CN104045544B - A kind of supported copper catalyst catalyzing glycerol produces the method for lactic acid - Google Patents

A kind of supported copper catalyst catalyzing glycerol produces the method for lactic acid Download PDF

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CN104045544B
CN104045544B CN201410296153.5A CN201410296153A CN104045544B CN 104045544 B CN104045544 B CN 104045544B CN 201410296153 A CN201410296153 A CN 201410296153A CN 104045544 B CN104045544 B CN 104045544B
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lactic acid
glycerine
reaction
prepares
carried copper
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CN104045544A (en
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张长华
尹海旭
殷恒波
沈灵沁
冯永海
王爱丽
鲁华胜
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Jiangsu University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/76—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
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
    • 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

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Abstract

The present invention relates to lactic acid preparing technical field, refer in particular to a kind of method that supported copper catalyst catalyzing glycerol prepares lactic acid, the selectivity of lactic acid can reach 70-90%, and glycerol conversion yield can reach 72-100%.It is characterized in that: being be raw material with glycerine, take supported copper oxide as catalyzer, under anaerobic, the alkaline condition that provided by alkali source, carry out being obtained by reacting lactic acid in autoclave, the carrier of described supported copper oxide catalyzer is for comprising MgO, ZrO 2, TiO 2, CeO 2with ZnO at interior metal oxide, gac or hydroxyapatite.This supported copper catalyst is easy to preparation, cheap, work-ing life is longer.The advantages such as the present invention has temperature of reaction and reaction pressure is low, catalyst activity is high and selectivity is good, speed of reaction fast, technological process safety and environmental protection, have good industrial prospect.

Description

A kind of supported copper catalyst catalyzing glycerol produces the method for lactic acid
Technical field
The present invention relates to lactic acid preparing technical field, refer in particular to a kind of method that supported copper catalyst catalyzing glycerol prepares lactic acid.
Background technology
Lactic acid (LacticAcid), chemical system name 2 hydroxy propanoic acid (2-HydroxypropanoicAcid), because alpha site of carboxyl group carbon atom in lactic acid molecules is unsymmetrical carbon, therefore lactic acid has left-handed (L-type) and dextrorotation (D type) enantiomer of two kinds of opticities; Lactic acid was found by Scheele early than 1850 in yogurt milk, and therefore lactic acid gain the name; Lactic acid is one of three large organic acids of generally acknowledging in the world, among the metabolism being extensively present in human body, animal and microorganism, is also present in all respects of people's life.
Lactic acid is broad-spectrum organic acid, is mainly used in food and medicine industry, in brewery industry functional quality mark be 80% lactic acid can prevent miscellaneous bacteria from breeding, promote yeast development, prevent the muddiness of wine and strengthen the local flavor of wine; In foodstuffs industry, general functional quality mark is the lactic acid of 50%, and lactic acid is as anticorrosive mildewproof oxidation inhibitor, and be also the acidic flavoring agent that beverage, cake, jam, candy etc. are conventional, its tart flavour is soft tasty and refreshing, and don't covers food preparation aroma and natural flavour mountaineous; Lactic acid can directly as compounding medicine patent medicine in medicine industry, also oral administration is used for enteron aisle sterilization, due to its strong polarity and hydrophilicity, solubilising protein, cutin and many insoluble medicines, and very responsive to pathological tissues corrosive nature, can be used for treating the diseases such as white monkey, lupus, aditus laryngis tuberculosis, it is again as convergency sterilant simultaneously, can also serum cholesterol be reduced, strengthen body immunity; Lactic acid has purposes widely in the industries such as leather industry, cosmetic industry, production of cigarettes.Lactic acid can synthesizing polylactic acid, and poly(lactic acid), as biodegradable plastic, can be widely used in manufacturing disposable food packing bag, food product containers, wrapping paper, shopping bag, sanitary paper, agricultural film etc., be conducive to preserving the ecological environment, prevent the pollution of the environment; Poly(lactic acid) can also be used as surgical sewing thread, drug controlled release system field, the immobilization material of field of orthopaedics and the propping material of field of tissue engineering technology, and therefore, the demand of lactic acid is by increasing.
