CN107826358A - Storage method of used phenol hydrogenation Pd @ CN catalyst - Google Patents
Storage method of used phenol hydrogenation Pd @ CN catalyst Download PDFInfo
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- CN107826358A CN107826358A CN201711002537.1A CN201711002537A CN107826358A CN 107826358 A CN107826358 A CN 107826358A CN 201711002537 A CN201711002537 A CN 201711002537A CN 107826358 A CN107826358 A CN 107826358A
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- catalyst
- storage method
- phenol
- phenol hydrogenation
- hydrogenation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000003860 storage Methods 0.000 title claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000002779 inactivation Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- -1 hexamethylene Alkoxide Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
- B65B63/00—Auxiliary devices, not otherwise provided for, for operating on articles or materials to be packaged
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
- B65B3/00—Packaging plastic material, semiliquids, liquids or mixed solids and liquids, in individual containers or receptacles, e.g. bags, sacks, boxes, cartons, cans, or jars
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B67—OPENING, CLOSING OR CLEANING BOTTLES, JARS OR SIMILAR CONTAINERS; LIQUID HANDLING
- B67C—CLEANING, FILLING WITH LIQUIDS OR SEMILIQUIDS, OR EMPTYING, OF BOTTLES, JARS, CANS, CASKS, BARRELS, OR SIMILAR CONTAINERS, NOT OTHERWISE PROVIDED FOR; FUNNELS
- B67C3/00—Bottling liquids or semiliquids; Filling jars or cans with liquids or semiliquids using bottling or like apparatus; Filling casks or barrels with liquids or semiliquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B67—OPENING, CLOSING OR CLEANING BOTTLES, JARS OR SIMILAR CONTAINERS; LIQUID HANDLING
- B67C—CLEANING, FILLING WITH LIQUIDS OR SEMILIQUIDS, OR EMPTYING, OF BOTTLES, JARS, CANS, CASKS, BARRELS, OR SIMILAR CONTAINERS, NOT OTHERWISE PROVIDED FOR; FUNNELS
- B67C3/00—Bottling liquids or semiliquids; Filling jars or cans with liquids or semiliquids using bottling or like apparatus; Filling casks or barrels with liquids or semiliquids
- B67C3/02—Bottling liquids or semiliquids; Filling jars or cans with liquids or semiliquids using bottling or like apparatus
- B67C3/22—Details
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a storage method of a phenol hydrogenation Pd @ CN catalyst after use. After the Pd @ CN catalyst is used for catalyzing phenol hydrogenation, the catalyst is recovered by filtration, and is cleaned by an ultrasonic cleaning machine at a certain temperature, ultrasonic power and ultrasonic time, so that most of organic matters adsorbed by the catalyst are removed, and then the catalyst is stored in an inert atmosphere. The storage method can effectively avoid the inactivation of the catalyst, realize the recycling of the catalyst, reduce the production cost, improve the resource utilization rate and provide guarantee for the green production process of preparing the cyclohexanone by phenol hydrogenation.
Description
Technical field
The present invention relates to the storage method after a kind of Pd CN catalyst uses, more particularly, to phenol hydrogenation process
Storage method after Pd@CN catalyst uses, belongs to catalysis technical field.
Background technology
Cyclohexanone is the important source material of industrial production nylon 6 and nylon66 fiber.Industrial traditional production technology is hexamethylene
Alkoxide method, but this method more, problems such as technological process complexity that accessory substance be present.The step Hydrogenation hexamethylene of phenol one in recent years
For ketone because its technological process is short, the advantages such as environmental pollution is low obtain the extensive concern of researchers.
In numerous phenol hydrogenation catalyst, with carbon nitrogen（CN）Material is carrier, and Pd is the Pd@CN catalyst in activated centre
Show excellent catalytic activity and stability.Patent（Application number 201410577494.X）Pd@CN catalyst is applied to benzene
Phenol is hydrogenated with, and is coupled with UF membrane, develops a kind of production technology of phenol hydrogenation preparing cyclohexanone.But its reactant concentration compared with
Low, economic benefit is low, and the concentration of reactant phenol must be improved during industrialized to improve economy.But with hexamethylene
Alkane is solvent, is found in high concentration phenol hydrogenation process is carried out, and the Pd@CN catalyst storages after use easily lose in air
It is living；Related experiment proves that the product cyclohexanone of Pd@CN Catalyst Adsorptions easily reacts with oxygen in air, generates by-product
Thing, and change catalyst performance itself, so as to cause catalyst inactivation.Therefore, it is a kind of effectively to prevent Pd@CN catalyst from using
The storing mode inactivated afterwards is urgently developed, to ensure the recycling of Pd@CN catalyst.
The content of the invention
The purpose of the present invention is to improve the deficiencies in the prior art and provide the storage side after a kind of Pd@CN catalyst uses
Method.This method can ensure the recovery and recycling of Pd@CN catalyst, reduce production cost, economize on resources, be the step of phenol one
Hydrogenation industrialization provides guarantee.
