CN107915628A - A kind of green synthesis process of pyruvate - Google Patents
A kind of green synthesis process of pyruvate Download PDFInfo
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- CN107915628A CN107915628A CN201711348403.5A CN201711348403A CN107915628A CN 107915628 A CN107915628 A CN 107915628A CN 201711348403 A CN201711348403 A CN 201711348403A CN 107915628 A CN107915628 A CN 107915628A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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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)
Abstract
The present invention provides a kind of green synthesis process of pyruvate, and using heterogeneous catalytic reaction, catalyst can recycle again, in addition, the catalytic reaction is not required to solvent, reaction condition is gentle, and the waste of generation is few, energy conservation and environmental protection.
Description
Technical field
The present invention relates to the preparing technical field of pyruvate, and in particular to a kind of green synthesis process of pyruvate.
Background technology
There is carbonyl and carboxyl Liang Ge functional groups at the same time in the molecule of pyruvic acid, compare vague generalization more because being showed reaction center
The even more important and special chemical property of compound.Pyruvic acid is the precursor for synthesizing various other products, such as pyruvic acid is exactly to close
Into some amino acid, as L-Trp, L. tyrosine, L. DOPA, L. cysteines, L. leucines important as precursors.Pyruvic acid
It can be also used for synthesis vitamin B6 and B12 etc..Pyruvic acid and its derivative also have many purposes in addition.Ethyl pyruvate
The superior performance in terms of heterocyclic compound is formed, is the raw material and intermediate for being difficult to substitute in pesticide synthesis, it is widely used
In the synthesis of fungicide and herbicide.
The synthetic intermediate of Pyruvate or important drugs, for example, recently, by Sodium Pyruvate, synthesis
One kind be referred to as the compound of " the anti-medicine of angiotensin ", it is just effective to suppress the " formation of angiotensins .2 ", so as to reach
It is evident in efficacy to the purpose to reduce blood pressure；From ethyl pyruvate, the elastase inhibitor of synthesis is serial protease suppression
One of preparation, prepares human leukocyte elastase's inhibitor, and the viral egg of the AntiHIV1 RT activity infection of synthesis treatment AIDS
White enzyme inhibitor, the antiviral miscellaneous quinoxaline of synthesis, sedative, analgesics anti-inflammatory quinophan, anti-tubercular drug isoniazid acetone
Sour calcium, medicine phosphoenolpyruvate, 4- first iminazole acids etc...In addition in terms of cosmetics, pyruvate also has good
Using for example, add ethyl pyruvate in cosmetics, for skin whitening, suppressing the formation of epidermis stain (melanin), especially
It is to suppress effect of the tyrosinase formed with uniqueness in epidermis.
Pyruvic acid has the function of good anti-corrosive fresh-keeping, the country is used to raise on a small quantity at present as feed and food additives
In the preservation of material and fruit wine；Pyruvic acid has been widely used as biotechnology diagnostic reagent, detection reagent.Additionally, it is contemplated that pyruvic acid exists
Vast potential for future development will be had in terms of biotechnology, as Biochemical Research is used for the calibrating of primary alconol and secondary alcohol；The measure of transaminase
Deng.It is the starting material of many kinds of substance such as synthesizing ethylene based polymer, hydratropic acid, historical relics protective agent.
