CN112237937A - Nitrogen-doped zirconia carrier and preparation method and application thereof - Google Patents
Nitrogen-doped zirconia carrier and preparation method and application thereof Download PDFInfo
- Publication number
- CN112237937A CN112237937A CN201910648794.5A CN201910648794A CN112237937A CN 112237937 A CN112237937 A CN 112237937A CN 201910648794 A CN201910648794 A CN 201910648794A CN 112237937 A CN112237937 A CN 112237937A
- Authority
- CN
- China
- Prior art keywords
- carrier
- zirconia
- nitrogen
- solution
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- C07C29/136—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 of >C=O containing groups, e.g. —COOH
- C07C29/14—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 of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—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 of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a nitrogen-doped zirconia carrier, a preparation method and hydrogenation application thereof. Mainly solves the problems of low activity and poor selectivity of the palladium catalyst in the carbonyl selective hydrogenation reaction in the prior art. The carrier comprises zirconium oxide and nitrogen, and the nitrogen in the carrier has electronic interaction with the zirconium oxide. The carrier-supported active component of the invention is used for typical carbonyl selective hydrogenation reaction and shows obviously better activity and selectivity than the traditional active carbon and metal oxide-supported palladium catalyst.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and relates to a preparation method of a zirconium oxide supported palladium catalyst and application thereof in the field of carbonyl selective hydrogenation.
Background
The selective hydrogenation reaction of carbonyl is an important catalytic reaction in the chemical field, and various fine chemicals and chemical intermediates can be obtained through the selective hydrogenation of carbonyl. Catalysts typically used for carbonyl selective hydrogenation reactions are supported metal catalysts, the active component typically being a group VIII metal, such as Pd, Pt, Ru and Ni, Co, Fe based catalysts. The support used is generally Al2O3,SiO2,TiO2And carbon materials and the like. The selective hydrogenation reaction of benzaldehyde and the hydrofining reaction of crude terephthalic acid both involve the selective hydrogenation of carbonyl. Benzyl alcohol is an important reaction intermediate and is widely used in the fields of spices, medicines, plastic additives and the like. Currently, benzyl alcohol can be prepared by a benzaldehyde liquid-phase hydrogenation method. Benzaldehyde can be hydrogenated to obtain benzyl alcohol shown in a formula 1, and the benzyl alcohol is easy to be further hydrogenated to obtain a byproduct of toluene, so that the selectivity of the target product of the benzyl alcohol is poor. The crude terephthalic acid hydrofining reaction refers to that a byproduct p-carboxybenzaldehyde (4-CBA) exists in the crude terephthalic acid, the 4-CBA is subjected to hydro-conversion under the action of a catalyst in a hydrogen atmosphere, and then the high-purity terephthalic acid is obtained by crystallization, centrifugation, drying and the like by utilizing the difference of product solubility. The 4-CBA hydrogenation conversion process is shown in a formula 2. Since hydroxymethylbenzoic acid has a higher solubility than p-toluic acid, hydroxymethylbenzoic acid is easier to remove than p-tolualdehyde in subsequent multi-step crystallization separations. Therefore, the method is beneficial to the separation and purification of subsequent products when the 4-CBA conversion rate is improved and more hydroxymethyl benzoic acid intermediates are obtained.
Chinese patent CN103030528B (benzaldehyde liquid phase hydrogenation for preparing benzyl alcohol) discloses a Ni/SiO2The composite catalyst is prepared through proper amount of MgO, CaO and P2O5After modification, the conversion rate of benzaldehyde is 93.0% and the selectivity of benzyl alcohol is as high as 95.3% at 120 ℃ and under 3.0MPa of hydrogen. Three vectors (SiO. RTM. SiO. RTM. in the literature (Applied Catalysis A: General,2001,219,195-200.) are reported2,Al2O3And activated carbon) is used for selective hydrogenation of benzaldehyde, and the activated carbon supported catalyst is found to have higher benzaldehyde conversion rate but has poor selectivity to the target product benzyl alcohol, namely only 83%. Chinese patent CN105268434B (crude terephthalic acid hydrofining catalyst) discloses a method for treating an amino acid salt aqueous solution of titanium dioxide as a carrier, and a palladium-ruthenium bimetallic catalyst loaded with titanium dioxide is prepared for the hydrofining reaction of crude terephthalic acid, thereby solving the problem of more byproducts in the hydrogenation process in the prior art.
