CN109369366B - Method for preparing lactic acid by catalytic dehydrogenation of glycerol - Google Patents
Method for preparing lactic acid by catalytic dehydrogenation of glycerol Download PDFInfo
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- CN109369366B CN109369366B CN201811344146.2A CN201811344146A CN109369366B CN 109369366 B CN109369366 B CN 109369366B CN 201811344146 A CN201811344146 A CN 201811344146A CN 109369366 B CN109369366 B CN 109369366B
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- glycerol
- lactic acid
- catalytic dehydrogenation
- bimetallic catalyst
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 298
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000004310 lactic acid Substances 0.000 title claims abstract description 64
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 64
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 40
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 6
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000292 calcium oxide Substances 0.000 abstract description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000395 magnesium oxide Substances 0.000 abstract description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000011787 zinc oxide Substances 0.000 abstract description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 2
- 235000011187 glycerol Nutrition 0.000 description 84
- 238000006243 chemical reaction Methods 0.000 description 79
- 239000012071 phase Substances 0.000 description 15
- 238000011049 filling Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000005070 sampling Methods 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 238000004064 recycling Methods 0.000 description 4
- 239000003225 biodiesel Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CMDGQTVYVAKDNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrate Chemical compound O.OCC(O)CO CMDGQTVYVAKDNA-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- -1 agriculture Substances 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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
- B01J23/72—Copper
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- C07C51/295—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with inorganic bases, e.g. by alkali fusion
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing lactic acid by catalytic dehydrogenation of glycerol, which comprises the following steps: under the protective atmosphere, adding a supported bimetallic catalyst and an alkaline additive into a glycerol aqueous solution, and carrying out catalytic dehydrogenation reaction to obtain lactic acid; the supported bimetallic catalyst takes at least one of active carbon, carbon nano fiber and carbon nano tube as a carrier, and the active component is M1And M2Ox，M1Is at least one of Cu and Ni, M2OxIs at least one of calcium oxide, magnesium oxide, barium oxide, cerium dioxide, lanthanum trioxide, zirconium dioxide and zinc oxide. The invention can realize the high-efficiency catalytic dehydrogenation of the glycerol to prepare the lactic acid, has high yield of the lactic acid, simple preparation process, low cost and easy separation and purification of products, and has potential industrial application prospect.
Description
Technical Field
The invention relates to a method for preparing lactic acid by catalytic dehydrogenation of glycerol.
Background
Lactic acid is an important platform compound, has wide application in the fields of food, medicine, cosmetics, agriculture, chemical industry and the like, and can be used as a monomer to synthesize polylactic acid and prepare biodegradable bioplastic. It is expected that by 2020, the global consumption of polylactic acid will reach 30 ten thousand tons, and thus the demand for monomeric lactic acid will increase dramatically. At present, the industrial production method of lactic acid mainly comprises a starch fermentation method and a chemical synthesis method. The starch fermentation method has the problems of high cost, low lactic acid yield, complex product separation and purification and the like. The chemical synthesis method needs to use highly toxic hydrocyanic acid, and has a large production risk. Therefore, the development of a green and efficient process for preparing lactic acid remains a hot issue.
Glycerol is a by-product of biodiesel production process, and 1 ton of glycerol is produced for every 10 tons of biodiesel produced. With the rapid development of the biodiesel industry, a large amount of glycerin byproduct is accumulated, and how to convert glycerin into high value-added chemicals is a problem. Research finds that glycerol can be converted into lactic acid through catalytic dehydrogenation, so that the problem of difficulty in handling glycerol can be solved, and lactic acid can be obtained.
The traditional method for preparing lactic acid by glycerol catalytic dehydrogenation mainly comprises a homogeneous catalysis method and a multi-phase catalysis method. The homogeneous catalyst is not easy to separate from the reaction system, and the heterogeneous catalyst is easy to separate, so that the multi-phase catalytic method is more beneficial to the industrial production of lactic acid. The catalysts used in the multi-phase catalytic method mainly comprise noble metal catalysts and Cu-based catalysts, wherein the Cu-based catalysts are low in price and are widely applied to the reaction of preparing lactic acid by catalyzing and dehydrogenating glycerol. However, the glycerol catalytic dehydrogenation reaction is carried out under the high-temperature water phase condition, under the reaction condition, Cu nano particles are easy to aggregate, so that the catalyst is deactivated and cannot be recycled, and the stability of the catalyst is poor.
