CN106000463B - The preparation method and application of immobilized Tricesium dodecatungstophosphate salt catalyst - Google Patents
The preparation method and application of immobilized Tricesium dodecatungstophosphate salt catalyst Download PDFInfo
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- CN106000463B CN106000463B CN201610366847.0A CN201610366847A CN106000463B CN 106000463 B CN106000463 B CN 106000463B CN 201610366847 A CN201610366847 A CN 201610366847A CN 106000463 B CN106000463 B CN 106000463B
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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 a kind of immobilized Tricesium dodecatungstophosphate salt catalysts, by introducing Tricesium dodecatungstophosphate during synthesizing metal-organic framework materials UiO-66, so that the mass ratio of active component phosphotungstic acid cesium salt and metal-organic framework UiO-66 reach 0.2 ~ 0.65 in the immobilized Tricesium dodecatungstophosphate catalyst of the metal organic framework prepared；The specific surface area of solid-carried catalyst reaches 794-1045m2/g.Preparation method of the present invention uses a step fabricated in situ, can effectively prevent the loss of activated centre phosphotungstic acid cesium salt, improves the physics and chemical stability of catalyst；It preferably maintains the structure with Keggin of phosphotungstic acid cesium salt and the double grading of highly acid and oxidation-reduction quality, application range is wider；Be conducive to the adsorption and diffusion of reactive material on a catalyst, to improve the catalytic efficiency of catalyst；Preparation method of the present invention is easy simultaneously, and method is simple, easily operated, is easy to be separated by filtration with product after reaction, non-corrosive, no pollution to the environment.
Description
Technical field
The present invention relates to the catalyst of chemical field, more particularly, to a kind of system of immobilized Tricesium dodecatungstophosphate salt catalyst
Preparation Method, the invention further relates to application of the catalyst in preparation in Long carbon chain fatty glyceride.
Background technique
Phosphotungstic acid is a kind of polyoxometallate with structure with Keggin, there is the dual of superpower acidity and oxidation-reduction quality
Characteristic.As a kind of superpower solid acid, (in nonaqueous solvents, acid strength is sulphur to alternative overwhelming majority inorganic acid catalyst
100 times of acid), it can be used in a variety of acid catalyzed reactions.However, phosphotungstic acid is homogeneous catalyst, reaction product last handling process
It is cumbersome, environment is polluted, can not be recycled.Phosphotungstic acid cesium salt not only remains the highly acid of phosphotungstic acid, high activity, highly selective
The advantages that, also have the advantages that it is undissolved in water isopolarity solvent, can be used as heterogeneous catalyst use.However, Tricesium dodecatungstophosphate
Salt specific surface area is small, cannot provide and enrich effective active site, and catalytic efficiency is lower.For this purpose, can be by phosphotungstic acid cesium salt
It is immobilized to easily separated, recyclable, reusable and environmentally protective novel solid acid catalyst is made on porous carrier.
