CN109433266A - Three center POMs catalysis oxidation glycerol of polylysine modification prepare the technology of lactic acid - Google Patents
Three center POMs catalysis oxidation glycerol of polylysine modification prepare the technology of lactic acid Download PDFInfo
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- CN109433266A CN109433266A CN201811448323.1A CN201811448323A CN109433266A CN 109433266 A CN109433266 A CN 109433266A CN 201811448323 A CN201811448323 A CN 201811448323A CN 109433266 A CN109433266 A CN 109433266A
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- glycerol
- lactic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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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
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
A method of lactic acid being prepared with the catalyst of three center polyoxometallates (POMs) oxidation glycerol, is related to (C6H15O2N2)xH3‑xPMo12O40Purposes of the catalyst in biomass orientation conversion, the composition of composite catalyst are as follows: (C6H15O2N2)xH3‑xPMo12O40(it is abbreviated as lyxH3‑xPMo, x=1,2,3).Ly is added in glycerine water solutionxH3‑xPMo, in certain oxygen pressure, temperature and time, the conversion ratio of glycerol can reach 80~96%, and the yield of lactic acid can reach 50~90%.
Description
Technical field:
The present invention relates to the purposes of three center polyacid catalysis oxidation glycerol, relate generally to the by-product glycerin in biodiesel
It is selectively convertered the new technical field for being prepared as lactic acid.
Technical background:
Biomass energy is considered as a kind of renewable, and the energy source of rich reserves.It can be incited somebody to action by photosynthesis
CO in atmosphere2It is stored in biomass in the form of organic matter, this means that not will increase greatly using biomass energy
CO in gas2.Biodiesel be it is a kind of cleaning and biodegradable fuel, can be from non-edible plant, algal oil or animal tallow
A kind of middle extraction, it is considered to be the feasible substitute or additive of petroleum derived gas oils at present.Commercial biodiesel at present may be used
Pass through liquid base catalysis C14–C20The synthesis of the ester exchange reaction of triglycerides (TAG) and unitary or dihydric alcohol.And biodiesel
One of the drawbacks of mass production is brought is exactly a large amount of accumulation of byproduct glycerol.Another important sources of glycerol are biomass
(such as rapeseed and sunflower oil) is generated by the hydrolysis or alcoholysis of triglyceride.Before a century, people
Methyl esters and glycerol can be converted by vegetable oil and animal oil by being known that.But glycerol is in just real quilt in the past 20 years
Concern, this is primarily due to cause during the ester exchange reaction next life generation diesel oil by vegetable seed, soybean and sunflower oil etc.
A large amount of accumulation of by-product glycerin.Every synthesis 3mol methyl esters just has the generation of 1mol glycerol, the about 10wt% of total output.Biology
As a kind of reproducible clean energy resource, European Union once pointed out in 2010 diesel oil, as soon as yield is up to annual 10000000 tons,
It is to say that glycerol will reach annual 1000000 tons as the yield of byproduct.In addition, since the U.S. is according to (2% life of B2 policy
Object diesel oil, 98% conventional diesel) change 2% low-sulfur diesel-oil into biodiesel, by 2012, there is nearly 3.6 × 105Ton
Glycerol enter market.Although the whole world is still limited for the production of biodiesel, the price of glycerol sharply declines, research
As a result it is even more to show that the market value of glycerol itself is limited, once increasing the yield of biodiesel, will immediately reduces the city of glycerol
Field value, only just reduces about 60% in 2008.Glycerol production in preparation of biodiesel was from 1992
6.0×105Ton becomes 2.9 × 10 in 20149Ton.The decline being worth with the increase of biodiesel demand and glycerol.People
Be sought for a kind of value of the glycerol as platform chemicals or basic material.
