CN108927203B - Regeneration method of phenol hydrogenation Pd @ CN catalyst - Google Patents
Regeneration method of phenol hydrogenation Pd @ CN catalyst Download PDFInfo
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- CN108927203B CN108927203B CN201811187476.5A CN201811187476A CN108927203B CN 108927203 B CN108927203 B CN 108927203B CN 201811187476 A CN201811187476 A CN 201811187476A CN 108927203 B CN108927203 B CN 108927203B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 28
- 238000011069 regeneration method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 abstract description 16
- 238000002474 experimental method Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- RPHMFCDGSSKPKI-UHFFFAOYSA-N cyclohexane;phenol Chemical compound C1CCCCC1.OC1=CC=CC=C1 RPHMFCDGSSKPKI-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/28—Regeneration or reactivation
-
- 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
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/58—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids and gas addition thereto
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a regeneration method of a Pd @ CN catalyst for phenol hydrogenation. After the Pd @ CN catalyst is used for catalyzing phenol to be hydrogenated, the catalyst is recovered by filtration, placed in a reaction kettle, added with a solvent, washed under certain conditions to regenerate the catalyst, and filtered again to carry out the next application experiment. The regeneration method can effectively regenerate the deactivated catalyst, realize the recycling of the catalyst, reduce the using amount of the catalyst, improve the economical efficiency of the process and provide guarantee for the green production process of preparing the cyclohexanone by phenol hydrogenation.
Description
Technical Field
The invention relates to a regeneration method of a Pd @ CN catalyst, in particular to a regeneration method of a Pd @ CN catalyst in a high-concentration phenol hydrogenation process, and belongs to the technical field of catalysis.
Background
The downstream products of cyclohexanone, caprolactam and adipic acid, are important intermediates for synthesizing nylon 6 and nylon 66. The main industrial production process of cyclohexanone is cyclohexane oxidation, but the method has the problems of more byproducts, more acid-containing wastewater and greater environmental pollution. In recent years, the preparation of cyclohexanone by phenol one-step hydrogenation has attracted attention due to its advantages of short process flow, high atom utilization rate, and the like.
The patent (publication No. 104402687A) applies Pd @ CN catalyst to phenol hydrogenation, and develops a novel phenol hydrogenation process, but the phenol concentration in the process is low, and the economic benefit in the industrial process is too low. Patent publication No. 106861741a has developed a method for post-treatment of phenol hydrogenation catalyst, which can solve the problem of deactivation of Pd @ CN catalyst at 10% phenol concentration in the water system, but as the phenol concentration continues to increase, the water system is no longer suitable for the phenol hydrogenation process. Researches show that the high-concentration phenol hydrogenation process shows more excellent catalytic activity in cyclohexane solvent, but the catalyst is inevitably deactivated, mainly because the organic matter is too high in concentration in the high-concentration phenol hydrogenation process, the organic matter is easy to block catalyst pore channels (most micropores), cover active sites and limit mass transfer. Therefore, the development of an effective Pd @ CN catalyst regeneration method becomes a problem which needs to be solved urgently in the phenol hydrogenation industrial process.
Disclosure of Invention
The invention aims to develop a regeneration method of a Pd @ CN catalyst. The method can ensure the recovery and the cyclic utilization of the activity of the Pd @ CN catalyst, reduce the production cost, save resources and provide guarantee for the one-step hydrogenation industrialization of phenol.
The technical scheme of the invention is as follows: a regeneration method of a phenol hydrogenation Pd @ CN catalyst comprises the following specific steps:
the method comprises the following steps: and filtering and separating the reaction liquid after the phenol hydrogenation reaction and the Pd @ CN catalyst mixture to recover the catalyst.
Step two: and (3) placing the Pd @ CN catalyst obtained in the step one in a reaction kettle, adding a certain amount of solvent, sealing the reaction kettle, and replacing for 5 times by using compressed gas.
