CN107930687A - The method of modifying of TS 1 and its application in solvent-free catalysis lactate prepares pyruvate - Google Patents
The method of modifying of TS 1 and its application in solvent-free catalysis lactate prepares pyruvate Download PDFInfo
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- CN107930687A CN107930687A CN201711075530.2A CN201711075530A CN107930687A CN 107930687 A CN107930687 A CN 107930687A CN 201711075530 A CN201711075530 A CN 201711075530A CN 107930687 A CN107930687 A CN 107930687A
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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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/36—Steaming
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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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
Abstract
A kind of method of modifying the present invention provides TS 1 and its application in solvent-free catalysis lactate prepares pyruvate.Wherein, the key step of method of modifying is followed successively by the TS of steam treatment commercialization first 1, secondary crystallization, secondary steam treatment and washing lotion processing.Steam treatment is carried out in fixed bed reactors first；Secondary crystallization process is that after template 4-propyl bromide and TS 1 are carried out solid-state grinding, solvent heat treatment is carried out in crystallizing kettle；Secondary steam treatment process is similar with steam treatment first；Washing lotion processing procedure need to pass through the washing of acid wash liquid, alkaline rinse and oxidized form washing lotion successively.It can realize in solvent-free system that efficient catalytic hydrogen peroxide oxidation lactate prepares pyruvate by modified TS 1, under temperate condition, pyruvate yield is up to more than 95%.The catalyst shows ultrastability, recycles 20 times, pyruvate yield remains at more than 95%.
Description
Technical field
The present invention relates to the method for modifying of TS-1 a kind of and its answering in solvent-free catalysis lactate prepares pyruvate
With.
Background technology
Pyruvic acid and its ester derivative are important chemical intermediates, are widely used in the energy, food, cosmetics, spices
Etc. industry；Meanwhile pyruvic acid (ester) can also be used to produce various bioactivators, such as antiviral drugs, animal cell culture
Base etc..At present, the commodity production of pyruvic acid (ester) is mainly dehydrated decarboxylation by tartaric acid and realizes.But this process needs to disappear
Consume excessive KHSO4As decarboxylating agent, cause that the technique productions are of high cost, and Atom economy is low, environmental pollution is serious.Pyruvic acid
(ester) can also be obtained by carbohydrate biofermentation, however, accurate control of the process to reaction condition require it is high, product design and
Space-time yield is low, meanwhile, product is separated and purified of high cost.Lactic acid (ester) can pass through various saccharides (such as glucose, fructose, third
Triol etc.), the conversion such as cellulose obtains, be the biomass-based compound of a kind of important highly functionalized, and pyruvic acid
(ester) has structural similarity.Pyruvic acid (ester) is prepared by lactic acid (ester) oxidized dehydrogenation, Atom economy is high, and being one has
The biomass transformation routes of great market potential.
Catalytic oxidation is to realize that lactate conversion prepares a kind of important method of pyruvate, and with polluting, small grade is notable
Advantage.Document report Ag bases catalyst can realize that catalytic molecular oxygen Oxidation of Lactic ester prepares pyruvate (US-4229590；
Chin.J.Catal.1998,19,428-431).But the catalyst system and catalyzing need higher reaction temperature (>400 DEG C), and produce
Thing yield is low.MoO3-TiO2It can realize that lactate conversion prepares pyruvate, but pyruvate under 200 DEG C of reaction temperature
Yield is relatively low (Green Chem.2017,19,3014-3022).The main reason for product yield is low is that higher reaction temperature is held
Easily lead to the decomposition of pyruvate.Chinese patent literature CN 103570532B are using Titanium Sieve Molecular Sieve as catalyst, with hydrogen peroxide
For oxidant, using alcohols or arene as solvent, under the conditions of 70 DEG C, pyruvate yield can reach 79%.However,
When not having solvent, under similarity condition, pyruvate yield is only 17%.The use of solvent can directly result in the increasing of production cost
Add.Therefore, in a mild condition, realize that solvent-free efficient catalytic lactate conversion prepares pyruvate and is of great significance.
The content of the invention
It is an object of the invention to provide a kind of method of modifying of TS-1, and in the absence of a solvent, utilization is modified
TS-1 efficient catalytic lactates prepare pyruvate.
