CN1301152C - Preparation and use of heteropolyacid catalyst carried on dealuminized super-stable gamma zeolite - Google Patents
Preparation and use of heteropolyacid catalyst carried on dealuminized super-stable gamma zeolite Download PDFInfo
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- CN1301152C CN1301152C CNB2004100448118A CN200410044811A CN1301152C CN 1301152 C CN1301152 C CN 1301152C CN B2004100448118 A CNB2004100448118 A CN B2004100448118A CN 200410044811 A CN200410044811 A CN 200410044811A CN 1301152 C CN1301152 C CN 1301152C
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Abstract
The present invention discloses a preparation method of a heteropolyacid catalyst carried on dealuminized super-stable Y-type zeolite and a use in a liquid phase esterifying reaction. The preparation method of the catalyst comprises: mixing the USY zeolite with deionized water according to a weight ratio of 1:0.8 to 5, processing the mixture with steam for 2 to 10h at 500 DEG C to 900 DEG C, filtering and washing the mixture with an acid solution with the concentration of 1 to 5 mol/L at 60 DEG C to 100 DEG C for 1 to 10 hours, filtering, drying and calcining to obtain the catalyst carrier, namely the dealuminized super-stable Y-type zeolite; soaking the carrier with the water solution of alkali metal carbonate or alkali metal nitrate, drying, calcining, soaking with a right amount of a heteropolyacid solution, drying and calcining to obtain the heteropolyacid salt catalyst carried on dealuminized super-stable Y-type zeolite. When used for the liquid phase esterifying reaction of acetic acid and normal butyl alcohol, the catalyst has the advantages of low reaction temperature and high conversion rate. The catalyst prepared by the method favorably solves the problem of easy dissolution of the active components of carried catalysts.
Description
Technical field
The present invention relates to a kind of preparation method and the application of this catalyst in esterification of carried heteropoly acid salt catalyst, relate in particular to the preparation method and the application of this catalyst in acetate and n-butanol liquid-phase esterification of the zeolite-loaded heteropolyacid salt catalyst of a kind of dealuminzation USY.
Background technology
In the liquid-phase esterification of carboxylic acid and fatty alcohol, traditional catalyst is inorganic liquid acid or lewis acid, comprises H
2SO
4, AlCl
3, HF etc.Though these traditional catalyst are active high, selectivity is good, all has strong corrosivity and toxicity, can cause equipment corrosion, a series of problems such as product post processing complexity and environmental pollution, so development environment close friend's solid acid catalyst becomes inevitable.
Heteropoly acid is a kind of novel solid acid catalyst, Bronsted acid and unique " accurate liquid phase " characteristic homogeneous owing to have strong, and the application in catalytic field receives increasing concern, but because the little (＜10m of pure heteropoly acid specific area
2/ g), be not fully utilized as the solid acid catalyst activated centre, in addition,, in the polar reaction system, be difficult to use as solid acid because pure heteropoly acid is soluble in polar solvent.In order to overcome above-mentioned defective, common way is that it is carried on the suitable carriers, to increase its specific area.In research in the past, some porous Large ratio surface materials are as the heteropoly acid carrier, silica gel for example, γ-Al
2O
3, MCM-41, active carbon, pillared material etc.Wherein silica gel and active carbon are the most frequently used, and have obtained better sign.Generally believe that in nonpolar reaction system, the activity of silica gel load heteropolyacid catalyst is the highest, and the reaction of in polar solvent, carrying out, active carbon is carried heteropoly acid the most securely.Chinese patent CN1235873A has described the preparation method of superfine silicon dioxide load phosphotungstic acid catalyst, and investigated the catalytic performance of this catalyst in benzene and laurylene alkylated reaction, the activity of finding the superfine silicon dioxide load phosphotungstic acid catalyst is 5 times of pure phosphotungstic acid catalyst, 6 times of HY, 8 times of common silica gel load phosphotungstic acid catalyst.The selectivity of superfine silicon dioxide carried heteropoly acid catalyst is apparently higher than the HY molecular sieve catalyst.In addition, also heteropoly acid can be changed into and comprise Cs
+, K
+And NH
4 +Deng insoluble heteropolyacid salt, Cs wherein
2.5H
0.5PW
12O
40Has been proved and has excellent catalytic performance, but because its particle diameter too little (about 10nm), preparation is difficult, and because of its insert reactor after bed resistance too big, and do not fit into reactor such as fixed bed.For addressing this problem, forefathers once attempted heteropolyacid salt is also loaded on the carrier with bigger serface, but be suitable for doing the generally all water insoluble and common solvent of heteropolyacid salt of catalysis material, therefore general infusion process is unsuitable for preparing the carried heteropoly acid salt catalyst, and needs to adopt special carrying method.Carry out brief summary with regard to representational relevant carried heteropoly acid salt catalyst preparation method in previous patent or the article below:
Nineteen ninety-five, Y.Izumi etc. take the lead in adopting sol-gel process (sol-gel method) to prepare support type H
3PW
12O
40/ SiO
2And Cs
2.5H
0.5PW
12O
40/ SiO
2Catalyst.This method is that H is being arranged
3PW
12O
40Or Cs
2.5H
0.5PW
12O
40Teos hydrolysis generates silica gel in the aqueous solution that exists, in the silica gel generative process with H
3PW
12O
4Or Cs
2.5H
0.5PW
12O
40Immobilized, thus prepare in the polar reaction system the not loaded catalyst of solution-off of heteropoly acid or salt.In recent years, this method for preparing catalyst is subjected to extensive studies.But the catalyst of this method preparation has tangible deficiency, the one, the load capacity of heteropoly acid or heteropolyacid salt is on the low side, be generally less than 15%, activity of such catalysts is also on the low side, reaction speed is not ideal enough in many reactions, the 2nd, the preparation process complexity, cost is also higher, and therefore having limited this method prepares Application of Catalyst.
