CN110860297B - Preparation method of Cu-Ag/La @ HAP catalyst and application of catalyst in preparation of lactic acid by catalytic oxidation of 1, 2-propanediol - Google Patents
Preparation method of Cu-Ag/La @ HAP catalyst and application of catalyst in preparation of lactic acid by catalytic oxidation of 1, 2-propanediol Download PDFInfo
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- CN110860297B CN110860297B CN201911017421.4A CN201911017421A CN110860297B CN 110860297 B CN110860297 B CN 110860297B CN 201911017421 A CN201911017421 A CN 201911017421A CN 110860297 B CN110860297 B CN 110860297B
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229960004063 propylene glycol Drugs 0.000 title claims abstract description 51
- 229910017770 Cu—Ag Inorganic materials 0.000 title claims abstract description 39
- 239000004310 lactic acid Substances 0.000 title claims abstract description 35
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 35
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 title claims abstract description 33
- 235000013772 propylene glycol Nutrition 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 title claims description 9
- 238000007254 oxidation reaction Methods 0.000 title claims description 8
- 230000003647 oxidation Effects 0.000 title claims description 7
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 14
- 239000000084 colloidal system Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000002105 nanoparticle Substances 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000011550 stock solution Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 abstract 4
- 230000001590 oxidative effect Effects 0.000 abstract 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 abstract 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
Classifications
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B01J35/23—
-
- 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
Abstract
The invention relates to a preparation method of a Cu-Ag/La @ HAP catalyst and an application of the catalyst in preparing lactic acid by catalyzing and oxidizing 1, 2-propanediol, in particular to a Cu-Ag bimetallic nano catalyst Cu-Ag/La @ HAP loaded by metal lanthanum-doped Hydroxyapatite (HAP) and an application in preparing lactic acid by catalyzing and oxidizing 1, 2-propanediol.
Description
Technical Field
The invention belongs to the technical field of catalysis, and relates to a preparation method of a Cu-Ag/La @ HAP catalyst and application of the Cu-Ag/La @ HAP catalyst in preparation of lactic acid by catalytic oxidation of 1, 2-propanediol.
Background
Lactic acid is commonly used as a fine chemical in the preparation of pharmaceuticals, cosmetics, foods, etc., with an annual global demand of up to 15 million tons. Also, lactic acid is mainly used as an important monomer for synthesizing degradable, non-toxic polylactic acid and lactate, which has prompted a year-by-year increase in the demand for lactic acid. At present, the preparation method of lactic acid mainly comprises a traditional chemical method and a traditional fermentation method, while the raw materials for preparing the lactic acid by adopting the chemical synthesis method mainly comprise acetaldehyde, hydrocyanic acid and concentrated sulfuric acid, so that the environmental pollution is easily caused; the reaction rate is slow in the process of preparing the lactic acid by the fermentation method, a large amount of biological sludge needs to be treated, and the production cost is increased. Therefore, a high-efficiency and environment-friendly path for preparing the lactic acid is researched and developed, and the method has important social and economic significance and environmental protection significance.
1, 2-propanediol is a hydrogenolysis product of biomass polyols such as glycerol, sorbitol, xylitol, and the like. In recent years, researches on the preparation of important chemicals by a chemical conversion method using 1, 2-propanediol as a renewable carbon source have attracted strong attention of researchers to establish a "biomass-to-chemical value chain" of 1, 2-propanediol. The main reasons for this are as follows: firstly, a large amount of glycerin is produced as a byproduct in the large-scale biodiesel production process (about 3000 ten thousand tons of global biodiesel production and about 300 ten thousand tons of byproduct glycerin are produced in 2015), and the upstream biomass raw material of 1, 2-propylene glycol is rich; secondly, dimethyl carbonate is prepared at present by mainly adopting a process of co-producing 1, 2-propylene glycol and dimethyl carbonate by an ester exchange method at home, and a large amount of 1, 2-propylene glycol is introduced into the market due to the expansion of the production scale of the dimethyl carbonate; thirdly, 1, 2-propylene glycol is used as an organic solvent, unsaturated resin raw materials and the like, which are difficult to consume increasing amounts of 1, 2-propylene glycol, and the problem of surplus market of 1, 2-propylene glycol in China is particularly prominent. The liquid-phase catalytic oxidation method has the characteristics of mild reaction conditions and easily controlled process, is a green way for efficiently converting the 1, 2-propylene glycol into the lactic acid, and has atom economy.
Disclosure of Invention
According to the invention, firstly, a hydrothermal method is used for preparing a lanthanum-doped catalyst carrier La @ HAP, a reduction method is used for preparing a Cu-Ag bimetallic nanoparticle colloid, a sol fixation method is used for preparing a lanthanum-doped Cu-Ag/La @ HAP bimetallic nano catalyst, and the lanthanum-doped Cu-Ag/La @ HAP bimetallic nano catalyst is applied to catalyzing 1, 2-propylene glycol to prepare lactic acid. In the invention, the catalyst has the advantages of small usage amount, high catalytic activity, low temperature required by reaction, small pressure and longer service life.
The technical scheme of the invention is as follows:
the preparation method of the Cu-Ag/La @ HAP nano catalyst comprises the following steps:
step 1, preparing a metal lanthanum-doped HAP carrier, and marking as La @ HAP for later use;
step 2, preparing Cu-Ag bimetal nanoparticle colloid:
dissolving a certain amount of copper salt and silver salt in polyvinyl alcohol solution, and then adding a certain amount of NaBH prepared in situ4Aging the aqueous solution at room temperature to obtain Cu-Ag bimetallic nanoparticle colloid;
step 3, preparing the Cu-Ag/La @ HAP doped bimetallic nano-catalyst by using a colloid fixation method:
and (2) adding a certain amount of the La @ HAP carrier prepared in the step (1) into the Cu-Ag bimetallic nanoparticle colloid prepared in the step (2), stirring and adsorbing, washing and filtering for a plurality of times by using deionized water, and drying to obtain the Cu-Ag/La @ HAP doped bimetallic nano-catalyst.
In the step 1, the preparation of the metal lanthanum-doped HAP carrier comprises the following steps: under the condition of water bath at 40 ℃, in prepared Ca (NO)3)2、H3PO4And La (NO)3)3·6H2Dropwise adding 25% ammonia water into an O aqueous solution to adjust the pH value of the solution to 10, reacting for 8 hours under a stirring condition, transferring the obtained solution into a reaction kettle, continuously reacting for 8 hours under a 100 ℃ condition, after the reaction is finished, washing and filtering the obtained powder for a plurality of times by deionized water, and drying for 12 hours in a 100 ℃ oven to obtain the La @ HAP carrier; wherein the ratio of the amount of the doped metal lanthanum to the amount of the metal calcium in the carrier is 1: 5.
in step 2, the copper salt is Cu (NO)3)2·3H2O, silver salt is AgNO3The mass ratio of metallic Cu to Ag was 1: 1.
In step 2, NaBH is used4The amount of the substance(s) is 5 times the sum of the amounts of the metallic Cu and Ag substances, wherein NaBH4The concentration of the solution is 0.1mol/L, and the aging time is 30 min.
In the step 2, the amount of the polyvinyl alcohol is 5 times of the total amount of the metal Cu and Ag substances, wherein the mass percentage concentration of the polyvinyl alcohol solution is 1%.
In the step 3, the load capacity of the Cu-Ag bimetallic nanoparticles is 5% of the mass of the carrier La @ HAP, the drying temperature is 60 ℃, the time is 12 hours, and the stirring adsorption time is 2-3 hours.
The Cu-Ag/La @ HAP nano catalyst prepared by the invention is used for preparing lactic acid by catalytic oxidation of 1, 2-propylene glycol, and the specific steps are as follows:
firstly, 1, 2-propylene glycol with a certain concentration is mixed with an aqueous solution of sodium hydroxide to form a mixed solution, then a Cu-Ag/La @ HAP nano catalyst with a certain mass is added, the reaction stock solution is added into a high-pressure reaction kettle and is sealed completely, then oxygen with a certain pressure is introduced to start a stirring device, the reaction temperature is regulated to a certain temperature for catalytic reaction, the reaction is ended after a certain time of reaction, the reaction product is acidified and filtered, and the high performance liquid chromatography and the gas chromatography are adopted for analysis and calculation of results.
In the mixed solution, the concentration of the used 1, 2-propylene glycol is 0.16-0.64mol/L, the concentration ratio of sodium hydroxide to 1, 2-propylene glycol is 0.5-2:1, the oxygen pressure is 0.1-1.5MPa, the stirring rotating speed is 600rpm, the catalytic reaction temperature is 100-160 ℃, the catalytic reaction time is 1-6h, and the dosage proportion of the mixed solution to the Cu-Ag/La @ HAP nano catalyst is 40 mL: 0.05-0.2 g.
Ca (NO) described in the above technical solution3)2、H3PO4、La(NO3)3·6H2O、Cu(NO3)2·3H2O、AgNO3Which function to provide Ca2+、P5+、La3+、Cu2+And Ag+。
The polyvinyl alcohol in the above technical scheme functions as a surfactant.
The NaBH in the technical scheme4A solution, the function of which is a reducing agent.
The invention has the beneficial effects that:
the catalyst provided by the invention can realize high-yield lactic acid under the low-temperature condition, and has higher application value.
Detailed Description
The Cu-Ag/La @ HAP bimetallic nano-catalyst prepared by the technical scheme is applied to catalyzing 1, 2-propylene glycol, and the invention is further explained by combining specific implementation examples.
Example 1
(1) Preparing a metal lanthanum-doped HAP carrier La @ HAP: under the condition of water bath at 40 ℃, 10mL of prepared Ca (NO)3)2(1mol/L)、10mL H3PO4(0.6mol/L) and 2mL of La (NO)3)3·6H2Adding an O (1mol/L) aqueous solution into a three-neck flask, dropwise adding 25% ammonia water to adjust the pH value of the solution to 10, reacting for 8 hours under the condition of stirring, transferring the obtained solution into a polytetrafluoroethylene high-pressure reaction kettle, and continuously reacting for 8 hours at the temperature of 100 ℃. After the reaction is finished, washing and filtering the obtained powder by deionized water for a plurality of times, and drying in an oven at 100 ℃ for 12 hours to obtain the La @ HAP carrier.
(2) Preparing Cu-Ag bimetal nanoparticle colloid: 0.07g of Cu (NO)3)2·3H2O、0.05g AgNO3Poly (phenylene Ether) (R) dissolved in 13mL of 1%Adding 30mL of 0.1mol/L NaBH prepared in situ into a vinyl alcohol solution4An aqueous solution. And aging for 30 minutes at room temperature to obtain the Cu-Ag bimetallic nanoparticle colloid.
(3) Preparing a Cu-Ag/La @ HAP nano catalyst by using a colloid fixation method: and (2) adding 1.0g of the La @ HAP carrier prepared in the step (1) into the Cu-Ag bimetallic nanoparticle colloid prepared in the step (2), stirring and adsorbing for 2-3 hours, washing and filtering for a plurality of times by deionized water, and drying for 12 hours at 60 ℃ to obtain the Cu-Ag/La @ HAP nano catalyst with the load of 5%.
(4)1, 2-propylene glycol catalytic oxidation reaction:
catalytic oxidation of 1, 2-propanediol: firstly, 40mL of 0.32mol/L mixed aqueous solution of 1, 2-propylene glycol and 0.48mol/L sodium hydroxide and 0.1g of Cu-Ag/La @ HAP nano catalyst are sequentially added into a high-pressure reaction kettle to form a mixed solution, pressure oxygen is introduced to the high-pressure reaction kettle to be 0.5MPa after the mixed solution is completely sealed, a stirring device is started, and the reaction temperature is adjusted to 140 ℃ for catalytic reaction. After 6 hours of reaction, the temperature is reduced to stop the reaction, and the reaction product is acidified and filtered, analyzed by high performance liquid chromatography and gas chromatography and calculated.
Example 2
Steps (1) to (3) were the same as in example 1, and step (4) was conducted while changing the concentrations of 1, 2-propanediol in example 1 to 0.16mol/L,0.48mol/L and 0.64mol/L, and the results of conversion of 1, 2-propanediol and selectivity of lactic acid were shown in Table 1. The results show that as the concentration of 1, 2-propanediol increases, its conversion gradually decreases and the selectivity to lactic acid also gradually decreases.
TABLE 1 Effect of different 1, 2-propanediol concentrations on the conversion of the final feedstock and the selectivity of the reaction products
Example 3
Steps (1) to (3) were the same as in example 1, and step (4) was carried out by changing the sodium hydroxide concentrations used in example 1 to 0.16mol/L,0.32mol/L and 0.64mol/L, respectively. The conversion of the obtained 1, 2-propanediol and the results of the selectivity to lactic acid are shown in Table 2. The results show that the conversion of 1, 2-propanediol gradually increases with increasing sodium hydroxide concentration, and that at a sodium hydroxide concentration of 0.48mol/L, i.e. a ratio of sodium hydroxide concentration to 1, 2-propanediol concentration of 1.5:1, the conversion of 1, 2-propanediol reaches 91.1%, while the selectivity of lactic acid reaches a maximum of 89.6%.
TABLE 2 Effect of different NaOH concentrations on the conversion of the final feedstock and the selectivity of the reaction products
| Sodium hydroxide concentration (mol/L) | Conversion of 1, 2-propanediol (%) | Lactic acid selectivity (%) |
| 0.16 | 81.5 | 81.6 |
| 0.32 | 89.6 | 84.7 |
| 0.48 | 91.1 | 89.6 |
| 0.64 | 96.2 | 88.1 |
Example 4
Steps (1) to (3) were the same as in example 1, and step (4) was carried out while changing the amounts of the catalysts used in example 1 to 0.05g,0.15g and 0.2g, respectively. The conversion of 1, 2-propanediol obtained and the lactic acid selectivity results are shown in Table 3. The results showed that as the amount of the catalyst used was increased, the conversion of 1, 2-propanediol was gradually increased, and the selectivity for lactic acid was also increased, and at a catalyst usage of 0.2g, the conversion of 1, 2-propanediol was 95.2%, and the selectivity for lactic acid was 92.3%.
TABLE 3 Effect of different amounts of catalyst on the conversion of the final feedstock and the selectivity of the reaction products
| Amount of catalyst (g) | Conversion of 1, 2-propanediol (%) | Lactic acid selectivity (%) |
| 0.05 | 83.8 | 82.9 |
| 0.1 | 91.1 | 89.6 |
| 0.15 | 93.6 | 91.6 |
| 0.2 | 95.2 | 92.3 |
Example 5
Steps (1) to (3) were the same as in example 1, and step (4) was conducted by changing the oxygen pressures used in example 1 to 0.1MPa,1.0MPa and 1.5MPa, respectively. The conversion of 1, 2-propanediol obtained and the lactic acid selectivity results are shown in Table 4. The results show that the conversion of 1, 2-propanediol increases with increasing oxygen pressure, whereas the selectivity for lactic acid reaches a maximum of 89.6% at an oxygen pressure of 0.5 MPa.
TABLE 4 Effect of different oxygen pressures on the conversion of the final feedstock and the selectivity of the reaction products
Example 6
Steps (1) to (3) were performed in the same manner as in example 1, and step (4) was performed by carrying out the catalytic reaction of 1, 2-propanediol after changing the reaction temperature of example 1 to 100 ℃ and 120 ℃ respectively, and the conversion of 1, 2-propanediol and the selectivity of lactic acid were as shown in Table 5. The results show that the conversion of 1, 2-propanediol increases gradually with increasing reaction temperature, whereas the selectivity for lactic acid reaches a maximum of 89.6% at a reaction temperature of 140 ℃.
TABLE 5 Effect of different reaction temperatures on the conversion of the final starting materials and the selectivity of the reaction products
| Temperature (. degree.C.) | Conversion of 1, 2-propanediol (%) | Lactic acid selectivity (%) |
| 100 | 70.6 | 78.5 |
| 120 | 82.3 | 82.7 |
| 140 | 91.1 | 89.6 |
| 160 | 96.8 | 85.3 |
Example 7
Steps (1) to (3) were the same as in example 1, and step (4) was conducted while changing the reaction time in example 1. The subsequent catalytic reaction gave 1, 2-propanediol conversion and lactic acid selectivity results as shown in Table 6. The results showed that as the catalytic reaction time was extended, the 1, 2-propanediol conversion and the lactic acid selectivity were gradually increased at the same time, and at 6 hours, the 1, 2-propanediol conversion reached 91.1% and the lactic acid selectivity reached 89.6%.
TABLE 6 Effect of different reaction times on the conversion of the final starting materials and the selectivity of the reaction products
| Reaction time (h) | Conversion of 1, 2-propanediol (%) | Lactic acid selectivity (%) |
| 1 | 18.6 | 88.9 |
| 2 | 35.8 | 88.9 |
| 3 | 51.3 | 89.1 |
| 4 | 65.5 | 89.2 |
| 5 | 78.6 | 89.5 |
| 6 | 91.1 | 89.6 |
Claims (8)
- A preparation method of a Cu-Ag/La @ HAP catalyst is characterized by comprising the following steps:step 1, preparing a metal lanthanum-doped HAP carrier, and marking as La @ HAP for later use;under the condition of water bath at 40 ℃, in prepared Ca (NO)3)2、H3PO4And La (NO)3)3·6H2Adding 25% ammonia water dropwise into O water solution to adjust pH to 10, reacting for 8 hr under stirring, transferring the obtained solution into a reaction kettle, reacting for 8 hr at 100 deg.C, and reactingAfter that, washing and filtering the obtained powder by deionized water for a plurality of times, and drying in an oven at 100 ℃ for 12 hours to obtain the La @ HAP carrier;wherein the ratio of the amount of the doped metal lanthanum to the amount of the metal calcium in the carrier is 1: 5;step 2, preparing Cu-Ag bimetal nanoparticle colloid:dissolving certain amount of copper salt and silver salt in polyvinyl alcohol solution, and adding certain amount of NaBH4Aging the aqueous solution at room temperature to obtain Cu-Ag bimetallic nanoparticle colloid;step 3, preparing the Cu-Ag/La @ HAP doped bimetallic nano-catalyst by using a colloid fixation method:and (3) adding a certain amount of La @ HAP carrier prepared in the step (1) into the Cu-Ag bimetal nanoparticle colloid prepared in the step (2), stirring and adsorbing, washing and filtering for a plurality of times by using deionized water, and drying to obtain the Cu-Ag/La @ HAP doped bimetal nano catalyst.
- 2. The method of claim 1, wherein in step 2, the copper salt is Cu (NO)3)2·3H2O, silver salt is AgNO3The mass ratio of metallic Cu to Ag was 1: 1.
- 3. The method of claim 1, wherein in step 2, NaBH is used4The amount of the substance(s) is 5 times the sum of the amounts of the metallic Cu and Ag substances, wherein NaBH4The concentration of the aqueous solution is 0.1mol/L, and the aging time is 30 min.
- 4. The method of preparing a Cu-Ag/La @ HAP catalyst according to claim 1, wherein in step 2, the amount of the polyvinyl alcohol used is 5 times the sum of the amounts of the metallic Cu and Ag species, wherein the polyvinyl alcohol solution has a mass percent concentration of 1%.
- 5. The preparation method of the Cu-Ag/La @ HAP catalyst as claimed in claim 1, wherein in the step 3, the loading amount of the Cu-Ag bimetallic nanoparticles is 5% of the mass of the La @ HAP carrier, the drying temperature is 60 ℃, the drying time is 12 hours, and the stirring and adsorbing time is 2-3 hours.
- 6. Use of a Cu-Ag/La @ HAP catalyst prepared by the process of any one of claims 1 to 5 for the catalytic oxidation of 1, 2-propanediol to produce lactic acid.
- 7. The use according to claim 6, characterized by the specific steps of:firstly, 1, 2-propylene glycol with certain concentration is mixed with sodium hydroxide aqueous solution to form mixed solution, then Cu-Ag/La @ HAP nano catalyst with certain mass is added, reaction stock solution is added into a high-pressure reaction kettle and is sealed completely, then oxygen with certain pressure is introduced to start a stirring device, the reaction temperature is regulated to certain temperature for catalytic reaction, after reaction for certain time, the reaction is finished, and reaction products are acidified and filtered.
- 8. The use according to claim 7,in the mixed solution, the concentration of the used 1, 2-propylene glycol is 0.16-0.64mol/L, the concentration ratio of sodium hydroxide to 1, 2-propylene glycol is 0.5-2:1, the oxygen pressure is 0.1-1.5MPa, the stirring rotating speed is 600rpm, the catalytic reaction temperature is 100-160 ℃, the catalytic reaction time is 1-6h, and the dosage proportion of the mixed solution to the Cu-Ag/La @ HAP nano catalyst is 40 mL: 0.05-0.2 g.
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| CN101623514A (en) * | 2009-08-07 | 2010-01-13 | 陕西科技大学 | Preparation method for nano hydroxylapatite doped with metal ions |
| CN104003865A (en) * | 2014-05-16 | 2014-08-27 | 江苏大学 | Method for catalytic oxidation of 1,2-propylene glycol at normal pressure |
| CN105126837A (en) * | 2015-09-06 | 2015-12-09 | 江苏大学 | Nano Pd-Ag bimetallic catalyst, preparation method and method for preparing lactic acid through catalytic oxidation of 1,2-propylene glycol |
| CN109954506A (en) * | 2019-04-04 | 2019-07-02 | 四川轻化工大学 | A kind of catalyst LaHAP and its application |
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| CN101623514A (en) * | 2009-08-07 | 2010-01-13 | 陕西科技大学 | Preparation method for nano hydroxylapatite doped with metal ions |
| CN104003865A (en) * | 2014-05-16 | 2014-08-27 | 江苏大学 | Method for catalytic oxidation of 1,2-propylene glycol at normal pressure |
| CN105126837A (en) * | 2015-09-06 | 2015-12-09 | 江苏大学 | Nano Pd-Ag bimetallic catalyst, preparation method and method for preparing lactic acid through catalytic oxidation of 1,2-propylene glycol |
| CN109954506A (en) * | 2019-04-04 | 2019-07-02 | 四川轻化工大学 | A kind of catalyst LaHAP and its application |
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