The technical scheme is that：A kind of storage method after phenol hydrogenation Pd@CN catalyst uses, its specific steps
For：
Step 1：The reacted mixture of Pd@CN catalyst phenol hydrogenations is separated by filtration to obtain Pd@CN catalysis
Agent.
Step 2：The Pd@CN catalyst that step 1 obtains is placed in container, a certain amount of solvent is added, in certain temperature
Certain time is washed under degree and ultrasonic power, is repeated several times.
Step 3：The Pd@CN that step 2 obtains are placed in closed container, seals, uses nitrogen or inert gas replacement 5
It is secondary, and preserve at room temperature.
Cleaning solvent described in preferred steps two is hexamethylene, deionized water or ethanol.
The single ultrasonic cleaning time described in preferred steps two is 5 ~ 15 min, and ultrasonic power is 200 ~ 300 W, ultrasound
Temperature is 30 ~ 50oC, washing times are 2 ~ 5 times.
Inert gas is argon gas or helium in condition of storage described in preferred steps three.
Catalysis of the present invention using the evaluation of phenol hydrogenation preparing cyclohexanone by the Pd@CN catalyst after storage method processing
Performance.Detailed process is as follows：
200 g phenol and 600 mL hexamethylenes are added into 2 L high-pressure hydrogenation reactors, and adds the fresh Pd@CN of 6.4 g and urges
Agent, kettle is closed, nitrogen leak detection, hydrogen displacement, is heated up, regulation speed of agitator to 200 rpm causes material to be well mixed；Treat temperature
Reach reaction temperature 140oDuring C, regulation Hydrogen Vapor Pressure to 0.5 MPa, regulation stir speed (S.S.) starts to react to 500 rpm.Instead
After answering 2 h, stop reaction, be passed through cooling water and reactor is cooled, discharge hydrogen, and use nitrogen displacement, sampling analysis
Product forms, and obtains phenol conversion and cyclohexanone selectivity.Repeated after catalyst filtration after handling and storing 24 h
State step and carry out catalytic performance test.
Beneficial effect：
1. the Pd@CN catalyst after present invention processing can keep the catalytic performance of fresh catalyst substantially, and can stably follow
Ring uses.
2. the present invention by controlling supersound washing time, power, temperature and number, effectively removes most of absorption and urged
Organic matter in agent surface and duct, so as to ensure that the catalytic activity of catalyst is basically unchanged.
Brief description of the drawings
Fig. 1 is unprocessed after Pd@CN catalyst reactions in comparative example, and the catalytic performance preserved in air is with applying mechanically number
Situation of change diagram.
Fig. 2 be in embodiment 1 the Pd@CN catalyst catalytic performances that are handled by storage method of the present invention with applying mechanically number
Situation of change illustrates.
Embodiment
Below by comparing comparative example and embodiment illustrates in the present invention storage method to Pd@CN catalysts
The influence of energy, the following example are merely to illustrate the present invention, are not used to limit the practical range of the present invention.
Comparative example
The reacted mixture of phenol hydrogenation is filtrated to get solid Pd@CN catalyst, the catalyst of recovery is positioned in air,
Dry at room temperature, be used for after shelving 24 h in phenol hydrogenation experiment, repeat the above steps and apply mechanically 10 times.As shown in figure 1, cyclohexanone
Selectivity is basically unchanged, but phenol conversion drops to 15%, Pd@CN catalyst from 86% and shows obvious deactivation phenomenom.
Embodiment 1
The reacted mixture of Pd@CN catalyst phenol hydrogenations is separated by filtration to obtain solid Pd@CN catalyst, will
Pd@CN catalyst is placed in beaker, 200 mL hexamethylenes is added, 50oC and ultrasonic power are when washing 15 min under 300 W
Between, it is repeated 5 times.Catalyst after filtering is placed in reactor and sealed, using nitrogen displacement 5 times, preserves 24 h at room temperature
After carry out next time phenol hydrogenation experiment, reaction terminate after repeat the above steps catalyst is handled after store, apply mechanically altogether
10 times, Pd@CN catalyst catalytic performance situations of change are as shown in Figure 2.Phenol conversion and selectivity be basically unchanged, show compared with
Good stability.
Embodiment 2
The reacted mixture of Pd@CN catalyst phenol hydrogenations is separated by filtration to obtain solid Pd@CN catalyst, will
Pd@CN catalyst is placed in beaker, 200 mL deionized waters is added, 40oC and ultrasonic power are to wash 10 min under 250 W
Time, it is repeated 3 times.Catalyst after filtering is placed in reactor and sealed, using helium replacement 5 times, preserves 24 at room temperature
Carried out after h next time phenol hydrogenation experiment, reaction terminate after repeat the above steps catalyst is handled after store, apply mechanically altogether
10 times, cyclohexanone selectivity is basically unchanged, and phenol conversion declines 5% or so.
