CN106000463A - Preparation method and application of immobilized cesium phosphotungstate catalyst - Google Patents
Preparation method and application of immobilized cesium phosphotungstate catalyst Download PDFInfo
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- CN106000463A CN106000463A CN201610366847.0A CN201610366847A CN106000463A CN 106000463 A CN106000463 A CN 106000463A CN 201610366847 A CN201610366847 A CN 201610366847A CN 106000463 A CN106000463 A CN 106000463A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract
The invention discloses an immobilized cesium phosphotungstate catalyst. Cesium phosphotungstate is introduced in the synthesis process of a metal-organic skeletal material UiO-66 to make the mass ratio of the active component cesium phosphotungstate to the metal-organic skeletal material UiO-66 in the metal organic skeletal immobilized cesium phosphotungstate catalyst reach 0.2-0.65 and the specific surface area of the immobilized catalyst reach 794-1045m<2>/g. A preparation method adopting one-step in situ synthesis can effectively prevent loss of the active site cesium phosphotungstate, so the physical and chemical stability of the catalyst is improved; the Keggin structure, the strong acidity and the oxidation reduction property of cesium phosphotungstate are well kept, so the catalyst has wide application range; adsorption and diffusion of reaction substances on the catalyst are facilitated, so the catalysis efficiency of the catalyst is increased; and the preparation method has the advantages of simplicity, easy operation, easy filtration and separation of the catalyst from products, no corrosion, and no pollution to environment.
Description
Technical field
The present invention relates to the catalyst of chemical field, especially relate to the system of a kind of immobilized Tricesium dodecatungstophosphate salt catalyst
Preparation Method, the invention still further relates to the application in preparation in Long carbon chain fatty glyceride of this catalyst.
Background technology
Phosphotungstic acid is a kind of polyoxometallate with structure with Keggin, has the dual of superpower acidity and oxidation-reduction quality
Characteristic.As a kind of superpower solid acid, (in nonaqueous solvent, its acid strength is sulfur to alternative overwhelming majority inorganic acid catalyst
100 times of acid), it is possible to for multiple acid catalyzed reaction.But, phosphotungstic acid is homogeneous catalyst, product last handling process
Loaded down with trivial details, pollute environment, it is impossible to recycle.Phosphotungstic acid cesium salt not only remains the highly acid of phosphotungstic acid, high activity, high selectivity
Etc. advantage, also there is undissolved advantage in water polar solvent, can use as heterogeneous catalyst.But, Tricesium dodecatungstophosphate
Salt specific surface area is little, it is impossible to providing abundant effective active site, catalytic efficiency is relatively low.To this end, can be by phosphotungstic acid cesium salt
Immobilized on porous carrier, make utilization easily separated, recyclable, repeatable and the novel solid acid catalyst of environmental protection.
Prepare the active charcoal of common carrier of multiphase solid acid catalyst, SiO at present2、TiO2, zeolite molecular sieve, macropore divide
Son sieve MCM-41, mesoporous molecular sieve SBA-15, Y-Al2O3、ZrO2, HMS, activated montmorillonite, ion exchange resin HRP-24 and
Metal-organic framework compound etc..Multiphase solid acid catalyst is applied in multiple organic chemical reactions, such as: middle promulgated by the State Council
Bright patent application CN102950023 A discloses the carried phospho-tungstic acid catalyst of a kind of acrylic acid synthesizing N-butyl, and it is prepared
Method is in the butanol solution that the hollow ball mesoporous silicon oxide of activation joins phosphotungstic acid, stirring, through filtering and dry
After dry, obtain carried phospho-tungstic acid catalyst.Application for a patent for invention CN 104248971 A discloses a kind of synthesizing cyclohexanone third
The carried phospho-tungstic acid catalyst of triol ketal, its preparation method is by preparing spherical SiO 2 and silica gel complex carrier and phosphotungstic acid
In the presence of deionized water, it is spray-dried after being configured to slurry, makes phosphotungstic acid be supported on preparing spherical SiO 2 and silica gel is multiple
Close on carrier.Application for a patent for invention CN 103586076 A discloses the carried phospho-tungstic acid solid of a kind of synthesizing ethyl acetate and urges
Agent, its preparation method is by sphericity mesoporous silicon dioxide carrier ball milling together with phosphotungstic acid, makes phosphotungstic acid be supported on described ball
On shape meso-porous titanium dioxide silicon carrier.Application for a patent for invention CN 103041863 A discloses a kind of phosphotungstic acid preparing ethyl acetate
Catalyst, its preparation method is to be immersed in phosphotungstic acid aqueous solution by metal-organic framework compound, then roasting make metal-
Organic backbone load phosphotungstic acid catalyst.Application for a patent for invention CN104437645 A disclose the metal of a kind of synthesis of glutaraldehyde-
Organic backbone solid-carrying heteropolyacid catalyst, its preparation method is by p-phthalic acid H2And ZrCl (BDC)4It is dissolved in DMF (N, N-bis-
Methyl methylamine) in, after stirring and dissolving, it is sequentially added into concentrated hydrochloric acid and phosphotungstic acid stirring and evenly mixing, filtration washing after crystallization, dries and live
Change the immobilized phosphotungstic acid heterogeneous catalyst preparing different loads amount.Application for a patent for invention CN102146296 A discloses a kind of use
In oxidation sweetening can Magneto separate carried phospho-tungstic acid cesium salt catalyst, its preparation method is first by silica gel coated magnetic Fe3O4System
For going out magnetic carrier, then by cesium carbonate aqueous solution and magnetic carrier stirring dipping, prepare the magnetic carrier of load cesium carbonate,
After by its stirring reaction with phosphotungstic acid aqueous solution, preparing can Magneto separate carried phospho-tungstic acid cesium salt catalyst.Above-mentioned prepared
The shortcomings such as it is little that catalyst exists active force, poor chemical stability, and recycling effect is undesirable.
