CN106732533A - A kind of catalyst, preparation method and application method that methacrylaldehyde is produced for dehydrating glycerin - Google Patents
A kind of catalyst, preparation method and application method that methacrylaldehyde is produced for dehydrating glycerin Download PDFInfo
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- CN106732533A CN106732533A CN201710002964.3A CN201710002964A CN106732533A CN 106732533 A CN106732533 A CN 106732533A CN 201710002964 A CN201710002964 A CN 201710002964A CN 106732533 A CN106732533 A CN 106732533A
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- 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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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
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Abstract
The present invention relates to a kind of catalyst, preparation method and application method that methacrylaldehyde is produced for dehydrating glycerin, with 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 difficult to recycle in easy carbon distribution, easy coking, selectivity in the prior art.By in acid and reproducibility environment, making tungstates and cesium salt carry out hydro-thermal reaction and obtaining the solid product containing pyrochlore-type wolframic acid caesium and caesium tungsten bronze two-phase coexistent, hydrothermal product obtains catalyst to the present invention 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 addition of reproducibility organic acid, and hydrothermal reaction condition.There is catalyst pyrochlore-type wolframic acid caesium and the technical scheme of 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 field, and in particular to a kind of to produce methacrylaldehyde for dehydrating glycerin
Catalyst, preparation method and application method.
Background technology
Biodiesel can be as the alternative fuel of fossil fuel, with cleaning, reproducible advantage, by more and more
Concern, promoted the fast development of bioenergy industry.Biodiesel is anti-by ester exchange by raw material of animal and plant fat
The diesel fuel that should be produced, can produce byproduct glycerine in the course of reaction, with the steady lifting of yield of biodiesel, glycerine
Yield also increase year by year, bring therewith how to realize glycerine efficiently utilize this major issue.
Glycerine can generate methacrylaldehyde by intramolecular dehydration, and methacrylaldehyde is a kind of important chemical intermediate, existing third
The production of olefine aldehydr mainly using oxidation of propylene this process route, but with the growing tension of petroleum resources, raw material propylene
Cost will rise steadily, so as to the price for causing methacrylaldehyde and its downstream product is raised, therefore, produce propylene by raw material of glycerine
Aldehyde can both realize the efficient utilization of superfluous glycerine, dependence of the methacrylaldehyde production to petrochemical industry can be broken away from again, with important meaning
Justice.
Preparing acrolein by dehydrating glycerin can be carried out under the conditions of gas phase reaction in fixed bed reactors, it is also possible in liquid phase bar
Carried out under part, catalyst is usually various solid acid catalysts, patent US 5387720 reports negative with aluminum oxide as carrier
Phosphoric acid catalyst is carried, the glycerine water solution with 20% (mass fraction) is raw material, and the yield of its methacrylaldehyde reaches 70.5%, patent
It is the load phosphoric acid catalyst of carrier that diatomite is used in US 2558520, under liquid-phase reaction condition, has obtained 72.3%
Methacrylaldehyde yield, the load that patent CN 101417928A are proposed with modified aluminas, silica, molecular sieve as carrier is miscellaneous more
Acid catalyst, it is said that highest catalysis 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, it is hot
Stability tend not to again meet require, except load phosphoric acid or carried heteropoly acid catalyst in addition to, molecular sieve catalysts also by with
In preparing acrolein by dehydrating glycerin reaction, patent CN103638965A provides a kind of system of multi-stage porous ZSM-5 molecular sieve catalyst
Preparation Method, uses it for preparing acrolein by dehydrating glycerin reaction, and glycerol conversion yield more than 80%, 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
Into composite catalyst, can improve glycerol conversion yield, stabilization time extension, as a whole, existing dehydrating glycerin propylene
Mostly there is more serious coking phenomenon in aldehyde catalyst, influence acrolein selectivity, and due to catalyst duct obstruction, with anti-
Catalysis activity should be carried out constantly to be reduced.
Load tungsten oxide catalyst turns into the class preparing acrolein by dehydrating glycerin catalyst by more concern, such as patent WO
2006/087084 catalyst announced can make methacrylaldehyde yield reach 74%, although show acrolein selectivity higher, but
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 have also discovered haves the shortcomings that the not high enough and easy coking of selectivity with the catalyst majority that tungsten oxide is active phase, existing
There are catalyst, the progressive improvement of preparation method and application method needs that methacrylaldehyde is produced for dehydrating glycerin.