The synthetic method of pyruvic acid can be divided into biotechnology method and chemical synthesis.Biotechnology method refers to utilize microorganism
Fermentation or microorganism in enzyme system make the method that substrate is converted into purpose product.Mainly include fermentation method and enzyme process.Change
Tartaric acid (salt) method, lactic acid (ester) oxidizing process, hydroxypropanone- method, propane diols method, acetone method, pyroracemic aldehyde can be divided into by learning synthetic method
Method, 2,2. dichloropropionic acid methods, acetyl chloride method, methacrylic acid (ester) method etc..This method of lactic acid (ester) air oxidation process because
The primary raw material of fermentation method production lactic acid is resourceful cornstarch, and efficiency of pcr product is high, and cost is low, and can also make from now on
By the use of more cheap plant fiber hydrolysate etc. as the raw material of production of lactic acid, lactic acid will be that the very cheap fermentation industry of cost is produced
Product.And as the air of oxidant, its price is also very low.As long as therefore can find it is a kind of efficiently, low consumption and cheap
Catalyst, the economic benefit that pyruvic acid is prepared using lactic acid as raw material direct oxidation dehydrogenation will be very considerable.Consider each
The influence of factor, the prospect of lactic acid (salt) air oxidation are the most wide.And especially using lactic acid as raw material under catalyst action it is straight
It is optimal synthetic route to connect oxidative dehydrogenation synthesis pyruvic acid, because so not only eliminating the esterification process of lactic acid but also saving
The hydrolytic process of reaction product pyruvate.The reaction equation of lactic acid oxidative dehydrogenation pyruvic acid is as follows：
But during due to gas phase air oxidation, C-C key oxidation scissions make lactic acid easily be converted into acetaldehyde and CO2Rather than pyruvic acid, because
And it is badly in need of exploitation a kind of efficiently, low consumption and cheap catalyst system and catalyzing.
The content of the invention
To solve the above problems, the present invention provides a kind of green synthesis process of pyruvate, its using lactate as raw material,
Oxygen-containing gas is oxidant, in the presence of Zn-CuO/ZSM-5 supported catalysts, through peroxidization, is directly prepared third
Keto ester；Concrete operation step is：
A certain amount of substrate, catalysts and solvents, closed reactor, with oxygen or air displacement reaction are added in pressure reactor
In device gas several times after, be filled with oxygen partial pressure to 0.7~1.5MPa, be heated to 40~160 DEG C, react 4~20h.
Further, the dosage of the catalyst is the 0.001-20.0wt% of raw milk acid esters.
Further, oxidant used is air or oxygen, and offering oxygen way is atmospheric bubbling.
Further, oxidant used is air or oxygen, and offering oxygen way supplies oxygen for high pressure, pressure value 0.01-5MPa.
Further, the method for preparing pyruvate is carried out without solvent or in aqueous solvent.
Further, the flow velocity of air or oxygen is 0.01-1000 liters/m of material/minute in the atmospheric bubbling.
Further, the raw milk acid esters is selected from methyl lactate, ethyl lactate, lactic acid n-propyl ester, isopropyl lactate, breast
One or more in the secondary butyl ester of acid butyl ester, isobutyl lactate, lactic acid.
The preparation method of the molecular sieve carried catalyst of Zn-CuO/ is：By forming zinc and copper and organic dispersing agent
Organic dispersing agent metal complex obtains Zn-Cu/ dispersants/ZSM-5 presomas on ZSM-5 is loaded to；At 380~550 DEG C
Zn-Cu/ dispersants/ZSM-5 presomas are roasted, the time is 2~6h, obtains required catalyst.
Organic dispersing agent of the present invention contains the functional group for the ion that can be complexed Zn-Cu, and complexing functional group can be amido
Or two amido.Also containing on the side chain of the organic dispersing agent of the present invention can be with the grafted moiety of ZSM-5.The acquisition of the catalyst
Preferably include following steps：Organic dispersing agent is loaded in catalyst carrier by grafted functional group, obtain organic dispersing agent/
ZSM-5 presomas；The solution of zinc-copper is prepared, functionalization-dispersant/ZSM-5 presomas will be loaded with and be impregnated into what is prepared
Reacted in zinc-copper solution, zinc, copper is complexed on organic dispersing agent, zinc and copper form organic point with organic dispersing agent
Powder metal complex, obtains Zn-Cu/ dispersants/ZSM-5 presomas；At 380~550 DEG C to (Zn-Cu)/dispersant/ZSM-
5 presomas are roasted, and the time is 2~6h, obtains required catalyst.
