WO2014157315A1 - Procédé de fabrication d'acide lactique - Google Patents

Procédé de fabrication d'acide lactique Download PDF

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WO2014157315A1
WO2014157315A1 PCT/JP2014/058487 JP2014058487W WO2014157315A1 WO 2014157315 A1 WO2014157315 A1 WO 2014157315A1 JP 2014058487 W JP2014058487 W JP 2014058487W WO 2014157315 A1 WO2014157315 A1 WO 2014157315A1
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lactic acid
reaction
glycerin
selectivity
catalyst
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PCT/JP2014/058487
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Japanese (ja)
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岸田　央範
治行 内谷
武彦 守谷
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日立造船株式会社
東北電力株式会社
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Publication of WO2014157315A1 publication Critical patent/WO2014157315A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides

Definitions

  • the present invention relates to a method for producing lactic acid as a raw material for polylactic acid using glycerin as a raw material.
  • Biodiesel fuel is a fatty acid ester obtained by transesterification of vegetable oil and alcohol and can be used as an alternative fuel for petroleum-based diesel fuel.
  • biodiesel fuel is derived from plants, it is considered to be a carbon neutral fuel and has attracted attention.
  • Bioplastics are plastics made from plants, not petroleum, and are attracting attention as carbon neutral.
  • Patent Document 1 reports a method for converting glycerin to lactic acid. According to Patent Document 1, it is described that glycerin can be converted into lactic acid by reacting with strong alkaline substance such as sodium hydroxide in high-temperature and high-pressure water. According to this method, lactic acid can be obtained in the form of an aqueous sodium lactate solution.
  • International Publication No. 07/001043 Pamphlet
  • the lactic acid produced by the above method contains organic acids such as formic acid and acetic acid and alcohols such as methanol and ethylene glycol as impurities. Therefore, in order to obtain lactic acid as a target product, it is necessary to go through a more complicated purification process, and there is a problem that the yield is low due to the high impurity content.
  • Patent Document 1 In order to produce lactic acid by the method described in WO07 / 001043 (Patent Document 1), it is necessary to carry out the reaction under high temperature and high pressure conditions of 280 to 350 ° C. and 7 to 15 MPa. Reaction conditions are thought to be related to increased impurity production.
  • the present invention has been made in view of such circumstances, and the content of impurities is small (preferably, the impurity selectivity is 40% or less), thereby requiring a complicated purification step. Furthermore, another object of the present invention is to provide a method capable of obtaining lactic acid as a target product from glycerin at a high yield of 30% or more from glycerin under conventional reaction conditions at a lower temperature / lower pressure. .
  • the present inventors have achieved the above object by hydrothermal reaction of glycerin with an alkaline substance if a catalyst containing a specific active element is used. The present inventors have found that this can be done and have completed the present invention.
  • the present invention relates to a method for producing lactic acid, characterized in that glycerin is hydrothermally reacted using glycerin as a raw material in the presence of a catalyst containing a specific active element and under alkaline conditions.
  • glycerin used as a raw material for lactic acid may be derived from any source. Examples include glycerin that is produced. If glycerin derived from such a source is used as a raw material, it is expected to promote not only biodiesel fuel but also the spread of bioplastics and contribute to the formation of a recycling society.
  • the catalyst used in the present invention may be in any form as long as it has a catalytic action under the conditions defined by the present invention.
  • a catalyst composed of a single element of a specific active element or Examples include a catalyst in which a specific active element is supported on an inert carrier such as alumina, silica, or carbon, or a catalyst in which an active element is dissolved in water as ions.
  • the specific active element used in the present invention may be mixed with other metal elements to be in an alloy state, or chemically bonded to oxygen, sulfuric acid, etc. It may be in a compound state and is not particularly limited.
  • the specific active element belongs to any of an iron group element, a noble metal element, a platinum group element, and a base metal element.
  • the iron group element include Fe, Ni, and Co.
  • the noble metal element include Cu, Ag, Au, and platinum group elements include Ru, Rh, Pd, Os, Ir, and Pt.
  • Base metal elements include Zn, Cd, Hg, Al, Ga, In, Tl, Sn, and Pb. Bi. These active elements may exist as a single species, or may exist as a combination of these plural types.
