CN106732533B - A kind of catalyst, preparation method and application method for producing methacrylaldehyde for dehydrating glycerin - Google Patents
A kind of catalyst, preparation method and application method for producing methacrylaldehyde for dehydrating glycerin Download PDFInfo
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- CN106732533B CN106732533B CN201710002964.3A CN201710002964A CN106732533B CN 106732533 B CN106732533 B CN 106732533B CN 201710002964 A CN201710002964 A CN 201710002964A CN 106732533 B CN106732533 B CN 106732533B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
Abstract
The present invention relates to a kind of catalyst, preparation method and application methods that methacrylaldehyde is produced for dehydrating glycerin, have pyrochlore-type wolframic acid caesium Cs1.1W1.65O5.5With caesium tungsten bronze CsxWO3The composition of two-phase composite construction mainly solves the problems, such as that catalyst is not high and be not easy to recycle in easy carbon distribution, easy coking, selectivity in the prior art.The present invention obtains the solid product containing pyrochlore-type wolframic acid caesium and caesium tungsten bronze two-phase coexistent by acid and reproducibility environment, making tungstates and cesium salt carry out hydro-thermal reaction, and hydrothermal product obtains catalyst through subsequent calcination process again.This catalyst can regulate and control the relative amount and tungsten reducing degree of above-mentioned two-phase by changing ethylenediamine tetra-acetic acid or its disodium salt, the additional amount of reproducibility organic acid and hydrothermal reaction condition.There is catalyst the technical solution of pyrochlore-type wolframic acid caesium and caesium tungsten bronze two-phase composite construction preferably to solve the technical problem, can be used in the industrial production of preparing acrolein by dehydrating glycerin catalyst.
Description
Technical field
The invention belongs to industrial catalyst synthesis technical fields, and in particular to a kind of to produce methacrylaldehyde for dehydrating glycerin
Catalyst, preparation method and application method.
Background technique
Biodiesel can be used as the alternative fuel of fossil fuel, have cleaning, reproducible advantage, by more and more
Concern, pushed the fast development of bioenergy industry.Biodiesel is anti-by transesterification by raw material of animal and plant fat
The diesel fuel that should be produced can generate byproduct glycerol in the reaction process, with the steady promotion of yield of biodiesel, glycerol
Yield also increase year by year, bring therewith how to realize glycerol efficiently using this major issue.
Methacrylaldehyde can be generated by intramolecular dehydration in glycerol, and methacrylaldehyde is a kind of important chemical intermediate, and existing third
The production of olefine aldehydr mainly uses this process route of oxidation of propylene, but with the growing tension of petroleum resources, raw material propylene
Cost will rise steadily, so that the price of methacrylaldehyde and its downstream product be caused to increase, therefore, produce propylene by raw material of glycerol
The efficient utilization of superfluous glycerol had not only may be implemented in aldehyde, but also can get rid of dependence of the methacrylaldehyde production to petrochemical industry, had important meaning
Justice.
Preparing acrolein by dehydrating glycerin can carry out under the conditions of gas phase reaction in fixed bed reactors, can also be in liquid phase item
It is carried out under part, catalyst is usually various solid acid catalysts, and patent US 5387720 is reported using aluminium oxide as the negative of carrier
Phosphoric acid catalyst is carried, using the glycerine water solution of 20% (mass fraction) as raw material, the yield of methacrylaldehyde reaches 70.5%, patent
Diatomite is used to obtain 72.3% under liquid-phase reaction condition for the load phosphoric acid catalyst of carrier in US 2558520
Methacrylaldehyde yield, patent CN 101417928A propose miscellaneous more as the load of carrier using modified aluminas, silica, molecular sieve
Acid catalyst, it is said that highest catalytic activity is up to glycerol conversion yield 100%, acrolein selectivity 83.7%, although heteropllyacids
Catalyst initial activity is higher, but research shows that this kind of catalysis is easier to carbon distribution inactivation, and if by high temperature coke burning regeneration, heat
Stability tends not to meet the requirements again, except load phosphoric acid or carried heteropoly acid catalyst in addition to, molecular sieve catalysts also by with
It is reacted in preparing acrolein by dehydrating glycerin, patent CN103638965A provides a kind of system of multi-stage porous ZSM-5 molecular sieve catalyst
Preparation Method is used for preparing acrolein by dehydrating glycerin reaction, and glycerol conversion yield 80% or more, selectively may be used by the highest of methacrylaldehyde
Up to 89%, but the catalyst stabilization time is shorter, and patent CN104475147A is disclosed by nano-ZSM-5 and nano oxidized aluminum
At composite catalyst, glycerol conversion yield can be made to improve, stablize the time extend, as a whole, existing dehydrating glycerin propylene
Mostly there is more serious coking phenomenon in aldehyde catalyst, acrolein selectivity is influenced, and since catalyst duct is blocked, with anti-
Should carry out catalytic activity constantly reduces.