The active charcoal of common carrier, the SiO of multiphase solid acid catalyst are prepared at present2、TiO2, zeolite molecular sieve, macropore point
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 a variety of organic chemical reactions, such as: middle promulgated by the State Council
Bright patent application CN102950023 A discloses a kind of carried phospho-tungstic acid catalyst of acrylic acid synthesizing N-butyl, preparation
Method is that the hollow sphere mesoporous silicon oxide of activation is added in the butanol solution of phosphotungstic acid, stirring, by filtering and doing
After dry, carried phospho-tungstic acid catalyst is obtained.104248971 A of application for a patent for invention CN discloses a kind of synthesizing cyclohexanone third
The carried phospho-tungstic acid catalyst of triol ketal, preparation method are by preparing spherical SiO 2 and silica gel complex carrier and phosphotungstic acid
It in the presence of deionized water, is spray-dried after being configured to slurry, so that phosphotungstic acid is supported on preparing spherical SiO 2 and silica gel multiple
It closes on carrier.The carried phospho-tungstic acid solid that 103586076 A of application for a patent for invention CN discloses a kind of synthesizing ethyl acetate is urged
Agent, preparation method be by sphericity mesoporous silicon dioxide carrier together with phosphotungstic acid ball milling, so that phosphotungstic acid is supported on the ball
On shape meso-porous titanium dioxide silicon carrier.103041863 A of application for a patent for invention CN discloses a kind of phosphotungstic acid for preparing ethyl acetate
Catalyst, preparation method are metal-organic framework compound to be immersed in phosphotungstic acid aqueous solution, then roast and metal-is made
Organic backbone load phosphotungstic acid catalyst.Application for a patent for invention CN104437645 A discloses a kind of metal-of synthesis of glutaraldehyde
Organic backbone solid-carrying heteropolyacid catalyst, preparation method are by terephthalic acid (TPA) H2(BDC) and ZrCl4It is dissolved in DMF (N, N- bis-
Methyl methylamine) in, it after stirring and dissolving, sequentially adds concentrated hydrochloric acid and phosphotungstic acid stirs and evenly mixs, filtration washing after crystallization is dried and living
Change the immobilized phosphotungstic acid heterogeneous catalyst that different loads amount is made.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, preparation method is first by silica gel coated magnetic Fe3O4System
Standby magnetic carrier out, then cesium carbonate aqueous solution and magnetic carrier stirring are impregnated, the magnetic carrier of load cesium carbonate is prepared, most
It is stirred to react with phosphotungstic acid aqueous solution afterwards, preparing can Magneto separate carried phospho-tungstic acid cesium salt catalyst.It is obtained above
The disadvantages of catalyst there are active forces small, poor chemical stability, recycling effect is undesirable.
Middle Long carbon chain fatty glyceride is a kind of structured lipid low in calories, after alimentary canal absorbs can directly by portal vein into
Enter liver, and decomposition and inversion not will cause hoarding for body fat at energy in a short time, so that reaching prevention there are related disorders
Effect.In terms of middle Long carbon chain fat emulsion injection has been widely used for medical treatment, be a kind of energy for intravenous drip and
Nutritional supplement.Middle long-chain fat acid lipid is approved as new resource food by the Ministry of Public Health, it can be used to produce low in calories cook
It prepares food with health-care edible oils and typical local food such as grease, 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 the replacement for being catalyzed acyl group in vegetable and animals oils triglycerides under mild conditions with various lipase, makes middle chain rouge
Fat acid is combined into the triglycerides 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).However, lipase is expensive, and swim
It is poor from the reusing of enzyme, cause production cost higher, and obtained product component is more complex, except middle long chain fatty acids oil
Outside rouge, there are also diglyceride, monoglyceride and raw oil materials, need to isolate and purify process (referring to Chinese invention using cumbersome
Patent " a kind of isolation and purification method of middle chain fatty acid triglycerides ", application number 2012100042302.6).
Summary of the invention
That the purpose of the present invention is to provide a kind of catalytic activity is good, reusing is good, physics and chemical stability are high
The preparation method of immobilized Tricesium dodecatungstophosphate salt catalyst, the present invention also provides the catalyst in preparation Long carbon chain fatty acid glycerine
Application in the grease acidolysis reaction of ester.
To achieve the above object, the present invention can take following technical proposals:
The preparation method of immobilized Tricesium dodecatungstophosphate salt catalyst of the present invention includes the following steps:
The first step takes the cesium carbonate (Cs of certain mass respectively2CO3) and phosphotungstic acid (H3PW12O40) it is made into respective concentration
Aqueous solution, and be at room temperature added drop-wise to cesium carbonate solution in Salkowski's solution with the rate of the mL/min of 0.1 mL/min ~ 2, it drips
Continue to stir 8h after adding, then at still aging 6 ~ 18h at room temperature；Then the slow evaporation moisture at a temperature of 323 K, obtains
White solid dries 12h at a temperature of 383 K, then at 473 ~ 673K roasting temperature 2h, obtains phosphotungstic acid cesium salt
(Cs2.5H0.5PW12O40) spare；
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, two
The molar ratio of person is cesium carbonate: phosphotungstic acid=5:4；
Second step, by a certain amount of terephthalic acid (TPA) (H2And zirconium chloride (ZrCl (BDC))4) it is added to a certain amount of N,
In dinethylformamide (DMF), magnetic force stirs strongly at 10 ~ 50 DEG C；Then concentrated hydrochloric acid is added, stirs 1 ~ 3h；It adds suitable
The phosphotungstic acid cesium salt for measuring first step preparation, continues 1 ~ 3h of stirring；Then 10 ~ 60h of crystallization at a temperature of 90 ~ 160 DEG C；Filtering, takes
Solids out, and washed respectively repeatedly with DMF and methanol, finally the solid after washing is dried, it is living at a temperature of 120 ~ 250 DEG C
Change 6 ~ for 24 hours, obtain cesium salt containing phosphotungstic acid 20 ~ 65%, specific surface area 794-1045m2Finished catalyst (the UiO-66- of/g
Cs2.5H0.5PW12O40)；
Wherein, the molar ratio of terephthalic acid (TPA) and zirconium chloride be 2 ~ 1, n,N-Dimethylformamide with zirconium chloride
Molar ratio is 40 ~ 130, and the molar ratio of concentrated hydrochloric acid and terephthalic acid (TPA) is 1 ~ 3.
The drop rate of cesium carbonate solution is 1 mL/min in the first step, and the still aging time is 12h, maturing temperature
For 573K.
Whipping temp is 30 ~ 40 DEG C in the second step, and the mixing time after phosphotungstic acid cesium salt is added is 2 ~ 3h, crystallization temperature
Degree be 110 ~ 140 DEG C, crystallization time be 20 ~ 40h, 150 ~ 220 DEG C of catalyst activation temperature, 8 ~ 16h of activation time.
Immobilized Tricesium dodecatungstophosphate salt catalyst prepared by the present invention is for Long carbon chain fatty acid in vegetable fat acidolysis preparation
Glyceride.The soybean oil centainly matched and medium chain fatty acid (octanoic acid and capric acid) are uniformly mixed, are heated to certain temperature, then plus
The solid acid catalyst for entering preparation, reacts certain time under stiring.When after reaction, n-hexane is added, by product negative pressure
It filters, and n-hexane is mutually subjected to alkali cleaning with potassium hydroxide-ethanol solution, then washed with saturated salt solution, decompression boils off just
Purification structure rouge can be obtained in hexane.Filter cake is successively washed with n-hexane, methanol and ether, removes adsorbing contaminant on catalyst, then
Put it into vacuum oven that negative pressure drying 12h, obtained recycling catalyst can be used for next acidolysis reaction at a temperature of 70 DEG C.
Compared with long-chain fat acid glyceride in traditional enzymatic grease acidolysis preparation (Food Chemistry, 2012,132
(1): 216-221), the solid acid catalysis method have that catalytic activity is high, reusing is good, the reaction time is short, selectivity is good and
The advantages that product impurity is few, is the structured lipid production method of green environment close friend a kind of.
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 terephthalic acid (TPA)s, specific surface area with higher, thermal stability, chemical stability and
Catalytic active center is integrated on metal-organic framework compound UiO-66 by mechanical performance, the present invention by in-situ synthesis,
Solid acid catalyst UiO-66-Cs obtained2.5H0.5PW12O40Activity and stability with higher.Its advantage embodies
:
1) preparation method of the present invention uses a step fabricated in situ, can effectively prevent the loss of activated centre phosphotungstic acid cesium salt,
Improve the physics and chemical stability of catalyst；
2) finished catalyst prepared by the present invention preferably maintains the structure with Keggin and highly acid of phosphotungstic acid cesium salt
With the double grading of oxidation-reduction quality, application range is wider, its characteristic is constant after load, so that it is higher to guarantee that the catalyst has
Catalytic activity；
3) finished catalyst prepared by the present invention maintains the skeleton structure of metal-organic framework UiO-66, specific surface area
Greatly, aperture is uniform, and active component is uniformly dispersed；This high-specific surface area and porous structure can make active catalyst sites height
Dispersion is conducive to the adsorption and diffusion of reactive material on a catalyst, reduces resistance to mass tranfer, to improve the catalysis effect of catalyst
Rate；
4) catalyst prepared by the present invention does not dissolve in polar solvent, can be applied in highly polar medium be catalyzed all kinds of organic anti-
It answers, and the long period can be used；
5) catalyst decomposition temperature prepared by the present invention is about 500oC or so, high temperature resistant, physical stability is good, is easy to protect
It deposits and never degenerates；
6) catalyst preparation prepared by the present invention is easy, and method is simple, easily operated, is easy to filter with product after reaction and divide
From non-corrosive, no pollution to the environment.