Since complex reaction is the chemical reaction of complex-metal ion, metal ion is by chemical reaction rather than thing
Reason absorption is attached on dispersant chain, therefore it is in uniform sequential distribution that the atom of zinc, copper, which is over a molecular sieve, each dispersant
The zinc combined on chain-copper atom quantity is proportional to the quantity of functional group on dispersant, during roasting, zinc-copper atom
Oxidation reaction can be carried out in the original location, during oxidation reaction, form zinc, the oxide eutectic of copper.Therefore the catalysis prepared
The distribution of zinc-copper is uniform that catalyst prepared by this method possesses excellent selectivity in agent activity crystalline phase.
Catalyst more specifically preparation method comprises the following steps in the present invention：
（1）The preparation of organic dispersing agent
Organic dispersing agent precursor is dissolved in organic solvent, forms dispersant solution, adds and amido or two amido officials is provided
The micromolecular compound that can be rolled into a ball, flow back 0.5~300min, and organic dispersing agent is prepared in solvent evaporated drying.
The organic dispersing agent premise body, refers to the high-molecular compound for containing the groups such as halogen, cyano group by side chain, such as
Polyvinyl chloride (PVC), polystyrene acrylonitrile (SAN), it is possible to provide the micromolecular compound of amido or two amidine functional groups can be with
It is dicyandiamide, it is one or more in monoethanolamine, ethylenediamine or hydroxylamine hydrochloride.
（2）The preparation of Zn-Cu/ dispersants/ZSM-5 presomas
Zinc-copper solution is prepared, and with inorganic acid for adjusting pH value 1~4, weighs the organic dispersing agent prepared, will be added to preparation
In the solution of good zinc-copper, 5~30min is reacted at 20~35 DEG C, then by carrier impregnation into above-mentioned solution, standing makes organic
Dispersant is deposited on ZSM-5 surfaces, is dried to obtain Zn-Cu/ dispersants/ZSM-5 presomas；
（3）High-temperature roasting
By the presoma of above-mentioned preparation at 600~700 DEG C 2~6h of high-temperature roasting, obtain Zn-CuO/ZSM-5 catalyst；It is above-mentioned
Roasting can carry out in having oxygen atmosphere, better.
By adopting the above-described technical solution, the beneficial effects of the invention are as follows：
1st, the reaction that lactate of the present invention prepares pyruvate is heterogeneous catalytic reaction, and catalyst can recycle again,
In addition, the catalytic reaction is not required to solvent, reaction condition is gentle, and the waste of generation is few, energy conservation and environmental protection.
2nd, the present invention provides the method that catalyzed conversion lactate prepares pyruvate, and catalyst is born for Zn-CuO/ molecular sieves
Carried catalyst, in its preparation process, metal ion is to be attached to by chemical reaction rather than physical absorption on dispersant chain, because
It is in uniform sequential distribution that this zinc, the atom of copper, which are over a molecular sieve, the zinc-copper atom quantity combined on each dispersant chain with
The quantity of functional group is proportional on dispersant, and during roasting, zinc-copper atom can carry out oxidation reaction in the original location, in oxygen
During changing reaction, zinc, the oxide eutectic of copper are formed.Therefore the distribution of zinc-copper is in the catalyst activity crystalline phase of preparation
Uniformly, catalyst prepared by this method possesses excellent selectivity.
Embodiment
The technical solution in the embodiment of the present invention is clearly and completely described below in conjunction with the embodiment of the present invention,
Obviously, described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, those of ordinary skill in the art's all other embodiments obtained on the premise of creative work is not made,
Belong to the scope of protection of the invention.
【Embodiment 1】
The preparation of catalyst：
（1）The preparation of organic dispersing agent
There to be PVC6.0g to be dissolved in Isosorbide-5-Nitrae-dioxane, and form solution, add 30g hydroxylamine hydrochlorides and 4.0gNaOH, flow back
60min, is prepared organic dispersing agent, solvent evaporated, and organic dispersing agent A is remembered in drying.
