CN114870911A - Regeneration method of carbon-supported metal catalyst - Google Patents
Regeneration method of carbon-supported metal catalyst Download PDFInfo
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- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 20
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- 238000001914 filtration Methods 0.000 claims description 28
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- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 5
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- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 239000010941 cobalt Substances 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 231100000614 poison Toxicity 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
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
-
- 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
- B01J38/02—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/354—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by hydrogenation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a regeneration method of a carbon-supported metal catalyst, which comprises the following steps: step (1), cleaning the waste catalyst by using a mixed solution of an organic solvent and water; step (2), the cleaned waste catalyst is placed in deionized water, and H is introduced into the waste catalyst under the stirring state 2 Adding nickel salt after full adsorption, and continuously stirring to load nickel on the waste catalyst, wherein the load of the nickel is 0.8-1.5 times of that of noble metal in the waste catalyst; then carrying out suction filtration, and washing the solid after suction filtration to be neutral(ii) a Step (3), carrying out vacuum drying treatment on the washed neutral solid; step (4), the dried catalyst is filled into a tubular reactor, and H is introduced 2 Carrying out reaction; washing the reacted catalyst with dilute hydrochloric acid until no nickel ions can be detected in the filtrate; washing with deionized water to neutrality; finally, vacuum drying is carried out to obtain the regenerated catalyst. The invention can recover the catalytic activity of the catalyst to more than 95% of the initial activity and prolong the service life to more than 90% of the initial service life.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a method for regenerating and recycling a carbon-supported metal waste catalyst.
Background
The regeneration of the catalyst refers to a method for recovering the activity and the selectivity of the catalyst after the catalyst is used after the activity and the selectivity are reduced to a certain degree by a proper treatment method, and the method is an important means for prolonging the service life of the catalyst and reducing the production cost. The carbon-supported noble metal catalyst is widely applied to catalytic hydrogenation reactions in chemical and pharmaceutical industries, but is expensive, easy to poison and relatively short in service life, so that the product cost is increased, and the further development of related finished products is limited. Therefore, it is a technical difficulty to find a method for regenerating noble metal catalyst which is simple to operate, economic and effective.
The carbon-supported noble metal catalyst can catalyze the hydrodechlorination of the chlorofluoroalkane to synthesize a new generation of refrigerant, electronic etching gas, insulating materials and the like, but the chlorofluoroalkane and a dechlorination intermediate state thereof are easy to deposit carbon, so that the noble metal catalyst is inactivated, and the catalytic performance and the generation cost are seriously influenced. A number of methods have been used to regenerate the noble metal catalyst caused by carbon deposition.
Patent CN107497420A discloses a regeneration method of a carbon-containing noble metal catalyst, which comprises the steps of controlling the oxygen content in the regeneration gas during the combustion process, removing carbon deposition in the catalyst by step combustion, and then recovering the activity of the catalyst by chlorination and reduction. In the regeneration process of the noble metal catalyst, when the chlorination operation is carried out, if the moisture content is too high, the activity of the catalyst is reduced, so that the method needs to strictly control the moisture in the process gas and the highest value of the operation temperature to ensure the regeneration efficiency.
Patent CN1589970A discloses a regeneration method of catalyst for producing alkyl alkenyl arene by dehydrogenation of alkyl arene, which introduces water vapor and air, and regenerates the catalyst by hydrothermal method, but this method needs higher regeneration temperature to completely burn off carbon deposit on the catalyst.
Patent CN107999057A discloses a regeneration method of a supported noble metal catalyst. The method uses CO as the inactive load type noble metal catalyst 2 And O 2 The mixed gas is oxidized and then reduced by a reducing agent in a tetrahydrofuran solvent to obtain the regenerated catalyst.
Patent CN105536885A discloses a regeneration method of a noble metal catalyst for preparing vinyl chloride, which comprises treating with nitrogen and regenerated gas, reducing to normal temperature under nitrogen atmosphere, and heating and refluxing with acid solution to improve the activity of the obtained noble metal catalyst again.