The content 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 the catalyst that methacrylaldehyde is produced for dehydrating glycerin,
Object of the invention is a kind of application process of the catalyst that methacrylaldehyde is produced for dehydrating glycerin.
It is an object of the invention to provide a kind of catalyst for preparing acrolein by dehydrating glycerin reaction and preparation method thereof, should
Catalyst has pyrochlore-type wolframic acid caesium and caesium tungsten bronze two-phase composite construction, particularly in acid and reproducibility environment,
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 addition 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, and have born
Carry tungsten oxide catalyst to compare, this catalyst shows to be difficult coking, is difficult carbon distribution, work high to preparing acrolein by dehydrating glycerin reaction
Property, the advantage for easily recycling.
A kind of catalyst that methacrylaldehyde is produced for dehydrating glycerin, with pyrochlore-type wolframic acid caesium Cs1.1W1.65O5.5And caesium
Tungsten bronze CsxWO3The composition of two-phase composite construction.
The present invention is devised, pyrochlore-type wolframic acid caesium Cs1.1W1.65O5.5With the caesium tungsten bronze CsxWO3Two-phase composite construction
Middle x values are 0.05-0.45.
The present invention is devised, and a kind of preparation method of the catalyst that methacrylaldehyde is produced for dehydrating glycerin, its step is as follows：
(1) tungstates is added to the water, adds ethylenediamine tetra-acetic acid (C10H16N2O8) or disodium ethylene diamine tetraacetate
(C10H16N2Na2O8), it is acidity to be subsequently adding the organic acid for adjusting pH value of reproducibility, 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 dropped to the described of step (1) than no more than 1.5 according to caesium tungsten
In first mixed solution, 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 is 50%-85%, 120
Hydro-thermal reaction 1-72 hours at DEG C -260 DEG C, mixture is obtained；
(4) mixture of step (3) is washed, dried, temperature be 300 DEG C -800 DEG C, intermediate medium be nitrogen
Calcining furnace in carry out 1-6 hours treatment obtain catalyst.
The preparing acrolein by dehydrating glycerin catalyst obtained using above-mentioned preparation method, its morphology microstructure is nano bar-shape, is led to
Control preparation condition is crossed, the powder of other patterns such as spherical, sheet can also be obtained.
The present invention is devised, and tungstates is set to one or more of ammonium paratungstate, ammonium metatungstate or sodium tungstate
Mixture.
The present invention is devised, and ethylenediamine tetra-acetic acid or the disodium ethylene diamine tetraacetate set with the mol ratio of the tungstates
It is set to 0.05-1, preferably 0.15-0.45.
The present invention is devised, and reproducibility organic acid is set to the mixed of one or more of citric acid, oxalic acid or formic acid
Compound, adds the pH value after reproducibility organic acid to be set to 1-6, and preferable ph is set to 2-4.
The present invention is devised, and caesium tungsten ratio is 0.05-1.5.
The present invention is devised, and hydrothermal temperature is set to 180 DEG C -220 DEG C, and hydro-thermal set of time is 18-36 hours.The present invention
Devise, a kind of application process of the catalyst that methacrylaldehyde is produced for dehydrating glycerin, be 10-70%, preferably 15- concentration
35% glycerine water solution, blender is delivered to by pump, while air is input to blender, makes the mol ratio of glycerine and air
It is set to 1: 1-1: 20, it 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：
The molal quantity of the glycerine in molal quantity/the be added to reaction of the glycerine consumed in glycerol conversion yield (%)=reaction ×
100%.
The molal quantity of the glycerine consumed in the 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 following advantages that：Catalysis
Agent is difficult carbon distribution, and acrolein selectivity is high；The catalyst stabilization time is long, and regeneration is easy, and the catalysis after activity is reduced is passed through
Roasting can recover completely；Overcome the problem that other catalyst are easily caused product polymerization.
Specific embodiment
By following examples, the present invention will be described, but therefore the scope of the present invention has not been limited.
A kind of preparation method of the catalyst that methacrylaldehyde is produced for dehydrating glycerin, one embodiment, its step is as follows：
(1) tungstates is added to the water, adds ethylenediamine tetra-acetic acid (C10H16N2O8) or disodium ethylene diamine tetraacetate
(C10H16N2Na2O8), it is acidity to be subsequently adding the organic acid for adjusting pH value of reproducibility, is stirred 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 dropped to the described of step (1) than no more than 1.5 according to caesium tungsten
In first mixed solution, 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 is 50%, the water at 120 DEG C
Thermal response 1 hour, obtains mixture；
(4) mixture of step (3) washed, dried, in the calcining that temperature is 300 DEG C, intermediate medium is nitrogen
Carry out processing the catalyst for obtaining methacrylaldehyde in 1 hour in stove.
