CN108772100A - A kind of heteropolyacid salt solid catalyst and its preparation method and application - Google Patents
A kind of heteropolyacid salt solid catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN108772100A CN108772100A CN201810496382.XA CN201810496382A CN108772100A CN 108772100 A CN108772100 A CN 108772100A CN 201810496382 A CN201810496382 A CN 201810496382A CN 108772100 A CN108772100 A CN 108772100A
- Authority
- CN
- China
- Prior art keywords
- heteropolyacid salt
- catalyst
- solid catalyst
- salt solid
- methyl lactate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
Abstract
The present invention relates to catalyst technical fields more particularly to a kind of heteropolyacid salt solid catalyst and its preparation method and application.The invention discloses a kind of heteropolyacid salt solid catalysts, including:Heteropolyacid salt and the M being supported on the heteropolyacid salt1The method for preparing catalyst is simple, the catalyst is good, methyl lactate yield obtained is high, catalytic reaction condition is mild, easily recycling, high recycling rate and stability are good, catalysis time is short, with good industrial applications foreground, biomass resource when solving existing catalyst biomass resource methyl lactate is relatively simple monosaccharide or oligosaccharide, and catalytic is poor, without a kind of catalyst can the polysaccharides breast ester methyl ester such as preferable catalytic cellulose catalyst the technical issues of.
Description
Technical field
The present invention relates to catalyst technical field more particularly to a kind of heteropolyacid salt solid catalyst and preparation method thereof and
Using.
Background technology
With the fast development of economic society, largely exploit fossil resource, result in fossil resource peter out and
Cause a large amount of problem of environmental pollution during exploitation and use, find the novel renewable energy of alternative fossil resource at
For active demand.Biomass is a kind of novel renewable resource for being most hopeful to replace fossil resource at present, and substance refers to by planting
The general name of the substance obtained synthesized by object, animal or microbial life is divided into plant biomass, animal organism matter and microorganism
Biomass.Plant biomass source includes:Trees, agricultural waste material, careless class and urban biomass waste.Plant biomass
Main component is C, H and O, and the essential element group of fossil resource becomes C and H.By photosynthesis, tellurian plant
The CO of annual about 200,000,000,000 tons of conversion2In carbon be carbohydrate, and store 3 × 1013The solar energy of GJ.Its energy stored
Amount is 10 times of current world energy consumption or so.The chemicals that high added value is produced with reproducible biomass resource is received at present
Extensive concern has been arrived, the hot fields of scientific research are become.
Cellulose is a kind of in plant biomass resource in biomass resource, is plant most abundant, most cheap on the earth
Biomass resource is easier to obtain in nature, is converted cellulose efficient catalytic to using biological or chemical method high attached
Value added chemicals has important social and economic benefit.
Methyl lactate also known as 2 hydroxy propanoic acid methyl esters are a kind of colourless liquids, inflammable, are dissolved in water, ethyl alcohol, organic solvent.
Methyl lactate is a kind of Important Platform chemicals prepared from plant biomass, is widely used in medicine food, cosmetics, change
Product and pharmaceuticals industry are also used as the raw material of green solvent and synthesising biological degradable polymer-polylactic acid.
Biomass resource when existing catalyst biomass resource methyl lactate is relatively simple monosaccharide
Or oligosaccharide, and catalytic is poor, such as:Liu Zhen (Liu Zhen, biology base carbohydrate catalytic cracking methyl lactate [D], Zhejiang
Jiang great Xue, 2012.) using NiO catalyzed conversion glucose methyl lactates, wherein methyl lactate yield reaches 39.7%, at present
There are no a kind of catalyst of the polysaccharides breast ester methyl esters such as the preferable catalytic cellulose of catalyst energy.
Therefore, the catalytic for researching and developing a kind of polysaccharide methyl lactates such as catalytic cellulose is good, and methyl lactate yield is high
The technical issues of catalyst is current urgent need to resolve.
Invention content
The present invention provides a kind of heteropolyacid salt solid catalysts and its preparation method and application, solve existing catalysis
Biomass resource when agent catalysis biomass resource methyl lactate is relatively simple monosaccharide or oligosaccharide, and catalytic
Difference, without a kind of catalyst can the polysaccharides breast ester methyl ester such as preferable catalytic cellulose catalyst the technical issues of.
Its specific technical solution is as follows:
The present invention provides a kind of heteropolyacid salt solid catalysts, which is characterized in that including:Heteropolyacid salt and it is supported on institute
State the M on heteropolyacid salt1;
The heteropolyacid salt is selected from CsxH3-xPW12O40、M2PW12O40、M2Si(W3O10)4Or M2Mo12O41P;
Wherein, M1For rare earth ion, M2For metal ion, x is 0.5~3.0.