Therefore, a new method is to be developed to realize the efficient catalytic dehydrogenation of glycerol to prepare lactic acid.
Disclosure of Invention
The invention aims to provide a method for preparing lactic acid by catalytic dehydrogenation of glycerol.
The technical scheme adopted by the invention is as follows:
a method for preparing lactic acid by catalytic dehydrogenation of glycerol comprises the following steps: under the protective atmosphere, adding a supported bimetallic catalyst and an alkaline additive into a glycerol aqueous solution, and carrying out catalytic dehydrogenation reaction to obtain lactic acid; the load type bimetalThe catalyst takes at least one of active carbon, carbon nano fiber and carbon nano tube as a carrier, and the active component is M1And M2Ox，M1Is at least one of Cu and Ni, M2OxIs at least one of calcium oxide, magnesium oxide, barium oxide, cerium dioxide, lanthanum trioxide, zirconium dioxide and zinc oxide.
Preferably, the protective atmosphere is a nitrogen atmosphere.
Preferably, the pressure of the nitrogen is 0.1-3.0 MPa.
Preferably, the glycerol aqueous solution has a mass concentration of 1% to 60%.
Preferably, said M1And M2OxThe total mass percentage of the catalyst in the supported bimetallic catalyst is 10-60%.
Preferably, said M1、M2OxThe mass ratio of (0.5-10): 1.
preferably, the dosage of the supported bimetallic catalyst is 5-50% of the mass of the glycerol aqueous solution.
Preferably, the alkaline additive is at least one of sodium hydroxide and potassium hydroxide.
Preferably, the molar ratio of the glycerol to the basic additive is 1: (0.8 to 1.5).
Preferably, the temperature of the catalytic dehydrogenation reaction is 150-260 ℃, and the reaction time is 2-8 h.
Further preferably, the temperature of the catalytic dehydrogenation reaction is 160-220 ℃, and the reaction time is 2-6 h.
The invention has the beneficial effects that:
the invention can realize the high-efficiency catalytic dehydrogenation of the glycerol to prepare the lactic acid, has high yield of the lactic acid, simple preparation process, low cost and easy separation and purification of products, and has potential industrial application prospect.
The supported bimetallic catalyst used in the invention has high catalyst activity, good stability, cyclic utilization, simple preparation method and low price.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
The content of each component in the supported bimetallic catalyst with the number of 1-8 is shown as the following table:
composition of supported bimetallic catalyst numbered 1-8 in Table 1
| Numbering | Active component | M1、M2OxMass ratio of | Active ingredient content (%) | Carrier |
| 1 | Cu-CaO | 1:2 | 30 | Activated carbon |
| 2 | Ni-MgO | 2:1 | 10 | Carbon nanotube |
| 3 | Cu-BaO | 5:1 | 20 | Carbon nanotube |
| 4 | Ni-CeO2 | 10:1 | 50 | Carbon nanofiber |
| 5 | Cu-La2O3 | 3:1 | 40 | Activated carbon |
| 6 | Ni-ZrO2 | 5:1 | 15 | Carbon nanofiber |
| 7 | Cu-ZnO | 8:1 | 25 | Carbon nanotube |
| 8 | Cu-ZrO2 | 6:1 | 60 | Activated carbon |
The preparation of the supported bimetallic catalysts shown in table 1 is as follows: preparing a precursor of an active component into an aqueous solution, adding a carrier, uniformly mixing, standing for 10-15 h, filtering, drying filter residues at 100-120 ℃ for 10-15 h, then placing in a hydrogen atmosphere, and reducing for 2-5 h at 200-500 ℃.
