EP3033322A2 - Supported metal catalyst and use thereof for selective oxidation of glycerol - Google Patents
Supported metal catalyst and use thereof for selective oxidation of glycerolInfo
- Publication number
- EP3033322A2 EP3033322A2 EP14796812.7A EP14796812A EP3033322A2 EP 3033322 A2 EP3033322 A2 EP 3033322A2 EP 14796812 A EP14796812 A EP 14796812A EP 3033322 A2 EP3033322 A2 EP 3033322A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- glycerol
- catalyst
- platinum
- acid
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 222
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 title abstract description 23
- 230000003647 oxidation Effects 0.000 title abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 44
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 30
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims abstract description 28
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 claims abstract description 22
- 229910052718 tin Inorganic materials 0.000 claims abstract description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011135 tin Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 20
- 239000002585 base Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910002846 Pt–Sn Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- -1 alkali metal salts Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229940120503 dihydroxyacetone Drugs 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- COFCNNXZXGCREM-UHFFFAOYSA-N methyl 2,3-dihydroxypropanoate Chemical compound COC(=O)C(O)CO COFCNNXZXGCREM-UHFFFAOYSA-N 0.000 description 2
- 239000013500 performance material Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910002839 Pt-Mo Inorganic materials 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- TZIHFWKZFHZASV-UHFFFAOYSA-N anhydrous methyl formate Natural products COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 208000019423 liver disease Diseases 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
Definitions
- the present invention relates to a supported catalyst comprising at least two metal elements (bimetallic catalyst) and its use for the selective oxidation of glycerol.
- a supported catalyst comprising at least two metal elements (bimetallic catalyst) and its use for the selective oxidation of glycerol.
- the use of glycerol, and in particular of biosourced glycerol, offers an alternative to the use of fossil resources such as hydrocarbons.
- Glycerolic acid is the starting material for the synthesis of many chemicals and cosmetics. It plays an important role, particularly in the pharmaceutical industry as a metabolic alcohol accelerator or as a treatment for liver diseases. AG can also be used in the synthesis of biopolymers.
- the present invention therefore aims to remedy one or more of these disadvantages, in particular by providing an alternative to the use of fossil resources for the production of glyceric acid, by the use of biosourced glycerol and / or unpurified glycerol.
- Another object of the invention is to obtain, at mild temperatures, the synthesis of glyceric acid from glycerol with a good selectivity and / or a good conversion value.
- the invention therefore relates to a process for the specific oxidation of glycerol to glyceric acid comprising a step of contacting a supported bimetallic catalyst, said catalyst comprising platinum and tin, with glycerol, in the presence of oxygen. .
- the invention also relates to a process for oxidizing glycerol to glyceric acid comprising a step of contacting glycerol and a supported metal catalyst in the presence of oxygen, said catalyst comprising platinum and a metallic element selected from the group consisting of tin, molybdenum, bismuth and a mixture thereof.
- the supported catalyst comprises platinum and only one other metallic species in association with platinum.
- the invention is based on the surprising finding made by the inventors that the process according to the invention makes it possible to specifically orient the oxidation of glycerol to glyceric acid (CH 2 OH-CHOH-COOH), largely limiting the formation of glyceraldehyde. and / or dihydroxyacetone.
- the process according to the invention because of the use of the aforementioned (bi) metal catalysts, drastically reduces the oxidation reaction temperature of glycerol to glyceric acid.
- the oxygen may be added in the form of a gas, preferably under pressure (for example between 1 and 10 atmospheres) and preferably pure or mixed with other gases.
- the invention also relates to the aforementioned method, wherein the (bi) metal catalyst comprises platinum and tin, platinum and bismuth or platinum and molybdenum.
- the catalyst of the process according to the invention can comprise
- platinum, tin, bismuth and molybdenum tetra-metal catalyst. It is preferable that the only metallic species present in the supported catalyst are platinum, tin, molybdenum and bismuth. In this case, in addition to the aluminum of the alumina supporting the catalyst, if other metallic species are present, they are in the form of traces.
- the invention relates to a method as defined above in which the contacting step is performed in the presence of base.
- base refers to a compound capable of capturing one or more protons and vice versa to yield one or more electrons.
- base refers in particular to compounds such as sodium hydroxide or alkoxylated alkali metal salts such as EtONa, MeONa or tBuOK, alone or as mixtures.
- the invention relates to a process as defined above in which the contacting step is carried out at a temperature of less than or equal to 120 ° C., preferably less than or equal to 100 ° C. ° C. Moreover, this temperature may be advantageously chosen in the range from 15 ° C to 100 ° C, particularly 20 ⁇ € 60 ⁇ €, more particularly 28 ⁇ € at 60 ° C.