In the present embodiment, tungstates is set to ammonium paratungstate.
In the present embodiment, ethylenediamine tetra-acetic acid or the disodium ethylene diamine tetraacetate set with the mol ratio of the tungstates
It is set to 0.05.
In the present embodiment, reproducibility organic acid is set to citric acid, adds the pH value after reproducibility organic acid to be set to
1。
In the present embodiment, caesium tungsten ratio is 0.05.
In the present embodiment, hydrothermal temperature is set to 180 DEG C, and hydro-thermal set of time is 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 values are 0.05, and catalyst is nano bar-shape body.
Second embodiment, its step is as follows：
(1) tungstates is added to the water, adds ethylenediamine tetra-acetic acid (C10H16N2O8) or disodium ethylene diamine tetraacetate
(C10H16N2Na2O8), it is acidity to be subsequently adding the organic acid for adjusting pH value of reproducibility, is stirred 3 hours at 80 DEG C, obtains first and mixes
Close solution；
(2) it is changed to that cesium carbonate solution or cesium nitrate solution are dropped to the described of step (1) than no more than 1.5 according to caesium tungsten
In first mixed solution, 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 is 85%, the water at 260 DEG C
Thermal response 72 hours, obtains mixture；
(4) mixture of step (3) washed, dried, in the calcining that temperature is 800 DEG C, intermediate medium is nitrogen
Carry out processing the catalyst for obtaining methacrylaldehyde in 6 hours in stove.
In the present embodiment, tungstates is set to ammonium metatungstate.
In the present embodiment, ethylenediamine tetra-acetic acid or the disodium ethylene diamine tetraacetate set with the mol ratio of the tungstates
It is set to 1.
In the present embodiment, reproducibility organic acid is set to oxalic acid, adds the pH value after reproducibility organic acid to be set to 6.
In the present embodiment, caesium tungsten ratio is 1.5.
In the present embodiment, hydrothermal temperature is set to 220 DEG C, and hydro-thermal set of time is 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 values are 0.45, and catalyst is spherical powder.
3rd embodiment, its step is as follows：
(1) tungstates is added to the water, adds ethylenediamine tetra-acetic acid (C10H16N2O8) or disodium ethylene diamine tetraacetate
(C10H16N2Na2O8), it is acidity to be subsequently adding the organic acid for adjusting pH value of reproducibility, is stirred 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 dropped to the described of step (1) than no more than 1.5 according to caesium tungsten
In first mixed solution, 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 is 65%, the water at 180 DEG C
Thermal response 37 hours, obtains mixture；
(4) mixture of step (3) washed, dried, in the calcining that temperature is 650 DEG C, intermediate medium is nitrogen
Carry out processing the catalyst for obtaining methacrylaldehyde in 4 hours in stove.
In the present embodiment, tungstates is set to sodium tungstate.
In the present embodiment, ethylenediamine tetra-acetic acid or the disodium ethylene diamine tetraacetate set with the mol ratio of the tungstates
It is set to 0.5.
In the present embodiment, reproducibility organic acid is set to formic acid, adds the pH value after reproducibility organic acid to be set to
3.5。
In the present embodiment, caesium tungsten ratio is 1.0.
In the present embodiment, hydrothermal temperature is set to 200 DEG C, and hydro-thermal set of time is 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 values are 0.20, and catalyst is flaky powder.
A kind of application process of the catalyst that methacrylaldehyde is produced for dehydrating glycerin, one embodiment is concentration
10% glycerine water solution, blender is delivered to by pump, while air is input to blender, make glycerine and air mole
Than being set to 1: 1, well-mixed reaction raw materials enter the fixed bed reactors equipped with catalyst, and bed temperature is 260 DEG C, anti-
It is 0.6h for normal pressure and liquid air speed to answer pressure-1, methacrylaldehyde is obtained to collecting condensation.
Second embodiment, the glycerine water solution that concentration is 70%, blender is delivered to by pump, while air is defeated
Enter to blender, glycerine is set to 1: 20 with the mol ratio of air, well-mixed reaction raw materials enter equipped with catalyst
Fixed bed reactors, bed temperature is 360 DEG C, reaction pressure is that normal pressure and liquid air speed are 7.0h-1, collecting condensation is obtained
Methacrylaldehyde.