Preferably, load capacity of the rare earth ion in the heteropolyacid salt solid catalyst be 5wt%~
30wt%, more preferably 20wt%.
Preferably, the metal in the rare earth ion be selected from chromium, praseodymium, lutetium, niobium, holmium, thulium, gadolinium, samarium, yttrium, europium, ytterbium,
Neodymium, dysprosium, indium or scandium.
Preferably, the metal in the rare earth ion is selected from yttrium or scandium, more preferably yttrium.
Preferably, the heteropolyacid salt is CsxH3-xPW12O40。
Preferably, the x is 2.5.
Preferably, heteropolyacid salt solid catalyst is 20Y/Cs2.5H0.5PW12O40。
The present invention also provides the preparation methods of above-mentioned heteropolyacid salt solid catalyst, include the following steps:
By M1Soluble salt solutions reacted with heteropolyacid salt, the heteropolyacid salt solid catalysis is obtained after roasting
Agent;
The heteropolyacid salt is selected from CsxH3-xPW12O40、M2PW12O40、M2Si(W3O10)4Or M2Mo12O41P;
Wherein, M1For rare earth ion, M2For metal ion, x is 0.5~3.0.
Preferably, the preparation method of heteropolyacid salt solid catalyst is specially:
It is 5wt%~30wt% according to the load capacity of rare earth ion, by rare earth ion using ion-exchange
Soluble-salt be added in deionized water, be stirred by ultrasonic 30~60 minutes, heteropolyacid salt Cs be addedxH3-xPW12O40(x is ranging from
0.5~3.0), stirring 6 at 40~120 DEG C~for 24 hours, stands, filters, be washed with deionized to no chlorion and exist, 100~
120 DEG C of dryings 10~12 hours roasts 1~5 hour, preparation M/Cs at being 200~500 DEG C in temperaturexH3-xPW12O40(the model of x
Enclose is 0.5~3.0) catalyst.
Preferably, soluble-salt is selected from nitrate, sulfate, acetate or villaumite, most preferably villaumite.
Preferably, heteropolyacid salt CsxH3-xPW12O40Preparation method be specially:
Cesium carbonate is mixed with phosphotungstic acid aqueous solution by different proportion, at 40~80 DEG C, 2~12h is reacted, obtains insoluble
In the acid carrier phosphotungstic acid cesium salt Cs of water and organic solventxH3-xPW12O40(ranging from the 0.5~3.0 of x), will be molten after reaction
It is dried overnight at 80~120 DEG C of liquid, obtains white solid heteropolyacid salt CsxH3-xPW12O40。
Preferably, the metal in rare earth ion is selected from yttrium or scandium, more preferably yttrium.
Preferably, the load capacity of rare earth ion is 5wt%~30wt%, more preferably 20wt%.
Preferably, 2.5 x.
Preferably, heteropolyacid salt solid catalyst is 20Y/Cs2.5H0.5PW12O40。
The present invention also provides heteropolyacid salt solids made from above-mentioned heteropolyacid salt solid catalyst or above-mentioned preparation method
Application of the catalyst in cellulose prepares methyl lactate.
Preferably, the mass ratio of the heteropolyacid salt solid catalyst and the cellulose is 2:1~5.
It is highly preferred that the mass ratio of heteropolyacid salt solid catalyst and cellulose is 2:3.
Preferably, the reaction dissolvent of cellulose described in the heteropolyacid salt catalysis of solid catalyst is the mixing of first alcohol and water
Solvent;
The mass percent of the water and the methanol is 2%~10%.
It is furthermore preferred that the mass percent of water and methanol is 2%.
Preferably, application of the heteropolyacid salt solid catalyst in preparing methyl lactate in cellulose be specially:
Be be uniformly mixed in mass ratio by cellulose and novel phosphotungstate solid catalyst, first alcohol and water, wherein water and
The mass ratio of methanol is 2%~10%, in 0.5~3.0MPa N2In atmosphere, 180~240 DEG C of 2~12h of reaction, reaction terminates
Afterwards, it is rapidly cooled to room temperature with ice bath, centrifuges catalyst, gas phase color is used after 0.22 μm of filtering with microporous membrane of reaction solution
Spectrum measures associated products yield.