Example 1:
a method for preparing lactic acid by catalytic dehydrogenation of glycerol comprises the following steps:
adding 10 wt% of glycerol aqueous solution into a high-pressure reaction kettle, adding a supported bimetallic catalyst (the addition amount is 20% of the mass of the glycerol aqueous solution), adding NaOH (the molar ratio of the glycerol to the NaOH is 1:1.2), finally sealing the reaction kettle, and adding N into the reaction kettle2Replacing air in the reaction kettle for 3 times, and then filling N2Heating to 240 ℃ till the pressure in the reaction kettle is 1MPa, reacting for 6h, sampling after the reaction is finished, carrying out gas phase and liquid phase analysis, and determining the conversion rate of the glycerol and the yield of the lactic acid, wherein the test results are shown in Table 2:
TABLE 2 test results of catalytic dehydrogenation reaction of glycerol
Example 2:
a method for preparing lactic acid by catalytic dehydrogenation of glycerol comprises the following steps:
adding 1 wt% glycerol aqueous solution into a high-pressure reaction kettle, adding a supported bimetallic catalyst 3 (the addition is 5% of the weight of the glycerol aqueous solution), adding KOH (the molar ratio of the glycerol to the KOH is 1:0.8), sealing the reaction kettle, and adding N2Replacing air in the reaction kettle for 3 times, and then filling N2Heating to 220 ℃ until the pressure in the reaction kettle is 1MPa, reacting for 4 hours, sampling after the reaction is finished, carrying out gas phase and liquid phase analysis, and determining the conversion rate of the glycerol and the yield of the lactic acid.
The test shows that the conversion rate of the glycerol is 75 percent, and the yield of the lactic acid is 70 percent.
Example 3:
a method for preparing lactic acid by catalytic dehydrogenation of glycerol comprises the following steps:
adding 30 wt% glycerol aqueous solution to the solutionPressing the reaction kettle, adding the supported bimetallic catalyst 5 (the addition amount is 25 percent of the weight of the glycerol aqueous solution), adding NaOH (the molar ratio of the glycerol to the NaOH is 1:1), sealing the reaction kettle, and adding N2Replacing air in the reaction kettle for 3 times, and then filling N2Heating to 250 deg.C under 1MPa, reacting for 8 hr, sampling, analyzing gas phase and liquid phase, and determining the conversion rate of glycerol and the yield of lactic acid.
The test shows that the conversion rate of the glycerol is 96 percent, and the yield of the lactic acid is 92 percent.
Example 4:
a method for preparing lactic acid by catalytic dehydrogenation of glycerol comprises the following steps:
adding 60 wt% glycerol water solution into a high-pressure reaction kettle, adding a supported bimetallic catalyst 6 (the addition amount is 40% of the weight of the glycerol water solution), adding KOH (the molar ratio of the glycerol to the KOH is 1:1.5), sealing the reaction kettle, and adding N2Replacing air in the reaction kettle for 3 times, and then filling N2Heating to 260 ℃ till the pressure in the reaction kettle is 1MPa, reacting for 8 hours, sampling after the reaction is finished, carrying out gas phase and liquid phase analysis, and determining the conversion rate of the glycerol and the yield of the lactic acid.
The test shows that the conversion rate of the glycerol is 80 percent, and the yield of the lactic acid is 71 percent.
Example 5:
a method for preparing lactic acid by catalytic dehydrogenation of glycerol comprises the following steps:
adding 45 wt% of glycerol aqueous solution into a high-pressure reaction kettle, adding a supported bimetallic catalyst 8 (the addition amount is 15% of the mass of the glycerol aqueous solution), adding NaOH (the molar ratio of the glycerol to the NaOH is 1:1.1), finally sealing the reaction kettle, and adding N into the reaction kettle2Replacing air in the reaction kettle for 3 times, and then filling N2Heating to 220 ℃ until the pressure in the reaction kettle is 1MPa, reacting for 8h, sampling after the reaction is finished, carrying out gas phase and liquid phase analysis, and determining the conversion rate of the glycerol and the yield of the lactic acid.
The test shows that the conversion rate of the glycerol is 82 percent and the yield of the lactic acid is 76 percent.