At present, noble metal catalysts used in the crude terephthalic acid hydrofining reaction and the benzaldehyde selective hydrogenation reaction are mainly concentrated on an active component palladium. The main problems in the prior art are that the palladium catalyst has low conversion rate in the crude terephthalic acid hydrofining reaction, and the product distribution is complex and difficult to control. In the reaction of preparing the benzyl alcohol by catalyzing the selective hydrogenation of the benzaldehyde, the obtained benzyl alcohol is easy to be excessively hydrogenated to obtain toluene along with the improvement of the conversion rate, so that the selectivity of the target product benzyl alcohol is reduced.
Disclosure of Invention
One of the technical problems to be solved by the present invention is to provide a zirconia carrier.
A zirconia support comprising zirconia and elemental nitrogen, the support having an electronic interaction between the elemental nitrogen and the zirconia.
In the technical scheme, the peak of 3d XPS of zirconium element in the carrier shifts 0.4-0.6 eV towards the direction of high binding energy.
In the above technical scheme, the nitrogen element content in the carrier is 1.1-7.4 at.%.
The second technical problem to be solved by the present invention is to provide a method for preparing a zirconia carrier.
A preparation method of a zirconium oxide carrier comprises the following steps of adding alkali into a solution containing a zirconium source and a nitrogen source, reacting to obtain a zirconium oxide precursor, and reducing the zirconium oxide precursor to obtain the nitrogen-containing zirconium oxide carrier.
In the above technical scheme, the solution is an alcohol-containing solution, preferably ethanol or propanol.
In the above technical scheme, the reaction conditions comprise a step of reacting at 40-120 ℃, preferably 60-100 ℃ for 1-10 h.
In the above technical scheme, the reaction further comprises washing and drying steps.
In the above technical solution, the reduction treatment includes a step of roasting in an atmosphere containing hydrogen.
In the technical scheme, the roasting comprises the step of roasting for 2-6h at the temperature of 300-700 ℃. Preferably 400-650 ℃ for 3-5 h.
In the above technical solution, the zirconium source is a zirconium salt, and includes one selected from zirconyl chloride, zirconyl nitrate, and zirconium nitrate. Preferably zirconyl nitrate.
In the above technical scheme, the nitrogen source comprises one selected from N, N-dimethylcyclohexanediamine, N-dimethylformamide, N-dimethylacetamide and ethylenediamine.
In the above technical solution, the alkali includes at least one selected from ammonia water, urea solution, sodium carbonate and sodium hydroxide. Preferably aqueous ammonia. In one embodiment of the invention, the pH is 9 after the addition of the base.
In the technical scheme, the mass ratio of the zirconium source to the nitrogen source is (24-6.5): 1.
The invention aims to solve the technical problem of providing a zirconium oxide supported palladium catalyst.
A zirconia supported palladium catalyst comprising the above carrier or the carrier prepared by the above method, and palladium.
In the technical scheme, the content of the palladium is 0.2-0.6% of the weight of the catalyst in percentage by weight.
In the technical scheme, the preparation method of the catalyst comprises the following steps of taking the zirconia as a carrier, loading active component palladium, reducing the active component palladium by adopting a reducing agent, washing and drying to obtain the zirconia-loaded palladium catalyst. The reducing agent comprises at least one of sodium formate, formaldehyde or hydrogen. The conditions for the impregnation and reduction are not critical to the present invention and researchers in this field are skilled in the art of preparing palladium catalysts by impregnation. The load of the palladium catalyst is obtained by adopting a conventional dipping-reduction method, and preferably, by adopting 3-10% sodium formate solution for reduction for 0.5-7 h.
