CN101786008A - Load-type heteropolyacid catalyst for aldolization and preparation method thereof - Google Patents
Load-type heteropolyacid catalyst for aldolization and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a load-type heteropolyacid catalyst and an application thereof in 1, 3-propanediol acetal synthesis and hydrolysis. The method is characterized in that: nanometer porous TiO2 is adopted as a carrier, and the heteropolyacid H3+3xPMo12-xFexO40(x=1 to 3) is adopted as a main active composition, so the load-type heteropolyacid catalyst is prepared through an immersion method, and the catalyst is used for catalyzing 1, 3-propanediol acetal to be synthesized and hydrolyzed. The technical process comprises the following steps that: 1. the heteropolyacid is prepared by an acidification extraction method, and phosphorus molybdenum iron H3+3xPMo12-xFexO40(x=1 to 3)/TiO2 load-type heteropolyacid catalyst is prepared by the immersion method. The load-type heteropolyacid catalyst prepared by the method has the advantages of strong acidity, high catalyze activity, large charge capacity, low leaching rate in a polarity system, environmental friendliness and the like.
Description
Technical field
The present invention relates to a kind of preparation method of carried heteropoly acid compound catalyst and in aldol reaction, use.Relate in particular to a kind of nano-TiO
2The preparation method of load phosphorus molybdenum-iron heteropolyacid catalyst and this catalyst be 1, the ammediol acetal synthetic with hydrolysis in application.The invention belongs to 1, the synthetic and hydrolysis field of ammediol acetal heterogeneous catalysis.
Background technology
Often utilize aldol reaction to shelter oh group in the organic reaction, aldol condensation use always Lewis acid (L acid) and
Acid (B acid) do catalyst (Meskens F A J.Synthesis, 1981,7:501-522), L acid is as AlCl
3, BF
3, ZnCl
2, SnCl
4, B acid is as H
2SO
4, HF, H
3PO
4, HCL, HNO
3, HBO
3Deng.Although catalysis aldol condensation activity is very strong, meet water and be liquid acid, liquid acid contaminated environment, etching apparatus, catalyst are difficult to separate with product, catalyst can't recycling etc. deficiency.
People such as Japan scientist Hino have synthesized SO first
4 2-Behind/MxOy type the solid super acid catalyst, solid acid demonstrates the wide industrial application prospect, up to the present, the solid acid of developing is broadly divided into multiclass solid acids such as immobilized liquid acid, oxide, slaine, zeolite solid acid, solid super-strong acid, cationic ion-exchange resin, clay pit, heteropoly acid solid acid.The solid acid of this type also respectively has pluses and minuses, for example immobilized liquid acid, the advantage of this type of catalyst is the catalytic efficiency height, the immobilized back of liquid acid is used, problem is reclaimed in the separation that has solved catalyst to a certain extent, but active component can constantly run off in the course of reaction, and equipment is had certain corrosion, and catalyst is short service life; Cationic ion-exchange resin has active high, advantages such as selectivity is good, easily separated, recycling, low corrosion, but allowable temperature is lower, price is higher is limited to owing to using.SO
4 2-/ MxOy type solid super-strong acid has that water stability, is good, the high advantage of serviceability temperature.
Solid heteropoly acid is a kind of green catalysis material of developing in recent years, and it is acid strong, and is acid stronger than the simple oxyacid of the corresponding component that constitutes them.In the aqueous solution, dissociate stepwise dissociation in organic solvent, catalytic activity height fully.
Heteropoly acid (HPA) be by central atom (as P, Si, As, Ge etc.) and coordination atom (as Mo, V, W, Fe etc.) with certain structure by oxygen atom ligand, contain the polyacid complex of oxo bridge.Heteropoly acid can be divided into five kinds: Keggin structure, Dwason structure, Anderson structure, Waugh structure and silverton structure by its anion primary structure.Wherein the heteropoly compound of Keggin structure is the most frequently used heteropolyacid catalyst, also be the active best heteropoly acid of acid catalysis (Bardin B B.J Phys Chem B, 2000,104:3556-3562).Substrate-anion intermediate that heteropoly acid is easy and substrate formation is more stable reduces reaction activity, helps the carrying out that reacts.But the heteropllyacids catalyst has, and specific area is little, poor stability, be soluble in polar solvent, recovery and reuse deficiencies such as difficulty, and therefore the heteropoly acid of loadization is more paid attention in up-to-date research.