The present invention is directed to commercialization TS-1 molecular sieves, successively using steam treatment, secondary crystallization, secondary vapor first
Processing and washing lotion processing procedure are modified, and modified molecular sieve is under condition of no solvent, it is possible to achieve efficient catalytic lactic acid
Ester prepares pyruvate, and under temperate condition (40~70 DEG C), pyruvate yield is up to more than 95%.And modified molecule
Sieve shows ultrastability, reuses 20 times, pyruvate yield is still maintained at more than 95%.
To achieve the above object, the technical solution adopted by the present invention is：
The method of modifying of TS-1, is included first at steam treatment, secondary crystallization, secondary steam treatment and washing lotion successively
Four steps are managed, the method for modifying is that commercialization TS-1 is modified；
Wherein, the detailed process of steam treatment is first：Commercialization TS-1 is placed in fixed bed reactors, 200
At~700 DEG C, using 100% steam treatment 0.5~5 it is small when；
The process of secondary crystallization is：TS-1 after steam treatment first is mixed with 4-propyl bromide and solid-state is ground
Mill, the solid after grinding is transferred in the crystallizing kettle with polytetrafluoroethyllining lining, and it is small to add alcoholic solvent stirring 0.1~1
When, by crystallizing kettle sealing when standing 3~72 is small under the conditions of 100~240 DEG C；
The secondary steam treatment is identical with steam treatment process first, and the TS-1 after secondary crystallization is handled is placed
In fixed bed reactors, at 200~700 DEG C, using 100% steam treatment 0.5~5 it is small when；
The washing lotion processing step is：The acidic aqueous solution for being first 0.01M~1M with concentration washs, then is with concentration
0.01M~1M alkaline aqueous solutions wash, and are finally 0.01M~10M oxidized form wash liquids with concentration；
Sample after the processing of steam treatment first, secondary crystallization, secondary steam treatment and washing lotion, through deionized water
After washing 3~5 times, when roasting 1~24 is small under the conditions of 300~600 DEG C, you can obtain modified TS-1.
As currently preferred technical solution, during the steam treatment first and secondary steam treatment,
At 400~600 DEG C, using 100% steam treatment 1~3 it is small when.
As currently preferred technical solution, during the secondary crystallization, first the TS-1 after steam treatment with
The weight ratio of 4-propyl bromide is 0.1:1~10:1, when solid-state milling time is 1~10 small.
As currently preferred technical solution, during the secondary crystallization, alcoholic solvent for 3~6 carbon atoms just
One or more in structure alcohol or isomery alcohol, after adding alcoholic solvent, the solid-liquid volume ratio in crystallizing kettle is 1:10~1:1.
As currently preferred technical solution, in the washing lotion processing step, the acidic aqueous solution is sulfuric acid, salt
One or more in acid, phosphoric acid, nitric acid and acetic acid；Alkaline aqueous solution is sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate
In one or more；Oxidized form washing lotion is one kind or more in hydrogen peroxide, potassium permanganate, sodium hypochlorite and postassium hypochlorite
Kind.
It is modified to obtain modified TS-1 in solvent-free catalysis lactate preparation third according to the method for modifying of above-mentioned TS-1
Applied in keto ester.
As currently preferred technical solution, modified TS-1 prepares pyruvate in solvent-free catalysis lactate
Detailed process is：Modified TS-1, lactate, hydrogen peroxide are added in flask, stirs, is reacted at 30 DEG C~70 DEG C
0.5~15 it is small when.
As currently preferred technical solution, the lactate is methyl lactate, ethyl lactate, propyl lactate and lactic acid
One or more in butyl ester.
As currently preferred technical solution, the weight ratio of the modified TS-1 and lactate are 1:100~1:
10, hydrogen peroxide is the aqueous solution that mass fraction is 20%~50%, and the molar ratio of hydrogen peroxide and lactate is 1:1~5:1.
As currently preferred technical solution, the modified TS-1 can be with Reusability.
