CN109369366A - A kind of method that glycerine catalytic dehydrogenation prepares lactic acid - Google Patents
A kind of method that glycerine catalytic dehydrogenation prepares lactic acid Download PDFInfo
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- CN109369366A CN109369366A CN201811344146.2A CN201811344146A CN109369366A CN 109369366 A CN109369366 A CN 109369366A CN 201811344146 A CN201811344146 A CN 201811344146A CN 109369366 A CN109369366 A CN 109369366A
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- lactic acid
- glycerine
- catalytic dehydrogenation
- prepares lactic
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 202
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 101
- 239000004310 lactic acid Substances 0.000 title claims abstract description 54
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 54
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000000654 additive Substances 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 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
- 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
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000292 calcium oxide Substances 0.000 claims abstract description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 4
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 4
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims abstract description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011787 zinc oxide Substances 0.000 claims abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract 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
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000003863 metallic catalyst Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 25
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 13
- 239000012071 phase Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 11
- 238000005070 sampling Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003225 biodiesel Substances 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 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
- 238000003786 synthesis reaction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 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
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
Abstract
The invention discloses a kind of methods that glycerine catalytic dehydrogenation prepares lactic acid, comprising the following steps: under protective atmosphere, load type bimetal catalyst and alkalinity additive are added in glycerin solution, carries out catalytic dehydrogenating reaction, obtains lactic acid；The load type bimetal catalyst at least one of active carbon, carbon nano-fiber, carbon nanotube for carrier, active component M1And M2Ox, M1For at least one of Cu, Ni, M2OxFor at least one of calcium oxide, magnesia, barium monoxide, ceria, lanthanum oxide, zirconium dioxide, zinc oxide.The present invention may be implemented glycerine efficient catalytic dehydrogenation and prepare lactic acid, and the high income of lactic acid, preparation process is simple, at low cost, and product can be easily separated purification, have potential prospects for commercial application.
Description
Technical field
The present invention relates to a kind of methods that glycerine catalytic dehydrogenation prepares lactic acid.
Background technique
Lactic acid is a kind of important platform chemicals, is had extensively in fields such as food, medicine, cosmetics, agricultural and chemical industry
General purposes, and lactic acid also acts as monomer and carrys out synthesizing polylactic acid, prepares biodegradable biological plastics.Expect 2020
Year, the consumption of global polylactic acid is up to 300,000 tons, therefore will increase severely with day to the demand of monomer lactic acid.Currently, industrial
The method of upper production lactic acid mainly has amylo process and chemical synthesis.There are at high cost, lactate yield is low for amylo process
The problems such as complicated with product separating-purifying.Chemical synthesis needs the hydrogen cyanide using severe toxicity, and there are biggish production risk.
Therefore, develop the method for green high-efficient to prepare lactic acid be still hot issue.
Glycerine is the by-product in preparation of biodiesel, and the biodiesel of every 10 tons of production will generate 1 ton
Glycerine.With the fast development of Biodiesel, glycerine by-product is largely accumulated, and how glycerine is converted to height
The chemicals of added value is always problem.It, not only can be with the study found that by catalytic dehydrogenation glycerine can be converted to lactic acid
It solves the problems, such as that glycerine is intractable, but also lactic acid can be obtained.
The method that traditional glycerine catalytic dehydrogenation prepares lactic acid mainly has homogeneous catalysis method and heterogeneous catalysis method.Homogeneously urge
Agent is not easy to separate from reaction system, and heterogeneous catalyst is then easily isolated, therefore heterogeneous catalysis method is more advantageous to the industry of lactic acid
Production.The catalyst that heterogeneous catalysis method uses mainly has noble metal catalyst and Cu base catalyst these two types of, and wherein Cu base is catalyzed
Agent price is cheap, has more application in the reaction of glycerine catalytic dehydrogenation lactic acid.But, glycerine catalytic dehydrogenating reaction exists
It is carried out under the conditions of high temperature water phase, under this reaction condition, Cu nanoparticle is easily assembled cannot so as to cause catalyst inactivation
It is recycled, the stability of catalyst is poor.
Therefore, realize that glycerine efficient catalytic dehydrogenation prepares lactic acid up for exploitation new method.
Summary of the invention
The purpose of the present invention is to provide a kind of methods that glycerine catalytic dehydrogenation prepares lactic acid.
The technical solution used in the present invention is:
A kind of method that glycerine catalytic dehydrogenation prepares lactic acid, comprising the following steps: water-soluble in glycerine under protective atmosphere
Load type bimetal catalyst and alkalinity additive are added in liquid, carries out catalytic dehydrogenating reaction, obtains lactic acid；The support type is double
Metallic catalyst at least one of active carbon, carbon nano-fiber, carbon nanotube for carrier, active component M1And M2Ox, M1
For at least one of Cu, Ni, M2OxFor calcium oxide, magnesia, barium monoxide, ceria, lanthanum oxide, zirconium dioxide, oxidation
At least one of zinc.