The invention also provides an application of the catalyst in carbonyl selective hydrogenation reaction.
The invention also provides an application of the catalyst in the hydrofining reaction of crude terephthalic acid. Has the characteristics of high catalytic activity, more intermediates accumulation and easy separation of subsequent products.
The invention also provides an application of the catalyst in a reaction for preparing benzyl alcohol by benzaldehyde hydrogenation. Meanwhile, the method has the characteristics of high benzaldehyde conversion efficiency and high benzyl alcohol selectivity.
Based on the catalyst obtained by the technical scheme, the performance of the carbonyl selective hydrogenation reaction is evaluated according to the following conditions. The selective hydrogenation reaction of benzaldehyde is carried out in a stainless steel reaction kettle of 250ml, and the specific reaction conditions are as follows: the adding amount of the catalyst is 0.1 g, the benzaldehyde is 1ml, the ethanol is 80ml, the hydrogen pressure is 2.5MPa, the reaction temperature is 70-130 ℃, and the reaction time is 1-10 h. The product obtained after the reaction was quantitatively analyzed by gas chromatography with a FID detector.
The crude terephthalic acid hydrofining reaction is carried out in a 250ml stainless steel reaction kettle, and the specific reaction conditions are as follows: the adding amount of the catalyst is 0.06 g, the adding amount of the 4-CBA is 0.3 g, the water solution is 130ml, the reaction pressure is 3.5MPa, the reaction temperature is 160 ℃ and 250 ℃, and the reaction time is 1-5 h. And carrying out quantitative analysis on the liquid product after reaction by using a high performance liquid chromatography and an ultraviolet detector.
Compared with the prior art, the invention has the following beneficial effects:
according to the nitrogen-doped zirconia carrier, the nitrogen element in the carrier has electronic interaction with zirconia. The catalyst is used for loading active components, which is beneficial to the dispersion and stability of the active components, and the obtained catalyst has better catalytic activity.
The preparation method of the zirconium oxide carrier is simple and easy to amplify, and in the obtained nitrogen-doped zirconium oxide carrier, nitrogen elements are chemically combined with zirconium oxide.
The zirconium oxide supported palladium catalyst has high carbonyl selective hydrogenation efficiency and high selectivity.
The zirconium oxide supported palladium catalyst provided by the invention has the advantages that the hydrogenation effect of 4-CBA is obviously improved, the content of intermediate hydroxymethyl benzaldehyde is increased, and the cost of subsequent product separation is reduced.
The zirconium oxide supported palladium catalyst is used for the selective hydrogenation reaction of benzaldehyde, and ensures the high selectivity of a target product, namely benzyl alcohol, while realizing the high conversion rate of the benzaldehyde.
Drawings
FIG. 1 is a Zr 3d XPS chart of the zirconia support obtained in example 1.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the following embodiments are exemplified. However, it is easily understood by those skilled in the art that the contents of the embodiments are only for illustrating the present invention and should not limit the present invention described in detail in the claims.
[ example 1 ]
(1) Dissolving 10 g of zirconyl chloride in a mixed solution of 40ml of N-propanol and 80ml of water, adding 0.5ml of N, N-dimethylacetamide, and uniformly stirring; gradually dropwise adding 5% ammonia water solution, adjusting the pH value of the solution to 9, transferring the obtained turbid solution to a reaction kettle, heating to 60 ℃, reacting for 5 hours, filtering, washing and drying to obtain a zirconium oxide precursor; (2) roasting the zirconia precursor in the step (1) for 3 hours at 400 ℃ in a hydrogen atmosphere to prepare zirconia; (3) weighing 2 g of zirconia as a carrier, soaking the carrier in 1.4ml of palladium chloride solution with the concentration of 0.055mol/L, reducing the carrier by adopting 5% sodium formate solution at 50 ℃ for 45min, washing the carrier by deionized water to be neutral, and drying the carrier at 110 ℃ to obtain the zirconia supported palladium catalyst. The content of nitrogen element in the catalyst was measured to be 1.22 at.% by X-ray photoelectron spectroscopy (XPS). While the Zr 3d XPS peak was shifted by 0.4eV towards the high binding energy direction.
