0 g glycerol in 51.0 ml 2-propanol, 0.5 g of 30% Ag-OMS-2 catalyst and of 0.1 g Ca(OH)2 as a promoter. There after autoclave is heated to the desired temperature, pressurized with 30 bar hydrogen and kept under these conditions for 8 hours. The autoclave is then cooled at room temperature and atmospheric pressure and opened to enable the reaction liquid to be filtered for analysis.
Table 6
% Ag Promoter Selectivity
Example Temperature Conversion in Quantity (%) No. (0C) (%) catalyst (wt %) 1,2-PDO Acetol EG Others
26. 30 180 1 30.32 92.07 0.98 5.04 1.91
27. 30 190 1 47.6 91.19 1.36 4.32 3.13
28. 30 200 1 69.27 91.59 2.20 3.78 2.43
29. 30 210 1 83.77 83.80 2.66 3.68 9.86
The symbols used in table θ have the following meanings:
1, 2-PDO: 1, 2-propanediol; EG: ethylene glycol
Others: This includes propan-1-ol, methanol and some unidentified by-products.

Claims

CLAIMS We claim:
1. A process for the hydrogenolysis of polyhydroxy alcohol to lower alcohols using manganese octahedral molecular sieve incorporated with at least one metal (M-OMS) as a catalyst comprising steps of: a. mixing polyhydroxy alcohol solution with M-OMS catalyst and promoter to form a reaction mixture; b. heating a reaction mixture to a temperature ranging from 50 °C to 300 °C over a reaction time interval ranging from 0.5 to 100 hours at a hydrogen pressure ranging from 1 to 100 bar and; c. purifying the product by separating the reaction components.
2. A process for the hydrogenolysis of polyhydroxy alcohol as claimed in claim 1 wherein, polyhydroxy alcohol solution is obtained by diluting polyhydroxy alcohol with solvent comprising: C1 to C8 alcohols, sulpholane, water, N-methyl pyrrolidone, dimethylformamide, dimethylsulfoxide and/or mixture thereof. More particularly solvent used is isopropanol.
3. A process for the hydrogenolysis of polyhydroxy alcohol as claimed in claim 1 wherein polyhydroxy alcohol has concentration of atleast 2% in the solution.
4. A process for the hydrogenolysis of polyhydroxy alcohol as claimed in claim 1 wherein, M-OMS catalyst is a heterogeneous catalyst comprising of: manganese oxide tunnel structure, more particularly octahedral molecular sieve type-2 doped with at least one metal other than manganese.
5. A process for the hydrogenolysis of polyhydroxy alcohol as claimed in claim 1 wherein, M-OMS catalyst comprises of doping of OMS with at least one of the metal selected from the group consisting of: silver, palladium, platinum, ruthenium, copper, cobalt, gold, scandium, tungsten, zinc, nickel, chromium, zirconium, vanadium, titanium, iron, cobalt, cerium, tin and rhodium.
6. A process for the hydrogenolysis of polyhydroxy alcohol as claimed in claim 1 wherein, M-OMS catalyst comprises of doping of OMS with at least one of the metal preferably Ag, Pd, Cu.
7. A process for the hydrogenolysis of polyhydroxy alcohol as claimed in claim 1, wherein M-OMS catalyst has active metal concentration in the range of 1% to 50% of the total catalyst.
8. A process for the hydrogenolysis of polyhydroxy alcohol as claimed in claim 1 wherein, promoter is hydroxide of alkali metals or alkaline earth metal and/or mixture thereof.
9. A process for the hydrogenolysis of polyhydroxy alcohol as claimed in claim 1 wherein, promoter has concentration in the range of 0 to 10% of polyhydroxy alcohol weight in the reaction solution.
10. A process for the hydrogenolysis of polyhydroxy alcohol as claimed in claim. 1 wherein, temperature for the reaction is preferably in the range of 150 to 200 °C.
11. A process for the hydrogenolysis of polyhydroxy alcohol as claimed in claim 1 wherein, heating of reaction mixture is carried out preferably for 3 to 20 hours.
12. A process for the hydrogenolysis of polyhydroxy alcohol as claimed in claim 1 wherein, hydrogen pressure of the reaction is preferably in the range of 10 to 40 bar.
13. A process for the hydrogenolysis of polyhydroxy alcohol as claimed in claim 1 wherein, polyhydroxy alcohol is glycerol.
14. A process for the hydrogenolysis of polyhydroxy alcohol as claimed in claim 4 and 5 wherein, M-OMS catalyst is Ag-OMS-2.
15. A process for the hydrogenolysis of polyhydroxy alcohol as claimed in claim 4 and 5 wherein, M-OMS catalyst is Cu-Ag-OMS-2.
16. A process for the hydrogenolysis of polyhydroxy alcohol as claimed in claim 4 and 5 wherein, M-OMS catalyst is Pd-Ag-OMS-2.
PCT/IN2010/000406 2009-06-15 2010-06-15 Hydrogenolysis of polyhydroxy alcohols using metal incorporated manganese oxide octahedral molecular sieve as a catalyst WO2010150278A2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
IN1435MU2009 2009-06-15
IN1435/MUM/2009 2009-06-15
IN1775/MUM/2010 2010-06-11
IN1775MU2010 2010-06-11