Detailed description of the invention
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.
Specific embodiment
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 immobilized Tricesium dodecatungstophosphate catalyst of the metal organic framework prepared, active component
The mass ratio of phosphotungstic acid cesium salt and metal-organic framework UiO-66 reach 0.2 ~ 0.65；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 1080 cm of characteristic feature peak 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.In addition, the UiO- of preparation
66-Cs2.5H0.5PW12O40Catalyst also has the characteristic feature peak of metal-organic framework structure UiO-66 carrier, in 1657cm-1
The characteristic peak at place can belong to the absorption of vibrations of C=O bond C=O in carboxyl in terephthalic acid (TPA), in 1400cm-1The characteristic peak at place
It can be attributed to the stretching vibration peak of COO- in terephthalic acid (TPA) in organic ligand, 700-400 cm-1The characteristic peak at place can belong to
In terephthalic acid (TPA) in COO- plane and out-of-plane flexural vibrations peak, characteristic peak caused by the vibration of C=C key exists in phenyl ring
1505 cm-1With 1600 cm-1Place occurs, and the eigen vibration peak of Zr-O is in 550 cm-1Place occurs, these the results of FT-IR are equal
Illustrate the catalyst UiO-66-Cs of step in-situ synthesis preparation2.5H0.5PW12O40Retaining, metal-is organic framework structured
While the skeleton structure of UiO-66 carrier, phosphotungstic acid cesium salt Cs2.5H0.5PW12O40Structure and characteristic do not change, be a kind of
Have both the new catalyst of the two structural advantages.
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 is carried
7.4 °, 8.5 °, 12.1 °, 14.2 °, 17.1 °, 22.3 °, 25.7 °, 31.1 ° and 33.1 ° of feature is distinguished at 2 angles θ in the spectrogram of body
Peak can be attributed to (111), (002), (022), (113), (004), (115), (224), (046) and (137) crystal face respectively and generate
Diffractive features absorption peak.After the load of phosphotungstic acid cesium salt, although its diffraction peak intensity reduces, substantially and metal-organic framework
The characteristic absorption peak of structure UiO-66 carrier is consistent.This illustrates the immobilized metal-organic framework that causes of phosphotungstic acid cesium salt
Crystal form density increases, but does not significantly affect to metal-organic framework generation, and phosphotungstic acid cesium salt is uniformly immobilized to have arrived gold
On category-organic backbone UiO-66, and the structure feature without changing 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 of no hysteresis loop, it was demonstrated that it is poromerics.In carrier UiO-66
Middle introducing Cs2.5H0.5PW12O40Afterwards, no change has taken place for the adsorption isotherm type of sample, but due to Cs2.5H0.5PW12O40?
Grain occupies in its micropore canals, leads to UiO-66-Cs2.5H0.5PW12O40Sample is to N2Adsorbance be less than UiO-66 pairs of pure carrier
N2Adsorbance.Acidic cs salts of heteropolyacid Cs2.5H0.5PW12O40Specific surface area be 138m2The specific surface area of/g, 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.With the increase of Tricesium dodecatungstophosphate load capacity, UiO-66-
Cs2.5H0.5PW12O40The BET specific surface area of sample gradually decreases, and pore volume is gradually lowered, and aperture is gradually increased, this is because
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 not much different, this shows Cs2.5H0.5PW12O40Active component is highly dispersed in the duct of carrier, remains to catalyst
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 it is similar to the pattern of metal-organic framework UiO-66, sample is all made of uniform cube of symbiosis crystal, reunite exist
Be rendered as spherical particle together, show that active specy is highly dispersed in UiO-66, so as to guarantee the catalyst have compared with
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 it is bent
Line maintains the weight-loss curve feature of metal-organic framework substantially, and weightless process of the sample when temperature is greater than 500 DEG C is attributed to
Metal-organic framework decomposes in catalyst, caused by structure collapse.Active component Cs2.5H0.5PW12O40Introducing there is no change
The thermal stability of metal-organic framework UiO-66, to guarantee the physical and chemical stability of the catalyst.Heat analysis result explanation
Solid catalyst keeps good stability when less than 500 DEG C.
