WO2014157315A1 - Method of manufacturing lactic acid - Google Patents

Method of manufacturing lactic acid 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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French (fr)
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/en

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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

Provided is a method capable of obtaining, from glycerin, desired lactic acid having a high yield of 30% or greater, which is similar to conventional methods, under reaction conditions at lower temperature and lower pressure than conventional methods, the method reducing the amount of impurities included (preferably the impurity selectivity is 40% or less), and therefore not requiring a complicated purifying process. The lactic acid manufacturing method is characterized in using glycerin as a raw material, and inducing a hydrothermal reaction of the glycerin under alkaline conditions and in the presence of a catalyst containing at least one type of active element belonging to iron family elements, noble metal family elements, platinum family elements, and base metal elements.

Description

乳酸の製造方法Method for producing lactic acid
　本発明は、グリセリンを原料として、ポリ乳酸の原料となる乳酸を製造する方法に関する。 The present invention relates to a method for producing lactic acid as a raw material for polylactic acid using glycerin as a raw material.
　近年、地球温暖化への懸念から、植物油を原料として製造されるバイオディーゼル燃料の生産量がヨーロッパを中心として増加している。バイオディーゼル燃料は植物油脂とアルコールをエステル交換して得られる脂肪酸エステルであり、石油系ディーゼル燃料の代替燃料として使用できる。しかも、バイオディーゼル燃料は植物由来であることから、カーボンニュートラルな燃料であると考えられて注目を集めている。 In recent years, due to concerns about global warming, the production volume of biodiesel fuel produced using vegetable oil as a raw material has been increasing mainly in Europe. 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. Moreover, since biodiesel fuel is derived from plants, it is considered to be a carbon neutral fuel and has attracted attention.
　しかしながら、バイオディーゼル燃料を製造する過程で約１／１０重量のグリセリンが副生成されることから、その有効利用方法が求められている。 However, since about 1/10 weight of glycerin is by-produced in the process of producing biodiesel fuel, an effective utilization method thereof is required.
　近年、グリセリンを効率的に乳酸に転換する方法が報告された。乳酸からは、バイオプラスチックの一種であるポリ乳酸を製造することができる。バイオプラスチックとは、石油ではなく植物を原料として製造されたプラスチックでありカーボンニュートラルとして注目を集めている。 Recently, a method for efficiently converting glycerin to lactic acid has been reported. From lactic acid, polylactic acid, a kind of bioplastic, can be produced. Bioplastics are plastics made from plants, not petroleum, and are attracting attention as carbon neutral.
　特許文献１には、グリセリンを乳酸に転換する方法が報告されている。特許文献１によると、グリセリンを水酸化ナトリウムのような強力なアルカリ性の物質と共に高温高圧の水中で反応させることによって乳酸に転換できることが記されている。この方法によると、乳酸は乳酸ナトリウム水溶液の状態で得ることができる。
国際公開第０７／００１０４３号パンフレット 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
　上記の方法によって製造された乳酸には、不純物としてギ酸、酢酸などの有機酸類およびメタノール、エチレングリコールなどのアルコール類が含まれている。そのため、目的物である乳酸を得るためにはさらに煩雑な精製工程を経る必要があり、また、不純物含有量が高いことに起因して収率が低いという問題があった。 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.
　WO07/001043号（特許文献１）に記載された方法により乳酸を製造するためには、２８０～３５０℃、７～１５ＭＰａという高温かつ高圧の条件下に反応を行う必要があり、このような苛酷な反応条件が不純物生成の増加に関連していると考えられる。 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.
　また、上記のような反応条件で乳酸を製造するため、それに耐える高強度の耐圧性反応容器が必要であった。 Moreover, in order to produce lactic acid under the reaction conditions as described above, a high-strength pressure-resistant reaction vessel that can withstand it was necessary.
　本発明は、このような事情に鑑みてなされたものであり、不純物の含有量が少なく（好ましくは、不純物選択率が４０％以下）、かつ、それにより煩雑な精製工程を必要とすることがなく、さらに、従来よりも低温度／低圧力の反応条件下において、グリセリンから従来と同様３０％以上の高収率で目的物である乳酸を得ることができる方法を提供することを目的とする。 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. .
　本発明者らは、かかる従来技術の問題を解決するために鋭意研究を重ねた結果、特定の活性元素を含む触媒を使えば、グリセリンをアルカリ性の物質と共に水熱反応させることによって上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the problems of the prior art, 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.
　すなわち、本発明は、グリセリンを原料とし、特定の活性元素を含む触媒の存在下、かつ、アルカリ性の条件下でグリセリンを水熱反応させることを特徴とする乳酸の製造方法に関するものである。 That is, 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.
　本発明において、乳酸の原料となるグリセリンは、いかなる由来のものであってもよいが、例えば、動物または植物の油脂のアルコールによるエステル交換によりバイオディーゼル燃料である脂肪酸エステルを得る際に副生物として生成してくるグリセリンが挙げられる。このような由来のグリセリンを原料とすれば、バイオディーゼル燃料だけでなくバイオプラスチックの普及も促進し、循環型社会の形成に貢献することが期待される。 In the present invention, 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.
　本発明において用いられる触媒は、本発明により規定される条件下に触媒作用を有していれば、いかなる形態のものであってもよいが、例えば、特定の活性元素の単体からなる触媒、あるいは特定の活性元素がアルミナやシリカや炭素などの不活性な担体に担持された触媒、あるいは活性元素がイオンとして水中に溶解した触媒などが挙げられる。 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. For example, 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.
　また、本発明において用いられる特定の活性元素は、他の金属元素と混合して合金状態になっていても良いし、あるいは酸素や硫酸などと化学的に結合し酸化物や硫酸化物のような化合物状態となっていても良く特に限定されるものではない。 Further, 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.
　特定の活性元素は、鉄族元素、貴金属元素、白金族元素および卑金属元素のいずれかに属するものであり、鉄族元素としては、Ｆｅ、Ｎｉ、Ｃｏが挙げられ、貴金属元素としては、Ｃｕ、Ａｇ、Ａｕが挙げられ、白金族元素としては、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ、Ｐｔが挙げられ、卑金属元素としては、Ｚｎ、Ｃｄ、Ｈｇ、Ａｌ、Ｇａ、Ｉｎ、Ｔｌ、Ｓｎ、Ｐｂ、Ｂｉが挙げられる。これらの活性元素は、単独種として存在していてもよいし、あるいは、これらの複数種を組み合わせたものとして存在していてもよい。 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. Examples of the iron group element include Fe, Ni, and Co. Examples of 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.
　上記本発明において、アルカリ性の条件にするために用いられるアルカリ性物質としては、アルカリ金属元素、アルカリ土類金属元素の水酸化物が挙げられる。 In the present invention, examples of the alkaline substance used for the alkaline condition include hydroxides of alkali metal elements and alkaline earth metal elements.
　上記本発明の方法を実施するための形態としては、連続式、回分式、半回分式のいずれであっても良く、特に限定されるものではない。回分式を採用して本発明を実施する場合には、触媒は、原料と共に一括して反応装置に仕込めば良い。また、連続式を採用して本発明を実施する場合には、反応装置に予め触媒を充填しておくか、あるいは反応装置に原料と共に触媒を連続的に供給すれば良い。触媒は、固定床、流動床、懸濁床などのいずれの形態であっても良い。 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. In the case of carrying out the present invention using a batch system, the catalyst may be charged into the reactor together with the raw materials. Further, when the present invention is carried out by adopting a continuous system, 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.
　上記触媒の使用量は、触媒の種類、反応条件などに応じて適宜決定すれば良い。 The amount of the catalyst used may be appropriately determined according to the type of catalyst, reaction conditions, and the like.
　反応時間は特に限定されるものではなく、設定した条件により異なるが、通常は反応時間または滞留時間は０．１～１０時間、好ましくは０．５～５時間程度とすれば良い。触媒の使用量を多くすれば、反応時間を短くすることができる。 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.