[ example 2 ]
(1) Dissolving 7 g of zirconyl nitrate in a mixed solution of 40ml of N-propanol and 80ml of water, adding 0.5ml of N, N-dimethylacetamide, and uniformly stirring; gradually dropwise adding 5% ammonia water solution, adjusting the pH value of the solution to 9, transferring the obtained turbid solution to a reaction kettle, heating to 60 ℃, reacting for 6 hours, filtering, washing and drying to obtain a zirconium oxide precursor; (2) roasting the zirconia precursor in the step (1) for 3 hours at 400 ℃ in a hydrogen atmosphere to prepare zirconia; (3) weighing 2 g of zirconia as a carrier, soaking the carrier in 1.4ml of palladium chloride solution with the concentration of 0.055mol/L, reducing the carrier by adopting 5% sodium formate solution at 50 ℃ for 45min, washing the carrier by deionized water to be neutral, and drying the carrier at 110 ℃ to obtain the zirconia supported palladium catalyst. The content of nitrogen element in the catalyst was measured to be 1.87 at.% by X-ray photoelectron spectroscopy (XPS).
[ example 3 ]
(1) Dissolving 10 g of zirconium nitrate in a mixed solution consisting of 60ml of ethanol and 80ml of water, adding 0.5ml of N, N-dimethylacetamide, and uniformly stirring; gradually dropwise adding 5% ammonia water solution, adjusting the pH value of the solution to 9, transferring the obtained turbid solution to a reaction kettle, heating to 60 ℃, reacting for 7 hours, filtering, washing and drying to obtain a zirconium oxide precursor; (2) roasting the zirconia precursor in the step (1) for 3 hours at 400 ℃ in a hydrogen atmosphere to prepare zirconia; (3) weighing 2 g of zirconia as a carrier, soaking the carrier in 1.4ml of palladium chloride solution with the concentration of 0.055mol/L, reducing the carrier by adopting 5% sodium formate solution at 50 ℃ for 45min, washing the carrier by deionized water to be neutral, and drying the carrier at 110 ℃ to obtain the zirconia supported palladium catalyst.
[ example 4 ]
(1) Dissolving 7 g of zirconyl nitrate in a mixed solution of 40ml of N-propanol and 80ml of water, adding 0.5ml of N, N-dimethylacetamide, and uniformly stirring; gradually dropwise adding 0.5mol/L sodium carbonate solution, adjusting the pH value of the solution to 9, transferring the obtained turbid solution into a reaction kettle, heating to 60 ℃, reacting for 5 hours, filtering, washing and drying to obtain a zirconium oxide precursor; (2) roasting the zirconia precursor in the step (1) for 3 hours at 450 ℃ in a hydrogen atmosphere to prepare zirconia; (3) weighing 2 g of zirconia as a carrier, soaking the carrier in 1.4ml of palladium chloride solution with the concentration of 0.055mol/L, reducing the carrier by adopting 5% sodium formate solution at 50 ℃ for 45min, washing the carrier by deionized water to be neutral, and drying the carrier at 110 ℃ to obtain the zirconia supported palladium catalyst.