Preferably, the protective atmosphere is nitrogen atmosphere.
Preferably, the pressure of the nitrogen is 0.1~3.0MPa.
Preferably, the mass concentration of the glycerin solution is 1%~60%.
Preferably, the M1And M2OxIn load type bimetal catalyst shared gross mass percentage be 10%~
60%.
Preferably, the M1、M2OxMass ratio be (0.5~10): 1.
Preferably, the dosage of the load type bimetal catalyst is the 5%~50% of glycerin solution quality.
Preferably, the alkalinity additive is at least one of sodium hydroxide, potassium hydroxide.
Preferably, the glycerine, alkalinity additive molar ratio be 1:(0.8~1.5).
Preferably, the temperature of the catalytic dehydrogenating reaction is 150~260 DEG C, and the reaction time is 2~8h.
It is further preferred that the temperature of the catalytic dehydrogenating reaction is 160~220 DEG C, the reaction time is 2~6h.
The beneficial effects of the present invention are:
The present invention may be implemented glycerine efficient catalytic dehydrogenation and prepare lactic acid, and the high income of lactic acid, preparation process is simple, at
This is low, and product can be easily separated purification, has potential prospects for commercial application.
The catalyst activity of load type bimetal catalyst used in the present invention is high, stability is good, and can recycle benefit
With preparation method is simple, cheap.
Specific embodiment
The present invention will be further explained combined with specific embodiments below and explanation.
The content of each component is as shown in the table in the load type bimetal catalyst of number 1~8:
The composition of the load type bimetal catalyst of 1 number 1~8 of table
| Number | Active component | M1、M2OxMass ratio | Active component content (%) | Carrier |
| 1 | Cu-CaO | 1:2 | 30 | Active carbon |
| 2 | Ni-MgO | 2:1 | 10 | Carbon nanotube |
| 3 | Cu-BaO | 5:1 | 20 | Carbon nanotube |
| 4 | Ni-CeO2 | 10:1 | 50 | Carbon nano-fiber |
| 5 | Cu-La2O3 | 3:1 | 40 | Active carbon |
| 6 | Ni-ZrO2 | 5:1 | 15 | Carbon nano-fiber |
| 7 | Cu-ZnO | 8:1 | 25 | Carbon nanotube |
| 8 | Cu-ZrO2 | 6:1 | 60 | Active carbon |
Load type bimetal catalyst shown in table 1 the preparation method is as follows: first the presoma of active component is configured to
Aqueous solution adds carrier, stands 10~15h after mixing, filters, filter residue dry 10~15h at 100~120 DEG C, then
It is placed under hydrogen atmosphere, 200~500 DEG C of reductase 12~5h.
Embodiment 1:
A kind of method that glycerine catalytic dehydrogenation prepares lactic acid, comprising the following steps:
The glycerin solution of 10wt% is added in autoclave, load type bimetal catalyst is then added
The 20% of glycerin solution quality (additive amount be), add NaOH (glycerine, NaOH molar ratio be 1:1.2), finally
Reaction kettle is sealed, N is used2Air 3 times, are then charged with N in replacement reaction kettle2Pressure is 1MPa in reaction kettle, is heated to 240 DEG C,
6h is reacted, after reaction, sampling carries out gas phase and liquid phase analysis, measures glycerine conversion ratio and lactate yield, test result
It is as shown in table 2:
2 glycerine catalytic dehydrogenating reaction test result of table
Embodiment 2:
A kind of method that glycerine catalytic dehydrogenation prepares lactic acid, comprising the following steps:
The glycerin solution of 1wt% is added in autoclave, load type bimetal catalyst 3 is then added
The 5% of glycerin solution quality (additive amount be), add KOH (glycerine, KOH molar ratio be 1:0.8), finally sealed
Reaction kettle uses N2Air 3 times, are then charged with N in replacement reaction kettle2Pressure is 1MPa in reaction kettle, is heated to 220 DEG C, reaction
4h, after reaction, sampling carry out gas phase and liquid phase analysis, measure glycerine conversion ratio and lactate yield.
After tested, the conversion ratio of glycerine is 75%, and the yield of lactic acid is 70%.