Outstanding advantage such as carried heteropoly acid has the catalytic activity height, easily separates with the aqueous phase reactions system, chemical reaction condition gentleness, the post processing of etching apparatus, institute's catalysis be not simple.And it is acid strong, nearly all acid catalyzed reaction is all shown good reaction activity and selectivity, thereby become one of research focus of catalytic field.
In carried heteropoly acid catalyst, the loaded article heteropoly acid is common phosphotungstic acid, phosphomolybdic acid, tungstosilicic acid etc.Carrier comprises active carbon, Al usually
2O
3, SiO
2, TiO
2, porous material such as diatomite, imvite, molecular sieve, ion exchange resin, polymer.Carrier material character has very important function to structure, acidity and the otherwise character of heteropoly acid: (1) increases effective surface area, and proper pore structure is provided; (2) heat endurance of raising catalyst; (3) carrier has certain soda acid structure can provide needed acid centre of reaction or basic center, improves the combination degree with loaded article; (4) with the active component acting in conjunction, form new compound or solid solution, produce new chemical combination form and crystalline texture, thereby cause the variation of catalyst activity, carrier has the effect of co-catalyst etc. concurrently.The preparation method of carried heteropoly acid commonly used mainly is infusion process and absorption method.
It is acid strong that the key problem in technology of this class carried heteropoly acid is how to obtain, and load capacity is big, and loaded article and carrier the aspect such as are not destroyed in conjunction with the heteropoly acid Keggin structure that firmly is difficult for solution-off, load simultaneously.Loaded by heteropoly acid on the nanoporous carrier material, can be obtained the carried heteropoly acid that specific area is big, load capacity is big, catalytic activity is high.
Technical problem: the technical problem to be solved in the present invention is to provide a kind of support type H
3+3xPMo
12-xFe
xO
40(x=1～3)/TiO
2The preparation method of heteropolyacid catalyst and this catalyst be 1, the ammediol acetal synthetic with hydrolysis in application.Promptly utilize nanoporous TiO
2High-ratio surface, high-efficient carrier phosphorus molybdenum-iron heteropoly acid, solve that the heteropllyacids specific surface area of catalyst is little, poor stability, be soluble in polar solvent, recovery and reuse deficiencies such as difficulty, preparation is difficult for solution-off, good stability, load capacity is big, catalytic activity is high carried heteropoly acid.
Technical scheme: the present invention relates to phosphorus molybdenum-iron heteropoly acid H with the Keggin structure
3+3XPMo
12-XFe
XO
40(x=1～3) are carried on nanoporous TiO
2On the carrier, it is strong to prepare acidity, and load capacity is big, has the carried heteropoly acid catalyst of heterogeneous catalysis activity.Because that carrier is selected is porous material TiO
2, its isoelectric point is 4.5～5.5, is a kind of acid carrier, TiO
2After surface hydroxyl is protonated, form extraneous surface complexes with heteropolyanion, make carried heteropoly acid catalyst have good catalytic activity (Wang Guangjian etc. organic chemistry, 2009,29 (7): 1039-1047).The nanoporous TiO that the present invention relates to simultaneously
2Carrier, specific area is big, porous, and this provides the place for the more heteropoly acid of load, has improved sour density; And the heteropoly acid of load, be to replace the heteropoly acid coordination atom with transition metal atoms, the vacant heteropoly compound that forms, because its structural " unsaturation ", may have higher catalytic activity and better stable (Zhang F M.Chin J Chem Eng, 2007,15 (6): 895-898).The formation in this heteropoly acid acid site mainly is to come from heteropoly acid in metal oxide surface coordination absorption, at first because heteropoly acid self acts on very strong
Acid can dissociate H
+, simultaneously it induces the metal Ti ion, increases Ti and gets electronic capability, makes that electron cloud is offset strongly on the Ti-O key, strengthens the Lewis acid site, H
3+3XPMo
12-XFe
XO
40/ TiO
2Type solid heteropoly acid (x=1～3) is existing
Also there is the Lewis acid site in the acid site.As shown in the formula
Carried heteropoly acid is used for aldol reaction, heterogeneous catalysis 1, the range of application of heteropolyacid catalyst has been expanded in condensation of ammediol acetal and hydrolysis.This characteristic has been given the reaction enrichment and has been extracted dihydroxylic alcohols 1, the ability of ammediol.