[ example 5 ]
(1) Dissolving 7 g of zirconyl nitrate in a mixed solution of 40ml of N-propanol and 80ml of water, adding 0.5ml of N, N-dimethylformamide, and uniformly stirring; gradually dropwise adding 0.5mol/L sodium hydroxide solution, adjusting the pH value of the solution to 9, transferring the obtained turbid solution into a reaction kettle, heating to 60 ℃, reacting for 5 hours, filtering, washing and drying to obtain a zirconium oxide precursor; (2) roasting the zirconia precursor in the step (1) for 5 hours at 450 ℃ in a hydrogen atmosphere to prepare zirconia; (3) weighing 2 g of zirconia as a carrier, soaking the carrier in 1.4ml of palladium chloride solution with the concentration of 0.055mol/L, reducing the carrier by adopting 5% sodium formate solution at 50 ℃ for 45min, washing the carrier by deionized water to be neutral, and drying the carrier at 110 ℃ to obtain the zirconia supported palladium catalyst.
[ example 6 ]
(1) Dissolving 7 g of zirconyl nitrate in a mixed solution of 40ml of N-propanol and 80ml of water, adding 0.8ml of N, N-dimethylcyclohexanediamine, and uniformly stirring; gradually dropwise adding 5% ammonia water solution, adjusting the pH value of the solution to 9, transferring the obtained turbid solution to a reaction kettle, heating to 60 ℃, reacting for 5 hours, filtering, washing and drying to obtain a zirconium oxide precursor; (2) roasting the zirconia precursor in the step (1) for 3 hours at 500 ℃ in a hydrogen atmosphere to prepare zirconia; (3) weighing 2 g of zirconia as a carrier, soaking the carrier in 1.4ml of palladium chloride solution with the concentration of 0.055mol/L, reducing the carrier by adopting 5% sodium formate solution at 50 ℃ for 45min, washing the carrier by deionized water to be neutral, and drying the carrier at 110 ℃ to obtain the zirconia supported palladium catalyst.
[ example 7 ]
(1) Dissolving 7 g of zirconyl nitrate in a mixed solution of 40ml of N-propanol and 80ml of water, adding 0.8ml of N, N-dimethylcyclohexanediamine, and uniformly stirring; gradually dropwise adding 5% ammonia water solution, adjusting the pH value of the solution to 9, transferring the obtained turbid solution to a reaction kettle, heating to 80 ℃, reacting for 5 hours, filtering, washing and drying to obtain a zirconium oxide precursor; (2) roasting the zirconia precursor in the step (1) for 3 hours at 550 ℃ in a hydrogen atmosphere to prepare zirconia; (3) weighing 2 g of zirconia as a carrier, soaking the carrier in 1.4ml of palladium chloride solution with the concentration of 0.055mol/L, reducing the carrier by adopting 5% sodium formate solution at 50 ℃ for 45min, washing the carrier by deionized water to be neutral, and drying the carrier at 110 ℃ to obtain the zirconia supported palladium catalyst.
[ example 8 ]
(1) Dissolving 6 g of zirconyl nitrate in a mixed solution of 40ml of n-propanol and 80ml of water, adding 1ml of ethylenediamine, and uniformly stirring; gradually dropwise adding 5% ammonia water solution, adjusting the pH value of the solution to 9, transferring the obtained turbid solution to a reaction kettle, heating to 100 ℃, reacting for 5 hours, filtering, washing and drying to obtain a zirconium oxide precursor; (2) roasting the zirconia precursor in the step (1) for 3 hours at 550 ℃ in a hydrogen atmosphere to prepare zirconia; (3) weighing 2 g of zirconia as a carrier, soaking the carrier in 1.4ml of palladium chloride solution with the concentration of 0.055mol/L, reducing the carrier by adopting 5% sodium formate solution at 50 ℃ for 45min, washing the carrier by deionized water to be neutral, and drying the carrier at 110 ℃ to obtain the zirconia supported palladium catalyst.
Comparative example 1
Weighing 2 g of commercial activated carbon as a carrier, soaking the carrier by using 1.4ml of palladium chloride solution with the concentration of 0.055mol/L, then reducing the carrier by using 5% sodium formate solution at 50 ℃ for 45min, washing the carrier by using deionized water to be neutral, and drying the carrier at 110 ℃ to obtain the activated carbon supported palladium catalyst.