As can be seen from the above technical solutions, a kind of heteropolyacid salt solid catalyst provided by the invention by rare earth metal from
Son is carried on heteropolyacid salt, a kind of supported rare earth metal ion phosphotungstate solid catalyst is obtained after roasting, by the present invention
For embodiment experimental data it is found that the method for preparing catalyst is simple, the catalyst is good, methyl lactate yield obtained
The yield of height, methyl lactate can reach 60% or more;Catalytic reaction condition is mild;Easily recycling, high recycling rate and stability
Good, the yield for being repeated 5 times rear methyl lactate is basically unchanged, and solid catalyst is easier to be filtered, washed, dry compared with liquid catalyst
And post-processing, it is used in reuse, and do not allow perishable container;Catalysis time is short, and the yield of methyl lactate is up to 60% or more
When catalysis time be 8~10 hours, therefore, the catalyst have good industrial applications foreground.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention without having to pay creative labor, may be used also for those of ordinary skill in the art
To obtain other attached drawings according to these attached drawings.
Fig. 1 is the XRD diffraction patterns for the heteropolyacid salt solid catalyst that one step 2 of the embodiment of the present invention is prepared.
Specific implementation mode
Below in conjunction with the embodiment of the present invention, technical scheme of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Other embodiment obtained by those of ordinary skill in the art without making creative efforts belongs to guarantor of the present invention
The range of shield.
Raw material and reagent used in heteropolyacid salt solid catalyst provided by the invention and its preparation method and application are equal
It is available on the market.
Just a kind of heteropolyacid salt solid catalyst provided by the present invention and its preparation method and application is done further below
Explanation.
Embodiment one
Prepare Y/CsxH3-xPW12O40(ranging from the 0.5~3.0 of x) catalyst, its step are as follows:
1, the preparation of acid carrier phosphotungstic acid cesium salt:At 50 DEG C, first by 0.1697g Cs2CO3It is dissolved in 20mL water,
Then by Cs2CO3Aqueous solution is added dropwise to 1g phosphotungstic acids (H3PW12O40) aqueous solution in, obtain white precipitate, continue 50
12h is stirred at DEG C, is dried overnight to obtain white solid at 120 DEG C, is roasted 2h at 400 DEG C, be prepared into Cs3PW12O40;
At 50 DEG C, first by 0.1414g Cs2CO3It is dissolved in 20mL water, then by Cs2CO3Aqueous solution is added dropwise to
1g phosphotungstic acids (H3PW12O40) aqueous solution in, obtain white precipitate, 12h is stirred in continuation at 50 DEG C, is dried overnight at 120 DEG C
White solid is obtained, 2h is roasted at 400 DEG C, is prepared into Cs2.5H0.5PW12O40;
At 50 DEG C, first by 0.1131g Cs2CO3It is dissolved in 20mL water, then by Cs2CO3Aqueous solution is added dropwise to
1g phosphotungstic acids (H3PW12O40) aqueous solution in, obtain white precipitate, 12h is stirred in continuation at 50 DEG C, is dried overnight at 120 DEG C
White solid is obtained, 2h is roasted at 400 DEG C, is prepared into Cs2HPW12O40;
At 50 DEG C, first by 0.0848g Cs2CO3It is dissolved in 20mL water, then by Cs2CO3Aqueous solution is added dropwise to
1g phosphotungstic acids (H3PW12O40) aqueous solution in, obtain white precipitate, 12h is stirred in continuation at 50 DEG C, is dried overnight at 120 DEG C
White solid is obtained, 2h is roasted at 400 DEG C, is prepared into Cs1.5H1.5PW12O40;
At 50 DEG C, first by 0.0566g Cs2CO3It is dissolved in 20mL water, then by Cs2CO3Aqueous solution is added dropwise to
3.0047g phosphotungstic acid (H3PW12O40) aqueous solution in, obtain white precipitate, 12h is stirred in continuation at 50 DEG C, at 120 DEG C overnight
It is dried to obtain white solid, 2h is roasted at 400 DEG C, is prepared into Cs1H2PW12O40;
At 50 DEG C, first by 0.0283g Cs2CO3It is dissolved in 20mL water, then by Cs2CO3Aqueous solution is added dropwise to
1g phosphotungstic acids (H3PW12O40) aqueous solution in, obtain white precipitate, 12h is stirred in continuation at 50 DEG C, is dried overnight at 120 DEG C
White solid is obtained, 2h is roasted at 400 DEG C, is prepared into Cs0.5H2.5PW12O40。
2、Y/CsxH3-xPW12O40The preparation of (ranging from the 0.5~3.0 of x) catalyst:
It is the YCl that 5~30wt% configures 50ml according to active component ruthenium ion load capacity3·7H2In O aqueous solutions, by step
Acid carrier Cs made from 1xH3-xPW12O40(1.0g) is added in above-mentioned solution, at 50 DEG C, is persistently stirred to react for 24 hours, quiet
12h is set, suction filtration is washed with deionized to no chlorion and exists, 110 DEG C of dry 12h, roasts 2h at 400 DEG C, is prepared into Y/
CsxH3-xPW12O40(ranging from the 0.5~3.0 of x) catalyst.