Tungsten oxide catalyst is loaded as a kind of preparing acrolein by dehydrating glycerin catalyst by more concern, such as patent WO
2006/087084 catalyst announced can make methacrylaldehyde yield reach 74%, although showing higher acrolein selectivity,
It is to carry out catalyst activity with reaction can constantly decline, patent WO2008/092534 has also been proposed the regeneration side of decaying catalyst
Method.Research, which has also discovered, has the shortcomings that selective not high enough and easy coking with the catalyst majority that tungsten oxide is active phase, existing
There are catalyst, the needs progress improvement of preparation method and application method that methacrylaldehyde is produced for dehydrating glycerin.
Summary of the invention
Object of the invention is a kind of catalyst that methacrylaldehyde is produced for dehydrating glycerin,
Object of the invention is a kind of preparation method of catalyst that methacrylaldehyde is produced for dehydrating glycerin,
Object of the invention is a kind of application method of catalyst that methacrylaldehyde is produced for dehydrating glycerin.
The object of the present invention is to provide a kind of catalyst and preparation method thereof for preparing acrolein by dehydrating glycerin reaction, should
Catalyst has pyrochlore-type wolframic acid caesium and caesium tungsten bronze two-phase composite construction, particularly in acid and reproducibility environment,
So that tungstates and cesium salt is carried out hydro-thermal reaction and obtain the solid product containing pyrochlore-type wolframic acid caesium and caesium tungsten bronze two-phase coexistent,
By changing ethylenediamine tetra-acetic acid or its disodium salt, the additional amount of reproducibility organic acid and hydrothermal reaction condition, can regulate and control
The relative amount of above-mentioned two-phase and the reducing degree of tungsten, hydrothermal product obtain catalyst through subsequent calcination process again, bear with having
It carries tungsten oxide catalyst to compare, this catalyst shows to be not easy coking, is not easy carbon distribution, high living to preparing acrolein by dehydrating glycerin reaction
Property, easy the advantages of recycling.
A kind of catalyst for producing methacrylaldehyde for dehydrating glycerin has pyrochlore-type wolframic acid caesium Cs1.1W1.65O5.5And caesium
Tungsten bronze CsxWO3The composition of two-phase composite construction.
The present invention devises, pyrochlore-type wolframic acid caesium Cs1.1W1.65O5.5With the caesium tungsten bronze CsxWO3Two-phase composite construction
Middle x value is 0.05-0.45.
The present invention devises, and a kind of preparation method of catalyst that producing methacrylaldehyde for dehydrating glycerin, its step are as follows:
(1) tungstates is added to the water, adds ethylenediamine tetra-acetic acid (C10H16N2O8) or disodium ethylene diamine tetraacetate
(C10H16N2Na2O8), it is acidity that the organic acid for adjusting pH value of reproducibility, which is then added, it is stirred 0.5-3 hours at 20 DEG C -80 DEG C,
Obtain the first mixed solution；
(2) it is changed to that cesium carbonate solution or cesium nitrate solution are added dropwise to the described of step (1) no more than 1.5 according to caesium tungsten ratio
In first mixed solution, is stirred 0.5-3 hours at 20 DEG C -80 DEG C, obtain the second mixed solution；
(3) second mixed solution of step (2) is added in water heating kettle, compactedness 50%-85%, 120
Hydro-thermal reaction 1-72 hours at DEG C -260 DEG C, mixture is obtained；
(4) by the mixture of step (3) washing, dry, temperature is 300 DEG C -800 DEG C, intermediate medium is nitrogen
Calcining furnace in carry out 1-6 hours processing obtain catalyst.