Comparative example 2
Weighing 2 g of commercially available zirconium oxide as a carrier, soaking the carrier by using 1.4ml of palladium chloride solution with the concentration of 0.055mol/L, then reducing the carrier by using 5% sodium formate solution at 50 ℃ for 45min, washing the carrier by using deionized water to be neutral, and drying the carrier at 110 ℃ to obtain the zirconium oxide supported palladium catalyst.
Comparative example 3
This comparative example is similar to the preparation of the zirconia supported palladium catalyst of example 4, except that the zirconia precursor was not subjected to a subsequent hydrogen calcination treatment during the preparation. The specific process is as follows: dissolving 7 g of zirconyl nitrate in a mixed solution of 40ml of n-propanol and 80ml of water, and uniformly stirring; adding 0.5ml of N, N-dimethylacetamide, gradually dropwise adding 0.5mol/L sodium carbonate solution, adjusting the pH value of the solution to 9, placing the obtained turbid solution in a reaction kettle, heating to 60 ℃, reacting for 5 hours, filtering, washing and drying to obtain a zirconium oxide precursor; weighing 2 g of zirconia precursor as a carrier, soaking the carrier by using 1.4ml of palladium chloride solution with the concentration of 0.055mol/L, then reducing the carrier by using 5% sodium formate solution at 50 ℃ for 45min, washing the carrier by using deionized water to be neutral, and drying the carrier at 110 ℃ to obtain the zirconia supported palladium catalyst.
The catalysts prepared in examples 1 to 4 and comparative examples 1 to 3 were subjected to 4-CBA hydrogenation evaluation, and the results are shown in Table 1. The adding amount of the catalyst is 0.06 g, the adding amount of the 4-CBA is 0.3 g, the water solution is 130ml, the reaction pressure is 3.5MPa, the reaction temperature is 175 ℃, and the reaction time is 1.5 h. The catalysts prepared in examples 5 to 8 and comparative examples 1 to 3 were evaluated for the selective hydrogenation of benzaldehyde, and the results are shown in Table 2. The reaction conditions are that the adding amount of the catalyst is 0.1 g, 1ml of benzaldehyde and 80ml of ethanol, the pressure of hydrogen is 2.5MPa, the reaction temperature is 110 ℃, and the reaction time is 6 h.
As can be seen from the results of the catalytic performance evaluation in table 1, compared with [ comparative examples 1 to 3 ], the palladium catalyst supported on zirconia according to the present invention has improved hydrogenation activity compared with conventional palladium-carbon catalysts and common palladium catalysts supported on zirconia, and also has significantly improved selectivity to the intermediate hydroxymethylbenzoic acid, which is more advantageous for the separation and purification of the subsequent products. From the catalytic performance evaluation results in table 2, it can be found that, in comparative example 2, when the palladium catalyst supported on the common zirconia catalyzes the selective hydrogenation reaction of benzaldehyde, the selectivity of benzyl alcohol is only 97.3% when the conversion rate of benzaldehyde is 80.4%; when the conversion rate of benzaldehyde is higher than 96%, the selectivity of benzyl alcohol can still be maintained above 98%, and a good technical effect is achieved. The invention provides important technical guidance for regulating and controlling the metal-oxide interaction mode and further developing the efficient and stable metal catalyst.
TABLE 1
TABLE 2
Claims (15)
1. A zirconia support comprising zirconia and elemental nitrogen, the support having an electronic interaction between the elemental nitrogen and the zirconia.
2. The zirconia support of claim 1 wherein the nitrogen content of the support is 1.1 to 7.4 at.%.
3. A preparation method of a zirconium oxide carrier comprises the following steps of adding alkali into a solution containing a zirconium source and a nitrogen source, reacting to obtain a zirconium oxide precursor, and reducing the zirconium oxide precursor to obtain the nitrogen-containing zirconium oxide carrier.