　本発明による方法は、水熱条件下に行われるものであるが、その際の反応温度や反応圧力などのより詳細な諸条件は、触媒の種類や使用量に応じて適宜決定すれば良い。触媒の使用により、反応温度を通常２００～２６０℃程度に抑えることができる。反応圧力は、反応器内の水が全て蒸発して無くならないように、反応温度に対する水の飽和蒸気圧以上の圧力とすれば良い。通常は１．６～５．０ＭＰａ程度である。このような温度、圧力範囲においても効率的に反応を進行させることができる。 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. By using a catalyst, 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.
　WO2007/001043（特許文献１）に記載された方法により乳酸を製造するためには、２８０～３５０℃、７～１５ＭＰａという高温かつ高圧の反応条件が要求されるため、高強度の耐圧性反応容器が必要であった。 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.
　これに対して、本発明の方法では、特定の活性元素を含む触媒の存在下に反応を行っているので、従来よりも低温度／低圧力の反応条件下に高収率で目的物である乳酸を得ることができる。 On the other hand, in the method of the present invention, 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.
　反応溶媒である水とグリセリンのモル比は通常１～５０（水／グリセリン；ｍｏｌ／ｍｏｌ）程度であり、好ましくは２～４０程度であり、より好ましくは３～３０程度とすれば良い。 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.
　WO2007/001043（特許文献１）に記載された方法により乳酸を製造する場合、その反応には高いアルカリ性の反応条件が要求されるため、反応器には、高価な耐腐食性の材質が必要であった。 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.
　本発明では、アルカリ性物質とグリセリンのモル比は通常０．２～２０（アルカリ性物質／グリセリン；ｍｏｌ／ｍｏｌ）程度であり、好ましくは０．５～１０程度であり、より好ましくは１．０～５程度とすればよい。このように従来の方法に比べて、より低いアルカリ性の反応条件とすることができる。 In the present invention, 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.
　得られる乳酸は、これらの金属元素による乳酸塩水溶液として得ることができる。 The lactic acid obtained can be obtained as an aqueous lactate solution with these metal elements.
　本発明の方法は、いずれの活性元素を含む触媒を用いて水熱条件下に反応を行っても乳酸を得ることができるが、使用する触媒によって、グリセリンから乳酸を生成させるための最適な反応条件は異なる。最適な反応条件を選ぶことによって、より効率的にグリセリンから乳酸を生成させることができる。 In the method of the present invention, 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.
　このようにして得られた乳酸は、ギ酸や酢酸などの有機酸類およびメタノールやエタノールなどのアルコール類からなる不純物の含有量が少なく、また、収率も高い。さらに、活性元素からなる触媒を使用しない場合に比べて、比較的低温度かつ低圧力の反応条件でグリセリンから乳酸を製造することができる。したがって、本発明によると、不純物の含有量が少なく、かつ、より低温度／低圧力の反応条件でグリセリンから乳酸を製造することができる。 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.
　本発明の乳酸の製造方法では、グリセリンを原料とし、鉄族元素、貴金属元素、白金族元素および卑金属元素のいずれかに属する活性元素のいずれか１種以上を含む触媒の存在下、かつ、アルカリ性の条件下でグリセリンを水熱反応させる。これにより、高い収率でグリセリンから乳酸を得ることができる。本発明により得られた乳酸には、ギ酸、酢酸、メタノール、エタノール、エチレングリコール、プロピレングリコールなどの不純物の含有量が少ない。従って、乳酸の精製工程におけるエネルギー的な負担を低減させることができる。 In the method for producing lactic acid of the present invention, 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.
　また上記により、本発明の方法によると、低コストでグリセリンから乳酸を得ることができる。 Further, according to the above, according to the method of the present invention, lactic acid can be obtained from glycerin at low cost.
　上記の効果は、本反応に活性な元素を見出したこと、および、各元素に適した反応条件を見出したことによって得られたものである。例えば、ＴｉやＶやＡｓなど本反応に対して不活性な元素も存在する。数多くの実験により、鉄族元素または貴金属元素または白金族元素または卑金属元素に属する元素が本反応に有益な活性を示すことを見出し、更に、Ｆｅ、Ｎｉ、Ｃｏ、Ｃｕ、Ａｇ、Ｒｕ、Ｐｄ、Ｐｔ、Ｚｎ、Ｈｇ、Ｐｂ、Ｓｎ、Ｂｉが本反応に特に有益な活性を示すことを見出した。 The above effect was obtained by finding active elements for this reaction and finding reaction conditions suitable for each element. For example, there are elements that are inert to the reaction, such as Ti, V, and As. Numerous experiments have found that elements belonging to iron group elements, noble metal elements, platinum group elements, or base metal elements exhibit beneficial activity for this reaction, and in addition, Fe, Ni, Co, Cu, Ag, Ru, Pd, It has been found that Pt, Zn, Hg, Pb, Sn, Bi show particularly beneficial activity for this reaction.
　また、数多くの実験により、反応温度２００～２６０℃程度、反応溶媒である水とグリセリンのモル比３～３０（水／グリセリン；ｍｏｌ／ｍｏｌ）、アルカリ性物質とグリセリンのモル比１．０～５（アルカリ性物質／グリセリン；ｍｏｌ／ｍｏｌ）が本反応に特に好ましい反応条件であることを見出した。 Further, through numerous experiments, a reaction temperature of about 200 to 260 ° C., a reaction solvent water to glycerol molar ratio of 3 to 30 (water / glycerol; mol / mol), an alkaline substance to glycerol molar ratio of 1.0 to 5 It has been found that (alkaline substance / glycerin; mol / mol) is a particularly preferable reaction condition for this reaction.
　高温、高圧の反応には、強度が強く、肉厚の大きくかつ耐食性の高い反応容器が必要とされるが、反応温度、反応圧力を低下させることで、従来よりも強度が弱く、肉厚が小さくかつ耐食性の低い反応容器でも良くなり、反応装置のイニシャルコストを大幅に低減することができる。 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.
本発明の乳酸の製造方法を実施するための反応装置の構成の一例を示す図である。It is a figure which shows an example of a structure of the reaction apparatus for enforcing the manufacturing method of lactic acid of this invention. 本発明の乳酸の製造方法によって得られた乳酸収率を示す図である。It is a figure which shows the lactic acid yield obtained by the manufacturing method of lactic acid of this invention.
　以下に実施例を示し、本発明の方法による反応の特徴を一層明確にする。ただし、本発明の方法は、実施例の範囲に限定されるものではない。 Examples are given below to further clarify the characteristics of the reaction by the method of the present invention. However, the method of the present invention is not limited to the scope of the examples.
　（反応装置）
　図１は、本発明の乳酸の製造方法を実施するための反応装置の構成の一例を示す図である。 (Reactor)
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.
　本発明の実施例に使用される反応装置は、高圧反応器（１）を有しており、その容積は３００ｍＬである。この高圧反応器（１）は、その内部に反応液および触媒を仕込み、これらを仕込んだ後に、密閉した状態とし加熱により高圧になっても耐えることができるようになっている。 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.
　高圧反応器（１）内には、反応器内の反応液を攪拌することができるように攪拌機（３）が設置されており、また、反応器（１）内の温度を測定する温度計（４）および反応器（１）内の圧力を測定する圧力計（５）が設けられている。 In the high-pressure reactor (1), 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).
　また、高圧反応器（１）の周囲には、高圧反応器（１）を加熱するためのヒータ（２）が設けられている。 In addition, a heater (2) for heating the high pressure reactor (1) is provided around the high pressure reactor (1).
　（反応生成物の測定）
　上記反応装置における反応後の反応液中の反応生成物は、液体クロマトグラフィーによって定量分析した。 (Measurement of reaction products)
The reaction product in the reaction solution after the reaction in the reaction apparatus was quantitatively analyzed by liquid chromatography.