The preparing acrolein by dehydrating glycerin catalyst obtained using above-mentioned preparation method, morphology microstructure are nano bar-shape, are led to
Control preparation condition is crossed, the powder of other patterns such as spherical, sheet can also be obtained.
The present invention devises, and tungstates is set as the one or more of ammonium paratungstate, ammonium metatungstate or sodium tungstate
Mixture.
The present invention devises, and the molar ratio of ethylenediamine tetra-acetic acid or the disodium ethylene diamine tetraacetate and the tungstates is set
It is set to 0.05-1, preferably 0.15-0.45.
The present invention devises, and reproducibility organic acid is set as the one or more kinds of of citric acid, oxalic acid or formic acid and mixes
Object is closed, the pH value after reproducibility organic acid is added is set as 1-6, and preferable ph is set as 2-4.
The present invention devises, and caesium tungsten ratio is 0.05-1.5.
The present invention devises, and hydrothermal temperature is set as 180 DEG C -220 DEG C, and the hydro-thermal time is set as 18-36 hours.The present invention
It devises, a kind of application method of catalyst that producing methacrylaldehyde for dehydrating glycerin, is 10-70%, preferably 15- concentration
35% glycerine water solution is delivered to mixer by pump, while air is input to mixer, makes the molar ratio of glycerol and air
It is set as 1:1-1:20, is preferably arranged to 1:5-1:10, it is anti-that well-mixed reaction raw materials enter the fixed bed equipped with catalyst
Device is answered, bed temperature is 260-360 DEG C, reaction pressure is normal pressure, liquid air speed is 0.6h-1-7.0h-1, collecting condensation is obtained
To methacrylaldehyde.Glycerol conversion yield and acrolein selectivity are defined as follows:
Glycerol conversion yield (%)=molal quantity of glycerol consumed in reaction/be added to the molal quantity of the glycerol in reaction ×
100%.
The molal quantity of the glycerol consumed in molal quantity/reaction of the methacrylaldehyde generated in acrolein selectivity (%)=reaction
× 100%.
The preparation and application method of preparing acrolein by dehydrating glycerin catalyst proposed by the present invention, has the advantages that catalysis
Agent is not easy carbon distribution, and acrolein selectivity is high；The catalyst stabilization time is long, and regenerates and be easy, and the catalysis after activity reduces is passed through
Roasting can restore completely；Overcome the problem of other catalyst are easy to cause product to polymerize.
Specific embodiment
By following embodiment, the present invention will be described, but is not therefore limited the scope of the present invention.
A kind of preparation method of catalyst that producing methacrylaldehyde for dehydrating glycerin, one embodiment, its step are as follows:
(1) tungstates is added to the water, adds ethylenediamine tetra-acetic acid (C10H16N2O8) or disodium ethylene diamine tetraacetate
(C10H16N2Na2O8), it is acidity that the organic acid for adjusting pH value of reproducibility, which is then added, stirs 0.5 hour at 20 DEG C, obtains first
Mixed solution；
(2) it is changed to that cesium carbonate solution or cesium nitrate solution are added dropwise to the described of step (1) no more than 1.5 according to caesium tungsten ratio
In first mixed solution, is stirred 0.5 hour at 20 DEG C, obtain the second mixed solution；
(3) second mixed solution of step (2) is added in water heating kettle, compactedness 50% is lauched at 120 DEG C
Thermal response 1 hour, obtain mixture；
(4) by mixture washing, the drying of step (3), in the calcining that temperature is 300 DEG C, intermediate medium is nitrogen
Processing in 1 hour is carried out in furnace obtains the catalyst of methacrylaldehyde.