  • examples of the alkaline substance used for the alkaline condition include hydroxides of alkali metal elements and alkaline earth metal elements.
  • the form for carrying out the method of the present invention may be any of a continuous type, a batch type, and a semibatch type, and is not particularly limited.
  • the catalyst may be charged into the reactor together with the raw materials.
  • the catalyst may be charged in advance in the reaction apparatus, or the catalyst may be continuously supplied together with the raw materials to the reaction apparatus.
  • the catalyst may be in any form such as a fixed bed, a fluidized bed, and a suspended bed.
  • the amount of the catalyst used may be appropriately determined according to the type of catalyst, reaction conditions, and the like.
  • the reaction time is not particularly limited and varies depending on the set conditions. Usually, the reaction time or residence time is about 0.1 to 10 hours, preferably about 0.5 to 5 hours. If the amount of the catalyst used is increased, the reaction time can be shortened.
  • the method according to the present invention is carried out under hydrothermal conditions, but more detailed conditions such as reaction temperature and reaction pressure at that time may be appropriately determined according to the type and amount of catalyst used.
  • the reaction temperature can be usually suppressed to about 200 to 260 ° C.
  • the reaction pressure may be set to a pressure equal to or higher than the saturated vapor pressure of water with respect to the reaction temperature so that all water in the reactor does not evaporate and disappear. Usually, it is about 1.6 to 5.0 MPa. The reaction can proceed efficiently even in such a temperature and pressure range.
  • Patent Document 1 In order to produce lactic acid by the method described in WO2007 / 001043 (Patent Document 1), high temperature and high pressure reaction conditions of 280 to 350 ° C. and 7 to 15 MPa are required. Was necessary.
  • the reaction is carried out in the presence of a catalyst containing a specific active element, so that the target product is obtained in a higher yield under lower temperature / low pressure reaction conditions than in the past. Lactic acid can be obtained.
  • the molar ratio of the reaction solvent water to glycerin is usually about 1 to 50 (water / glycerin; mol / mol), preferably about 2 to 40, more preferably about 3 to 30.
  • Patent Document 1 When lactic acid is produced by the method described in WO2007 / 001043 (Patent Document 1), since the reaction requires high alkaline reaction conditions, an expensive corrosion-resistant material is required for the reactor. there were.
  • the molar ratio of the alkaline substance to glycerin is usually about 0.2 to 20 (alkaline substance / glycerin; mol / mol), preferably about 0.5 to 10, more preferably 1.0 to It may be about 5. Thus, it can be set as a lower alkaline reaction condition compared with the conventional method.
  • the lactic acid obtained can be obtained as an aqueous lactate solution with these metal elements.
  • lactic acid can be obtained even if the reaction is carried out under hydrothermal conditions using a catalyst containing any active element, but the optimum reaction for producing lactic acid from glycerin by the catalyst used. Conditions are different. By selecting optimal reaction conditions, lactic acid can be more efficiently produced from glycerin.
  • the lactic acid thus obtained has a low content of impurities consisting of organic acids such as formic acid and acetic acid and alcohols such as methanol and ethanol, and has a high yield. Furthermore, lactic acid can be produced from glycerin under relatively low temperature and low pressure reaction conditions as compared with the case where a catalyst comprising an active element is not used. Therefore, according to the present invention, lactic acid can be produced from glycerin under a low temperature / low pressure reaction condition with a low impurity content.
  • glycerol is used as a raw material, and in the presence of a catalyst containing any one or more of active elements belonging to any of iron group elements, noble metal elements, platinum group elements and base metal elements, and alkaline
  • the glycerin is hydrothermally reacted under the conditions of Thereby, lactic acid can be obtained from glycerin with high yield.
  • the lactic acid obtained by the present invention has a low content of impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, and propylene glycol. Therefore, the energy burden in the lactic acid purification process can be reduced.
  • lactic acid can be obtained from glycerin at low cost.
  • reaction temperature of about 200 to 260 ° C.
  • reaction solvent water to glycerol molar ratio of 3 to 30 water / glycerol; mol / mol
  • alkaline substance to glycerol molar ratio of 1.0 to 5
  • High-temperature and high-pressure reactions require a reaction vessel with high strength, large wall thickness, and high corrosion resistance, but by lowering the reaction temperature and reaction pressure, the strength is weaker than before and the wall thickness is low.