Glycerine is the by product in production of biodiesel process, the biofuel of often producing ten tons just has the glycerine of one ton to produce, along with the growth year by year of yield of biodiesel, the output of glycerine also very huge, utilize transformation of glycerol to produce product in the middle of a series of chemical and chemistry, there is feature that is renewable and carbon dioxide zero discharge, and in glycerine, be rich in active hydroxyl, be easy to through replacing synthesis special chemical article, therefore the exploitation of glycerine have huge prospect; Recent research finds, utilize glycerine to prepare novelty teabag that lactic acid not only develops glycerine, also for lactic acid provides continuable raw material sources; From bibliographical information, lactic acid prepared by glycerine fermentation method and chemical synthesis, and chemical synthesis has precious metal aerobic catalysis method and high temperature hydro-thermal anaerobic oxidation method; And the cost of fermentation method and precious metal aerobic catalysis method is very high, glycerine reaction concentration is low and the reaction times waits so long shortcoming; High temperature hydro-thermal anaerobic oxidation method requires higher to temperature of reaction and reaction pressure; DebdutRoy etc. adopt industrial Cu/SiO 2, CuO/Al 2o 3and Cu 2o, can significantly reduce temperature of reaction, but temperature of reaction, reaction times and lactic acid selectivity are all to be improved.
Summary of the invention
The object of the present invention is to provide a kind of carried copper in the basic conditions catalyzing glycerol prepare the method for lactic acid.
Method provided by the present invention take glycerine as raw material, temperature of reaction 150-230 DEG C, the reaction times is 0.5-4h, under the anaerobic alkaline condition that supported copper catalyst exists, carry out being obtained by reacting lactic acid in autoclave.
Alkaline condition of the present invention is provided by following alkali source: comprise sodium hydroxide, potassium hydroxide, sodium carbonate and salt of wormwood.
The glycerine of described reaction adds form for glycerol is become the aqueous solution, and the glycerine solution concentration of its preparation is 1.0-10mol/L.
The alkali number of reaction process is 0.5-1.5mol/mol glycerine, is preferably 1.0-1.2mol/mol glycerine.
The carrier of described supported copper catalyst is for comprising MgO, ZrO 2, TiO 2, CeO 2with ZnO at interior metal oxide, gac or hydroxyapatite.
The charge capacity of described supported copper catalyst is 1 ~ 20%.
The addition of described carried copper and the mass ratio of glycerine are than being 0.1%-10%.
Described oxygen free condition is for carry out emptying with High Purity Nitrogen before the reaction.The pressure of nitrogen does not almost affect reaction.
Described supported copper catalyst adopts equi-volume impregnating to prepare: the copper-loading catalyst preparing different loads amount, takes a certain amount of Cu (NO 3) 2﹒ 3H 2the carrier of O and respective quality, adds the water yield mixing of just thorough impregnation, leaves standstill 5 ~ 6h, then by moisture evaporate to dryness, put into oven drying 12h, calcine 4h, by calcinate via H in retort furnace at 550 DEG C 2at 250 DEG C, reduce 4h, required catalyzer can be obtained.
The technical characteristic that the present invention distinguishes prior art is: employing carried copper is catalyzer, its carrier is different with the carrier of bibliographical information, itself and reaction soln are had an effect, and have the effect of concerted catalysis, temperature of reaction and the reaction pressure that lactic acid prepared by glycerine can be reduced well, improve the concentration of glycerine reaction simultaneously, effectively shorten the reaction times, improve the transformation efficiency of glycerine and the selectivity of lactic acid.
The present invention by oxidative pathway, in the basic conditions, utilizes nitrogen purge, and the rearrangement reaction of the intermediate product obtained through peroxidation glycerine in autoclave obtains lactic acid; The inventive method is under anaerobic alkaline condition, and achieve glycerine and transformed by the highly selective of mode of oxidizing to lactic acid, the selectivity of lactic acid can reach 67-90%, and glycerol conversion yield can reach 75-100%; The inventive method does not need too high temperature of reaction, gets final product completing of realization response, saved a large amount of energy at 150-230 DEG C; The inventive method is carried out under anaerobic alkaline condition, and the requirement for conversion unit is low, invests little; The inventive method system is simple, and be easy to industrialization, catalyst life is long, without running off.