　（転化率、選択率および収率）
　グリセリン転化率、乳酸選択率、不純物選択率および乳酸収率は、それぞれ次の式に基づいて算出した。 (Conversion, selectivity and yield)
The glycerin conversion, lactic acid selectivity, impurity selectivity, and lactic acid yield were calculated based on the following equations, respectively.
　　グリセリン転化率（％）＝（１－Ｂ／Ａ）×１００
　　乳酸選択率（％）＝（Ｃ／（Ａ－Ｂ））×１００
　　不純物選択率（％）＝（Ｄ／（Ａ－Ｂ））×１００
　　乳酸収率（％）＝（Ｃ／Ａ）×１００
　　（乳酸収率（％）＝グリセリン転化率×乳酸選択率／１００）
式中、
　　　Ａ　＝　仕込みグリセリンの重量
　　　Ｂ　＝　反応後のグリセリンの残存重量
　　　Ｃ　＝　生成した乳酸の重量
　　　Ｄ　＝　生成した不純物の総重量
である。 Glycerin conversion rate (%) = (1−B / A) × 100
Lactic acid selectivity (%) = (C / (AB)) × 100
Impurity selectivity (%) = (D / (AB)) × 100
Lactic acid yield (%) = (C / A) × 100
(Lactic acid yield (%) = glycerin conversion rate × lactic acid selectivity / 100)
Where
A = Weight of charged glycerin B = Residual weight of glycerin after reaction C = Weight of produced lactic acid D = Total weight of produced impurities.
　（無触媒または不活性な元素を使用した場合）
　（比較例１：触媒なし）
　触媒を使用せずに乳酸生成を行った。図１に示す高圧反応器（１）に、グリセリン４６．０ｇ（０．５ｍｏｌ）、水酸化ナトリウム３０ｇ（０．７５ｍｏｌ）、水９０ｇ（５．０ｍｏｌ）を仕込んで密封した。撹拌下で２４０℃に加熱して５時間にわたり本反応条件における飽和蒸気圧力で保持して反応を行った。その後、冷却して開封し、反応生成物を液体クロマトグラフィーで分析した。 (When non-catalytic or inert elements are used)
(Comparative example 1: no catalyst)
Lactic acid production was performed without using a catalyst. The high pressure reactor (1) shown in FIG. 1 was charged with 46.0 g (0.5 mol) of glycerin, 30 g (0.75 mol) of sodium hydroxide and 90 g (5.0 mol) of water 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.
　その結果、グリセリンの転化率は１２．１％で、乳酸選択率は６１．２％、乳酸収率は７．４％であった。一方、不純物であるギ酸、酢酸、メタノール、エタノール、エチレングリコール、プロピレングリコールなどを合わせた不純物選択率は３８．８％であった。 As a result, the conversion of glycerin was 12.1%, the lactic acid selectivity was 61.2%, and the lactic acid yield was 7.4%. On the other hand, the impurity selectivity of the impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like was 38.8%.
　（比較例２：触媒なし）
　反応温度を２６０℃に上げた以外は、比較例１と同じ条件で反応を行った。 (Comparative example 2: no catalyst)
The reaction was performed under the same conditions as in Comparative Example 1 except that the reaction temperature was raised to 260 ° C.
　その結果、グリセリンの転化率は２４．３％で、乳酸選択率は５４．８％、乳酸収率は１３．３％、不純物選択率は４５．２％であった。 As a result, the conversion rate of glycerin was 24.3%, the lactic acid selectivity was 54.8%, the lactic acid yield was 13.3%, and the impurity selectivity was 45.2%.
　（比較例３：触媒なし）
　グリセリンの仕込み量を２３．０ｇ（０．２５ｍｏｌ）に下げて、水酸化ナトリウム２０ｇ（０．５ｍｏｌ）に下げて、反応温度を２８０℃に上げた以外は、比較例１と同じ条件で反応を行った。 (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.
　その結果、グリセリンの転化率は６９．６％で、乳酸選択率は５１．５％、乳酸収率は３５．８％、不純物選択率は４８．５％であった。 As a result, the conversion of glycerin was 69.6%, the lactic acid selectivity was 51.5%, the lactic acid yield was 35.8%, and the impurity selectivity was 48.5%.
　（比較例４：触媒なし）
　グリセリンの仕込み量を２３．０ｇ（０．２５ｍｏｌ）に下げて、水酸化ナトリウム２０ｇ（０．５ｍｏｌ）に下げて、反応温度を３００℃に上げた以外は、比較例１と同じ条件で反応を行った。 (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.
　その結果、グリセリンの転化率は９０．７％で、乳酸選択率は４９．４％、乳酸収率は４４．８％、不純物選択率は５０．６％であった。 As a result, the conversion of glycerol was 90.7%, the lactic acid selectivity was 49.4%, the lactic acid yield was 44.8%, and the impurity selectivity was 50.6%.
　（比較例５：不活性な元素触媒）
　本反応に対して不活性な元素の効果を確かめるため、酸化チタン（IV）を触媒として用いた。酸化チタン（IV）には市販の試薬（キシダ化学社製、ＴｉＯ２粉末、特級、純度９９．５％）を使用した。 (Comparative Example 5: Inactive elemental catalyst)
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).
　高圧反応器（１）に、グリセリン４６．０ｇ（０．５ｍｏｌ）、水酸化ナトリウム３０ｇ（０．７５ｍｏｌ）、水９０ｇ（５．０ｍｏｌ）、および上記触媒２５ｇを仕込んで密封した。撹拌下で２４０℃に加熱して５時間にわたり本反応条件における飽和蒸気圧力で保持して反応を行った。その後、冷却して開封し、反応生成物を液体クロマトグラフィーで分析した。 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.
　その結果、グリセリンの転化率は１０．１％で、乳酸選択率は４７．６％、乳酸収率は４．８％であった。一方、不純物であるギ酸、酢酸、メタノール、エタノール、エチレングリコール、プロピレングリコールなどを合わせた不純物選択率は５２．４％であった。 As a result, the conversion rate of glycerin was 10.1%, the lactic acid selectivity was 47.6%, and the lactic acid yield was 4.8%. On the other hand, the impurity selectivity of the impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like was 52.4%.
　（比較例６：不活性な元素触媒）
　本反応に対して不活性な元素の効果を確かめるため、触媒を酸化バナジウム（V）に替えて反応を行った。酸化バナジウム（V）には市販の試薬（キシダ化学社製、Ｖ２Ｏ５粉末、特級、純度９９％）を使用した。触媒の種類を替えた以外は、比較例５と同じ条件で反応を行った。 (Comparative Example 6: Inactive elemental catalyst)
In order to confirm the effect of the elements inert to this reaction, the reaction was carried out by replacing the catalyst with vanadium oxide (V). A commercially available reagent (Kishida Chemical Co., V 2 O 5 powder, special grade, purity 99%) was used for vanadium oxide (V). The reaction was performed under the same conditions as in Comparative Example 5, except that the type of catalyst was changed.
　その結果、グリセリンの転化率は１５．２％で、乳酸選択率は３９．３％、乳酸収率は６．０％であった。一方、不純物であるギ酸、酢酸、メタノール、エタノール、エチレングリコール、プロピレングリコールなどを合わせた不純物選択率は６０．７％であった。 As a result, the conversion of glycerin was 15.2%, the lactic acid selectivity was 39.3%, and the lactic acid yield was 6.0%. On the other hand, the impurity selectivity combining impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like was 60.7%.
　（比較例７：不活性な元素触媒）
　本反応に対して不活性な元素の効果を確かめるため、触媒を酸化砒素（V）に替えて反応を行った。酸化砒素（V）には市販の試薬（キシダ化学社製、Ａｓ２Ｏ５粉末、化学用、純度９０％）を使用した。触媒の種類を替えた以外は、比較例５と同じ条件で反応を行った。 (Comparative Example 7: Inactive elemental catalyst)
In order to confirm the effect of the elements inert to this reaction, the reaction was carried out by replacing the catalyst with arsenic oxide (V). A commercially available reagent (manufactured by Kishida Chemical Co., As 2 O 5 powder, chemical use, purity 90%) was used for arsenic oxide (V). The reaction was performed under the same conditions as in Comparative Example 5, except that the type of catalyst was changed.