Lactic acid as a kind of very important chemical platform molecule, food (as acidulant, preservative, even carefully
The inhibitor that bacterium property addles), pharmacy, Biodegradable fibers, poly-lactic acid ester and acrylic acid and environmentally friendly solvent etc. neck
Domain, which suffers from, to be widely applied, and before ranking 12 biological plateform molecules are cited as, and annual output is 1.2 × 105Ton, is expected to not
It plays a role in the biocatalysis synthesis process come.The scheme that lactic acid is a kind of low-cost high-efficiency is prepared by raw material of glycerol,
And about 95% lactic acid is from the fermentation of sugar and sugar alcohol in the world, this is a slow and complicated process, low efficiency, cost
Height, by-product is more and not easy purification.The scheme that lactic acid is a kind of low-cost high-efficiency is prepared by raw material of glycerol.Research shows that
Preparing lactic acid with glycerol can be realized by various catalytic processes, including hydrothermal conversion, hydrogenesis and selective oxidation.Example
Such as, Chaudhari seminar, which is recently reported, is converted into lactic acid based on copper catalyzing glycerol under the conditions of no reducing agent and oxidant
Reaction.(200 DEG C, NaOH/ glycerol molar ratio 1.5) in a mild condition, Cu2O catalyzing glycerol high conversion rate is newborn up to 95.1%
The selectivity of acid is up to 80%.Alkali or Lewis acid can promote benzilic acid rearrangement to react, to improve lactic acid
Yield.Recently, Fan seminar reports a kind of composite catalyst Pt/Sn-MFI molecular sieve, is catalyzed under the conditions of non-alkaline sweet
Oily oxidation prepares lactic acid reaction.Sn-MFI is as a kind of heterogeneous catalysis, and in a mild condition (100 DEG C, for 24 hours), glycerol turns
Rate reaches 89.8%, and the selectivity of lactic acid reaches 80.5%.The polycentric complex catalyst system of result above can be catalyzed
Glycerol one kettle way prepares lactic acid.
Polyacid (HPAs) i.e. polyoxometallate (POMs) is a kind of polynary gold with redox center and acid site
Category-oxygen cluster compound, it is in widespread attention as catalyst in the orientation conversion of biomass.This patent is using amino acid as alkali
Center is introduced into POMs, the three center catalyst Ly of Acid-Base-oxidation that available lysine is combined with polyacidxH3-xPMo,
Oxidation for catalyzing glycerol orients conversion.Conversion lactic acid is oriented in dioxygen oxidation glycerol using lysine and polyacid compound
Using can solve many technical matters:
(1)LyxH3-xPMo catalyst series can be by adjusting lysine soda acid different from the synthesis of the burden control of POMs
Property and oxidation-reduction quality POMs composite catalyst, can satisfy multistep cascade reaction needs；Ly simultaneouslyxH3-xPMo is
With amphiphatic compound system, nanometer reaction can be provided for catalysis reaction using self assembly as the micella of nano-scale in water
?.
The Ly at (2) three centersxH3-xPMo stepping action is in the conversion of glycerol: PMo12O40 3-Mainly act on glycerol oxygen
Oxidative dehydrogenation；Alkali center mainly acts on DHA dehydration preparation PRA；Acid site is conducive to prepare lactic acid.
(3) under temperate condition, catalytic activity highest, glycerol conversion yield reaches 96%, and lactic acid yield reaches 87%.
(4) catalyst can be reused 10 times or more and keep good catalytic activity, good recycling
Property derive from the good stability of catalyst.
Summary of the invention
The object of the present invention is to provide a kind of lysines and polyacid compound to orient conversion lactic acid in dioxygen oxidation glycerol
New method.
The present invention relates to one kind (C of offer6H15O2N2)xH3-xPMo12O40Three centers of (x=1~3) catalyzing glycerol are catalyzed
Agent has composition (C below6H15O2N2)xH3-xPMo12O40(x=1~3), the compound are preferred are as follows:
(1)(C6H15O2N2)H3PMo12O40
(2)(C6H15O2N2)2HPMo12O40
(3)(C6H15O2N2)3PMo12O40
(C provided by the invention6H15O2N2)xH3-xPMo12O40The synthetic method of (x=1~3) is as follows:
A certain amount of H3PMo12O40It is dissolved in 20-100mL distilled water.Lysine solution (lysine and H3-xPMo12O40
Molar ratio be 1~3:1) be added dropwise in HPMo solution, reaction 10~60min start yellow mercury oxide occur, continue to stir
It is filtered after 30~120min, product is washed with distilled water 2-3 times, drying at room temperature, obtains LyxH3-xPMo, yield 70~90%.