  • a reaction vessel that is small and has low corrosion resistance can be used, and the initial cost of the reactor can be greatly reduced.
  • FIG. 1 is a diagram showing an example of the configuration of a reaction apparatus for carrying out the method for producing lactic acid according to the present invention.
  • the reactor used in the examples of the present invention has a high-pressure reactor (1), and its volume is 300 mL.
  • the high-pressure reactor (1) is charged with a reaction solution and a catalyst, and after these are charged, it is sealed and can withstand high pressure due to heating.
  • a stirrer (3) is installed so that the reaction liquid in the reactor can be stirred, and a thermometer for measuring the temperature in the reactor (1) ( 4) and a pressure gauge (5) for measuring the pressure in the reactor (1).
  • a heater (2) for heating the high pressure reactor (1) is provided around the high pressure reactor (1).
  • reaction product in the reaction solution after the reaction in the reaction apparatus was quantitatively analyzed by liquid chromatography.
  • A Weight of charged glycerin
  • B Residual weight of glycerin after reaction
  • C Weight of produced lactic acid
  • D Total weight of produced impurities.
  • the conversion of glycerin was 12.1%
  • the lactic acid selectivity was 61.2%
  • the lactic acid yield was 7.4%
  • the impurity selectivity of the impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like was 38.8%.
  • the conversion rate of glycerin was 24.3%
  • the lactic acid selectivity was 54.8%
  • the lactic acid yield was 13.3%
  • the impurity selectivity was 45.2%.
  • Comparative Example 3 No catalyst
  • the reaction was carried out under the same conditions as in Comparative Example 1 except that the amount of glycerin charged was reduced to 23.0 g (0.25 mol), sodium hydroxide 20 g (0.5 mol), and the reaction temperature was increased to 280 ° C. went.
  • the conversion of glycerin was 69.6%
  • the lactic acid selectivity was 51.5%
  • the lactic acid yield was 35.8%
  • the impurity selectivity was 48.5%.
  • Comparative Example 4 No catalyst
  • the reaction was carried out under the same conditions as in Comparative Example 1, except that the amount of glycerin charged was reduced to 23.0 g (0.25 mol), sodium hydroxide 20 g (0.5 mol), and the reaction temperature was raised to 300 ° C. went.
  • the conversion of glycerol was 90.7%
  • the lactic acid selectivity was 49.4%
  • the lactic acid yield was 44.8%
  • the impurity selectivity was 50.6%.
  • Titanium (IV) oxide was used as a catalyst to confirm the effect of elements inert to this reaction.
  • a commercially available reagent manufactured by Kishida Chemical Co., TiO 2 powder, special grade, purity 99.5% was used for titanium oxide (IV).
  • a high pressure reactor (1) was charged with 46.0 g (0.5 mol) of glycerin, 30 g (0.75 mol) of sodium hydroxide, 90 g (5.0 mol) of water, and 25 g of the catalyst and sealed. The reaction was conducted by heating to 240 ° C. with stirring and maintaining the saturated vapor pressure under the reaction conditions for 5 hours. Then, it was cooled and opened, and the reaction product was analyzed by liquid chromatography.
  • the conversion rate of glycerin was 10.1%
  • the lactic acid selectivity was 47.6%
  • the lactic acid yield was 4.8%.
  • the impurity selectivity of the impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like was 52.4%.
  • the conversion of glycerin was 15.2%
  • the lactic acid selectivity was 39.3%
  • the lactic acid yield was 6.0%
  • the impurity selectivity combining impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like was 60.7%.
  • the conversion rate of glycerin was 11.8%
  • the lactic acid selectivity was 41.8%
  • the lactic acid yield was 4.9%.
  • the impurity selectivity of the impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like was 58.2%.
  • Example 1 Iron group compound NiO
  • nickel (II) oxide was used as a catalyst.
  • a commercially available reagent manufactured by Kishida Chemical Co., NiO, chemical, powder, purity 98%) was used for nickel oxide (II).