　その結果、グリセリンの転化率は１１．８％で、乳酸選択率は４１．８％、乳酸収率は４．９％であった。一方、不純物であるギ酸、酢酸、メタノール、エタノール、エチレングリコール、プロピレングリコールなどを合わせた不純物選択率は５８．２％であった。 As a result, the conversion rate of glycerin was 11.8%, the lactic acid selectivity was 41.8%, and the lactic acid yield was 4.9%. On the other hand, the impurity selectivity of the impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like was 58.2%.
　（触媒を使用しない場合のまとめ）
　上記の比較例を実施した結果を下記の表１にまとめる。 (Summary when no catalyst is used)
The results of implementing the above comparative examples are summarized in Table 1 below.
　触媒を使用しない場合、高いグリセリン転化率を得るためには２８０～３００℃の反応温度が必要である。２４０～２６０℃の反応温度ではグリセリンはほとんど転化しない。また、不純物が多く生成されるため、乳酸選択率および乳酸収率は低い。 When no catalyst is used, a reaction temperature of 280 to 300 ° C. is necessary to obtain a high glycerol conversion. Glycerol is hardly converted at a reaction temperature of 240 to 260 ° C. Moreover, since many impurities are produced, lactic acid selectivity and lactic acid yield are low.
　また、ＴｉやＶやＡｓのような元素は本反応に対して不活性であることが分かった。これらの元素を触媒として使用しても、グリセリン転化率や乳酸選択率の向上は望めないことが分かった。 It was also found that elements such as Ti, V and As are inactive for this reaction. It has been found that even when these elements are used as catalysts, an improvement in glycerol conversion rate and lactic acid selectivity cannot be expected.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　（鉄族元素の触媒効果）
　（実施例１：鉄族化合物ＮｉＯ）
　鉄属元素化合物の効果を確かめるため、酸化ニッケル（II）を触媒として用いた。酸化ニッケル（II）には市販の試薬（キシダ化学社製、ＮｉＯ、化学用、粉末、純度９８％）を使用した。 (Catalytic effect of iron group elements)
(Example 1: Iron group compound NiO)
In order to confirm the effect of the iron group element compound, 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).
　高圧反応器（１）に、グリセリン４６．０ｇ（０．５ｍｏｌ）、水酸化ナトリウム２０ｇ（０．５ｍｏｌ）、水９０ｇ（５．０ｍｏｌ）、および上記触媒２５ｇを仕込んで密封した。撹拌下で２００℃に加熱して５時間にわたり本反応条件における飽和蒸気圧力で保持して反応を行った。その後、冷却して開封し、反応生成物を液体クロマトグラフィーで分析した。 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.
　その結果、グリセリンの転化率は８１．７％で、乳酸選択率は７３．８％、乳酸収率は６０．３％であった。一方、不純物であるギ酸、酢酸、メタノール、エタノール、エチレングリコール、プロピレングリコールなどを合わせた不純物選択率は２６．２％であった。 As a result, the conversion of glycerol was 81.7%, the lactic acid selectivity was 73.8%, and the lactic acid yield was 60.3%. On the other hand, the impurity selectivity combining impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like was 26.2%.
　（実施例２：鉄族化合物ＮｉＯ）
　グリセリンの仕込み量を２３．０ｇ（０．２５ｍｏｌ）に下げた以外は、実施例１と同じ条件で反応を行った。 (Example 2: Iron group compound NiO)
The reaction was performed under the same conditions as in Example 1 except that the amount of glycerin charged was reduced to 23.0 g (0.25 mol).
　その結果、グリセリンの転化率は８６．２％で、乳酸選択率は６４．０％、乳酸収率は５５．２％、不純物選択率は３６．０％であった。 As a result, the conversion of glycerol was 86.2%, the lactic acid selectivity was 64.0%, the lactic acid yield was 55.2%, and the impurity selectivity was 36.0%.
　（実施例３：鉄族化合物ＮｉＯ）
　反応温度を２２０℃に上げた以外は、実施例１と同じ条件で反応を行った。 (Example 3: Iron group compound NiO)
The reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was raised to 220 ° C.
　その結果、グリセリンの転化率は９３．１％で、乳酸選択率は６８．３％、乳酸収率は６３．６％、不純物選択率は３１．７％であった。 As a result, the conversion of glycerin was 93.1%, the lactic acid selectivity was 68.3%, the lactic acid yield was 63.6%, and the impurity selectivity was 31.7%.
　（実施例４：鉄族化合物ＮｉＯ）
　グリセリンの仕込み量を２３．０ｇ（０．２５ｍｏｌ）に下げて、反応温度を２４０℃に上げた以外は、実施例１と同じ条件で反応を行った。 (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.
　その結果、グリセリンの転化率は９８．４％で、乳酸選択率は７６．０％、乳酸収率は７４．８％、不純物選択率は２４．０％であった。 As a result, the conversion of glycerin was 98.4%, the lactic acid selectivity was 76.0%, the lactic acid yield was 74.8%, and the impurity selectivity was 24.0%.
　（実施例５：鉄族Ｎｉ）
　触媒をニッケルに替えて反応を行った。ニッケルには市販の試薬（キシダ化学社製、Ｎｉ粉末、特級、７５μｍ、純度９９．９％）を使用した。 (Example 5: Iron group Ni)
The reaction was carried out by replacing the catalyst with nickel. A commercially available reagent (Kishida Chemical Co., Ni powder, special grade, 75 μm, purity 99.9%) was used for nickel.
　高圧反応器（１）に、グリセリン４６．０ｇ（０．５ｍｏｌ）、水酸化ナトリウム２０ｇ（０．５ｍｏｌ）、水９０ｇ（５．０ｍｏｌ）、および上記触媒２５ｇを仕込んで密封した。撹拌下で２４０℃に加熱して５時間にわたり本反応条件における飽和蒸気圧力で保持して反応を行った。その後、冷却して開封し、反応生成物を液体クロマトグラフィーで分析した。 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.
　その結果、グリセリンの転化率は８７．６％で、乳酸選択率は６７．３％、乳酸収率は５９．０％であった。一方、不純物であるギ酸、酢酸、メタノール、エタノール、エチレングリコール、プロピレングリコールなどを合わせた不純物選択率は３２．７％であった。 As a result, the conversion of glycerol was 87.6%, the lactic acid selectivity was 67.3%, and the lactic acid yield was 59.0%. On the other hand, the impurity selectivity combining impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, and propylene glycol was 32.7%.
　（実施例６；鉄族化合物ＣｏＯ）
　触媒を酸化コバルトに替えた以外は、実施例５と同じ条件で反応を行った。酸化コバルトは市販の試薬（キシダ化学社製、ＣｏＯ、化学用、３８μｍ、純度７５％）を使用した。 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 μm, purity 75%).
　その結果、グリセリンの転化率は７４．８％で、乳酸選択率は６８．５％、乳酸収率は５１．２％、不純物選択率は３１．５％であった。 As a result, the conversion of glycerin was 74.8%, the lactic acid selectivity was 68.5%, the lactic acid yield was 51.2%, and the impurity selectivity was 31.5%.
　（実施例７：鉄族Ｆｅ）
　触媒を鉄に替えた以外は、実施例５と同じ条件で反応を行った。鉄には市販の試薬（キシダ化学社製、Ｆｅ、粉末、特級、１５０μｍ、純度９９．５％）を使用した。 (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 (Kishida Chemical Co., Fe, powder, special grade, 150 μm, purity 99.5%) was used for iron.