Step three: and washing the Pd @ CN obtained in the step two for a certain time at a certain temperature, a certain hydrogen pressure and a certain stirring rate.
Step four: and (4) filtering and recovering the catalyst treated in the step three.
Preferably, the cleaning solvent in the second step is cyclohexane, water or ethanol.
Preferably, the gas in step two is hydrogen, nitrogen or argon.
The regeneration condition in the preferred step three is the temperature of 80-140 DEG CoC, hydrogen pressure is 0.1-1.5 MPa, stirring speed is 100-500 rpm, and time is 30-90 min.
The invention adopts phenol hydrogenation to prepare cyclohexanone to evaluate the catalytic performance of the Pd @ CN catalyst treated by the regeneration method. The specific process is as follows:
200 g of phenol and600 mL of cyclohexane were made up to about 30% phenol-cyclohexane system and 6.4 g Pd @ CN catalyst was weighed into the kettle. Sealing, detecting leakage, replacing with hydrogen for 5 times, heating, and stirring the mixed materials. When the temperature reaches 140 DEG CoAfter C, the hydrogen pressure was adjusted to 0.5 MPa, the stirring speed was adjusted to 500 rpm, and the reaction was started. And after 2 h, stopping the reaction, cooling the system, discharging gas, filtering the reaction mixture, and analyzing the composition of a liquid phase to obtain the conversion rate of phenol and the selectivity of cyclohexanone. And (4) after the filtered catalyst is subjected to regeneration treatment, repeating the steps and checking the activity change of the catalyst.
Has the advantages that:
1. the Pd @ CN catalyst treated by the regeneration method can recover the catalytic performance of a fresh catalyst, and the performance is basically stable after repeated application of the catalyst.
2. According to the invention, the regeneration conditions in the kettle are changed, including the types of cleaning liquid, the types of gas, the gas pressure, the cleaning temperature, the stirring speed and the cleaning time, so that organic matters adsorbed in the pore channel of the catalyst are removed, and the catalytic activity of the catalyst is recovered.
Drawings
FIG. 1 shows the change of catalytic activity with the number of times of application of Pd @ CN catalyst directly after reaction without treatment in the comparative example.
FIG. 2 is a graph of the catalytic performance of the Pd @ CN catalyst treated by the regeneration method as a function of the number of applications in example 1.
Detailed Description
The effect of the regeneration method of the present invention on the catalytic performance of the Pd @ CN catalyst will be specifically illustrated by comparing the comparative examples and examples, and the following examples are only illustrative of the present invention and are not intended to limit the scope of the present invention.
Comparative example
Filtering the mixture after the phenol hydrogenation reaction to obtain a solid Pd @ CN catalyst, and recovering the catalyst
The next phenol hydrogenation experiment was performed directly and repeated for 10 times. The performance changes are shown in figure 1, the conversion rate of phenol is reduced from 85% to 60%, and the phenomenon of deactivation is more obvious.
Example 1
And (2) filtering and separating a mixture obtained after the hydrogenation reaction of phenol catalyzed by the Pd @ CN catalyst to recover the catalyst, placing the recovered catalyst in a reaction kettle, adding a certain amount of cyclohexane, sealing the reaction kettle, and replacing 5 times by using hydrogen. At 110oC. Washing at 500 rpm under 0.5 MPa for 60 min. The catalyst is filtered and recovered, and then enters the next phenol hydrogenation activity test experiment, and the catalyst is used for 10 times. The change of the catalytic performance of the Pd @ CN catalyst is shown in FIG. 2. The conversion rate and the selectivity of the phenol are basically unchanged, and the better stability is shown.