Method with catalyst provided by the invention oxidation glycerol is as follows:
In a high pressure reaction kettle, the glycerite and (C of 1-2M is added6H15O2N2)xH3-xPMo12O40(substrate is sweet for catalyst
Oil and catalyst quality ratio are 100:5~20).When mixed liquor is heated to 50-70 DEG C, being passed through pressure is 4-15bar
Oxygen, reaction carry out 6~10h.After reaction, catalyst is centrifugated reuse.Product high-efficient liquid phase color spectral test, it is sweet
The conversion ratio of oil and the yield of lactic acid can achieve 70% -90% and 70% -90% respectively.
Specific embodiment
Embodiment 1
1:2 weighs H in molar ratio3PMo12O40And lysine, it is added separately to the distilled water of 30mL, lysine solution is dropwise
It is added in HPMo solution, reaction 60min starts yellow mercury oxide occur, continues to filter after stirring 30min, product distillation washing
It washs 3 times, drying at room temperature, obtains Ly2HPMo, yield 76%.
Embodiment 2
In a high pressure reaction kettle, it is added and contains 1M glycerine water solution, while Ly is added3(substrate is sweet for HPMo composite catalyst
Oil and catalyst quality ratio are 100:20), when this mixture is heated to 60 DEG C, it is passed through the oxygen that pressure is 10bar, is reacted
Carry out 6h.After reaction, catalyst centrifuge separation is used for next secondary response.Product high-efficient liquid phase color spectral test, glycerol
Conversion ratio reach 75%, the yield of lactic acid reaches 65%.
Claims (2)
1. a kind of three center POMs catalyst for preparing lactic acid for dioxygen oxidation glycerol, it is characterised in that it is polyacid and amino
Amphipathic system that acid is self-assembly of has independent oxidation-reduction quality, acidity and alkalinity, ensure that the same of one pot reaction
Shi Jinhang has following general formula:
(C6H15O2N2)xH3-xPMo12O40(x=1~3).
2. a kind of three center catalyst for catalyzing glycerol as described in claim 1, the compound are preferred are as follows:
(1)(C6H15O2N2)H3PMo12O40
(2)(C6H15O2N2)2HPMo12O40
(3)(C6H15O2N2)3PMo12O40。
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| CN201811448323.1A CN109433266A (en) | 2018-11-29 | 2018-11-29 | Three center POMs catalysis oxidation glycerol of polylysine modification prepare the technology of lactic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110026217A (en) * | 2019-04-19 | 2019-07-19 | 东北师范大学 | A kind of application of more molybdic acid catalyst of argentiferous in oxycellulose |
| CN113600240A (en) * | 2021-07-16 | 2021-11-05 | 清华大学 | Amino acid or derivative modified polyoxometallate and preparation method and application thereof |
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| US20150005526A1 (en) * | 2009-09-18 | 2015-01-01 | Arkema France | Catalyst and process for preparing acrolein and/or acrylic acid by dehydration reaction of glycerin |
| CN105693512A (en) * | 2016-04-06 | 2016-06-22 | 青岛科技大学 | Method for catalyzing alpha-pinene ethyl esterification by using glutamic-acid-functionalized phosphotungstic acid dihydric salt |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110026217A (en) * | 2019-04-19 | 2019-07-19 | 东北师范大学 | A kind of application of more molybdic acid catalyst of argentiferous in oxycellulose |
| CN113600240A (en) * | 2021-07-16 | 2021-11-05 | 清华大学 | Amino acid or derivative modified polyoxometallate and preparation method and application thereof |
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