Example 6:
a method for preparing lactic acid by catalytic dehydrogenation of glycerol comprises the following steps:
adding 15 wt% of glycerol aqueous solution into a high-pressure reaction kettle, then adding a supported bimetallic catalyst 1 (the addition amount is 50% of the mass of the glycerol aqueous solution), adding KOH (the molar ratio of the glycerol to the KOH is 1:1.1), finally sealing the reaction kettle, and adding N into the reaction kettle2Replacing air in the reaction kettle for 3 times, and then filling N2Heating to 240 ℃ until the pressure in the reaction kettle is 3MPa, reacting for 2h, sampling after the reaction is finished, carrying out gas phase and liquid phase analysis, and determining the conversion rate of the glycerol and the yield of the lactic acid.
The test shows that the conversion rate of the glycerol is 88 percent, and the yield of the lactic acid is 82 percent.
Example 7:
a method for preparing lactic acid by catalytic dehydrogenation of glycerol comprises the following steps:
adding 10 wt% of glycerol aqueous solution into a high-pressure reaction kettle, adding a supported bimetallic catalyst 4 (the addition amount is 50% of the mass of the glycerol aqueous solution), adding NaOH (the molar ratio of the glycerol to the NaOH is 1:1.5), finally sealing the reaction kettle, and adding N into the reaction kettle2Replacing air in the reaction kettle for 3 times, and then filling N2Heating to 150 deg.C under 0.8MPa, reacting for 8 hr, sampling, analyzing gas phase and liquid phase, and determining the conversion rate of glycerol and the yield of lactic acid.
The test shows that the conversion rate of the glycerol is 65 percent, and the yield of the lactic acid is 56 percent.
Example 8:
a method for preparing lactic acid by catalytic dehydrogenation of glycerol comprises the following steps:
adding 20 wt% glycerol aqueous solution into a high-pressure reaction kettle, adding a supported bimetallic catalyst 5 (the addition is 20% of the weight of the glycerol aqueous solution), adding KOH (the molar ratio of the glycerol to the KOH is 1:1.2), sealing the reaction kettle, and adding N2Replacing air in the reaction kettle for 3 times, and then filling N2Heating to 200 deg.C under 2MPa, reacting for 6 hr, and finishing reactionThen, a sample was taken for gas phase and liquid phase analysis, and the conversion of glycerol and the yield of lactic acid were determined.
The test shows that the conversion rate of the glycerol is 88 percent, and the yield of the lactic acid is 82 percent.
Example 9:
a method for preparing lactic acid by catalytic dehydrogenation of glycerol comprises the following steps:
adding 22 wt% of glycerol aqueous solution into a high-pressure reaction kettle, adding a supported bimetallic catalyst 8 (the addition amount is 15% of the mass of the glycerol aqueous solution), adding NaOH (the molar ratio of the glycerol to the NaOH is 1:1.1), finally sealing the reaction kettle, and adding N into the reaction kettle2Replacing air in the reaction kettle for 3 times, and then filling N2Heating to 220 ℃ until the pressure in the reaction kettle is 0.1MPa, reacting for 5h, sampling after the reaction is finished, performing gas phase and liquid phase analysis, and determining the conversion rate of the glycerol and the yield of the lactic acid.
Tests show that the conversion rate of the glycerol is 95 percent, and the yield of the lactic acid is 90 percent.
Example 10:
a method for preparing lactic acid by catalytic dehydrogenation of glycerol comprises the following steps:
adding 15 wt% of glycerol aqueous solution into a high-pressure reaction kettle, adding a supported bimetallic catalyst 5 (the addition amount is 10% of the mass of the glycerol aqueous solution), adding KOH (the molar ratio of the glycerol to the KOH is 1:1.1), finally sealing the reaction kettle, and adding N2Replacing air in the reaction kettle for 3 times, and then filling N2Heating to 240 ℃ until the pressure in the reaction kettle is 3MPa, reacting for 3h, sampling after the reaction is finished, carrying out gas phase and liquid phase analysis, and determining the conversion rate of the glycerol and the yield of the lactic acid.
The test shows that the conversion rate of the glycerol is 90 percent, and the yield of the lactic acid is 85 percent.