More detailed explanation is done to the present invention below by specific embodiment.Wherein unless otherwise indicated, the present invention adopts
Reagent and equipment are the art regular market purchase product.
Embodiment 1
Immobilized Tricesium dodecatungstophosphate salt catalyst 20% (w) UiO-66-Cs of the present invention2.5H0.5PW12O40Preparation method include
Following step:
Step 1: activated centre Cs2.5H0.5PW12O40Preparation:
1.00 g cesium carbonate (Cs are taken 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, rate is maintained at 1mL/min,
Magnetic force stirs 8h, still aging 12h strongly again, and then mixed liquor is slowly evaporated under the conditions of 50 DEG C；The white that will be obtained again
Solid dries 12h in 383 K, and 573 K roast 2 h, obtain phosphotungstic acid cesium salt (Cs2.5H0.5PW12O40) spare.
Step 2: catalyst 20% (w) UiO-66-Cs2.5H0.5PW12O40Preparation:
Reactor is placed in 35 DEG C of water baths, 80mL DMF (n,N-Dimethylformamide) is added in the reactor, it will
2.0g terephthalic acid (TPA) H2(BDC) and 2.8g ZrCl4It is dissolved in DMF, after stirring and dissolving, then 1.5mL concentrated hydrochloric acid is added thereto,
3h is stirred, 0.6g phosphotungstic acid cesium salt is then added, continues to stir 2h, above-mentioned reaction raw materials is transferred to stainless steel after being uniformly mixed
In reaction kettle, crystallization 30h at 120 DEG C, taking-up is filtered, washed, dries.Before use, by it in air atmosphere constant temperature at 180 DEG C
10h is activated, 20% (w) UiO-66-Cs is obtained2.5H0.5PW12O40Catalyst, BET specific surface area are 1045 m2/g。
Embodiment 2
Immobilized Tricesium dodecatungstophosphate salt catalyst 35% (w) UiO-66-Cs of the present invention2.5H0.5PW12O40Preparation method include
Following step:
Step 1: with embodiment 1.
Step 2: catalyst 35% (w) UiO-66-Cs2.5H0.5PW12O40Preparation:
Reactor is placed in 35 DEG C of water baths, 80mL DMF (n,N-Dimethylformamide) is added in the reactor, it will
2.0g terephthalic acid (TPA) H2(BDC) and 2.8g ZrCl4It is dissolved in DMF, after stirring and dissolving, then 1.5mL concentrated hydrochloric acid is added thereto,
3h is stirred, 1.05g phosphotungstic acid cesium salt is then added, continues to stir 2h, be transferred to above-mentioned reaction raw materials after being uniformly mixed stainless
In steel reaction kettle, crystallization 30h at 120 DEG C, taking-up is filtered, washed, dries.Before use, it is permanent at 180 DEG C in air atmosphere
Temperature activation 10h, obtains 35% (w) UiO-66-Cs2.5H0.5PW12O40Catalyst, BET specific surface area are 888 m2/g。
Embodiment 3
Immobilized Tricesium dodecatungstophosphate salt catalyst 50% (w) UiO-66-Cs of the present invention2.5H0.5PW12O40Preparation method include
Following step:
Step 1: with embodiment 1.