Middle Long carbon chain fatty glyceride is a kind of structured lipid low in calories, can directly be entered by portal vein after digestive tract absorbs
Enter liver, and decomposition and inversion becomes energy at short notice, do not result in hoarding of body fat, thus reach prevention and have related disorders
Effect.Middle Long carbon chain fat emulsion injection has been widely used for medical treatment aspect, be a kind of energy for intravenous drip with
Supplementary.Middle long-chain fat acid lipid is approved as new resource food by Ministry of Public Health, and it can be used to produce low in calories cooking
Prepare food with health-care edible oil and typical local food such as oils and fats, cheese low in calories, ice creams.With animal and plant fat and free medium-chain fatty acid
For raw material, middle long-chain fat acid lipid can be produced by acid hydrolyzation, be divided into enzyme process and chemistry according to the difference of used catalyst
Method.Enzyme process is to be catalyzed the replacement of acyl group in vegetable and animals oils triglyceride under mild conditions with various lipases, makes middle chain fat
Fat acid is combined in the triglyceride skeleton of raw oil material (Chnadhapuram M, Sunkireddy Y R.
Preparation of palm olein enriched with medium chain fatty acids by lipase
Acidolysis [J]. Food Chemistry, 2012,132 (1): 216 221).But, lipase is expensive, and trip
Poor from the reusing of enzyme, cause production cost higher, and the product component obtained is more complicated, a good appetite suddenly appearing in a serious disease long-chain fatty acid oil
Outside fat, also diglyceride, monoglyceride and raw oil material, cumbersome isolated and purified process need to be used (to see Chinese invention
Patent " isolation and purification method of a kind of middle chain fatty acid triglycerides ", application number 2012100042302.6).
Summary of the invention
It is an object of the invention to provide a kind of be catalyzed activity good, reusing is good, physics and chemical stability high
The preparation method of immobilized Tricesium dodecatungstophosphate salt catalyst, the present invention also provides for this catalyst Long carbon chain fatty acid glycerine in preparation
Application in the oils and fats acidolysis reaction of ester.
For achieving the above object, the present invention can take following technical proposals:
The preparation method of immobilized Tricesium dodecatungstophosphate salt catalyst of the present invention comprises the steps:
The first step, takes the cesium carbonate (Cs of certain mass respectively2CO3) and phosphotungstic acid (H3PW12O40) it is made into the water-soluble of respective concentration
Liquid, and at room temperature cesium carbonate solution is added drop-wise in Salkowski's solution with the speed of 0.1 mL/min ~ 2 mL/min, drip
Rear continuation stirs 8h, is aged 6 ~ 18h then at left at room temperature；Then slow evaporation moisture at a temperature of 323 K, the white obtained
Solid dries 12h at a temperature of 383 K, then at 473 ~ 673K roasting temperature 2h, obtains phosphotungstic acid cesium salt
(Cs2.5H0.5PW12O40) standby；
Wherein the concentration of aqueous solution of cesium carbonate is 0.25 mol/L, and the concentration of aqueous solution of phosphotungstic acid is 0.08 mol/L, the two
Mol ratio is cesium carbonate: phosphotungstic acid=5:4；
Second step, by a certain amount of p-phthalic acid (H2) and Zirconium tetrachloride. (ZrCl (BDC)4) join a certain amount of N, N-bis-
In methylformamide (DMF), magnetic force strong agitation at 10 ~ 50 DEG C；It is subsequently adding concentrated hydrochloric acid, stirs 1 ~ 3h；Add appropriate
Phosphotungstic acid cesium salt prepared by one step, continues stirring 1 ~ 3h；Then crystallization 10 ~ 60h at a temperature of 90 ~ 160 DEG C；Filter, take out solid
Body thing, and washing respectively repeatedly with DMF and methanol, finally dries the solid after washing, at a temperature of 120 ~ 250 DEG C, activate 6 ~
24h, obtaining containing phosphotungstic acid cesium salt 20 ~ 65%, specific surface area is 794-1045m2Finished catalyst (the UiO-66-of/g
Cs2.5H0.5PW12O40)；
Wherein, the mol ratio of p-phthalic acid and Zirconium tetrachloride. is 2 ~ 1, DMF with Zirconium tetrachloride. mole
Ratio is 40 ~ 130, and concentrated hydrochloric acid is 1 ~ 3 with the mol ratio of p-phthalic acid.
In the described first step, the drop rate of cesium carbonate solution is 1 mL/min, and the still aging time is 12h, sintering temperature
For 573K.
In described second step, whipping temp is 30 ~ 40 DEG C, and adding the mixing time after phosphotungstic acid cesium salt is 2 ~ 3h, crystallization temperature
Degree is 110 ~ 140 DEG C, and crystallization time is 20 ~ 40h, catalyst activation temperature 150 ~ 220 DEG C, soak time 8 ~ 16h.