Embodiment 3:
A kind of method that glycerine catalytic dehydrogenation prepares lactic acid, comprising the following steps:
The glycerin solution of 30wt% is added in autoclave, load type bimetal catalyst 5 is then added
The 25% of glycerin solution quality (additive amount be), add NaOH (glycerine, NaOH molar ratio be 1:1), it is last close
Reaction kettle is sealed, N is used2Air 3 times, are then charged with N in replacement reaction kettle2Pressure is 1MPa in reaction kettle, is heated to 250 DEG C, instead
8h is answered, after reaction, sampling carries out gas phase and liquid phase analysis, measures glycerine conversion ratio and lactate yield.
After tested, the conversion ratio of glycerine is 96%, and the yield of lactic acid is 92%.
Embodiment 4:
A kind of method that glycerine catalytic dehydrogenation prepares lactic acid, comprising the following steps:
The glycerin solution of 60wt% is added in autoclave, load type bimetal catalyst 6 is then added
The 40% of glycerin solution quality (additive amount be), add KOH (glycerine, KOH molar ratio be 1:1.5), it is last close
Reaction kettle is sealed, N is used2Air 3 times, are then charged with N in replacement reaction kettle2Pressure is 1MPa in reaction kettle, is heated to 260 DEG C, instead
8h is answered, after reaction, sampling carries out gas phase and liquid phase analysis, measures glycerine conversion ratio and lactate yield.
After tested, the conversion ratio of glycerine is 80%, and the yield of lactic acid is 71%.
Embodiment 5:
A kind of method that glycerine catalytic dehydrogenation prepares lactic acid, comprising the following steps:
The glycerin solution of 45wt% is added in autoclave, load type bimetal catalyst 8 is then added
The 15% of glycerin solution quality (additive amount be), add NaOH (glycerine, NaOH molar ratio be 1:1.1), finally
Reaction kettle is sealed, N is used2Air 3 times, are then charged with N in replacement reaction kettle2Pressure is 1MPa in reaction kettle, is heated to 220 DEG C,
8h is reacted, after reaction, sampling carries out gas phase and liquid phase analysis, measures glycerine conversion ratio and lactate yield.
After tested, the conversion ratio of glycerine is 82%, and the yield of lactic acid is 76%.
Embodiment 6:
A kind of method that glycerine catalytic dehydrogenation prepares lactic acid, comprising the following steps:
The glycerin solution of 15wt% is added in autoclave, load type bimetal catalyst 1 is then added
The 50% of glycerin solution quality (additive amount be), add KOH (glycerine, KOH molar ratio be 1:1.1), it is last close
Reaction kettle is sealed, N is used2Air 3 times, are then charged with N in replacement reaction kettle2Pressure is 3MPa in reaction kettle, is heated to 240 DEG C, instead
2h is answered, after reaction, sampling carries out gas phase and liquid phase analysis, measures glycerine conversion ratio and lactate yield.
After tested, the conversion ratio of glycerine is 88%, and the yield of lactic acid is 82%.
Embodiment 7:
A kind of method that glycerine catalytic dehydrogenation prepares lactic acid, comprising the following steps:
The glycerin solution of 10wt% is added in autoclave, load type bimetal catalyst 4 is then added
The 50% of glycerin solution quality (additive amount be), add NaOH (glycerine, NaOH molar ratio be 1:1.5), finally
Reaction kettle is sealed, N is used2Air 3 times, are then charged with N in replacement reaction kettle2Pressure is 0.8MPa in reaction kettle, is heated to 150
DEG C, 8h is reacted, after reaction, sampling carries out gas phase and liquid phase analysis, measures glycerine conversion ratio and lactate yield.
After tested, the conversion ratio of glycerine is 65%, and the yield of lactic acid is 56%.
Embodiment 8:
A kind of method that glycerine catalytic dehydrogenation prepares lactic acid, comprising the following steps:
The glycerin solution of 20wt% is added in autoclave, load type bimetal catalyst 5 is then added
The 20% of glycerin solution quality (additive amount be), add KOH (glycerine, KOH molar ratio be 1:1.2), it is last close
Reaction kettle is sealed, N is used2Air 3 times, are then charged with N in replacement reaction kettle2Pressure is 2MPa in reaction kettle, is heated to 200 DEG C, instead
6h is answered, after reaction, sampling carries out gas phase and liquid phase analysis, measures glycerine conversion ratio and lactate yield.
After tested, the conversion ratio of glycerine is 88%, and the yield of lactic acid is 82%.
Embodiment 9:
A kind of method that glycerine catalytic dehydrogenation prepares lactic acid, comprising the following steps:
The glycerin solution of 22wt% is added in autoclave, load type bimetal catalyst 8 is then added
The 15% of glycerin solution quality (additive amount be), add NaOH (glycerine, NaOH molar ratio be 1:1.1), finally
Reaction kettle is sealed, N is used2Air 3 times, are then charged with N in replacement reaction kettle2Pressure is 0.1MPa in reaction kettle, is heated to 220
DEG C, 5h is reacted, after reaction, sampling carries out gas phase and liquid phase analysis, measures glycerine conversion ratio and lactate yield.