1, ammediol is important hardware and software platform compound, has strong polarity and strongly hydrophilic, and General Physics extracts and ethanol, the effective complexing abstraction of butanol solution all are difficult to prove effective to this system.Reduce the polarity and the hydrophily of extract, a feasible way is the Reaction Separation extraction method, utilize the synthetic and hydrolysis of the reversible acetal of carried heteropoly acid heterogeneous catalysis, with 1, the ammediol hydroxyl is sheltered, and obtains hydrophobicity cyclic acetal compound, separates this organic facies, the approach of living again by hydrolysis can obtain concentrating 1, ammediol.
H
3+3xPMo
12-xFe
xO
40(x=1～3)/TiO
2Type solid heteropoly acid catalyst 1, the synthetic and hydrolysis of ammediol acetal, reaction equation is as follows:
Positive reaction, aldol condensation: with the carried heteropoly acid is catalyst, 1, ammediol and aldehyde condensation obtain hydrophobicity cyclic acetal compound, and system forms new organic facies;
Back reaction, organic facies acetal hydrolysis: with the carried heteropoly acid is catalyst, in the presence of water, cyclic acetal generation hydrolysis;
Wherein:
R
1Be H, C
1～C
10Alkyl, C
1～C
10Alkoxyl, C
1～C
10Aldehyde radical;
R
2Be H, C
1～C
10Alkyl, C
1～C
10Alkoxyl, C
1～C
10Aldehyde radical;
Utilize the carried heteropoly acid high-ratio surface, adsorption capacity is big, is difficult for solution-off, characteristics such as good stability, heterogeneous catalysis 1, ammediol and aldehyde, letones generation aldol reaction, with 1 of strong polarity, the ammediol dihydroxylic is sheltered, obtain hydrophobicity cyclic acetal compound, utilize the hydrolysis of solid heteropoly acid catalysis acetal again, enrichment 1, ammediol.The present invention can be generalized to polar water system environment, effectively enrichment 1 from zymotic fluid, ammediol.
The present invention is with nanoporous TiO
2For carrier, with phosphorus molybdenum-iron heteropoly acid H
3+3xPMo
12-xFe
xO
40(x=1～3) are loaded article, obtain the supported solid heteropolyacid catalyst by immersion process for preparing, and have investigated this catalyst in heterogeneous catalysis 1, and the catalytic activity of reversible condensation and hydrolytic process takes place for ammediol and aldehyde, ketone.Outstanding advantages such as that carried heteropoly acid has is acid strong, catalytic activity is high, easily separate with the aqueous phase reactions system, etching apparatus, post processing be not simple.Specific embodiment of the present invention is:
A), the preparation of phosphorus molybdenum-iron heteropoly acid; Heteropoly acid adopts the preparation of acidizing extraction method, concrete steps are: add an amount of sodium molybdate, sodium hydrogen phosphate and ferric nitrate in water, n (Fe): n (Mo): n (P) :=(1.0～3.0): (11.0～9.0): 1.0, (n (Fe)+n (Mo): n (P)=12: 1, water-bath is heated to backflow, after stirring dropping dilute sulfuric acid acidifying down, cool off after stirring 1.0～3.0h again, use extracted with diethyl ether, add some sulfuric acid simultaneously, vibrate, leave standstill, layering, water reextraction ether layer again obtains H after the drying at last
3+3xPMo
12-xFe
xO
40(x=1～3) heteropoly acid.