- Another advantageous embodiment of the invention relates to a method according to the foregoing definition, wherein the metal catalyst comprises tin and platinum.
- the relative proportion of the second metal relative to platinum can be chosen in a range from 1 to 30, preferably from 5 to 20 and more particularly from 8 to 12 (for example the ratio Sn / Pt, Mo / Pt and Bi / Pt can be chosen around 10) by weight of these elements.
- the catalyst is supported by alumina.
- a particularly advantageous catalyst for practicing the process of the invention is a catalyst comprising, or consisting of, platinum and tin, platinum and molybdenum or platinum and bismuth, on an alumina support.
- Such catalysts according to the invention are described in the examples below.
- Another advantageous embodiment of the invention relates to a process according to the above definition, in which the base is sodium hydroxide.
- the invention relates to a process as defined above, in which the products of the reaction mainly comprise glyceric acid and tartronic acid.
- the invention may relate to a method for synthesizing tartronic acid.
- the process according to the invention makes it possible to obtain glycerol as the main products of oxidation: glyceric acid and, to a lesser extent, tartronic acid (HOOC-CHOH-COOH).
- the invention relates to a process as defined above, said method further comprising a step of separating the products of the reaction.
- Example 7 An example of a process for separating products from the glycerol oxidation reaction according to the invention is presented in Example 7, hereinafter.
- the glycerol used is unrefined glycerol.
- the process according to the invention can be implemented with a composition based on glycerol but which also comprises other compounds, or impurities. This is particularly advantageous because the process can exclude the need to purify or refine the glycerol, in particular by allowing the use of biosourced glycerol, or to substantially reduce the level of purification required.
- glycerol comprising up to 50% by weight of impurities (crude glycerol) can be used as starting substrate.
- said supported catalyst may be recycled.
- the catalyst could undergo a regeneration step before being brought into the presence of glycerol.
- the supported catalyst if it loses its effectiveness during the synthesis process due to fouling and / or impurities blocking the reaction sites during the oxidation reaction, can be separated from the reaction medium and treated to restore its effectiveness, at least in part.
- the catalysts according to the invention are particularly suitable for being recycled (regenerated). Indeed, once regenerated, they do not lose, or very little, their effectiveness.
- regeneration is meant in the invention the action of returning the catalyst its initial properties.
- the regeneration treatment advantageously comprises a washing step, in particular with distilled water, and drying, advantageously above 100 ° C. (for example approximately ⁇ ⁇ ' ⁇ ) for a sufficient period of time (for example 24 hours). .
- the invention also relates to the use of a catalyst as defined above, for the production of glyceric acid or tartronic acid, from glycerol.
- the invention also relates to a (bi) metal catalyst consisting of 0.5 to 10% by weight of platinum and tin, molybdenum or bismuth, said catalyst being supported, as well as its use in the process according to the invention.
- a metal catalyst consisting of 0.5 to 10% by weight of platinum and tin, molybdenum or bismuth, said catalyst being supported, as well as its use in the process according to the invention.
- the catalysts Pt / Sn, Pt / Mo and Pt / Bi supported, in particular with alumina, are covered by the invention, as well as their manufacturing process and their use, in particular in the process according to the invention.
- the invention relates to a (bi) metal catalyst consisting of 0.5 to 10% by weight of platinum and 1 to 30% by weight of tin, molybdenum or bismuth, said catalyst being supported, in particular supported by alumina.
- the invention also relates to a composition
- a composition comprising glycerol, a supported catalyst as described above and a base.
- the invention also relates to glycerol directly obtained by the process according to the invention.
- FIG. 1 represents a graph showing the percentage of products obtained over time as part of the glycerol oxidation reaction at ⁇ ⁇ ' ⁇ in the absence of a base.
- the x-axis represents the time expressed in minutes, and the y-axis represents the percentage of products.
- the legend of Figure 1 is as follows: 1: carbon balance
- Figure 2 shows a graph showing the percentage of products obtained over time as part of the glycerol oxidation reaction at 60 ° C in the presence of base.
- the x-axis represents the time expressed in minutes, and the y-axis represents the percentage of products.
- the legend of Figure 2 is as follows:
- Figure 3 shows a graph showing the percentage of products obtained over time as part of the glycerol oxidation reaction at 40 ° C in the presence of base.
- the x-axis represents the time expressed in minutes, and the y-axis represents the percentage of products.
- the legend of Figure 3 is as follows:
- Figure 4 is a graph showing the percentage of products obtained over time as part of the glycerol oxidation reaction at 28 ° C in the presence of base.
- the x-axis represents the time expressed in minutes, and the y-axis represents the percentage of products.
- the legend of Figure 4 is the following :
- the supported catalyst is prepared by incipient wetness impregnation of an alumina (15.7271 g) (Merck) with a solution of SnCl 2 .2H 2 O (5.3232g) (Aldrich) followed by drying at 110 ° C. 24h and calcination under air for 3 hours at 550 ° C. to obtain a support comprising 1.5 mmol of Sn per gram of alumina.
- the support (Sn / alumina) (4.487 g) is immersed in water and refluxed for 30 minutes. Then 20.809 mL of an aqueous solution of K 2 PtCl 6 salt (0.0164 mol.L 1 ) is added dropwise with vigorous stirring and reduced with NaBH 4 (2 mol.L 1 ).
- 14.9 wt% of tin is dried for 24h at ⁇ ⁇ ' ⁇ before being used for the oxidation reaction of glycerol.
- Oxidation experiments of pure glycerol in the liquid phase were carried out in a 300 mL stainless steel reactor equipped with a gas turbine, 4 counterpanes, a thermocouple, a thermo-oxygen supply system - regulated.
- the reaction starts when the sodium hydroxide and / or the catalyst are introduced into the reactor (t0) and that the system is pressurized with oxygen (5 bar) with continuous stirring (1500 rpm).
- the amount of base is adjusted to obtain a molar ratio NaOH / glycerol between 0 and 4.
- the weight ratio glycerol / catalyst is 11.
- the temperature and partial pressure of 0 2 are continuously monitored while the sampling takes place periodically.
- the products are analyzed with an Agilent 1200 HPLC equipped with a Rezex ROA-Organic Acid H + column (300x7.8 mm) and a refractive index detector (RID).
- a solution of H 2 S0 4 (0.0025 M) in deionized water (0.5 mL-min -1 ) was used as the eluent
- the identification and quantification of the products obtained are made by comparison with the curves 3: Oxidation of glycerol in the presence of a Pt / Sn bimetallic catalyst supported at 100 ° C. in the absence of base.
- the reaction is carried out under the conditions described in Example 2 at a temperature of ⁇ ⁇ ' ⁇ and in the absence of base.
- the conversion of glycerol reaches a maximum of 43.1% after 2.5 hours of reaction.
- the majority products are glyceraldehyde and glyceric acid with respective yields of 16.8 and 15.6%.
- Example 4 Oxidation of glycerol in the presence of a bimetallic catalyst Pt / Sn supported at 60 ⁇ and in the presence of base.
- the reaction is carried out under the conditions described in Example 2 at a temperature of 60 ° C., in the presence of base.
- the glycerol conversion reaches 95% after 1.5 hours of reaction.
- the majority products are glyceric acid and tartronic with a respective yield of 50.9% and 20.0%.
- the reaction is carried out under the conditions described in Example 2 at a temperature of 40 ° C., in the presence of base.
- the conversion of glycerol reached 86.3% after 1.5 hours of reaction.
- the majority products are glyceric acid and tartronic acid with a respective yield of 56% and 13.7%.
- the reaction is carried out under the conditions described in Example 2 at a temperature of 28 ° C. in the presence of base.
- the conversion of glycerol reaches 78.3% after 2.5 hours of reaction.
- the majority products are glyceric acid and tartronic with a respective yield of 54.2% and 13.1%.
- esters have a wide range of boiling temperatures thus allowing separation by fractional distillation. Re-acidification of the various fractions then makes it possible to obtain the various carboxylic acids.
- the supported catalyst is prepared by incipient wetness impregnation of an alumina (15.6664 g) (Merck) with a solution of Bi (NO 3 ) 3 ⁇ 5H 2 O (11.3989 g) (Avantor Performance Materials Tru SA) followed by drying at 110 ° C. for 24 hours and calcining in air for 3 hours at 550 ° C. to obtain a support comprising
- the supported catalyst is prepared by impregnation of an alumina (14.9976 g) (Merck) with a solution of MoO 3 (3.2381 g) (Avantor Performance Materials Tru SA): the MoO 3 solution is previously prepared by solubilization of MoO 3. 3 in a solution of boiling water and reflux, in the presence of a few drops of nitric acid (the water is used in excess until complete solubilization Mo0 3 ); then the alumina is added to this solution, hot, with stirring; after homogenization, the water is evaporated. The solid obtained is then dried at 110 ° C. for 24 hours and then calcined under air for 3 hours at 550 ° C. to obtain a support comprising 1.5 mmol of Mo per gram of alumina.
- the support (Mo / alumina) (4.430 g) is immersed in water and refluxed for 30 minutes. Then 20.55 mL of a K salt aqueous solution 2 PtCl 6 (0.016 mol L ”) was added dropwise with vigorous stirring and reduced by NaBH 4 (2 mol L" 1). After stirring for 1 hour, the solution is cooled to room temperature, filtered and washed with water. Finally, the powder comprising 1.46 wt% Pt and 14.2 wt% Mo is dried for 24h at ⁇ ⁇ ' ⁇ before being used for the glycerol oxidation reaction.