In summary, the existing regeneration mostly uses an oxidation method, i.e. introducing an oxidizing substance (water, CO) 2 、O 2 Etc.) to generate carbon dioxide to remove the carbon deposit. However, the carrier of the catalyst is mostly a carbon carrier, and the catalyst is oxidativeThe material inevitably contacts with the carrier, and the carbon on the carrier is destroyed while the carbon deposition is eliminated. Therefore, such regeneration methods are harsh to operate and have poor results.
Disclosure of Invention
The invention aims to provide a more effective method for regenerating a waste carbon-supported metal catalyst for hydrodechlorination of chlorofluoroalkane, in order to ensure that the activity and selectivity of the regenerated waste catalyst are excellent and the catalytic cost is greatly reduced.
Therefore, the invention adopts the following technical scheme:
a method for regenerating a carbon-supported metal catalyst, comprising the steps of:
step (1), cleaning the waste catalyst by using a mixed solution of an organic solvent and water, aiming at cleaning the residual hydrocarbon compounds and powdered carbon deposits in the reaction;
step (2), the cleaned waste catalyst is placed in deionized water, and H is continuously introduced under the stirring state 2 Adding nickel salt after full adsorption, and continuously stirring to load nickel on the waste catalyst, wherein the load of the nickel is 0.8-1.5 times of that of noble metal in the waste catalyst; then carrying out suction filtration, and washing the solid after suction filtration to be neutral;
step (3), carrying out vacuum drying treatment on the neutral solid washed in the step (2);
step (4), the dried catalyst is filled into a tubular reactor, and H is introduced 2 Carrying out reaction;
washing the reacted catalyst with dilute hydrochloric acid until no nickel ions can be detected in the filtrate; then, continuously washing the mixture by deionized water to be neutral; finally, vacuum drying is carried out to obtain the regenerated catalyst.
It is noted that the spent catalyst is a hydrodechlorination catalyst, is in the form of particles, has a particle diameter of not less than 1mm, and has an activity of not less than 50% of its initial activity.
The waste catalyst can be a noble metal loaded activated carbon catalyst, and can also be a noble metal-auxiliary agent loaded activated carbon catalyst. The noble metal can be palladium, platinum and rhodium, and the auxiliary agent can be cobalt, silver and copper.
In the step (2), when the total amount of the introduced hydrogen is consistent with the noble metal loading, the nickel loading can be excessively added and can be washed away by a subsequent washing step.
Through the step (2), after the noble metal adsorbs hydrogen, the hydrogen is dissociated into active H in an adsorption state to become an active site; after the nickel salt is added, the oxidized nickel reacts with the active H on the surface of the noble metal to be reduced and deposited on the active sites. Through the step (4), the active components of the catalyst are all reduced, and the active components are prevented from being oxidized due to contact with air in the process of filling the catalyst.
Preferably, in the step (1), the spent catalyst is washed with a mixed solution of methanol and water; the proportion of methanol to water in the mixed solution is 1 (1-5), and the dosage ratio of the waste catalyst to the mixed solution is 1 (2-7).
Further, in the step (1), the temperature for cleaning is 35-55 ℃, the cleaning is carried out for 5-10 times, each time for 10-30min, and the powdered carbon is filtered and removed by a sieve.
Preferably, in the step (2), the volume using ratio of the waste catalyst to the deionized water is 1 (2-5), and the temperature is 25-90 ℃; the waste catalyst is arranged on the filter screen and is arranged above the magneton stirring, the waste catalyst is strictly prevented from contacting the magneton, the stirring speed is 800-1000r/min, the hydrogen is inserted below the filter screen, and the flow rate is 20-40 mL/min.
Further, the loading amount of the nickel is 0.9 to 1.2 times of the loading amount of the noble metal in the spent catalyst, and more preferably, the loading amount of the nickel is the same as or similar to the loading amount of the noble metal in the spent catalyst.