From figure 1 it appears that the catalyst essential characteristic diffraction maximum after one step 2 of the present embodiment load Y does not occur
It substantially change, shows that Y has successfully been supported on catalyst.
Embodiment two
A series of Cs prepared using one step 1 of embodimentxH3-xPW12O40(ranging from the 0.5~3.0 of x) catalyst
Cellulose methyl lactate:
Weigh 0.15g celluloses, 0.1g CsxH3-xPW12O40(ranging from the 0.5~3.0 of x) catalyst, 11.76g methanol,
For 0.24g water in 25mL stainless steel autoclaves, the air being passed through at room temperature in nitrogen displacement autoclave repeats three
It is secondary, then it is passed through the nitrogen of 2MPa, under 600rpm stirring conditions, 220 DEG C of reaction 8h centrifuge catalyst after reaction,
After 0.22 μm of filtering with microporous membrane of reaction solution, with the yield of high performance liquid chromatography measure and calculation methyl lactate, as a result such as 1 institute of table
Show.
As can be known from Table 1, the Cs that one step 1 of the embodiment of the present invention is prepared2.5H0.5PW12O40Catalyst fiber element system
The yield highest of methyl lactate and by-product, therefore, the catalytic performance of the catalyst is best.
1 Cs of tablexH3-xPW12O40The yield of catalytic cellulose methyl lactate and by-product
Embodiment three
Utilize a series of Y/Cs of difference Y load capacity prepared by one step 2 of embodiment2.5H0.5PW12O40Catalyst is fine
Tie up element methyl lactate:
Weigh 0.15g celluloses, 0.1g Y/Cs2.5H0.5PW12O40Catalyst, 11.76g methanol, 0.24g water in 25mL not
It becomes rusty in steel autoclave, the air being passed through at room temperature in nitrogen displacement autoclave in triplicate, then is passed through the nitrogen of 2MPa
Gas, under 600 revs/min of stirring conditions, 220 DEG C are reacted 8 hours, centrifuge catalyst after reaction, and reaction solution is used
After 0.22 μm of filtering with microporous membrane, with the yield of high performance liquid chromatography measure and calculation lactic acid, the results are shown in Table 2.
As can be known from Table 2, the Y/Cs for the different Y load capacity that prepared by one step 2 of the embodiment of the present invention2.5H0.5PW12O40Catalysis
The yield for the catalyst cellulose methyl lactate and by-product of agent prepared than one step 1 of the embodiment of the present invention is high,
That is Y/Cs2.5H0.5PW12O40Catalyst is good, therefore, Y/Cs when metal Y load capacity is 20%2.5H0.5PW12O40Catalyst
Cellulose methyl lactate yield highest, catalytic are best.
The Y/Cs of 2 difference Y load capacity of table2.5H0.5PW12O40The yield of catalytic cellulose methyl lactate and by-product
Example IV
The 20Y/Cs prepared using one step 2 of embodiment2.5H0.5PW12O40The cellulose system of catalyst different quality
Methyl lactate:
Weigh a certain amount of cellulose, 0.1g 20Y/Cs2.5H0.5PW12O40Catalyst, 11.76g methanol, 0.24g water in
In 25mL stainless steel autoclaves, the air being passed through at room temperature in nitrogen displacement autoclave in triplicate, then is passed through
The nitrogen of 2MPa, under 600 revs/min of stirring conditions, 220 DEG C are reacted 8 hours, centrifuge catalyst after reaction, instead
After answering 0.22 μm of filtering with microporous membrane of liquid, with the yield of high performance liquid chromatography measure and calculation lactic acid, the results are shown in Table 3.
As can be known from Table 3, the 20Y/Cs that prepared by one step 2 of the embodiment of the present invention2.5H0.5PW12O40Catalyst is different
When the cellulose of quality, the yield of methyl lactate is gradually decreased with the increase of cellulose quality, considers lactic acid first
The influence of ester yield and cellulose addition to entirely reacting, it is optimal addn that selection cellulose addition, which is 0.15g,.