Step 2: catalyst 50% (w) UiO-66-Cs2.5H0.5PW12O40Preparation:
Reactor is placed in 35 DEG C of water baths, 80mL DMF (n,N-Dimethylformamide) is added in the reactor, it will
2.0g terephthalic acid (TPA) H2(BDC) and 2.8g ZrCl4It is dissolved in DMF, after stirring and dissolving, then 1.5mL concentrated hydrochloric acid is added thereto,
3h is stirred, 1.5g phosphotungstic acid cesium salt is then added, continues to stir 2h, above-mentioned reaction raw materials is transferred to stainless steel after being uniformly mixed
In reaction kettle, crystallization 30h at 120 DEG C, taking-up is filtered, washed, dries.Before use, by it in air atmosphere constant temperature at 180 DEG C
10h is activated, 50% (w) UiO-66-Cs is obtained2.5H0.5PW12O40Catalyst, BET specific surface area are 814 m2/g。
Embodiment 4
Immobilized Tricesium dodecatungstophosphate salt catalyst 65% (w) UiO-66-Cs of the present invention2.5H0.5PW12O40Preparation method include
Following step:
Step 1: with embodiment 1.
Step 2: catalyst 65% (w) UiO-66-Cs2.5H0.5PW12O40Preparation:
Reactor is placed in 35 DEG C of water baths, 80mL DMF (n,N-Dimethylformamide) is added in the reactor, it will
2.0g terephthalic acid (TPA) H2(BDC) and 2.8g ZrCl4It is dissolved in DMF, after stirring and dissolving, then 1.5mL concentrated hydrochloric acid is added thereto,
3h is stirred, 1.95g phosphotungstic acid cesium salt is then added, continues to stir 2h, be transferred to above-mentioned reaction raw materials after being uniformly mixed stainless
In steel reaction kettle, crystallization 30h at 120 DEG C, taking-up is filtered, washed, dries.Before use, it is permanent at 180 DEG C in air atmosphere
Temperature activation 10h, is made 65% (w) UiO-66-Cs2.5H0.5PW12O40Catalyst, BET specific surface area be 794 m2/g。
Embodiment 5
By 0.85g(0.001mol) soybean oil, 0.72g(0.005mol) sad and 0.86g(0.005mol) capric acid addition
Into 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, stirring rate 250rpm, react 10h by 160 DEG C of reaction temperature.After the reaction was completed to production
Object purifying, first uses n-hexane dissolution, and negative pressure leaching goes out solid catalyst, mutually uses n-hexane the potassium hydroxide-ethanol solution of 0.8M
Alkali cleaning is carried out, is washed with saturated salt solution, is evaporated under reduced pressure, is obtained purification structure lipid, use gas chromatograph after esterification
Measuring sad Percentage bound is 20.3%, and capric acid Percentage bound is 25.4%, and total medium-chain fatty acid Percentage bound is 45.7%.
Embodiment 6
By 0.85g(0.001mol) soybean oil, 0.72g(0.005mol) sad and 0.86g(0.005mol) capric acid addition
Into 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, stirring rate 250rpm, react 10h by 160 DEG C of reaction temperature.After the reaction was completed to production
Object purifying, first uses n-hexane dissolution, and negative pressure leaching goes out solid catalyst, mutually uses n-hexane the potassium hydroxide-ethanol solution of 0.8M
Alkali cleaning is carried out, is washed with saturated salt solution, is evaporated under reduced pressure, is obtained purification structure lipid, use gas chromatograph after esterification
Measuring sad Percentage bound is 15.3%, and capric acid Percentage bound is 18.1%, and total medium-chain fatty acid Percentage bound is 33.4%.
Embodiment 7
By 0.85g(0.001mol) soybean oil, 0.72g(0.005mol) sad and 0.86g(0.005mol) capric acid addition
Into 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, stirring rate 250rpm, react 10h by 160 DEG C of reaction temperature.After the reaction was completed to production
Object purifying, first uses n-hexane dissolution, and negative pressure leaching goes out solid catalyst, mutually uses n-hexane the potassium hydroxide-ethanol solution of 0.8M
Alkali cleaning is carried out, is washed with saturated salt solution, is evaporated under reduced pressure, is obtained purification structure lipid, use gas chromatograph after esterification
Measuring sad Percentage bound is 21.4%, and capric acid Percentage bound is 26.2%, and total medium-chain fatty acid Percentage bound is 47.6%.