　その結果、グリセリンの転化率は５２．７％で、乳酸選択率は６５．２％、乳酸収率は３４．４％、不純物選択率は３４．８％であった。 As a result, the conversion of glycerol was 52.7%, the lactic acid selectivity was 65.2%, the lactic acid yield was 34.4%, and the impurity selectivity was 34.8%.
　（実施例８：鉄族化合物ＦｅＯ）
　触媒を酸化鉄（II）に替えた以外は、実施例５と同じ条件で反応を行った。酸化鉄（II）には市販の試薬（キシダ化学社製、ＦｅＯ、化学用、粉末、純度６０％）を使用した。 (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).
　その結果、グリセリンの転化率は６６．２％で、乳酸選択率は６０．４％、乳酸収率は４０．０％、不純物選択率は３９．６％であった。 As a result, the conversion of glycerin was 66.2%, the lactic acid selectivity was 60.4%, the lactic acid yield was 40.0%, and the impurity selectivity was 39.6%.
　（鉄族元素の触媒効果のまとめ）
　鉄族元素を触媒に使用した実施例の結果を表２にまとめる。 (Summary of catalytic effects of iron group elements)
The results of the examples using iron group elements as catalysts are summarized in Table 2.
　２００～２４０℃の低い反応温度でグリセリン転化率は５０～９５％程度と高く、しかも、乳酸選択率は６０～７５％程度、乳酸収率も３５～７５％程度と高かった。触媒を使用しない場合と比較すると、低い反応温度にもかかわらず高いグリセリン転化率で、しかも、高い選択率で乳酸を生成することができた。 At a low reaction temperature of 200 to 240 ° C., the glycerol conversion was as high as about 50 to 95%, the lactic acid selectivity was as high as 60 to 75%, and the lactic acid yield was as high as 35 to 75%. Compared with the case where no catalyst was used, lactic acid could be produced with a high glycerin conversion rate and a high selectivity despite a low reaction temperature.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　（貴金属元素の触媒効果）
　（実施例９：貴金属Ａｇ）
　貴金属元素の効果を確かめるため、銀を触媒として用いた。銀には市販の試薬（キシダ化学社製、Ａｇ粉末、特級、４５μｍ、純度９９％）を使用した。 (Catalytic effect of precious metal elements)
(Example 9: noble metal Ag)
In order to confirm the effect of the noble metal element, silver was used as a catalyst. A commercially available reagent (Kishida Chemical Co., Ltd., Ag powder, special grade, 45 μm, purity 99%) was used for silver.
　高圧反応器（１）に、グリセリン４６．０ｇ（０．５ｍｏｌ）、水酸化ナトリウム２０ｇ（０．５ｍｏｌ）、水９０ｇ（５．０ｍｏｌ）、および上記触媒２５ｇを仕込んで密封した。撹拌下で２２０℃に加熱して５時間にわたり本反応条件における飽和蒸気圧力で保持して反応を行った。その後、冷却して開封し、反応生成物を液体クロマトグラフィーで分析した。 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.
　その結果、グリセリンの転化率は５１．７％で、乳酸選択率は６９．４％、乳酸収率は３５．９％であった。一方、不純物であるギ酸、酢酸、メタノール、エタノール、エチレングリコール、プロピレングリコールなどを合わせた不純物選択率は３０．６％であった。 As a result, the conversion of glycerin was 51.7%, the lactic acid selectivity was 69.4%, and the lactic acid yield was 35.9%. On the other hand, the impurity selectivity including formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like, which are impurities, was 30.6%.
　（実施例１０：貴金属Ａｇ）
　グリセリンの仕込み量を２３．０ｇ（０．２５ｍｏｌ）に下げた以外は、実施例９と同じ条件で反応を行った。 (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).
　その結果、グリセリンの転化率は６０．３％で、乳酸選択率は８３．０％、乳酸収率は５０．０％、不純物選択率は１７．０％であった。 As a result, the conversion rate of glycerin was 60.3%, lactic acid selectivity was 83.0%, lactic acid yield was 50.0%, and impurity selectivity was 17.0%.
　（実施例１１：貴金属Ａｇ）
　水酸化ナトリウムの仕込み量を４０ｇ（１．０ｍｏｌ）に上げて、反応温度を２４０℃に上げた以外は、実施例９と同じ条件で反応を行った。 (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.
　その結果、グリセリンの転化率は７４．０％で、乳酸選択率は８６．２％、乳酸収率は６３．８％、不純物選択率は１３．８％であった。 As a result, the conversion of glycerin was 74.0%, the lactic acid selectivity was 86.2%, the lactic acid yield was 63.8%, and the impurity selectivity was 13.8%.
　（実施例１２：貴金属Ａｇ）
　グリセリンの仕込み量を２３．０ｇ（０．２５ｍｏｌ）に下げて、水酸化ナトリウムの仕込み量を３０ｇ（０．７５ｍｏｌ）に上げて、反応温度を２６０℃に上げた以外は、実施例９と同じ条件で反応を行った。 (Example 12: Noble metal Ag)
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.
　その結果、グリセリンの転化率は８３．５％で、乳酸選択率は７８．１％、乳酸収率は６５．２％、不純物選択率は２１．９％であった。 As a result, the conversion of glycerin was 83.5%, the lactic acid selectivity was 78.1%, the lactic acid yield was 65.2%, and the impurity selectivity was 21.9%.
　（実施例１３：貴金属化合物ＡｇＮＯ３）
　触媒を硝酸銀（I）に替えて反応を行った。硝酸銀（I）には市販の試薬（キシダ化学社製、ＡｇＮＯ３、特級、純度９９．８％）を使用した。 (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.
　高圧反応器（１）に、グリセリン４６．０ｇ（０．５ｍｏｌ）、水酸化ナトリウム４０ｇ（１．０ｍｏｌ）、水９０ｇ（５．０ｍｏｌ）、および上記触媒２５ｇを仕込んで密封した。撹拌下で２６０℃に加熱して５時間にわたり本反応条件における飽和蒸気圧力で保持して反応を行った。その後、冷却して開封し、反応生成物を液体クロマトグラフィーで分析した。 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.
　その結果、グリセリンの転化率は７０．０％で、乳酸選択率は６４．４％、乳酸収率は４５．１％であった。一方、不純物であるギ酸、酢酸、メタノール、エタノール、エチレングリコール、プロピレングリコールなどを合わせた不純物選択率は３５．６％であった。 As a result, the conversion rate of glycerin was 70.0%, the lactic acid selectivity was 64.4%, and the lactic acid yield was 45.1%. On the other hand, the impurity selectivity of the impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like was 35.6%.
　（実施例１４：貴金属Ｃｕ）
　触媒を銅に替えた以外は、実施例１３と同じ条件で反応を行った。銅には市販の試薬（キシダ化学社製、Ｃｕ粉末、特級、４５μｍ、純度９７％）を使用した。 (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 (Kishida Chemical Co., Ltd., Cu powder, special grade, 45 μm, purity 97%) was used for copper.
　その結果、グリセリンの転化率は６３．２％で、乳酸選択率は７６．９％、乳酸収率は４８．６％、不純物選択率は２３．１％であった。 As a result, the conversion of glycerin was 63.2%, the lactic acid selectivity was 76.9%, the lactic acid yield was 48.6%, and the impurity selectivity was 23.1%.
　（実施例１５：貴金属化合物ＣｕＯ）
　触媒を酸化銅（II）に替えた以外は、実施例１３と同じ条件で反応を行った。酸化銅（II）には市販の試薬（キシダ化学社製、ＣｕＯ、特製、４５μｍ、純度９９％）を使用した。 (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 (Kishida Chemical Co., Ltd., CuO, special product, 45 μm, purity 99%) was used for copper (II) oxide.
　その結果、グリセリンの転化率は７９．７％で、乳酸選択率は７２．１％、乳酸収率は５７．５％、不純物選択率は２７．９％であった。 As a result, the conversion of glycerin was 79.7%, the lactic acid selectivity was 72.1%, the lactic acid yield was 57.5%, and the impurity selectivity was 27.9%.