3rd embodiment, is 35% glycerine water solution concentration, blender is delivered to by pump, while air is input into
To blender, glycerine is set to be set to 1: 10 with the mol ratio of air, well-mixed reaction raw materials enter consolidating equipped with catalyst
Fixed bed reactor, bed temperature is 300 DEG C, reaction pressure is that normal pressure and liquid air speed are 3.5h-1, third is obtained to collecting condensation
Olefine aldehydr.
4th embodiment, the glycerine water solution that concentration is 40%, blender is delivered to by pump, while air is defeated
Enter to blender, glycerine is set to 1: 9 with the mol ratio of air, well-mixed reaction raw materials enter consolidating equipped with catalyst
Fixed bed reactor, bed temperature is 310 DEG C, reaction pressure is that normal pressure and liquid air speed are 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) dihydrates are weighed, is added into 100ml water, constant temperature stirring 0.5 hour at 80 DEG C, then
4.0g ethylenediamine tetra-acetic acids are added, then keeps constant temperature to stir 0.5 hour, add citric acid 4.2028g, continue to keep constant temperature stirring
2 hours, 2.6066g cesium carbonates are dissolved in 80ml water, be then added dropwise in above-mentioned solution, be transferred to after dripping off with poly- four
In the hydrothermal reaction kettle of PVF liner, 210 DEG C are risen to 1 DEG C/min of heating rate, are incubated 24 hours, then with 1 DEG C/
The rate of temperature fall of minute is down to room temperature, isolates the solid in product, is successively washed with water and ethanol, and 12 are dried at 120 DEG C
Hour, load tube calciner, calcined 6 hours at 500 DEG C in the nitrogen atmosphere, obtain 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 blender, and air enters blender with the flow velocity of 20ml/min, and reaction is entered after both are well mixed
Pipe, reaction pressure is 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) dihydrates are weighed, is added into 100ml water, constant temperature stirring 0.5 hour at 80 DEG C, then
4.0g ethylenediamine tetra-acetic acids are added, then keeps constant temperature to stir 0.5 hour, add citric acid 8.4056g, continue to keep constant temperature stirring
2 hours, 2.6066g cesium carbonates are dissolved in 80ml water, be then added dropwise in above-mentioned solution, be transferred to after dripping off with poly- four
In the hydrothermal reaction kettle of PVF liner, 210 DEG C are risen to 1 DEG C/min of heating rate, are incubated 24 hours, then with 1 DEG C/
The rate of temperature fall of minute is down to room temperature, isolates the solid in product, is successively washed with water and ethanol, and 12 are dried at 120 DEG C
Hour, load tube calciner, calcined 6 hours at 500 DEG C in the nitrogen atmosphere, obtain 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 blender, and air enters blender with the flow velocity of 20ml/min, and reaction is entered after both are well mixed
Pipe, reaction pressure is 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) dihydrates are weighed, is added into 100ml water, constant temperature stirring 0.5 hour at 80 DEG C, then
4.0g disodium ethylene diamine tetraacetates are added, then keeps constant temperature to stir 0.5 hour, add formic acid 0.5g, continue to keep constant temperature stirring 2
Hour, 1.5593g cesium nitrates are dissolved in 80ml water, then it is added dropwise in above-mentioned solution, it is transferred to after dripping off with poly- four
In the hydrothermal reaction kettle of PVF liner, 190 DEG C are risen to 1 DEG C/min of heating rate, are incubated 24 hours, then with 1 DEG C/
The rate of temperature fall of minute is down to room temperature, isolates the solid in product, is successively washed with water and ethanol, and 12 are dried at 120 DEG C
Hour, load tube calciner, calcined 6 hours at 500 DEG C in the nitrogen atmosphere, obtain 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 blender, and air enters blender with the flow velocity of 20ml/min, and reaction is entered after both are well mixed
Pipe, reaction pressure is 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) dihydrates are weighed, is added into 100ml water, constant temperature stirring 0.5 hour at 80 DEG C, then
1.7536g ethylenediamine tetra-acetic acids are added, then keeps constant temperature to stir 0.5 hour, add oxalic acid 2.5g, continue to keep constant temperature stirring 2
Hour, 2.3388g cesium nitrates are dissolved in 80ml water, then it is added dropwise in above-mentioned solution, it is transferred to after dripping off with poly- four
In the hydrothermal reaction kettle of PVF liner, 190 DEG C are risen to 1 DEG C/min of heating rate, are incubated 24 hours, then with 1 DEG C/