Embodiment 3
The reacted mixture of Pd@CN catalyst phenol hydrogenations is separated by filtration to obtain solid Pd@CN catalyst, will
Pd@CN catalyst is placed in beaker, 200 mL ethanol is added, 30oC and ultrasonic power are to wash for 5 min times under 200 W,
It is repeated 2 times.Catalyst after filtering is placed in reactor and sealed, is replaced 5 times using argon gas, it is laggard to preserve 24 h at room temperature
Row next time phenol hydrogenation test, reaction terminate after repeat the above steps catalyst is handled after store, apply mechanically altogether 10 times,
Cyclohexanone selectivity is basically unchanged, and phenol conversion declines 15% or so.
Claims (4)
1. the storage method after a kind of phenol hydrogenation Pd@CN catalyst uses, it is characterised in that concretely comprise the following steps：
Step 1：The reacted mixture of Pd@CN catalyst phenol hydrogenations is separated by filtration to obtain Pd@CN catalysis
Agent；
Step 2：The Pd@CN catalyst that step 1 obtains is placed in container, adds a certain amount of solvent, in certain temperature and
Certain time is washed under ultrasonic power, is repeated several times；
Step 3：The Pd@CN that step 2 obtains are placed in closed container, sealed, using nitrogen or inert gas replacement 5 times,
And preserve at room temperature.
2. the storage method after phenol hydrogenation Pd@CN catalyst uses according to patent requirements 1, it is characterised in that step 2
Middle cleaning solvent is hexamethylene, deionized water or ethanol.
3. the storage method after phenol hydrogenation Pd@CN catalyst uses according to patent requirements 1, it is characterised in that step 2
The middle single ultrasonic cleaning time is 5 ~ 15 min, and ultrasonic power is 200 ~ 300 W, and ultrasonic temperature is 30 ~ 50oC, washing times
For 2 ~ 5 times.
4. the storage method after phenol hydrogenation Pd@CN catalyst uses according to patent requirements 1, it is characterised in that step 3
Middle inert gas is argon gas or helium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711002537.1A CN107826358A (en) | 2017-10-24 | 2017-10-24 | Storage method of used phenol hydrogenation Pd @ CN catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711002537.1A CN107826358A (en) | 2017-10-24 | 2017-10-24 | Storage method of used phenol hydrogenation Pd @ CN catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN107826358A true CN107826358A (en) | 2018-03-23 |
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| CN201711002537.1A Pending CN107826358A (en) | 2017-10-24 | 2017-10-24 | Storage method of used phenol hydrogenation Pd @ CN catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108927203A (en) * | 2018-10-12 | 2018-12-04 | 南京膜材料产业技术研究院有限公司 | Regeneration method of phenol hydrogenation Pd @ CN catalyst |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57113837A (en) * | 1981-01-06 | 1982-07-15 | Mitsubishi Chem Ind Ltd | Method for regeneration of dehydrogenation catalyst |
| JP2000144151A (en) * | 1998-11-06 | 2000-05-26 | Idemitsu Kosan Co Ltd | Regeneration of hydrogenation treatment catalyst |
| CN201445960U (en) * | 2009-04-29 | 2010-05-05 | 常州市肯创环境工程技术有限公司 | Structure of catalyst cleaning and regenerating device |
| CN102397787A (en) * | 2010-09-14 | 2012-04-04 | 中国石油化工股份有限公司 | Method and apparatus for preparing palladium carbon catalyst |
| CN103816923A (en) * | 2012-11-16 | 2014-05-28 | 万华化学集团股份有限公司 | Method for regenerating ruthenium hydrogenation catalyst |
| CN103894230A (en) * | 2012-12-28 | 2014-07-02 | 中国石油天然气股份有限公司 | Preparation and application of supported iron catalyst |
| CN106861741A (en) * | 2017-01-06 | 2017-06-20 | 南京工业大学 | Post-treatment method of phenol hydrogenation Pd @ CN catalyst |
-
2017
- 2017-10-24 CN CN201711002537.1A patent/CN107826358A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57113837A (en) * | 1981-01-06 | 1982-07-15 | Mitsubishi Chem Ind Ltd | Method for regeneration of dehydrogenation catalyst |
| JP2000144151A (en) * | 1998-11-06 | 2000-05-26 | Idemitsu Kosan Co Ltd | Regeneration of hydrogenation treatment catalyst |
| CN201445960U (en) * | 2009-04-29 | 2010-05-05 | 常州市肯创环境工程技术有限公司 | Structure of catalyst cleaning and regenerating device |
| CN102397787A (en) * | 2010-09-14 | 2012-04-04 | 中国石油化工股份有限公司 | Method and apparatus for preparing palladium carbon catalyst |
| CN103816923A (en) * | 2012-11-16 | 2014-05-28 | 万华化学集团股份有限公司 | Method for regenerating ruthenium hydrogenation catalyst |
| CN103894230A (en) * | 2012-12-28 | 2014-07-02 | 中国石油天然气股份有限公司 | Preparation and application of supported iron catalyst |
| CN106861741A (en) * | 2017-01-06 | 2017-06-20 | 南京工业大学 | Post-treatment method of phenol hydrogenation Pd @ CN catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108927203A (en) * | 2018-10-12 | 2018-12-04 | 南京膜材料产业技术研究院有限公司 | Regeneration method of phenol hydrogenation Pd @ CN catalyst |
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