Embodiment 8
By 0.85g(0.001mol) soybean oil, 0.72g(0.005mol) sad and 0.86g(0.005mol) capric acid addition
Into 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, stirring rate 250rpm, react 10h by 160 DEG C of reaction temperature.After the reaction was completed to production
Object purifying, first uses n-hexane dissolution, and negative pressure leaching goes out solid catalyst, mutually uses n-hexane the potassium hydroxide-ethanol solution of 0.8M
Alkali cleaning is carried out, is washed with saturated salt solution, is evaporated under reduced pressure, is obtained purification structure lipid, use gas chromatograph after esterification
Measuring sad Percentage bound is 21.6%, and capric acid Percentage bound is 26.5%, and total medium-chain fatty acid Percentage bound is 48.1%.
Embodiment 9
By 0.85g(0.001mol) soybean oil, 0.72g(0.005mol) sad and 0.86g(0.005mol) capric acid addition
Into 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, stirring rate 250rpm, react 10h by 100 DEG C of reaction temperature.After the reaction was completed to production
Object purifying, first uses n-hexane dissolution, and negative pressure leaching goes out solid catalyst, mutually uses n-hexane the potassium hydroxide-ethanol solution of 0.8M
Alkali cleaning is carried out, is washed with saturated salt solution, is evaporated under reduced pressure, is obtained purification structure lipid, use gas chromatograph after esterification
Measuring sad Percentage bound is 4.6%, and capric acid Percentage bound is 5.9%, and total medium-chain fatty acid Percentage bound is 10.5%.
Embodiment 10
By 0.85g(0.001mol) soybean oil, 0.72g(0.005mol) sad and 0.86g(0.005mol) capric acid addition
Into 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, stirring rate 250rpm, react 10h by 140 DEG C of reaction temperature.After the reaction was completed to production
Object purifying, first uses n-hexane dissolution, and negative pressure leaching goes out solid catalyst, mutually uses n-hexane the potassium hydroxide-ethanol solution of 0.8M
Alkali cleaning is carried out, is washed with saturated salt solution, is evaporated under reduced pressure, is obtained purification structure lipid, use gas chromatograph after esterification
Measuring sad Percentage bound is 13.6%, and capric acid Percentage bound is 14.6%, and total medium-chain fatty acid Percentage bound is 29.9%.
Embodiment 11
By 0.85g(0.001mol) soybean oil, 0.72g(0.005mol) sad and 0.86g(0.005mol) capric acid addition
Into 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, stirring rate 250rpm, react 10h by 160 DEG C of reaction temperature.After the reaction was completed to production
Object purifying, first uses n-hexane dissolution, and negative pressure leaching goes out solid catalyst, mutually uses n-hexane the potassium hydroxide-ethanol solution of 0.8M
Alkali cleaning is carried out, is washed with saturated salt solution, is evaporated under reduced pressure, is obtained purification structure lipid, use gas chromatograph after esterification
Measuring sad Percentage bound is 11.3%, and capric acid Percentage bound is 13.1%, and total medium-chain fatty acid Percentage bound 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 adds
Enter into 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, stirring rate 250rpm, react 10h by 160 DEG C of reaction temperature.After the reaction was completed to production
Object purifying, first uses n-hexane dissolution, and negative pressure leaching goes out solid catalyst, mutually uses n-hexane the potassium hydroxide-ethanol solution of 0.8M
Alkali cleaning is carried out, is washed with saturated salt solution, is evaporated under reduced pressure, is obtained purification structure lipid, use gas chromatograph after esterification
Measuring sad Percentage bound is 8%, and capric acid Percentage bound is 9.8%, and total medium-chain fatty acid Percentage bound is 17.8%.
Embodiment 13
By 0.85g(0.001mol) soybean oil, 0.72g(0.005mol) sad and 0.86g(0.005mol) capric acid addition
Into 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, stirring rate 250rpm, react 6h by 160 DEG C of reaction temperature.After the reaction was completed to production
Object purifying, first uses n-hexane dissolution, and negative pressure leaching goes out solid catalyst, mutually uses n-hexane the potassium hydroxide-ethanol solution of 0.8M
Alkali cleaning is carried out, is washed with saturated salt solution, is evaporated under reduced pressure, is obtained purification structure lipid, use gas chromatograph after esterification
Measuring sad Percentage bound is 13.9%, and capric acid Percentage bound is 16.4%, and total medium-chain fatty acid Percentage bound is 30.3%.
Embodiment 14
Catalyst after use in embodiment 5 is recycled, washing is dry with spare.0.85g(0.001mol) is big
Soya-bean oil, 0.72g(0.005mol) octanoic acid and 0.86g(0.005mol) capric acid is added in 50mL round-bottomed flask, in 70 DEG C of conditions
Lower magnetic agitation, negative pressure leaching remove water 30min, add 35% (w) UiO-66-Cs after recycling2.5H0.5PW12O40Catalysis
Agent 0.219g, stirring rate 250rpm, react 10h by 160 DEG C of reaction temperature.After the reaction was completed to product purification, n-hexane is first used
Dissolution, negative pressure leaching go out solid catalyst, mutually carry out alkali cleaning with the potassium hydroxide-ethanol solution of 0.8M to n-hexane, are eaten with saturation
Salt water is washed, and vacuum distillation obtains purification structure lipid, is with gas chromatograph for determination octanoic acid Percentage bound after esterification
18.8%, capric acid Percentage bound is 23.3%, and total medium-chain fatty acid Percentage bound is 42.1%.
Catalyst is recycled according to the method for embodiment 14, put into lower batch acidolysis reaction (reaction condition with use for the first time
Shi Xiangtong), so the catalyst is reused 5 times (when catalytic amount deficiency, recycling catalyst make-up with parallel test).
Acidolysis reaction product postprocessing method is the same as embodiment 14.
Table 1: solid acid catalyst reuses test result
As can be seen from Table 1, the present invention in solid acid catalyst soya-bean oil and octanoic acid, capric acid acidolysis reaction in through 5 weights
Activity remains at 80% or more after multiple utilization, illustrates that the catalytic stability of the catalyst is high, can connect in intermittent reaction device
It is continuous to use.
Claims (2)
1. a kind of application of immobilized Tricesium dodecatungstophosphate salt catalyst in preparation in Long carbon chain fatty glyceride, feature exist
In: the preparation method of the immobilized Tricesium dodecatungstophosphate salt catalyst includes the following steps:
The first step takes the cesium carbonate of certain mass and phosphotungstic acid to be made into the aqueous solution of respective concentration respectively, and at room temperature by carbon
Sour caesium solution is added drop-wise in Salkowski's solution with the rate of the mL/min of 0.1 mL/min~2, continues to stir 8h after dripping, then
Still aging 6~18h at room temperature；Then slow evaporation moisture at a temperature of 323 K, obtained white solid is in 383 K temperature
It is spare to obtain phosphotungstic acid cesium salt then at 473~673K roasting temperature 2h by the lower drying 12h of degree；
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
Molar ratio is cesium carbonate: phosphotungstic acid=5:4；
A certain amount of terephthalic acid (TPA) and zirconium chloride are added in a certain amount of n,N-Dimethylformamide, 30 by second step
Magnetic force stirs strongly at~40 DEG C；Then concentrated hydrochloric acid is added, stirs 1~3h；Add the Tricesium dodecatungstophosphate of appropriate first step preparation
Salt continues 2~3h of stirring；Then 20~40h of crystallization at a temperature of 110~140 DEG C；Solids is taken out, and with N, N- dimethyl
Formamide and CH3OH filtration washing is multiple, finally by after washing solid dry, at a temperature of 120~220 DEG C activate 8~
16h obtains cesium salt containing phosphotungstic acid 20~65%, specific surface area 794-1045m2The finished catalyst of/g；
Wherein, the molar ratio of terephthalic acid (TPA) and zirconium chloride is 2~1, mole of n,N-Dimethylformamide and zirconium chloride
Than being 40~130, the molar ratio of concentrated hydrochloric acid and terephthalic acid (TPA) is 1~3.
2. immobilized Tricesium dodecatungstophosphate salt catalyst according to claim 1 is in preparation in Long carbon chain fatty glyceride
Using, it is characterised in that: the drop rate of cesium carbonate solution is 1 mL/min in the first step, and the still aging time is 12h,
Maturing temperature is 573K.
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