The rate of temperature fall of minute is down to room temperature, isolates the solid in product, is successively washed with water and ethanol, and 24 are dried at 210 DEG C
Hour, load tube calciner, calcined 6 hours at 500 DEG C in the nitrogen atmosphere, obtain 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 blender, and air enters blender with the flow velocity of 20ml/min, and reaction is entered after both are well mixed
Pipe, reaction pressure is 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 paratungstates are weighed, is added into 160ml water, constant temperature is stirred 0.5 hour at 80 DEG C, is subsequently adding
4.608g ethylenediamine tetra-acetic acids, then keep constant temperature to stir 0.5 hour, citric acid 1.2g is added, continue to keep constant temperature stirring 2 small
When, 2.342g cesium nitrates are dissolved in 80ml water, then it is added dropwise in above-mentioned solution, it is transferred to polytetrafluoroethyl-ne after dripping off
In the hydrothermal reaction kettle of alkene liner, 210 DEG C are risen to 1 DEG C/min of heating rate, 24 hours are incubated, then with 1 DEG C/min
Rate of temperature fall be down to room temperature, isolate the solid in product, successively washed with water and ethanol, at 120 DEG C dry 12 hours,
Load tube calciner, calcined 6 hours at 500 DEG C in the nitrogen atmosphere, obtain 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 blender, and air enters blender with the flow velocity of 20ml/min, and reaction is entered after both are well mixed
Pipe, reaction pressure is 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 paratungstates are weighed, is added into 160ml water, constant temperature is stirred 0.5 hour at 80 DEG C, is subsequently adding
4.608g ethylenediamine tetra-acetic acids, then keep constant temperature to stir 0.5 hour, citric acid 1.2g is added, continue to keep constant temperature stirring 2 small
When, 3.513g cesium nitrates are dissolved in 80ml water, then it is added dropwise in above-mentioned solution, it is transferred to polytetrafluoroethyl-ne after dripping off
In the hydrothermal reaction kettle of alkene liner, 210 DEG C are risen to 1 DEG C/min of heating rate, 24 hours are incubated, then with 1 DEG C/min
Rate of temperature fall be down to room temperature, isolate the solid in product, successively washed with water and ethanol, at 120 DEG C dry 12 hours,
Load tube calciner, calcined 6 hours at 500 DEG C in the nitrogen atmosphere, obtain 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 blender, and air enters blender with the flow velocity of 20ml/min, and reaction is entered after both are well mixed
Pipe, reaction pressure is 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 metatungstates are weighed, is added into 100ml water, constant temperature is stirred 0.5 hour at 80 DEG C, is subsequently adding
5.2608g ethylenediamine tetra-acetic acids, then keep constant temperature to stir 0.5 hour, citric acid 1.2g is added, continue to keep constant temperature stirring 2 small
When, 0.7796g cesium nitrates are dissolved in 80ml water, then it is added dropwise in above-mentioned solution, it is transferred to polytetrafluoro after dripping off
In the hydrothermal reaction kettle of ethene liner, 210 DEG C are risen to 1 DEG C/min of heating rate, 24 hours are incubated, then with 1 DEG C/minute
The rate of temperature fall of clock is down to room temperature, isolates the solid in product, is successively washed with water and ethanol, 12 is dried at 120 DEG C small
When, load tube calciner, calcined 6 hours at 500 DEG C in the nitrogen atmosphere, obtain 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 blender, and air enters blender with the flow velocity of 20ml/min, and reaction is entered after both are well mixed
Pipe, reaction pressure is 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, is only presently preferred embodiments of the present invention, and not technical scope of the invention is imposed any restrictions.
Therefore it is every according to technical spirit of the invention to any trickle amendment made for any of the above embodiments, equivalent variations and modification, still
Belong in the range of technical solution of the present invention.
Claims (10)
1. a kind of catalyst that methacrylaldehyde is produced for dehydrating glycerin, it is characterised in that with pyrochlore-type wolframic acid caesium
Cs1.1W1.65O5.5With caesium tungsten bronze CsxWO3The composition of two-phase composite construction.
2. the catalyst that methacrylaldehyde is produced for dehydrating glycerin according to claim 1, it is characterised in that pyrochlore-type tungsten
Sour caesium Cs1.1W1.65O5.5With the caesium tungsten bronze CsxWO3X values are 0.05-0.45 in two-phase composite construction.