A kind of composition, preparation method and application in aromatic hydrocarbons and olefin alkylation reaction thereof with porous carrier carried heteropoly acids such as titanium dioxide, silica and zirconia or heteropolyacid salt catalyst described among the patent WO95/13869.Preparation of catalysts is carried out in two steps, and the first step is earlier with carrier impregnation Cs
2CO
3, after roasting, second step was flooded H again
3PW
12O
40The catalyst of preparing like this, active component Cs
2.5H
0.5PW
12O
40On carrier, be distributed as eggshell type, have catalytic activity preferably.Jean-Michel (Tatibouet J M, Montalescot C, Bruckman K.[J] .Appl Catal A, 1996,138:L1-L6) adopt similar methods to prepare CaHPMo
12O
40/ SiO
2Catalyst.The method of obvious two step immersion process for preparing carried heteropoly acid salt catalysts, process is simple, and the yield height is for the application of carried heteropoly acid salt catalyst lays the foundation.
Having described a kind of among the CN1431052A is the method for carrier loaded heteropolyacid salt catalyst with silica gel.Its preparation process is in two steps:
(1) conditioned reaction condition, earlier synthetic heteropoly acid on carrier silica gel.
(2) carried heteropoly acid with preparation is immersed in water miscible carbonate or the organic amine solution, after leave standstill, filter, drying promptly gets the heteropolyacid salt catalyst of silica gel load.
U.S. Pat 6472344 has reported that with mesopore total silicon material MCM-41 be carrier loaded Cs
2.5H
0.5PW
12O
40The Preparation of catalysts method.This Preparation of catalysts method and patent WO95/13869 are described similar, and its difference is to adopt low pole or nonpolar dissolution with solvents H
3PW
12O
40, rather than with the very strong water of polarity.The inventor thinks that this catalyst has following advantage: (1) carrier is to have certain pore size to distribute, the inert substance that specific area is huge, and in its duct, it is very complete that the Keggin structure of heteropolyanion not only keeps, and be the high degree of dispersion shape; (2) overcome the shortcoming of pure heteropoly acid poor heat stability; (3), thereby in some catalytic reaction, has tangible shape selectivity because the aperture of carrier modulation within the specific limits.
In sum, up to now among the preparation method of all carried heteropoly acid salt catalysts, all be that as the carrier of carried heteropoly acid salt, difference only is that heteropoly acid is different with the order that the metal soluble-salt loads on the carrier with inertia total silicon material (or to wherein adding an amount of other oxide).In these patents, all do not investigate the solution-off performance of catalyst, and this performance is the deciding factor whether this type of catalyst has industrial application value simultaneously, this point is that of these patents is obviously not enough.In addition, in patent in the past, not occurring as yet with zeolite is the report of carrier loaded heteropolyacid salt.
Summary of the invention
The purpose of this invention is to provide a kind of prior art that is different from, the preparation method of the dealuminzation overstable gamma zeolite carried heteropoly acid salt catalyst that catalytic activity and stability are high; Another object of the present invention is the application of the prepared catalyst of above-mentioned preparation method in acetate and n-butanol liquid-phase esterification.
It is generally acknowledged that it is heteropolyanion about 1nm that the micropore of zeolite is difficult to hold molecular diameter, so zeolite is very rarely seen as the research of heteropolyacid salt carrier.And the Y zeolite has big surface area and three-dimensional open-framework, includes the supercage of 1.3nm, is that the twelve-ring duct of 0.74nm links to each other by the aperture between the supercage.USY claims super steady Y again, be the product of ammonium type Y zeolite after hydrothermal treatment consists, be widely used as the catalyst of the catalytic cracking process of petroleum refining, further the duct of the USY after the dealuminzation modification obtains mediation, and be rich in more secondary mesopore, common infusion process just can make phosphotungstic acid be easy to enter and be dispersed in the secondary pore, and because removing and the wash-out of the outer aluminium of skeleton of part aluminium species can reduce the destruction that it brings heteropolyanion.Although interacting, heteropoly acid and zeolite surface group may cause the acidity of catalyst to have a spot of loss, but in fact because the interaction between heteropolyacid salt and the carrier dealuminzation USY, and the constraint effect in duct, make loading on this carrier that it can be comparatively firm, add the slightly solubility of heteropolyacid salt, even so in polar reaction, tangible heteropoly acid solution-off phenomenon does not take place yet, thereby the zeolite-loaded heteropolyacid salt catalyst of the USY behind the dealuminzation has obvious prospects for commercial application.
The present invention has prepared the zeolite-loaded heteropolyacid salt catalyst of dealuminzation USY, and The effect the catalytic performance of such catalyst in acetate and n-butanol liquid-phase esterification.