3 20Y/Cs of table2.5H0.5PW12O40The cellulose methyl lactate of catalyst different quality and the production of by-product
Rate
Embodiment five
The 20Y/Cs prepared using one step 2 of embodiment2.5H0.5PW12O40Catalyst catalytic cellulose at different temperatures
Methyl lactate processed:
Weigh 0.15g celluloses, 0.1g 20Y/Cs2.5H0.5PW12O40Catalyst, 11.76g methanol, 0.24g water are in 25mL
In stainless steel autoclave, the air being passed through at room temperature in nitrogen displacement autoclave in triplicate, then is passed through 2MPa's
Nitrogen reacts 8h under 600rpm stirring conditions under different temperatures, centrifuge catalyst after reaction, and reaction solution is used
After 0.22 μm of filtering with microporous membrane, with the yield of high performance liquid chromatography measure and calculation lactic acid, the results are shown in Table 4.
As can be known from Table 4, the 20Y/Cs that prepared by one step 2 of the embodiment of the present invention2.5H0.5PW12O40Catalyst at 220 DEG C and
At 240 DEG C, the yield for the methyl lactate that catalytic cellulose obtains is higher, and catalytic is good, but 240 DEG C of temperature are excessively high, therefore, comprehensive
Determine that the best reaction temperature of the catalyst is 220 DEG C after consideration.
4 20Y/Cs of table2.5H0.5PW12O40Catalyst catalytic cellulose methyl lactate and by-product at different temperatures
Yield
Embodiment six
The 20Y/Cs prepared using one step 2 of embodiment2.5H0.5PW12O40Catalyst catalytic cellulose under different time
Methyl lactate processed:
Weigh 0.15g celluloses, 0.1g 20Y/Cs2.5H0.5PW12O40Catalyst, 11.76g methanol, 0.24g water are in 25mL
In stainless steel autoclave, the air being passed through at room temperature in nitrogen displacement autoclave in triplicate, then is passed through 2MPa's
Nitrogen reacts different time under 600rpm stirring conditions at 220 DEG C, centrifuge catalyst after reaction, and reaction solution is used
After 0.22 μm of filtering with microporous membrane, with the yield of high performance liquid chromatography measure and calculation lactic acid, the results are shown in Table 5.
As can be known from Table 5, the 20Y/Cs that prepared by the embodiment of the present invention one2.5H0.5PW12O40Catalyst is urged in 8h and 10h
Cellulose methyl lactate yield highest, catalytic is best, and when considering 8h and 10h, the yield of methyl lactate is close, therefore,
Select the reaction time short for the best reaction time:8h.
5 20Y/Cs of table2.5H0.5PW12O40Production of the catalyst in different time catalytic cellulose methyl lactate and by-product
Rate
Embodiment seven
The 20Y/Cs prepared using one step 2 of embodiment2.5H0.5PW12O40Catalyst cellulose methyl lactate:
Weigh 0.15g celluloses, 0.1g 20Y/Cs2.5H0.5PW12O40Catalyst, 11.76g methanol, 0.24g water are in 25mL
In stainless steel autoclave, the air being passed through at room temperature in nitrogen displacement autoclave in triplicate, then is passed through 2MPa's
Nitrogen reacts different time under 600rpm stirring conditions at 220 DEG C, centrifuge catalyst after reaction, and reaction solution is used
After 0.22 μm of filtering with microporous membrane, with the yield of high performance liquid chromatography measure and calculation lactic acid.Catalyst after centrifugation is used
Distilled water repeatedly washs, and 8~12h of drying in 80~120 DEG C of baking ovens is put into, by the catalyst after drying according to above-mentioned experiment condition
Continue to test.5 repetitions are carried out according to above-mentioned condition to test.Experimental result is as shown in table 6.
As can be known from Table 6, the 20Y/Cs that prepared by one step 2 of the embodiment of the present invention2.5H0.5PW12O40Catalyst is through 5 repetitions
After experiment, catalyst performance is not substantially change, it was demonstrated that the stability of the catalyst is good.
