CN111085193A - Impregnation method of supported palladium catalyst - Google Patents
Impregnation method of supported palladium catalyst Download PDFInfo
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- CN111085193A CN111085193A CN201811243526.7A CN201811243526A CN111085193A CN 111085193 A CN111085193 A CN 111085193A CN 201811243526 A CN201811243526 A CN 201811243526A CN 111085193 A CN111085193 A CN 111085193A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 238000005470 impregnation Methods 0.000 title claims abstract description 75
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 34
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000007524 organic acids Chemical class 0.000 claims abstract description 15
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims abstract description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000011054 acetic acid Nutrition 0.000 claims abstract description 4
- 235000015165 citric acid Nutrition 0.000 claims abstract description 4
- 235000019253 formic acid Nutrition 0.000 claims abstract description 4
- 239000001530 fumaric acid Substances 0.000 claims abstract description 4
- 235000011087 fumaric acid Nutrition 0.000 claims abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 4
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 238000007654 immersion Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 238000011068 loading method Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of catalysts, and discloses an impregnation method of a supported palladium catalyst. The method comprises the steps of immersing a carrier in an immersion liquid, wherein the immersion liquid comprises a palladium-containing compound and an inorganic acid and/or an organic acid; the inorganic acid is hydrochloric acid and/or nitric acid; the organic acid is one or more of citric acid, fumaric acid, formic acid, acetic acid, propionic acid, malonic acid and butyric acid. The impregnation method can greatly improve the palladium utilization rate of the supported palladium catalyst.
Description
Technical Field
The invention relates to the field of catalysts, in particular to an impregnation method of a supported palladium catalyst.
Background
Supported palladium catalysts in the chemical industry and their useThe organic synthesis reaction is very important, for example, catalytic reforming and pyrolysis gasoline hydrogenation in petroleum refining, and Pd/Al is used in hydrogenation, oxidative dehydrogenation, coupling and other reactions in organic synthesis2O3As a catalyst. Pd has good sintering resistance and can slow down the influence of high-temperature thermal deactivation; al (Al)2O3Has good thermal stability, large specific surface area, excellent thermal shock and mechanical shock resistance, relatively low manufacturing cost and is often used as a carrier in the catalyst industry. Pd is passed through with Al2O3The coordination of the functional group on the carrier can overcome the defects of low stability, poor repeatability and the like of the catalyst in a reaction system, and the activity and the selectivity of the catalyst can be adjusted by adjusting the Pd loading amount and the distribution area of the active components.
In the previous process of producing the supported palladium catalyst, the utilization rate of Pd is low, and Pd/Al is used2O3The catalyst is only about 81% for example. Therefore, in the catalyst preparation process, the dosage of the noble metal Pd needs to be increased to enable the Pd content to meet the quality index requirement, so that the catalyst manufacturing cost is increased.
Disclosure of Invention
The invention aims to overcome the technical problem of low palladium utilization rate in the preparation process of the supported palladium catalyst in the prior art, and provides an impregnation method of the supported palladium catalyst, which can greatly improve the palladium utilization rate of the supported palladium catalyst.
The inventors of the present application have found through intensive studies that, in the existing catalyst preparation process, the pH of the impregnation solution is adjusted by adding a suitable base to bring the pH of the impregnation solution close to the vicinity of the isoelectric point of the carrier, the impregnation solution can interact with the carrier during the impregnation process, Pd is rapidly absorbed by the carrier, and an eggshell-shaped distribution is generally formed when the loading amount is low, that is, the Pd component is significantly concentrated on the outer surface of the carrier. The fine particles on the surface of the carrier and the mutual friction between the carriers in the dipping process can cause the active components on the surface of the catalyst to be peeled off, thereby causing the lower utilization rate of Pd in the catalyst preparation process.