The objective of the invention is to realize by following scheme:
The preparation method of a kind of dealuminzation overstable gamma zeolite (Dealuminated Ultra-Stable Y Zeolite) carried heteropoly acid salt may further comprise the steps:
1) taking by weighing granularity is above overstable gamma zeolite (USY) zeolite (the Zhou village catalyst plants of 200 orders, n (Si)/n (Al)=8.2) in container, with weight ratio is 1: the ratio of (0.8～5) is mixed with deionized water, is mixed and pinch the formation pastel, adding crucible cover then is put in the Muffle furnace, be rapidly heated to 500～900 ℃ with 10～15 ℃/minute heating rates, handled 2～10 hours down from water vapour (self-steaming) environment, take out sample, the cooling back is at H
+Ion concentration is in the aqueous acid of 0.1～5mol/L, and diafiltration is 1～10 hour under 60～100 ℃ temperature, after filtration, washing, drying and roasting, makes dealuminzation USY zeolite, is designated as DUSY.
2) will contain Cs
+, NH
4 +Or K
+Being mixed with molar concentration etc. the cationic solubility nitrate of target or carbonate is 0.025～0.5mol/L aqueous solution, solid impregnating with the step 1) acquisition, stirred 5～24 hours down in 20～25 ℃, at 60～95 ℃, 0.05 under the condition of～1atm with the moisture evaporate to dryness, in Muffle furnace in 300～600 ℃ of roastings 3～8 hours.
3) take by weighing a certain amount of heteropoly acid (analyzing pure), be dissolved into and be made into the solution that concentration is 0.002～1mol/L in the solvent, with step 2) solid impregnating that obtains, stirred 5～24 hours down in 20～25 ℃, then with the suspension of gained at 60～100 ℃, with the solvent evaporate to dryness, under 20～25 ℃, further dry under the condition of 0.05～1atm, in Muffle furnace,, get the heteropolyacid salt catalyst of dealuminzation USY load in 150～400 ℃ of roastings 3～10 hours.
Weight ratio when wherein raw material USY mixes with deionized water is preferably 1: (1～3); The molar concentration of contained target cationic solution is preferably 0.1～0.3mol/L; USY is preferably 600～800 ℃ from the steam treatment temperature in the step 1); Preferred H
+The concentration of ion is between 1～3mol/L, 70～90 ℃ following processing 2～5 hours; Flooded the DUSY of soluble-salt, preferred sintering temperature is 450～550 ℃, 4～6 hours time.In the step 3), preferred suspension is at 80～95 ℃, and with the solvent evaporate to dryness, the sintering temperature of catalyst is 200～300 ℃, time 3～6h under the condition of 0.1～0.4atm.The used solvent of preparation heteropoly acid solution is water, methyl alcohol, ethanol, n-butanol, acetone or ether, heteropoly acid is to be contained oxygen polyacid, preferred 12 phosphotungstic acids, 12 phosphomolybdate or 12 silico-tungstic acids by the hetero atom that comprises P, Si, Fe, Co and the polyatom that comprises Mo, W, V by what the coordination of oxygen atom bridging constituted.
X-ray diffraction spectrogram in the accompanying drawing demonstrates the still fine crystal structure that keeps the Y zeolite of dealuminzation overstable gamma zeolite carrier that the dealuminzation modification from the method for steam treatment associating pickling overstable gamma zeolite carried out with using of describing of the present invention obtains, load thereon up to 30% phosphotungstic acid or phosphotungstic acid cesium salt after, heteropoly compound still can be on carrier high degree of dispersion, and carrier structure remains intact.
Esterification is carried out in the three-neck flask that has magnetic stirring apparatus, water knockout drum and reflux condensing tube.Reaction raw materials is acetate (Shanghai chemical reagents corporation of Chinese Medicine group analyzes pure) and n-butanol (Shanghai Ling Feng chemical reagent Co., Ltd analyzes pure), and catalyst grain size is greater than 200 orders.Raw material joins in the three-neck flask with certain proportioning (mol ratio is 1: 1～1.2) and the catalyst that accounts for reaction system mass fraction 2.3～3.6%, reactant liquor is heated to 100～110 ℃, pick up counting when treating to begin backflow phenomenon to occur in the reflux, till no longer including moisture to the water knockout drum and going out.Product is regularly taken out from reactor by syringe, SP-6800A gas chromatograph by Shandong southern Shandong analytical instrument factory is analyzed, chromatographic column is 15 a meters long FFAP capillary column, detector is a flame ionization ditector, 65 ℃～115 ℃ of column temperatures (after 2 minutes, rise to 115 ℃ in 65 ℃ of constant temperature, and kept 2 minutes) with 25 ℃/minute speed, carry out quantitatively with external standard method, calculate the conversion ratio of n-butanol.
