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WO2015072871A1 - Catalyseur à base d'hydrotalcite pour l'hydrogénation d'esters d'acide gras - Google Patents

Catalyseur à base d'hydrotalcite pour l'hydrogénation d'esters d'acide gras Download PDF

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Publication number
WO2015072871A1
WO2015072871A1 PCT/RO2013/000022 RO2013000022W WO2015072871A1 WO 2015072871 A1 WO2015072871 A1 WO 2015072871A1 RO 2013000022 W RO2013000022 W RO 2013000022W WO 2015072871 A1 WO2015072871 A1 WO 2015072871A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
hydrogenation
fatty acid
acid esters
hydrotalcite
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/RO2013/000022
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English (en)
Inventor
Augustin Constantin CRUCEAN
Nicoleta TEODORUT
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.)
SC CHIMIGAZ Srl
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SC CHIMIGAZ Srl
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 SC CHIMIGAZ Srl filed Critical SC CHIMIGAZ Srl
Publication of WO2015072871A1 publication Critical patent/WO2015072871A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • 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
    • B01J37/0201—Impregnation
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases

Definitions

  • the present invention is related to a hydrotalcit-based catalyst used for the selective hydrogenation of the fatty acid esters and the process of obtaining thereof.
  • a hydrotalcit-based catalyst used for the selective hydrogenation of the fatty acid esters and the process of obtaining thereof.
  • U.S. Patent 8,426,654 discloses a process for the production of fatty alcohols by the hydrogenation of the ester-type waxes at a temperature ranging from 180°C to 220°C and pressure from 70 bar up to 100 bar, by granulated catalyst in a fixed bed, obtained by extrusion, containing the main component such as copper and copper oxide, secondary components such as chromium and zinc, aluminum, iron, silicon and alkaline-earth elements.
  • the process has the disadvantage related to the use of toxic metals to obtain catalyst such as chromium.
  • Patent CN 101733124 discloses a method for obtaining the fatty alcohols, in a fixed bed continuous flow system, over a catalyst based on copper and zinc as active ingredients, one or more manganese, barium or zirconium metals are used as co-catalysts, and silicon and aluminum are used as structural promoters.
  • the content of active components is 40 to 95% by weight; co-catalysts content is 1-30 wt% and the content of promoter structure is 0.01 to 50% by weight.
  • the catalyst shows high activity and high selectivity to fatty alcohols, long life and the ability to catalyze the hydrogenation reaction at a relatively low pressure.
  • the method has the disadvantage related to the high content in heavy metals.
  • Patent CN 102476056 discloses a catalyst for use in the production of fatty alcohols composed of a mixture of zinc oxide and copper oxide in a content of 18 - 66%, of one or two metals selected from manganese oxide and nickel oxide at a concentration of 0-40%, alumina at a concentration of 5-17%, and 0-45% support which is either diatomite or calcium carbonate.
  • the catalyst shows high activity and also good stability.
  • the method of preparation is simple and shows a high operability and is easily industrialized.
  • the process has the disadvantages related to the use of a high content of heavy metals in the catalyst preparation.
  • U.S. Patent 5,043,485 discloses a process for the production of fatty alcohols by catalytic hydrogenation of mixtures of fatty acid methyl esters at a pressure between 100 to 300 bar, at temperatures ranging from 160 to 270°C and at a molar ratio hydrogen / methyl ester fatty acids from 10: 1 to 500: 1.
  • the reaction is carried out in the presence of a catalyst which contains 30-40 wt% copper, from 23 to 30 wt% chromium, 1-10 wt% manganese, from 1 to 10 wt% silicon and 1 to 7 wt%. barium.
  • the catalyst is granulated with 1 to 10 wt% graphite type binder and activated with hydrogen or a hydrogen-containing gas mixture.
  • This process allows the production of fatty alcohols in high yield from mixtures of methyl esters of fatty acids containing C8 fatty acid residues C22.
  • the method has disadvantages related to the use of the catalyst in getting toxic metals such as chromium.
  • U.S. Patent 5, 124,491 discloses a process for the production of fatty alcohols by catalytic hydrogenation of fatty acid methyl esters, at a pressure of 20 to 100 bar and at temperatures ranging from 160 to 270°C, the molar ratio hydrogen/oil fatty acid methyl esters from 10: 1 to 500: 1.
  • the reaction is carried out on catalysts which contain 30-40% by weight of copper, from 23 to 30 wt%.
  • the method has disadvantages related to the use of the catalyst in getting toxic metals such as chromium.
  • U.S. Patent 5,364,986 discloses a process for the production of C8-C22 fatty alcohols which consists of a catalytic hydrogenation of triglycerides with hydrogen in the presence of a copper-zinc catalyst.
  • the pressure in the reaction zone ranges from about 200 to 280 bar, at a temperature of 200 to 230°C and the reaction zone outlet temperature, from about 190 to about 220°C.
  • the process shows the drawback generally of high pressure hydrogenation.
  • fatty alcohol esters consists in the catalytic hydrogenation of fatty acids, preferably methyl esters of fatty acids.
  • the execution of the process, in continuous fixed bed catalytic system requires the use of a catalyst in granulated form.
  • the commonly used catalysts usually, are hydrogenating the olefin bonds of the unsaturated fatty acid chains also to form saturated fatty alcohols with high melting point therefore they are more difficult to handle.
  • the technical problem to be solved by the invention relates to a catalyst, for the selective hydrogenation of esters of fatty acids to unsaturated fatty alcohols, based on Ru and Sn deposited on granulated hydrotalcite and a process of obtaining thereof.
  • the process of the invention minimises the previously mentioned disadvantages in that the catalyst does not imply the usage of environmentally unfriendly metals such as chromium in the preparation and also the metal content is low. Furthermore the operating pressure is relatively low.
  • the used catalytic support is a hydrotalcite, which is not raising environmental pollution problems in the process of preparation and after depletion catalyst; 3. Method of active metal deposition onto the catalyst proceeds through incipient wetting of the catalyst precursor granular catalyst so that the process does not result in water loaded with heavy metals or toxic byproducts;
  • the proposed hydrogenation catalyst for the hydrogenation of fatty acid esters to fatty alcohols eliminates the mentioned disadvantages in that: it is prepared by sequential impregnation of the support by incipient wetting method based hydrotalcite-type Mg- AI-CO3 having a ratio Mg: Al 2: 1, in the presence of granular bentonite, with a Ru concentration of 0.1% to 1.1% and after drying, the Sn at a concentration of 0.2% to2.2% of catalyst support , at a impregnating solution liquid hourly space velocity of 0.2 h "1 to 1.9 h "1 , followed by calcination at 350°C to 500°C, activated by treatment with sodium borohydride in aqueous solution in excess of 5% to 90% reported to the required stoichiometric amount of hydrogen at a temperature of 250°C to 550°C over a period of 3h to 12 h.
  • the Mg-Al-C03 hydrotalcite having a ratio Mg: Al of 2: 1 was prepared by co- precipitation at room temperature of a solution of 250g Mg(N0 3 ) 2 ⁇ 6H 2 0 and 121.95g A1(N0 3 ) 2 dissolved in 1170g double distilled water, by adding a solution containing 88.66g NaOH and 73.52g of Na 2 C0 3 dissolved in 520g of double distilled water at pH 10 and then aged for 3 hours at 60°C, after which it was filtered, washed with distilled water until the pH of the wash water shows the amount of 7, dried at 105°C for 12 hours, calcinated at 460°C for 5 hours, after which it was hydrated with ultra pure water and allowed to stand at room temperature for 12h , then filtered and dried at 105°C for 12 hours
  • Granulation of hydrotalcite was made by mixing in the presence of bentonite in a volume ratio hydrotalcite/bentonite of 6:4 in the presence of distilled water to a proportion of the water / solid of 2:5, and then extruding and drying at 120 0 C for 8 h.
  • Preparation of the 1.4% Sn 0.7% Ru/hydrotalcite catalyst was made by sequential impregnation, followed by drying at 120°C for 4 hours with the aqueous solution of RuCl 3 and SnCl 2 by incipient wetting method at liquid hourly space velocity identical to the impregnation solutions 1.5 h "1 , followed by calcination at 400°C for 8 hours.
  • the concentration of the acidic centers was determined by diethylamine thermodesorpion : i) the strong acid centers of 0.19 meq / g, ii) a medium strength acid centers 0 28 meq / g, iii) the weak acid centers of 0.15 meq / g .
  • the catalyst was activated in two steps: i) the first stage by treatment with 10% aqueous solution of sodium borohydride in a 20% excess of the stoichiometric amount required ii) in phase 2 by hydrogen flow at a temperature of 350°C for a period of 5 hours.

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

Abstract

L'invention concerne un catalyseur de type Ru-Sn/ hydrotalcite pour l'hydrogénation sélective et un procédé d'hydrogénation d'esters d'acide gras en présence du catalyseur préparé. Le catalyseur selon la présente invention est préparé par imprégnation séquentielle au moyen d'un procédé de mouillage naissant de Ru à une concentration de 0,1 % à 1,1 % et de Sn à une concentration de 0,2 % à 2,2 % (par rapport à la masse du support), sur un support de type hydrotalcite de type Mg-Al-CO3 granulaire, suivie par une calcination de 350 °C à 500 °C et une activation par un traitement avec une solution aqueuse de borohydrure de sodium et écoulement d'hydrogène. Le procédé selon l'invention consiste en l'hydrogénation sélective d'esters d'acide gras en alcools gras, par le catalyseur préparé dans un catalyseur à lit fixe à une température de 200 °C à 340 °C, une pression de 10 atm à 150 atm, une vitesse spatiale horaire de liquide (LHSV) d'oléate de méthyle de 0,1 h-1 à 0,8 h-1, un rapport molaire de H2/ oléate de méthyle de 5 à 20.
PCT/RO2013/000022 2013-11-18 2013-11-26 Catalyseur à base d'hydrotalcite pour l'hydrogénation d'esters d'acide gras Ceased WO2015072871A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ROA201300866 2013-11-18
ROA201300866A RO129990A0 (ro) 2013-11-19 2013-11-19 Catalizator de hidrogenare a esterilor acizilor graşi pe bază de hidrotalcit şi procedeu de obţinere a acestuia

Publications (1)

Publication Number Publication Date
WO2015072871A1 true WO2015072871A1 (fr) 2015-05-21

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PCT/RO2013/000022 Ceased WO2015072871A1 (fr) 2013-11-18 2013-11-26 Catalyseur à base d'hydrotalcite pour l'hydrogénation d'esters d'acide gras

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RO (1) RO129990A0 (fr)
WO (1) WO2015072871A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107128984A (zh) * 2017-06-05 2017-09-05 湖州师范学院 一种含亚甲基蓝染料废水耦合加氢脱色处理方法
CN111686812A (zh) * 2019-03-13 2020-09-22 北京大学深圳研究生院 配体活化的过渡金属层状双羟基化合物、制备方法及用途

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MIYAKE, TAKANORI ET AL.: "Alcohol synthesis by hydrogenation of fatty acid methyl esters on supported Ru-Sn and Rh-Sn catalysts.", APPLIED CATALYSIS A: GENERAL, vol. 364, 2009, pages 108 - 112 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107128984A (zh) * 2017-06-05 2017-09-05 湖州师范学院 一种含亚甲基蓝染料废水耦合加氢脱色处理方法
CN107128984B (zh) * 2017-06-05 2020-09-08 湖州师范学院 一种含亚甲基蓝染料废水耦合加氢脱色处理方法
CN111686812A (zh) * 2019-03-13 2020-09-22 北京大学深圳研究生院 配体活化的过渡金属层状双羟基化合物、制备方法及用途

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