  • a high pressure reactor (1) was charged with 46.0 g (0.5 mol) of glycerin, 20 g (0.5 mol) of sodium hydroxide, 90 g (5.0 mol) of water, and 25 g of the catalyst and sealed. The reaction was conducted by heating to 200 ° C. with stirring and maintaining the saturated vapor pressure under the reaction conditions for 5 hours. Then, it was cooled and opened, and the reaction product was analyzed by liquid chromatography.
  • the conversion of glycerol was 81.7%
  • the lactic acid selectivity was 73.8%
  • the lactic acid yield was 60.3%
  • the impurity selectivity combining impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like was 26.2%.
  • Example 2 Iron group compound NiO
  • the conversion of glycerol was 86.2%
  • the lactic acid selectivity was 64.0%
  • the lactic acid yield was 55.2%
  • the impurity selectivity was 36.0%.
  • Example 3 Iron group compound NiO
  • the conversion of glycerin was 93.1%
  • the lactic acid selectivity was 68.3%
  • the lactic acid yield was 63.6%
  • the impurity selectivity was 31.7%.
  • Example 4 Iron group compound NiO
  • the reaction was performed under the same conditions as in Example 1 except that the amount of glycerin charged was lowered to 23.0 g (0.25 mol) and the reaction temperature was raised to 240 ° C.
  • the conversion of glycerin was 98.4%
  • the lactic acid selectivity was 76.0%
  • the lactic acid yield was 74.8%
  • the impurity selectivity was 24.0%.
  • Example 5 Iron group Ni
  • the reaction was carried out by replacing the catalyst with nickel.
  • a commercially available reagent Korean Chemical Co., Ni powder, special grade, 75 ⁇ m, purity 99.9%
  • a high pressure reactor (1) was charged with 46.0 g (0.5 mol) of glycerin, 20 g (0.5 mol) of sodium hydroxide, 90 g (5.0 mol) of water, and 25 g of the catalyst and sealed. The reaction was conducted by heating to 240 ° C. with stirring and maintaining the saturated vapor pressure under the reaction conditions for 5 hours. Then, it was cooled and opened, and the reaction product was analyzed by liquid chromatography.
  • the conversion of glycerol was 87.6%
  • the lactic acid selectivity was 67.3%
  • the lactic acid yield was 59.0%.
  • the impurity selectivity combining impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, and propylene glycol was 32.7%.
  • Example 6 Iron Group Compound CoO The reaction was performed under the same conditions as in Example 5 except that the catalyst was changed to cobalt oxide.
  • Cobalt oxide was a commercially available reagent (Kishida Chemical Co., CoO, chemical, 38 ⁇ m, purity 75%).
  • the conversion of glycerin was 74.8%
  • the lactic acid selectivity was 68.5%
  • the lactic acid yield was 51.2%
  • the impurity selectivity was 31.5%.
  • Example 7 Iron group Fe
  • the reaction was performed under the same conditions as in Example 5 except that the catalyst was changed to iron.
  • a commercially available reagent Korean Chemical Co., Fe, powder, special grade, 150 ⁇ m, purity 99.5% was used for iron.
  • the conversion of glycerol was 52.7%
  • the lactic acid selectivity was 65.2%
  • the lactic acid yield was 34.4%
  • the impurity selectivity was 34.8%.
  • Example 8 Iron group compound FeO
  • the reaction was carried out under the same conditions as in Example 5 except that the catalyst was changed to iron (II) oxide.
  • a commercially available reagent manufactured by Kishida Chemical Co., FeO, chemical, powder, purity 60% was used for iron oxide (II).
  • the conversion of glycerin was 66.2%
  • the lactic acid selectivity was 60.4%
  • the lactic acid yield was 40.0%
  • the impurity selectivity was 39.6%.
  • the glycerol conversion was as high as about 50 to 95%
  • the lactic acid selectivity was as high as 60 to 75%
  • the lactic acid yield was as high as 35 to 75%.
  • lactic acid could be produced with a high glycerin conversion rate and a high selectivity despite a low reaction temperature.
  • a high pressure reactor (1) was charged with 46.0 g (0.5 mol) of glycerin, 20 g (0.5 mol) of sodium hydroxide, 90 g (5.0 mol) of water, and 25 g of the catalyst and sealed. The reaction was conducted by heating to 220 ° C. with stirring and maintaining the saturated vapor pressure under the reaction conditions for 5 hours. Then, it was cooled and opened, and the reaction product was analyzed by liquid chromatography.
