CN105195216A - Catalyst as well as preparation method and application thereof - Google Patents
Catalyst as well as preparation method and application thereof Download PDFInfo
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- CN105195216A CN105195216A CN201510676789.7A CN201510676789A CN105195216A CN 105195216 A CN105195216 A CN 105195216A CN 201510676789 A CN201510676789 A CN 201510676789A CN 105195216 A CN105195216 A CN 105195216A
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Abstract
The invention discloses a preparation method of a catalyst for preparation of acrolein through selective dehydration of glycerin. The method comprises three steps including synthesis of Zr-MCM-41, synthesis of heteropoly acid/Zr-MCM-41 and synthesis of Pd-heteropoly acid/Zr-MCM-41. Compared with the prior art, the method has the advantages that the used raw material source is wide and required reaction conditions are mild. Meanwhile, compared with existing products, the product obtained with the method has the advantages that the carbon deposition amount is greatly decreased, the service life is long, the glycerin conversion rate and the acrolein selectivity are high, and the activity is stable for a long time.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to a kind of Catalysts and its preparation method and application.
Background technology
Along with the growing tension of world petroleum resource, the biodiesel can making alternative energy source is extensively favored.Constantly increase along with its output, a large amount of by-product glycerins result in glut the market.Glycerine is a kind of important bio-regeneration resource, has very large purposes at present in fields such as medicine, food, tobacco and cosmetics.Therefore, be that the research of high value added product gains great popularity by transformation of glycerol.
Methacrylaldehyde is a kind of important fine-chemical intermediate, is mainly used in the fields such as pharmaceutical synthesis, papermaking, coating, oil field, organic synthesis industry.The current most important purposes of methacrylaldehyde is synthesis animal feed additive methionine and prepares 1,3-PD; In addition, also for the preparation of essence, glutaraldehyde etc.The method mainly oxidation of propylene of current industrial production methacrylaldehyde.But oxidation of propylene take oil as initial raw material, not only do not meet the requirement of low-carbon economy, but also there is the problem of contending over raw materials with other chemical products.Glycerin dehydration preparing propone aldehyde take renewable resource as raw material, and technique is simple, has very strong competitive advantage and industrial applications prospect.Therefore, the extensive concern of academia and industrial circle is more and more subject to.
Dehydrating glycerin prepares the catalyst that acrolein reaction studied probably can be divided into inorganic acid and salt, metal oxide, rare earth pyrophosphate, heteropllyacids and molecular sieve etc.Wherein, heteropoly acid has very strong because of it
sour and stable Keggin anion structure and preparing acrolein by dehydrating glycerin reaction in show the highest catalytic activity.But, because current carried heteropoly acid catalyst exists the problem of life-span short or poor heat stability, the requirement of commercial Application cannot be reached.For loaded catalyst, except the acidity of catalyst and architectural characteristic, suitable carrier is also the key factor affecting glycerine high conversion and methacrylaldehyde high selectivity.And in order to catalyst to burned carbon distribution, it is also very important for finding the catalyst with high thermal stability.
Molecular sieve catalyst is widely used at catalytic field because of the pore passage structure of its uniqueness, good hydrothermal stability and suitable acidity itself, MCM-41 molecular sieve is as research mesoporous molecular sieve the most widely, have that specific area is large, the feature such as even aperture distribution and better heat stability, be subject to the close attention of people always.Because Siliceous MCM-41 molecular sieve catalyst does not have acidity, carrier be it can be used as to be applied to dehydrating glycerin preparing propone aldehyde reaction, sour modification or metal-modified must be carried out to it.