　（貴金属元素の触媒効果のまとめ）
　貴金属元素を触媒に使用した実施例の結果を表３にまとめる。 (Summary of catalytic effects of precious metal elements)
The results of the examples using noble metal elements as the catalyst are summarized in Table 3.
　２２０～２６０℃の低い反応温度でグリセリン転化率は５０～８５％程度と高く、しかも、乳酸選択率は７０～８５％程度、乳酸収率も３５～６５％程度と高かった。触媒を使用しない場合と比較すると、低い反応温度にもかかわらず高いグリセリン転化率で、しかも、高い選択率で乳酸を生成することができた。また、鉄族元素と比較すると、若干高い反応温度が必要であるが乳酸選択率はより高い。 At a low reaction temperature of 220 to 260 ° C., the glycerin conversion was as high as about 50 to 85%, the lactic acid selectivity was as high as about 70 to 85%, and the lactic acid yield was as high as about 35 to 65%. Compared with the case where no catalyst was used, lactic acid could be produced with a high glycerin conversion rate and a high selectivity despite a low reaction temperature. Also, compared with iron group elements, a slightly higher reaction temperature is required, but lactic acid selectivity is higher.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　（白金族元素の触媒効果）
　（実施例１６：白金族Ｐｄ／Ｃ）
　白金族元素の効果を確かめるため、炭素上にパラジウムが担持されているパラジウムカーボンを触媒として反応を行った。パラジウムカーボンには市販の試薬（キシダ化学社製、Ｐｄ／Ｃ、パラジウム含有率１０％）を使用した。 (Catalytic effect of platinum group elements)
(Example 16: Platinum group Pd / C)
In order to confirm the effect of the platinum group element, 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.
　高圧反応器（１）に、グリセリン４６．０ｇ（０．５ｍｏｌ）、水酸化ナトリウム２０ｇ（０．５ｍｏｌ）水９０ｇ（５．０ｍｏｌ）、および上記触媒１０ｇを仕込んで密封した。撹拌下で２００℃に加熱して５時間にわたり本反応条件における飽和蒸気圧力で保持して反応を行った。その後、冷却して開封し、反応生成物を液体クロマトグラフィーで分析した。 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.
　その結果、グリセリンの転化率は７８．８％で、乳酸選択率は６５．２％、乳酸収率は５１．４％であった。一方、不純物であるギ酸、酢酸、メタノール、エタノール、エチレングリコール、プロピレングリコールなどを合わせた不純物選択率は３４．８％であった。 As a result, the conversion of glycerin was 78.8%, the lactic acid selectivity was 65.2%, and the lactic acid yield was 51.4%. On the other hand, the impurity selectivity combining impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like was 34.8%.
　（実施例１７：白金族Ｐｄ／Ｃ）
　グリセリンの仕込み量を２３．０ｇ（０．２５ｍｏｌ）に下げた以外は、実施例１６と同じ条件で反応を行った。 (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).
　その結果、グリセリンの転化率は９０．４％で、乳酸選択率は７８．３％、乳酸収率は７０．８％、不純物選択率は２１．７％であった。 As a result, the conversion of glycerin was 90.4%, lactic acid selectivity was 78.3%, lactic acid yield was 70.8%, and impurity selectivity was 21.7%.
　（実施例１８：白金族Ｐｄ／Ｃ）
　反応温度を２２０℃に上げた以外は、実施例１６と同じ条件で反応を行った。 (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.
　その結果、グリセリンの転化率は９５．１％で、乳酸選択率は６９．５％、乳酸収率は６６．１％、不純物選択率は３０．５％であった。 As a result, the conversion rate of glycerin was 95.1%, the lactic acid selectivity was 69.5%, the lactic acid yield was 66.1%, and the impurity selectivity was 30.5%.
　（実施例１９：白金族Ｐｄ／Ｃ）
　グリセリンの仕込み量を２３．０ｇ（０．２５ｍｏｌ）に下げて、反応温度を２４０℃に上げた以外は、実施例１６と同じ条件で反応を行った。 (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.
　その結果、グリセリンの転化率は９８．６％で、乳酸選択率は６１．０％、乳酸収率は６０．１％、不純物選択率は３９．０％であった。 As a result, the conversion of glycerol was 98.6%, the lactic acid selectivity was 61.0%, the lactic acid yield was 60.1%, and the impurity selectivity was 39.0%.
　（実施例２０：白金族Ｐｔ／Ｃ）
　触媒を、炭素上に白金が担持されている白金炭素に替えて反応を行った。白金炭素には市販の試薬（キシダ化学社製、Ｐｔ／Ｃ、元素分析用、白金含有率５０％）を使用した。 (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 (Kishida Chemical Co., Pt / C, for elemental analysis, platinum content 50%) was used for platinum carbon.
　高圧反応器（１）に、グリセリン４６．０ｇ（０．５ｍｏｌ）、水酸化ナトリウム２０ｇ（０．５ｍｏｌ）、水９０ｇ（５．０ｍｏｌ）、および上記触媒１０ｇを仕込んで密封した。撹拌下で２４０℃に加熱して５時間にわたり本反応条件における飽和蒸気圧力で保持して反応を行った。その後、冷却して開封し、反応生成物を液体クロマトグラフィーで分析した。 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.
　その結果、グリセリンの転化率は８６．９％で、乳酸選択率は５８．６％、乳酸収率は５０．９％であった。一方、不純物であるギ酸、酢酸、メタノール、エタノール、エチレングリコール、プロピレングリコールなどを合わせた不純物選択率は４１．４％であった。 As a result, the conversion of glycerin was 86.9%, the lactic acid selectivity was 58.6%, and the lactic acid yield was 50.9%. On the other hand, the impurity selectivity including formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like as impurities was 41.4%.
　（実施例２１：白金族Ｒｕ／Ｃ）
　触媒を、炭素上にルテニウムが担持されてなるルテニウムカーボンに替えた以外は、実施例２０と同じ条件で反応を行った。ルテニウムカーボンには市販の試薬（キシダ化学社製、Ｒｕ／Ｃ、ルテニウム含有率５％）を使用した。 (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 (Kishida Chemical Co., Ru / C, ruthenium content 5%) was used for ruthenium carbon.
　その結果、グリセリンの転化率は９４．４％で、乳酸選択率は６３．７％、乳酸収率は６０．１％、不純物選択率は３６．３％であった。 As a result, the conversion of glycerin was 94.4%, lactic acid selectivity was 63.7%, lactic acid yield was 60.1%, and impurity selectivity was 36.3%.
　（白金族元素の触媒効果のまとめ）
　白金族元素を触媒に使用した実施例の結果を表４にまとめる。 (Summary of catalytic effects of platinum group elements)
The results of Examples using platinum group elements as catalysts are summarized in Table 4.
　２００～２４０℃の低い反応温度でもグリセリン転化率は８０～９５％程度と高く、しかも、乳酸選択率は６０～７５％程度、乳酸収率も５０～７０％程度と高かった。触媒を使用しない場合と比較すると、低い反応温度にもかかわらず高いグリセリン転化率で、しかも、高い選択率で乳酸を生成することができた。また、貴金属元素と比較すると、より低い反応温度で高いグリセリン転化率を得ることができるが、乳酸選択率は若干低かった。 Even at a low reaction temperature of 200 to 240 ° C., the glycerol conversion was as high as about 80 to 95%, the lactic acid selectivity was as high as about 60 to 75%, and the lactic acid yield was as high as about 50 to 70%. Compared with the case where no catalyst was used, lactic acid could be produced with a high glycerin conversion rate and a high selectivity despite a low reaction temperature. Moreover, compared with the noble metal element, a high glycerin conversion rate can be obtained at a lower reaction temperature, but the lactic acid selectivity was slightly lower.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　（卑金属元素の効果）
　（実施例２２：卑金属ＺｎＯ）
　卑金属元素の効果を確かめるため、酸化亜鉛を触媒として反応を行った。酸化亜鉛には市販の試薬（キシダ化学社製、ＺｎＯ、特級、純度９９．５％）を使用した。 (Effects of base metal elements)
(Example 22: Base metal ZnO)
In order to confirm the effect of the base metal element, the reaction was carried out using zinc oxide as a catalyst. A commercially available reagent (Kishida Chemical Co., Ltd., ZnO, special grade, purity 99.5%) was used for zinc oxide.