Compared with prior art, beneficial effects of the present invention are：
1st, method of modifying provided by the invention is at the same time modified the structural property and Acidity of TS-1.It can not only take off
Except the unformed component in TS-1, the diffusion admittance of reactant and product is dredged, the Acidity of TS-1 is further improved, only retains tool
There is the skeleton Ti of high activity, beneficial to the progress of goal response.
2nd, it is modified to TS-1 by method of modifying provided by the invention, can be under solvent-free and temperate condition, efficiently
Catalysis lactate prepares pyruvate, and product yield is up to more than 95%.
3rd, the modified TS-1 of the present invention has ultrastability, and preparing pyruvate in catalysis lactate is repeated 20 times,
Pyruvate yield is still maintained at more than 95%.
Brief description of the drawings
Fig. 1 is the result figure that the modified TS-1 of the present invention is reused.
Embodiment
The present invention provides a kind of method of modifying of commercialization TS-1, and will it is modified made from TS-1 be applied to catalysis lactate
Prepare in pyruvate.The method of modifying of commercialization TS-1 specifically includes steam treatment, secondary crystallization, secondary vapor first
Processing and washing lotion handle four steps.
Wherein, steam treatment is identical with secondary steam treatment process first, is carried out in fixed bed reactors, tool
Body treatment conditions are：Material at 200~700 DEG C, using 100% steam treatment 0.5~5 it is small when.Currently preferred bar
Part is at 400~600 DEG C, using 100% steam treatment 1~3 it is small when.
The detailed process of secondary crystallization is：First, the TS-1 after steam treatment first is mixed with 4-propyl bromide
And solid-state is ground, and the solid after grinding is transferred in the crystallizing kettle with polytetrafluoroethyllining lining, and add alcoholic solvent stirring
0.1~1 it is small when, by crystallizing kettle sealing after under the conditions of 100~240 DEG C stand 3~72 it is small when.A kind of as the present invention implements
Mode, the weight ratio of the TS-1 after steam treatment and 4-propyl bromide is 0.1 first:1~10:1, solid-state milling time is
1~10 it is small when.As one embodiment of the present invention, in n-alkanol or isomery alcohol of the alcoholic solvent for 3~6 carbon atoms
One or more, after adding alcoholic solvent, solid-liquid volume ratio in crystallizing kettle is 1:10~1:1.
Washing lotion processing concretely comprises the following steps：First, the acidic aqueous solution for being 0.01M~1M with concentration washs, acid water-soluble
Liquid is the one or more in sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and acetic acid；Then washed again with the alkaline aqueous solution of 0.01M~1M
Wash, alkaline aqueous solution is the one or more in sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate；Finally with 0.01M~
The oxidized form wash liquid of 10M, oxidized form washing lotion are one kind in hydrogen peroxide, potassium permanganate, sodium hypochlorite and postassium hypochlorite
It is or a variety of.
The above-mentioned sample after the processing of steam treatment first, secondary crystallization, secondary steam treatment and washing lotion successively, warp
After deionized water is washed 3~5 times, when roasting 1~24 is small under the conditions of 300~600 DEG C, you can obtain modified TS-1.
Under condition of no solvent, the modified TS-1 of method described above is catalyst, using hydrogen peroxide as oxidant, catalysis
Lactate prepares pyruvate.Wherein, lactate is one kind in methyl lactate, ethyl lactate, propyl lactate and butyl lactate
It is or a variety of.The weight ratio of catalyst and lactate is 1:100~1:10, hydrogen peroxide is the water that mass fraction is 20%~50%
The molar ratio of solution, hydrogen peroxide and lactate is 1:1~5:1, reaction temperature is 30 DEG C~70 DEG C, the reaction time for 0.5~
15 it is small when.Using this method, pyruvate yield reaches more than 95%.
Modified TS-1 shows ultrastability, recycles 20 times, pyruvate yield remain at 95% with
On.
A variety of in the present invention refer to twice and more than twice.
With reference to embodiment, the present invention is described in further detail.
Propyl alcohol used, isobutanol are commercially available organic solvent in following embodiments, to analyze pure, concentration >=99%.
Embodiment 1
In the present embodiment commercialization TS-1 modification and catalysis ethyl lactate oxidation prepare ethyl pyruvate：
The modifying process of TS-1 passes through first at steam treatment, secondary crystallization, secondary steam treatment and washing lotion successively
Reason process.