  • the conversion of glycerin was 51.7%
  • the lactic acid selectivity was 69.4%
  • the lactic acid yield was 35.9%.
  • the impurity selectivity including formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like, which are impurities, was 30.6%.
  • Example 10 noble metal Ag
  • the reaction was performed under the same conditions as in Example 9 except that the amount of glycerin charged was reduced to 23.0 g (0.25 mol).
  • the conversion rate of glycerin was 60.3%
  • lactic acid selectivity was 83.0%
  • lactic acid yield was 50.0%
  • impurity selectivity was 17.0%.
  • Example 11 Noble metal Ag
  • the reaction was performed under the same conditions as in Example 9, except that the amount of sodium hydroxide charged was increased to 40 g (1.0 mol) and the reaction temperature was increased to 240 ° C.
  • the conversion of glycerin was 74.0%
  • the lactic acid selectivity was 86.2%
  • the lactic acid yield was 63.8%
  • the impurity selectivity was 13.8%.
  • Example 12 Noble metal Ag
  • Example 12 The same as Example 9 except that the amount of glycerin charged was reduced to 23.0 g (0.25 mol), the amount of sodium hydroxide charged was increased to 30 g (0.75 mol), and the reaction temperature was increased to 260 ° C. The reaction was conducted under conditions.
  • the conversion of glycerin was 83.5%
  • the lactic acid selectivity was 78.1%
  • the lactic acid yield was 65.2%
  • the impurity selectivity was 21.9%.
  • Example 13 Noble metal compound AgNO 3
  • the reaction was performed by changing the catalyst to silver (I) nitrate.
  • a commercially available reagent manufactured by Kishida Chemical Co., AgNO 3 , special grade, purity 99.8% was used for silver nitrate.
  • a high pressure reactor (1) was charged with 46.0 g (0.5 mol) of glycerin, 40 g (1.0 mol) of sodium hydroxide, 90 g (5.0 mol) of water, and 25 g of the catalyst, and sealed. The reaction was conducted by heating to 260 ° C. with stirring and maintaining the saturated vapor pressure under the reaction conditions for 5 hours. Then, it was cooled and opened, and the reaction product was analyzed by liquid chromatography.
  • the conversion rate of glycerin was 70.0%
  • the lactic acid selectivity was 64.4%
  • the lactic acid yield was 45.1%
  • the impurity selectivity of the impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like was 35.6%.
  • Example 14 Precious metal Cu
  • the reaction was performed under the same conditions as in Example 13 except that the catalyst was changed to copper.
  • a commercially available reagent Korean Chemical Co., Ltd., Cu powder, special grade, 45 ⁇ m, purity 97%) was used for copper.
  • the conversion of glycerin was 63.2%
  • the lactic acid selectivity was 76.9%
  • the lactic acid yield was 48.6%
  • the impurity selectivity was 23.1%.
  • Example 15 Noble metal compound CuO
  • the reaction was carried out under the same conditions as in Example 13 except that the catalyst was changed to copper (II) oxide.
  • a commercially available reagent Karl Fischer Chemical Co., Ltd., CuO, special product, 45 ⁇ m, purity 99% was used for copper (II) oxide.
  • the conversion of glycerin was 79.7%
  • the lactic acid selectivity was 72.1%
  • the lactic acid yield was 57.5%
  • the impurity selectivity was 27.9%.
  • the glycerin conversion was as high as about 50 to 85%
  • the lactic acid selectivity was as high as about 70 to 85%
  • the lactic acid yield was as high as about 35 to 65%.
  • lactic acid could be produced with a high glycerin conversion rate and a high selectivity despite a low reaction temperature.
  • iron group elements a slightly higher reaction temperature is required, but lactic acid selectivity is higher.
  • Example 16 Platinum group Pd / C
  • the reaction was carried out using palladium carbon on which palladium is supported on carbon as a catalyst.
  • a commercially available reagent manufactured by Kishida Chemical Co., Pd / C, palladium content 10% was used for palladium carbon.