Example 2
And (2) filtering and separating the mixture obtained after the hydrogenation reaction of phenol catalyzed by the Pd @ CN catalyst to recover the catalyst, placing the recovered catalyst in a reaction kettle, adding a certain amount of water, sealing the reaction kettle, and replacing 5 times by using nitrogen. At 80oC. Washing at 100 rpm under 0.1 MPa for 30 min. The catalyst is filtered and recovered, and then enters the next phenol hydrogenation activity test experiment, and the catalyst is used for 10 times. The results show that cyclohexanone selectivity is essentially unchanged and phenol conversion is reduced by about 15%.
Example 3
And (2) filtering and separating the mixture obtained after the hydrogenation reaction of phenol catalyzed by the Pd @ CN catalyst to recover the catalyst, placing the recovered catalyst in a reaction kettle, adding a certain amount of ethanol, sealing the reaction kettle, and replacing 5 times by using argon. At 140oC. Washing at 300 rpm under 1.5 MPa for 90 min. The catalyst is filtered and recovered, and then enters the next phenol hydrogenation activity test experiment, and the catalyst is used for 10 times. The results show that cyclohexanone selectivity is essentially unchanged and phenol conversion is reduced by about 25%.
Claims (2)
1. A regeneration method of a phenol hydrogenation Pd @ CN catalyst comprises the following specific steps:
the method comprises the following steps: filtering and separating a mixture of a reaction liquid obtained after phenol hydrogenation reaction and a Pd @ CN catalyst, and recovering the catalyst;
step two: placing the Pd @ CN catalyst obtained in the step one in a reaction kettle, adding a certain amount of solvent, sealing the reaction kettle, and replacing for 5 times by using compressed gas hydrogen;
step three: washing the Pd @ CN catalyst obtained in the step two for a certain time at a certain temperature, a certain hydrogen pressure and a certain stirring rate; wherein the temperature is 80-140 deg.CoC, the hydrogen pressure is 0.1-1.5 MPa, the stirring speed is 100-500 rpm, and the time is 30-90 min;
step four: and (4) filtering and recovering the catalyst treated in the step three.
2. The method for regenerating the Pd @ CN catalyst used in the phenol hydrogenation process according to the patent claim 1, wherein the washing solvent in the second step is cyclohexane, water or ethanol.
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| CN201811187476.5A CN108927203B (en) | 2018-10-12 | 2018-10-12 | Regeneration method of phenol hydrogenation Pd @ CN catalyst |
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| CN201811187476.5A CN108927203B (en) | 2018-10-12 | 2018-10-12 | Regeneration method of phenol hydrogenation Pd @ CN catalyst |
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| CN108927203B true CN108927203B (en) | 2021-04-23 |
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| CN109701669B (en) * | 2019-02-27 | 2021-06-25 | 青岛科技大学 | Regeneration method of hydrogenation catalyst for preparing arylamine antioxidant |
| CN109772416B (en) * | 2019-03-04 | 2021-11-19 | 南京工业大学 | Oxygen vacancy-containing phenol hydrogenation catalyst and preparation method thereof |
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| JP4240568B2 (en) * | 1998-04-07 | 2009-03-18 | 住友化学株式会社 | Method for activating hydrogenation catalyst and method for producing 4-aminodiphenylamine |
| CN104226377B (en) * | 2013-06-17 | 2016-08-24 | 中国石油化工股份有限公司 | The renovation process of inactivation hydrogenation catalyst |
| CN105032503B (en) * | 2015-05-13 | 2018-01-30 | 辽宁石油化工大学 | A kind of renovation process of noble metal catalyst |
| CN105435815B (en) * | 2015-12-16 | 2018-05-11 | 南京大学扬州化学化工研究院 | It is used to prepare the renovation process of the catalyst of adjacent methyl cyclohexanol |
| CN106861741B (en) * | 2017-01-06 | 2019-07-02 | 南京工业大学 | Post-treatment method of phenol hydrogenation Pd @ CN catalyst |
| CN107826358A (en) * | 2017-10-24 | 2018-03-23 | 南京工业大学 | Storage method of used phenol hydrogenation Pd @ CN catalyst |
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