4. The method according to claim 3, wherein the solution is an alcoholic solution, preferably ethanol, propanol.
5. The method of claim 3, wherein the reaction conditions comprise a step of reaction at 40-120 ℃, preferably 60-100 ℃, for 1-10 h.
6. The method according to claim 3, further comprising washing and drying steps after the reaction.
7. The production method according to claim 3, wherein the reduction treatment includes a step of firing in an atmosphere containing hydrogen gas.
8. The method as claimed in claim 7, wherein the calcination comprises calcination at 300-700 ℃ for 2-6 h.
9. The method according to claim 3, wherein the zirconium source is a zirconium salt comprising one selected from the group consisting of zirconyl chloride, zirconyl nitrate and zirconium nitrate.
10. The method according to claim 3, wherein the nitrogen source comprises one selected from the group consisting of N, N-dimethylcyclohexanediamine, N-dimethylformamide, N-dimethylacetamide and ethylenediamine.
11. The production method according to claim 3, wherein the base comprises at least one selected from the group consisting of aqueous ammonia, a urea solution, sodium carbonate, and sodium hydroxide.
12. The production method according to claim 3, wherein the mass ratio of the zirconium source to the nitrogen source is (24-6.5): 1.
13. A zirconia-supported palladium catalyst comprising the support of any one of claims 1 to 2 or the support produced by the process of any one of claims 3 to 12, and palladium.
14. Use of the catalyst of claim 13 in carbonyl selective hydrogenation reactions.
15. Use of the catalyst according to claim 13 in a crude terephthalic acid hydrofinishing reaction or a reaction for preparing benzyl alcohol by benzaldehyde hydrogenation.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910648794.5A CN112237937B (en) | 2019-07-18 | 2019-07-18 | Nitrogen-doped zirconia carrier, and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910648794.5A CN112237937B (en) | 2019-07-18 | 2019-07-18 | Nitrogen-doped zirconia carrier, and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112237937A true CN112237937A (en) | 2021-01-19 |
CN112237937B CN112237937B (en) | 2023-08-29 |
Family
ID=74167506
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910648794.5A Active CN112237937B (en) | 2019-07-18 | 2019-07-18 | Nitrogen-doped zirconia carrier, and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112237937B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116173960A (en) * | 2023-03-09 | 2023-05-30 | 福州大学 | Preparation method and application of zirconia/cobalt/carbon composite catalyst |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102078810A (en) * | 2009-11-30 | 2011-06-01 | 葛昌华 | Oxide supported palladium hydrogenation catalyst and preparation method thereof |
CN106000459A (en) * | 2016-06-06 | 2016-10-12 | 南京工业大学 | Preparation method of supported palladium nano catalyst |
CN106732559A (en) * | 2016-12-26 | 2017-05-31 | 青岛大学 | A kind of palladium catalyst of cherry stone carbon load and preparation method and application |
CN107011107A (en) * | 2017-05-16 | 2017-08-04 | 中国科学技术大学 | A kind of method that use load type metal catalyst prepares alcohol |
CN107282080A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | Hydrofining crude terephthalic acid catalyst and preparation method thereof |
CN108940346A (en) * | 2018-08-02 | 2018-12-07 | 浙江大学 | Beta-unsaturated ketone selective hydrocatalyst and its preparation method and application |
-
2019
- 2019-07-18 CN CN201910648794.5A patent/CN112237937B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102078810A (en) * | 2009-11-30 | 2011-06-01 | 葛昌华 | Oxide supported palladium hydrogenation catalyst and preparation method thereof |
CN107282080A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | Hydrofining crude terephthalic acid catalyst and preparation method thereof |