（2）The preparation of Zn-Cu/ dispersants/ZSM-5 presomas
Weigh 0.68gZn (NO3)2, 1.26gCu（NO3）2, 0.5mL hydrochloric acid is measured, the mixed solution B of 1200ml is configured to, weighs
The organic dispersing agent A6g prepared, will add in mixed solution B, 30min be reacted at 35 DEG C, then 300g carriers ZSM-5 is impregnated
Into above-mentioned solution, standing makes organic dispersing agent be deposited on ZSM-5 surfaces, is dried to obtain Zn-Cu/ dispersants/ZSM-5 forerunner
Body；
（3）High-temperature roasting
By the presoma of above-mentioned preparation at 600~700 DEG C, under oxygen atmosphere, high-temperature roasting 5h, obtains Zn-CuO/ZSM-5 catalysis
Agent.
Catalytic oxidation：Ethyl lactate 1mol is added into normal-pressure reaction kettle, adds the Zn-CuO/ of the above-mentioned preparations of 0.9g
ZSM-5, air is passed through into reaction kettle, and air velocity is 0.01 liter/m of material/minute, and reaction kettle is heated to 50 DEG C,
React 6 it is small when after, cooling discharging, to reuse, product passes through efficient liquid phase chromatographic analysis for recycling after catalyst filtration.Reaction
As a result：Ethyl lactate conversion ratio is 100%, and ethyl pyruvate yield is 95.4%.
【Embodiment 2】
The preparation of catalyst：
（1）The preparation of organic dispersing agent
There to be PVC6.0g to be dissolved in Isosorbide-5-Nitrae-dioxane, and form solution, add 30g hydroxylamine hydrochlorides and 4.0gNaOH, flow back
60min, is prepared organic dispersing agent, solvent evaporated, and organic dispersing agent A is remembered in drying.
（2）The preparation of Zn-Cu/ dispersants/ZSM-5 presomas
Weigh 0.68gZn (NO3)2, 1.26gCu（NO3）2, 0.5mL hydrochloric acid is measured, the mixed solution B of 1200ml is configured to, weighs
The organic dispersing agent A6g prepared, will add in mixed solution B, 30min be reacted at 35 DEG C, then 300g carriers ZSM-5 is impregnated
Into above-mentioned solution, standing makes organic dispersing agent be deposited on ZSM-5 surfaces, is dried to obtain Zn-Cu/ dispersants/ZSM-5 forerunner
Body；
（3）High-temperature roasting
By the presoma of above-mentioned preparation at 600~700 DEG C, under oxygen atmosphere, high-temperature roasting 5h, obtains Zn-CuO/ZSM-5 catalysis
Agent.
Catalytic oxidation：Ethyl lactate 1mol is added into autoclave, adds the Zn-CuO/ of the above-mentioned preparations of 0.9g
ZSM-5, is passed through oxygen into reaction kettle, oxygen pressure 0.01MPa, and reaction kettle is heated to 100 DEG C, when reaction 8 is small after, it is cold
But discharge, to reuse, product passes through efficient liquid phase chromatographic analysis for recycling after catalyst filtration.Reaction result：Ethyl lactate
Conversion ratio is 100%, and ethyl pyruvate yield is 97.7%.
【Embodiment 3】
The preparation of catalyst：
（1）The preparation of organic dispersing agent
There to be PVC6.0g to be dissolved in Isosorbide-5-Nitrae-dioxane, and form solution, add 30g hydroxylamine hydrochlorides and 4.0gNaOH, flow back
60min, is prepared organic dispersing agent, solvent evaporated, and organic dispersing agent A is remembered in drying.