B), the load of heteropoly acid; Infusion process is adopted in load, with the hydrolysis of titanium precursor body sol-gel, to carry out in order making to be reflected in the homogeneous system, to add a kind of as cosolvent in tributyl phosphate, acetylacetone,2,4-pentanedione, formamide, dimethyl formamide, the dioxane, the mol ratio of cosolvent and titanium is 0.05～1: 1; Regulate gelation process pH value, behind stirring at room 30～60min, carry out TiO
2Sol-gel process heats up, and 293～333K stirs 1～6h down, ageing 12～24h under the room temperature, then with sample in 363～383K dried overnight, become porous nano TiO
2Xerogel, be ground to≤100 orders sieve.The phosphorus molybdenum-iron heteropoly acid solution of configuration 0.01～1.0mol/L is joined the ratio of 1～20mL phosphorus molybdenum-iron heteropoly acid solution in every gram xerogel, and dipping 2～48h filters, in 363～383K oven dry, be ground to≤100 orders sieve, and 473～723K roasting, 0.5～6h makes H
3+3xPMo
12-xFe
xO
40(x=1～3)/TiO
2Carried heteropoly acid catalyst.
Beneficial effect: the present invention has the following advantages: 1) the present invention replaces the acidity that molybdenum has strengthened the loaded article heteropoly acid by transition metal iron; 2) the present invention is with the big nanoporous TiO of specific area
2For preparing carriers acid strong, carried heteropoly acid that load capacity is big, catalyst cupport thing component can load on the carrier securely simultaneously, even 1, in the strong polar reaction system of ammediol or water, loaded article component solution-off is not obvious, and catalyst stability is good; 3) adopt the preparation method who the present invention relates to, active component can high degree of dispersion on carrier, the catalytic activity height, 1, ammediol acetal productive rate is up to 96%; 4) catalyst involved in the present invention is easy to reclaim and serialization production.
The specific embodiment:
The present invention relates to nanoporous TiO
2The preparation of the phosphorus molybdenum-iron heteropolyacid catalyst of load, and be used for 1, in the aldolisation of ammediol and aldehyde, ketone, investigated the catalytic activity of specific area, load capacity and the supported catalyst of carrier, character such as solution-off.
Specific embodiment of the present invention is:
Load phosphorus molybdenum-iron H
3+3xPMo
12-xFe
xO
40(x=1～3)/TiO
2The preparation of type heteropolyacid catalyst
A), the preparation of phosphorus molybdenum-iron heteropoly acid; Heteropoly acid adopts the preparation of acidizing extraction method, concrete steps are: add an amount of sodium molybdate, sodium hydrogen phosphate and ferric nitrate in water, n (Fe): n (Mo): n (P) :=(1.0～3.0): (11.0～9.0): 1.0, (n (Fe)+n (Mo): n (P)=12: 1, water-bath is heated to backflow, after stirring dropping dilute sulfuric acid acidifying down, cool off after stirring 1.0～3.0h again, use extracted with diethyl ether, add some sulfuric acid simultaneously, vibrate, leave standstill, layering, water reextraction ether layer again obtains H after the drying at last
3+3xPMo
12-xFe
xO
40(x=1～3) heteropoly acid;
B), the load of heteropoly acid; Infusion process is adopted in load, with the hydrolysis of titanium precursor body sol-gel, to carry out in order making to be reflected in the homogeneous system, to add a kind of as cosolvent in tributyl phosphate, acetylacetone,2,4-pentanedione, formamide, dimethyl formamide, the dioxane, the mol ratio of cosolvent and titanium is 0.05～1: 1; Regulate gelation process pH value, behind stirring at room 30～60min, carry out TiO
2Sol-gel process heats up, and 293～333K stirs 1～6h down, ageing 12～24h under the room temperature, then with sample in 363～383K dried overnight, become porous nano TiO
2Xerogel, be ground to≤100 orders sieve.The phosphorus molybdenum-iron heteropoly acid solution of configuration 0.01～1.0mol/L, in 1～20mL phosphorus molybdenum-iron/g xerogel ratio, dipping 2～48h filters, and dries in 363～383K, be ground to≤100 orders sieve, and 473～723K roasting, 0.5～6h makes H
3+3xPMo
12-xFe
xO
40(x=1～3)/TiO
2Carried heteropoly acid catalyst.
Activity of such catalysts is investigated
1, ammediol acetal synthetic reaction:
Aldol reaction is to carry out in the three-neck flask that has magnetic stirring apparatus, water knockout drum and reflux condensing tube.Reaction raw materials is propionic aldehyde 1～1.5mol, 1, ammediol 0.8～1.2mol, and catalyst amount 0.1～0.4g, band aqua cyclohexane 10～40mL, reaction temperature 273～363K no longer includes moisture to the water knockout drum and comes out, and stops reaction.Isolate H with centrifuge
3+3xPMo
12-xFe
xO
40(x=1～3)/TiO
2Catalyst granules, separated liquid is collected organic facies 1, the ammediol acetal.With gas chromatographic analysis and calculate 1, ammediol acetal productive rate.
Organic facies acetal hydrolysis:
In the single port flask, add 8～15g acetal and 2～5mL deionized water, 0.1～0.4gH
3+3xPMo
12-xFe
xO
40(x=1～3)/TiO
2Carried heteropoly acid catalyst.373～403K back flow reaction is by gas chromatographic analysis and calculate 1, ammediol acetal hydrolysis yield.Embodiment one: the phosphorus molybdenum-iron H of different sintering temperatures
6PMo
11FeO
40/ TiO
2The preparation of carried heteropoly acid catalyst
A), phosphorus molybdenum-iron (H
6PMo
11FeO
40) preparation of heteropoly acid; Heteropoly acid adopts the preparation of acidizing extraction method, and concrete steps are: 3.58g Na
2HPO
412H
2O is dissolved in the 70mL deionized water, 26.61g Na
2MoO
42H
2O is dissolved in the 80mL deionized water, and two kinds of solution mix, and adds in the 1000mL flask, stirs, and is heated to 333K, behind the 0.5h, will be dissolved in the 4.04g Fe (NO of 50mL deionized water
3)
39H
2O under agitation adds in the above-mentioned mixed liquor, and water-bath is heated to backflow, adds H while stirring
2SO
4Adjust about pH value of solution=2.0, behind the reaction 2h, cooling adds the 60mL ether in reactant liquor, fully after the vibration, adds some H again
2SO
4Continuing to oscillate to does not have under the oil droplet shape fluid drips, leaves standstill back solution and is divided into three layers, and the upper strata is an ether, and the middle level is water, inorganic salt deposit, and lower floor is yellow heteropoly acid ether grease.Take off a layer thing, purge and to remove ether, water reextraction ether layer again obtains H after the drying at last
6PMo
11FeO
40Heteropoly acid;
B), the load of heteropoly acid; Infusion process is adopted in the load of phosphorus molybdenum-iron heteropoly acid, 7.2mL the mixed solution of deionized water, 10mL absolute ethyl alcohol and 6mL glacial acetic acid joins in the 250mL four-hole boiling flask, again with 34mL tetra-n-butyl titanate and 50mL absolute ethyl alcohol mixed solution, dropwise join in the 250mL four-hole boiling flask, dropwise the back and continue to stir 3h, carry out the sol-gel hydrolysis, carry out in order to make to be reflected in the homogeneous system, add tributyl phosphate as cosolvent, the mol ratio of cosolvent and titanium is 0.2: 1; Regulate gelation process pH value, stirring at room 30min carries out TiO
2Sol-gel process heats up, and 323K stirs 3h down; Ageing 24h under the room temperature, then with sample in the 368K dried overnight, become porous nano TiO
2Xerogel is ground to≤100 order sieving for standby.The phosphorus molybdenum-iron heteropoly acid solution of configuration 0.02mol/L, heteropoly acid solution and xerogel are according to 5mL: 1g ratio dipping, dipping 12h filters, and in the 373K oven dry, is ground to≤100 orders and sieves, and 473～723K roasting 3h makes H
6PMo
11FeO
40/ TiO
2The type heteropolyacid catalyst.