In order to solve the problems, the inventor of the invention analyzes the condition of low utilization rate of the catalyst Pd, samples the falling powder in the preparation process of the catalyst and determines the Pd content, and finds that the Pd content in the falling powder is as high as 1-3 wt%. This indicates that the active components on the surface of the catalyst carrier fall off due to abrasion during the impregnation process, and the powder falling condition is serious. Thus, the inventors considered that an attempt was made to appropriately bury the active component of the catalyst in a position slightly below the surface layer of the carrier to prevent exfoliation of the Pd component by attrition, while it was desired to reduce the fine particles electrostatically adsorbed on the surface of the catalyst carrier. In order to achieve the above object, the inventors further studied and creatively proposed the following technical solutions of the present invention.
That is, the present invention provides a method for impregnating a supported palladium catalyst, comprising the step of impregnating a carrier in an impregnation solution, wherein the impregnation solution comprises a palladium-containing compound and an inorganic acid and/or an organic acid; the inorganic acid is hydrochloric acid and/or nitric acid; the organic acid is one or more of citric acid, fumaric acid, formic acid, acetic acid, propionic acid, malonic acid and butyric acid.
Preferably, the content of the inorganic acid and/or the organic acid in the impregnation solution is 0.01 to 0.2 wt%, preferably 0.03 to 0.08 wt%.
Preferably, the pH of the impregnation solution is between 2.8 and 3.2.
Preferably, the palladium-containing compound is one or more of chloropalladic acid, palladium chloride, palladium nitrate and dichlorodiammine palladium.
Preferably, the concentration of the palladium-containing compound in the impregnation liquid is more than 1000 μ g/g, preferably 3000-10000 μ g/g, calculated by palladium element.
Preferably, the dipping temperature is 50-95 ℃ and the dipping time is more than 10 min.
Preferably, the stirring rate of the impregnation is 3 to 30r/min
Preferably, the method further comprises washing the support prior to impregnation.
Preferably, the washing is performed using pure water, more preferably in a bubbling overflow manner.
Preferably, the carrier is Al2O3Carrier, SiO2Support, TiO2One or more of a carrier and an activated carbon carrier, preferably Al2O3And (3) a carrier.
Through the technical scheme, the impregnation method can improve the utilization rate of palladium in the impregnation process, so that the use amount of noble metal palladium can be reduced, and the preparation cost of the supported palladium catalyst is reduced. Moreover, the impregnation method is simple and convenient to operate, high in practicability and convenient to apply to industrial production.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The impregnation method of the supported palladium catalyst comprises the steps of impregnating a carrier in an impregnation liquid, wherein the impregnation liquid comprises a palladium-containing compound and an inorganic acid and/or an organic acid; the inorganic acid is hydrochloric acid and/or nitric acid; the organic acid is one or more of citric acid, fumaric acid, formic acid, acetic acid, propionic acid, malonic acid and butyric acid.
The inventor of the invention researches the preparation process of the supported palladium catalyst, and aims at solving the problem of low utilization rate of palladium in the prior art, and finds that the addition of inorganic acid and/or organic acid in the impregnation solution can appropriately bury the active component to a position slightly below the surface layer of the carrier, prevent the stripping of the Pd component caused by abrasion, and reduce the fine particles adsorbed by static electricity on the surface of the catalyst carrier, thereby greatly improving the utilization rate of palladium, reducing the feeding amount of palladium and reducing the preparation cost of the supported palladium catalyst.
According to the invention, among the inorganic and/or organic acids, preference is given to using organic acids, for example, preference is given to using citric acid.
In the present invention, the content of the inorganic acid and/or the organic acid in the impregnation solution is 0.01 to 0.2% by weight, preferably 0.03 to 0.08% by weight, and more preferably 0.03 to 0.05% by weight. By making the content of the inorganic acid and/or the organic acid within the above range, the palladium utilization rate can be further improved.
According to a preferred embodiment of the invention, the pH of the impregnation solution is between 2.8 and 3.2, preferably between 2.9 and 3.1. By using the impregnation solution having the above pH range, the impregnation efficiency of the carrier and the palladium utilization rate can be improved. The pH can be adjusted by adding an acidic or basic compound to the immersion liquid, for example, NaOH or K can be added2CO3、NaHCO3、Na2CO3And the like.
