CN114031493A - Method for preparing high-purity glycollic acid by selective oxidation of ethylene glycol - Google Patents
Method for preparing high-purity glycollic acid by selective oxidation of ethylene glycol Download PDFInfo
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- CN114031493A CN114031493A CN202111422954.8A CN202111422954A CN114031493A CN 114031493 A CN114031493 A CN 114031493A CN 202111422954 A CN202111422954 A CN 202111422954A CN 114031493 A CN114031493 A CN 114031493A
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- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 title claims abstract description 137
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 17
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 239000011259 mixed solution Substances 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 5
- 238000000967 suction filtration Methods 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- 239000012141 concentrate Substances 0.000 claims abstract description 4
- 238000002386 leaching Methods 0.000 claims abstract description 4
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- 229910052684 Cerium Inorganic materials 0.000 claims description 27
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 25
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 21
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052797 bismuth Inorganic materials 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 16
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 11
- -1 electroplating Substances 0.000 description 11
- 229910017604 nitric acid Inorganic materials 0.000 description 11
- 229910001451 bismuth ion Inorganic materials 0.000 description 10
- 229910000420 cerium oxide Inorganic materials 0.000 description 10
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 239000012297 crystallization seed Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical group C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6447—Bismuth
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing high-purity glycolic acid by selective oxidation of ethylene glycol. The method comprises the following steps: (1) using oxygen as an oxidant, and selectively oxidizing raw materials of glycol and sodium hydroxide in the presence of a solvent and a catalyst to prepare glycolic acid; (2) neutralizing the reaction product with phosphoric acid until the reaction product is acidic to obtain a glycolic acid mixed solution, and continuously evaporating to concentrate the content of glycolic acid to 70-80%; (3) and (3) purifying the glycolic acid concentrated solution obtained in the step (2) by adopting a crystallization method, carrying out suction filtration on the precipitated crystals, leaching, and carrying out vacuum drying to obtain the high-purity glycolic acid. The one-step method realizes the synthesis of the high-purity glycolic acid by efficiently and selectively catalyzing the reaction of the ethylene glycol, and has the advantages of simple process, easily obtained raw materials, milder reaction, environmental protection and no pollution.
Description
Technical Field
The invention relates to a method for producing high-purity glycolic acid by using ethylene glycol as a raw material.
Background
Glycolic acid, is an important organic synthetic raw material and chemical products, is widely applied to the fields of organic synthesis, printing and dyeing, cosmetics, electroplating, petroleum industry and the like, and the polymer can also be used as a biodegradable material in medical treatment, packaging and other fields.
In 1940, DuPont successfully produced glycolic acid by chemical synthesis, and later developed corresponding production technology in Japan, Germany, etc. Through decades of development, a series of glycolic acid synthesis methods are developed at home and abroad, wherein: the method for preparing glycolic acid by selective oxidation of ethylene glycol has received extensive attention in various aspects due to the single and easily available raw materials and simple process. As the market demand for high purity glycolic acid crystal products increases, it is of great importance to develop a process for the selective oxidation of ethylene glycol to produce high purity glycolic acid.
Disclosure of Invention
The invention aims to provide a method for preparing high-purity glycolic acid by selective oxidation of ethylene glycol aiming at the current state of the prior art.
A method for preparing high-purity glycolic acid by selective oxidation of ethylene glycol comprises the following steps:
(1) oxygen is taken as an oxidant, ethylene glycol and sodium hydroxide are taken as raw materials in a solvent and Pd-Bi-CeO2The selective oxidation is carried out in the presence of a catalyst to prepare the glycollic acid, and the molar ratio of the raw materials is ethylene glycol: sodium hydroxide 1.0: (0.25-1.5), wherein the solvent is water; the dosage of the catalyst is 0.5-2 wt% of the ethylene glycol based on the ethylene glycol; the catalyst consists of metal palladium as an active component, active carbon as a carrier, and metal bismuth and cerium dioxide as auxiliary catalysts, wherein the content of the metal palladium is 0.1-1.5% of the weight of the carrier, and the total content of the metal bismuth and the cerium dioxide is 0.25-1.5% of the weight of the carrier by the content of cerium;
(2) neutralizing the reaction product with phosphoric acid until the reaction product is acidic to obtain a glycolic acid mixed solution; continuously evaporating to concentrate the content of the glycolic acid to 70-80%;
(3) and (3) purifying the glycolic acid concentrated solution obtained in the step (2) by adopting a crystallization method, carrying out suction filtration on the precipitated crystals, leaching, and carrying out vacuum drying to obtain the high-purity glycolic acid.