Steam treatment first：1.0g commercializations TS-1 is taken to be placed in fixed bed reactors, rise temperature is led to 500 DEG C
Enter 100% steam treatment 2h.Then stop being passed through vapor, and temperature of reactor is down to room temperature in nitrogen atmosphere.
Secondary crystallization：TS-1 is taken out, it is placed in mortar with 0.5g 4-propyl bromides and grinds 3h.Then, will grind
Solid afterwards is transferred in the crystallizing kettle with polytetrafluoroethyllining lining, and is added 10mL propanol solvents and stirred 30 minutes.By crystalline substance
Change kettle sealing when standing 24 is small under the conditions of 180 DEG C.
Secondary steam treatment：After crystallizing kettle is cooled to room temperature, solid is separated using the method for centrifugation, and uses respectively
Ethanol and deionized water respectively washing 3 times.After drying, solid is transferred in fixed bed reactors, using with first at vapor
Manage identical treatment conditions and carry out secondary steam treatment.
Washing lotion processing：After the completion of secondary steam treatment, 0.5g solids are taken to be scattered in 5mL dilute sulfuric acids (0.1M), stirring 1
After hour, filter and be washed with deionized to neutrality.Then solid is scattered in 5mL sodium hydroxide solutions (0.1M), and
Stir 1 it is small when, then, by the way that solid is obtained by filtration, and be washed with deionized to neutrality.Finally, by the solid after washing point
Dissipate in the aqueous hydrogen peroxide solution that 5mL mass fractions are 30%, when stirring 1 is small.Solid is filtered out, is washed with deionized 3
It is secondary, when drying 12 is small under the conditions of 120 DEG C.
So far, TS-1, which is modified, completes.
Modified TS-1 is used for catalysis ethyl lactate oxidation under condition of no solvent and prepares ethyl pyruvate.Detailed process
For：Take 10mL ethyl lactates, 25mL hydrogen peroxide, 0.2g to be modified TS-1 and be placed in the three-necked flask of 50mL, under stirring condition, rise
High reaction temperature is to 50 DEG C, when reaction 10 is small.Reaction result is as shown in table 1.
Comparing embodiment 1
In this comparing embodiment, under condition of no solvent, third is prepared with non-modified TS-1 catalysis ethyl lactate oxidations
Keto acid ethyl ester, reaction condition is same as Example 1, and reaction result is as shown in table 1.
Embodiment 2
In the present embodiment commercialization TS-1 modification and catalysis ethyl lactate oxidation prepare ethyl pyruvate：
In method of modifying, in addition to the dilute sulfuric acid of the 0.1M in washing lotion processing procedure is replaced with the phosphoric acid of 0.1M, other
Modified condition is same as Example 1.
Modified TS-1 is used for catalysis ethyl lactate oxidation under condition of no solvent and prepares ethyl pyruvate, reaction condition
It is identical with embodiment 1.Reaction result is as shown in table 1.
Embodiment 3
In the present embodiment commercialization TS-1 modification and catalysis ethyl lactate oxidation prepare ethyl pyruvate：
In method of modifying, except the hydrogen peroxide that the mass fraction in washing lotion processing procedure is 30% is replaced with 0.1M's
Outside sodium hypochlorite, other modified conditions are same as Example 1.
Modified TS-1 is used for catalysis ethyl lactate oxidation under condition of no solvent and prepares ethyl pyruvate, reaction condition
It is identical with embodiment 1.Reaction result is as shown in table 1.
Embodiment 4
In the present embodiment commercialization TS-1 modification and catalysis ethyl lactate oxidation prepare ethyl pyruvate：
In method of modifying, in addition to the propanol solvent during by secondary crystallization replaces with iso-butanol solvent, other modifications
Condition is same as Example 1.
Modified TS-1 is used for catalysis ethyl lactate oxidation under condition of no solvent and prepares ethyl pyruvate, reaction condition
It is identical with embodiment 1.Reaction result is as shown in table 1.
