CN108927203A - Regeneration method of phenol hydrogenation Pd @ CN catalyst - Google Patents
Regeneration method of phenol hydrogenation Pd @ CN catalyst Download PDFInfo
- Publication number
- CN108927203A CN108927203A CN201811187476.5A CN201811187476A CN108927203A CN 108927203 A CN108927203 A CN 108927203A CN 201811187476 A CN201811187476 A CN 201811187476A CN 108927203 A CN108927203 A CN 108927203A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- phenol hydrogenation
- regeneration method
- phenol
- hydrogenation
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 29
- 238000011069 regeneration method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000004064 recycling Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 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
- 238000000926 separation method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter 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
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 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
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-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
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012257 stirred material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater 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
- 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
Landscapes
- 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 present invention relates to Pd@CN in the regeneration method more particularly to high concentration phenol hydrogenation process of a kind of Pd@CN catalyst
The regeneration method of catalyst, belongs to catalysis technical field.
Background technique
The downstream product caprolactam and adipic acid of cyclohexanone are the important intermediates of synthetic nylon 6 and nylon66 fiber.Industry
The main production of upper cyclohexanone is cyclohexane oxidation process, but that there are by-products is more for this method, and acid-bearing wastewater is more, environment
Pollute larger problem.In recent years, one step of phenol adds hydrogen preparing cyclohexanone due to the advantages that its process flow is short, and atom utilization is high
It is concerned.
Pd@CN catalyst is applied to phenol hydrogenation by patent (publication number 104402687A), develops a kind of novel benzene
Phenol hydrogenation technique, but phenol concentration is lower in the technique, economic benefit is too low in course of industrialization.Patent (publication number
Phenol concentration 106861741A) is improved, is had studied under 10% phenol concentration, phenol hydrogenation process when taking water as a solvent develops
A kind of post-processing approach of phenol hydrogenation catalyst, this method are able to solve in aqueous systems Pd@CN catalyst under 10% phenol concentration
Inactivation, but as phenol concentration continues to improve, aqueous systems have been no longer desirable for phenol hydrogenation process.Research shows that high concentration
Phenol hydrogenation process shows more excellent catalytic activity in solvent hexamethylene, but catalyst inevitably occurs
Deactivation phenomenom, mainly due in high concentration phenol hydrogenation process organic concentration it is excessively high, organic matter be easier block catalysis
Agent duct (most of micropore), covering active site, limit mass transfer.Therefore a kind of effective catalyst regeneration side Pd@CN
Method is developed into problem in the urgent need to address in phenol hydrogenation course of industrialization.
Summary of the invention
The purpose of the present invention is develop a kind of regeneration method of Pd@CN catalyst.This method can guarantee Pd@CN catalyst
It is active to restore and recycle, production cost is reduced, is economized on resources, adds hydrogen industrialization to provide guarantee for one step of phenol.
The technical solution of the present invention is as follows: a kind of regeneration method of phenol hydrogenation Pd@CN catalyst, the specific steps are that:
Step 1: reaction solution and Pd@CN catalyst mixture after phenol hydrogenation is reacted are filtered separation and recovery catalyst.
Step 2: the Pd@CN catalyst that step 1 obtains is placed in reaction kettle, a certain amount of solvent is added, to reaction
Kettle is sealed, and is replaced 5 times using compressed gas.
Step 3: the Pd@CN that step 2 obtains is washed under certain temperature, certain Hydrogen Vapor Pressure, certain stirring rate
Wash certain time.
Step 4: step 3 treated catalyst filtration is recycled.
Cleaning solvent described in preferred steps two is hexamethylene, water or ethyl alcohol.
Gas described in preferred steps two is hydrogen, nitrogen or argon gas.
Regeneration condition described in preferred steps three is temperature 80-140oC, Hydrogen Vapor Pressure 0.1-1.5 MPa, stirring rate
100-500 rpm, time 30-90 min.