CN106000459A (en) * | 2016-06-06 | 2016-10-12 | 南京工业大学 | Preparation method of supported palladium nano catalyst |
CN106732559A (en) * | 2016-12-26 | 2017-05-31 | 青岛大学 | A kind of palladium catalyst of cherry stone carbon load and preparation method and application |
CN107011107A (en) * | 2017-05-16 | 2017-08-04 | 中国科学技术大学 | A kind of method that use load type metal catalyst prepares alcohol |
CN108940346A (en) * | 2018-08-02 | 2018-12-07 | 浙江大学 | Beta-unsaturated ketone selective hydrocatalyst and its preparation method and application |
Non-Patent Citations (3)
Title |
---|
CAN AO,ET AL.: "Dispersing Pd nanoparticles on N-doped TiO2: a highly selective catalyst for H2O2 synthesis", 《CATAL. SCI. TECHNOL.》 * |
YUANYANG WANG,ET AL.: "Novel N-doped ZrO2 with enhanced visible-light photocatalytic activity for hydrogen production and degradation of organic dyes", 《RSC ADV.》 * |
刘国秀: ""负载金属催化剂的制备及其合成油醇和异辛醇的研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116173960A (en) * | 2023-03-09 | 2023-05-30 | 福州大学 | Preparation method and application of zirconia/cobalt/carbon composite catalyst |
Also Published As
Publication number | Publication date |
---|---|
CN112237937B (en) | 2023-08-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3092072B1 (en) | A process for vapor-phase methanol carbonylation to methyl formate | |
KR102121079B1 (en) | Process for making ethylene and acetic acid | |
JP2000176287A (en) | Catalyst for methanol synthesis and synthetic method of methanol | |
CN111215084A (en) | Copper-based catalyst for preparing methanol by carbon dioxide hydrogenation, preparation and application thereof | |
CN112717928A (en) | Catalyst for preparing butylene by dehydrogenating n-butane | |
CN110368967B (en) | Acetic acid hydrogenation catalyst, preparation method and application thereof | |
JP2009254981A (en) | Ammonia decomposing catalyst and method of decomposing ammonia | |
CN114849694B (en) | Catalyst for hydrogenation of nitroaromatic hydrocarbon based on metal-loaded tungsten oxide, preparation method and application thereof | |
CN104974016A (en) | Method for preparing cinnamyl alcohol through cinnamaldehyde hydrogenation | |
CN113058613B (en) | Zirconium-manganese-zinc composite oxide supported nickel-based catalyst for methane dry gas reforming reaction and preparation and application thereof | |
CN112237937B (en) | Nitrogen-doped zirconia carrier, and preparation method and application thereof | |
CN108970632A (en) | A kind of load type bimetal catalyst and preparation method thereof efficiently synthesizing DBE | |
CN114433100A (en) | Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by maleic anhydride hydrogenation | |
CN111217673B (en) | Method for high-energy utilization of ethanol | |
CN109092301B (en) | Catalyst for preparing isopropyl benzene and preparation method thereof | |
CN109092295B (en) | Isopropyl benzene catalyst and preparation method thereof | |
CN113813952B (en) | Preparation and application methods of chlorine-modified cubic cerium oxide nanocrystalline catalyst | |
WO2018141826A1 (en) | Production of acetonitrile and/or hydrogen cyanide from ammonia and methanol | |
CN109824634A (en) | A kind of method that furfural direct oxidation esterification prepares methylfuroate | |
JP7144208B2 (en) | Catalyst for producing cumene and its application | |
CN107754802A (en) | A kind of catalyst and preparation method and application for ethylene carbonate ester through hydrogenation | |
CN110871075B (en) | Iron-cobalt-potassium-loaded zirconium dioxide catalyst, preparation method and application thereof | |
CN109096031B (en) | Method for producing isopropyl benzene | |
Benhmid et al. | Highly active and selective Pd–Cu–TiO2 catalyst for the direct synthesis of benzyl acetate by gas phase acetoxylation of toluene | |
CN115894196B (en) | Method for continuously synthesizing cyclopentanone |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |