CN113262783A - Catalyst for catalyzing glycerol to be subjected to directional hydrogenolysis to propylene glycol and preparation method thereof - Google Patents

Catalyst for catalyzing glycerol to be subjected to directional hydrogenolysis to propylene glycol and preparation method thereof Download PDF

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CN113262783A
CN113262783A CN202110367142.1A CN202110367142A CN113262783A CN 113262783 A CN113262783 A CN 113262783A CN 202110367142 A CN202110367142 A CN 202110367142A CN 113262783 A CN113262783 A CN 113262783A
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glycerol
catalyst
hydrogenolysis
propylene glycol
deposition
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郝海刚
孙瑞琴
卢珂
高瑞
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Inner Mongolia University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • B01J35/23—
    • B01J35/393—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0234—Impregnation and coating simultaneously
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group

Abstract

The invention discloses a catalyst for catalyzing the directional hydrogenolysis of glycerol to propylene glycol and a preparation method thereof. The catalyst is prepared by loading monoatomic Pt on a WOx carrier with oxygen vacancies by using an ALD (atomic layer deposition) technology, and the catalyst prepared by the method is used for directly and directionally hydrogenolyzing glycerol to prepare the propylene glycol, wherein the glycerol conversion rate can reach 65.23 percent, and the selectivity of 1, 3-propylene glycol can reach 48.34 percent.

Description

Catalyst for catalyzing glycerol to be subjected to directional hydrogenolysis to propylene glycol and preparation method thereof
Technical Field
The invention relates to a catalyst for catalyzing the directional hydrogenolysis of glycerol to propylene glycol and a preparation method thereof, belonging to the field of chemical synthesis.
Background
The molecular formula of the 1, 3-propylene glycol is C3H8O2Structural formula HOCH2CH2CH2OH, with the relative molecular mass of 76.09, is colorless, tasteless, grey yellow, sticky and transparent liquid, is an important high-end chemical raw material, can be used as a solvent, an antifreeze, an emulsifier, a plasticizer, a detergent, a preservative and a lubricant, and plays an important role in medicines, foods, cosmetics and organic synthesis. In addition, 1, 3-propanediol is also an important monomer for the synthesis of novel polyester fibers (PTT). 1, 2-propylene glycol is an important product of glycerol hydrogenolysis, and is widely applied to the production of polyester and polyurethane as a chemical raw material harmless to human bodies. Has relatively common application in the cosmetic, pharmaceutical and food processing industries.
Currently, the production methods of 1, 3-propanediol include ethylene oxide carbonylation hydrogenation, acrolein hydration hydrogenation, biological fermentation, and glycerol hydrogenation. The Chinese patent CN120140A applied by Shell company discloses a method for generating 1, 3-propylene glycol by ethylene oxide carbonylation hydrogenation, and the Chinese patent CN93114516.3 applied by Degussa and Dupont company discloses a method for preparing 1, 3-propylene glycol by acrolein hydration method, and the two synthetic methods have the technical characteristics of high technical difficulty, high device investment, higher reaction pressure, ethylene oxide hydroformylation reaction pressure of about 15MPa and quite complex reactor structure. The reaction cost of the acrolein route is high, and the acrolein belongs to extremely toxic, inflammable and explosive articles and is difficult to store and transport. Dupont and Geneneor (CN101146) propose the preparation of 1, 3-propanediol by microbial fermentation. The raw material of the production process is glucose or saccharides of starch. Under the action of yeast, glucose firstly generates intermediate glycerol, and then the glycerol is converted into propylene glycol under the action of biological strains. The process can convert 50% of the glucose to 1, 3-propanediol. The method has the advantages of environmental protection, but has the disadvantages of low conversion rate of raw materials and low concentration of products, more byproducts and high separation cost of products and strains.
At present, the main preparation method of 1, 2-propylene glycol is a direct hydration method of propylene oxide, and the direct hydration method of propylene oxide is a process for quickly consuming fossil fuels, and the propylene used as a raw material for producing propylene oxide is from petrochemical products, which violates the advocated development and utilization of renewable green energy.
The glycerol hydrogenolysis method can prepare propylene glycol and ethylene glycol, the glycerol can generate 1, 2-propylene glycol and 1, 3-propylene glycol through hydrogenolysis action on C-O bonds, further hydrogenolysis action can generate n-propanol and isopropanol, and finally excessive hydrogenolysis products such as propane and the like are generated. However, the selective formation of 1, 3-propanediol is very difficult, and most catalytic systems use 1, 2-propanediol as the main product. And 1, 2-propylene glycol can be used as a monomer of polyester resin, an antifreeze agent, a component of pigment and the like, and is also an important chemical basic raw material.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides a catalyst for catalyzing the directional hydrogenolysis of glycerol into propylene glycol and a preparation method thereof. The present invention is to prepare a catalyst using ALD (atomic layer deposition) technique to support monatomic Pt on a WOx support having oxygen vacancies and use this catalyst for the direct hydrogenolysis of glycerol to propylene glycol.
A preparation method of a catalyst for catalyzing the directional hydrogenolysis of glycerol into propylene glycol comprises the following steps:
1) 2-5g of ammonium metatungstate is put into a tube furnace and calcined for 2-6h at the temperature of 400 ℃ under the temperature of 300-3；
2) Subjecting the WO prepared in step 1)3Cooling to room temperature, switching the calcining atmosphere, introducing mixed gas, heating to 400-700 ℃, keeping the temperature for 4h at the gas flow rate of 50ml/min to obtain WO containing oxygen vacanciesxA carrier;
3) taking 0.5-2g of the WO containing oxygen vacancies obtained in step 2)xDispersing the carrier in 5-50ml of absolute ethyl alcohol, coating the dispersion liquid on a quartz glass sheet, drying at room temperature, and putting the dried glass sheet into an ALD reaction cavity;
4) starting the ALD deposition system to perform the deposition reaction of Pt at 230-350 ℃, wherein the deposition precursor of Pt is (trimethyl) methyl cyclopentadienyl platinum (MeCpPtMe)3Strem Chemicals, 99%) with N as carrier gas2And ending the deposition when the number of deposition cycles (Q represents the number of deposition cycles) is 60-300 cycles, obtaining the catalysisAgent Pt (Q)/WOx。
Further, the mixed gas in the step 1) is a mixed gas of 20% of hydrogen and 80% of nitrogen, and preferably 20%.
Further, WO containing oxygen vacancies as described in step 2)xX in the carrier is more than 0 and less than 3; step 4) the Pt (Q)/WOxWherein x is more than 0 and less than 3.
Further, the above Pt (Q)/WOxThe application of the compound in catalyzing hydrogenolysis reaction of glycerol.
Further, the above Pt (Q)/WOxA method for use in catalyzing the hydrogenolysis reaction of glycerol comprising the steps of:
Pt(Q)/WOxand adding the glycerol aqueous solution into a high-pressure reaction kettle, replacing air in the high-pressure reaction kettle with hydrogen for three times, introducing the hydrogen to the pressure of 1-6MPa, heating to 150 ℃ and 200 ℃, reacting for 10-36h, naturally cooling after the reaction, filtering and centrifuging, and retaining the supernatant to obtain the glycerol hydrolysate.
Further, the volume fraction of glycerin in the above-mentioned glycerin aqueous solution was 10%.
Further, the above Pt (Q)/WOxAnd glycerol in a mass ratio of 1: 4, and mixing.
Further, the above Pt (Q)/WOxWherein x is more than 0 and less than 3, Q represents the number of deposition cycle turns, and Q is more than or equal to 60 and less than or equal to 300.
Has the advantages that:
(1) due to WOxThe surface oxygen vacancy content is the highest, so that the specific surface area is increased, and the high surface area can improve the dispersity of Pt; at the same time, a large number of oxygen vacancies can enhance WOxAnd Pt, thereby preventing aggregation of platinum.
(2) The invention uses the ALD technology, greatly improves the dispersion degree of the noble metal Pt, and improves the interaction between the active site Pt and the carrier, thereby improving the utilization rate of the noble metal.
(3) The application uses a reducing gas calcination method to prepare WO containing oxygen vacanciesxA carrier and depositing the active component directly onto the WO in the form of a single atom using ALD techniquesxPt (Q)/WO catalyst prepared on carrierxThe prepared catalyst can directly perform directional hydrogenolysis on the glycerol into the propylene glycol.
Drawings
FIG. 1 WO3XRD patterns of the substrate at different vacuum calcination temperatures.
FIG. 2 WO3EPR plots of substrates at different vacuum calcination temperatures.
FIG. 3 is a scanning electron micrograph and a transmission electron micrograph of a catalyst prepared according to the present invention.
Detailed Description
In order to make the technical solutions in the present application better understood, the present invention is further described below with reference to examples, which are only a part of examples of the present application, but not all examples, and the present invention is not limited by the following examples.
The first test example: preparation of catalyst Pt (240)/WOx-20％H2-T, (T represents the calcination temperature, 400-
Example 1
1) 5g of ammonium metatungstate is put into a tube furnace, the temperature is raised to 300 ℃ at the heating rate of 1 ℃/min for calcination, and the calcination is kept for 3 hours to obtain WO3；
2) Subjecting the WO prepared in step 1)3Naturally cooling to room temperature, switching the calcining atmosphere, introducing a gas mixed by 20% of hydrogen and 80% of nitrogen, heating to 400 ℃, keeping the temperature for 4 hours, and obtaining WO containing oxygen vacancies at the gas flow rate of 50ml/minxA support (where oxygen vacancies have been burnt out, the stoichiometric number X is less than 3);
3) taking 2g of the WO containing oxygen vacancies obtained in step 2)xUltrasonically dispersing a carrier in 10ml of absolute ethyl alcohol, coating the dispersion liquid on a quartz glass sheet, drying at room temperature, and putting the dried glass sheet into an ALD reaction cavity;
4) starting the ALD deposition system, and performing deposition reaction of Pt at 275 ℃, wherein the deposition precursor of Pt is (trimethyl) methyl cyclopentadienyl platinum (MeCpPtMe)3Strem Chemicals, 99%) with N as carrier gas2Ending the deposition when the number of deposition rings is 240 circles to obtain a catalyst product Pt (240)/WOx-20％H2Marked Pt (240)WO3-400℃20％H24h。
Example 2
In step (2) of example 1, the catalyst product, labeled as Pt (240)/WO, was obtained by maintaining the reducing gas of the heat treatment constant and changing the calcination temperature to 500 deg.C3-500℃20％H24h。
Example 3
In step (2) of example 1, the catalyst product, labeled as Pt (240)/WO, was obtained by maintaining the reducing gas of the heat treatment at 600 ℃ and changing the calcination temperature3-600℃20％H24h。
Example 4
In step (2) of example 1, the catalyst product, labeled as Pt (240)/WO, was obtained by maintaining the reducing gas of the heat treatment constant and changing the calcination temperature to 700 deg.C3-700℃20％H24h。
Example 5
In step (2) of example 1, the calcination temperature was changed to 800 ℃ while maintaining the reducing gas used in the heat treatment, and a catalyst product, labeled as Pt (240)/WO, was obtained3-800℃20％H24h。
The structures and oxygen vacancy concentrations of the catalyst products obtained in examples 1 to 5 were characterized by X-ray powder diffraction (XRD) and electron paramagnetic resonance spectrometer analysis (EPR), respectively, as shown in fig. 1 and 2. Analysis of XRD pattern revealed that the diffraction peaks at diffraction angles of 23.08 °, 23.70 °, 24.10 °, and 28.76 ° are ascribed to WO of typical orthorhombic system3(PDF: 20-1324). As the calcination temperature was sequentially increased, the intensity of diffraction peaks of monoclinic system was gradually decreased, indicating that WO3The degree of crystallinity of (A) is continuously decreasing, indicating that WO is present during the heat treatment3The crystal structure of (2) is difficult to maintain. When the temperature reaches 700 ℃, the monoclinic system WO3The diffraction peak of (A) is not significant, and the crystal phase is transformed into WO2(PDF: 20-1393), when the temperature reaches 800 ℃, WO can be seen from the XRD pattern2Exists but has a reduced intensity and shows a diffraction peak containing a tungsten simple substance (PDF: 04-0806). It can be seen that the oxygen atoms are reduced to form oxygen vacancies, and the reducing atmosphere is not changedAt higher temperatures, WO3The greater the degree of reduction of (A), at 800 ℃ WO3Is over-reduced to WO2And part of the W simple substance.
FIG. 2 is WO3EPR spectra at different vacuum calcination temperatures. The presence and concentration of oxygen vacancies in the sample can be tested by EPR characterization. Original WO3The sample did not detect the EPR signal. However, all heat treated samples had a strong EPR signal at a g value of 2.002. Since the EPR signal intensity is related to the density of oxygen vacancies, the number of oxygen vacancies can be qualitatively reflected by measuring the signal intensity at g ═ 2.002. After heat treatment, WOxThe number of mid-oxygen vacancies increases with increasing temperature. In FIG. 3, (a) is WO3From the scanning electron micrograph, it can be seen that WO which is not reduced3The morphology of (a) is a relatively uniform sphere with a size of about 20 microns. FIG. 3 shows (b) Pt/WO3Scanning electron microscopy images of (a); no Pt metal particles were observed from the figure, and WO3The morphology of (a) is not changed. FIG. 3 (c)20nm Pt/WO3FIG. 3 (d)5nm Pt/WO3In the transmission electron microscope image of (2), it can be observed from the low power transmission image that the black small particles are metal Pt, the distribution is relatively uniform, and the lattice fringes of Pt can be observed under the high power mirror.
Test example two: experimental effect control of catalytic hydrogenolysis of glycerol
Example 6
The catalyst product prepared in example 1 of test example one and an aqueous glycerol solution were charged into an autoclave, the volume fraction of glycerol in the aqueous glycerol solution being 10%. The catalyst product and the glycerol are mixed according to the mass ratio of 1: 4, replacing air in the high-pressure reaction kettle with hydrogen for three times, introducing the hydrogen until the pressure is 5.5MPa, heating to 180 ℃, reacting for 36 hours, naturally cooling after the reaction, filtering and centrifuging, keeping supernatant, transferring the supernatant into a 50ml volumetric flask for constant volume, taking out 1ml to 25ml volumetric flasks for constant volume again, and finally qualitatively and quantitatively analyzing the product by using Gas Chromatography (GC).
Example 7
The catalyst product prepared in example 5 of the first experimental example was used as the catalyst product of this example, which was used in the method of hydrogenolysis of glycerin by catalysis in example 6.
Example 8
In the step (4) of example 1 in test example one, the number of Pt deposition cycles was changed to 60, and a catalyst product of this example was obtained. The catalyst product of this example catalyzes the hydrogenolysis process of glycerol as in example 6.
Example 9
The catalyst product prepared according to example 5 in the first experimental example catalyzes the glycerin hydrogenolysis method as in example 6, other conditions are not changed, and the time for the catalyst to catalyze the glycerin hydrogenolysis reaction is changed to 72 h.
Comparative example 1
In step (1) of example 1 in test one, WO which had not been subjected to the heat treatment was used3The catalyst product of this example, i.e., this example, catalyzed the process for the hydrogenolysis of glycerol as in example 6.
Comparative example 2
The active component Pt was not loaded in step (2) of example 1 in run one, i.e., in this example, the catalyst product of this example catalyzes the hydrogenolysis process of glycerol as in example 6.
TABLE 1 catalytic hydrogenolysis of glycerol results for different catalyst products
Figure BDA0003007595260000051
A series of previous researches show that the carrier treated at high temperature contains a large number of surface oxygen vacancies, and the catalyst which is not subjected to heat treatment and does not load active component metal Pt has little effect on the catalytic hydrogenolysis of glycerol to prepare propylene glycol. The analysis experiment result (table 1) shows that the number of cycles of the supported metal Pt is 240, the catalytic temperature is 180 ℃, the hydrogen pressure is 5.5MPa, the reaction time is 72 hours, the catalytic effect is optimal, the conversion rate of glycerol is 65.23%, and the selectivity of 1, 3-propanediol is 48.34%.

Claims (9)

1. A preparation method of a catalyst for catalyzing the directional hydrogenolysis of glycerol to propylene glycol is characterized by comprising the following steps:
1) putting ammonium metatungstate into a tube furnace, calcining at the temperature of 300-400 ℃ for 2-6h to obtain WO3；
2) Subjecting the WO prepared in step 1)3Cooling to room temperature, switching the calcining atmosphere, introducing mixed gas, heating to 400-plus-700 ℃, and keeping for 4h to obtain WO containing oxygen vacanciesxA carrier;
3) taking the WO containing oxygen vacancies obtained in the step 2)xDispersing a carrier in absolute ethyl alcohol, coating the dispersion liquid on a quartz glass sheet, drying at room temperature, and putting the dried glass sheet into an ALD reaction cavity;
4) starting the ALD deposition system to perform the deposition reaction of Pt at the temperature of 230-350 ℃, wherein the deposition precursor of Pt is (trimethyl) methyl cyclopentadienyl platinum, and the carrier gas is N2Depositing for 60-300 circles and then finishing deposition to obtain the catalyst Pt (Q)/WOx。
2. The method according to claim 1, wherein the mixed gas in step 1) is a mixed gas of hydrogen and nitrogen, and the volume fraction of hydrogen is 8% to 100%.
3. The method of claim 1, wherein the gas flow rate of the mixed gas in step 1) is >20ml/min, preferably 50 ml/min.
4. The method of claim 1, wherein the WO containing oxygen vacancies in step 2)xX is more than 0 and less than 3 in the carrier.
5. The method according to claim 1, wherein the catalyst Pt (Q)/WO in the step (4)xWhere 0 < x < 3, Q represents the number of deposition cycles.
6. Pt (Q)/WO prepared by the preparation method according to claim 1xThe application of the compound in the catalytic hydrogenolysis reaction of glycerol.
7. Pt (Q)/WO as set forth in claim 6xThe application method in the catalytic hydrogenolysis reaction of glycerol is characterized by comprising the following steps:
Pt(Q)/WOxand adding the glycerol aqueous solution into a high-pressure reaction kettle, replacing air in the high-pressure reaction kettle with hydrogen for three times, introducing the hydrogen, boosting the pressure to 1-6MPa, heating to 150-.
8. The method of use according to claim 7, wherein the aqueous glycerol solution has a glycerol volume fraction of 10%.
9. The method of claim 7, wherein Pt (Q)/WO is usedxAnd glycerol in a mass ratio of 1: 4, and mixing.
CN202110367142.1A 2021-04-06 2021-04-06 Catalyst for catalyzing glycerol to be subjected to directional hydrogenolysis to propylene glycol and preparation method thereof Pending CN113262783A (en)

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