  • a high-pressure reactor (1) was charged with 46.0 g (0.5 mol) of glycerin, 90 g (5.0 mol) of sodium hydroxide 20 g (0.5 mol), and 10 g of the catalyst and sealed. The reaction was conducted by heating to 200 ° C. with stirring and maintaining the saturated vapor pressure under the reaction conditions for 5 hours. Then, it was cooled and opened, and the reaction product was analyzed by liquid chromatography.
  • the conversion of glycerin was 78.8%
  • the lactic acid selectivity was 65.2%
  • the lactic acid yield was 51.4%
  • the impurity selectivity combining impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like was 34.8%.
  • Example 17 Platinum group Pd / C
  • the reaction was performed under the same conditions as in Example 16 except that the amount of glycerin charged was reduced to 23.0 g (0.25 mol).
  • Example 18 Platinum group Pd / C
  • the reaction was performed under the same conditions as in Example 16 except that the reaction temperature was raised to 220 ° C.
  • the conversion rate of glycerin was 95.1%
  • the lactic acid selectivity was 69.5%
  • the lactic acid yield was 66.1%
  • the impurity selectivity was 30.5%.
  • Example 19 Platinum group Pd / C
  • the reaction was carried out under the same conditions as in Example 16 except that the amount of glycerin charged was lowered to 23.0 g (0.25 mol) and the reaction temperature was raised to 240 ° C.
  • the conversion of glycerol was 98.6%
  • the lactic acid selectivity was 61.0%
  • the lactic acid yield was 60.1%
  • the impurity selectivity was 39.0%.
  • Example 20 Platinum group Pt / C
  • the reaction was carried out by replacing the catalyst with platinum carbon in which platinum was supported on carbon.
  • a commercially available reagent Karl Fischer Co., Pt / C, for elemental analysis, platinum content 50% was used for platinum carbon.
  • a high-pressure reactor (1) was charged with 46.0 g (0.5 mol) of glycerin, 20 g (0.5 mol) of sodium hydroxide, 90 g (5.0 mol) of water, and 10 g of the catalyst, and sealed. The reaction was conducted by heating to 240 ° C. with stirring and maintaining the saturated vapor pressure under the reaction conditions for 5 hours. Then, it was cooled and opened, and the reaction product was analyzed by liquid chromatography.
  • the conversion of glycerin was 86.9%
  • the lactic acid selectivity was 58.6%
  • the lactic acid yield was 50.9%
  • the impurity selectivity including formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like as impurities was 41.4%.
  • Example 21 Platinum group Ru / C
  • the reaction was performed under the same conditions as in Example 20 except that the catalyst was changed to ruthenium carbon in which ruthenium was supported on carbon.
  • a commercially available reagent Karl Fischer Co., Ru / C, ruthenium content 5% was used for ruthenium carbon.
  • the glycerol conversion was as high as about 80 to 95%
  • the lactic acid selectivity was as high as about 60 to 75%
  • the lactic acid yield was as high as about 50 to 70%.
  • lactic acid could be produced with a high glycerin conversion rate and a high selectivity despite a low reaction temperature.
  • a high glycerin conversion rate can be obtained at a lower reaction temperature, but the lactic acid selectivity was slightly lower.
  • a high pressure reactor (1) was charged with 46.0 g (0.5 mol) of glycerin, 20 g (0.5 mol) of sodium hydroxide, 90 g (5.0 mol) of water, and 25 g of the catalyst and sealed. The reaction was conducted by heating to 200 ° C. with stirring and maintaining the saturated vapor pressure under the reaction conditions for 5 hours. Then, it was cooled and opened, and the reaction product was analyzed by liquid chromatography.
  • the conversion of glycerol was 49.2%
  • the lactic acid selectivity was 82.7%
  • the lactic acid yield was 40.7%
  • the impurity selectivity including formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol, and the like as impurities was 17.3%.
  • Example 23 Base metal ZnO
  • the reaction was performed under the same conditions as in Example 22 except that the amount of glycerin charged was lowered to 23.0 g (0.25 mol) and the reaction temperature was raised to 240 ° C.
  • the conversion of glycerol was 58.4%
  • the lactic acid selectivity was 83.8%
  • the lactic acid yield was 48.9%
  • the impurity selectivity was 16.2%.
  • Example 24 Base metal ZnO
  • the reaction was performed under the same conditions as in Example 22 except that the amount of sodium hydroxide charged was increased to 40.0 g (1.0 mol) and the reaction temperature was increased to 240 ° C.