Activity of such catalysts is investigated
1, ammediol acetal synthetic reaction: aldol reaction is to carry out in the three-neck flask that has magnetic stirring apparatus, water knockout drum and reflux condensing tube.Reaction raw materials is propionic aldehyde 1.2mol, 1, ammediol 1.0mol, and the catalyst amount of different sintering temperatures preparation is 0.2g, band aqua cyclohexane 20mL, reaction temperature 343K no longer includes moisture to the water knockout drum and comes out, and stops reaction, isolates H with centrifuge
6PMo
11FeO
40/ TiO
2Catalyst granules, separated liquid is collected organic facies 1, the ammediol acetal.With gas chromatographic analysis and calculate 1, ammediol acetal productive rate.The results are shown in Table one:
The different sintering temperatures of table one are to the influence of catalytic performance
Know sintering temperature not simultaneously from table one, the effect difference of catalyst, wherein #4 catalyst activity is higher, and this is because sintering temperature is the key factor that influences catalytic activity.Suitable sintering temperature exerts an influence to character such as the formation in acid site, acid strength, particle diameter, specific surfaces, and then influences catalytic performance.When sintering temperature 623K, 1, ammediol acetal productive rate is best, reaches 82.13%.But when sintering temperature was too high, the Keggin structure of breaking load thing caused acidity to reduce easily.
Embodiment two: the impregnating ratio of different heteropoly acid solution and xerogel
Phosphorus molybdenum-iron (H
6PMo
11FeO
40)/TiO
2The preparation of carried heteropoly acid and embodiment one are similar, heteropoly acid concentration or 0.02mol/L, the dipping ratio of change heteropoly acid solution and xerogel, scope is (2.5～15) mL: 1g, dipping 12h, filter,, be ground to≤100 orders and sieve in the 373K oven dry, 623K roasting 3h, make sample #1, #2, #3, #4, #5, each sample catalysis 1, ammediol acetal synthetic reaction the results are shown in Table two:
The impregnating ratio of different heteropoly acid solution of table two and xerogel
Heteropoly acid solution: xerogel 1, ammediol acetal
Numbering sintering temperature (K) roasting time (h)
(mL/g) productive rate (%)
#1 2.5∶1 623 3 51.05
#2 5∶1 623 3 75.64
#3 10∶1 623 3 95.95
#4 12.5∶1 623 3 80.06
#5 15∶1 623 3 68.14
Heteropoly acid solution under the concentration of the same race, when the impregnating ratio of heteropoly acid solution and xerogel not simultaneously, can influence load capacity and the deployment conditions of heteropoly acid on carrier material.Low impregnating ratio, load capacity is low, and heteropoly acid is high degree of dispersion on carrier, and at this moment, along with impregnating ratio improves, load capacity increases, and total acid content also increases along with the increase of load capacity, and catalytic activity increases progressively; But during the high capacity amount, because the formation of big heteropoly acid crystal grain, surperficial proton concentration significantly descends, dispersed decline, and catalytic activity descends on the contrary.From table two, learn impregnating ratio 10mL when heteropoly acid solution and xerogel: during 1g, promptly 1 of sample #3 catalysis, ammediol acetal synthetic reaction effect is best, and productive rate reaches 95.95%.