In the present embodiment, tungstates is set as ammonium paratungstate.
In the present embodiment, the molar ratio of ethylenediamine tetra-acetic acid or the disodium ethylene diamine tetraacetate and the tungstates is set
It is set to 0.05.
In the present embodiment, reproducibility organic acid is set as citric acid, and the pH value after reproducibility organic acid is added is set as
1。
In the present embodiment, caesium tungsten ratio is 0.05.
In the present embodiment, hydrothermal temperature is set as 180 DEG C, and the hydro-thermal time is set as 18 hours.
By chemical analysis, the catalyst of methacrylaldehyde has pyrochlore-type wolframic acid caesium Cs1.1W1.65O5.5With caesium tungsten bronze
CsxWO3Two-phase composite construction, pyrochlore-type wolframic acid caesium Cs1.1W1.65O5.5With the caesium tungsten bronze CsxWO3In two-phase composite construction
X value is 0.05, and catalyst is nano bar-shape body.
Second embodiment, its step are as follows:
(1) tungstates is added to the water, adds ethylenediamine tetra-acetic acid (C10H16N2O8) or disodium ethylene diamine tetraacetate
(C10H16N2Na2O8), it is acidity that the organic acid for adjusting pH value of reproducibility, which is then added, is stirred 3 hours at 80 DEG C, and it is mixed to obtain first
Close solution；
(2) it is changed to that cesium carbonate solution or cesium nitrate solution are added dropwise to the described of step (1) no more than 1.5 according to caesium tungsten ratio
In first mixed solution, is stirred 3 hours at 80 DEG C, obtain the second mixed solution；
(3) second mixed solution of step (2) is added in water heating kettle, compactedness 85% is lauched at 260 DEG C
Thermal response 72 hours, obtain mixture；
(4) by mixture washing, the drying of step (3), in the calcining that temperature is 800 DEG C, intermediate medium is nitrogen
Processing in 6 hours is carried out in furnace obtains the catalyst of methacrylaldehyde.
In the present embodiment, tungstates is set as ammonium metatungstate.
In the present embodiment, the molar ratio of ethylenediamine tetra-acetic acid or the disodium ethylene diamine tetraacetate and the tungstates is set
It is set to 1.
In the present embodiment, reproducibility organic acid is set as oxalic acid, and the pH value after reproducibility organic acid is added is set as 6.
In the present embodiment, caesium tungsten ratio is 1.5.
In the present embodiment, hydrothermal temperature is set as 220 DEG C, and the hydro-thermal time is set as 36 hours.
By chemical analysis, the catalyst of methacrylaldehyde has pyrochlore-type wolframic acid caesium Cs1.1W1.65O5.5With caesium tungsten bronze
CsxWO3Two-phase composite construction, pyrochlore-type wolframic acid caesium Cs1.1W1.65O5.5With the caesium tungsten bronze CsxWO3In two-phase composite construction
X value is 0.45, and catalyst is spherical powder.
Third embodiment, its step are as follows:
(1) tungstates is added to the water, adds ethylenediamine tetra-acetic acid (C10H16N2O8) or disodium ethylene diamine tetraacetate
(C10H16N2Na2O8), it is acidity that the organic acid for adjusting pH value of reproducibility, which is then added, stirs 1.5 hours at 50 DEG C, obtains first
Mixed solution；
(2) it is changed to that cesium carbonate solution or cesium nitrate solution are added dropwise to the described of step (1) no more than 1.5 according to caesium tungsten ratio
In first mixed solution, is stirred 1.5 hours at 50 DEG C, obtain the second mixed solution；
(3) second mixed solution of step (2) is added in water heating kettle, compactedness 65% is lauched at 180 DEG C
Thermal response 37 hours, obtain mixture；
(4) by mixture washing, the drying of step (3), in the calcining that temperature is 650 DEG C, intermediate medium is nitrogen
Processing in 4 hours is carried out in furnace obtains the catalyst of methacrylaldehyde.
In the present embodiment, tungstates is set as sodium tungstate.
In the present embodiment, the molar ratio of ethylenediamine tetra-acetic acid or the disodium ethylene diamine tetraacetate and the tungstates is set
It is set to 0.5.
In the present embodiment, reproducibility organic acid is set as formic acid, and the pH value after reproducibility organic acid is added is set as
3.5。
In the present embodiment, caesium tungsten ratio is 1.0.
In the present embodiment, hydrothermal temperature is set as 200 DEG C, and the hydro-thermal time is set as 27 hours.
By chemical analysis, the catalyst of methacrylaldehyde has pyrochlore-type wolframic acid caesium Cs1.1W1.65O5.5With caesium tungsten bronze
CsxWO3Two-phase composite construction, pyrochlore-type wolframic acid caesium Cs1.1W1.65O5.5With the caesium tungsten bronze CsxWO3In two-phase composite construction
X value is 0.20, and catalyst is flaky powder.
A kind of application method of catalyst that producing methacrylaldehyde for dehydrating glycerin, one embodiment are concentration
10% glycerine water solution is delivered to mixer by pump, while air is input to mixer, makes mole of glycerol and air
Than being set as 1:1, well-mixed reaction raw materials enter the fixed bed reactors equipped with catalyst, and bed temperature is 260 DEG C, instead
Answer that pressure is normal pressure and liquid air speed is 0.6h-1, methacrylaldehyde is obtained to collecting condensation.
Second embodiment, the glycerine water solution for being 70% concentration are delivered to mixer by pump, while air is defeated
Enter to mixer, the molar ratio of glycerol and air is made to be set as 1:20, well-mixed reaction raw materials enter equipped with catalyst
Fixed bed reactors, bed temperature is 360 DEG C, reaction pressure is normal pressure and liquid air speed is 7.0h-1, collecting condensation is obtained
Methacrylaldehyde.
Third embodiment, is 35% glycerine water solution concentration, is delivered to mixer by pump, while air is inputted
To mixer, the molar ratio of glycerol and air is made to be set as 1:10, well-mixed reaction raw materials enter consolidating equipped with catalyst
Fixed bed reactor, bed temperature is 300 DEG C, reaction pressure is normal pressure and liquid air speed is 3.5h-1, third is obtained to collecting condensation
Olefine aldehydr.
4th embodiment, the glycerine water solution for being 40% concentration are delivered to mixer by pump, while air is defeated
Enter to mixer, the molar ratio of glycerol and air is made to be set as 1:9, well-mixed reaction raw materials enter consolidating equipped with catalyst
Fixed bed reactor, bed temperature is 310 DEG C, reaction pressure is normal pressure and liquid air speed is 3.0h-1, third is obtained to collecting condensation
Olefine aldehydr.
The embodiment of other forms of the invention:
Embodiment 1:
13.1944g Disodium tungstate (Na2WO4) dihydrate is weighed, is added into 100ml water, constant temperature stirring 0.5 hour at 80 DEG C, then
4.0g ethylenediamine tetra-acetic acid is added, then constant temperature is kept to stir 0.5 hour, citric acid 4.2028g is added, continues to keep constant temperature stirring
2 hours, 2.6066g cesium carbonate is dissolved in 80ml water, is then added dropwise in above-mentioned solution, is transferred to after dripping off with poly- four
In the hydrothermal reaction kettle of vinyl fluoride liner, rise to 210 DEG C with 1 DEG C/min of heating rate, keep the temperature 24 hours, then with 1 DEG C/
The rate of temperature fall of minute is down to room temperature, isolates the solid in product, successively uses water and ethanol washing, dry 12 at 120 DEG C
Hour, it is packed into tube calciner, is calcined 6 hours at 500 DEG C in nitrogen atmosphere, obtains catalyst.