Immobilized Tricesium dodecatungstophosphate salt catalyst prepared by the present invention is Long carbon chain fatty acid in prepared by Vegetable oil lipoprotein acidolysis
Glyceride.By soybean oil and medium-chain fatty acid (octanoic acid and the capric acid) mix homogeneously of certain proportioning, it is heated to uniform temperature, then adds
Enter the solid acid catalyst of preparation, under agitation react certain time.After reaction terminates, add normal hexane, by product negative pressure
Sucking filtration, and normal hexane potassium hydroxide-ethanol solution is carried out alkali cleaning, then wash with saturated aqueous common salt, decompression just boils off
Hexane, available purification structure fat.Filter cake with normal hexane, methanol and ether washing, removes adsorbing contaminant on catalyst successively, then
Putting it in vacuum drying oven negative pressure drying 12h at a temperature of 70 DEG C, the recovery catalyst obtained can be used for acidolysis reaction next time.
Compared with long-chain fat acid glyceride in traditional enzyme catalysis oils and fats acidolysis preparation (Food Chemistry, 2012,132
(1): 216 221), this solid acid catalysis method have that catalysis activity is high, reusing is good, the response time is short, selectivity is good and
The advantages such as product impurity is few, are the structured lipid production methods of a kind of green environment close friend.
Metal-organic framework UiO-66 carrier has the 3D cubic pore structure of rigidity, by eight-coordinate ZrO6(OH)2Six aggressiveness
The polymer composition being connected to form with 12 p-phthalic acids, have higher specific surface area, heat stability, chemical stability and
Mechanical performance, catalytic active center is attached on metal-organic framework compound UiO-66 by the present invention by in-situ synthesis,
The solid acid catalyst UiO-66-Cs prepared2.5H0.5PW12O40There is higher activity and stability.Its advantage specifically embodies
:
1) preparation method of the present invention uses a step fabricated in situ, can effectively prevent the loss of active center phosphotungstic acid cesium salt, improves
The physics of catalyst and chemical stability；
2) finished catalyst prepared by the present invention preferably maintains the structure with Keggin of phosphotungstic acid cesium salt and highly acid and oxygen
Changing the double grading of reproducibility, range of application is relatively wide, and after load, its characteristic is constant, thus ensures that this catalyst has higher urging
Change activity；
3) finished catalyst prepared by the present invention maintains the framing structure of metal-organic framework UiO-66, and specific surface area is big, hole
Footpath is homogeneous, and active component is uniformly dispersed；This high-specific surface area and loose structure, can make active catalyst sites high degree of dispersion,
Be conducive to reacting substance adsorption and diffusion on a catalyst, reduce resistance to mass tranfer, thus improve the catalytic efficiency of catalyst；
4) catalyst prepared by the present invention does not dissolves in polar solvent, can be applicable to be catalyzed in highly polar medium all kinds of organic reaction,
And the long period can be used；
5) the catalyst decomposition temperature that prepared by the present invention is about 500oAbout C, high temperature resistant, physical stability is good, it is easy to preserve not
Rotten；
6) the catalyst preparation simplicity that prepared by the present invention, method is simple, it is easy to operation, is prone to filter with product separate after reaction,
Non-corrosiveness, environmentally safe.
Accompanying drawing explanation
Fig. 1 is the IR spectrogram of catalyst prepared by the present invention.
Fig. 2 is the XRD spectra of catalyst prepared by the present invention.
Fig. 3 is the nitrogen adsorption desorption figure of catalyst prepared by the present invention.
Fig. 4 is the SEM spectrogram of catalyst prepared by the present invention.
Fig. 5 is the TG spectrogram of catalyst prepared by the present invention.
Detailed description of the invention
Immobilized Tricesium dodecatungstophosphate salt catalyst of the present invention, by synthesis metal-organic framework materials UiO-66
During introduce Tricesium dodecatungstophosphate so that in the Tricesium dodecatungstophosphate catalyst that the metallic organic framework prepared is immobilized, active component
Phosphotungstic acid cesium salt reaches 0.2 ~ 0.65 with the mass ratio of metal-organic framework UiO-66；The specific surface area of solid-carried catalyst reaches
794-1045m2/g。
Fig. 1 is the IR spectrogram of catalyst prepared by the present invention.It will be seen from figure 1 that UiO-66-prepared by the present invention
Cs2.5H0.5PW12O40Catalyst has typical characteristic peak 1080 cm of structure with Keggin-1 (P-O) 、984 cm-1 (W=O) 、
889 cm -1With 800 cm-1(W-O-W), it is respectively belonging to P-O stretching vibration in the tetrahedron of center, terminal W=O stretching vibration,
W-Ob-W stretching vibration and W-Oc-W stretching vibration, wherein ObAnd OcFor bridging oxygen in structure with Keggin.It addition, the UiO-of preparation
66-Cs2.5H0.5PW12O40Catalyst also has the typical characteristic peak of metal-organic framework structure UiO-66 carrier, at 1657cm-1
The characteristic peak at place can belong in p-phthalic acid the absorption of vibrations of C=O bond C=O in carboxyl, at 1400cm-1The characteristic peak at place
The stretching vibration peak of COO-, 700-400 cm in p-phthalic acid can be attributed in organic ligand-1The characteristic peak at place can belong to
In COO-plane and out-of-plane bending vibration peak in p-phthalic acid, the characteristic peak that in phenyl ring, the vibration of C=C key causes exists
1505 cm-1With 1600 cm-1Place occurs, the eigen vibration peak of Zr-O is at 550 cm-1Place occurs, these the results of FT-IR are equal
Illustrate catalyst UiO-66-Cs prepared by a step in-situ synthesis2.5H0.5PW12O40Retaining metal-organic framework structured
While the framing structure of UiO-66 carrier, phosphotungstic acid cesium salt Cs2.5H0.5PW12O40Structure and characteristic do not change, be a kind of
Have the new catalyst of both structural advantages concurrently.