Advantage of the present invention:
(1) the present invention proposes first with the carrier of zeolite as heteropolyacid salt, the catalyst activity component can be firm load on the carrier, even in acetate and this strong polar reaction of n-butanol liquid phase esterification, tangible solution-off phenomenon does not take place in the active component heteropolyacid salt yet, and catalyst only need leave standstill with regard to separable recovery after reaction;
(2) adopt method provided by the invention, heteropolyacid salt original position on carrier is synthetic carries out simultaneously with load, the activated centre also can reach high degree of dispersion on dealuminzation USY when the high capacity amount, thereby obtains good catalytic effect in reaction, and the ester productive rate can reach 98.6%;
(3) method for preparing catalyst provided by the present invention is simple, be convenient to operation, and it is also lower than the sol-gal process cost to utilize this method to prepare loaded catalyst, has tangible prospects for commercial application.
Description of drawings
Fig. 1: the XRD spectra of part typical catalyst sample.
The specific embodiment
Following example will be described the present invention, but therefore scope of the present invention not limited to some extent.
Example 1
30%Cs
1H
2PW
12O
40/ DUSY-650 ℃ of Preparation of catalysts
(1) takes by weighing 100g USY zeolite in crucible, add the 120g deionized water and fully mix, add a cover then and be put in the Muffle furnace, be rapidly heated to 650 ℃ with the speed of 15 ℃/min, this roasting temperature 4 hours, take out sample, after the cooling, diafiltration 2 hours under 95 ℃ temperature in the HCl of 2mol/L solution, deionized water filtration washing three times, in 110 ℃ of dryings,, promptly get dealuminzation overstable gamma zeolite (DUSY-650 ℃) again 500 ℃ of roastings 8 hours.
(2) 0.457g cesium carbonate (analyzing pure) being mixed with concentration is the 0.028mol/L aqueous solution, with 21gDUSY-650 ℃ of sample mix taking from step (1), stirred 12 hours under the room temperature, in temperature is 95 ℃, pressure be under the condition of 1atm with the moisture evaporate to dryness, in Muffle furnace, handled 4 hours in 500 ℃.
(3) (analyze purely, molecular formula is H with the 9.084g tungstophosphoric acid
3PW
12O
40.20H
2O, be abbreviated as PW) be made into the butanol solution that concentration is 0.003mol/L, then with sample mixed by step (2) gained, stirred 12 hours under the room temperature, then with the suspension of gained at 90 ℃,, dry down under the condition of 0.2atm in 110 ℃ with the solvent evaporate to dryness, 200 ℃ of following roastings 3 hours, promptly get 30%Cs again
1H
2PW
12O
40/ DUSY-650 ℃ of catalyst.
Example 2
30%Cs
1.5H
1.5PW
12O
40/ DUSY-650 ℃ of Preparation of catalysts
(1) treatment conditions of carrier and example 1 are in full accord.
(2) with example 1 (2) term harmonization, difference is that the consumption of cesium carbonate changes 0.685g into.
(3) with example 1 (3) term harmonization.
Example 3
30%Cs
2HPW
12O
40/ DUSY-650 ℃ of Preparation of catalysts
(1) treatment conditions of carrier and example 1 are in full accord.
(2) with example 1 (2) term harmonization, difference is that the consumption of cesium carbonate changes 0.913g into.
(3) with example 1 (3) term harmonization.
Example 4
30%Cs
2.5H
0.5PW
12O
40/ DUSY-650 ℃ of Preparation of catalysts
(1) treatment conditions of carrier and example 1 are in full accord.
(2) with example 1 (2) term harmonization, difference is that the consumption of cesium carbonate changes 1.142g into.
(3) with example 1 (3) term harmonization.
Example 5
30%Cs
3H
0PW
12O
40/ DUSY-650 ℃ of Preparation of catalysts
(1) treatment conditions of carrier and example 1 are in full accord.
(2) with example 1 (2) term harmonization, difference is that the consumption of cesium carbonate changes 1.370g into.
(3) with example 1 (3) term harmonization
Example 6
Cs
2.5H
0.5PW
12O
40Preparation of catalysts
(1) take by weighing 4.075g cesium carbonate solid, being mixed with concentration is the 0.24mol/L aqueous solution.
(2) take by weighing the 32.42g tungstophosphoric acid, be made into the ethanolic solution that concentration is 0.1mol/L.
(3) under strong agitation, cesium carbonate solution dropwise is added drop-wise in the tungstophosphoric acid solution,, dry under 110 ℃ under the condition of 0.2atm then at 90 ℃ with the solvent evaporate to dryness, again 200 ℃ of following roastings 3 hours, promptly get Cs
2.5H
0.5PW
12O
40Catalyst.
Example 7
30% (NH
4)
2.5H
0.5PMo
12O
40/ DUSY-750 ℃ of Preparation of catalysts
(1) takes by weighing 100g USY zeolite in crucible, adding the 200g deionized water fully mixes, add a cover then and be put in the Muffle furnace, be rapidly heated to 750 ℃, take out sample after 4 hours at this roasting temperature with the speed of 12 ℃/min, after the cooling, diafiltration 2 hours under 92 ℃ temperature in the HCl of 3mol/L solution, deionized water filtration washing three times is in 120 ℃ of dryings, again in stove in 550 ℃ of roastings 6 hours, promptly get dealuminzation overstable gamma zeolite carrier (DUSY-750 ℃).
(2) 0.963g ammonium nitrate (analyzing pure) being mixed with concentration is the 0.028mol/L aqueous solution, mixing with 21gDUSY-750 ℃ that takes from step (1), stirred 12 hours under the room temperature, is 95 ℃ in temperature, pressure be under the condition of 1atm with the moisture evaporate to dryness, in Muffle furnace, handled 3 hours in 300 ℃.