　高圧反応器（１）に、グリセリン４６．０ｇ（０．５ｍｏｌ）、水酸化ナトリウム２０ｇ（０．５ｍｏｌ）、水９０ｇ（５．０ｍｏｌ）、および上記触媒２５ｇを仕込んで密封した。撹拌下で２００℃に加熱して５時間にわたり本反応条件における飽和蒸気圧力で保持して反応を行った。その後、冷却して開封し、反応生成物を液体クロマトグラフィーで分析した。 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.
　その結果、グリセリンの転化率は４９．２％で、乳酸選択率は８２．７％、乳酸収率は４０．７％であった。一方、不純物であるギ酸、酢酸、メタノール、エタノール、エチレングリコール、プロピレングリコールなどを合わせた不純物選択率は１７．３％であった。 As a result, the conversion of glycerol was 49.2%, the lactic acid selectivity was 82.7%, and the lactic acid yield was 40.7%. On the other hand, the impurity selectivity including formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol, and the like as impurities was 17.3%.
　（実施例２３：卑金属ＺｎＯ）
　グリセリンの仕込み量を２３．０ｇ（０．２５ｍｏｌ）に下げて、反応温度を２４０℃に上げた以外は、実施例２２と同じ条件で反応を行った。 (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.
　その結果、グリセリンの転化率は５８．４％で、乳酸選択率は８３．８％、乳酸収率は４８．９％、不純物選択率は１６．２％であった。 As a result, the conversion of glycerol was 58.4%, the lactic acid selectivity was 83.8%, the lactic acid yield was 48.9%, and the impurity selectivity was 16.2%.
　（実施例２４：卑金属ＺｎＯ）
　水酸化ナトリウムの仕込み量を４０．０ｇ（１．０ｍｏｌ）に上げて、反応温度を２４０℃に上げた以外は、実施例２２と同じ条件で反応を行った。 (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.
　その結果、グリセリンの転化率は７４．４％で、乳酸選択率は７９．１％、乳酸収率は５８．９％、不純物選択率は２０．９％であった。 As a result, the conversion of glycerin was 74.4%, the lactic acid selectivity was 79.1%, the lactic acid yield was 58.9%, and the impurity selectivity was 20.9%.
　（実施例２５：卑金属ＺｎＯ）
　グリセリンの仕込み量を２３．０ｇ（０．２５ｍｏｌ）に下げて、水酸化ナトリウムの仕込み量を３０．０ｇ（０．７５ｍｏｌ）に上げて、反応温度を２６０℃に上げた以外は、実施例２２と同じ条件で実験を行った。 (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.
　その結果、グリセリンの転化率は８５．１％で、乳酸選択率は７０．７％、乳酸収率は６０．２％、不純物選択率は２９．３％であった。 As a result, the conversion of glycerin was 85.1%, lactic acid selectivity was 70.7%, lactic acid yield was 60.2%, and impurity selectivity was 29.3%.
　（実施例２６：卑金属Ｚｎ）
　触媒を亜鉛に替えて反応を行った。亜鉛には市販の試薬（キシダ化学社製、Ｚｎ粉末、特級、純度９０％）を使用した。 (Example 26: Base metal Zn)
The reaction was carried out by replacing the catalyst with zinc. A commercially available reagent (Kishida Chemical Co., Ltd., Zn powder, special grade, purity 90%) was used for zinc.
　高圧反応器（１）に、グリセリン４６．０ｇ（０．５ｍｏｌ）、水酸化ナトリウム４０ｇ（１．０ｍｏｌ）、水９０ｇ（５．０ｍｏｌ）、および上記触媒２５ｇを仕込んで密封した。撹拌下で２６０℃に加熱して５時間にわたり本反応条件における飽和蒸気圧力で保持して反応を行った。その後、冷却して開封し、反応生成物を液体クロマトグラフィーで分析した。 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.
　その結果、グリセリンの転化率は７４．０％で、乳酸選択率は８０．６％、乳酸収率は５９．６％であった。一方、不純物であるギ酸、酢酸、メタノール、エタノール、エチレングリコール、プロピレングリコールなどを合わせた不純物選択率は１９．４％であった。 As a result, the conversion of glycerin was 74.0%, the lactic acid selectivity was 80.6%, and the lactic acid yield was 59.6%. On the other hand, the impurity selectivity combining impurities such as formic acid, acetic acid, methanol, ethanol, ethylene glycol, propylene glycol, etc. was 19.4%.
　（実施例２７：卑金属Ｓｎ）
　触媒を錫に替えた以外は、実施例２６と同じ条件で反応を行った。錫には市販の試薬（キシダ化学社製、特級、粒径７５μｍ、純度９９％）を使用した。 (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 μm, purity 99%) was used for tin.
　その結果、グリセリンの転化率は５９．５％で、乳酸選択率は８５．３％、乳酸収率は５０．８％、不純物選択率は１４．７％であった。 As a result, the conversion of glycerin was 59.5%, the lactic acid selectivity was 85.3%, the lactic acid yield was 50.8%, and the impurity selectivity was 14.7%.
　（実施例２８：卑金属Ｐｂ）
　触媒を鉛に替えた以外は、実施例２６と同じ条件で反応を行った。鉛には市販の試薬（キシダ化学社製、特級、粒径７５μｍ、純度９９．５％）を使用した。 (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 μm, purity 99.5%) was used for lead.
　その結果、グリセリンの転化率は７２．１％で、乳酸選択率は６８．４％、乳酸収率は４９．３％、不純物選択率は３１．６％であった。 As a result, the conversion of glycerin was 72.1%, the lactic acid selectivity was 68.4%, the lactic acid yield was 49.3%, and the impurity selectivity was 31.6%.
　（実施例２９：卑金属ＨｇＯ）
　触媒を酸化水銀に替えた以外は、実施例２６と同じ条件で反応を行った。酸化水銀（II）には市販の試薬（キシダ化学社製、ＨｇＯ、１級、純度９８％）を使用した。 (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).
　その結果、グリセリンの転化率は６２．２％で、乳酸選択率は６９．８％、乳酸収率は４３．４％、不純物選択率は３０．２％であった。 As a result, the conversion of glycerol was 62.2%, the lactic acid selectivity was 69.8%, the lactic acid yield was 43.4%, and the impurity selectivity was 30.2%.
　（実施例３０：卑金属Ｂｉ）
　触媒をビスマスに替えた以外は、実施例２６と同じ条件で反応を行った。ビスマスには市販の試薬（キシダ化学社製、Ｂｉ、粉末、純度９９％）を使用した。 (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.
　その結果、グリセリンの転化率は５３．９％で、乳酸選択率は６６．２％、乳酸収率は３５．７％、不純物選択率は３３．８％であった。 As a result, the conversion of glycerin was 53.9%, the lactic acid selectivity was 66.2%, the lactic acid yield was 35.7%, and the impurity selectivity was 33.8%.
　（卑金属元素の触媒効果のまとめ）
　卑金属元素を触媒に使用した実施例の結果を表５にまとめる。 (Summary of catalytic effects of base metal elements)
The results of the examples using base metal elements as the catalyst are summarized in Table 5.