（2）The preparation of Zn-Cu/ dispersants/ZSM-5 presomas
Weigh 0.68gZn (NO3)2, 1.26gCu（NO3）2, 0.5mL hydrochloric acid is measured, the mixed solution B of 1200ml is configured to, weighs
The organic dispersing agent A6g prepared, will add in mixed solution B, 30min be reacted at 35 DEG C, then 300g carriers ZSM-5 is impregnated
Into above-mentioned solution, standing makes organic dispersing agent be deposited on ZSM-5 surfaces, is dried to obtain Zn-Cu/ dispersants/ZSM-5 forerunner
Body；
（3）High-temperature roasting
By the presoma of above-mentioned preparation at 600~700 DEG C, under oxygen atmosphere, high-temperature roasting 5h, obtains Zn-CuO/ZSM-5 catalysis
Agent.
Catalytic oxidation：Isopropyl lactate 1mol is added into normal-pressure reaction kettle, adds the Zn- of the above-mentioned preparations of 0.9g
CuO/ZSM-5, air is passed through into reaction kettle, and air velocity is 0.01 liter/m of material/minute, and reaction kettle is heated to
50 DEG C, when reaction 6 is small after, cooling discharging, to reuse, product passes through high performance liquid chromatography point for recycling after catalyst filtration
Analysis.Reaction result：Lactic acid isopropyl ester conversion ratio is 99.8%, and pyruvic acid isopropyl ester yield is 95.6%.
【Embodiment 4】
The preparation of catalyst：
（1）The preparation of organic dispersing agent
There to be PVC6.0g to be dissolved in Isosorbide-5-Nitrae-dioxane, and form solution, add 30g hydroxylamine hydrochlorides and 4.0gNaOH, flow back
60min, is prepared organic dispersing agent, solvent evaporated, and organic dispersing agent A is remembered in drying.
（2）The preparation of Zn-Cu/ dispersants/ZSM-5 presomas
Weigh 0.68gZn (NO3)2, 1.26gCu（NO3）2, 0.5mL hydrochloric acid is measured, the mixed solution B of 1200ml is configured to, weighs
The organic dispersing agent A6g prepared, will add in mixed solution B, 30min be reacted at 35 DEG C, then 300g carriers ZSM-5 is impregnated
Into above-mentioned solution, standing makes organic dispersing agent be deposited on ZSM-5 surfaces, is dried to obtain Zn-Cu/ dispersants/ZSM-5 forerunner
Body；
（3）High-temperature roasting
By the presoma of above-mentioned preparation at 600~700 DEG C, under oxygen atmosphere, high-temperature roasting 5h, obtains Zn-CuO/ZSM-5 catalysis
Agent.
Catalytic oxidation：Methyl lactate 1mol is added into autoclave, adds the Zn-CuO/ of the above-mentioned preparations of 0.9g
ZSM-5, is passed through oxygen into reaction kettle, oxygen pressure 0.01MPa, and reaction kettle is heated to 100 DEG C, when reaction 8 is small after, it is cold
But discharge, to reuse, product passes through efficient liquid phase chromatographic analysis for recycling after catalyst filtration.Reaction result：Methyl lactate
Conversion ratio is 100%, and methyl pyruvate yield is 98.9%.
【Comparative example 1】
The preparation of catalyst：
（1）The preparation of Zn-Cu/ZSM-5 presomas
Weigh 0.68gZn (NO3)2, 1.26gCu（NO3）2, 0.5mL hydrochloric acid is measured, the mixed solution B of 1200ml is configured to, weighs
300g carriers ZSM-5 is impregnated into above-mentioned solution, and standing makes organic dispersing agent be deposited on ZSM-5 surfaces, is dried to obtain Zn-Cu/
ZSM-5 presomas；
（2）High-temperature roasting
By the presoma of above-mentioned preparation at 600~700 DEG C, under oxygen atmosphere, high-temperature roasting 5h, obtains Zn-CuO/ZSM-5 catalysis
Agent.