  • the conversion of glycerin was 74.4%
  • the lactic acid selectivity was 79.1%
  • the lactic acid yield was 58.9%
  • the impurity selectivity was 20.9%.
  • Example 25 Base metal ZnO
  • Example 22 except that the amount of glycerin charged was reduced to 23.0 g (0.25 mol), the amount of sodium hydroxide charged was increased to 30.0 g (0.75 mol), and the reaction temperature was increased to 260 ° C. The experiment was conducted under the same conditions.
  • Example 26 Base metal Zn
  • the reaction was carried out by replacing the catalyst with zinc.
  • a commercially available reagent Korean Chemical Co., Ltd., Zn powder, special grade, purity 90%
  • Zn powder Zn powder, special grade, purity 90%
  • a high pressure reactor (1) was charged with 46.0 g (0.5 mol) of glycerin, 40 g (1.0 mol) of sodium hydroxide, 90 g (5.0 mol) of water, and 25 g of the catalyst, and sealed. The reaction was conducted by heating to 260 ° C. with stirring and maintaining the saturated vapor pressure under the reaction conditions for 5 hours. Then, it was cooled and opened, and the reaction product was analyzed by liquid chromatography.
  • the conversion of glycerin was 74.0%
  • the lactic acid selectivity was 80.6%
  • the lactic acid yield was 59.6%
  • the impurity selectivity combining impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol, etc. was 19.4%.
  • Example 27 Base metal Sn
  • the reaction was performed under the same conditions as in Example 26 except that the catalyst was changed to tin.
  • a commercially available reagent manufactured by Kishida Chemical Co., Ltd., special grade, particle size 75 ⁇ m, purity 99% was used for tin.
  • the conversion of glycerin was 59.5%
  • the lactic acid selectivity was 85.3%
  • the lactic acid yield was 50.8%
  • the impurity selectivity was 14.7%.
  • Example 28 Base metal Pb
  • the reaction was performed under the same conditions as in Example 26 except that the catalyst was changed to lead.
  • a commercially available reagent manufactured by Kishida Chemical Co., Ltd., special grade, particle size 75 ⁇ m, purity 99.5% was used for lead.
  • the conversion of glycerin was 72.1%
  • the lactic acid selectivity was 68.4%
  • the lactic acid yield was 49.3%
  • the impurity selectivity was 31.6%.
  • Example 29 Base metal HgO
  • the reaction was carried out under the same conditions as in Example 26 except that the catalyst was changed to mercury oxide.
  • a commercially available reagent manufactured by Kishida Chemical Co., HgO, grade 1, purity 98%) was used for mercury oxide (II).
  • the conversion of glycerol was 62.2%
  • the lactic acid selectivity was 69.8%
  • the lactic acid yield was 43.4%
  • the impurity selectivity was 30.2%.
  • Example 30 Base metal Bi
  • the reaction was carried out under the same conditions as in Example 26 except that the catalyst was changed to bismuth.
  • a commercially available reagent (Kishida Chemical Co., Bi, powder, purity 99%) was used for bismuth.
  • the conversion of glycerin was 53.9%
  • the lactic acid selectivity was 66.2%
  • the lactic acid yield was 35.7%
  • the impurity selectivity was 33.8%.
  • the glycerol conversion was as high as about 50 to 85%
  • the lactic acid selectivity was as high as 65 to 85%
  • the lactic acid yield was as high as 35 to 60%.
  • lactic acid could be produced with a high glycerin conversion rate and a high selectivity despite a low reaction temperature.
  • FIG. 2 is a graph showing the lactic acid yield obtained by the lactic acid production method of the present invention.
  • FIG. 2 shows that in the temperature range of 200 to 260 ° C. shown in FIG. 2, Examples 1 to 30 that match the above-described method of the present invention can obtain lactic acid with a higher yield than Comparative Examples 1 to 4.