Fig. 2 is the XRD spectra of catalyst prepared by the present invention.From Figure 2 it can be seen that metal-organic framework structure UiO-66 carries
2 θ angles 7.4 °, 8.5 °, 12.1 °, 14.2 °, 17.1 °, 22.3 °, 25.7 °, 31.1 ° and the feature of 33.1 ° respectively in the spectrogram of body
Peak can be attributed to (111), (002), (022), (113), (004), (115), (224), (046) and (137) crystal face respectively and produce
Diffractive features absworption peak.After the load of phosphotungstic acid cesium salt, although its diffraction peak intensity reduces, basic and metal-organic framework
The characteristic absorption peak of structure UiO-66 carrier keeps consistent.The immobilized metal-organic framework that causes of this explanation phosphotungstic acid cesium salt
Crystal formation density increases, but does not produce metal-organic framework and significantly affect, and phosphotungstic acid cesium salt is the most immobilized has arrived gold
On genus-organic backbone UiO-66, and do not change the architectural feature of metal-organic framework.
Fig. 3 is the nitrogen adsorption desorption figure of catalyst prepared by the present invention.From the figure 3, it may be seen that metal-organic framework carrier
The N of UiO-662Adsorption isotherm belongs to the I type adsorption isotherm without hysteresis loop, it was demonstrated that it is poromerics.At carrier UiO-66
Middle introducing Cs2.5H0.5PW12O40After, the adsorption isotherm type of sample does not change, but due to Cs2.5H0.5PW12O40?
Grain occupies in its micropore canals, causes UiO-66-Cs2.5H0.5PW12O40Sample is to N2Adsorbance less than UiO-66 pair, pure carrier
N2Adsorbance.Acidic cs salts of heteropolyacid Cs2.5H0.5PW12O40Specific surface area be 138m2/ g, the specific surface area of carrier UiO-66 is
1159m2/ g, 20% (w) UiO-66-Cs2.5H0.5PW12O40Specific surface area be 1045m2/ g, 35% (w) UiO-66-
Cs2.5H0.5PW12O40Specific surface area be 888m2/ g, 50% (w) UiO-66-Cs2.5H0.5PW12O40Specific surface area is 814m2/ g,
65%(w)UiO-66-Cs2.5H0.5PW12O40Specific surface area is 794m2/g.Along with the increase of Tricesium dodecatungstophosphate load capacity, UiO-66-
Cs2.5H0.5PW12O40The BET specific surface area of sample is gradually lowered, and pore volume is gradually lowered, and aperture is gradually increased, this be due to
A large amount of Cs2.5H0.5PW12O40Introducing and occupy in carrier duct, cause specific surface area and pore volume to reduce.But two kinds of samples
Aperture be more or less the same, this shows Cs2.5H0.5PW12O40Active component is highly dispersed in the duct of carrier, makes catalyst remain to
Enough show preferable catalytic performance.
Fig. 4 is the SEM spectrogram of catalyst prepared by the present invention.As shown in Figure 4, UiO-66-Cs2.5H0.5PW12O40Catalyst
Pattern similar to the pattern of metal-organic framework UiO-66, sample is all made up of uniform cube of symbiosis crystal, reunite exist
It is rendered as spherical particle together, shows that active specy is highly dispersed in UiO-66 such that it is able to ensure that this catalyst has relatively
Good catalytic performance.
Fig. 5 is the TG spectrogram of catalyst prepared by the present invention.As shown in Figure 5, UiO-66-Cs2.5H0.5PW12O40TG bent
Line maintains the weight-loss curve feature of metal-organic framework substantially, and the sample weightless process when temperature is more than 500 DEG C is attributed to
In catalyst, metal-organic framework decomposes, caused by structure collapse.Active component Cs2.5H0.5PW12O40Introducing not do not change
The heat stability of metal-organic framework UiO-66, thus ensure the physical and chemical stability of this catalyst.Hot analysis result explanation
Solid catalyst keeps good stability when less than 500 DEG C.
Below by specific embodiment, the present invention done more detailed explanation.The most unless otherwise indicated, the present invention adopts
Reagent and equipment be the art routine commercial products.
Embodiment 1
The present invention immobilized Tricesium dodecatungstophosphate salt catalyst 20% (w) UiO-66-Cs2.5H0.5PW12O40Preparation method include following
Step:
The first step: active center Cs2.5H0.5PW12O40Preparation:
Take 1.00 g cesium carbonate (Cs respectively2CO3) and 7.07 g phosphotungstic acid (H3PW12O40) it is made into 0.25 mol/L and 0.08
The aqueous solution of mol/L, at room temperature, by Cs2CO3Solution is added dropwise to H3PW12O40In solution, speed is maintained at 1mL/min,
Magnetic force strong agitation 8h again, still aging 12h, then mixed liquor is slowly evaporated under the conditions of 50 DEG C；The white that will obtain again
Solid dries 12h, 573 K roasting 2 h in 383 K, obtains phosphotungstic acid cesium salt (Cs2.5H0.5PW12O40) standby.