6 20Y/Cs of table2.5H0.5PW12O40The yield of methyl lactate and by-product is made in catalyst circulation catalytic cellulose
Embodiment eight
The 20Y/Cs prepared using one step 2 of embodiment2.5H0.5PW12O40Methanol solution of the catalyst in different moisture content
Lower catalytic cellulose methyl lactate:
Weigh 0.15g celluloses, 0.1g 20Y/Cs2.5H0.5PW12O40Catalyst, total 12g water and methanol (the wherein matter of water
Measure score be 2%, 5%, 8%, 10%) in 25mL stainless steel autoclaves, be passed through nitrogen displacement reaction under high pressure at room temperature
Air in kettle in triplicate, then is passed through the nitrogen of 2MPa, under 600rpm stirring conditions, reacts different time at 220 DEG C,
Catalyst is centrifuged after reaction, after 0.22 μm of filtering with microporous membrane of reaction solution, with high performance liquid chromatography measure and calculation
The yield of lactic acid, the results are shown in Table 7.
As can be known from Table 7, the 20Y/Cs that prepared by one step 2 of the embodiment of the present invention2.5H0.5PW12O40Catalyst contains 2%
The yield highest of methyl lactate, reaches 61% when water.
7 20Y/Cs of table2.5H0.5PW12O40Catalyst catalytic cellulose lactic acid first under the methanol solution of different moisture content
The yield of ester and by-product
Embodiment nine
Prepare different metal load M1/Cs2.5H0.5PW12O40Catalyst.
Different metal load C s2.5H0.5PW12O40The preparation method of catalyst is as in the first embodiment, living in only changing the step 2
Property component (M1=Y, In, Sc, Ge, Ho), M can be obtained1/Cs2.5H0.5PW12O40Catalyst.
Embodiment ten
M is loaded using different metal prepared by embodiment nine1/Cs2.5H0.5PW12O40Catalyst cellulose lactic acid
Methyl esters:
Weigh 0.15g celluloses, 0.1g 20Y/Cs2.5H0.5PW12O40Catalyst, 11.76g methanol, 0.24g water are in 25mL
In stainless steel autoclave, the air being passed through at room temperature in nitrogen displacement autoclave in triplicate, then is passed through 2MPa's
Nitrogen reacts 8h under 600 revs/min of stirring conditions at 220 DEG C, centrifuge catalyst after reaction, and reaction solution is used
After 0.22 μm of filtering with microporous membrane, with the yield of high performance liquid chromatography measure and calculation methyl lactate, the results are shown in Table 8.
As can be known from Table 8, the different metal that prepared by the embodiment of the present invention six loads M/Cs2.5H0.5PW12O40Catalyst,
In, Y/Cs2.5H0.5PW12O40The yield highest of catalytic cellulose methyl lactate, therefore, the best carried metal of the catalyst
For Y.
8 different metal of table loads M/Cs2.5H0.5PW12O40The production of catalyst cellulose methyl lactate and by-product
Rate
The above, the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations;Although with reference to before
Stating embodiment, invention is explained in detail, it will be understood by those of ordinary skill in the art that:It still can be to preceding
The technical solution recorded in each embodiment is stated to modify or equivalent replacement of some of the technical features;And these
Modification or replacement, the spirit and scope for various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of heteropolyacid salt solid catalyst, which is characterized in that including:It heteropolyacid salt and is supported on the heteropolyacid salt
M1;
The heteropolyacid salt is selected from CsxH3-xPW12O40、M2PW12O40、M2Si(W3O10)4Or M2Mo12O41P;
Wherein, M1For rare earth ion, M2For metal ion, x is 0.5~3.0.
2. heteropolyacid salt solid catalyst according to claim 1, which is characterized in that the rare earth ion is described
Load capacity in heteropolyacid salt solid catalyst is 5wt%~30wt%.
3. heteropolyacid salt solid catalyst according to claim 1 or 2, which is characterized in that in the rare earth ion
Metal be selected from chromium, praseodymium, lutetium, niobium, holmium, thulium, gadolinium, samarium, yttrium, europium, ytterbium, neodymium, dysprosium, indium or scandium.
4. heteropolyacid salt solid catalyst according to claim 3, which is characterized in that the gold in the rare earth ion
Belong to and is selected from yttrium or scandium.
5. heteropolyacid salt solid catalyst according to claim 1, which is characterized in that the heteropolyacid salt is CsxH3- xPW12O40。
6. heteropolyacid salt solid catalyst according to claim 1 or 5, which is characterized in that the x is 2.5.
7. the preparation method of the heteropolyacid salt solid catalyst described in claim 1 to 6 any one, which is characterized in that including
Following steps:
By M1Soluble salt solutions reacted with heteropolyacid salt, the heteropolyacid salt solid catalyst is obtained after roasting;
The heteropolyacid salt is selected from CsxH3-xPW12O40、M2PW12O40、M2Si(W3O10)4Or M2Mo12O41P;
Wherein, M1For rare earth ion, M2For metal ion, x is 0.5~3.0.