Shown in example one, two, select the impregnating ratio (10mL: carried heteropoly acid catalyst 1g) of 623K sintering temperature, heteropoly acid solution and xerogel for use, investigate it to 1, ammediol acetal hydrolyzation catalysis activity, concrete steps are, in the single port flask, add 10g acetal and 2mL deionized water, 0.2gH
6PMo
11FeO
40/ TiO
2Carried heteropoly acid catalyst.Back flow reaction under the 378K, by gas chromatographic analysis and calculate 1, ammediol acetal hydrolysis yield finally obtains 1, and the ammediol productive rate is 82.23%
Embodiment three: the test of carried heteropoly acid catalyst solution-off rate:
The solution-off rate of carried heteropoly acid records by ultraviolet-uisible spectrophotometer, and the #3 catalyst in a certain amount of the foregoing description two is added in the distilled water, and is centrifugal behind the stirring 2h, collects filtrate.Centrifugal gained catalyst is measured the variation of solution-off rate once more through the 373K dried overnight.Filtrate is measured the absorbance of heteropoly acid in the filtrate with ultraviolet-uisible spectrophotometer 310nm, according to calibration curve, obtains in the filtrate by solid catalyst and is lost to heteropoly acid concentration in the aqueous solution, and calculate solution-off amount and solution-off rate with this.The results are shown in Table three.
The test of table three solution-off amount
Therefrom as can be known, in the polar water system, the solution-off rate of carried heteropoly acid catalyst is smaller, and catalyst is difficult for solution-off, stability better.
Embodiment four: cosolvent is to the influence of carrier specific area
According to carrier TiO among the embodiment one
2The sol-gel hydrolytic process, investigate to add of the influence of cosolvent tributyl phosphate to the carrier specific area, the mol ratio of cosolvent and titanium is 0.2: 1.Sintering temperature 623K, the impregnating ratio (10mL: 1g) of heteropoly acid solution and xerogel.The load capacity of catalyst is determined by the variation of heteropoly acid amount in the solution before and after the dipping.
Record carrier TiO
2Specific area is 297m
2/ g, load capacity are 38%, with blank TiO
2(specific area 72m
2/ g, load capacity are 17%) to compare, specific area and load capacity increase significantly.Big specific area has guaranteed the high capacity of heteropoly acid.
Claims (6)
1. a load-type heteropolyacid catalyst for aldolization is characterized in that this catalyst is with nanoporous TiO
2For carrier, with phosphorus molybdenum-iron heteropoly acid H
3+3xPMo
12-xFe
xO
40Be loaded article, x=1～3 obtain the supported solid heteropolyacid catalyst.
2. the preparation method of a load-type heteropolyacid catalyst for aldolization as claimed in claim 1 is characterized in that this preparation method's technical process is:
A), the preparation of phosphorus molybdenum-iron heteropoly acid; Heteropoly acid adopts the preparation of acidizing extraction method, concrete steps are: add sodium molybdate, sodium hydrogen phosphate and ferric nitrate in water, n (Fe): n (Mo): n (P) :=(1.0～3.0): (11.0～9.0): 1.0, (n (Fe)+n (Mo)): n (P)=12: 1, water-bath is heated to backflow, after stirring dropping dilute sulfuric acid acidifying down, cool off after stirring 1.0～3.0h again, use extracted with diethyl ether, add some sulfuric acid simultaneously, vibrate, leave standstill, layering, water reextraction ether layer again obtains H after the drying at last
3+3xPMo
12-xFe
xO
40Heteropoly acid;
B), heteropoly acid is immobilized; Infusion process is adopted in load, with the hydrolysis of titanium precursor body sol-gel, to carry out in order making to be reflected in the homogeneous system, to add a kind of as cosolvent in tributyl phosphate, acetylacetone,2,4-pentanedione, formamide, dimethyl formamide, the dioxane, the mol ratio of cosolvent and titanium is 0.05～1: 1; Regulate gelation process pH value, stirring at room 30～60min carries out TiO
2Sol-gel process heats up, and 293～333K stirs 1～6h down; Ageing under the room temperature, then with sample in 363～383K dried overnight, become porous nano TiO
2Xerogel, be ground to≤100 orders sieve; Infusion process load phosphorus molybdenum-iron: the phosphorus molybdenum-iron heteropoly acid solution of configuration 0.01～1.0mol/L, join the ratio of 1～20mL phosphorus molybdenum-iron heteropoly acid solution in every gram xerogel, dipping 2～48h, dry in 363～383K, be ground to≤100 orders sieve, and 473～723K roasting, 0.5～6h makes H
3+3xPMo
12-xFe
xO
40Carried heteropoly acid catalyst.
3. the preparation method of a kind of load-type heteropolyacid catalyst for aldolization according to claim 2, it is characterized in that the acidizing extraction legal system is equipped with in the phosphorus molybdenum-iron heteropoly acid, iron molar content 1.69～4.62%, molybdenum molar content 13.8～18.8%, phosphorus molar content 1.53～1.70%.
4. the preparation method of a kind of load-type heteropolyacid catalyst for aldolization according to claim 2, it is characterized in that in titanium precursor body sol-gel hydrolytic process, add a kind of as cosolvent in tributyl phosphate, acetylacetone,2,4-pentanedione, formamide, dimethyl formamide, the dioxane, the mol ratio of cosolvent and titanium is 0.05～1: 1.
5. the preparation method of a kind of load-type heteropolyacid catalyst for aldolization according to claim 2 is characterized in that at TiO
2In the sol-gel process, regulate gelation process pH value, the pH value is 5～10.
6. the application of an a kind of load-type heteropolyacid catalyst for aldolization as claimed in claim 1 is characterized in that this carried heteropoly acid catalyst relates to a kind of support type H
3+3xPMo
12-xFe
xO
40/ TiO
2Heteropolyacid catalyst, this catalyst is applied in 1, the ammediol acetal synthetic with hydrolysis in.
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| CN102658200A (en) * | 2012-04-25 | 2012-09-12 | 上海师范大学 | Sulfonic acid-functionalized ordered mesoporous polymer-silicon oxide composite material and synthetic method thereof |
| CN103130767A (en) * | 2011-11-24 | 2013-06-05 | 中国科学院大连化学物理研究所 | 1,3-dioxane preparation method |
| CN109160907A (en) * | 2018-10-09 | 2019-01-08 | 江苏扬农化工集团有限公司 | A method of it improves propane catalyst activity co-production ketal (aldehyde) |
| CN110198744A (en) * | 2017-03-21 | 2019-09-03 | 株式会社科特拉 | Except aldehyde adsorbent and deodoring materials and their manufacturing method |
| CN110937745A (en) * | 2019-12-12 | 2020-03-31 | 万华化学集团股份有限公司 | Method for treating high-concentration wastewater in citral synthesis process |
| CN113058647A (en) * | 2021-03-26 | 2021-07-02 | 福州大学 | Iron-substituted heteropoly acid-loaded polyphenylene sulfide denitration sulfur-resistant composite filter material |
| CN114433057A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Solid acid catalyst and preparation method thereof |
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| CN103130767A (en) * | 2011-11-24 | 2013-06-05 | 中国科学院大连化学物理研究所 | 1,3-dioxane preparation method |
| CN102658200A (en) * | 2012-04-25 | 2012-09-12 | 上海师范大学 | Sulfonic acid-functionalized ordered mesoporous polymer-silicon oxide composite material and synthetic method thereof |
| CN110198744A (en) * | 2017-03-21 | 2019-09-03 | 株式会社科特拉 | Except aldehyde adsorbent and deodoring materials and their manufacturing method |
| CN109160907A (en) * | 2018-10-09 | 2019-01-08 | 江苏扬农化工集团有限公司 | A method of it improves propane catalyst activity co-production ketal (aldehyde) |
| CN110937745A (en) * | 2019-12-12 | 2020-03-31 | 万华化学集团股份有限公司 | Method for treating high-concentration wastewater in citral synthesis process |
| CN110937745B (en) * | 2019-12-12 | 2022-07-12 | 万华化学集团股份有限公司 | Method for treating high-concentration wastewater in citral synthesis process |
| CN114433057A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Solid acid catalyst and preparation method thereof |
| CN114433057B (en) * | 2020-10-31 | 2023-09-01 | 中国石油化工股份有限公司 | Solid acid catalyst and preparation method thereof |
| CN113058647A (en) * | 2021-03-26 | 2021-07-02 | 福州大学 | Iron-substituted heteropoly acid-loaded polyphenylene sulfide denitration sulfur-resistant composite filter material |
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