Catalytic oxidation：Ethyl lactate 1mol is added into normal-pressure reaction kettle, adds the Zn-CuO/ of the above-mentioned preparations of 0.9g
ZSM-5, air is passed through into reaction kettle, and air velocity is 0.01 liter/m of material/minute, and reaction kettle is heated to 50 DEG C,
React 6 it is small when after, cooling discharging, to reuse, product passes through efficient liquid phase chromatographic analysis for recycling after catalyst filtration.Reaction
As a result：Lactic acid isopropyl ester second conversion ratio is 84%, and ethyl pyruvate yield is 66%.
【Comparative example 2】
（1）The preparation of organic dispersing agent
There to be PVC6.0g to be dissolved in Isosorbide-5-Nitrae-dioxane, and form solution, add 30g hydroxylamine hydrochlorides and 4.0gNaOH, flow back
60min, is prepared organic dispersing agent, solvent evaporated, and organic dispersing agent is remembered in drying
（2）The preparation of dispersant ZSM-5 presomas
Weigh and measure 0.5mL hydrochloric acid, be configured to the mixed solution of 1200ml, weighing the above-mentioned organic dispersing agent 6g prepared will add
Enter wherein, 30min is reacted at 35 DEG C, then 300g carriers ZSM-5 is impregnated into above-mentioned solution, standing deposits organic dispersing agent
In ZSM-5 surfaces, dispersant/ZSM-5 presomas are dried to obtain；
（3）High-temperature roasting
By the presoma of above-mentioned preparation at 600~700 DEG C, under oxygen atmosphere, high-temperature roasting 5h, obtains modified ZSM-5 catalyst.
Catalytic oxidation：Ethyl lactate 1mol is added into normal-pressure reaction kettle, adds the modification of the above-mentioned preparations of 0.9g
ZSM-5, air is passed through into reaction kettle, and air velocity is 0.01 liter/m of material/minute, and reaction kettle is heated to 50 DEG C,
React 6 it is small when after, cooling discharging, to reuse, product passes through efficient liquid phase chromatographic analysis for recycling after catalyst filtration.Reaction
As a result：Ethyl lactate conversion ratio is 35%, and ethyl pyruvate yield is 12%.
Described above has fully disclosed the embodiment of the present invention.It is pointed out that it is familiar with the field
Scope of the technical staff to any change that the embodiment of the present invention is done all without departing from claims of the present invention.
Correspondingly, the scope of claim of the invention is also not limited only to previous embodiment.
Claims (8)
- A kind of 1. green synthesis process of pyruvate, it is characterised in that：Using lactate as raw material, oxygen-containing gas is oxidant, In the presence of Zn-CuO/ZSM-5 supported catalysts, through peroxidization, pyruvate is directly prepared；Concrete operations walk Suddenly it is：A certain amount of substrate, catalysts and solvents are added in pressure reactor, closed reactor, is replaced anti-with oxygen or air After answering in device gas several times, oxygen partial pressure is filled with to 0.7~1.5MPa, 40~160 DEG C is heated to, reacts 4~20h.
- 2. the green synthesis process of pyruvate according to claim 1, it is characterised in that：The dosage of the catalyst is The 0.001-20.0wt% of raw milk acid esters.
- 3. the green synthesis process of pyruvate according to claim 1, it is characterised in that：Oxidant used for air or Oxygen, offering oxygen way are atmospheric bubbling.
- 4. the green synthesis process of pyruvate according to claim 1, it is characterised in that：Oxidant used for air or Oxygen, offering oxygen way supply oxygen for high pressure, pressure value 0.01-5MPa.
- 5. the green synthesis process of pyruvate according to claim 1, it is characterised in that：Oxidant used for air or Oxygen, offering oxygen way are high pressure pressure supply, pressure value 0.01-5MPa.