The reaction result of 1 embodiment 1~4 of table and comparing embodiment 1
| Ethyl lactate conversion ratio (%) | Ethyl pyruvate yield (%) | Hydrogen peroxide utilization rate (%) | |
| Embodiment 1 | 100 | 98.2 | 95.0 |
| Comparing embodiment 1 | 22.4 | 13.6 | 79.8 |
| Embodiment 2 | 100 | 96.3 | 94.2 |
| Embodiment 3 | 100 | 95.1 | 90.8 |
| Embodiment 4 | 100 | 98.4 | 96.6 |
Wherein, hydrogen peroxide utilization rate=ethyl lactate consumption molal quantity/hydrogen peroxide consumption molal quantity × 100%.
Embodiment 5
Modified commercialization TS-1 is in catalysis ethyl lactate oxidation prepares ethyl pyruvate reaction in the present embodiment
Reuse：
The modified condition of commercialization TS-1 and catalysis ethyl lactate oxidation prepare reaction condition and the implementation of ethyl pyruvate
Example 1 is identical.First after reaction, TS-1 is filtered, washed and be directly used in the second secondary response, so repeated with 20
Secondary, reaction result is as shown in Figure 1.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of changes, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (10)
- The method of modifying of 1.TS-1, it is characterised in that include successively first steam treatment, secondary crystallization, at secondary vapor Reason and washing lotion handle four steps, and the method for modifying is that commercialization TS-1 is modified；Wherein, the detailed process of steam treatment is first：Commercialization TS-1 is placed in fixed bed reactors, 200 ~ 700 At DEG C, using 100% steam treatment 0.5 ~ 5 it is small when；The process of secondary crystallization is：TS-1 after steam treatment first is mixed with 4-propyl bromide and solid-state is ground, will Solid after grinding is transferred in the crystallizing kettle with polytetrafluoroethyllining lining, and add alcoholic solvent stirring 0.1 ~ 1 it is small when, by crystalline substance Change kettle sealing when standing 3 ~ 72 is small under the conditions of 100 ~ 240 DEG C；The secondary steam treatment is identical with steam treatment process first, and the TS-1 after secondary crystallization is handled is placed on In fixed bed reactors, at 200 ~ 700 DEG C, using 100% steam treatment 0.5 ~ 5 it is small when；The washing lotion processing step is：The acidic aqueous solution for being first 0.01M ~ 1M with concentration washs, then with concentration be 0.01M ~ 1M alkaline aqueous solutions wash, and are finally 0.01M ~ 10M oxidized form wash liquids with concentration；Sample after the processing of steam treatment first, secondary crystallization, secondary steam treatment and washing lotion, is washed through deionized water After 3 ~ 5 times, when roasting 1 ~ 24 is small under the conditions of 300 ~ 600 DEG C, you can obtain modified TS-1.
- 2. the method for modifying of TS-1 according to claim 1, it is characterised in that the steam treatment first and secondary water During steam treated, at 400 ~ 600 DEG C, using 100% steam treatment 1 ~ 3 it is small when.
- 3. the method for modifying of TS-1 according to claim 1, it is characterised in that during the secondary crystallization, water first The weight ratio of TS-1 and 4-propyl bromide after steam treated are 0.1:1~10:1, when solid-state milling time is 1 ~ 10 small.
- 4. the method for modifying of TS-1 according to claim 3, it is characterised in that during the secondary crystallization, alcoholic solvent For the one or more in the n-alkanol or isomery alcohol of 3 ~ 6 carbon atoms, after adding alcoholic solvent, the solid-liquid volume ratio in crystallizing kettle For 1:10~1:1.
- 5. the method for modifying of TS-1 according to claim 1, it is characterised in that in the washing lotion processing step, the acid Property aqueous solution be sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and acetic acid in one or more；Alkaline aqueous solution is sodium hydroxide, carbonic acid One or more in sodium, potassium hydroxide and potassium carbonate；Oxidized form washing lotion is hydrogen peroxide, potassium permanganate, sodium hypochlorite and secondary One or more in potassium chlorate.
- Urged 6. being modified to obtain modified TS-1 according to the method for modifying of claim 1 ~ 5 any one of them TS-1 solvent-free Change lactate, which is prepared in pyruvate, to be applied.