8. the preparation method system described in heteropolyacid salt solid catalyst or claim 7 described in claim 1 to 6 any one
Application of the heteropolyacid salt solid catalyst obtained in cellulose prepares methyl lactate.
9. application according to claim 8, which is characterized in that the cellulose and the heteropolyacid salt solid catalyst
Mass ratio is 2:1~5.
10. application according to claim 8, which is characterized in that fiber described in the heteropolyacid salt catalysis of solid catalyst
The reaction dissolvent of element is the mixed solvent of first alcohol and water;
The mass percent of the water and the methanol is 2%~10%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810496382.XA CN108772100B (en) | 2018-05-22 | 2018-05-22 | Heteropolyacid salt solid catalyst, and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810496382.XA CN108772100B (en) | 2018-05-22 | 2018-05-22 | Heteropolyacid salt solid catalyst, and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108772100A true CN108772100A (en) | 2018-11-09 |
CN108772100B CN108772100B (en) | 2021-04-16 |
Family
ID=64027498
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810496382.XA Active CN108772100B (en) | 2018-05-22 | 2018-05-22 | Heteropolyacid salt solid catalyst, and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108772100B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110028397A (en) * | 2019-05-15 | 2019-07-19 | 东北师范大学 | A kind of application of the polyacid catalyst of the structure containing Dawson in cellulose hydrothermal conversion |
CN110292933A (en) * | 2019-07-25 | 2019-10-01 | 盐城工学院 | A kind of catalyst and the preparation method and application thereof for the synthesis of diisooctyl phthalate plasticizer |
CN114904587A (en) * | 2022-05-26 | 2022-08-16 | 东南大学 | Preparation method of cesium-modified phosphotungstic acid @ UiO-66/porous carbon-based composite material |
CN114957039A (en) * | 2021-02-27 | 2022-08-30 | 大加香料技术(天津)有限公司 | Preparation method of octocrilene |
CN114956995A (en) * | 2021-02-25 | 2022-08-30 | 大加香料技术(天津)有限公司 | Preparation method of acetate |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20120089918A (en) * | 2010-12-22 | 2012-08-16 | 한국화학연구원 | Preparing method of bio-diesel from bio-oils of high acid value using acid-base catalyst combinations |
CN102764668A (en) * | 2011-05-06 | 2012-11-07 | 天津神能科技有限公司 | Preparation of phosphomolybdate catalyst loaded on gamma-Al2O3 |
US20130281733A1 (en) * | 2012-04-10 | 2013-10-24 | King Abdullah University Of Science And Technology | Molybdenum-containing Acidic Catalysts to Convert Cellulosic Biomass to Glycolic Acid |
CN103657689A (en) * | 2013-12-09 | 2014-03-26 | 陕西师范大学 | Solid acid catalyst, preparation method thereof, and applications of solid acid catalyst in catalytic conversion of biomass into lactic acid |
CN105061201A (en) * | 2015-07-31 | 2015-11-18 | 福建农林大学 | Preparation method of lactic ester |
-
2018
- 2018-05-22 CN CN201810496382.XA patent/CN108772100B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20120089918A (en) * | 2010-12-22 | 2012-08-16 | 한국화학연구원 | Preparing method of bio-diesel from bio-oils of high acid value using acid-base catalyst combinations |
CN102764668A (en) * | 2011-05-06 | 2012-11-07 | 天津神能科技有限公司 | Preparation of phosphomolybdate catalyst loaded on gamma-Al2O3 |
US20130281733A1 (en) * | 2012-04-10 | 2013-10-24 | King Abdullah University Of Science And Technology | Molybdenum-containing Acidic Catalysts to Convert Cellulosic Biomass to Glycolic Acid |
CN103657689A (en) * | 2013-12-09 | 2014-03-26 | 陕西师范大学 | Solid acid catalyst, preparation method thereof, and applications of solid acid catalyst in catalytic conversion of biomass into lactic acid |
CN105061201A (en) * | 2015-07-31 | 2015-11-18 | 福建农林大学 | Preparation method of lactic ester |
Non-Patent Citations (3)
Title |
---|
D. ZHAO ET AL.: ""Cesium substituted 12-tungstophosphoric (CsxH3−xPW12O40) loaded on ceria-degradation mitigation in polymer electrolyte membranes"", 《JOURNAL OF POWER SOURCES》 * |
于洪全: "《功能材料》", 30 June 2014, 北京交通大学出版社 * |
王基铭等: "《石油化工技术进展》", 30 April 2002, 中国石化出版社出版 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110028397A (en) * | 2019-05-15 | 2019-07-19 | 东北师范大学 | A kind of application of the polyacid catalyst of the structure containing Dawson in cellulose hydrothermal conversion |