After tested, the conversion ratio of glycerine is 95%, and the yield of lactic acid is 90%.
Embodiment 10:
A kind of method that glycerine catalytic dehydrogenation prepares lactic acid, comprising the following steps:
The glycerin solution of 15wt% is added in autoclave, load type bimetal catalyst 5 is then added
The 10% of glycerin solution quality (additive amount be), add KOH (glycerine, KOH molar ratio be 1:1.1), it is last close
Reaction kettle is sealed, N is used2Air 3 times, are then charged with N in replacement reaction kettle2Pressure is 3MPa in reaction kettle, is heated to 240 DEG C, instead
3h is answered, after reaction, sampling carries out gas phase and liquid phase analysis, measures glycerine conversion ratio and lactate yield.
After tested, the conversion ratio of glycerine is 90%, and the yield of lactic acid is 85%.
The recycling of embodiment 11:(load type bimetal catalyst)
A kind of method that glycerine catalytic dehydrogenation prepares lactic acid, comprising the following steps:
1) glycerin solution of 15wt% is added in autoclave, load type bimetal catalyst is then added
5 the 20% of glycerin solution quality (additive amounts be), add NaOH (glycerine, NaOH molar ratio be 1:1.1), finally
Reaction kettle is sealed, N is used2Air 3 times, are then charged with N in replacement reaction kettle2Pressure is 1MPa in reaction kettle, is heated to 220 DEG C,
6h is reacted, after reaction, sampling carries out gas phase and liquid phase analysis, measures glycerine conversion ratio and lactate yield；
2) it is centrifugated out load type bimetal catalyst 5, washes 3 times, lower secondary response is directly used in, by catalyst circulation
Using 3 times, test result is as follows shown in table for the recycling performance of load type bimetal catalyst 5:
The recycling performance test result of 3 load type bimetal catalyst 5 of table
| Number is recycled | Glycerine conversion ratio (%) | Lactate yield (%) |
| 1 | 98 | 93 |
| 2 | 96 | 92 |
| 3 | 95 | 91 |
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of method that glycerine catalytic dehydrogenation prepares lactic acid, it is characterised in that: the following steps are included: under protective atmosphere,
Load type bimetal catalyst and alkalinity additive are added in glycerin solution, carries out catalytic dehydrogenating reaction, obtains lactic acid；Institute
Load type bimetal catalyst is stated at least one of active carbon, carbon nano-fiber, carbon nanotube as carrier, active component is
M1And M2Ox, M1For at least one of Cu, Ni, M2OxFor calcium oxide, magnesia, barium monoxide, ceria, lanthanum oxide, two
At least one of zirconium oxide, zinc oxide.
2. the method that glycerine catalytic dehydrogenation according to claim 1 prepares lactic acid, it is characterised in that: the protective atmosphere
For nitrogen atmosphere.
3. the method that glycerine catalytic dehydrogenation according to claim 2 prepares lactic acid, it is characterised in that: the pressure of the nitrogen
It is by force 0.1~3.0MPa.
4. the method that glycerine catalytic dehydrogenation according to claim 1 or 3 prepares lactic acid, it is characterised in that: described the third three
The mass concentration of alcohol solution is 1%~60%.
5. the method that glycerine catalytic dehydrogenation according to claim 1 prepares lactic acid, it is characterised in that: the M1And M2Ox
Shared gross mass percentage is 10%~60% in load type bimetal catalyst.
6. the method that glycerine catalytic dehydrogenation prepares lactic acid according to claim 1 or 5, it is characterised in that: the M1、
M2OxMass ratio be (0.5~10): 1.
7. the method that glycerine catalytic dehydrogenation according to claim 1 prepares lactic acid, it is characterised in that: the support type is double
The dosage of metallic catalyst is the 5%~50% of glycerin solution quality.
8. the method that glycerine catalytic dehydrogenation according to claim 1 prepares lactic acid, it is characterised in that: the alkalinity addition
Agent is at least one of sodium hydroxide, potassium hydroxide.
9. the method that glycerine catalytic dehydrogenation according to claim 1 or 8 prepares lactic acid, it is characterised in that: described the third three
Alcohol, alkalinity additive molar ratio be 1:(0.8~1.5).
10. the method that glycerine catalytic dehydrogenation according to claim 1 prepares lactic acid, it is characterised in that: the catalysis is de-
The temperature of hydrogen reaction is 150~260 DEG C, and the reaction time is 2~8h.
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