The catalysis that the present invention passes through the regeneration method treated Pd@CN catalyst using the evaluation of phenol hydrogenation preparing cyclohexanone
Performance.Detailed process is as follows:
Weigh 200 g phenol and 600 mL hexamethylenes be configured to about 30% phenol-hexamethylene system, weigh 6.4 g Pd@CN and urge
Agent is successively added in kettle.Sealing, leak detection, hydrogen are replaced 5 times, and heating, unlatching is stirred material.Reach 140 to temperatureoC
Afterwards, Hydrogen Vapor Pressure is adjusted to 0.5 MPa, adjusts speed of agitator to 500 rpm, reaction starts.After 2 h, stop reaction, to system
Cool down, gas is discharged, processing is filtered to reaction mixture, analysis liquid phase composition obtains phenol conversion and hexamethylene
Ketone selectivity.It repeats the above steps after filtered catalyst is carried out regeneration treatment, examines its activity change.
The utility model has the advantages that
1. the catalytic performance of regeneration method treated Pd@CN catalyst can be restored to fresh catalyst in the present invention, repeatedly
It is basicly stable to apply experimental performance.
2. the present invention is by changing regeneration condition in kettle, including cleaning solution type, gaseous species, gas pressure, cleaning temperature
Degree, stirring rate and scavenging period, to remove the attached organic matter of catalyst duct interior suction, and then the catalysis for restoring catalyst is living
Property.
Detailed description of the invention
Fig. 1 be it is unprocessed after Pd@CN catalyst reaction in comparative example, directly carry out applying experiment, catalytic activity is with set
With the situation of change of number.
Fig. 2 be in embodiment 1 the Pd@CN catalyst catalytic performance that is handled by the regeneration method with the variation for applying number
Situation.
Specific embodiment
Below by comparing comparative example and embodiment illustrates in the present invention regeneration method to Pd@CN catalyst
The influence of energy, the following example are merely to illustrate the present invention, are not used to limit practical range of the invention.
Comparative example
Solid Pd@CN catalyst, the catalyst of recycling is obtained by filtration in mixture after phenol hydrogenation is reacted
It directly carries out phenol hydrogenation next time to test, repetition is applied 10 times.Performance change as shown in Figure 1, phenol conversion from 85%
60% is dropped to, shows more apparent deactivation phenomenom.
Embodiment 1
Mixture after the reaction of Pd@CN catalyst phenol hydrogenation is filtered separation and recovery catalyst, by urging for recycling
Agent is placed in reaction kettle, and a certain amount of hexamethylene is added, is sealed to reaction kettle, is replaced 5 times using hydrogen.110oC, 60 min are washed under 0.5 MPa, 500 rpm.It is real to enter phenol hydrogenation active testing next time after catalyst filtration recycling
It tests, applies altogether 10 times.Pd@CN catalyst catalytic performance situation of change is as shown in Figure 2.Phenol conversion and selectivity are substantially not
Become, shows preferable stability.
Embodiment 2
Mixture after the reaction of Pd@CN catalyst phenol hydrogenation is filtered separation and recovery catalyst, by urging for recycling
Agent is placed in reaction kettle, and a certain amount of water is added, is sealed to reaction kettle, is replaced 5 times using nitrogen.80oC、0.1
30 min are washed under MPa, 100 rpm.It tests after catalyst filtration recycling into phenol hydrogenation active testing next time, applies altogether
10 times.Cyclohexanone selectivity is basically unchanged as the result is shown, phenol conversion decline about 15%.
Embodiment 3
Mixture after the reaction of Pd@CN catalyst phenol hydrogenation is filtered separation and recovery catalyst, by urging for recycling
Agent is placed in reaction kettle, and a certain amount of ethyl alcohol is added, is sealed to reaction kettle, is replaced 5 times using argon gas.140oC、
90 min are washed under 1.5 MPa, 300 rpm.It is tested after catalyst filtration recycling into phenol hydrogenation active testing next time, altogether
It applies 10 times.Cyclohexanone selectivity is basically unchanged as the result is shown, phenol conversion decline about 25%.