CN110292933A (en) * | 2019-07-25 | 2019-10-01 | 盐城工学院 | A kind of catalyst and the preparation method and application thereof for the synthesis of diisooctyl phthalate plasticizer |
CN110292933B (en) * | 2019-07-25 | 2022-02-18 | 盐城工学院 | Catalyst for synthesis of diisooctyl phthalate plasticizer and preparation method and application thereof |
CN114956995A (en) * | 2021-02-25 | 2022-08-30 | 大加香料技术(天津)有限公司 | Preparation method of acetate |
CN114957039A (en) * | 2021-02-27 | 2022-08-30 | 大加香料技术(天津)有限公司 | Preparation method of octocrilene |
CN114957039B (en) * | 2021-02-27 | 2024-02-02 | 大加香料技术(天津)有限公司 | Preparation method of octocrylene |
CN114904587A (en) * | 2022-05-26 | 2022-08-16 | 东南大学 | Preparation method of cesium-modified phosphotungstic acid @ UiO-66/porous carbon-based composite material |
CN114904587B (en) * | 2022-05-26 | 2024-02-23 | 东南大学 | Preparation method of cesium modified phosphotungstic acid@UiO-66/porous carbon-based composite material |
Also Published As
Publication number | Publication date |
---|---|
CN108772100B (en) | 2021-04-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108772100A (en) | A kind of heteropolyacid salt solid catalyst and its preparation method and application | |
CN107011154B (en) | A method of adipic acid is prepared by furans -2,5- dicarboxylic acids | |
CN103657689A (en) | Solid acid catalyst, preparation method thereof, and applications of solid acid catalyst in catalytic conversion of biomass into lactic acid | |
CN102989490B (en) | Copper-hydroxyapatite catalyst for synthesizing methyl glycolate and ethylene glycol and preparation method thereof | |
JP2006129735A (en) | Method for hydrolyzing cellulose using catalyst and method for producing glucose using the catalyst | |
CN100446858C (en) | Zirconium-base loaded vanadium-phosphor oxide catalyst, and its preparing and use | |
CN112279825B (en) | Preparation method of 5-halogenated methyl furfural | |
CN108440463A (en) | A method of preparing 5 hydroxymethyl furfural with load type metal molecular sieve catalyst catalysis | |
CN102430414A (en) | Zirconium-based magnetic solid superacid catalyst, its preparation and method for preparing levoglucose ketone by catalytic pyrolysis of cellulose or biomass | |
CN104888775A (en) | Catalyst for preparing C5 or C6 alkane from sugar or sugar alcohol via water-phase hydrogenolysis | |
CN110483268A (en) | A kind of method that heteropoly acid catalysis microcrystalline cellulose prepares levulic acid | |
CN101780419B (en) | Zinc polycarboxylate composition catalyst and application for preparing aliphatic polycarbonate | |
CN112517033A (en) | Vanadium phosphorus oxide catalyst and preparation method and application thereof | |
CN106944050B (en) | A kind of catalyst and its preparation method and application synthesizing 1,3- propylene glycol | |
CN102319571B (en) | Catalyst for catalyzing hydrocracking of biomass oil and preparation method and application thereof | |
CN106831391A (en) | The method that chemicals is prepared by microalgae Direct Hydrothermal oxidation | |
CN116273120A (en) | Carbon-nitrogen doped supported cobalt-based catalyst and preparation method and application thereof | |
CN102060671A (en) | Method for preparing 3,4-carane diol as mosquito and fly evading agent | |
CN102516322A (en) | Method for preparing levoglucosenone with magnetic solid phosphoric acid catalyst | |
CN104262367A (en) | Method utilizing heterocyclic zinc carboxylate complex to catalyze synthesis of aliphatic polycarbonate | |
CN111036306B (en) | Cobalt-phosphine catalyst and preparation method and application thereof | |
CN104759294B (en) | A kind of preparation method and applications of heteropolyanion Modified Cu base class hydrotalcite catalyst | |
CN108129311A (en) | A kind of method from carbon dioxide and glycerine manufacture glycerol carbonate | |
CN110026217A (en) | A kind of application of more molybdic acid catalyst of argentiferous in oxycellulose | |
CN105597800A (en) | Lanthanum-based phosphomolybdate catalyst and application thereof in catalyzing hydrolysis of fructose for preparing lactic acid |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |