CN114749214A - Preparation method of Salen metal complex intercalated hydrotalcite catalyst and method for preparing lactic acid from glycerol - Google Patents
Preparation method of Salen metal complex intercalated hydrotalcite catalyst and method for preparing lactic acid from glycerol Download PDFInfo
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- CN114749214A CN114749214A CN202210265076.1A CN202210265076A CN114749214A CN 114749214 A CN114749214 A CN 114749214A CN 202210265076 A CN202210265076 A CN 202210265076A CN 114749214 A CN114749214 A CN 114749214A
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- lactic acid
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 132
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 52
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 52
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 52
- 239000004310 lactic acid Substances 0.000 title claims abstract description 43
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 43
- -1 Salen metal complex Chemical class 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 230000001737 promoting effect Effects 0.000 claims abstract description 4
- 238000004064 recycling Methods 0.000 claims abstract description 4
- 239000011949 solid catalyst Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 20
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims description 14
- 239000003446 ligand Substances 0.000 claims description 14
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 238000010926 purge Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 238000009830 intercalation Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 235000015110 jellies Nutrition 0.000 claims description 3
- 239000008274 jelly Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- PPICZOBUVZNXEQ-UHFFFAOYSA-N ethane-1,2-diamine;ethanol Chemical compound CCO.NCCN PPICZOBUVZNXEQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000020477 pH reduction Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000007664 blowing Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000004075 alteration 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
- 239000003225 biodiesel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/22—Magnesium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a Salen metal complex intercalated hydrotalcite catalyst and a method for preparing lactic acid by using glycerol. It comprises the following steps: A. adding a glycerol aqueous solution and a Salen metal complex intercalated hydrotalcite catalyst into a reaction kettle with a stirrer, and blowing air in the reaction kettle by oxygen; B. heating and maintaining stirring, and promoting the selective oxidation of glycerol to directly prepare lactic acid after reacting for a period of time; C. after the reaction is finished, cooling to room temperature, filtering and separating the solid catalyst, washing and drying by methanol, and recycling; the liquid is rectified to obtain the lactic acid. The beneficial effects are that: the glycerol is directly catalyzed and converted into the lactic acid, and the complicated subsequent separation and acidification steps are avoided. The synthesized catalyst has high activity and high selectivity, the selectivity of the target product lactic acid can reach 83%, and the catalyst has more excellent catalytic performance. The reaction for preparing the lactic acid is safer, the reaction is carried out under mild conditions, the synthesis reaction is safer, and the space-time yield is high.
Description
Technical Field
The invention relates to a preparation method of a Salen metal complex intercalated hydrotalcite catalyst and a method for preparing lactic acid from glycerol, belonging to the technical field of organic matter synthesis.
Background
Lactic acid is one of three major organic acids, is a fine chemical with wide application range, can be used for producing novel degradable plastics, food additives, preservatives, carrier agents, medicinal preparations and the like, and has wide application in various industries; in recent years, the yield of lactic acid in Asia range is about 120 kt/year, and the lactic acid is a main chemical raw material with large demand and has higher commercial application value.
In the traditional process, lactic acid is prepared by fermenting glucose, starch and sugarcane, however, the traditional fermentation route is expensive, and complex products are difficult to separate and purify, so that an efficient and environment-friendly lactic acid production route needs to be explored; glycerol is a main byproduct of biodiesel, is a highly functionalized molecule, is considered as a raw material of various chemicals with high added values due to the fact that glycerol has primary and secondary carbon hydroxyl functional groups, contains hydroxyl functional groups, and is prepared into lactic acid through steps of carbon chain breakage, hydroxyl oxidation, dehydration rearrangement and the like, and the route meets the requirements of sustainable development strategy, green chemistry and market economy.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a Salen metal complex intercalated hydrotalcite catalyst which has the advantages of simple process, good catalytic performance of the catalyst, high activity, high selectivity, high safety in the preparation process and high yield, and a method for preparing lactic acid by catalyzing glycerol.
In order to solve the technical problems, the preparation method of the Salen metal complex intercalated hydrotalcite catalyst comprises the following steps:
A. taking Mg (NO)3)2·6H2O aqueous solution and Al (NO)3)3·9H2O aqueous solution, which is slowly added to a vigorously stirred equal volume of C-containing solution at room temperature6H5Stirring COOH and NaOH aqueous solution for 0.3-0.8h, placing the obtained jelly in a crystallization kettle, performing hydrothermal reaction at 95-100 deg.C for 23-26h, suction filtering, washing, and drying to obtain C6H5COO-Intercalation hydrotalcite;
B. dropwise adding the salicylaldehyde ethanol solution into the ethylenediamine ethanol solution, keeping stirring, refluxing the obtained mixture for 7-9h after dropwise adding is finished, cooling, filtering and drying to obtain a Salen ligand;
C. dissolving Salen ligand in deionized water at 55-65 deg.C, adjusting pH, and adding C6H5COO-Intercalated hydrotalcite is added into the solution, in N2Stirring for 22-28h at 55-65 ℃ under protection, performing suction filtration, washing and drying to obtain Salen ligand intercalated hydrotalcite;
D. taking Pd (NO)3)2·2H2Adding Salen ligand intercalated hydrotalcite into O water solution, adding sodium hydroxide into the mixture, and adding sodium hydroxide into the mixture to obtain the product2Refluxing and stirring for 1.5-3.5h at 55-65 ℃ under protection, filtering, washing and drying to obtain Salen metal complex intercalated hydrotalciteThe Pd catalyst was supported.