Abstract

L'invention concerne un procédé permettant d'obtenir, à partir de glycérine, un acide lactique désiré ayant un rendement élevé de 30 % ou plus, qui est similaire à celui des procédés classiques, dans des conditions de réaction de température plus basse et de pression plus basse que celles des procédés classiques, le procédé permettant de réduire la quantité d'impuretés incluses (de préférence, la sélectivité pour les impuretés est inférieure ou égale à 40 %), et ne nécessitant donc pas de processus de purification compliqué. Le procédé de fabrication d'acide lactique se caractérise par l'utilisation de glycérine comme matière première et l'induction d'une réaction hydrothermique de la glycérine en conditions alcalines et en présence d'un catalyseur contenant au moins un type d'élément actif appartenant aux éléments de la famille du fer, aux éléments de la famille des métaux nobles, aux éléments de la famille du platine et aux éléments métalliques de base.
PCT/JP2014/058487 2013-03-26 2014-03-26 Procédé de fabrication d'acide lactique WO2014157315A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105541608A (zh) * 2016-03-04 2016-05-04 江苏大学 一种石墨烯负载镍铜双金属催化剂催化转化甘油制取乳酸的方法
CN105601505A (zh) * 2016-03-04 2016-05-25 江苏大学 一种低温高活性石墨烯负载镍催化转化甘油制取乳酸的方法
CN105669422A (zh) * 2016-03-04 2016-06-15 江苏大学 一种纳米镍催化转化甘油制取乳酸的方法
CN106810436A (zh) * 2015-11-30 2017-06-09 中国科学院大连化学物理研究所 一种催化氧化甘油制备乳酸的方法
CN108654667A (zh) * 2018-04-20 2018-10-16 东北电力大学 一种利用NiCu合金负载型催化剂在温和条件下将甘油转化成乳酸的工艺
RU2731184C1 (ru) * 2019-12-27 2020-08-31 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" (ТГУ, НИ ТГУ) Катализатор для жидкофазной конверсии глицерина в молочную кислоту и способ его получения
CN112246281A (zh) * 2020-10-28 2021-01-22 南京工程学院 一种用于甘油制备乳酸的催化剂、制备方法及应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61260039A (ja) * 1985-05-14 1986-11-18 シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ カルボン酸塩の製造方法
JPH04356436A (ja) * 1990-12-05 1992-12-10 Kao Corp カルボニル化合物の製造方法
EP0523014A2 (fr) * 1991-07-10 1993-01-13 NOVAMONT S.p.A. Méthode catalytique d'hydrogénation du glycérol
JP2002524548A (ja) * 1998-09-14 2002-08-06 ダウ・アグロサイエンス・エル・エル・シー カルボン酸の製造法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61260039A (ja) * 1985-05-14 1986-11-18 シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ カルボン酸塩の製造方法
JPH04356436A (ja) * 1990-12-05 1992-12-10 Kao Corp カルボニル化合物の製造方法
EP0523014A2 (fr) * 1991-07-10 1993-01-13 NOVAMONT S.p.A. Méthode catalytique d'hydrogénation du glycérol
JP2002524548A (ja) * 1998-09-14 2002-08-06 ダウ・アグロサイエンス・エル・エル・シー カルボン酸の製造法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106810436A (zh) * 2015-11-30 2017-06-09 中国科学院大连化学物理研究所 一种催化氧化甘油制备乳酸的方法
CN106810436B (zh) * 2015-11-30 2020-06-30 中国科学院大连化学物理研究所 一种催化氧化甘油制备乳酸的方法
CN105541608A (zh) * 2016-03-04 2016-05-04 江苏大学 一种石墨烯负载镍铜双金属催化剂催化转化甘油制取乳酸的方法
CN105601505A (zh) * 2016-03-04 2016-05-25 江苏大学 一种低温高活性石墨烯负载镍催化转化甘油制取乳酸的方法
CN105669422A (zh) * 2016-03-04 2016-06-15 江苏大学 一种纳米镍催化转化甘油制取乳酸的方法
CN108654667A (zh) * 2018-04-20 2018-10-16 东北电力大学 一种利用NiCu合金负载型催化剂在温和条件下将甘油转化成乳酸的工艺
RU2731184C1 (ru) * 2019-12-27 2020-08-31 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" (ТГУ, НИ ТГУ) Катализатор для жидкофазной конверсии глицерина в молочную кислоту и способ его получения
CN112246281A (zh) * 2020-10-28 2021-01-22 南京工程学院 一种用于甘油制备乳酸的催化剂、制备方法及应用

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