- the commercial catalyst Pt / Al 2 O 3 is used for comparison.
- the catalyst is separated from the reaction medium by filtration, then washed with 200 mL of distilled water, and dried at 105 ° C. for 24 hours. The catalyst is then reused directly for a second reaction carried out under the same conditions as the first without adding a new catalyst. The procedure recycle is repeated between each subsequent reaction.
- the conversion level remains constant for the bimetallic catalysts Pt-Bi / Al 2 0 3 and Pt-Mo / AI 2 0 3. There is no loss of selectivity in glyceric acid which remains constant (about 60% for the commercial catalyst, 65-75% for the bimetallic catalysts).
- the reaction is carried out at 60 ° C. under the conditions described in Example 2 using crude glycerol (purity of about 50%).
- the commercial catalyst Pt / Al 2 O 3 is used for comparison.
- the conversion of glycerol reached 9.0% with the commercial catalyst Pt / Al 2 O 3 after 1 hour of reaction, and 32.3% with the Pt-Sn / Al 2 O 3 catalyst.
- the activity of the commercial Pt / Al 2 O 3 catalyst decreases by a factor of 5 with unpurified glycerol. This loss is a factor of 3 with the Pt-Sn / Al 2 O 3 bimetallic catalyst.
- the major products are glycerolic acid and tartronic acid with yields similar to those obtained from crude glycerol.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1360029A FR3011838B1 (en) | 2013-10-15 | 2013-10-15 | SUPPORTED BIMETALLIC CATALYST AND USE THEREOF FOR SELECTIVE GLYCEROL OXIDATION |
PCT/FR2014/052612 WO2015055942A2 (en) | 2013-10-15 | 2014-10-14 | Supported metal catalyst and use thereof for selective oxidation of glycerol |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3033322A2 true EP3033322A2 (en) | 2016-06-22 |
Family
ID=50231276
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP14796812.7A Withdrawn EP3033322A2 (en) | 2013-10-15 | 2014-10-14 | Supported metal catalyst and use thereof for selective oxidation of glycerol |
Country Status (4)
Country | Link |
---|---|
US (1) | US9745243B2 (en) |
EP (1) | EP3033322A2 (en) |
FR (1) | FR3011838B1 (en) |
WO (1) | WO2015055942A2 (en) |
Families Citing this family (3)
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CN108911961B (en) * | 2018-06-07 | 2021-09-24 | 广东石油化工学院 | Method for preparing tartronic acid by catalytic oxidation of glycerin |
CN113956150B (en) * | 2020-07-21 | 2024-03-22 | 中国石油大学(华东) | Preparation method of glyceric acid |
CN113956149B (en) * | 2020-07-21 | 2024-03-15 | 中国石油大学(华东) | Separation method of glyceric acid product prepared by glycerol oxidation |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
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GB8512230D0 (en) | 1985-05-14 | 1985-06-19 | Shell Internationale Researche | Preparation of carboxylic acid salt |
CN100588641C (en) | 2008-02-02 | 2010-02-10 | 北京大学 | Method for synthesizing lactic acid by using glycerol |
CN101695657B (en) | 2009-10-27 | 2012-10-10 | 北京大学 | Method for producing lactic acid by using glycerin and special catalyst for production of lactic acid by using glycerin |
LV14079B (en) * | 2009-12-10 | 2010-05-20 | Univ Rigas Tehniska | The method of glyceric acid selective preparation and catalysts for its realization |
US9085521B2 (en) | 2011-03-30 | 2015-07-21 | University Of Kansas | Catalyst system and process for converting glycerol to lactic acid |
FR2999571B1 (en) | 2012-12-19 | 2015-02-27 | Novance | TRANSFORMATION OF GLYCEROL BY HETEROGENEOUS CATALYSIS |
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2013
- 2013-10-15 FR FR1360029A patent/FR3011838B1/en active Active
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2014
- 2014-10-14 WO PCT/FR2014/052612 patent/WO2015055942A2/en active Application Filing
- 2014-10-14 US US15/027,395 patent/US9745243B2/en not_active Expired - Fee Related
- 2014-10-14 EP EP14796812.7A patent/EP3033322A2/en not_active Withdrawn
Non-Patent Citations (2)
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Also Published As
Publication number | Publication date |
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US9745243B2 (en) | 2017-08-29 |
FR3011838A1 (en) | 2015-04-17 |
FR3011838B1 (en) | 2015-11-13 |
WO2015055942A2 (en) | 2015-04-23 |
WO2015055942A3 (en) | 2015-06-11 |
US20160272565A1 (en) | 2016-09-22 |
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