The advantages such as the present invention has temperature of reaction and reaction pressure is low, catalyst activity is high and selectivity is good, speed of reaction fast, technological process safety and environmental protection, have good industrial prospect.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described: method described in following embodiment, if no special instructions, is ordinary method.
embodiment 1
Take 4.58g sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.46g5%Cu/MgO, join in 400mL autoclave together, take 9.20g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) again and carry out constant volume with 100mL volumetric flask, join in reactor, passing into nitrogen carries out emptying, then airtight good, timing after being heated to 230 DEG C, reacts 2 hours.
At the end of reaction, getting that 20mL reaction solution hydrochloric acid carries out being acidified to pH is 2 ~ 3, measures volume after acidifying, pipettes 1mL deionized water constant volume to 25mL, carry out high performance liquid chromatography detection, the output of mensuration lactic acid with transfer pipet; After pipetting 1mL acidifying with transfer pipet again, sample 20 μ L propyl carbinol carries out gas chromatographic analysis; Analysis draws, glycerol conversion yield 87%, lactic acid selectivity 78%.
Reaction conditions: glycerol concentration: 1.0M; NaOH/ glycerine mol ratio: 1.1:1; 5%CuO/MgO/ qualities of glycerin compares: 0.05.
embodiment 2
Take 4.58g sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.46g20%Cu/ZrO 2, join together in 400mL autoclave, then take 9.20g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) and carry out constant volume with 100mL volumetric flask, join in reactor, pass into nitrogen and carry out emptying, then airtight good, timing after being heated to 220 DEG C, reacts 2 hours.
At the end of reaction, getting that 20mL reaction solution hydrochloric acid carries out being acidified to pH is 2 ~ 3, measures volume after acidifying, pipettes 1mL deionized water constant volume to 25mL, carry out high performance liquid chromatography detection, the output of mensuration lactic acid with transfer pipet; After pipetting 1mL acidifying with transfer pipet again, sample 20 μ L carries out gas chromatographic analysis; Analysis draws, glycerol conversion yield 80%, lactic acid selectivity 70%.
Reaction conditions: glycerol concentration: 1.0M; NaOH/ glycerine mol ratio: 1.1:1; 20%Cu/ZrO 2/ qualities of glycerin compares: 0.05.
embodiment 3
Take 4.58g sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.46g20%Cu/TiO 2, join together in 400mL autoclave, then take 9.20g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) and carry out constant volume with 100mL volumetric flask, join in reactor, pass into nitrogen and carry out emptying, then airtight good, timing after being heated to 220 DEG C, reacts 2 hours.
At the end of reaction, getting that 20mL reaction solution hydrochloric acid carries out being acidified to pH is 2 ~ 3, measures volume after acidifying, pipettes 1mL deionized water constant volume to 25mL, carry out high performance liquid chromatography detection, the output of mensuration lactic acid with transfer pipet; After pipetting 1mL acidifying with transfer pipet again, sample 20 μ L carries out gas chromatographic analysis; Analysis draws, glycerol conversion yield 76%, lactic acid selectivity 78%.
Reaction conditions: glycerol concentration: 1.0M; NaOH/ glycerine mol ratio: 1.1:1; 20%Cu/TiO 2/ qualities of glycerin compares: 0.05.
embodiment 4
Take 4.58g sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.46g5%Cu/CeO 2, join together in 400mL autoclave, then take 9.20g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) and carry out constant volume with 100mL volumetric flask, join in reactor, pass into nitrogen and carry out emptying, then airtight good, timing after being heated to 220 DEG C, reacts 2 hours.
At the end of reaction, getting that 20mL reaction solution hydrochloric acid carries out being acidified to pH is 2 ~ 3, measures volume after acidifying, pipettes 1mL deionized water constant volume to 25mL, carry out high performance liquid chromatography detection, the output of mensuration lactic acid with transfer pipet; After pipetting 1mL acidifying with transfer pipet again, sample 20 μ L carries out gas chromatographic analysis; Analysis draws, glycerol conversion yield 80%, lactic acid selectivity 76%.