According to the scheme, the reaction pressure for preparing the glycollic acid by the selective oxidation of the ethylene glycol in the step (1) is 0.1-0.3 MPa, the reaction temperature is 70-90 ℃, and the oxygen space velocity is 1500-2500 h-1And the reaction time is 4-8 h.
According to the scheme, the molar ratio of the raw materials in the step (1) is ethylene glycol: sodium hydroxide is between 1: (1.0-1.5).
According to the scheme, the dosage of the catalyst in the step (1) is 0.5-1.5 wt% of the ethylene glycol.
According to the scheme, the reaction pressure in the step (1) is 0.2-0.3 MPa, the reaction temperature is 70-80 ℃, and the reaction time is 4-6 h.
According to the above scheme, it is preferable to ensure that the conversion rate of the selective oxidation to produce glycolic acid in step (1) is higher than 80%, more preferably higher than 90%, the selectivity is higher than 80%, and more preferably higher than 90%.
According to the scheme, the evaporation in the step (2) enables the content of the glycolic acid to be concentrated to be 70-78%.
According to the scheme, the evaporation concentration pressure in the step (2) is minus 0.05-0.1 MPa, and the temperature is 30-40 ℃.
According to the scheme, the crystallization temperature in the step (3) is-16 ℃ to-5 ℃, and the temperature is reduced while stirring.
According to the scheme, the cooling rate in the step (3) is 1-2 ℃/min.
According to the scheme, glycolic acid crystallization seed crystals are added in the step (3) near the crystallization temperature, the addition amount of the glycolic acid crystallization seed crystals is 1-2.5 wt%, and the seed crystals are added in the stirring process and the temperature is maintained for 6-12 hours.
According to the scheme, the vacuum drying temperature of the glycolic acid crystals in the step (3) is 60-70 ℃.
According to the scheme, the Pd-Bi-CeO2In the catalyst, the cerium dioxide is calculated by cerium content, the total content of metal bismuth and cerium dioxide is preferably 0.3-1.2% of the weight of the carrier, wherein the metal bismuth is 0.2-0.9%, and the cerium dioxide is 0.1-0.6% of the cerium content.
According to the scheme, the Pd-Bi-CeO2In the catalyst, the carrier is active carbon, preferably sheet active carbon or granular active carbon.
According to the scheme, the Pd-Bi-CeO2In the catalyst, the specific surface area of the used active carbon carrier is 800-1500 m2A preferred concentration is 1000 to 1200m2/g。
According to the scheme, the Pd-Bi-CeO2In the catalyst, the active carbon carrier has a pore volume of 0.6-0.7 ml/g, a pore diameter of 8-20 nm and an iodine value of 600-1100, preferably a pore volume of 0.5-0.8 ml/g, a pore diameter of 2-30 nm and an iodine value of 400-1300.
Providing the above Pd-Bi-CeO2A method for preparing a catalyst, comprising the steps of:
dissolving nitrates of metal bismuth and cerium into dilute nitric acid or water to prepare corresponding solutions, then adding a palladium chloride acid solution into the solutions to form mixed solutions, and then putting the weighed corresponding carriers into the mixed solutions to dip for 3-18 h to obtain catalyst precursors.
Drying the catalyst precursor at 100-120 ℃ for 2-5 hours, then roasting at 200-500 ℃ for 2-5 hours, and then reducing with hydrogen at 230-280 ℃ for 2-4 hours to obtain the catalyst.
According to the scheme, the carrier is heated in a water bath in the process of impregnating the carrier with the metal mixed solution, and the temperature is 40-60 ℃.
According to the scheme, the hydrogen content in the hydrogen reducing atmosphere used for reduction is 1-10%, and the balance is high-purity nitrogen.
The invention provides Pd-Bi-CeO2The catalyst/C takes active carbon as a carrier, metal palladium as a main catalytic component and bismuth and cerium dioxide as promoters, and can achieve the purpose of efficiently and selectively catalyzing glycol reaction to synthesize glycolic acid under the condition of low metal Pd loading under the bimetallic promoter action of bismuth and cerium dioxide, so that on the basis of ensuring low impurity content of reaction products obtained with high conversion rate and high selectivity, the optimization of a glycolic acid post-treatment process comprises the following steps: firstly, neutralizing a reaction product with phosphoric acid until the reaction product shows acidity to obtain a glycolic acid mixed solution; secondly, regulating and controlling the concentration of the glycolic acid crystallization stock solution, and further comprising the regulation and control of the concentration temperature, thereby not only avoiding the polymerization of glycolic acid at high temperature, but also reducing the glycolic acid in waterIntermolecular dehydration polymerization to form dimers or multimers; and thirdly, further selecting a proper crystallization temperature interval to obtain the high-purity glycolic acid crystal. The method for synthesizing glycolic acid by ethylene glycol reaction can obtain reaction products with low impurity content with high conversion rate and high selectivity, also provides a precondition foundation for obtaining the final high-purity glycolic acid target product, and provides guarantee for the yield of the target product.
The invention has the beneficial effects that:
the method for preparing the high-purity glycolic acid by selective oxidation of the ethylene glycol provided by the invention realizes the synthesis of the high-purity glycolic acid by efficiently and selectively catalyzing the reaction of the ethylene glycol through a one-step method, and has the advantages of simple process, easily obtained raw materials, milder reaction, environmental protection and no pollution; and poly-generation can be realized with the existing industrial device for preparing ethylene glycol from coal, thereby not only solving the problem of excess production capacity of ethylene glycol, but also being an effective supplement for an ethylene glycol industrial chain.
Detailed Description
The present invention will be described in further detail with reference to examples.
Pd-Bi-CeO2Preparation of the/C catalyst:
example 1
Bismuth nitrate is dissolved in dilute nitric acid, and then a palladium chloride solution is added to form a mixed solution, wherein the concentration of bismuth ions in the mixed solution is 0.022g/mL, and the concentration of Pd in the mixed solution is 0.015 g/mL. The specific surface area is 1000m2The activated carbon/g was immersed in this solution at 60 ℃ for 6 hours, dried at 120 ℃ for 2 hours, then calcined at 350 ℃ for 3 hours, and then reduced with 3% hydrogen at 260 ℃ for 3 hours, and then taken out to obtain catalyst 1. In the obtained catalyst 1, the palladium content was 1.0% by mass of the carrier, and the bismuth content was 1.5% by mass of the carrier.
Example 2
Preparing an aqueous solution from cerium nitrate and deionized water, and then adding a palladium chloride solution to form a mixed solution, wherein the concentration of cerium ions in the mixed solution is 0.022g/mL, and the concentration of Pd in the mixed solution is 0.015 g/mL. The specific surface area is 1000m2The activated carbon/g is impregnated in this solution at 60 ℃ for 6 hours, dried at 120 ℃ for 2 hours, calcined at 400 ℃ for 3 hours and then at 260 DEGAfter 3% hydrogen reduction at a temperature of 3 ℃ for 3 hours, the catalyst was taken out to obtain catalyst 2. Catalyst 2 was obtained. In the obtained catalyst 2, the palladium content was 1.0% by mass of the carrier, and the cerium content (cerium oxide content) was 1.5% by mass of the carrier.
Example 3
Dissolving bismuth nitrate and cerium nitrate in dilute nitric acid, and then adding a palladium chloride solution to form a mixed solution, wherein the concentration of bismuth ions in the mixed solution is 0.0135g/mL, the concentration of cerium ions in the mixed solution is 0.0135g/mL, and the concentration of Pd in the mixed solution is 0.015 g/mL. The specific surface area is 1000m2The activated carbon/g was immersed in this solution at 60 ℃ for 6 hours, dried at 120 ℃ for 2 hours, then calcined at 400 ℃ for 3 hours, and then reduced with 3% hydrogen at 260 ℃ for 3 hours, and then taken out to obtain catalyst 3. In the obtained catalyst 3, the palladium content was 1.0% by mass of the carrier, the bismuth content was 0.9% by mass of the carrier, and the cerium content (cerium oxide content) was 0.9% by mass of the carrier.
Example 4
Bismuth nitrate and cerium nitrate are dissolved in dilute nitric acid, and then a palladium chloride solution is added to form a mixed solution, wherein the concentration of bismuth ions in the mixed solution is 0.009g/mL, the concentration of cerium ions in the mixed solution is 0.009g/mL, and the concentration of Pd in the mixed solution is 0.015 g/mL. The specific surface area is 1000m2The activated carbon/g was immersed in this solution at 60 ℃ for 6 hours, dried at 120 ℃ for 2 hours, then calcined at 400 ℃ for 3 hours, and then reduced with 3% hydrogen at 260 ℃ for 3 hours, and then taken out to obtain catalyst 4. In the obtained catalyst 4, the palladium content was 1.0% by mass of the carrier, the bismuth content was 0.6% by mass of the carrier, and the cerium content (cerium oxide content) was 0.6% by mass of the carrier.
Example 5
Dissolving bismuth nitrate and cerium nitrate in dilute nitric acid, and then adding a palladium chloride solution to form a mixed solution, wherein the concentration of bismuth ions in the mixed solution is 0.0135g/mL, the concentration of cerium ions in the mixed solution is 0.009g/mL, and the concentration of Pd in the mixed solution is 0.015 g/mL. The specific surface area is 1000m2The activated carbon/g is impregnated in this solution at 60 ℃ for 6 hours, dried at 120 ℃ for 2 hours, calcined at 400 ℃ for 3 hours and then at 260 ℃ forAfter 3% hydrogen reduction for 3 hours, the catalyst was taken out to obtain catalyst 5. In the obtained catalyst 5, the palladium content was 1.0% by mass of the carrier, the bismuth content was 0.9% by mass of the carrier, and the cerium content (cerium oxide content) was 0.6% by mass of the carrier.
Example 6
Dissolving bismuth nitrate and cerium nitrate in dilute nitric acid, and then adding a palladium chloride solution to form a mixed solution, wherein the concentration of bismuth ions in the mixed solution is 0.009g/mL, the concentration of cerium ions in the mixed solution is 0.0135g/mL, and the concentration of Pd in the mixed solution is 0.015 g/mL. The specific surface area is 1000m2The activated carbon/g was immersed in this solution at 60 ℃ for 6 hours, dried at 120 ℃ for 2 hours, then calcined at 400 ℃ for 3 hours, and then reduced with 3% hydrogen at 260 ℃ for 3 hours, and then taken out to obtain catalyst 6. In the obtained catalyst 6, the palladium content was 1.0% by mass of the carrier, the bismuth content was 0.6% by mass of the carrier, and the cerium content (cerium oxide content) was 0.9% by mass of the carrier.
Example 7
Dissolving bismuth nitrate and cerium nitrate in dilute nitric acid, and then adding a palladium chloride solution to form a mixed solution, wherein the concentration of bismuth ions in the mixed solution is 0.003g/mL, the concentration of cerium ions in the mixed solution is 0.009g/mL, and the concentration of Pd in the mixed solution is 0.015 g/mL. The specific surface area is 1000m2The activated carbon/g was immersed in this solution at 60 ℃ for 6 hours, dried at 120 ℃ for 2 hours, then calcined at 400 ℃ for 3 hours, and then reduced with 3% hydrogen at 260 ℃ for 3 hours, and then taken out to obtain catalyst 7. In the obtained catalyst 7, the palladium content was 1.0% by mass of the carrier, the bismuth content was 0.2% by mass of the carrier, and the cerium content (cerium oxide content) was 0.6% by mass of the carrier.
Example 8
Dissolving bismuth nitrate and cerium nitrate in dilute nitric acid, and then adding a palladium chloride solution to form a mixed solution, wherein the concentration of bismuth ions in the mixed solution is 0.0135g/mL, the concentration of cerium ions in the mixed solution is 0.0015g/mL, and the concentration of Pd in the mixed solution is 0.015 g/mL. The specific surface area is 1000m2The activated carbon/g is impregnated in this solution at 60 ℃ for 6 hours, dried at 120 ℃ for 2 hours, calcined at 400 ℃ for 3 hours and then at 260 ℃ forAnd reducing the obtained product with medium 3% hydrogen for 3 hours, and then taking out the product to obtain a catalyst 8. In the obtained catalyst 8, the palladium content was 1.0% by mass of the carrier, the bismuth content was 0.9% by mass of the carrier, and the cerium content (cerium oxide content) was 0.1% by mass of the carrier.
Example 9
Dissolving bismuth nitrate and cerium nitrate in dilute nitric acid, and then adding a palladium chloride solution to form a mixed solution, wherein the concentration of bismuth ions in the mixed solution is 0.003g/mL, the concentration of cerium ions in the mixed solution is 0.0015g/mL, and the concentration of Pd in the mixed solution is 0.015 g/mL. The specific surface area is 1000m2The catalyst 9 was obtained by immersing activated carbon/g in this solution at 60 ℃ for 6 hours, drying at 120 ℃ for 2 hours, calcining at 400 ℃ for 3 hours, reducing with 3% hydrogen at 260 ℃ for 3 hours, and removing. In the obtained catalyst 9, the palladium content was 1.0% by mass of the carrier, the bismuth content was 0.2% by mass of the carrier, and the cerium content (cerium oxide content) was 0.1% by mass of the carrier.
Example 10
Dissolving bismuth nitrate and cerium nitrate in dilute nitric acid, and then adding a palladium chloride solution to form a mixed solution, wherein the concentration of bismuth ions in the mixed solution is 0.003g/mL, the concentration of cerium ions is 0.00075g/mL, and the concentration of Pd is 0.015 g/mL. The specific surface area is 1000m2The catalyst 10 was obtained by immersing activated carbon/g in this solution at 60 ℃ for 6 hours, drying at 120 ℃ for 2 hours, calcining at 400 ℃ for 3 hours, reducing with 3% hydrogen at 260 ℃ for 3 hours, and then taking out. In the obtained catalyst 10, the palladium content was 1.0% by mass of the carrier, the bismuth content was 0.2% by mass of the carrier, and the cerium content (cerium oxide content) was 0.05% by mass of the carrier.
Example 11
Dissolving bismuth nitrate and cerium nitrate in dilute nitric acid, and then adding a palladium chloride solution to form a mixed solution, wherein the concentration of bismuth ions in the mixed solution is 0.0015g/mL, the concentration of cerium ions in the mixed solution is 0.0015g/mL, and the concentration of Pd in the mixed solution is 0.015 g/mL. The specific surface area is 1000m2The activated carbon/g was immersed in this solution at 60 ℃ for 6 hours, dried at 120 ℃ for 2 hours, then calcined at 400 ℃ for 3 hours, and then at 260 DEG CIs reduced with 3% hydrogen for 3 hours at the temperature of (2) and then taken out to obtain a catalyst 11. In the obtained catalyst 11, the palladium content was 1.0% by mass of the carrier, the bismuth content was 0.1% by mass of the carrier, and the cerium content (cerium oxide content) was 0.1% by mass of the carrier.
Pd-Bi-CeO based on the catalyst2A process for the preparation of high purity glycolic acid by selective oxidation of ethylene glycol comprising the steps of:
(1) the method comprises the following steps of selectively oxidizing raw materials of ethylene glycol and sodium hydroxide in the presence of a solvent and a catalyst by taking oxygen as an oxidant to prepare glycolic acid, wherein the molar ratio of the raw materials is ethylene glycol: sodium hydroxide 1.0: (0.25-1.5), the solvent is water, and the catalyst is a palladium-carbon catalyst; the dosage of the catalyst is based on ethylene glycol, the dosage of the catalyst is 0.5-2 wt%, the reaction pressure is 0.1-0.3 MPa, the reaction temperature is 70-90 ℃, and the oxygen airspeed is 1500-2500 h-1The reaction time is 4-8 h;
(2) neutralizing the reaction product with phosphoric acid until the reaction product is acidic to obtain a glycolic acid mixed solution; continuously evaporating to concentrate the content of the glycolic acid to 70-80%;
(3) and (3) purifying the glycolic acid concentrated solution obtained in the step (2) by adopting a crystallization method, carrying out suction filtration on the precipitated crystals, leaching, and carrying out vacuum drying to obtain the high-purity glycolic acid.
Further describing the method for producing glycolic acid, the catalysts of examples 4, 7, 8 and 9 were used specifically in the following methods.
The catalyst of example 7 was used in examples 1 to 10, and the catalysts of examples 4, 8 and 9 were used in examples 11 to 13, respectively
Adding 250g of water into a 500mL pressure reaction kettle with a stirring function, wherein the molar ratio of ethylene glycol to sodium hydroxide is 1: (0.75 to 1.5) Pd-Bi-CeO2The amount of the/C catalyst is based on the mass of ethylene glycol. Setting a heating program of the reaction kettle to gradually heat the reactants, and introducing oxygen (oxygen space velocity of 2000 h) into the reaction kettle in the heating process-1) And maintaining the set reaction pressure, stopping introducing oxygen after the reactants reach the preset temperature, and finishing the required reaction time at the set temperature. After the reaction was complete and cooling, the pressure was released to give a pale yellow liquid, examplesThe specific reaction conditions are shown in Table 1.
The reaction product composition was analyzed by gas chromatography and ion chromatography, and the ethylene glycol conversion, glycolic acid selectivity and yield were calculated, and the results are shown in table 2.
TABLE 1
TABLE 2
| Examples | Conversion of ethylene glycol,% | Glycolic acid selectivity% | Yield of glycolic acid% |
| 1 | 78 | 65 | 50.7 |
| 2 | 81 | 68 | 55.1 |
| 3 | 89 | 80 | 71.2 |
| 4 | 86 | 86 | 74.0 |
| 5 | 90 | 94 | 84.6 |
| 6 | 93 | 96 | 89.3 |
| 7 | 93 | 90 | 83.7 |
| 8 | 95 | 96 | 91.2 |
| 9 | 97 | 98 | 95.1 |
| 10 | 99 | 89 | 88.1 |
| 11 | 91 | 93 | 84.6 |
| 12 | 98 | 91 | 89.2 |
| 13 | 94 | 90 | 84.6 |
Glycolic acid crystallization purification process
Examples 14 to 26
The oxidation reaction product was neutralized with phosphoric acid to obtain a glycolic acid mixed solution, and the glycolic acid solutions obtained in examples 5 to 10 were mixed (glycolic acid content: about 23 wt%), 700g of the mixed solution was placed in a 1000mL three-necked flask, and the mixture was distilled under reduced pressure at 30 to 40 ℃ and-0.05 MPa to remove water and concentrated to a glycolic acid concentration of 70 to 80%.
400g of concentrated glycolic acid solution was added to a 500mL flask equipped with a stirring and cooling device, and cooled to the set crystallization temperature. And (3) cooling to the temperature close to the crystallization temperature of 0.5 ℃, starting to add glycolic acid seed crystals, wherein the addition amount is 1-2.5 percent, specifically 1 percent, of the glycolic acid content in the concentrated solution, maintaining the temperature and stirring for 6-12 hours to ensure that glycolic acid crystals are completely precipitated.
Transferring the materials in the flask out, performing suction filtration, washing and vacuum drying to obtain high-purity glycolic acid crystals, and measuring the product purity by using high performance liquid chromatography.
Specific conditions of glycolic acid content, crystallization temperature interval, time used for crystallization process, and glycolic acid crystallization purity of the concentrated solutions in examples 14 to 26 are shown in Table 3.
TABLE 3
Claims (10)
1. The method for preparing the high-purity glycolic acid by selective oxidation of the ethylene glycol is characterized by comprising the following steps: the method comprises the following steps:
(1) oxygen is taken as an oxidant, ethylene glycol and sodium hydroxide are taken as raw materials in a solvent and Pd-Bi-CeO2The selective oxidation is carried out in the presence of a catalyst to prepare the glycollic acid, and the molar ratio of the raw materials is ethylene glycol: sodium hydroxide 1.0: (0.25-1.5), wherein the solvent is water; the dosage of the catalyst is 0.5-2 wt% of the ethylene glycol based on the ethylene glycol; the catalyst consists of metal palladium as an active component, active carbon as a carrier, and metal bismuth and cerium dioxide as auxiliary catalysts, wherein the content of the metal palladium is 0.1-1.5% of the weight of the carrier, and the total content of the metal bismuth and the cerium dioxide is 0.25-1.5% of the weight of the carrier by the content of cerium;
(2) neutralizing the reaction product with phosphoric acid until the reaction product is acidic to obtain a glycolic acid mixed solution; continuously evaporating to concentrate the content of the glycolic acid to 70-80%;
(3) and (3) purifying the glycolic acid concentrated solution obtained in the step (2) by adopting a crystallization method, carrying out suction filtration on the precipitated crystals, leaching, and carrying out vacuum drying to obtain the high-purity glycolic acid.
2. The method of claim 1, wherein: the reaction pressure for preparing the glycollic acid by the selective oxidation of the ethylene glycol in the step (1) is 0.1-0.3 MPa, the reaction temperature is 70-90 ℃, and the oxygen space velocity is 1500-2500 h-1And the reaction time is 4-8 h.
3. The method of claim 1, wherein: the conversion rate of preparing the glycollic acid by selective oxidation in the step (1) is higher than 80%, and the selectivity is higher than 80%.
4. The method of claim 1, wherein: the raw material molar ratio of the step (1) is ethylene glycol: sodium hydroxide is between 1: (1.0-1.5).
5. The method of claim 1, wherein: the reaction pressure in the step (1) is 0.2-0.3 MPa, the reaction temperature is 70-80 ℃, and the reaction time is 4-6 h; and (3) concentrating the content of the glycolic acid to 70-78% by evaporation in the step (2).
6. The method of claim 1, wherein: the dosage of the catalyst in the step (1) is 0.5-1.5 wt% of ethylene glycol; the evaporation concentration pressure in the step (2) is minus 0.05-0.1 MPa, and the temperature is 30-40 ℃; the crystallization temperature in the step (3) is-16 ℃ to-5 ℃, and the temperature is reduced while stirring.
7. The method of claim 1, wherein: and (3) adding glycolic acid crystal seeds at the temperature close to the crystallization temperature, wherein the addition amount of the crystal seeds is 1-2.5 wt%, and adding the crystal seeds and maintaining the temperature during stirring for 6-12 hours.
8. The method of claim 1, wherein: Pd-Bi-CeO2In the catalyst, the cerium dioxide is calculated by cerium content, the total content of metal bismuth and the cerium dioxide is 0.3-1.2% of the weight of the carrier, wherein the metal bismuth is 0.2-0.9%, and the cerium dioxide is 0.1-0.6% calculated by the cerium content.
9. The method of claim 1, wherein: Pd-Bi-CeO2In the catalyst, the carrier is activated carbon, preferably sheet activated carbon or granular activated carbon; the specific surface area of the used active carbon carrier is 800-1500 m2/g。
10. The method of claim 1, wherein: the above Pd-Bi-CeO2In the catalyst, the active carbon carrier has a pore volume of 0.6-0.7 ml/g, a pore diameter of 8-20 nm and an iodine value of 600-1100.
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| CN102153461A (en) * | 2011-02-12 | 2011-08-17 | 上海多纶化工有限公司 | Method for preparing glycollic acid with ethylene glycol |
| CN108911961A (en) * | 2018-06-07 | 2018-11-30 | 广东石油化工学院 | A kind of method that catalysis oxidation glycerol prepares hydroxymalonic acid |
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| CN102153461A (en) * | 2011-02-12 | 2011-08-17 | 上海多纶化工有限公司 | Method for preparing glycollic acid with ethylene glycol |
| CN108911961A (en) * | 2018-06-07 | 2018-11-30 | 广东石油化工学院 | A kind of method that catalysis oxidation glycerol prepares hydroxymalonic acid |
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