The n (Mg (NO)3)2·6H2O)∶n(Al(NO3)3·9H2O)＝3：1。
Said C6H5The ratio of the amounts of COOH to NaOH was 1: 5.
The mass ratio of the salicylaldehyde to the ethylenediamine is 2: 1.
A method for preparing lactic acid from glycerol based on a Salen metal complex intercalated hydrotalcite catalyst comprises the following steps:
A. adding a glycerol aqueous solution and a Salen metal complex intercalated hydrotalcite loaded Pd catalyst into a reaction kettle with a stirrer, and purging air in the reaction kettle by oxygen;
B. heating and maintaining stirring, and promoting the selective oxidation of glycerol to directly prepare the lactic acid after reacting for a period of time;
C. after the reaction is finished, cooling to room temperature, filtering and separating the solid catalyst, washing and drying by methanol, and recycling; the liquid is rectified to obtain the lactic acid.
In the step A, the concentration of the glycerol aqueous solution is 1 mol.L-1To 10 mol. L-1。
The dosage of the Salen metal complex intercalated hydrotalcite loaded Pd catalyst in the step A is as follows: 100mg-300 mg.
In the step B, the reaction temperature is 60-160 ℃, and the reaction time is 1-4 h.
The solution in step B was maintained at a stirring rate of 200 rpm.
The invention has the beneficial effects that:
1. the glycerol is directly catalyzed and converted into the lactic acid, and the complicated subsequent separation and acidification steps are avoided.
2. The synthesized catalyst has high activity and high selectivity, and the selectivity of the target product lactic acid can reach 83 percent.
3. The hydrotalcite loaded Pd catalyst for preparing the Salen metal complex intercalation has synergistic effect among metal, ligand and hydrotalcite, so that the hydrotalcite loaded Pd catalyst has more excellent catalytic performance.
4. The reaction for preparing the lactic acid is safer, the reaction is carried out under mild conditions, the synthesis reaction is safer, and the space-time yield is high.
Detailed Description
The preparation method of the Salen metal complex intercalated hydrotalcite catalyst and the method for preparing lactic acid by glycerol are further described in detail with reference to specific embodiments, the selectivity of the lactic acid prepared by the method can reach 83%, and the prepared catalyst has good selectivity and catalytic activity.
The first embodiment is as follows:
the preparation method of the Salen metal complex intercalated hydrotalcite catalyst is characterized by comprising the following steps:
A. 100mL of 3mol L are taken-1Mg(NO3)2·6H2O aqueous solution and 100mL of 1mol L-1Al(NO3)3·9H2O aqueous solution, which was slowly added to a vigorously stirred equal volume containing 100mL of 3mol L at room temperature-1C of (A)6H5COOH with 100mL of 15mol L-1Stirring NaOH aqueous solution for 0.5h, placing the obtained jelly in a crystallization kettle, performing hydrothermal reaction at 100 ℃ for 24h, performing suction filtration, washing and drying to obtain C6H5COO-Intercalation hydrotalcite;
B. 50mL of 0.5mol L-1The salicylaldehyde ethanol solution is dripped to 50mL of 0.25 mol L-1Stirring the ethylene diamine ethanol solution, refluxing the obtained mixture for 8 hours after the dropwise addition is finished, cooling, filtering and drying to obtain a Salen ligand;
C. 2g of Salen ligand were dissolved in deionized water at 60 ℃ to adjust the pH to 10, and 2g C was added6H5COO-Intercalated hydrotalcite is added into the solution, in N2Stirring for 24h at 60 ℃ under protection, performing suction filtration, washing and drying to obtain Salen ligand intercalated hydrotalcite;
D. 100ml of 0.1mol L are taken-1Pd (NO)3)2·2H2Adding 1g Salen ligand intercalated hydrotalcite into O aqueous solution, adding sodium hydroxide into the solution, adding sodium hydroxide, sodium hydroxide and sodium hydroxide into the solution, adding 1g Salen ligand intercalated hydrotalcite into the solution, adding sodium hydroxide and sodium hydroxide into the solution, adding sodium hydroxide and sodium hydroxide, adding sodium hydroxide, and sodium hydroxide, adding2Stirring under reflux at 60 deg.C for 2 hr under protection, filtering, washing, and drying to obtain Salen metal complexThe compound intercalated hydrotalcite supports Pd catalyst.