　２００～２６０℃の低い反応温度でもグリセリン転化率は５０～８５％程度と高く、しかも、乳酸選択率は６５～８５％程度、乳酸収率も３５～６０％程度と高かった。触媒を使用しない場合と比較すると、低い反応温度にもかかわらず高いグリセリン転化率で、しかも、高い選択率で乳酸を生成することができた。 Even at a low reaction temperature of 200 to 260 ° C., the glycerol conversion was as high as about 50 to 85%, the lactic acid selectivity was as high as 65 to 85%, and the lactic acid yield was as high as 35 to 60%. Compared with the case where no catalyst was used, lactic acid could be produced with a high glycerin conversion rate and a high selectivity despite a low reaction temperature.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　図２は、本発明の乳酸の製造方法によって得られた乳酸収率を示す図である。 FIG. 2 is a graph showing the lactic acid yield obtained by the lactic acid production method of the present invention.
　図２の２００～２６０℃の温度範囲において、以上の本発明の方法に合致する実施例１～３０が比較例１～４と比較して高い収率で乳酸を得ることができることを示す。 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.
　図２によると、銀（Ａｇ）を触媒として用いた実施例１０～１２、パラジウム（Ｐｄ／Ｃ）を触媒として用いた実施例１７～２０および亜鉛（ＺｎＯ）を触媒として用いた実施例２２～２５が、従来法の触媒を用いていない比較例１～４の場合と比較して、より低温の反応条件で３０％以上の乳酸収率を得ることができたことが明らかである。 According to FIG. 2, Examples 10 to 12 using silver (Ag) as a catalyst, Examples 17 to 20 using palladium (Pd / C) as a catalyst, and Examples 22 to 20 using zinc (ZnO) as a catalyst. 25, it was clear that a lactic acid yield of 30% or more could be obtained under the lower temperature reaction conditions as compared with Comparative Examples 1 to 4 in which the conventional catalyst was not used.
　また、比較例の中で比較例４の場合に最も良好な乳酸収率が得られているが（４４．８％）、同程度の乳酸が得られている実施例２２、２３では、不純物選択率がそれぞれ１７．３％および１６．２％と非常に低いのに対して、比較例４では、不純物選択率が５０．６％と非常に大きな値になっている点で、本発明に合致する実施例の方が良好な結果が得られることが理解され得る。 Further, among the comparative examples, the best lactic acid yield was obtained in the case of Comparative Example 4 (44.8%), but in Examples 22 and 23 where the same level of lactic acid was obtained, impurity selection was performed. While the rates are very low at 17.3% and 16.2%, respectively, in Comparative Example 4, the impurity selectivity is very large at 50.6%, which is consistent with the present invention. It can be seen that better results are obtained with the embodiment.
　なお、図２には、図面を見やすくするため、同じ触媒を用いて異なる温度条件で反応を行っている実施例１０～１２、１７～２０および２２～２５および比較例１～４の結果のみをグラフに表示しているが、他の実施例の場合も、グラフで示した場合と同程度の低温領域（２００～２６０℃）において３０％以上の良好な乳酸収率が得られることは上記の各表中に示した数値から明らかである。 In FIG. 2, only the results of Examples 10 to 12, 17 to 20 and 22 to 25 and Comparative Examples 1 to 4 in which the reaction is carried out using the same catalyst under different temperature conditions are shown in order to make the drawing easy to see. As shown in the graph, in the other examples, a good lactic acid yield of 30% or more can be obtained in the low temperature region (200 to 260 ° C.) similar to that shown in the graph. It is clear from the numerical values shown in each table.
１　高圧反応器
２　ヒータ
３　攪拌機
４　温度計
５　圧力計 1 High-pressure reactor 2 Heater 3 Stirrer 4 Thermometer 5 Pressure gauge

Claims (4)

  1. 　グリセリンを原料とし、鉄族元素、貴金属元素、白金族元素および卑金属元素のいずれかに属する活性元素のいずれか１種以上を含む触媒の存在下、かつ、アルカリ性の条件下でグリセリンを水熱反応させることを特徴とする乳酸の製造方法。 Using glycerin as a raw material, hydrothermal reaction of glycerin 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 under alkaline conditions A method for producing lactic acid, characterized by comprising:
  2. 　前記活性元素は、Ｆｅ、Ｎｉ、Ｃｏ、Ｃｕ、Ａｇ、Ｒｕ、Ｐｄ、Ｐｔ、Ｚｎ、Ｈｇ、Ｐｂ、ＳｎおよびＢｉからなる群から選択される１種以上である、請求項１に記載の乳酸の製造方法。 The lactic acid according to claim 1, wherein the active element is at least one selected from the group consisting of Fe, Ni, Co, Cu, Ag, Ru, Pd, Pt, Zn, Hg, Pb, Sn, and Bi. Manufacturing method.
  3. 　反応溶媒である水とグリセリンのモル比が１～５０（水／グリセリン；ｍｏｌ／ｍｏｌ）であり、アルカリ性物質とグリセリンのモル比が０．２～２０（アルカリ性物質／グリセリン；ｍｏｌ／ｍｏｌ）である、請求項１または２に記載の乳酸の製造方法。 The molar ratio of water and glycerin as a reaction solvent is 1 to 50 (water / glycerin; mol / mol), and the molar ratio of alkaline substance to glycerin is 0.2 to 20 (alkaline substance / glycerin; mol / mol). The method for producing lactic acid according to claim 1 or 2.
  4. 　前記水熱反応を２００～２６０℃の温度で行う、請求項１～３のいずれかに記載の乳酸の製造方法。 The method for producing lactic acid according to any one of claims 1 to 3, wherein the hydrothermal reaction is carried out at a temperature of 200 to 260 ° C.
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CN105601505A (en) * 2016-03-04 2016-05-25 江苏大学 Method for preparing lactic acid by catalyzing and converting glycerin through graphene-loaded nickel with high activity at low temperature
CN105669422A (en) * 2016-03-04 2016-06-15 江苏大学 Method for preparing lactic acid by converting glycerol under catalytic action of nano nickel
CN106810436A (en) * 2015-11-30 2017-06-09 中国科学院大连化学物理研究所 A kind of method that catalysis oxidation glycerine prepares lactic acid
CN108654667A (en) * 2018-04-20 2018-10-16 东北电力大学 A kind of technique converting glycerol into lactic acid in a mild condition using NiCu alloys loaded catalyst
RU2731184C1 (en) * 2019-12-27 2020-08-31 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" (ТГУ, НИ ТГУ) Catalyst for liquid-phase conversion of glycerine to lactic acid and a method for production thereof
CN112246281A (en) * 2020-10-28 2021-01-22 南京工程学院 Catalyst for preparing lactic acid from glycerol, preparation method and application

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CN106810436A (en) * 2015-11-30 2017-06-09 中国科学院大连化学物理研究所 A kind of method that catalysis oxidation glycerine prepares lactic acid
CN106810436B (en) * 2015-11-30 2020-06-30 中国科学院大连化学物理研究所 Method for preparing lactic acid by catalytic oxidation of glycerol
CN105541608A (en) * 2016-03-04 2016-05-04 江苏大学 Method for preparing lactic acid through catalytic conversion of glycerin by graphene-supported nickel-copper bimetallic catalyst
CN105601505A (en) * 2016-03-04 2016-05-25 江苏大学 Method for preparing lactic acid by catalyzing and converting glycerin through graphene-loaded nickel with high activity at low temperature
CN105669422A (en) * 2016-03-04 2016-06-15 江苏大学 Method for preparing lactic acid by converting glycerol under catalytic action of nano nickel
CN108654667A (en) * 2018-04-20 2018-10-16 东北电力大学 A kind of technique converting glycerol into lactic acid in a mild condition using NiCu alloys loaded catalyst
RU2731184C1 (en) * 2019-12-27 2020-08-31 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" (ТГУ, НИ ТГУ) Catalyst for liquid-phase conversion of glycerine to lactic acid and a method for production thereof
CN112246281A (en) * 2020-10-28 2021-01-22 南京工程学院 Catalyst for preparing lactic acid from glycerol, preparation method and application

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