(3) (analyze purely, molecular formula is H with the 10.703g phosphomolybdic acid
3PMo
12O
40.22H
2O) be made into the acetone soln that concentration is 0.003mol/L,, stirred 12 hours under the room temperature then with sample mixed by step (2) gained, then with the suspension of gained at 90 ℃,, dry down under the condition of 0.25atm in 120 ℃ with the solvent evaporate to dryness, 200 ℃ of following roastings 3 hours, promptly get 30% (NH again
4)
2.5H
0.5PMo
12O
40/ DUSY-750 ℃ of catalyst.
Example 8
30%K
2.5H
0.5SiW
12O
40/ DUSY-550 ℃ of Preparation of catalysts
(1) takes by weighing 50g USY zeolite in crucible, add the 140g deionization and fully mix, add a cover then and be put in the stove, be rapidly heated to 550 ℃ with the speed of 14 ℃/min, this roasting temperature 4 hours, take out sample, after the cooling, diafiltration 2 hours under 94 ℃ temperature in the HCl of 4mol/L solution, deionized water filtration washing three times, in 110 ℃ of dryings 12 hours,, promptly get dealuminzation overstable gamma zeolite (DUSY-550 ℃) again 550 ℃ of roastings 6 hours.
(2) 0.686g potash (analyzing pure) being mixed with concentration is the 0.035mol/L aqueous solution, mixing with 28gDUSY-550 ℃ that takes from step (1), stirred 12 hours under the room temperature, is 95 ℃ in temperature, pressure be under the condition of 1atm with the moisture evaporate to dryness, in Muffle furnace, handled 4 hours in 500 ℃.
(3) (analyze purely, molecular formula is H with the 13.360g silico-tungstic acid
3SiW
12O
40.24H
2O) be made into the diethyl ether solution that concentration is 0.042mol/L,, stirred 12 hours under the room temperature then with sample mixed by step (2) gained, then with the suspension of gained at 90 ℃,, dry down under the condition of 0.2atm in 110 ℃ with the solvent evaporate to dryness, at 200 ℃ of following roasting 3h, promptly get 30%K again
2.5H
0.5SiW
12O
40/ DUSY-550 ℃.
Comparative example 1
The USY zeolite
Take by weighing 10g USY (Zhou village catalyst plant, n (Si)/n (Al)=8.2) zeolite in crucible, be rapidly heated to 600 ℃ with the speed of 15 ℃/min, this roasting temperature 4 hours, take out sample, cooling is placed in the drier standby.
Comparative example 2
DUSY-650 ℃ of zeolite
Take by weighing 10g USY zeolite in crucible, add the 25g deionized water and fully mix, add a cover then and be put in the Muffle furnace, be rapidly heated to 650 ℃ with the speed of 14 ℃/min, this roasting temperature 4 hours, take out sample, after the cooling, diafiltration 2 hours under 95 ℃ temperature in the HCl of 2mol/L solution, deionized water filtration washing three times, in 110 ℃ of dryings,, promptly get DUSY-650 ℃ of zeolite again 500 ℃ of roastings 8 hours.
Comparative example 3
PW
(analyze purely, molecular formula is H with a certain amount of tungstophosphoric acid with Keggin structure
3PW
12O
40.20H
2O is abbreviated as PW) place Muffle furnace, 200 ℃ of following roastings 4 hours, take out sample, be placed in the drier standby.
Comparative example 4
30％PW/USY
(1) take by weighing 50g USY (Zhou village catalyst plant, n (Si)/n (Al)=8.2) zeolite in crucible, be rapidly heated to 650 ℃ with the speed of 15 ℃/min, take out sample at this roasting temperature after 4 hours, cooling is placed in the drier standby.
(2) taking by weighing 6.0g has the tungstophosphoric acid of Keggin structure (analyze purely, molecular formula is H
3PW
12O
40.20H
2O, be abbreviated as PW) be made into the aqueous solution that concentration is 0.01mol/L, with the 14g USY dipping of taking from step (1), at room temperature stirred 12 hours, then with the suspension of gained at 75 ℃,, dry down under the condition of 0.41atm in 110 ℃ with the solvent evaporate to dryness, 200 ℃ of following roastings 3 hours, promptly get the 30%PW/USY catalyst again.
Comparative example 5
30％PW/DUSY-500℃
(1) takes by weighing 100g USY zeolite in crucible, add the 300g deionized water and fully stir evenly, add a cover then and be put in the Muffle furnace, be rapidly heated to 500 ℃ with the speed of 13 ℃/min, this roasting temperature 5 hours, take out sample, after the cooling, diafiltration 2 hours under 96 ℃ temperature in the HCl of 2.5mol/L solution, deionized water filtration washing three times, in 110 ℃ of dryings,, promptly get dealuminzation overstable gamma zeolite (DUSY-500 ℃) again 500 ℃ of roastings 7 hours.
(2) in full accord with the step of comparative example 4 (2).
Comparative example 6
30％PW/DUSY-650℃
(1) acquisition of carrier is the same with the step of comparative example 2.