Claims (4)
1. a kind of regeneration method of phenol hydrogenation Pd@CN catalyst, the specific steps are that:
Step 1: the mixture of reaction solution and Pd@CN catalyst after phenol hydrogenation is reacted is filtered separation, recycling catalysis
Agent；
Step 2: the Pd@CN catalyst that step 1 obtains being placed in reaction kettle, a certain amount of solvent is added, to reaction kettle into
Row sealing, is replaced 5 times using compressed gas；
Step 3: the Pd@CN catalyst that step 2 is obtained is under certain temperature, certain Hydrogen Vapor Pressure, certain stirring rate
Wash certain time；
Step 4: step 3 treated catalyst filtration is recycled.
2. according to the regeneration method of phenol hydrogenation Pd@CN catalyst described in patent requirements 1, which is characterized in that clear in step 2
Washing solvent is hexamethylene, water or ethyl alcohol.
3. according to the regeneration method of phenol hydrogenation Pd@CN catalyst described in patent requirements 1, which is characterized in that gas in step 2
Body is hydrogen, nitrogen or argon gas.
4. according to the regeneration method of phenol hydrogenation Pd@CN catalyst described in patent requirements 1, which is characterized in that step 3 medium temperature
Degree is 80-140oC, Hydrogen Vapor Pressure are 0.1-1.5 MPa, and stirring rate is 100-500 rpm, and the time is 30-90 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811187476.5A CN108927203B (en) | 2018-10-12 | 2018-10-12 | Regeneration method of phenol hydrogenation Pd @ CN catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811187476.5A CN108927203B (en) | 2018-10-12 | 2018-10-12 | Regeneration method of phenol hydrogenation Pd @ CN catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108927203A true CN108927203A (en) | 2018-12-04 |
| CN108927203B CN108927203B (en) | 2021-04-23 |
Family
ID=64444207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811187476.5A Active CN108927203B (en) | 2018-10-12 | 2018-10-12 | Regeneration method of phenol hydrogenation Pd @ CN catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108927203B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109701669A (en) * | 2019-02-27 | 2019-05-03 | 青岛科技大学 | A kind of arylamine kind antioxidant prepares the regeneration method of spent hydroprocessing catalyst |
| CN109772416A (en) * | 2019-03-04 | 2019-05-21 | 南京工业大学 | Oxygen vacancy-containing phenol hydrogenation catalyst and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11292828A (en) * | 1998-04-07 | 1999-10-26 | Sumitomo Chem Co Ltd | Activation of hydrogenation catalyst |
| CN104226377A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Regeneration method of inactivated hydrogenation catalyst |
| CN105032503A (en) * | 2015-05-13 | 2015-11-11 | 辽宁石油化工大学 | Regeneration method of noble metal catalyst |
| CN105435815A (en) * | 2015-12-16 | 2016-03-30 | 南京大学扬州化学化工研究院 | Regeneration method of catalyst for preparing o-methylcyclohexanol |
| CN106861741A (en) * | 2017-01-06 | 2017-06-20 | 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 |
-
2018
- 2018-10-12 CN CN201811187476.5A patent/CN108927203B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11292828A (en) * | 1998-04-07 | 1999-10-26 | Sumitomo Chem Co Ltd | Activation of hydrogenation catalyst |
| CN104226377A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Regeneration method of inactivated hydrogenation catalyst |
| CN105032503A (en) * | 2015-05-13 | 2015-11-11 | 辽宁石油化工大学 | Regeneration method of noble metal catalyst |
| CN105435815A (en) * | 2015-12-16 | 2016-03-30 | 南京大学扬州化学化工研究院 | Regeneration method of catalyst for preparing o-methylcyclohexanol |
| CN106861741A (en) * | 2017-01-06 | 2017-06-20 | 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 |