The investigation and comparison H such as Trakarnpruk
3pW
12o
40/ ZrMCM-41 and Pt/H
3pW
12o
40the activity of/ZrMCM-41 catalyst in preparing acrolein by dehydrating glycerin reaction, result shows, is conducive to the adding of precious metals pt the generation reducing carbon distribution, thus improves catalyst stability.Alhanash etc. have prepared Cs
2.5h
0.5pW
12o
40(CsPW) catalyst is used for dehydrating glycerin, and reaction 1h, glycerine can transform completely, and acrolein selectivity is up to 98%.But due to a large amount of carbon distributions that catalyst surface generates, after reaction 6h, glycerol conversion yield is down to 40%, and acrolein selectivity is constant.In order to improve catalyst stability, on CsPW catalyst, carried noble metal (Ru, Pt and Pd) passes into hydrogen simultaneously.Research shows, adding noble metal can improve catalyst stability, suppresses carbon distribution, and wherein Pd suppresses the effect of carbon distribution to be better than Ru and Pt.Park etc. report one and catch carbon matrix precursor thus the technology of reduction carbon distribution generation with palladium lattice.They have prepared Pd-H
3pW
12o
40/ C (Pd-PWC) catalyst is used for dehydrating glycerin reaction, and show higher catalytic activity, carbon deposition quantity reduces greatly.And the method is carried out when not needing to pass into hydrogen or oxygen.Although prior art inhibits carbon distribution to a certain extent, extend catalyst life, DeGrain, and need to pass into a large amount of hydrogen or oxygen is used as assisting.The Zr-MCM-41 material of heteropoly acid modification is used for as carrier loaded Pd the research that dehydrating glycerin prepares acrolein reaction have not been reported.This patent is that raw material is produced in the process of methacrylaldehyde adopting with glycerine, by the Zr-MCM-41 of the heteropoly acid modification of precious metals pd load as catalyst, effectively reduce the carbon deposition quantity on catalyst, not only increase glycerol conversion yield and acrolein selectivity, and be conducive to the service life of extending catalyst.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of catalyst, to solve the glycerol conversion yield that prior art exists and the problem that acrolein selectivity is lower and the service life of catalyst is shorter.
The technical problem that the present invention also will solve is to provide the preparation method of above-mentioned catalyst.
The technical problem that the present invention finally will solve is to provide above-mentioned catalyst and prepares application in acrolein reaction at selective glycerol dehydration.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A preparation method for catalyst, it comprises the steps:
(1) synthesis of Zr-MCM-41 carrier: by behind zirconium source and the mixing of silicon source to obtain mixed system I for subsequent use, for subsequent use by obtaining mixed system II after mixing with ammonia spirit after water-soluble for template; Under constantly stirring, mixed system I is dropped in mixed system II, after stirring 2 ~ 5h with the rotating speed of 500r/min under room temperature, then at 80 ~ 100 DEG C crystallization 40 ~ 50h, cooled and filtered, gets solid portion washing, dry, after roasting, obtain Zr-MCM-41 carrier;
(2) synthesis of heteropoly acid/Zr-MCM-41: by the Zr-MCM-41 carrier impregnation that obtains in step (1) in the heteropoly acid aqueous solution, after boiling off moisture under constantly stirring at 70 ~ 100 DEG C, get solid portion drying, after roasting, obtain heteropoly acid/Zr-MCM-41;
(3) synthesis of Pd-heteropoly acid/Zr-MCM-41: the heteropoly acid/Zr-MCM-41 obtained in step (2) be impregnated in the aqueous solution of Pd presoma, boil off moisture under constantly stirring after, get solid portion drying, insulation, after roasting, obtain Pd-heteropoly acid/Zr-MCM-41 catalyst.
In step (1), described zirconium source is zirconium chloride, zirconium oxychloride or zirconium-n-propylate, described silicon source is sodium metasilicate, silica or ethyl orthosilicate, and described template is softex kw, hexadecyltrimethylammonium chloride or cetyltriethylammonium bromide;
Wherein,
The mol ratio of zirconium source, silicon source, template and ammonia is 0.01 ~ 2:0.5 ~ 3:0.3:16.5;
The consumption mol ratio of template and dissolving template water used is 1:150 ~ 200;
Described ammonia spirit is the ammonia spirit of 28wt%.
In step (1), washing methods is for using deionized water rinsing solid portion 3 ~ 5 times; Drying means is dry 8 ~ 12h, preferred 12h at 80 ~ 110 DEG C; Method of roasting is roasting 3 ~ 6h at 400 ~ 600 DEG C, preferred 6h.
In step (2), described heteropoly acid is phosphotungstic acid, silico-tungstic acid or phosphomolybdic acid;
Wherein,
In the heteropoly acid/Zr-MCM-41 of gained, the load capacity of heteropoly acid is 10 ~ 50wt% (mass ratio of heteropoly acid and Zr-MCM-41 carrier).
In the heteropoly acid aqueous solution, the concentration of solute heteropoly acid is 0.001 ~ 0.02mol/L.
In step (2), drying means is dry 5 ~ 10h, preferred 8h at 80 ~ 120 DEG C; Method of roasting is roasting 3 ~ 6h at 300 ~ 400 DEG C, preferred 4h.
In step (3), described Pd presoma is palladium nitrate, palladium bichloride or ammonium chloropalladate; Wherein, in the aqueous solution of Pd presoma, the concentration of solute Pd presoma is 0.01 ~ 0.1mol/L.
In step (3), in the Pd-heteropoly acid/Zr-MCM-41 catalyst of gained, the load capacity of Pd is 1 ~ 5wt% (mass ratio of Pd and heteropoly acid/Zr-MCM-41).
In step (3), drying means be 80 ~ 120 DEG C down to bone dry, heat preserving method be at 80 ~ 120 DEG C place 10 ~ 12h, method of roasting is roasting 3 ~ 6h at 300 ~ 400 DEG C, preferred 4h.
The catalyst that in above-mentioned preparation method, any one prepares is also within protection scope of the present invention.
Above-mentioned catalyst prepares application in methacrylaldehyde also within protection scope of the present invention at selective glycerol dehydration.
Compared with prior art, the present invention has following advantage:
In the selection of raw material glycerine, both can select industrial pure glycerin, also can select crude glycerine prepared by biodiesel, raw material sources are extensive; The reaction condition that Pd-heteropoly acid/Zr-MCM-41 catalyst needs is gentle, and the carbon deposition quantity of catalyst after Pd load reduces greatly, and the life-span is long, glycerol conversion yield and acrolein selectivity high, active long-time stable is constant; Zr-MCM-41 carrier heat endurance and chemical stability good, skeleton structure keeps stable; Heteropoly acid and Zr-MCM-41 carrier intermolecular forces are comparatively strong, not easily run off.
Detailed description of the invention
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, the content described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
Embodiment 1
The synthesis of Zr-MCM-41 (Si/Zr=5) carrier: first by 5ml zirconium-n-propylate and the mixing of 6.9g sodium metasilicate; Then add 12.2g cetyltriethylammonium bromide and 110ml deionized water, then add 110ml ammonia spirit; At room temperature the rotating speed of 500r/min stirs after 2h to gel-forming, is transferred to by mixed solution in the Hydrothermal Synthesis still of polytetrafluoroethylene (PTFE) material liner, and is positioned in the baking oven of 80 DEG C and heats 45h, is then cooled to room temperature; Mixed liquor in reactor is filtered, and spends deionized water 3 times, then solid is placed in the dry 12h of drying box of 110 DEG C; After dried solid is placed in the Muffle furnace roasting 6h of 450 DEG C, obtained Zr-MCM-41 (Si/Zr=5) carrier.
The synthesis of 10wt% phosphotungstic acid/Zr-MCM-41 (Si/Zr=5): first the phosphotungstic acid of 0.1g is dissolved in deionized water, stir wiring solution-forming, the Zr-MCM-41 carrier impregnation prepared by 1g is in phosphotungstic acid aqueous solution, stir evaporation water solution, then 80 DEG C of oven drying 10h are put into, 400 DEG C of roasting 4h in Muffle furnace, obtained 10wt% phosphotungstic acid/Zr-MCM-41 (Si/Zr=5) catalyst.
The synthesis of 1wt%Pd-10wt% phosphotungstic acid/Zr-MCM-41 (Si/Zr=5): first 0.03g palladium bichloride is dissolved in deionized water, stir wiring solution-forming, the phosphotungstic acid prepared by 2g/Zr-MCM-41 catalyst soakage is in palladium chloride aqueous solution, stir evaporation water solution, then 80 DEG C of vacuum drying chambers are put into until bone dry, place 8h for 100 DEG C in an oven, finally 400 DEG C of roasting 4h in Muffle furnace, obtained 1wt%Pd-10wt% phosphotungstic acid/Zr-MCM-41 (Si/Zr=5) catalyst.
Catalyst performance evaluation adopts fixed bed reactors, and using the glycerine water solution of 10wt% as raw material, Pd-phosphotungstic acid/Zr-MCM-41 catalyst amount 0.5g, reaction temperature is 280 DEG C, and mass space velocity is 1.0h
-1under, there is no the phosphotungstic acid/Zr-MCM-41 catalyst of load P d, after reaction 1h, glycerol conversion yield 76.5%, acrolein selectivity 60.2%, after reaction 50h, glycerol conversion yield 48.6%, acrolein selectivity 54.3%, the catalyst of reaction 50h is carried out carbon distribution test analysis, and carbon deposition quantity is 4.4%; Under the same reaction conditions, Pd-phosphotungstic acid/Zr-MCM-41 is adopted to be catalyst, after reaction 1h, glycerol conversion yield 78.4%, acrolein selectivity 69.1%, after reaction 50h, glycerol conversion yield 72.5%, acrolein selectivity 65.2%, the catalyst of reaction 50h is carried out carbon distribution test analysis, and carbon deposition quantity is 1.6%.
Embodiment 2
The synthesis of Zr-MCM-41 (Si/Zr=7) carrier: first by 6.5ml zirconium-n-propylate and 22.8ml ethyl orthosilicate mix and blend; Then 12.2g softex kw is dissolved in 110ml deionized water, then adds 110ml ammonia spirit; Then under constantly stirring, the first solution of configuration is added drop-wise in the second solution, after stirring 2h to gel-forming under the rotating speed of at room temperature 500r/min, mixed solution is transferred in the Hydrothermal Synthesis still of polytetrafluoroethylene (PTFE) material liner, and be positioned in the baking oven of 100 DEG C and heat 50h, be then cooled to room temperature; Mixed liquor in reactor is filtered, and spends deionized water 4 times, then solid is placed in the dry 12h of drying box of 100 DEG C; After dried solid is placed in the Muffle furnace roasting 6h of 550 DEG C, obtained Zr-MCM-41 (Si/Zr=7) carrier.
The synthesis of 30wt% silico-tungstic acid/Zr-MCM-41 (Si/Zr=7): first the silico-tungstic acid of 0.3g is dissolved in deionized water, stir wiring solution-forming, the Zr-MCM-41 carrier impregnation prepared by 1g is in silicon tungsten acid solution, stir evaporation water solution, then 80 DEG C of oven drying 8h are put into, 300 DEG C of roasting 3h in Muffle furnace, obtained 30wt% silico-tungstic acid/Zr-MCM-41 (Si/Zr=7) catalyst.
The synthesis of 2wt%Pd-30wt% silico-tungstic acid/Zr-MCM-41 (Si/Zr=7): first 0.05g palladium nitrate is dissolved in deionized water, stir wiring solution-forming, the silico-tungstic acid prepared by 1.5g/Zr-MCM-41 catalyst soakage is in palladium nitrate aqueous solution, stir evaporation water solution, then 80 DEG C of vacuum drying chambers are put into until bone dry, place 8h for 120 DEG C in an oven, finally 300 DEG C of roasting 4h in Muffle furnace, obtained 2wt%Pd-30wt% silico-tungstic acid/Zr-MCM-41 (Si/Zr=7) catalyst.
Catalyst performance evaluation adopts fixed bed reactors, and using the glycerine water solution of 20wt% as raw material, silico-tungstic acid/Zr-MCM-41 catalyst amount 0.5g, reaction temperature is 360 DEG C, and mass space velocity is 2.0h
-1under, there is no the silico-tungstic acid/Zr-MCM-41 catalyst of load P d, after reaction 1h, glycerol conversion yield 91.0%, acrolein selectivity 70.4%, after reaction 50h, glycerol conversion yield 64.6%, acrolein selectivity 56.2%, the catalyst of reaction 50h is carried out carbon distribution test analysis, and carbon deposition quantity is 5.6%; Under the same reaction conditions, Pd-silico-tungstic acid/Zr-MCM-41 is adopted to be catalyst, after reaction 1h, glycerol conversion yield 93.5%, acrolein selectivity 78.5%, after reaction 50h, glycerol conversion yield 84.5%, acrolein selectivity 73.6%, the catalyst of reaction 50h is carried out carbon distribution test analysis, and carbon deposition quantity is 2.6%.
Embodiment 3
The synthesis of Zr-MCM-41 (Si/Zr=10) carrier: first by 3.3g zirconium oxychloride and 22.8ml ethyl orthosilicate mix and blend; Then 12.2g hexadecyltrimethylammonium chloride is dissolved in 110ml deionized water, then adds 110ml ammonia spirit; Then under constantly stirring, the first solution of configuration is added drop-wise in the second solution, after stirring 2h to gel-forming under the rotating speed of at room temperature 500r/min, mixed solution is transferred in the Hydrothermal Synthesis still of polytetrafluoroethylene (PTFE) material liner, and be positioned in the baking oven of 80 DEG C and heat 40h, be then cooled to room temperature; Mixed liquor in reactor is filtered, and spends deionized water 5 times, then solid is placed in the dry 10h of drying box of 100 DEG C; After dried solid is placed in the Muffle furnace roasting 5h of 550 DEG C, obtained Zr-MCM-41 (Si/Zr=10) carrier.
The synthesis of 20wt% silico-tungstic acid/Zr-MCM-41 (Si/Zr=10): first the silico-tungstic acid of 0.2g is dissolved in deionized water, stir wiring solution-forming, the Zr-MCM-41 carrier impregnation prepared by 1g is in silicon tungsten acid solution, stir evaporation water solution, then 100 DEG C of oven drying 8h are put into, 350 DEG C of roasting 4h in Muffle furnace, obtained 20wt% silico-tungstic acid/Zr-MCM-41 (Si/Zr=10) catalyst.
The synthesis of 1wt%Pd-20wt% silico-tungstic acid/Zr-MCM-41 (Si/Zr=10): first 0.025g palladium nitrate is dissolved in deionized water, stir wiring solution-forming, the silico-tungstic acid prepared by 1.5g/Zr-MCM-41 catalyst soakage is in palladium nitrate aqueous solution, stir evaporation water solution, then 80 DEG C of vacuum drying chambers are put into until bone dry, place 10h for 110 DEG C in an oven, finally 350 DEG C of roasting 4h in Muffle furnace, obtained 1wt%Pd-20wt% silico-tungstic acid/Zr-MCM-41 (Si/Zr=10) catalyst.
Catalyst performance evaluation adopts fixed bed reactors, and using the glycerine water solution of 5wt% as raw material, catalyst amount 0.5g, reaction temperature is 300 DEG C, and mass space velocity is 0.5h
-1under, there is no the silico-tungstic acid/Zr-MCM-41 catalyst of load P d, after reaction 1h, glycerol conversion yield 87.2%, acrolein selectivity 67.4%, after reaction 50h, glycerol conversion yield 59.6%, acrolein selectivity 55.9%, carries out carbon distribution test analysis by the catalyst of reaction, and carbon deposition quantity is 5.0%; Under the same reaction conditions, Pd-silico-tungstic acid/Zr-MCM-41 is adopted to be catalyst, after reaction 1h, glycerol conversion yield 90.6%, acrolein selectivity 73.2%, after reaction 50h, glycerol conversion yield 83.5%, acrolein selectivity 69.4%, the catalyst of reaction 50h is carried out carbon distribution test analysis, and carbon deposition quantity is 2.3%.
Embodiment 4
The synthesis of Zr-MCM-41 (Si/Zr=15) carrier: first by 3.0ml zirconium-n-propylate and 22.8ml ethyl orthosilicate mix and blend; Then 12.2g softex kw is dissolved in 110ml deionized water, then adds 110ml ammonia spirit; Then under constantly stirring, the first solution of configuration is added drop-wise in the second solution, after stirring 2h to gel-forming under the rotating speed of at room temperature 500r/min, mixed solution is transferred in the Hydrothermal Synthesis still of polytetrafluoroethylene (PTFE) material liner, and be positioned in the baking oven of 100 DEG C and heat 50h, be then cooled to room temperature; Mixed liquor in reactor is filtered, and spends deionized water repeatedly, then solid is placed in the dry 12h of drying box of 80 DEG C; After dried solid is placed in the Muffle furnace roasting 6h of 600 DEG C, obtained Zr-MCM-41 (Si/Zr=15) carrier.
The synthesis of 30wt% phosphotungstic acid/Zr-MCM-41 (Si/Zr=15): first the phosphotungstic acid of 0.3g is dissolved in deionized water, stir wiring solution-forming, the Zr-MCM-41 carrier impregnation prepared by 1g is in phosphotungstic acid aqueous solution, stir evaporation water solution, then 100 DEG C of oven drying 8h are put into, 350 DEG C of roasting 4h in Muffle furnace, obtained 30wt% phosphotungstic acid/Zr-MCM-41 (Si/Zr=15) catalyst.
The synthesis of 2wt%Pd-30wt% phosphotungstic acid/Zr-MCM-41 (Si/Zr=15): first 0.07g palladium bichloride is dissolved in deionized water, stir wiring solution-forming, the phosphotungstic acid prepared by 2g/Zr-MCM-41 catalyst soakage is in palladium chloride aqueous solution, stir evaporation water solution, then 80 DEG C of vacuum drying chambers are put into until bone dry, place 10h for 100 DEG C in an oven, finally 350 DEG C of roasting 4h in Muffle furnace, obtained 2wt%Pd-30wt% phosphotungstic acid/Zr-MCM-41 (Si/Zr=15) catalyst.
Catalyst performance evaluation adopts fixed bed reactors, and using the glycerine water solution of 10wt% as raw material, catalyst amount 0.5g, reaction temperature is 320 DEG C, and mass space velocity is 0.8h
-1under, there is no the phosphotungstic acid Zr-MCM-41 catalyst of load P d, after reaction 1h, glycerol conversion yield 92.2%, acrolein selectivity 75.4%, after reaction 50h, glycerol conversion yield 70.6%, acrolein selectivity 65.3%, carries out carbon distribution test analysis by the catalyst of reaction, and carbon deposition quantity is 4.9%; Under the same reaction conditions, Pd-phosphotungstic acid/Zr-MCM-41 is adopted to be catalyst, after reaction 1h, glycerol conversion yield 96.2%, acrolein selectivity 82.2%, after reaction 50h, glycerol conversion yield 87.5%, acrolein selectivity 78.4%, the catalyst of reaction 50h is carried out carbon distribution test analysis, and carbon deposition quantity is 1.9%.
Method for preparing catalyst according to patent CN103657730 report: single-steeping method and secondary dipping process.We adopt its method Kaolinite Preparation of Catalyst and contrast the method related in this patent.First synthesize MCM-41 molecular sieve catalyst: be dissolved in by 1.8g softex kw in 20ml distilled water, stir; Then with vigorous stirring 5.3g teos solution is dropwise joined above-mentioned solution.The white gels solution obtained at room temperature is stirred 2h, then 100 DEG C of insulation 52h in crystallizing kettle.The solution obtained is filtered, washing, 80 DEG C of dry 12h, finally 550 DEG C of roasting 4h in Muffle furnace.As follows according to single-steeping method operating procedure: 3.0ml zirconium-n-propylate, 0.3g phosphotungstic acid, 0.07g palladium bichloride are dissolved in distilled water, be impregnated on the MCM-41 carrier of above-mentioned preparation, leave standstill 10h, 100 DEG C of oven dry, 350 DEG C of roasting 5h, obtain Pd-HPW-Zr/MCM-41 catalyst.According to reaction condition identical in embodiment 4, evaluate its preparing acrolein by dehydrating glycerin reaction in activity.After reaction 1h, glycerol conversion yield 72.6%, acrolein selectivity 60.4%, after reaction 50h, glycerol conversion yield 45.6%, acrolein selectivity 53.3%, the catalyst of reaction 50h is carried out carbon distribution test analysis, and carbon deposition quantity is 8.0%.As follows according to secondary dipping process operating procedure: to be dissolved in distilled water by 3.0ml zirconium-n-propylate, 0.3g phosphotungstic acid, be impregnated on the MCM-41 carrier of above-mentioned preparation, leave standstill 10h, 100 DEG C of oven dry, 350 DEG C of roasting 5h, obtain HPW-Zr/MCM-41 catalyst; Then taking 0.07g palladium bichloride is dissolved in distilled water, is impregnated on HPW-Zr/MCM-41 carrier, and leave standstill 10h, 100 DEG C of oven dry, 350 DEG C of roasting 5h, obtain Pd-HPW-Zr/MCM-41 catalyst.According to reaction condition identical in embodiment 4, evaluate its preparing acrolein by dehydrating glycerin reaction in activity.After reaction 1h, glycerol conversion yield 76.5%, acrolein selectivity 65.2%, after reaction 50h, glycerol conversion yield 50.1%, acrolein selectivity 58.8%, the catalyst of reaction 50h is carried out carbon distribution test analysis, and carbon deposition quantity is 7.4%.
The catalyst prepared with this patent is active in preparing acrolein by dehydrating glycerin reacts to be contrasted, and the catalyst activity prepared in this patent is far away higher than according to the standby catalyst activity of CN103657730 patent system.In this patent, _ Zr-MCM-41 is prepared by one-step method, and zirconium enters MCM-41 mesopore orbit, thus the active force of zirconium and heteropoly acid is strengthened, and acidity of catalyst not easily runs off.And less according to the specific surface area of catalyst that CN103657730 patent system is standby, easily cause duct to block, catalyst surface is acid easily to run off; Catalyst structure prepared by this patent is stablized, and hydrothermal stability is higher, and acidity not easily runs off.
Embodiment 5
The synthesis of Zr-MCM-41 (Si/Zr=20) carrier: first by 10g zirconium chloride and 0.13g silica mix and blend; Then add 12.2g cetyltriethylammonium bromide and 110ml deionized water, then add 110ml ammonia spirit; After stirring 2h to gel-forming under the rotating speed of at room temperature 500r/min, mixed solution is transferred in the Hydrothermal Synthesis still of polytetrafluoroethylene (PTFE) material liner, and is positioned in the baking oven of 80 DEG C and heats 50h, be then cooled to room temperature; Mixed liquor in reactor is filtered, and spends deionized water repeatedly, then solid is placed in the dry 12h of drying box of 110 DEG C; After dried solid is placed in the Muffle furnace roasting 6h of 500 DEG C, obtained Zr-MCM-41 (Si/Zr=20) carrier.
The synthesis of 40wt% phosphomolybdic acid/Zr-MCM-41 (Si/Zr=20): first the phosphomolybdic acid of 0.4g is dissolved in deionized water, stir wiring solution-forming, the Zr-MCM-41 carrier impregnation prepared by 1g is in the phosphomolybdic acid aqueous solution, stir evaporation water solution, then 80 DEG C of oven drying 8h are put into, 400 DEG C of roasting 4h in Muffle furnace, obtained 40wt% phosphomolybdic acid/Zr-MCM-41 (Si/Zr=20) catalyst.
The synthesis of 3wt%Pd-40wt% phosphomolybdic acid/Zr-MCM-41 (Si/Zr=20): first 0.1g ammonium chloropalladate is dissolved in deionized water, stir wiring solution-forming, the phosphomolybdic acid prepared by 2g/Zr-MCM-41 catalyst soakage is in the ammonium chloropalladate aqueous solution, stir evaporation water solution, then 80 DEG C of vacuum drying chambers are put into until bone dry, place 10h for 120 DEG C in an oven, finally 400 DEG C of roasting 4h in Muffle furnace, obtained 3wt%Pd-40wt% phosphomolybdic acid/Zr-MCM-41 (Si/Zr=20) catalyst.
Catalyst performance evaluation adopts fixed bed reactors, and using the glycerine water solution of 20wt% as raw material, catalyst amount 0.5g, reaction temperature is 340 DEG C, and mass space velocity is 1.5h
-1under, there is no the phosphomolybdic acid/Zr-MCM-41 catalyst of load P d, after reaction 1h, glycerol conversion yield 72.2%, acrolein selectivity 58.4%, after reaction 50h, glycerol conversion yield 50.6%, acrolein selectivity 55.3%, carries out carbon distribution test analysis by the catalyst of reaction, and carbon deposition quantity is 7.0%; Under the same reaction conditions, Pd-phosphomolybdic acid/Zr-MCM-41 is adopted to be catalyst, after reaction 1h, glycerol conversion yield 79.2%, acrolein selectivity 63.2%, after reaction 50h, glycerol conversion yield 71.5%, acrolein selectivity 57.6%, the catalyst of reaction 50h is carried out carbon distribution test analysis, and carbon deposition quantity is 3.3%.
Claims (10)
1. selective glycerol dehydration prepares a preparation method for the catalyst of methacrylaldehyde, it is characterized in that, it comprises the steps:
(1) synthesis of Zr-MCM-41 carrier: by behind zirconium source and the mixing of silicon source to obtain mixed system I for subsequent use, for subsequent use by obtaining mixed system II after mixing with ammonia spirit after water-soluble for template; Under constantly stirring, mixed system I is dropped in mixed system II, after stirred at ambient temperature 2 ~ 5h, then at 80 ~ 100 DEG C crystallization 40 ~ 50h, cooled and filtered, gets solid portion washing, dry, after roasting, obtains Zr-MCM-41 carrier;
(2) synthesis of heteropoly acid/Zr-MCM-41: by the Zr-MCM-41 carrier impregnation that obtains in step (1) in the heteropoly acid aqueous solution, after boiling off moisture under constantly stirring at 70 ~ 100 DEG C, get solid portion drying, after roasting, obtain heteropoly acid/Zr-MCM-41;
(3) synthesis of Pd-heteropoly acid/Zr-MCM-41: the heteropoly acid/Zr-MCM-41 obtained in step (2) be impregnated in the aqueous solution of Pd presoma, boil off moisture under constantly stirring after, get solid portion drying, insulation, after roasting, obtain Pd-heteropoly acid/Zr-MCM-41 catalyst.
2. preparation method according to claim 1, it is characterized in that, in step (1), described zirconium source is zirconium chloride, zirconium oxychloride or zirconium-n-propylate, described silicon source is sodium metasilicate, silica or ethyl orthosilicate, and described template is softex kw, hexadecyltrimethylammonium chloride or cetyltriethylammonium bromide;
Wherein,
The mol ratio of zirconium source, silicon source, template and ammonia is 0.01 ~ 2:0.5 ~ 3:0.3:16.5;
The consumption mol ratio of template and dissolving template water used is 1:150 ~ 200.
3. preparation method according to claim 1, is characterized in that, in step (1), washing methods is for using deionized water rinsing solid portion 3 ~ 5 times; Drying means is dry 8 ~ 12h at 80 ~ 110 DEG C; Method of roasting is roasting 3 ~ 6h at 400 ~ 600 DEG C.
4. preparation method according to claim 1, is characterized in that, in step (2), described heteropoly acid is phosphotungstic acid, silico-tungstic acid or phosphomolybdic acid;
Wherein,
In the heteropoly acid/Zr-MCM-41 of gained, the load capacity of heteropoly acid is 10 ~ 50wt%.
In the heteropoly acid aqueous solution, the concentration of solute heteropoly acid is 0.001 ~ 0.02mol/L.
5. preparation method according to claim 1, is characterized in that, in step (2), drying means is dry 5 ~ 10h at 80 ~ 120 DEG C; Method of roasting is roasting 3 ~ 6h at 300 ~ 400 DEG C.
6. preparation method according to claim 1, is characterized in that, in step (3), described Pd presoma is palladium nitrate, palladium bichloride or ammonium chloropalladate; Wherein, in the aqueous solution of Pd presoma, the concentration of solute Pd presoma is 0.01 ~ 0.1mol/L.
7. preparation method according to claim 1, is characterized in that, in step (3), in the Pd-heteropoly acid/Zr-MCM-41 catalyst of gained, the load capacity of Pd is 1 ~ 5wt%.
8. preparation method according to claim 1, is characterized in that, in step (3), drying means be 80 ~ 120 DEG C down to bone dry, heat preserving method be at 80 ~ 120 DEG C place 10 ~ 12h, method of roasting is roasting 3 ~ 6h at 300 ~ 400 DEG C.
9. in claim 1 ~ 8, any one preparation method prepares catalyst.
10. the application in methacrylaldehyde prepared by catalyst according to claim 9 at selective glycerol dehydration.
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| CN107008478A (en) * | 2017-03-14 | 2017-08-04 | 西北大学 | A kind of preparation method of magnetic nano-catalyst |
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| CN102781580A (en) * | 2009-10-15 | 2012-11-14 | 日本化药株式会社 | Process for preparing catalyst used in production of unsaturated aldehyde and/or unsaturated carboxylic acid by dehydration reaction of glycerin, and catalyst obtained |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102781580A (en) * | 2009-10-15 | 2012-11-14 | 日本化药株式会社 | Process for preparing catalyst used in production of unsaturated aldehyde and/or unsaturated carboxylic acid by dehydration reaction of glycerin, and catalyst obtained |
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| DAE SUNG PARK ET AL.: "Capturing Coke Precursors in a Pd Lattice: A Carbon-Supported Heteropoly Acid Catalyst for the Dehydration of Glycerol into Acrolein", 《CHEMCATCHEM》 * |
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| CN107008478A (en) * | 2017-03-14 | 2017-08-04 | 西北大学 | A kind of preparation method of magnetic nano-catalyst |
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