(2) in full accord with the step of comparative example 4 (2)
Comparative example 7
30％PW/DUSY-750℃
(1) takes by weighing 100g USY zeolite in crucible, add the 90g deionized water and fully mix, add a cover then and be put in the Muffle furnace, be rapidly heated to 750 ℃ with the speed of 11 ℃/min, this roasting temperature 4 hours, take out sample, after the cooling, diafiltration 2 hours under 96 ℃ temperature in the HCl of 2.8mol/L solution, deionized water filtration washing three times, in 110 ℃ of dryings,, promptly get dealuminzation overstable gamma zeolite (DUSY-750 ℃) again 500 ℃ of roastings 8 hours.
(2) in full accord with the step of comparative example 4 (2).
Comparative example 8
30％PW/DUSY-850℃
(1) takes by weighing 100g USY zeolite in crucible, it is even to add the 160g deionized water and stirring, adds a cover then to be put in the Muffle furnace, is rapidly heated to 850 ℃ with the speed of 10 ℃/min, this roasting temperature 4 hours, take out sample, after the cooling, diafiltration 2 hours under 95 ℃ temperature in the HCl of 3.6mol/L solution, deionized water filtration washing three times, in 110 ℃ of dryings,, promptly get dealuminzation overstable gamma zeolite (DUSY-850 ℃) again 500 ℃ of roastings 8 hours.
(2) in full accord with the step of comparative example 4 (2).
Comparative example 9
30％PW/DUSY-900℃
(1) takes by weighing 100g USY zeolite in crucible, it is even to add the 190g deionized water and stirring, adds a cover then to be put in the Muffle furnace, is rapidly heated to 900 ℃ with the speed of 14 ℃/min, this roasting temperature 4 hours, take out sample, after the cooling, diafiltration 2 hours under 91 ℃ temperature in the HCl of 3.0mol/L solution, deionized water filtration washing three times, in 110 ℃ of dryings,, promptly get this dealuminzation overstable gamma zeolite (DUSY-900 ℃) again 500 ℃ of roastings 8 hours.
(3) in full accord with the step of comparative example 4 (2).
Example 9
The prepared catalyst of this case expedition comparative example 1～9 is in the catalytic activity of acetate and n-butanol liquid-phase esterification.
Esterification is carried out in the three-neck flask that has magnetic stirring apparatus, water knockout drum and reflux condensing tube.Reaction raw materials is acetate (Shanghai chemical reagents corporation of Chinese Medicine group analyzes pure) and n-butanol (Shanghai Ling Feng chemical reagent Co., Ltd analyzes pure), and catalyst grain size is greater than 200 orders.Raw material joins in the three-neck flask with certain proportioning (mol ratio is 1: 1) and the catalyst that accounts for system quality mark 2.4%, reactant liquor is heated to 105 ℃, pick up counting when treating to begin backflow phenomenon to occur in the reflux, till no longer including moisture to the water knockout drum and going out.Product is regularly taken out from reactor by syringe, SP-6800A gas chromatograph by Shandong southern Shandong analytical instrument factory is analyzed, chromatographic column is a 15m FFAP capillary column, detector is a flame ionization ditector, 65 ℃～115 ℃ of column temperatures (behind 65 ℃ of constant temperature 2min, rise to 115 ℃ with the speed of 25 ℃/min, and keep 2min), carry out quantitatively with external standard method, calculate the conversion ratio of n-butanol.Under this reaction condition, concerning all catalyst, only detected a kind of product of n-butyl acetate, that is to say that the conversion ratio of n-butanol can be represented the ester productive rate, the reaction result in the literary composition all obtains under above-mentioned typical reaction condition.
Table one
| Comparative example | Catalyst | Specific surface, m 2/g | The ester productive rate, % |
| Comparative example 1 comparative example 2 comparative examples 3 comparative examples 4 comparative examples 5 comparative examples 6 comparative examples 7 comparative examples 8 comparative examples 9 | USY DUSY-650 PW 30％PW/USY 30％PW/DUSY-550℃ 30％PW/DUSY-650℃ 30％PW/DUSY-750℃ 30％PW/DUSY-850℃ 30％PW/DUSY-900℃ | 645 716 6.0 382 422 466 436 355 312 | 24.6％ 49.6％ 69.4％ 31.7％ 76.8％ 86.4％ 81.2％ 77.2％ 71.3％ |
By table one as can be seen, the catalytic activity of pure USY is relatively poor, and the ester productive rate has only 24.6%, though load mass fraction be behind 30% the phosphotungstic acid, active improve still not obvious.USY (is example with DUSY-650 ℃) through dealuminzation, itself catalytic activity is compared with pure USY just 1 times raising, corresponding ester productive rate is 49.6%, if the phosphotungstic acid of load same amount again, be shown in comparative example 6---30%PW/DUSY-650 ℃, activity of such catalysts has great raising again, and is higher than the ester productive rate of the pure PW correspondence of comparative example 3---.Although the ester productive rate of other condition dealuminzation USY load phosphotungstic acid catalyst correspondence is also apparently higher than comparative example 4 pairing not dealuminzation USY load 30wt% phosphotungstic acid catalysts, but 30%PW/DUSY-650 ℃ of catalyst of comparative example 6 correspondences shows best catalytic activity, and corresponding ester productive rate reaches 86.4%.This explanation carrier dealuminzation has significant effects to improving activity of such catalysts, and utilizes this experimental technique, and there are optimal conditions in the carrier dealuminzation, this condition be 650 ℃ from steam treatment and hydrochloric acid diafiltration.