In the present invention, the palladium-containing compound is not particularly limited, and any palladium-containing compound that can be conventionally used for the preparation of a supported palladium catalyst can be used, and examples thereof include one or more of chloropalladic acid, palladium chloride, palladium nitrate and dichlorodiammine palladium, and among them, chloropalladic acid is preferable.
In the present invention, the carrier is not particularly limited, and any carrier that can be conventionally used for producing a supported palladium catalyst can be used, and examples thereof include Al2O3Carrier, SiO2Support, TiO2One or more of a carrier and an activated carbon carrier, wherein Al is preferred2O3And (3) a carrier.
According to the preferred impregnation method of the invention, the concentration of the palladium-containing compound in the impregnation liquid is more than 1000 μ g/g, preferably 3000-10000 μ g/g, more preferably 3000-5000 μ g/g, calculated by palladium element.
According to a preferred impregnation method of the present invention, the impregnation can be performed using the conventional impregnation conditions for the supported palladium catalyst, for example, the impregnation temperature may be 50 to 95 ℃, the impregnation time may be 10min or more, preferably, the impregnation temperature may be 70 to 95 ℃, and the impregnation time may be 15 to 22 min. In addition, the stirring rate for the impregnation may be 3 to 30r/min, preferably 3 to 18 r/min.
Furthermore, the inventors of the present invention have also surprisingly found that the use of the washed carrier for impregnation further improves the utilization of palladium in the preparation process. Therefore, preferably the method further comprises washing the support prior to impregnation. The washing is carried out using pure water, and the amount of the washing solution may be, for example, 10 to 30 times by volume of the carrier, and the number of washing may be 1 or more, for example, 2 to 3 times.
According to the invention, the impregnated catalyst can be further dried, calcined and the like, so as to prepare the final supported palladium catalyst. The conditions for the above treatment may be specifically selected depending on the catalyst to be prepared.
The present invention will be described in detail below by way of examples. In the following examples, the Pd loading was measured by inductively coupled plasma spectroscopy (ICP); the utilization rate of Pd is the ratio of Pd loading capacity to Pd feeding capacity. In the following examples, the acceptable ranges for the required Pd loadings for the catalysts of designations A-F are as follows (in. mu.g/g): a:2800 + -300; b, 3500 plus or minus 300; c, 5000 +/-300; d is 5500 plus or minus 300; e, 2700 plus or minus 300; f:4900 +/-300.
Examples 1 to 4 and comparative examples 1 to 3
The supported palladium catalyst was impregnated using a stirred tank with a steam jacket, chloropalladic acid and citric acid were added to the impregnation solution according to the feed amounts in Table 1, and K was used2CO3Adjusting the pH of the soaking solution to 3.0, using the soaking solution with a volume of 48L
Clover strip Al2O3The carrier is 20kg, and the impregnation is carried out under the conditions of stirring speed of 10r/min and temperature of 85 ℃, and the impregnation time is 20 min. In addition, according to the explanation in table 1, the carrier was washed 2 times with 15 times volume of pure water before impregnation in the examples and comparative examples where washing was performed. The results are shown in Table 1.
TABLE 1
From the data in table 1, it can be seen that by comparing examples 1 to 3 with comparative example 1, example 4 and comparative examples 2 to 3, respectively, the use ratio of Pd can be improved by 10% or more by adding citric acid to the impregnation solution. In addition, as can be seen from comparing examples 1 and 2, the palladium utilization rate can be further improved by washing the carrier before impregnation.
Examples 4 to 6
Impregnation of the supported palladium catalyst was carried out as in example 1, except that the citric acid content shown in table 2 was used, and the results are shown in table 2.
TABLE 2
As is clear from the data in table 2, the addition of 0.03 to 0.05 wt% citric acid to the impregnation solution enabled the palladium utilization to be 90% or more, and to a high value of 96.29% at the highest.