Second step: catalyst 20% (w) UiO-66-Cs2.5H0.5PW12O40Preparation:
Reactor is placed in 35 DEG C of water baths, adds 80mL DMF (DMF) in the reactor, by 2.0g
P-phthalic acid H2And 2.8g ZrCl (BDC)4It is dissolved in DMF, after stirring and dissolving, then is added thereto to 1.5mL concentrated hydrochloric acid, stirring
3h, is subsequently adding 0.6g phosphotungstic acid cesium salt, continues stirring 2h, after mix homogeneously, above-mentioned reaction raw materials is proceeded to stainless steel reaction
In still, crystallization 30h at 120 DEG C, taking-up is filtered, washs, is dried.Before using, by its constant temperature activation at 180 DEG C in air atmosphere
10h, obtains 20% (w) UiO-66-Cs2.5H0.5PW12O40Catalyst, its BET specific surface area is 1045 m2/g。
Embodiment 2
The present invention immobilized Tricesium dodecatungstophosphate salt catalyst 35% (w) UiO-66-Cs2.5H0.5PW12O40Preparation method include following
Step:
The first step: with embodiment 1.
Second step: catalyst 35% (w) UiO-66-Cs2.5H0.5PW12O40Preparation:
Reactor is placed in 35 DEG C of water baths, adds 80mL DMF (DMF) in the reactor, by 2.0g
P-phthalic acid H2And 2.8g ZrCl (BDC)4It is dissolved in DMF, after stirring and dissolving, then is added thereto to 1.5mL concentrated hydrochloric acid, stirring
3h, is subsequently adding 1.05g phosphotungstic acid cesium salt, continues stirring 2h, after mix homogeneously, above-mentioned reaction raw materials is proceeded to rustless steel anti-
In answering still, crystallization 30h at 120 DEG C, taking-up is filtered, washs, is dried.Before using, by its constant temperature work at 180 DEG C in air atmosphere
Change 10h, obtain 35% (w) UiO-66-Cs2.5H0.5PW12O40Catalyst, its BET specific surface area is 888 m2/g。
Embodiment 3
The present invention immobilized Tricesium dodecatungstophosphate salt catalyst 50% (w) UiO-66-Cs2.5H0.5PW12O40Preparation method include following
Step:
The first step: with embodiment 1.
Second step: catalyst 50% (w) UiO-66-Cs2.5H0.5PW12O40Preparation:
Reactor is placed in 35 DEG C of water baths, adds 80mL DMF (DMF) in the reactor, by 2.0g
P-phthalic acid H2And 2.8g ZrCl (BDC)4It is dissolved in DMF, after stirring and dissolving, then is added thereto to 1.5mL concentrated hydrochloric acid, stirring
3h, is subsequently adding 1.5g phosphotungstic acid cesium salt, continues stirring 2h, after mix homogeneously, above-mentioned reaction raw materials is proceeded to stainless steel reaction
In still, crystallization 30h at 120 DEG C, taking-up is filtered, washs, is dried.Before using, by its constant temperature activation at 180 DEG C in air atmosphere
10h, obtains 50% (w) UiO-66-Cs2.5H0.5PW12O40Catalyst, its BET specific surface area is 814 m2/g。
Embodiment 4
The present invention immobilized Tricesium dodecatungstophosphate salt catalyst 65% (w) UiO-66-Cs2.5H0.5PW12O40Preparation method include following
Step:
The first step: with embodiment 1.
Second step: catalyst 65% (w) UiO-66-Cs2.5H0.5PW12O40Preparation:
Reactor is placed in 35 DEG C of water baths, adds 80mL DMF (DMF) in the reactor, by 2.0g
P-phthalic acid H2And 2.8g ZrCl (BDC)4It is dissolved in DMF, after stirring and dissolving, then is added thereto to 1.5mL concentrated hydrochloric acid, stirring
3h, is subsequently adding 1.95g phosphotungstic acid cesium salt, continues stirring 2h, after mix homogeneously, above-mentioned reaction raw materials is proceeded to rustless steel anti-
In answering still, crystallization 30h at 120 DEG C, taking-up is filtered, washs, is dried.Before using, by its constant temperature work at 180 DEG C in air atmosphere
Change 10h, prepare 65% (w) UiO-66-Cs2.5H0.5PW12O40Catalyst, its BET specific surface area is 794 m2/g。
Embodiment 5
By 0.85g(0.001mol) soybean oil, 0.72g(0.005mol) octanoic acid and 0.86g(0.005mol) capric acid joins
In 50mL round-bottomed flask, magnetic agitation under the conditions of 70 DEG C, negative pressure leaching removes water 30min, adds 35% (w) UiO-66-
Cs2.5H0.5PW12O40Catalyst 0.219g, stir speed (S.S.) 250rpm, reaction temperature 160 DEG C, react 10h.To product after having reacted
Thing purification, first with n-hexane dissolution, negative pressure leaching goes out solid catalyst, to normal hexane mutually with the potassium hydroxide-ethanol solution of 0.8M
Carry out alkali cleaning, wash with saturated aqueous common salt, decompression distillation, obtain purification structure lipid, after esterification, use gas chromatograph
Measuring octanoic acid combination rate is 20.3%, and capric acid combination rate is 25.4%, and total medium-chain fatty acid combination rate is 45.7%.
Embodiment 6
By 0.85g(0.001mol) soybean oil, 0.72g(0.005mol) octanoic acid and 0.86g(0.005mol) capric acid joins
In 50mL round-bottomed flask, magnetic agitation under the conditions of 70 DEG C, negative pressure leaching removes water 30min, adds 20% (w) UiO-66-
Cs2.5H0.5PW12O40Catalyst 0.219g, stir speed (S.S.) 250rpm, reaction temperature 160 DEG C, react 10h.To product after having reacted
Thing purification, first with n-hexane dissolution, negative pressure leaching goes out solid catalyst, to normal hexane mutually with the potassium hydroxide-ethanol solution of 0.8M
Carry out alkali cleaning, wash with saturated aqueous common salt, decompression distillation, obtain purification structure lipid, after esterification, use gas chromatograph
Measuring octanoic acid combination rate is 15.3%, and capric acid combination rate is 18.1%, and total medium-chain fatty acid combination rate is 33.4%.
Embodiment 7
By 0.85g(0.001mol) soybean oil, 0.72g(0.005mol) octanoic acid and 0.86g(0.005mol) capric acid joins
In 50mL round-bottomed flask, magnetic agitation under the conditions of 70 DEG C, negative pressure leaching removes water 30min, adds 50% (w) UiO-66-
Cs2.5H0.5PW12O40Catalyst 0.219g, stir speed (S.S.) 250rpm, reaction temperature 160 DEG C, react 10h.To product after having reacted
Thing purification, first with n-hexane dissolution, negative pressure leaching goes out solid catalyst, to normal hexane mutually with the potassium hydroxide-ethanol solution of 0.8M
Carry out alkali cleaning, wash with saturated aqueous common salt, decompression distillation, obtain purification structure lipid, after esterification, use gas chromatograph
Measuring octanoic acid combination rate is 21.4%, and capric acid combination rate is 26.2%, and total medium-chain fatty acid combination rate is 47.6%.
Embodiment 8
By 0.85g(0.001mol) soybean oil, 0.72g(0.005mol) octanoic acid and 0.86g(0.005mol) capric acid joins
In 50mL round-bottomed flask, magnetic agitation under the conditions of 70 DEG C, negative pressure leaching removes water 30min, adds 65% (w) UiO-66-
Cs2.5H0.5PW12O40Catalyst 0.219g, stir speed (S.S.) 250rpm, reaction temperature 160 DEG C, react 10h.To product after having reacted
Thing purification, first with n-hexane dissolution, negative pressure leaching goes out solid catalyst, to normal hexane mutually with the potassium hydroxide-ethanol solution of 0.8M
Carry out alkali cleaning, wash with saturated aqueous common salt, decompression distillation, obtain purification structure lipid, after esterification, use gas chromatograph
Measuring octanoic acid combination rate is 21.6%, and capric acid combination rate is 26.5%, and total medium-chain fatty acid combination rate is 48.1%.
Embodiment 9
By 0.85g(0.001mol) soybean oil, 0.72g(0.005mol) octanoic acid and 0.86g(0.005mol) capric acid joins
In 50mL round-bottomed flask, magnetic agitation under the conditions of 70 DEG C, negative pressure leaching removes water 30min, adds 35% (w) UiO-66-
Cs2.5H0.5PW12O40Catalyst 0.219g, stir speed (S.S.) 250rpm, reaction temperature 100 DEG C, react 10h.To product after having reacted
Thing purification, first with n-hexane dissolution, negative pressure leaching goes out solid catalyst, to normal hexane mutually with the potassium hydroxide-ethanol solution of 0.8M
Carry out alkali cleaning, wash with saturated aqueous common salt, decompression distillation, obtain purification structure lipid, after esterification, use gas chromatograph
Measuring octanoic acid combination rate is 4.6%, and capric acid combination rate is 5.9%, and total medium-chain fatty acid combination rate is 10.5%.
Embodiment 10
By 0.85g(0.001mol) soybean oil, 0.72g(0.005mol) octanoic acid and 0.86g(0.005mol) capric acid joins
In 50mL round-bottomed flask, magnetic agitation under the conditions of 70 DEG C, negative pressure leaching removes water 30min, adds 35% (w) UiO-66-
Cs2.5H0.5PW12O40Catalyst 0.219g, stir speed (S.S.) 250rpm, reaction temperature 140 DEG C, react 10h.To product after having reacted
Thing purification, first with n-hexane dissolution, negative pressure leaching goes out solid catalyst, to normal hexane mutually with the potassium hydroxide-ethanol solution of 0.8M
Carry out alkali cleaning, wash with saturated aqueous common salt, decompression distillation, obtain purification structure lipid, after esterification, use gas chromatograph
Measuring octanoic acid combination rate is 13.6%, and capric acid combination rate is 14.6%, and total medium-chain fatty acid combination rate is 29.9%.
Embodiment 11
By 0.85g(0.001mol) soybean oil, 0.72g(0.005mol) octanoic acid and 0.86g(0.005mol) capric acid joins
In 50mL round-bottomed flask, magnetic agitation under the conditions of 70 DEG C, negative pressure leaching removes water 30min, adds 35% (w) UiO-66-
Cs2.5H0.5PW12O40Catalyst 0.122g, stir speed (S.S.) 250rpm, reaction temperature 160 DEG C, react 10h.To product after having reacted
Thing purification, first with n-hexane dissolution, negative pressure leaching goes out solid catalyst, to normal hexane mutually with the potassium hydroxide-ethanol solution of 0.8M
Carry out alkali cleaning, wash with saturated aqueous common salt, decompression distillation, obtain purification structure lipid, after esterification, use gas chromatograph
Measuring octanoic acid combination rate is 11.3%, and capric acid combination rate is 13.1%, and total medium-chain fatty acid combination rate is 24.4%.
Embodiment 12
By 0.85g(0.001mol) soybean oil, 0.288g(0.002mol) octanoic acid and 0.344g(0.002mol) capric acid joins
In 50mL round-bottomed flask, magnetic agitation under the conditions of 70 DEG C, negative pressure leaching removes water 30min, adds 35% (w) UiO-66-
Cs2.5H0.5PW12O40Catalyst 0.219g, stir speed (S.S.) 250rpm, reaction temperature 160 DEG C, react 10h.To product after having reacted
Thing purification, first with n-hexane dissolution, negative pressure leaching goes out solid catalyst, to normal hexane mutually with the potassium hydroxide-ethanol solution of 0.8M
Carry out alkali cleaning, wash with saturated aqueous common salt, decompression distillation, obtain purification structure lipid, after esterification, use gas chromatograph
Measuring octanoic acid combination rate is 8%, and capric acid combination rate is 9.8%, and total medium-chain fatty acid combination rate is 17.8%.
Embodiment 13
By 0.85g(0.001mol) soybean oil, 0.72g(0.005mol) octanoic acid and 0.86g(0.005mol) capric acid joins
In 50mL round-bottomed flask, magnetic agitation under the conditions of 70 DEG C, negative pressure leaching removes water 30min, adds 35% (w) UiO-66-
Cs2.5H0.5PW12O40Catalyst 0.219g, stir speed (S.S.) 250rpm, reaction temperature 160 DEG C, react 6h.To product after having reacted
Thing purification, first with n-hexane dissolution, negative pressure leaching goes out solid catalyst, to normal hexane mutually with the potassium hydroxide-ethanol solution of 0.8M
Carry out alkali cleaning, wash with saturated aqueous common salt, decompression distillation, obtain purification structure lipid, after esterification, use gas chromatograph
Measuring octanoic acid combination rate is 13.9%, and capric acid combination rate is 16.4%, and total medium-chain fatty acid combination rate is 30.3%.
Embodiment 14
Catalyst after using in embodiment 5 reclaims, and washing is dried with standby.By 0.85g(0.001mol) soybean oil,
0.72g(0.005mol) octanoic acid and 0.86g(0.005mol) capric acid joins in 50mL round-bottomed flask, magnetic force under the conditions of 70 DEG C
Stirring, negative pressure leaching removes water 30min, adds 35% (w) UiO-66-Cs after recycling2.5H0.5PW12O40Catalyst
0.219g, stir speed (S.S.) 250rpm, reaction temperature 160 DEG C, react 10h.To product purification after having reacted, first molten with normal hexane
Solving, negative pressure leaching goes out solid catalyst, the potassium hydroxide-ethanol solution of normal hexane 0.8M is carried out alkali cleaning, uses saturated common salt
Water is washed, decompression distillation, obtains purification structure lipid, after esterification by gas chromatograph for determination octanoic acid combination rate is
18.8%, capric acid combination rate is 23.3%, and total medium-chain fatty acid combination rate is 42.1%.
According to the method for embodiment 14, catalyst is reclaimed, put into lower batch acidolysis reaction (reaction condition with use first
Shi Xiangtong), so this catalyst is reused 5 times (when catalytic amount deficiency, reclaim catalyst make-up with parallel test).
Acidolysis reaction product postprocessing method is with embodiment 14.
Table 1: solid acid catalyst recycling test result
As can be seen from Table 1, in the present invention solid acid catalyst Oleum Glycines with octanoic acid, capric acid acidolysis reaction in through 5 times repeat profit
Remain at more than 80% by rear activity, illustrate that the catalytic stability of this catalyst is high, can make continuously in intermittent reaction device
With.
Claims (4)
1. the preparation method of an immobilized Tricesium dodecatungstophosphate salt catalyst, it is characterised in that: comprise the steps:
The first step, takes the cesium carbonate of certain mass respectively and phosphotungstic acid is made into the aqueous solution of respective concentration, and at room temperature by carbon
Acid caesium solution is added drop-wise in Salkowski's solution with the speed of 0.1 mL/min ~ 2 mL/min, continues stirring 8h after dripping, then at
Left at room temperature ageing 6 ~ 18h；Then slow evaporation moisture at a temperature of 323 K, the white solid obtained is at a temperature of 383 K
Dry 12h, then at 473 ~ 673K roasting temperature 2h, obtain phosphotungstic acid cesium salt standby；
Wherein the concentration of aqueous solution of cesium carbonate is 0.25 mol/L, and the concentration of aqueous solution of phosphotungstic acid is 0.08 mol/L, the two
Mol ratio is cesium carbonate: phosphotungstic acid=5:4；
Second step, joins a certain amount of p-phthalic acid and Zirconium tetrachloride. in a certain amount of DMF, 10 ~
Magnetic force strong agitation at 50 DEG C；It is subsequently adding concentrated hydrochloric acid, stirs 1 ~ 3h；Add phosphotungstic acid cesium salt prepared by the appropriate first step,
Continue stirring 1 ~ 3h；Then crystallization 10 ~ 60h at a temperature of 90 ~ 160 DEG C；Take out solids, and with DMF with
CH3Solid after washing repeatedly, is finally dried by OH filtration washing, activates 6 ~ 24h, obtain phosphorous at a temperature of 120 ~ 250 DEG C
Wolframic acid cesium salt 20 ~ 65%, specific surface area are 794-1045m2The finished catalyst of/g；
Wherein, p-phthalic acid is 2 ~ 1 with the mol ratio of Zirconium tetrachloride., DMF and the mol ratio of Zirconium tetrachloride.
Being 40 ~ 130, concentrated hydrochloric acid is 1 ~ 3 with the mol ratio of p-phthalic acid.
The preparation method of immobilized Tricesium dodecatungstophosphate salt catalyst the most according to claim 1, it is characterised in that: described first
In step, the drop rate of cesium carbonate solution is 1 mL/min, and the still aging time is 12h, and sintering temperature is 573K.
The preparation method of immobilized Tricesium dodecatungstophosphate salt catalyst the most according to claim 1, it is characterised in that: described second
In step, whipping temp is 30 ~ 40 DEG C, and adding the mixing time after phosphotungstic acid cesium salt is 2 ~ 3h, and crystallization temperature is 110 ~ 140 DEG C, brilliant
The change time is 20 ~ 40h, catalyst activation temperature 150 ~ 220 DEG C, soak time 8 ~ 16h.
4. the immobilized Tricesium dodecatungstophosphate salt catalyst of claim 1 preparation answering in Long carbon chain fatty glyceride in preparation
With.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108816215A (en) * | 2018-06-04 | 2018-11-16 | 福州华博立乐新材料科技有限公司 | It is a kind of for synthesizing the catalyst of 4- phenyl -1- butyric acid |
| CN109908957A (en) * | 2019-03-18 | 2019-06-21 | 江南大学 | A kind of corrdination type phosphotungstic acid Zr catalyst and its application in catalytic hydrogenation furfural |
| CN110787811A (en) * | 2019-11-11 | 2020-02-14 | 怀化学院 | Solid super acid and preparation method thereof, glycerol cyclohexanone ketal and preparation method thereof |
| CN111359663A (en) * | 2020-02-19 | 2020-07-03 | 浙江工业大学 | Application of catalyst based on organic metal framework UiO-66 in cellulose hydrolysis |
| CN111375433A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Method for oligomerization of isobutene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3197483A (en) * | 1962-07-30 | 1965-07-27 | Pennsalt Chemicals Corp | Preparation of cyclic thioethers |
| CN101481306A (en) * | 2009-01-13 | 2009-07-15 | 湖南瑞源石化股份有限公司 | Preparation of lower fatty acid ester and apparatus for preparing lower fatty acid ester |
| CN102146296A (en) * | 2011-01-30 | 2011-08-10 | 山东大学 | Oxidative desulfurization method based on magnetically separable supported cesium phosphotungstate catalyst |
-
2016
- 2016-05-30 CN CN201610366847.0A patent/CN106000463B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3197483A (en) * | 1962-07-30 | 1965-07-27 | Pennsalt Chemicals Corp | Preparation of cyclic thioethers |
| CN101481306A (en) * | 2009-01-13 | 2009-07-15 | 湖南瑞源石化股份有限公司 | Preparation of lower fatty acid ester and apparatus for preparing lower fatty acid ester |
| CN102146296A (en) * | 2011-01-30 | 2011-08-10 | 山东大学 | Oxidative desulfurization method based on magnetically separable supported cesium phosphotungstate catalyst |
Non-Patent Citations (3)
| Title |
|---|
| 刘洋: "新型含磷钨酸金属-有机骨架的制备及其催化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 李念等: "采用固体磷钨酸铯盐催化光皮树油制备生物柴油", 《中南大学（自然科学版）》 * |
| 金万勤等著: "《材料化学工程进展》", 30 September 2007, 北京：化学工业出版社 * |
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| CN108816215A (en) * | 2018-06-04 | 2018-11-16 | 福州华博立乐新材料科技有限公司 | It is a kind of for synthesizing the catalyst of 4- phenyl -1- butyric acid |
| CN111375433A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Method for oligomerization of isobutene |
| CN109908957A (en) * | 2019-03-18 | 2019-06-21 | 江南大学 | A kind of corrdination type phosphotungstic acid Zr catalyst and its application in catalytic hydrogenation furfural |
| CN110787811A (en) * | 2019-11-11 | 2020-02-14 | 怀化学院 | Solid super acid and preparation method thereof, glycerol cyclohexanone ketal and preparation method thereof |
| CN110787811B (en) * | 2019-11-11 | 2022-07-12 | 怀化学院 | Solid super acid and preparation method thereof, glycerol cyclohexanone ketal and preparation method thereof |
| CN111359663A (en) * | 2020-02-19 | 2020-07-03 | 浙江工业大学 | Application of catalyst based on organic metal framework UiO-66 in cellulose hydrolysis |
| CN111359663B (en) * | 2020-02-19 | 2023-03-28 | 浙江工业大学 | Application of catalyst based on organic metal framework UiO-66 in cellulose hydrolysis |
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