Example 10
The prepared catalyst of this case expedition example 1～8 is to the effect of acetate and n-butanol liquid-phase esterification.
Reaction and analysis condition and example 9 are just the same.
As shown in Table 2, DUSY-650 ℃ of load phosphotungstic acid cesium salt catalyst all has catalytic activity preferably, especially 30%Cs
2.5H
.05PW
12O
40/ DUSY-650 ℃ of optimum the catalytic activity of catalyst performance, its corresponding ester productive rate is 98.6%, not only apparently higher than the cesium salt catalyst of other form, the heteropolyacid salt catalyst that is higher than other cationic form, also be higher than corresponding carried heteropoly acid catalyst in the table one, be 30%PW/DUSY-650 ℃, corresponding ester productive rate.
Table two
| Example | Catalyst | Specific surface, m 2/g | The ester productive rate, % |
| Example 1 example 2 examples 3 examples 4 examples 5 examples 6 examples 7 examples 8 | 30％Cs 1H 2PW 12O 40/DUSY-650℃ 30％Cs 1.5H 1.5PW 12O 40/DUSY-650℃ 30％Cs 2HPW 12O 40/DUSY-650℃ 30％Cs 2.5H .05PW 12O 40/DUSY-650℃ 30％Cs 3H 0PW 12O 40/DUSY-650℃ Cs 2.5H 0.5PW 12O 40 30％(NH 4) 2.5H 0.5PMo 12O 40/DUSY-750℃ 30％K 2.5H 0.5SiW 12O 40/DUSY-550℃ | 530 527 512 496 441 154 480 436 | 89.4 84.2 81.3 98.6 78.7 61.2 90.1 88.4 |
Example 11
This example is to 30%PW/DUSY-650 ℃ and 30%Cs
2.5H
.05PW
12O
40The stability of/DUSY-650 ℃ of catalyst compares.
Reaction and analysis condition and example 9 are just the same.After difference is that each reaction finishes, by the method for centrifugation catalyst is separated from reactant liquor and to reclaim out,, be directly used in and react next time without any processing.Catalyst has small loss in reclaiming transfer process, do not add raw catelyst when being used for reacting next time.
As shown in Table 3, after catalyst is reused 5 times, the ester productive rate of 30%PW/DUSY-650 ℃ of correspondence drops to 47.6%, than fresh catalyst, activity has nearly descended half, and the repeated use along with catalyst is described, active constituent PW constantly from the carrier solution-off get off and run off, cause catalyst activity reduction, the stable bad of this carried heteropoly acid catalyst is described.And catalyst 30%Cs
2.5H
.05PW
12O
40/ DUSY-650 ℃ reuse 5 times after, still show 81.6% higher catalytic activity, should be noted that, each post catalyst reaction activity all has decline slightly, the loss of catalyst in reclaiming transfer process is one of the main reasons, the stability of this explanation catalyst itself better, with the carrying out of reaction, active component phosphotungstic acid cesium salt difficult from the carrier solution-off get off.This result shows, this method for preparing catalyst preferably resolves the supported heteropoly compound catalyst activity component problem that easily solution-off is got off from the carrier, is a kind of solid acid catalyst with obvious prospects for commercial application.
Table three
| Catalyst | 30％PW/DUSY-650℃ | 30％Cs 2.5H .05PW 12O 40/DUSY-650℃ | ||||||||
| Reaction times | 1 | 2 | 3 | 4 | 5 | 1 | 2 | 3 | 4 | 5 |
| The ester productive rate, % | 86.4 | 80.2 | 66.2 | 53.4 | 47.6 | 98.6 | 93.5 | 90.4 | 87.4 | 81.6 |
Claims (12)
1, a kind of preparation method who is used for the dealuminzation overstable gamma zeolite carried heteropoly acid salt catalyst of acetate and n-butanol liquid-phase esterification, its step comprises:
A. taking by weighing granularity is that the above overstable gamma zeolite of 200 orders is in container, be that alunite is mixed, mixed to 1: 0.8～5 ratio with deionized water with weight ratio, heating rate with 10～15 ℃/min is rapidly heated to 500～900 ℃ then, under water vapor, handling 2～10 hours, take out sample, the cooling back is in H
+Ion concentration is in the aqueous acid of 1～5mol/L, and diafiltration is 1～10 hour under 60～100 ℃ temperature, after filtration, washing, drying and roasting, the dealuminzation overstable gamma zeolite;
B. will contain Cs
+, NH
4 +Or K
+It is 0.025～0.5mol/L aqueous solution that cationic solubility nitrate of target or carbonate are mixed with molar concentration, the solid of step a acquisition is put into this aqueous solution to be flooded, stirred 5～24 hours down in 20～25 ℃, at 60～95 ℃, 0.05 under the condition of～1atm with the moisture evaporate to dryness, in Muffle furnace in 300～600 ℃ of roasting temperatures 3～8 hours;
C. take by weighing the pure heteropoly acid of a certain amount of analysis, be dissolved into and be made into the solution that concentration is 0.002～1mol/L in the solvent, the solid of step b acquisition is put into this solution to be flooded, 20～25 ℃ were stirred 5～24 hours down, then with the suspension of gained at 60～100 ℃, with the solvent evaporate to dryness, under 20～25 ℃, further dry under the condition of 0.05～1atm, in stove,, promptly get the heteropolyacid salt catalyst of dealuminzation overstable gamma zeolite load in 150～400 ℃ of roastings 3～10 hours;
Wherein said heteropoly acid is to be contained the oxygen polyacid by hetero atom P, Si, Fe or Co and polyatom Mo, W or V by what the coordination of oxygen atom bridging constituted.