Examples 7 to 13
Impregnation of the supported palladium catalyst was carried out in the same manner as in example 1 except that the acids shown in Table 3 were used (the addition concentrations were all 0.05% by weight), and the results are shown in Table 3.
TABLE 3
From the data in Table 3, it can be seen that the addition of the acids of examples 7-13 can improve the utilization of palladium as compared to comparative example 2.
Examples 14 to 16, comparative examples 4 to 6
Impregnation of the supported palladium catalyst was carried out in the same manner as in example 1 except that the carriers shown in Table 4 were used, the concentrations of citric acid in the impregnation solutions in examples 14 to 16 were all 0.05% by weight, and citric acid was not added in comparative examples 4 to 6. The results are shown in Table 4.
TABLE 4
From the data in table 4, it can be seen that by adding citric acid to the impregnation solution, the palladium loading rates of various carriers can be increased, comparing example 14 and comparative example 4, example 15 and comparative example 5, and example 16 and comparative example 6, respectively.
Example 17
Aiming at Pd/Al with different grades2O3Optimizing the impregnation process of the catalyst, wherein citric acid is not added into the impregnation liquid of the scheme before optimization, and washing is not carried out; the optimized scheme is that 0.05 weight percent of citric acid is added into the impregnation liquid, and the carrier is washed before impregnation. The washing method and the rest of the preparation method were the same as in example 1. The results are shown in Table 5.
TABLE 5
The results in table 5 show that the optimized impregnation method of the present invention can greatly increase the palladium utilization rate by 14% or more, and reach 94% or even 98% or more, in the preparation of different grades of supported palladium catalysts, so that the palladium dosage is reduced by 8% or more, and the subsequent 4 grades can be reduced by 15% or more, thereby reducing the preparation cost of the supported palladium catalysts.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for impregnating a supported palladium catalyst, comprising the step of impregnating a carrier in an impregnating solution,
wherein the impregnation liquid comprises a palladium-containing compound and an inorganic acid and/or an organic acid;
the inorganic acid is hydrochloric acid and/or nitric acid;
the organic acid is one or more of citric acid, fumaric acid, formic acid, acetic acid, propionic acid, malonic acid and butyric acid.
2. The impregnation method according to claim 1, wherein the content of the inorganic acid and/or the organic acid in the impregnation solution is 0.01 to 0.2 wt%, preferably 0.03 to 0.08 wt%.
3. The impregnation method according to claim 1, wherein the pH of the impregnation liquid is 2.8 to 3.2.
4. The impregnation method according to claim 1, wherein the palladium-containing compound is one or more of chloropalladic acid, palladium chloride, palladium nitrate, and dichlorodiamminepalladium.
5. The impregnation method according to any one of claims 1 to 4, wherein the concentration of the palladium-containing compound in the impregnation solution is 1000 μ g/g or more, preferably 3000-10000 μ g/g, in terms of palladium element.
6. The impregnation method according to any one of claims 1 to 4, wherein the impregnation temperature is 50 to 95 ℃ and the impregnation time is 10min or more.
7. The impregnation process according to any one of claims 1 to 4, wherein the stirring rate of the impregnation is from 3 to 30 r/min.
8. The impregnation process of any of claims 1-4, wherein the process further comprises washing the support prior to impregnation.
9. The impregnation method according to claim 8, wherein the washing is performed using pure water.
10. Impregnation method according to any one of claims 1 to 4, wherein the support is Al2O3Carrier, SiO2Support, TiO2One or more of a support and an activated carbon support;
preferably Al2O3And (3) a carrier.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113663736A (en) * | 2021-09-27 | 2021-11-19 | 长春工业大学 | Preparation and application of Pd/UiO-66 by strong electrostatic adsorption method |
| WO2023285793A1 (en) | 2021-07-12 | 2023-01-19 | Johnson Matthey Public Limited Company | Highly dispersed palladium catalysts |
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