Example 11: (Recycling of Supported bimetallic catalysts)
A method for preparing lactic acid by catalytic dehydrogenation of glycerol comprises the following steps:
1) adding 15 wt% of glycerol aqueous solution into a high-pressure reaction kettle, and then adding a supported bimetallic catalyst 5 (adding)The amount of the aqueous solution of the glycerol is 20 percent of the mass of the aqueous solution of the glycerol, NaOH is added (the molar ratio of the glycerol to the NaOH is 1:1.1), and finally the reaction kettle is sealed and N is used2Replacing air in the reaction kettle for 3 times, and then filling N2Heating to 220 ℃ until the pressure in the reaction kettle is 1MPa, reacting for 6 hours, sampling after the reaction is finished, carrying out gas phase and liquid phase analysis, and determining the conversion rate of the glycerol and the yield of the lactic acid;
2) centrifugally separating out the supported bimetallic catalyst 5, washing for 3 times, directly using for the next reaction, recycling the catalyst for 3 times, wherein the recycling performance test results of the supported bimetallic catalyst 5 are shown in the following table:
TABLE 3 Cyclic use Performance test results for Supported bimetallic catalyst 5
| Number of times of recycling | Conversion of glycerol (%) | Lactic acid yield (%) |
| 1 | 98 | 93 |
| 2 | 96 | 92 |
| 3 | 95 | 91 |
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A method for preparing lactic acid by catalytic dehydrogenation of glycerol is characterized by comprising the following steps: the method comprises the following steps: under the protective atmosphere, adding a supported bimetallic catalyst and an alkaline additive into a glycerol aqueous solution, and carrying out catalytic dehydrogenation reaction to obtain lactic acid;
the supported bimetallic catalyst takes carbon nano-fiber as a carrier and takes Ni-CeO as an active component2The Ni-CeO2In the presence of Ni and CeO2The medium mass ratio is 10: 1, the Ni and CeO2The total mass percentage in the supported bimetallic catalyst is 50 percent;
or the supported bimetallic catalyst takes active carbon as a carrier and the active component is Cu-La2O3The Cu-La2O3Middle Cu and La2O3The medium mass ratio is 3: 1, the Cu and La2O3The total mass percentage in the supported bimetallic catalyst is 40 percent;
or the supported bimetallic catalyst takes a carbon nano tube as a carrier, the active component is Cu-ZnO, and the mass ratio of Cu to ZnO in the Cu-ZnO is 8: 1, the total mass percentage of Cu and ZnO in the supported bimetallic catalyst is 25 percent;
or the supported bimetallic catalyst takes active carbon as a carrier and the active component is Cu-ZrO2Said Cu-ZrO2In Cu and ZrO2The medium mass ratio is 6: 1, the Cu and ZrO2The total mass percentage in the supported bimetallic catalyst was 60%.
2. The method for preparing lactic acid by catalytic dehydrogenation of glycerol according to claim 1, wherein: the protective atmosphere is a nitrogen atmosphere.
3. The method for preparing lactic acid by catalytic dehydrogenation of glycerol according to claim 2, wherein: the pressure of the nitrogen is 0.1-3.0 MPa.
4. The process for the catalytic dehydrogenation of glycerol to produce lactic acid according to claim 1 or 3, characterized in that: the mass concentration of the glycerol aqueous solution is 1-60%.
5. The method for preparing lactic acid by catalytic dehydrogenation of glycerol according to claim 1, wherein: the dosage of the supported bimetallic catalyst is 5-50% of the mass of the glycerol aqueous solution.
6. The method for preparing lactic acid by catalytic dehydrogenation of glycerol according to claim 1, wherein: the alkaline additive is at least one of sodium hydroxide and potassium hydroxide.
7. The process for the catalytic dehydrogenation of glycerol to produce lactic acid according to claim 1 or 6, characterized in that: the molar ratio of the glycerol to the alkaline additive is 1: (0.8 to 1.5).
8. The method for preparing lactic acid by catalytic dehydrogenation of glycerol according to claim 1, wherein: the temperature of the catalytic dehydrogenation reaction is 150-260 ℃, and the reaction time is 2-8 h.
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