3. the catalyst that methacrylaldehyde is produced for dehydrating glycerin according to claim 1, it is characterised in that composition is to receive
Rice clava, spherical powder or flaky powder.
4. a kind of preparation method of the catalyst that methacrylaldehyde is produced for dehydrating glycerin, it is characterised in that its step is as follows：
(1) tungstates is added to the water, adds ethylenediamine tetra-acetic acid (C10H16N2O8) or disodium ethylene diamine tetraacetate
(C10H16N2Na2O8), it is acidity to be subsequently adding the organic acid for adjusting pH value of reproducibility, is stirred 0.5-3 hours at 20 DEG C -80 DEG C,
Obtain the first mixed solution；
(2) cesium carbonate solution or cesium nitrate solution are dropped to than no more than 1.5 according to caesium tungsten first mixing of step (1)
In solution, 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 is 50%-85%, 120 DEG C-
Hydro-thermal reaction 1-72 hours at 260 DEG C, mixture is obtained；
(4) mixture of step (3) is washed, dried, temperature be 300 DEG C -800 DEG C, intermediate medium is for nitrogen forges
Treatment in 1-6 hours is carried out in burning stove and obtains catalyst.
5. the preparation method of the catalyst that methacrylaldehyde is produced for dehydrating glycerin according to claim 4, it is characterised in that
Tungstates is set to the mixture of one or more of ammonium paratungstate, ammonium metatungstate or sodium tungstate.
6. the preparation method of the catalyst that methacrylaldehyde is produced for dehydrating glycerin according to claim 4, it is characterised in that
Ethylenediamine tetra-acetic acid or the disodium ethylene diamine tetraacetate are set to 0.05-1 with the mol ratio of the tungstates, preferably
0.15-0.45。
7. the preparation method of the catalyst that methacrylaldehyde is produced for dehydrating glycerin according to claim 4, it is characterised in that
Reproducibility organic acid is set to one or more mixture of citric acid, oxalic acid or formic acid, adds reproducibility organic acid
PH value afterwards is set to 1-6, and preferable ph is set to 2-4.
8. the preparation method of the catalyst that methacrylaldehyde is produced for dehydrating glycerin according to claim 4, it is characterised in that
Caesium tungsten ratio is 0.05-1.5.
9. the preparation method of the catalyst that methacrylaldehyde is produced for dehydrating glycerin according to claim 4, it is characterised in that
Hydrothermal temperature is set to 180 DEG C -220 DEG C, and hydro-thermal set of time is 18-36 hours.
10. a kind of application process of the catalyst that methacrylaldehyde is produced for dehydrating glycerin, is 10%-70% concentration, preferably
15%-35% glycerine water solutions, blender is delivered to by pump, while air is input to blender, makes glycerine with air
Mol ratio is set to 1: 1-1: 20, it is preferably arranged to 1: and 5-1: 10, well-mixed reaction raw materials enter consolidating equipped with catalyst
Fixed bed reactor, bed temperature is 260 DEG C -360 DEG C, reaction pressure is normal pressure, liquid air speed is 0.6h-1-7.0h-1, to condensation
Thing is collected and obtains methacrylaldehyde.
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|---|---|---|---|---|
| CN101284245A (en) * | 2007-04-13 | 2008-10-15 | 湖南大学 | Reaction for preparing hydroxyacetone by selectively dewatering natural glycerol and catalyst |
| CN102471090A (en) * | 2009-07-07 | 2012-05-23 | 巴斯夫欧洲公司 | Potassium cesium tungsten bronze particles |
| WO2013018915A2 (en) * | 2011-07-29 | 2013-02-07 | Arkema France | Improved process of dehydration reactions |
| CN103041864A (en) * | 2012-11-22 | 2013-04-17 | 清华大学 | Method for preparing catalyst of acraldehyde catalyst by selective dehydration of glycerol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284245A (en) * | 2007-04-13 | 2008-10-15 | 湖南大学 | Reaction for preparing hydroxyacetone by selectively dewatering natural glycerol and catalyst |
| CN102471090A (en) * | 2009-07-07 | 2012-05-23 | 巴斯夫欧洲公司 | Potassium cesium tungsten bronze particles |
| WO2013018915A2 (en) * | 2011-07-29 | 2013-02-07 | Arkema France | Improved process of dehydration reactions |
| CN103041864A (en) * | 2012-11-22 | 2013-04-17 | 清华大学 | Method for preparing catalyst of acraldehyde catalyst by selective dehydration of glycerol |
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