2, preparation method according to claim 1 is characterized in that among the step a that the weight ratio when overstable gamma zeolite mixes with deionized water is 1: 1～3.
3, preparation method according to claim 1, the molar concentration that it is characterized in that containing the target cationic solution is 0.1～0.3mol/L.
4, preparation method according to claim 1, it is characterized in that among the step a overstable gamma zeolite from the steam treatment temperature between 600～800 ℃.
5, preparation method according to claim 1 is characterized in that, among the step a, and the H of described aqueous acid
+The concentration of ion is 1～3mol/L, and described diafiltration temperature is 70～90 ℃, and the diafiltration time is 2～5 hours.
6, preparation method according to claim 1 is characterized in that, among the step b, has flooded the dealuminzation overstable gamma zeolite of soluble-salt, and sintering temperature is 450～550 ℃, 4～6 hours time.
7, preparation method according to claim 1 is characterized in that, among the step c, the used solvent of preparation heteropoly acid solution is water, methyl alcohol, ethanol, n-butanol, acetone or ether.
8, preparation method according to claim 1 is characterized in that, among the step c, suspension is at 80～95 ℃, under the condition of 0.1～0.4atm with the solvent evaporate to dryness.
9, preparation method according to claim 1 is characterized in that, among the step c, the sintering temperature in stove is 200～300 ℃, 3～6 hours time.
10, preparation method according to claim 1 is characterized in that heteropoly acid is to be contained the oxygen polyacid by hetero atom P or Si and polyatom Mo or W by what the coordination of oxygen atom bridging constituted.
11, preparation method according to claim 1 is characterized in that heteropoly acid is 12 phosphotungstic acids, 12 phosphomolybdate or 12 silico-tungstic acids.
12, the prepared application of catalyst in acetate and n-butanol liquid-phase esterification of the described preparation method of claim 1.
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| KR101399376B1 (en) * | 2009-09-18 | 2014-05-27 | 아르끄마 프랑스 | Catalyst and process for preparing acrolein and/or acrylic acid by dehydration reaction of glycerin |
| US9988337B2 (en) | 2014-09-10 | 2018-06-05 | Council Of Scientific And Industrial Research | Single step process for the preparation of butyl acetate |
| CN108126751B (en) * | 2017-12-27 | 2020-11-24 | 中海油天津化工研究设计院有限公司 | Multi-stage pore molecular sieve supported heteropoly acid alkylation desulfurization catalyst and preparation method thereof |
| CN108435234A (en) * | 2018-04-26 | 2018-08-24 | 郑州大学 | Application of the molecular sieve carried heteropolyacid catalyst in cyclohexyl benzene synthesis |
| CN114956995A (en) * | 2021-02-25 | 2022-08-30 | 大加香料技术(天津)有限公司 | Preparation method of acetate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5110776A (en) * | 1991-03-12 | 1992-05-05 | Mobil Oil Corp. | Cracking catalysts containing phosphate treated zeolites, and method of preparing the same |
| US5866739A (en) * | 1993-11-19 | 1999-02-02 | Exxon Research And Engineering Company | Heteropoly salts or acid salts deposited in the interior of porous supports |
| CN1088625C (en) * | 1995-12-06 | 2002-08-07 | 南京师范大学 | Catalyst series for synthesizing 1-,2- and 3- substituted alkylphenols with different proportion by one-step process |
| CN1389545A (en) * | 2002-06-17 | 2003-01-08 | 中国科学院山西煤炭化学研究所 | Low temperaure catalyst for producing intermediate fraction oil with heavy alkane and its preparation method |
| CN1101265C (en) * | 1999-09-29 | 2003-02-12 | 中国石油化工集团公司 | Solid acid catalyst containing heteropoly acid and its preparing process |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5110776A (en) * | 1991-03-12 | 1992-05-05 | Mobil Oil Corp. | Cracking catalysts containing phosphate treated zeolites, and method of preparing the same |
| US5866739A (en) * | 1993-11-19 | 1999-02-02 | Exxon Research And Engineering Company | Heteropoly salts or acid salts deposited in the interior of porous supports |
| CN1088625C (en) * | 1995-12-06 | 2002-08-07 | 南京师范大学 | Catalyst series for synthesizing 1-,2- and 3- substituted alkylphenols with different proportion by one-step process |
| CN1101265C (en) * | 1999-09-29 | 2003-02-12 | 中国石油化工集团公司 | Solid acid catalyst containing heteropoly acid and its preparing process |
| CN1389545A (en) * | 2002-06-17 | 2003-01-08 | 中国科学院山西煤炭化学研究所 | Low temperaure catalyst for producing intermediate fraction oil with heavy alkane and its preparation method |
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