Publications (2)

Publication Number Publication Date
WO2010150278A2 true WO2010150278A2 (en) 2010-12-29
WO2010150278A3 WO2010150278A3 (en) 2011-07-21

Family

ID=43244792

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IN2010/000406 WO2010150278A2 (en) 2009-06-15 2010-06-15 Hydrogenolysis of polyhydroxy alcohols using metal incorporated manganese oxide octahedral molecular sieve as a catalyst

Country Status (1)

Country Link
WO (1) WO2010150278A2 (en)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012096323A1 (en) * 2011-01-13 2012-07-19 Jnc株式会社 Method for producing glycol from polyhydric alcohol
WO2012096324A1 (en) * 2011-01-13 2012-07-19 Jnc株式会社 Method for producing hydroxy ketone from polyhydric alcohol
CN102633599A (en) * 2012-04-20 2012-08-15 江苏联东化工股份有限公司 Hydrogenation method of 1,2-propylene glycol by bio-based glycerol
WO2014141198A1 (en) * 2013-03-14 2014-09-18 Johnson Matthey Public Limited Company Cerium-modified manganese octahedral molecular sieves as catalysts for selective catalytic reduction
CN104086369A (en) * 2014-06-18 2014-10-08 华南理工大学 Method for preparing lower alcohols from cassava dreg through hydrogenolysis
US9447011B2 (en) 2012-11-21 2016-09-20 University Of Tennessee Research Foundation Methods, systems and devices for simultaneous production of lactic acid and propylene glycol from glycerol
CN111036284A (en) * 2018-10-15 2020-04-21 中国石油化工股份有限公司 Catalyst, preparation method thereof and method for preparing low-carbon olefin from synthesis gas
CN111036287A (en) * 2018-10-15 2020-04-21 中国石油化工股份有限公司 Supported catalyst, preparation method thereof and glycerol hydrogenation method
CN111036277A (en) * 2018-10-15 2020-04-21 中国石油化工股份有限公司 Supported catalyst, preparation method thereof and glycerol hydrogenation method
CN112717968A (en) * 2019-10-28 2021-04-30 中国石油化工股份有限公司 System and method for preparing 1, 2-propylene glycol from glycerol
CN112723991A (en) * 2019-10-28 2021-04-30 中国石油化工股份有限公司 System and method for preparing 1, 2-propylene glycol from glycerol
CN112723990A (en) * 2019-10-28 2021-04-30 中国石油化工股份有限公司 System and method for preparing 1, 2-propylene glycol from glycerol
CN112791737A (en) * 2019-10-28 2021-05-14 中国石油化工股份有限公司 Supported catalyst, preparation method and application
CN112791721A (en) * 2019-10-28 2021-05-14 中国石油化工股份有限公司 Supported catalyst precursor, supported catalyst, preparation method and activation method
CN112791723A (en) * 2019-10-28 2021-05-14 中国石油化工股份有限公司 Supported catalyst and preparation method and application thereof
CN112794790A (en) * 2019-10-28 2021-05-14 中国石油化工股份有限公司 System and method for preparing 1, 2-propylene glycol from glycerol
CN113264568A (en) * 2021-06-01 2021-08-17 中国科学院新疆生态与地理研究所 Method for degrading quinolone antibiotics in wastewater by using visible light catalyst
CN115155579A (en) * 2022-07-23 2022-10-11 重庆科技学院 Reductive noble metal loaded manganese oxide catalyst for catalytic combustion of multi-component organic waste gas and preparation method thereof

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE54362C (en) J. MERRITT, Arzt, in 842 President Str., und W. Ii. SPENCER, Arzt, in 293 Dekalb Avenue in Brooklyn, County of Kings, State of New-York, V. St. A Photographic camera
US3214236A (en) 1961-11-13 1965-10-26 Socony Mobil Oil Co Inc Method of catalytically oxidizing hydrocarbon and carbon monoxide to carbon dioxide
EP0072629A1 (en) 1981-07-22 1983-02-23 E.I. Du Pont De Nemours And Company Hydrogenolysis of polyols to ethylene glycol
US4476331A (en) 1982-02-11 1984-10-09 Ethyl Corporation Two stage hydrogenolysis of carbohydrate to glycols using sulfide modified ruthenium catalyst in second stage
US4624394A (en) 1982-11-30 1986-11-25 Kyoto Kikai Kogu Kabushiki Kaisha Tube container squeezer
EP0523014A2 (en) 1991-07-10 1993-01-13 NOVAMONT S.p.A. A catalytic method of hyrogenating glycerol
US5214219A (en) 1991-07-10 1993-05-25 Novamont S.P.A. Method of hydrogenating glycerol
DE4302464A1 (en) 1993-01-29 1994-08-04 Henkel Kgaa Prepn. of propylene glycol from re-generable fossil fuel sources
WO1995025693A1 (en) 1994-03-21 1995-09-28 Texaco Development Corporation Framework metal-substituted manganese oxide octahedral molecular sieve and process for its preparation
US5545393A (en) 1994-11-07 1996-08-13 Texaco Inc. Method of preparing manganese oxide octahedral molecular sieve
US5616817A (en) 1994-11-26 1997-04-01 Basf Aktiengesellschaft Preparation of 1,2-propanediol
US6291725B1 (en) 2000-03-03 2001-09-18 Board Of Trustees Operating Michigan State University Catalysts and process for hydrogenolysis of sugar alcohols to polyols
WO2006019560A2 (en) 2004-07-20 2006-02-23 Fuelcell Energy, Inc. Oms-2 catalysts in pem fuel cell applications
WO2007099161A1 (en) 2006-03-03 2007-09-07 Basf Se Process for the preparation of 1,2-propanediol
EP1836147A1 (en) 2005-07-15 2007-09-26 Davy Process Technology Limited Vapour phase hydrogenation of glycerol
WO2009005536A2 (en) 2006-11-22 2009-01-08 3M Innovative Properties Company Methods of capturing bacterial whole cells and methods of analyzing samples for bacteria

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7663004B2 (en) * 2002-04-22 2010-02-16 The Curators Of The University Of Missouri Method of producing lower alcohols from glycerol

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE54362C (en) J. MERRITT, Arzt, in 842 President Str., und W. Ii. SPENCER, Arzt, in 293 Dekalb Avenue in Brooklyn, County of Kings, State of New-York, V. St. A Photographic camera
US3214236A (en) 1961-11-13 1965-10-26 Socony Mobil Oil Co Inc Method of catalytically oxidizing hydrocarbon and carbon monoxide to carbon dioxide
EP0072629A1 (en) 1981-07-22 1983-02-23 E.I. Du Pont De Nemours And Company Hydrogenolysis of polyols to ethylene glycol
US4476331A (en) 1982-02-11 1984-10-09 Ethyl Corporation Two stage hydrogenolysis of carbohydrate to glycols using sulfide modified ruthenium catalyst in second stage
US4624394A (en) 1982-11-30 1986-11-25 Kyoto Kikai Kogu Kabushiki Kaisha Tube container squeezer
EP0523014A2 (en) 1991-07-10 1993-01-13 NOVAMONT S.p.A. A catalytic method of hyrogenating glycerol
US5214219A (en) 1991-07-10 1993-05-25 Novamont S.P.A. Method of hydrogenating glycerol
DE4302464A1 (en) 1993-01-29 1994-08-04 Henkel Kgaa Prepn. of propylene glycol from re-generable fossil fuel sources
WO1995025693A1 (en) 1994-03-21 1995-09-28 Texaco Development Corporation Framework metal-substituted manganese oxide octahedral molecular sieve and process for its preparation
US5545393A (en) 1994-11-07 1996-08-13 Texaco Inc. Method of preparing manganese oxide octahedral molecular sieve
US5616817A (en) 1994-11-26 1997-04-01 Basf Aktiengesellschaft Preparation of 1,2-propanediol
US6291725B1 (en) 2000-03-03 2001-09-18 Board Of Trustees Operating Michigan State University Catalysts and process for hydrogenolysis of sugar alcohols to polyols
WO2006019560A2 (en) 2004-07-20 2006-02-23 Fuelcell Energy, Inc. Oms-2 catalysts in pem fuel cell applications
EP1836147A1 (en) 2005-07-15 2007-09-26 Davy Process Technology Limited Vapour phase hydrogenation of glycerol
WO2007099161A1 (en) 2006-03-03 2007-09-07 Basf Se Process for the preparation of 1,2-propanediol
WO2009005536A2 (en) 2006-11-22 2009-01-08 3M Innovative Properties Company Methods of capturing bacterial whole cells and methods of analyzing samples for bacteria

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103298773B (en) * 2011-01-13 2015-12-23 捷恩智株式会社 The method of glycol is manufactured by polyvalent alcohol
KR101877082B1 (en) * 2011-01-13 2018-07-10 제이엔씨 주식회사 Method for producing glycol from polyhydric alcohol
WO2012096323A1 (en) * 2011-01-13 2012-07-19 Jnc株式会社 Method for producing glycol from polyhydric alcohol
JP2012144492A (en) * 2011-01-13 2012-08-02 Jnc Corp Method for producing hydroxy ketone from multihydric alcohol
US8921616B2 (en) * 2011-01-13 2014-12-30 Clariant Catalysts (Japan) K.K. Method for producing glycol from polyhydric alcohol
CN103298773A (en) * 2011-01-13 2013-09-11 捷恩智株式会社 Method for producing glycol from polyhydric alcohol
US20130338405A1 (en) * 2011-01-13 2013-12-19 Tetsuro Kizaki Method for producing glycol from polyhydric alcohol
TWI494295B (en) * 2011-01-13 2015-08-01 捷恩智股份有限公司 Method of preparing glycol from polyalcohol
JP2012144491A (en) * 2011-01-13 2012-08-02 Jnc Corp Method for producing glycol from multihydric alcohol
WO2012096324A1 (en) * 2011-01-13 2012-07-19 Jnc株式会社 Method for producing hydroxy ketone from polyhydric alcohol
CN102633599A (en) * 2012-04-20 2012-08-15 江苏联东化工股份有限公司 Hydrogenation method of 1,2-propylene glycol by bio-based glycerol
US9447011B2 (en) 2012-11-21 2016-09-20 University Of Tennessee Research Foundation Methods, systems and devices for simultaneous production of lactic acid and propylene glycol from glycerol
CN105050711A (en) * 2013-03-14 2015-11-11 庄信万丰股份有限公司 Cerium-modified manganese octahedral molecular sieves as catalysts for selective catalytic reduction
GB2532133B (en) * 2013-03-14 2018-12-26 Johnson Matthey Plc A system for treating exhaust gas generated by a combustion process comprising cerium-modified manganese OMS as catalysts for selective catalytic reduction
GB2532133A (en) * 2013-03-14 2016-05-11 Johnson Matthey Plc Cerium-modified manganese octahedral molecular sieves as catalysts for selective catalytic reduction
CN105050711B (en) * 2013-03-14 2018-03-30 庄信万丰股份有限公司 Cerium modified manganese octahedron molecular screen as the catalyst for SCR
WO2014141198A1 (en) * 2013-03-14 2014-09-18 Johnson Matthey Public Limited Company Cerium-modified manganese octahedral molecular sieves as catalysts for selective catalytic reduction
CN104086369A (en) * 2014-06-18 2014-10-08 华南理工大学 Method for preparing lower alcohols from cassava dreg through hydrogenolysis
CN111036284A (en) * 2018-10-15 2020-04-21 中国石油化工股份有限公司 Catalyst, preparation method thereof and method for preparing low-carbon olefin from synthesis gas
CN111036287A (en) * 2018-10-15 2020-04-21 中国石油化工股份有限公司 Supported catalyst, preparation method thereof and glycerol hydrogenation method
CN111036277A (en) * 2018-10-15 2020-04-21 中国石油化工股份有限公司 Supported catalyst, preparation method thereof and glycerol hydrogenation method
CN111036284B (en) * 2018-10-15 2023-05-05 中国石油化工股份有限公司 Catalyst, preparation method thereof and method for preparing light olefins from synthesis gas
CN112791723A (en) * 2019-10-28 2021-05-14 中国石油化工股份有限公司 Supported catalyst and preparation method and application thereof
CN112723990A (en) * 2019-10-28 2021-04-30 中国石油化工股份有限公司 System and method for preparing 1, 2-propylene glycol from glycerol
CN112791737A (en) * 2019-10-28 2021-05-14 中国石油化工股份有限公司 Supported catalyst, preparation method and application
CN112791721A (en) * 2019-10-28 2021-05-14 中国石油化工股份有限公司 Supported catalyst precursor, supported catalyst, preparation method and activation method
CN112723991A (en) * 2019-10-28 2021-04-30 中国石油化工股份有限公司 System and method for preparing 1, 2-propylene glycol from glycerol
CN112794790A (en) * 2019-10-28 2021-05-14 中国石油化工股份有限公司 System and method for preparing 1, 2-propylene glycol from glycerol
CN112717968B (en) * 2019-10-28 2022-09-27 中国石油化工股份有限公司 System and method for preparing 1, 2-propylene glycol from glycerol
CN112791721B (en) * 2019-10-28 2023-02-17 中国石油化工股份有限公司 Supported catalyst precursor, supported catalyst, preparation method and activation method
CN112791737B (en) * 2019-10-28 2023-04-07 中国石油化工股份有限公司 Supported catalyst, preparation method and application
CN112717968A (en) * 2019-10-28 2021-04-30 中国石油化工股份有限公司 System and method for preparing 1, 2-propylene glycol from glycerol
CN113264568A (en) * 2021-06-01 2021-08-17 中国科学院新疆生态与地理研究所 Method for degrading quinolone antibiotics in wastewater by using visible light catalyst
CN115155579A (en) * 2022-07-23 2022-10-11 重庆科技学院 Reductive noble metal loaded manganese oxide catalyst for catalytic combustion of multi-component organic waste gas and preparation method thereof

Also Published As

Publication number Publication date
WO2010150278A3 (en) 2011-07-21

Similar Documents

Publication Publication Date Title
WO2010150278A2 (en) Hydrogenolysis of polyhydroxy alcohols using metal incorporated manganese oxide octahedral molecular sieve as a catalyst
Zhao et al. Hydrogenolysis of glycerol to 1, 2-propanediol over Cu-based catalysts: A short review
Esteves et al. Effect of support on selective 5-hydroxymethylfurfural hydrogenation towards 2, 5-dimethylfuran over copper catalysts
Talebian-Kiakalaieh et al. Oxidation of bio-renewable glycerol to value-added chemicals through catalytic and electro-chemical processes
Molleti et al. Novel synthesis of Ru/OMS catalyst by solvent-free method: Selective hydrogenation of levulinic acid to γ-valerolactone in aqueous medium and kinetic modelling
Mane et al. Simultaneous glycerol dehydration and in situ hydrogenolysis over Cu–Al oxide under an inert atmosphere
KR101650966B1 (en) Direct and selective production of ethanol from acetic acid utilizing a platinum/tin catalyst
Jiang et al. Catalytic performance of Pd–Ni bimetallic catalyst for glycerol hydrogenolysis
Gumina et al. Hydrogenolysis of sorbitol into valuable C3-C2 alcohols at low H2 pressure promoted by the heterogeneous Pd/Fe3O4 catalyst
KR101437072B1 (en) Catalyst for efficient co2 conversion and method for preparing thereof
Wang et al. Supported Ru nanocatalyst over phosphotungstate intercalated Zn-Al layered double hydroxide derived mixed metal oxides for efficient hydrodeoxygenation of guaiacol
Miao et al. Mn-promoted hydrogenation of microalgae (Chlorococcum sp.) to 1, 2-propanediol and ethylene glycol over Ni-ZnO catalysts
Sayas et al. Sustainable production of hydrogen via steam reforming of furfural (SRF) with Co-catalyst supported on sepiolite
Ribeiro et al. Paving the way towards an eco-and budget-friendly one-pot catalytic conversion of cellulose and lignocellulosic residues into ethylene glycol over Ni–W/CNT catalysts
Hernández-Soto et al. Valorization of alcoholic wastes from the vinery industry to produce H2
Kannapu et al. Simultaneous synthesis of aniline and γ-butyrolactone from nitrobenzene and 1, 4-butanediol over Cu-CoOx-MgO catalyst via catalytic hydrogen transfer process: Effect of calcination temperature
Du et al. Xylitol Production from Xylose by Catalytic Hydrogenation over an Efficient Cu–Ni/SiO2 Bimetallic Catalyst
EP2565175A1 (en) Catalytic process for the production of 1,2-propanediol from crude glycerol stream
Ochoa et al. Gas-phase oxidation of alcohols: Innovation in industrial technologies and recent developments
JP3885139B2 (en) Ethanol steam reforming catalyst, method for producing the same, and method for producing hydrogen
CN114345353B (en) For CO 2 Low-temperature copper-based core-shell catalyst for preparing methanol by hydrogenation and preparation method thereof
CN108970604B (en) Molybdenum vanadium niobium-based composite oxide and synthesis method and application thereof
US20060199981A1 (en) Catalyst
Liang et al. Synergistic bimetallic CeNi/SiO2 for boosting the catalytic activity of levulinic acid hydrogenation in gas phase
Gahtori et al. Advances in Direct Thermocatalytic CO 2 Conversion to Chemicals and Hydrocarbons

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: 10778732

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10778732

Country of ref document: EP

Kind code of ref document: A2