CN114345337A - Preparation method of lactic acid - Google Patents
Preparation method of lactic acid Download PDFInfo
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- CN114345337A CN114345337A CN202111551363.0A CN202111551363A CN114345337A CN 114345337 A CN114345337 A CN 114345337A CN 202111551363 A CN202111551363 A CN 202111551363A CN 114345337 A CN114345337 A CN 114345337A
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- lactic acid
- glycerol
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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 126
- 239000004310 lactic acid Substances 0.000 title claims abstract description 63
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 187
- 239000010949 copper Substances 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 26
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 16
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 11
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 44
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000004220 aggregation Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 235000011187 glycerol Nutrition 0.000 description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 238000004729 solvothermal method Methods 0.000 description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- 239000013384 organic framework Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 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
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- -1 agriculture Substances 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 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 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001914 filtration Methods 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
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of lactic acid, which comprises the following steps: mixing glycerol, a catalyst, alkali and water, and carrying out catalytic reaction in an inert atmosphere to obtain the lactic acid; the catalyst comprises nitrogen-doped carbon-coated copper and cuprous oxide nanoparticles. The preparation method of the lactic acid disclosed by the invention has the characteristics of simple process, low material cost, high yield and selectivity, and difficult aggregation, good stability and excellent catalytic performance of the nitrogen-doped carbon-coated copper and cuprous oxide nano particles as the catalyst in the reaction of preparing the lactic acid by catalyzing glycerol.
Description
Technical Field
The invention belongs to the field of chemistry, and particularly relates to a preparation method of lactic acid.
Background
Lactic acid is an organic acid with wide application, and has wide application in the fields of food, medicine, cosmetics, agriculture, chemical industry and the like. Meanwhile, lactic acid can also be used as a monomer to synthesize polylactic acid to prepare biodegradable bioplastic, and the lactic acid is widely applied to the fields of manufacturing disposable food packaging bags, food containers, packaging paper, shopping bags, sanitary paper, agricultural films and the like, so that the demand of the market for the lactic acid is ever increasing. 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 huge production risk. Therefore, the development of a green and efficient method for preparing lactic acid is still a hot issue of urgent need in industry.
Glycerol is a by-product of the biodiesel manufacturing 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 byproducts are accumulated, and how to convert glycerin into high value-added chemicals is a hot problem in the chemical industry. Research finds that the glycerin is converted into the lactic acid through a catalytic reaction, so that not only can the glycerin be efficiently utilized, but also the lactic acid with high added value can be obtained.
The traditional method for preparing lactic acid by catalytic dehydrogenation of glycerol 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 catalytic dehydrogenation of glycerol. The Cu-based catalyst reported in the literature is Cu2O nanoparticles, Cu/carbon nanofibers, Cu/ZrO2Cu/hydrotalcite, Cu/MgO, and the like. However, the reaction for catalyzing and converting the glycerol into the lactic acid is carried out under the condition of high-temperature water phase, and under the reaction condition, the stability of Cu nano particles is poor, so that the problem that the catalyst is easy to aggregate, so that the catalyst is deactivated and cannot be recycled is caused. Currently, no method for preparing lactic acid by stably catalyzing glycerol exists in the industry, and therefore, the market urgently needs to develop a method for stably preparing lactic acid.
Disclosure of Invention
In order to overcome the problems of the prior art, one of the objectives of the present invention is to provide an application of nitrogen-doped carbon-coated copper and cuprous oxide nanoparticles; the second purpose of the present invention is to provide a method for producing lactic acid.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides nitrogen-doped carbon-coated copper and cuprous oxide nanoparticles (Cu-Cu)2O @ NC) in preparing lactic acid by catalyzing glycerol.
Preferably, the preparation method of the nitrogen-doped carbon-coated copper and cuprous oxide nanoparticles comprises the following steps:
1) mixing a copper salt, 4' -bipyridyl, terephthalic acid, an alcohol solvent and an amine solvent, and carrying out solvothermal reaction to obtain a copper organic framework precursor;
2) and roasting the copper organic framework precursor to obtain the nitrogen-doped carbon-coated copper and cuprous oxide nanoparticles.
Preferably, in the step 1), the copper salt includes at least one of copper nitrate, copper chloride and copper sulfate; further preferably, in the step 1), the copper salt is copper nitrate.
Preferably, in the step 1), the alcohol solvent includes at least one of methanol, ethanol and butanol; further preferably, in the step 1), the alcohol solvent is methanol.
Preferably, in the step 1), the amine solvent includes at least one of N, N-dimethylformamide and N, N-dimethylacetamide; further preferably, in the step 1), the amine solvent is N, N-dimethylformamide.
Preferably, in the step 1), the temperature of the solvothermal reaction is 100-140 ℃; further preferably, in the step 1), the temperature of the solvothermal reaction is 115-125 ℃.
Preferably, in the step 1), the solvothermal reaction time is 36-60 h; further preferably, in the step 1), the solvothermal reaction time is 42h to 54 h.
Preferably, in the step 1), the mass ratio of the copper salt, the 4,4' -bipyridine, the terephthalic acid, the alcohol solvent and the amine solvent is 1: (0.3-0.34): (0.6-0.8): (30-50): (30-50).
Preferably, in the step 1), the copper organic framework precursor is Cu2(BDC)2(BPY)。
Preferably, in the step 2), the roasting temperature is 300-800 ℃; further preferably, in the step 2), the roasting temperature is 400-700 ℃.
Preferably, in the step 2), the roasting is performed under an inert atmosphere; further preferably, in the step 2), the calcination is performed in a nitrogen atmosphere.
The second aspect of the present invention provides a method for preparing lactic acid, comprising the steps of:
mixing glycerol, a catalyst, alkali and water, and carrying out catalytic reaction in an inert atmosphere to obtain the lactic acid;
the catalyst comprises nitrogen-doped carbon-coated copper and cuprous oxide nanoparticles.
Preferably, the molar ratio of glycerol to base is 1: (1.01-1.5); further preferably, the molar ratio of glycerol to base is 1: (1.03-1.4); still further preferably, the molar ratio of glycerol to base is 1: (1.05-1.3).
Preferably, the base comprises at least one of an alkali metal hydroxide, an alkaline earth metal hydroxide; further preferably, the alkali includes at least one of sodium hydroxide and potassium hydroxide.
Preferably, the mass ratio of the glycerol to the water is 1: (1-50); further preferably, the mass ratio of the glycerol to the water is 1: (1.5-30); still further preferably, the mass ratio of glycerol to water is 1: (2-20); still more preferably, the mass ratio of glycerol to water is 1: (2.3-19).
Preferably, the mass ratio of the catalyst to the glycerol is (0.02-0.5): 1; further preferably, the mass ratio of the catalyst to the glycerin is (0.05-0.2): 1.
preferably, the temperature of the catalytic reaction is 160-240 ℃; further preferably, the temperature of the catalytic reaction is 180 ℃ to 220 ℃.
Preferably, the time of the catalytic reaction is 20 min-120 min; further preferably, the time of the catalytic reaction is 30min to 100 min.
Preferably, the inert atmosphere is a nitrogen atmosphere.
Preferably, the pressure intensity of the catalytic reaction is 0.1MPa to 2.0 MPa; further preferably, the pressure of the catalytic reaction is 0.5MPa to 1.5 MPa; still further preferably, the pressure of the catalytic reaction is 0.8MPa to 1.2 MPa; more preferably, the pressure of the catalytic reaction is 0.9MPa to 1.1 MPa.
The invention has the beneficial effects that:
the preparation method of the lactic acid disclosed by the invention has the characteristics of simple process, low material cost, high yield and selectivity, and difficult aggregation, good stability and excellent catalytic performance of the nitrogen-doped carbon-coated copper and cuprous oxide nano particles as the catalyst in the reaction of preparing the lactic acid by catalyzing glycerol.
Specifically, the invention has the following advantages:
1. the invention relates to nitrogen-doped carbon-coated copper and cuprous oxide nanoparticles (Cu-Cu)2O @ NC) as catalyst, and doping C with N to Cu and Cu2Coating of O nanoparticles to avoid Cu and Cu during reaction2The aggregation of O nano particles grows up, thereby leading the Cu-Cu to be2The O @ NC catalyst can be recycled for multiple times and has better stability. The Cu-Cu2The O @ NC catalyst has the advantages of simple preparation method, low cost and wide material source, and can be industrially produced in a large scale.
2. The invention discloses a Cu-Cu2The method has the advantages of high glycerol conversion rate, high lactic acid yield, short reaction time, excellent catalyst stability and the like, and has a good industrial application scene.
Drawings
FIG. 1 shows a Cu-Cu catalyst2XRD characterization pattern of O @ NC-400.
FIG. 2 shows a Cu-Cu catalyst2XRD pattern of O @ NC-400 after 8 cycles.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available through commercial purchase.
The preparation of the catalyst is further illustrated below with reference to the examples.
Catalyst preparation examples
Cu-Cu2The preparation steps of the O @ NC catalyst are as follows:
1)Cu2(BDC)2(BPY) Synthesis: to a 100mL beaker were added 0.72g of copper nitrate, 0.23g of 4,4' -bipyridine, 0.50g of terephthalic acid, 30mL of methanol, and 30mL of DMF in this order, followed by stirring at room temperature for 1 h. And transferring the mixed solution into a hydrothermal reaction kettle, and reacting for 48 hours at 120 ℃. Finally, obtaining a copper organic framework precursor Cu through centrifugal filtration, washing and vacuum drying2(BDC)2(BPY)。
2)Cu-Cu2Preparation of O @ NC: in N2Under an atmosphere, adding Cu2(BDC)2(BPY) is respectively roasted at 400 ℃, 550 ℃ and 700 ℃ for 2h to respectively obtain the catalysts Cu-Cu2O@NC-400、Cu-Cu2O@NC-550、Cu-Cu2O@NC-700(Cu-Cu2T in O @ NC-T represents the calcination temperature).
FIG. 1 shows a Cu-Cu catalyst2XRD characterization pattern of O @ NC-400. In fig. 1, diffraction peaks at the positions of 43.2 °, 50.4 ° and 74.1 ° are ascribed to Cu; diffraction peaks at 36.4 ° and 61.3 ° positions ascribed to Cu2And O. The above results show that the active components on the prepared catalyst are Cu and Cu2And (3) O nanoparticles.
The preparation of lactic acid by catalyzing glycerol with copper nanoparticles is further described below with reference to examples.
Example 1
The method for preparing lactic acid in this example comprises the following steps:
adding 5 wt% glycerol aqueous solution into a 100mL high-temperature high-pressure reaction kettle, and then adding Cu-Cu2O @ NC-400 catalyst (the addition amount is 2 percent of the mass of the glycerol aqueous solution), and then NaOH (the molar ratio of the glycerol to the NaOH is 1:1.2), finally sealing the reaction kettle and using N2Replacing air in the reaction kettle for 3 times, and then filling N2Heating to 180 deg.C under 1MPa, reacting for 100min, sampling, analyzing gas phase and liquid phase, and determining glycerol conversion rate and lactic acid selectivity. The conversion of glycerol was tested to be 90% and the selectivity to lactic acid 80%.
Example 2
The method for preparing lactic acid in this example comprises the following steps:
adding 10 wt% glycerol aqueous solution into a 100mL high-temperature high-pressure reaction kettle, and then adding Cu-Cu2O @ NC-550 catalyst (the addition amount is 1.2 percent of the mass of the glycerol aqueous solution), KOH (the molar ratio of the glycerol to the KOH is 1:1.05) is added, finally the reaction kettle is sealed, and N is used2Replacing air in the reaction kettle for 3 times, and then filling N2Heating to 220 deg.C under 1MPa, reacting for 60min, sampling, analyzing gas phase and liquid phase, and determining glycerol conversion rate and lactic acid selectivity. The conversion of glycerol was tested to be 95% and the selectivity to lactic acid was tested to be 75%.
Example 3
The method for preparing lactic acid in this example comprises the following steps:
adding 30 wt% glycerol aqueous solution into a 100mL high-temperature high-pressure reaction kettle, and then adding Cu-Cu2O @ NC-700 catalyst (the addition amount is 2 percent of the mass of the glycerol aqueous solution), NaOH (the molar ratio of the glycerol to the NaOH is 1:1.3) is added, and finally the reaction kettle is sealed and N is used2Replacing air in the reaction kettle for 3 times, and then filling N2Heating to 200 deg.C under 1MPa, reacting for 80min, sampling, analyzing gas phase and liquid phase, and determining glycerol conversion rate and lactic acid selectivity. The conversion of glycerol was 100% and the selectivity to lactic acid was 72% as measured.
Example 4
The method for preparing lactic acid in this example comprises the following steps:
adding 5 wt% glycerol aqueous solution into a 100mL high-temperature high-pressure reaction kettle, and then adding Cu-Cu2O @ NC-700 catalyst (added in the amount of glycerol aqueous solution)0.5% of the amount of the catalyst, adding KOH (the molar ratio of the glycerol to the KOH is 1:1.2), finally sealing the reaction kettle, and adding N2Replacing air in the reaction kettle for 3 times, and then filling N2Heating to 220 deg.C under 1MPa, reacting for 30min, sampling, analyzing gas phase and liquid phase, and determining glycerol conversion rate and lactic acid selectivity. The conversion of glycerol was 100% and the selectivity to lactic acid was 73% as tested.
Example 5
The method for preparing lactic acid in this example comprises the following steps:
adding 12 wt% glycerol aqueous solution into a 100mL high-temperature high-pressure reaction kettle, and then adding Cu-Cu2O @ NC-400 catalyst (the addition amount is 1 percent of the mass of the glycerol aqueous solution), NaOH (the molar ratio of the glycerol to the NaOH is 1:1.1) is added, 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 deg.C under 1MPa, reacting for 60min, sampling, analyzing gas phase and liquid phase, and determining glycerol conversion rate and lactic acid selectivity. The conversion of glycerol was tested to be 95% and the selectivity to lactic acid was 84%.
Example 6
The method for preparing lactic acid in this example comprises the following steps:
adding 10 wt% glycerol aqueous solution into a 100mL high-temperature high-pressure reaction kettle, and then adding Cu-Cu2O @ NC-400 catalyst (the addition amount is 1.5 percent of the mass of the glycerol aqueous solution), NaOH (the molar ratio of the glycerol to the NaOH is 1:1.1) is added, finally, the reaction kettle is sealed, and N is used2Replacing air in the reaction kettle for 3 times, and then filling N2Heating to 220 deg.C under 1MPa, reacting for 90min, sampling, analyzing gas phase and liquid phase, and determining glycerol conversion rate and lactic acid selectivity.
The catalyst of this example was Cu-Cu2The recycling steps of O @ NC-400 are as follows:
separating Cu-Cu from the mixture after the reaction2O @ NC-400 catalyst was washed 4 times with water and used directly in the next reaction under the same conditions as described above for the preparation of lactic acid in this example.The catalyst is recycled for 8 times, and the catalyst Cu-Cu is shown in the table 12And O @ NC-400 cyclic use performance test results.
Table 1: catalyst Cu-Cu2O @ NC-400 cyclic use performance test result
| Number of times of recycling | Glycerol conversion (%) | Lactic acid selectivity (%) |
| 1 | 100 | 86 |
| 2 | 100 | 86 |
| 3 | 100 | 86 |
| 4 | 100 | 85 |
| 5 | 100 | 85 |
| 6 | 100 | 85 |
| 7 | 100 | 84 |
| 8 | 100 | 84 |
The examples of the invention show that the catalyst Cu-Cu2O @ NC has high-efficiency catalytic performance for catalyzing glycerol to prepare lactic acid, the conversion rate of the glycerol in the reaction is 90-100%, and the selectivity of the lactic acid is 72-86%. The catalyst Cu-Cu prepared by the invention2The stable catalytic effect can still be kept after the O @ NC is recycled for 8 times, which shows that the catalyst solves the problem that after the reaction is carried out under the condition of high-temperature water phase, copper nano particles are easy to aggregate, so that the catalyst is inactivated. FIG. 2 shows a Cu-Cu catalyst2XRD pattern of O @ NC-400 after 8 cycles. As can be seen from a comparison of FIGS. 1 and 2, the catalyst Cu-Cu2XRD patterns of O @ NC-400 before and after reaction are almost the same, and further shows that the catalyst has good stability.
Comparative example:
table 2 shows the number of times of recycling of the Cu-based catalyst in the published literature.
TABLE 2 number of cycles of Cu-based catalysts in published literature
As can be seen from table 2, the Cu-based catalyst in the published literature has a small number of cycles, and cannot satisfy the requirement of stably catalyzing glycerol to produce lactic acid.
The above examples are preferred embodiments of the present invention, but the present invention is not limited to the above examples, 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 they are included in the scope of the present invention.
Claims (10)
1. Application of nitrogen-doped carbon-coated copper and cuprous oxide nanoparticles in preparation of lactic acid by catalyzing glycerol.
2. A method for preparing lactic acid is characterized in that: the method comprises the following steps:
mixing glycerol, a catalyst, alkali and water, and carrying out catalytic reaction in an inert atmosphere to obtain the lactic acid;
the catalyst comprises nitrogen-doped carbon-coated copper and cuprous oxide nanoparticles.
3. The method for producing lactic acid according to claim 2, characterized in that: the molar ratio of glycerol to base is 1: (1.01-1.5).
4. The method for producing lactic acid according to claim 3, characterized in that: the base comprises at least one of an alkali metal hydroxide and an alkaline earth metal hydroxide.
5. The method for producing lactic acid according to claim 2, characterized in that: the mass ratio of the catalyst to the glycerol is (0.02-0.5): 1.
6. the method for producing lactic acid according to claim 2, characterized in that: the mass ratio of the glycerol to the water is 1: (1-50).
7. The method for producing lactic acid according to claim 2, characterized in that: the temperature of the catalytic reaction is 160-240 ℃.
8. The method for producing lactic acid according to claim 2, characterized in that: the time of the catalytic reaction is 20 min-120 min.
9. The method for producing lactic acid according to claim 2, characterized in that: the inert atmosphere is a nitrogen atmosphere.
10. The method for producing lactic acid according to claim 9, characterized in that: the pressure intensity of the catalytic reaction is 0.1 MPa-2.0 MPa.
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