- 6. the green synthesis process of pyruvate according to claim 1, it is characterised in that：The raw milk acid esters is selected from One in the secondary butyl ester of methyl lactate, ethyl lactate, lactic acid n-propyl ester, isopropyl lactate, butyl lactate, isobutyl lactate, lactic acid Kind is a variety of.
- 7. the green synthesis process of pyruvate according to claim 1, it is characterised in that：The Zn-CuO/ molecular sieves The preparation method of supported catalyst is：Loaded by making zinc and copper and organic dispersing agent form organic dispersing agent metal complex Onto ZSM-5, Zn-Cu/ dispersants/ZSM-5 presomas are obtained；At 380~550 DEG C to Zn-Cu/ dispersants/ZSM-5 presomas Roasted, the time is 2~6h, obtains required catalyst.
- 8. the green synthesis process of pyruvate according to claim 6, it is characterised in that：Specific preparation method includes Following step：（1）The preparation of organic dispersing agentOrganic dispersing agent precursor is dissolved in organic solvent, forms dispersant solution, adds and amido or two amido officials is provided The micromolecular compound that can be rolled into a ball, flow back 0.5~300min, and organic dispersing agent is prepared in solvent evaporated drying；The organic dispersing agent premise body, refers to the high-molecular compound for containing the groups such as halogen, cyano group by side chain, such as polychlorostyrene Ethene (PVC), polystyrene acrylonitrile (SAN), it is possible to provide the micromolecular compound of amido or two amidine functional groups can be double Cyanamide, it is one or more in monoethanolamine, ethylenediamine or hydroxylamine hydrochloride；（2）The preparation of Zn-Cu/ dispersants/ZSM-5 presomasZinc-copper solution is prepared, and with inorganic acid for adjusting pH value 1~4, weighs the organic dispersing agent prepared, will be added to preparation In the solution of good zinc-copper, 5~30min is reacted at 20~35 DEG C, then by carrier impregnation into above-mentioned solution, standing makes organic Dispersant is deposited on ZSM-5 surfaces, is dried to obtain Zn-Cu/ dispersants/ZSM-5 presomas；（3）High-temperature roastingBy the presoma of above-mentioned preparation at 600~700 DEG C 2~6h of high-temperature roasting, obtain Zn-CuO/ZSM-5 catalyst；It is above-mentioned Roasting can carry out in having oxygen atmosphere, better.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591171A (en) * | 2022-03-17 | 2022-06-07 | 苏州仁晟新材料科技有限公司 | Preparation method of pharmaceutical grade ultra-high purity ethyl pyruvate |
| CN116217393A (en) * | 2022-12-05 | 2023-06-06 | 天津理工大学 | Method for preparing ethyl pyruvate by photocatalysis of ethyl lactate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101579625A (en) * | 2008-05-15 | 2009-11-18 | 湖南大学 | Catalyst and reaction process for preparing pyruvic acid by lactic acid in catalytic oxydehydrogenation way |
| CN104860824A (en) * | 2014-02-24 | 2015-08-26 | 中国科学院大连化学物理研究所 | Method for preparing pyruvate through catalyzing oxygen to oxidize lactate |
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2017
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101579625A (en) * | 2008-05-15 | 2009-11-18 | 湖南大学 | Catalyst and reaction process for preparing pyruvic acid by lactic acid in catalytic oxydehydrogenation way |
| CN104860824A (en) * | 2014-02-24 | 2015-08-26 | 中国科学院大连化学物理研究所 | Method for preparing pyruvate through catalyzing oxygen to oxidize lactate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591171A (en) * | 2022-03-17 | 2022-06-07 | 苏州仁晟新材料科技有限公司 | Preparation method of pharmaceutical grade ultra-high purity ethyl pyruvate |
| CN116217393A (en) * | 2022-12-05 | 2023-06-06 | 天津理工大学 | Method for preparing ethyl pyruvate by photocatalysis of ethyl lactate |
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