- 7. modified TS-1 according to claim 6 is applied in solvent-free catalysis lactate prepares pyruvate, its It is characterized in that, modified TS-1 is in the detailed process that solvent-free catalysis lactate prepares pyruvate：By modified TS- 1st, lactate, hydrogen peroxide are added in all flasks, stirring, when reaction 0.5 ~ 15 is small at 30 DEG C ~ 70 DEG C.
- 8. modified TS-1 according to claim 7 is applied in solvent-free catalysis lactate prepares pyruvate, its It is characterized in that, the lactate is the one or more in methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
- 9. modified TS-1 according to claim 7 is applied in solvent-free catalysis lactate prepares pyruvate, its It is characterized in that, the weight ratio of the modified TS-1 and lactate are 1:100~1:10, hydrogen peroxide is that mass fraction is 20% The molar ratio of ~ 50% aqueous solution, hydrogen peroxide and lactate is 1:1~5:1.
- 10. modified TS-1 according to claim 7 is applied in solvent-free catalysis lactate prepares pyruvate, its It is characterized in that, the modified TS-1 Reusabilities.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108863796A (en) * | 2018-06-12 | 2018-11-23 | 大连理工大学 | A kind of method that liquid phase catalytic oxidation lactate prepares pyruvate |
| CN110054564A (en) * | 2019-05-24 | 2019-07-26 | 中触媒新材料股份有限公司 | A kind of method that serialization prepares ethyl pyruvate |
| CN113198492A (en) * | 2021-05-12 | 2021-08-03 | 郑州大学 | Catalyst for preparing pyruvate by photocatalytic oxidation of lactate and method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040110970A1 (en) * | 2002-11-26 | 2004-06-10 | Thomas Haas | Process for the epoxidation of olefins |
| CN103570532A (en) * | 2012-07-30 | 2014-02-12 | 中国石油化学工业开发股份有限公司 | Process for preparing pyruvate |
| CN105363499A (en) * | 2015-12-02 | 2016-03-02 | 中国天辰工程有限公司 | In-situ regeneration method for Ti-Si molecular sieve catalyst |
| CN105622386A (en) * | 2014-10-27 | 2016-06-01 | 湖南师范大学 | Green process for synthesizing adipic acid from cyclohexanone |
-
2017
- 2017-11-06 CN CN201711075530.2A patent/CN107930687B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040110970A1 (en) * | 2002-11-26 | 2004-06-10 | Thomas Haas | Process for the epoxidation of olefins |
| CN103570532A (en) * | 2012-07-30 | 2014-02-12 | 中国石油化学工业开发股份有限公司 | Process for preparing pyruvate |
| CN105622386A (en) * | 2014-10-27 | 2016-06-01 | 湖南师范大学 | Green process for synthesizing adipic acid from cyclohexanone |
| CN105363499A (en) * | 2015-12-02 | 2016-03-02 | 中国天辰工程有限公司 | In-situ regeneration method for Ti-Si molecular sieve catalyst |
Non-Patent Citations (2)
| Title |
|---|
| MENG LIU ET AL.: "Highly Selective Epoxidation of Propylene in a Low-Pressure Continuous Slurry Reactor and the Regeneration of Catalyst", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 * |
| 徐保明等: "TS-1分子筛催化剂的修饰改性方法研究进展", 《河南大学学报（自然科学版）》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108863796A (en) * | 2018-06-12 | 2018-11-23 | 大连理工大学 | A kind of method that liquid phase catalytic oxidation lactate prepares pyruvate |
| CN108863796B (en) * | 2018-06-12 | 2021-06-11 | 大连理工大学 | Method for preparing pyruvate by liquid-phase catalytic oxidation of lactate |
| CN110054564A (en) * | 2019-05-24 | 2019-07-26 | 中触媒新材料股份有限公司 | A kind of method that serialization prepares ethyl pyruvate |
| CN113198492A (en) * | 2021-05-12 | 2021-08-03 | 郑州大学 | Catalyst for preparing pyruvate by photocatalytic oxidation of lactate and method thereof |
| CN113198492B (en) * | 2021-05-12 | 2022-11-01 | 郑州大学 | Catalyst for preparing pyruvate by photocatalytic oxidation of lactate and method thereof |
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