Non-Patent Citations (3)
| Title |
|---|
| SHUO HU ET AL.: ""Insights into deactivation mechanism of Pd@CN catalyst in the liquid-phase hydrogenation of phenol to cyclohexanone"", 《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》 * |
| 刘晓云等: ""纳米 Pd 催化剂的制备及其催化苯酚加氢反应"", 《南京工业大学学报(自然科学版)》 * |
| 贺红军等: ""烷基苯酚加氢制烷基环己醇的Pd/C催化剂的制备"", 《烟台大学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109701669A (en) * | 2019-02-27 | 2019-05-03 | 青岛科技大学 | A kind of arylamine kind antioxidant prepares the regeneration method of spent hydroprocessing catalyst |
| CN109701669B (en) * | 2019-02-27 | 2021-06-25 | 青岛科技大学 | Regeneration method of hydrogenation catalyst for preparing arylamine antioxidant |
| CN109772416A (en) * | 2019-03-04 | 2019-05-21 | 南京工业大学 | Oxygen vacancy-containing phenol hydrogenation catalyst and preparation method thereof |
| CN109772416B (en) * | 2019-03-04 | 2021-11-19 | 南京工业大学 | Oxygen vacancy-containing phenol hydrogenation catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108927203B (en) | 2021-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103816923B (en) | A kind of method of ruthenium hydrogenation catalyst regeneration | |
| CN107353186B (en) | Method for preparing 1, 3-cyclohexanedione | |
| CN108927203A (en) | Regeneration method of phenol hydrogenation Pd @ CN catalyst | |
| CN105435815A (en) | Regeneration method of catalyst for preparing o-methylcyclohexanol | |
| CN100364663C (en) | Supported nano Au catalyst and method for preparing the same | |
| CN106111173A (en) | A kind of for being prepared the catalyst of pyruvate by lactate and preparing the method for pyruvate | |
| CN104815650A (en) | Preparation method and application of graphene loaded Ru catalyst | |
| CN106582709A (en) | Catalyst for synthesizing primary aromatic amine by virtue of hydrogenation of aromatic nitrile and preparation method of catalyst | |
| CN106861741B (en) | Post-treatment method of phenol hydrogenation Pd @ CN catalyst | |
| CN111646921A (en) | Catalyst regeneration method for preparing hexamethylene diamine key intermediate 6-aminocapronitrile by caprolactam method | |
| CN104276951A (en) | Method for using water phase to catalytically oxidize lactates for preparing pyruvates | |
| CN111715290B (en) | Method for recycling catalyst containing transition metal and carbon | |
| CN108579740B (en) | Preparation method and application of efficient catalyst for preparing aldehyde by olefin hydroformylation | |
| CN108554395B (en) | Regeneration method of inactivated activated carbon in acetaminophen refining stage | |
| CN103864597B (en) | The application that a kind of loading type Ru is catalyst based | |
| CN114436809B (en) | Method for preparing diethyl maleate by carrying out depolymerization on lignin under catalysis of iron oxide loaded by USY molecular sieve | |
| CN103709010B (en) | A kind of by tetrahydrobenzene, carboxylic acid and water Reactive Synthesis hexalin method | |
| CN102824926A (en) | Regeneration method of inactivated titanium silicon molecular sieve | |
| CN101768033B (en) | Method for reducing carbonyl to methylene by catalytic hydrogenation | |
| CN101830789B (en) | Method for preparing cyclohexanone | |
| CN107826358A (en) | Storage method of used phenol hydrogenation Pd @ CN catalyst | |
| CN114605246A (en) | Method for preparing cyclopentanone by high-selectivity hydrogenation with furfural as raw material | |
| CN1915517B (en) | Catalyst in use for producing cyclohexene | |
| CN107930693B (en) | Modified resin catalyst and method for removing residual formaldehyde in 3-methyl-3-butene-1-alcohol solution | |
| CN108640829B (en) | Method for preparing pyruvic acid by catalyzing and oxidizing lactic acid in water phase |
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 |