Reaction conditions: glycerol concentration: 1.0M; NaOH/ glycerine mol ratio: 1.1:1; 5%Cu/CeO 2/ qualities of glycerin compares: 0.05.
embodiment 5
Take 4.58g sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.46g5%Cu/ZnO, join in 400mL autoclave together, take 9.20g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) again and carry out constant volume with 100mL volumetric flask, join in reactor, passing into nitrogen carries out emptying, then airtight good, timing after being heated to 210 DEG C, reacts 2 hours.
At the end of reaction, getting that 20mL reaction solution hydrochloric acid carries out being acidified to pH is 2 ~ 3, measures volume after acidifying, pipettes 1mL deionized water constant volume to 25mL, carry out high performance liquid chromatography detection, the output of mensuration lactic acid with transfer pipet; After pipetting 1mL acidifying with transfer pipet again, sample 20 μ L carries out gas chromatographic analysis; Analysis draws, glycerol conversion yield 75%, lactic acid selectivity 78%.
Reaction conditions: glycerol concentration: 1.0M; NaOH/ glycerine mol ratio: 1.1:1; 5%Cu/ZnO/ qualities of glycerin compares: 0.05.
embodiment 6
Take 6.88g sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.46g10%Cu/ gac, join in 400mL autoclave together, take 13.80g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) again and carry out constant volume with 100mL volumetric flask, join in reactor, passing into nitrogen carries out emptying, then airtight good, timing after being heated to 220 DEG C, reacts 4 hours.
At the end of reaction, getting that 20mL reaction solution hydrochloric acid carries out being acidified to pH is 2 ~ 3, measures volume after acidifying, pipettes 1mL deionized water constant volume to 25mL, carry out high performance liquid chromatography detection, the output of mensuration lactic acid with transfer pipet; After pipetting 1mL acidifying with transfer pipet again, sample 20 μ L carries out gas chromatographic analysis; Analysis draws, glycerol conversion yield 75%, lactic acid selectivity 76%.
Reaction conditions: glycerol concentration: 1.5M; NaOH/ glycerine mol ratio: 1.1:1; 10%Cu/ gac/qualities of glycerin ratio: 0.033.
embodiment 7
Take 4.58g sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.46g20%Cu/HAP, join in 400mL autoclave together, take 9.20g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) again and carry out constant volume with 100mL volumetric flask, join in reactor, passing into nitrogen carries out emptying, then airtight good, timing after being heated to 220 DEG C, reacts 2 hours.
At the end of reaction, getting that 20mL reaction solution hydrochloric acid carries out being acidified to pH is 2 ~ 3, measures volume after acidifying, pipettes 1mL deionized water constant volume to 25mL, carry out high performance liquid chromatography detection, the output of mensuration lactic acid with transfer pipet; After pipetting 1mL acidifying with transfer pipet again, sample 20 μ L carries out gas chromatographic analysis; Analysis draws, glycerol conversion yield 92%, lactic acid selectivity 90%.
Reaction conditions: glycerol concentration: 1.0M; NaOH/ glycerine mol ratio: 1.1:1; 20%Cu/HAP/ qualities of glycerin compares: 0.05.
embodiment 8
Take 45.8g sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 2.3g20%Cu/HAP, join in 400mL autoclave together, take 92.0g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) again and carry out constant volume with 100mL volumetric flask, join in reactor, passing into nitrogen carries out emptying, then airtight good, timing after being heated to 150 DEG C, reacts 4 hours.
At the end of reaction, getting that 20mL reaction solution hydrochloric acid carries out being acidified to pH is 2 ~ 3, measures volume after acidifying, pipettes 1mL deionized water constant volume to 25mL, carry out high performance liquid chromatography detection, the output of mensuration lactic acid with transfer pipet; After pipetting 1mL acidifying with transfer pipet again, sample 20 μ L carries out gas chromatographic analysis; Analysis draws, glycerol conversion yield 75%, lactic acid selectivity 70%.
Reaction conditions: glycerol concentration: 10.0M; NaOH/ glycerine mol ratio: 1.1:1; 20%Cu/HAP/ qualities of glycerin compares: 0.025.
embodiment 9
Take 5.83g sodium carbonate (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.46g10%Cu/ZrO 2, join together in 400mL autoclave, then take 9.20g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) and carry out constant volume with 100mL volumetric flask, join in reactor, pass into nitrogen and carry out emptying, then airtight good, timing after being heated to 220 DEG C, reacts 0.5 hour.
At the end of reaction, getting that 20mL reaction solution hydrochloric acid carries out being acidified to pH is 2 ~ 3, measures volume after acidifying, pipettes 1mL deionized water constant volume to 25mL, carry out high performance liquid chromatography detection, the output of mensuration lactic acid with transfer pipet; After pipetting 1mL acidifying with transfer pipet again, sample 20 μ L carries out gas chromatographic analysis; Analysis draws, glycerol conversion yield 78%, lactic acid selectivity 68%.
Reaction conditions: glycerol concentration: 1.0M; Na 2cO 3/ glycerine mol ratio: 0.55:1; 10%Cu/ZrO 2/ qualities of glycerin compares: 0.05.
embodiment 10
Take 6.16g potassium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.6g10%Cu/ZnO, join in 400mL autoclave together, take 13.80g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) again and carry out constant volume with 100mL volumetric flask, join in reactor, passing into nitrogen carries out emptying, then airtight good, timing after being heated to 220 DEG C, reacts 4 hours.
At the end of reaction, getting that 20mL reaction solution hydrochloric acid carries out being acidified to pH is 2 ~ 3, measures volume after acidifying, pipettes 1mL deionized water constant volume to 25mL, carry out high performance liquid chromatography detection, the output of mensuration lactic acid with transfer pipet; After pipetting 1mL acidifying with transfer pipet again, sample 20 μ L carries out gas chromatographic analysis; Analysis draws, glycerol conversion yield 80%, lactic acid selectivity 72%.
Reaction conditions: glycerol concentration: 1.0M; KOH/ glycerine mol ratio: 1.1:1; 10%Cu/ZnO/ qualities of glycerin compares: 0.043.
comparative example
Take 4.58g sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.46g5%CuO/SiO 2, join together in 400mL autoclave, then take 9.20g glycerine (Chemical Reagent Co., Ltd., Sinopharm Group) and carry out constant volume with 100mL volumetric flask, join in reactor, pass into nitrogen and carry out emptying, then airtight good, timing after being heated to 230 DEG C, reacts 2 hours.
At the end of reaction, getting that 20mL reaction solution hydrochloric acid carries out being acidified to pH is 2 ~ 3, measures volume after acidifying, pipettes 1mL deionized water constant volume to 25mL, carry out high performance liquid chromatography detection, the output of mensuration lactic acid with transfer pipet; After pipetting 1mL acidifying with transfer pipet again, sample 20 μ L carries out gas chromatographic analysis; Analysis draws, glycerol conversion yield 38%, lactic acid selectivity 50%.
Reaction conditions: glycerol concentration: 1.0M; NaOH/ glycerine mol ratio: 1.1:1; 5%CuO/SiO 2/ qualities of glycerin compares: 0.05.
comparative example 2
Other reaction conditionss and step are all identical with comparative example 1, by CuO/SiO 2be changed to CuO/Al 2o 3, glycerol conversion yield 33%, lactic acid selectivity 45%.
Carry out contrast by embodiment 1 and comparative example 1 and 2 can obtain, identical at reaction conditions, when using carrier different, carrier is not had an effect down with solution, is that the transformation efficiency of glycerine or the selectivity of lactic acid are all significantly improved.

Claims (11)

1. a carried copper catalyzing glycerol prepares the method for lactic acid, it is characterized in that: be take glycerine as raw material, take carried copper as catalyzer, under anaerobic, the alkaline condition that provided by alkali source, carry out being obtained by reacting lactic acid in autoclave, the carrier of described supported copper catalyst is for comprising MgO, ZrO 2, TiO 2, CeO 2with ZnO at interior metal oxide, gac or hydroxyapatite.
2. a kind of carried copper catalyzing glycerol according to claim 1 prepares the method for lactic acid, it is characterized in that: described temperature of reaction is 150-230 DEG C, and the described reaction times is 0.5-4h.
3. a kind of carried copper catalyzing glycerol according to claim 1 prepares the method for lactic acid, it is characterized in that: the described alkaline condition provided by alkali source refers to adopt the alkali source comprising sodium hydroxide, potassium hydroxide, sodium carbonate and salt of wormwood.
4. a kind of carried copper catalyzing glycerol according to claim 1 prepares the method for lactic acid, it is characterized in that: described anaerobic refers to carry out emptying with High Purity Nitrogen before the reaction.
5. a kind of carried copper catalyzing glycerol according to claim 1 prepares the method for lactic acid, it is characterized in that: described glycerine add form for glycerol is become the aqueous solution, its preparation glycerine solution concentration be 1.0-10mol/L.
6. a kind of carried copper catalyzing glycerol according to claim 1 prepares the method for lactic acid, it is characterized in that: the add-on of described alkali source is 0.5-1.5mol/mol glycerine.
7. a kind of carried copper catalyzing glycerol according to claim 1 prepares the method for lactic acid, it is characterized in that: the add-on of described alkali source is 1.0-1.2mol/mol glycerine.
8. a kind of carried copper catalyzing glycerol according to claim 1 prepares the method for lactic acid, it is characterized in that: the charge capacity of described carried copper is 1 ~ 20%.
9. a kind of carried copper catalyzing glycerol according to claim 1 prepares the method for lactic acid, it is characterized in that: the addition of described carried copper and the mass ratio of glycerine are 0.1%-10%.
10. a kind of carried copper catalyzing glycerol according to claim 1 prepares the method for lactic acid, and it is characterized in that, reaction conditions is: glycerol concentration: 1.0M; NaOH/ glycerine mol ratio: 1.1:1; 20%Cu/HAP/ qualities of glycerin compares: 0.05, and temperature of reaction is 220 DEG C, and the reaction times is 2h.
11. a kind of carried copper catalyzing glycerols according to claim 1 prepare the method for lactic acid, it is characterized in that, described supported copper catalyst adopts equi-volume impregnating to prepare: the copper-loading catalyst preparing different loads amount, takes a certain amount of Cu (NO 3) 2﹒ 3H 2the carrier of O and respective quality, adds the water yield mixing of just thorough impregnation, leaves standstill 5 ~ 6h, then by moisture evaporate to dryness, put into oven drying 12h, calcine 4h, by calcinate via H in retort furnace at 550 DEG C 2at 250 DEG C, reduce 4h, required catalyzer can be obtained.
CN201410296153.5A 2014-06-27 2014-06-27 A kind of supported copper catalyst catalyzing glycerol produces the method for lactic acid Expired - Fee Related CN104045544B (en)

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CN106807366B (en) * 2015-11-30 2020-02-07 中国科学院大连化学物理研究所 Core-shell catalyst for preparing lactic acid and pyruvic acid from glycerol, and preparation and application thereof
CN106810436B (en) * 2015-11-30 2020-06-30 中国科学院大连化学物理研究所 Method for preparing lactic acid by catalytic oxidation of glycerol
CN105601505B (en) * 2016-03-04 2017-08-04 江苏大学 A kind of method that graphene-supported nickel catalyzed conversion glycerine of low temperature high activity produces lactic acid
CN106316839B (en) * 2016-08-18 2019-03-05 江苏大学 A method of by biomass glycerol one-step synthesis method methyl lactate
CN108786790A (en) * 2018-05-25 2018-11-13 中国石油大学(华东) A kind of highly selective catalyst for preparing lactic acid
CN109174183A (en) * 2018-08-28 2019-01-11 东北师范大学 The method for preparing oxalic acid with POMs/HAP catalysis of solid catalyst glycerol
CN109529833A (en) * 2018-10-18 2019-03-29 江苏大学 A kind of graphene oxide-loaded copper catalyst and its preparation method and application
CN109627155B (en) * 2018-11-13 2021-08-24 广东省石油与精细化工研究院 Method for preparing acid by alcohol catalytic dehydrogenation under solvent-free condition
CN115254125A (en) * 2022-08-17 2022-11-01 江苏大学 Calcium oxide loaded nano copper oxide catalyst and preparation method and application thereof
CN115894213A (en) * 2022-10-26 2023-04-04 辽宁圣德华星化工有限公司 Method for catalytically synthesizing calcium lactate and hydrogen by Cu/apatite nano-catalyst
CN115888711B (en) * 2022-10-26 2024-03-19 辽宁圣德华星化工有限公司 Sodium titanate nanowire supported copper catalyst and preparation method and application thereof

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