1.0g catalyst is weighed to be fitted into the reaction tube of fixed bed reactors, mass concentration be 20% glycerine water solution with
The speed of 3ml/h is passed through mixer, and air enters mixer with the flow velocity of 20ml/min, and the two enters reaction after mixing
Pipe, reaction pressure are normal pressure, and reaction temperature is 315 DEG C, and product condensation is collected, and gas chromatographic detection, reaction 7 as a child measured sweet
Oily conversion ratio 89.3%, acrolein selectivity 82.7%.
Embodiment 2:
13.1944g Disodium tungstate (Na2WO4) dihydrate is weighed, is added into 100ml water, constant temperature stirring 0.5 hour at 80 DEG C, then
4.0g ethylenediamine tetra-acetic acid is added, then constant temperature is kept to stir 0.5 hour, citric acid 8.4056g is added, continues to keep constant temperature stirring
2 hours, 2.6066g cesium carbonate is dissolved in 80ml water, is then added dropwise in above-mentioned solution, is transferred to after dripping off with poly- four
In the hydrothermal reaction kettle of vinyl fluoride liner, rise to 210 DEG C with 1 DEG C/min of heating rate, keep the temperature 24 hours, then with 1 DEG C/
The rate of temperature fall of minute is down to room temperature, isolates the solid in product, successively uses water and ethanol washing, dry 12 at 120 DEG C
Hour, it is packed into tube calciner, is calcined 6 hours at 500 DEG C in nitrogen atmosphere, obtains catalyst.
1.0g catalyst is weighed to be fitted into the reaction tube of fixed bed reactors, mass concentration be 20% glycerine water solution with
The speed of 3ml/h is passed through mixer, and air enters mixer with the flow velocity of 20ml/min, and the two enters reaction after mixing
Pipe, reaction pressure are normal pressure, and reaction temperature is 315 DEG C, and product condensation is collected, and gas chromatographic detection, reaction 7 as a child measured sweet
Oily conversion ratio 94.1%, acrolein selectivity 78.9%.
Embodiment 3:
13.1944g Disodium tungstate (Na2WO4) dihydrate is weighed, is added into 100ml water, constant temperature stirring 0.5 hour at 80 DEG C, then
4.0g disodium ethylene diamine tetraacetate is added, then constant temperature is kept to stir 0.5 hour, formic acid 0.5g is added, continues to keep constant temperature stirring 2
Hour, 1.5593g cesium nitrate is dissolved in 80ml water, is then added dropwise in above-mentioned solution, is transferred to after dripping off with poly- four
In the hydrothermal reaction kettle of vinyl fluoride liner, rise to 190 DEG C with 1 DEG C/min of heating rate, keep the temperature 24 hours, then with 1 DEG C/
The rate of temperature fall of minute is down to room temperature, isolates the solid in product, successively uses water and ethanol washing, dry 12 at 120 DEG C
Hour, it is packed into tube calciner, is calcined 6 hours at 500 DEG C in nitrogen atmosphere, obtains catalyst.
1.0g catalyst is weighed to be fitted into the reaction tube of fixed bed reactors, mass concentration be 20% glycerine water solution with
The speed of 3ml/h is passed through mixer, and air enters mixer with the flow velocity of 20ml/min, and the two enters reaction after mixing
Pipe, reaction pressure are normal pressure, and reaction temperature is 315 DEG C, and product condensation is collected, and gas chromatographic detection, reaction 7 as a child measured sweet
Oily conversion ratio 90.5%, acrolein selectivity 78.1%.
Embodiment 4:
13.1944g Disodium tungstate (Na2WO4) dihydrate is weighed, is added into 100ml water, constant temperature stirring 0.5 hour at 80 DEG C, then
1.7536g ethylenediamine tetra-acetic acid is added, then constant temperature is kept to stir 0.5 hour, oxalic acid 2.5g is added, continues to keep constant temperature stirring 2
Hour, 2.3388g cesium nitrate is dissolved in 80ml water, is then added dropwise in above-mentioned solution, is transferred to after dripping off with poly- four
In the hydrothermal reaction kettle of vinyl fluoride liner, rise to 190 DEG C with 1 DEG C/min of heating rate, keep the temperature 24 hours, then with 1 DEG C/
The rate of temperature fall of minute is down to room temperature, isolates the solid in product, successively uses water and ethanol washing, dry 24 at 210 DEG C
Hour, it is packed into tube calciner, is calcined 6 hours at 500 DEG C in nitrogen atmosphere, obtains catalyst.
1.0g catalyst is weighed to be fitted into the reaction tube of fixed bed reactors, mass concentration be 20% glycerine water solution with
The speed of 3ml/h is passed through mixer, and air enters mixer with the flow velocity of 20ml/min, and the two enters reaction after mixing
Pipe, reaction pressure are normal pressure, and reaction temperature is 315 DEG C, and product condensation is collected, and gas chromatographic detection, reaction 7 as a child measured sweet
Oily conversion ratio 87.2%, acrolein selectivity 85.6%.
Embodiment 5:
10.142g ammonium paratungstate is weighed, is added into 160ml water, constant temperature stirs 0.5 hour at 80 DEG C, is then added
4.608g ethylenediamine tetra-acetic acid, then constant temperature is kept to stir 0.5 hour, citric acid 1.2g is added, continues to keep constant temperature stirring 2 small
When, 2.342g cesium nitrate is dissolved in 80ml water, is then added dropwise in above-mentioned solution, is transferred to after dripping off with polytetrafluoroethyl-ne
In the hydrothermal reaction kettle of alkene liner, 210 DEG C are risen to 1 DEG C/min of heating rate, 24 hours are kept the temperature, then with 1 DEG C/min
Rate of temperature fall be down to room temperature, isolate the solid in product, successively use water and ethanol washing, dry 12 hours at 120 DEG C,
It is packed into tube calciner, is calcined 6 hours at 500 DEG C in nitrogen atmosphere, obtains catalyst.
1.0g catalyst is weighed to be fitted into the reaction tube of fixed bed reactors, mass concentration be 20% glycerine water solution with
The speed of 3ml/h is passed through mixer, and air enters mixer with the flow velocity of 20ml/min, and the two enters reaction after mixing
Pipe, reaction pressure are normal pressure, and reaction temperature is 315 DEG C, and product condensation is collected, and gas chromatographic detection, reaction 7 as a child measured sweet
Oily conversion ratio 93.7%, acrolein selectivity 89.2%.
Embodiment 6:
10.142g ammonium paratungstate is weighed, is added into 160ml water, constant temperature stirs 0.5 hour at 80 DEG C, is then added
4.608g ethylenediamine tetra-acetic acid, then constant temperature is kept to stir 0.5 hour, citric acid 1.2g is added, continues to keep constant temperature stirring 2 small
When, 3.513g cesium nitrate is dissolved in 80ml water, is then added dropwise in above-mentioned solution, is transferred to after dripping off with polytetrafluoroethyl-ne
In the hydrothermal reaction kettle of alkene liner, 210 DEG C are risen to 1 DEG C/min of heating rate, 24 hours are kept the temperature, then with 1 DEG C/min
Rate of temperature fall be down to room temperature, isolate the solid in product, successively use water and ethanol washing, dry 12 hours at 120 DEG C,
It is packed into tube calciner, is calcined 6 hours at 500 DEG C in nitrogen atmosphere, obtains catalyst.
1.0g catalyst is weighed to be fitted into the reaction tube of fixed bed reactors, mass concentration be 20% glycerine water solution with
The speed of 3ml/h is passed through mixer, and air enters mixer with the flow velocity of 20ml/min, and the two enters reaction after mixing
Pipe, reaction pressure are normal pressure, and reaction temperature is 315 DEG C, and product condensation is collected, and gas chromatographic detection, reaction 7 as a child measured sweet
Oily conversion ratio 88.6%, acrolein selectivity 87.5%.
Embodiment 7:
9.86g ammonium metatungstate is weighed, is added into 100ml water, constant temperature stirs 0.5 hour at 80 DEG C, is then added
5.2608g ethylenediamine tetra-acetic acid, then constant temperature is kept to stir 0.5 hour, citric acid 1.2g is added, continues to keep constant temperature stirring 2 small
When, 0.7796g cesium nitrate is dissolved in 80ml water, is then added dropwise in above-mentioned solution, is transferred to after dripping off with polytetrafluoro
In the hydrothermal reaction kettle of ethylene liner, 210 DEG C are risen to 1 DEG C/min of heating rate, 24 hours are kept the temperature, then with 1 DEG C/minute
The rate of temperature fall of clock is down to room temperature, isolates the solid in product, successively uses water and ethanol washing, and dry 12 is small at 120 DEG C
When, it is packed into tube calciner, is calcined 6 hours at 500 DEG C in nitrogen atmosphere, obtains catalyst.
1.0g catalyst is weighed to be fitted into the reaction tube of fixed bed reactors, mass concentration be 20% glycerine water solution with
The speed of 3ml/h is passed through mixer, and air enters mixer with the flow velocity of 20ml/min, and the two enters reaction after mixing
Pipe, reaction pressure are normal pressure, and reaction temperature is 315 DEG C, and product condensation is collected, and gas chromatographic detection, reaction 7 as a child measured sweet
Oily conversion ratio 86.2%, acrolein selectivity 80.7%.
The above described is only a preferred embodiment of the present invention, being not intended to limit the scope of the present invention.
Therefore any trickle amendment, equivalent variations and modification made to the above embodiment according to the technical essence of the invention, still
Belong in the range of technical solution of the present invention.
Claims (6)
1. a kind of preparation method for the catalyst for producing methacrylaldehyde for dehydrating glycerin, which is characterized in that its step are as follows:
(1) tungstates is added to the water, adds ethylenediamine tetra-acetic acid or disodium ethylene diamine tetraacetate, reproducibility, which is then added, to be had
Machine acid for adjusting pH value is acidity, stirs 0.5-3 hours at 20 DEG C -80 DEG C, obtains the first mixed solution；
(2) cesium carbonate solution or cesium nitrate solution are added dropwise to no more than 1.5 according to caesium tungsten ratio first mixing of step (1)
In solution, is stirred 0.5-3 hours at 20 DEG C -80 DEG C, obtain the second mixed solution；
(3) second mixed solution of step (2) is added in water heating kettle, compactedness 50%-85%, 120 DEG C-
Hydro-thermal reaction 1-72 hours at 260 DEG C, mixture is obtained；
(4) by the mixture of step (3) washing, dry, temperature is 300 DEG C -800 DEG C, intermediate medium is forging for nitrogen
It burns to carry out handling for 1-6 hours in furnace and obtains catalyst, the catalyst has pyrochlore-type wolframic acid caesium Cs1.1W1.65O5.5With caesium tungsten
Bronze CsxWO3Two-phase composite construction, x value is 0.05-0.45 in structure.
2. the preparation method of the catalyst according to claim 1 for producing methacrylaldehyde for dehydrating glycerin, which is characterized in that
Tungstates is set as one or more kinds of mixtures of ammonium paratungstate, ammonium metatungstate or sodium tungstate.
3. the preparation method of the catalyst according to claim 1 for producing methacrylaldehyde for dehydrating glycerin, which is characterized in that
The molar ratio of ethylenediamine tetra-acetic acid or the disodium ethylene diamine tetraacetate and the tungstates is set as 0.15-0.45.
4. the preparation method of the catalyst according to claim 1 for producing methacrylaldehyde for dehydrating glycerin, which is characterized in that
Reproducibility organic acid is set as one or more kinds of mixtures of citric acid, oxalic acid or formic acid, and reproducibility organic acid is added
PH value afterwards is set as 2-4.
5. the preparation method of the catalyst according to claim 1 for producing methacrylaldehyde for dehydrating glycerin, which is characterized in that
Caesium tungsten ratio is 0.05-1.5.
6. the preparation method of the catalyst according to claim 4 for producing methacrylaldehyde for dehydrating glycerin, which is characterized in that
Hydrothermal temperature is set as 180 DEG C -220 DEG C, and the hydro-thermal time is set as 18-36 hours.
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