Although the specific mixture ratio is adopted in the embodiment, the invention can be actually selected according to the following mixture ratio: n (Mg (NO)3)2·6H2O)∶ n(Al(NO3)3·9H2O)＝3：1，C6H5The ratio of the amounts of COOH to NaOH was 1:5 and the ratio of the amounts of salicylaldehyde to ethylenediamine was 2: 1.
In this embodiment, the method for preparing lactic acid from glycerol based on the Salen metal complex intercalated hydrotalcite catalyst comprises the following steps:
A. adding a glycerol aqueous solution and a Salen metal complex intercalated hydrotalcite loaded Pd catalyst into a reaction kettle with a stirrer, and purging air in the reaction kettle by oxygen;
B. heating and maintaining stirring, and promoting the selective oxidation of glycerol to directly prepare the lactic acid after reacting for a period of time;
C. after the reaction is finished, cooling to room temperature, filtering and separating the solid catalyst, washing and drying by methanol, and recycling; the liquid is rectified to obtain the lactic acid.
Wherein 9.209g of glycerol are taken to be dissolved in 100mL of water (1 mol. L) in the specific preparation process-1) And 0.1g of Salen metal complex intercalated hydrotalcite loaded Pd catalyst, purging air in the kettle by oxygen, heating to 160 ℃, maintaining the stirring speed of 200rpm, reacting for 2 hours, cooling to room temperature, recovering the catalyst, and analyzing the product, wherein the conversion rate of the glycerol is 90 percent, and the selectivity of the lactic acid is 76 percent.
Although the above specific ratios or parameters are used in the present embodiment for the method for preparing lactic acid from glycerol according to the present invention, the present invention may be actually selected according to the following ratios or parameters: the concentration of the glycerol aqueous solution is 1 mol.L-1To 10 mol. L-1The dosage of the Salen metal complex intercalated hydrotalcite supported Pd catalyst is as follows: 100mg-300mg, the reaction temperature is 60-160 ℃, the reaction time is 1-4h, and the stirring speed of the solution in the step B is kept at 200 rpm.
Example two:
the catalyst was prepared as in example one.
9.209g of glycerol were dissolved in 100mL of water (1 mol. L)-1) And 0.3g of Salen metal complex intercalated hydrotalcite loaded Pd catalyst, purging air in the kettle by oxygen, heating to 160 ℃, maintaining the stirring speed of 200rpm, reacting for 2 hours, cooling to room temperature, recovering the catalyst, and analyzing the product, wherein the conversion rate of the glycerol is 92% and the selectivity of the lactic acid is 79%.
Example three:
the catalyst was prepared as in example one.
92.09g of glycerol were dissolved in 100mL of water (10 mol. L)-1) And 0.3g of Salen metal complex intercalated hydrotalcite loaded Pd catalyst, purging air in the kettle by oxygen, heating to 160 ℃, maintaining the stirring speed of 200rpm, reacting for 2 hours, cooling to room temperature, recovering the catalyst, and analyzing the product, wherein the conversion rate of the glycerol is 60 percent, and the selectivity of the lactic acid is 46 percent.
Example four:
the catalyst was prepared as in example one.
9.209g of glycerol were dissolved in 100mL of water (1 mol. L)-1) And 0.3g of Salen metal complex intercalated hydrotalcite loaded Pd catalyst, purging the air in the kettle by oxygen, heating to 60 ℃, maintaining the stirring rate of 200rpm, reacting for 2 hours, cooling to room temperature, recovering the catalyst, and analyzing the product, wherein the conversion rate of glycerol is 65%, and the selectivity of lactic acid is 57%.
Example five:
the catalyst was prepared as in example one.
9.209g of glycerol were dissolved in 100mL of water (1 mol. L)-1) And 0.3g of Salen metal complex intercalated hydrotalcite loaded Pd catalyst, purging the kettle with oxygen, heating the air to 60 ℃, maintaining the stirring speed of 200rpm, reacting for 1h, cooling to room temperature, recovering the catalyst, and analyzing the product. The glycerol conversion was 54% and the selectivity to lactic acid was 67%.
Example six:
the catalyst was prepared as in example one.
9.209g of glycerol were dissolved in 100mL of water (1 mol. L)-1) 0.3g of Salen metal complex intercalated hydrotalcite loaded Pd catalyst, and oxygen purgingThe temperature of the air in the kettle is raised to 60 ℃ and the stirring speed of 200rpm is maintained, the temperature is reduced to room temperature after 4 hours of reaction, the catalyst is recovered, and the product is analyzed, wherein the conversion rate of the glycerol is 77 percent, and the selectivity of the lactic acid is 54 percent.
Example seven:
the catalyst was prepared as in example one.
9.209g of glycerol were dissolved in 100mL of water (1 mol. L)-1) And 0.3g of Salen metal complex intercalated hydrotalcite supported Pd catalyst, purging the air in the kettle by oxygen, heating to 100 ℃, maintaining the stirring rate of 200rpm, reacting for 2 hours, cooling to room temperature, recovering the catalyst, and analyzing the product, wherein the conversion rate of glycerol is 88 percent, and the selectivity of lactic acid is 83 percent.
The verification proves that the glycerol conversion rate of the invention is 54-92%, the highest selectivity of lactic acid can reach 83%, and the prepared Salen metal complex intercalated hydrotalcite loaded Pd catalyst has high catalytic activity and reusability, and has good industrial application prospect.
It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art may make modifications, alterations, additions or substitutions within the spirit and scope of the present invention.
Claims (9)
1. A preparation method of a Salen metal complex intercalated hydrotalcite catalyst is characterized by comprising the following steps:
A. taking Mg (NO)3)2·6H2O aqueous solution and Al (NO)3)3·9H2O aqueous solution, which is slowly added to a vigorously stirred equal volume of C-containing solution at room temperature6H5Stirring COOH and NaOH aqueous solution for 0.3-0.8h, placing the obtained jelly in a crystallization kettle, performing hydrothermal reaction at 95-100 deg.C for 23-26h, suction filtering, washing, and drying to obtain C6H5COO-Intercalation hydrotalcite;
B. dropwise adding the salicylaldehyde ethanol solution into the ethylenediamine ethanol solution, keeping stirring, refluxing the obtained mixture for 7-9h after dropwise adding is finished, cooling, filtering and drying to obtain a Salen ligand;
C. dissolving Salen ligand in deionized water at 55-65 deg.C, adjusting pH, and adding C6H5COO-Intercalated hydrotalcite is added into the solution, in N2Stirring for 22-28h at 55-65 ℃ under protection, performing suction filtration, washing and drying to obtain Salen ligand intercalated hydrotalcite;
D. taking Pd (NO)3)2·2H2Adding Salen ligand intercalated hydrotalcite into O water solution, adding sodium hydroxide into the mixture, and adding sodium hydroxide into the mixture to obtain the product2And (3) refluxing and stirring for 1.5-3.5h at 55-65 ℃ under protection, and performing suction filtration, washing and drying to obtain the Salen metal complex intercalated hydrotalcite supported Pd catalyst.
2. The method for preparing the Salen metal complex intercalated hydrotalcite catalyst according to claim 1, wherein: the n (Mg (NO)3)2·6H2O)∶n(Al(NO3)3·9H2O)＝3：1。
3. The method for preparing the Salen metal complex intercalated hydrotalcite catalyst according to claim 1 or 2, characterized in that: said C6H5The mass ratio of COOH to NaOH was 1: 5.
4. The method for preparing the Salen metal complex intercalated hydrotalcite catalyst according to claim 3, characterized in that: the mass ratio of the salicylaldehyde to the ethylenediamine is 2: 1.
5. A method for preparing lactic acid from glycerol based on a Salen metal complex intercalated hydrotalcite catalyst is characterized by comprising the following steps:
A. adding a glycerol aqueous solution and a Salen metal complex intercalated hydrotalcite loaded Pd catalyst into a reaction kettle with a stirrer, and purging air in the reaction kettle by oxygen;
B. heating and maintaining stirring, and promoting the selective oxidation of glycerol to directly prepare the lactic acid after reacting for a period of time;
C. after the reaction is finished, cooling to room temperature, filtering and separating the solid catalyst, washing and drying by methanol, and recycling; the liquid is rectified to obtain the lactic acid.
6. The method for preparing lactic acid from glycerol based on the Salen metal complex intercalated hydrotalcite catalyst according to claim 5, characterized in that: in the step A, the concentration of the glycerol aqueous solution is 1 mol.L-1To 10 mol. L-1。
7. The method for preparing lactic acid from glycerol based on the Salen metal complex intercalated hydrotalcite catalyst according to claim 5 or 6, characterized in that: the dosage of the Salen metal complex intercalated hydrotalcite loaded Pd catalyst in the step A is as follows: 100mg-300 mg.
8. The method for preparing lactic acid from glycerol based on the Salen metal complex intercalated hydrotalcite catalyst according to claim 7, characterized in that: in the step B, the reaction temperature is 60-160 ℃, and the reaction time is 1-4 h.
9. The method for preparing lactic acid from glycerol based on the Salen metal complex intercalated hydrotalcite catalyst according to claim 8, characterized in that: the solution in step B was maintained at a stirring rate of 200 rpm.
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