Further, in the step (2), the time for continuing stirring after adding the nickel salt is 0.5-3 h. The filtrate from the suction filtration can be retained for further use.
Further, the nickel salt may be Ni (NO) 3 ) 2 ·6H 2 O,NiCl 2 (H 2 O)·6H 2 O or NiSO 4 ·6H 2 And O is one of the compounds.
Preferably, in the steps (3) and (5), the vacuum drying is carried out by adopting temperature programming, wherein the temperature programming of the vacuum drying is that the temperature is kept between 30 and 50 ℃ for 1 to 2 hours, between 70 and 80 ℃ for 1 to 2 hours, and between 100 and 120 ℃ for 2 to 3 hours.
Preferably, the reaction temperature in step (4) is 300-500 ℃ and the hydrogen pressure is 1.0-3.0 MPa.
Further, in the step (4), the reaction time is 2-5 h.
Preferably, in the step (5), the concentration of the dilute hydrochloric acid is 0.1-0.5mol/L, and the washing temperature is 20-50 ℃. And (3) combining the washed metal and the metal obtained in the step (2), collecting, and adding a proper amount of nickel salt to be used in the step (2).
Further, the detection method of nickel ions in the step (5) is an AAS test method. AAS testing is a well known method to those skilled in the art and will not be described further herein.
Compared with the prior art, the invention has the advantages that:
1) the method utilizes active hydrogen adsorbed by noble metal in the waste catalyst as a reduction point, selectively adsorbs nickel on the noble metal active site, and then removes the carbon deposition on the active site by hydrogenation to generate methane under proper temperature and pressure by utilizing the methanation catalytic performance of the nickel, and the carrier carbon beside the noble metal active site is preserved, thereby achieving the purpose of selectively removing the carbon deposition.
2) The regeneration method of the invention can recover the catalytic activity of the catalyst to more than 95% of the initial activity of the catalyst, and the service life of the catalyst is prolonged to more than 90% of the initial service life.
3) The regeneration method of the invention can be used repeatedly, and can not damage the original catalyst.
Drawings
FIG. 1 is a graph comparing the catalytic activity (feedstock conversion) of fresh catalyst of the second application example of the present invention and regenerated catalyst obtained by the method of example 1 at different reaction times.
Detailed Description
The embodiments of the present invention are described in detail below by way of specific examples, but the scope of the present invention is not limited to the following examples.
The nickel salt, methanol and dilute hydrochloric acid used in the examples are all from chemical reagents of national drug group, ltd.
Experimental sample of spent catalyst: active carbon with the granularity of 2-5mm is used as a carrier, 1 wt% of palladium is soaked in the carrier in an equal volume, and the active carbon is dried for 3 hours at 120 ℃ to obtain a fresh catalyst which is used for the reaction of preparing chlorotrifluoroethylene/trifluoroethylene by the hydrogenation and dechlorination of trichlorotrifluoroethane. In the reaction process, the space velocity is 1000h -1 And the reaction temperature is 300 ℃, the reaction is carried out for 50 hours, and the reaction is stopped when the activity is reduced to 55 percent of the initial activity of the fresh catalyst. The deactivated catalyst was taken out and subjected to the following regeneration treatment using the deactivated catalyst as a regeneration target (i.e., a spent catalyst).
Example 1
The embodiment provides a regeneration method of a carbon-supported metal catalyst, which specifically comprises the following steps:
(1) fully mixing methanol and water in the dosage ratio of 1:1 to prepare the required mixed solution. And (3) taking 2g of the waste catalyst, washing with 4mL of mixed liquor, setting the temperature to be 35 ℃ during washing, repeatedly washing for 5 times, washing for 10min each time, and filtering out the powdered carbon by using a sieve after washing is finished.
(2) And (3) placing the washed waste catalyst into 4mL of deionized water with a filter screen, keeping the temperature at 25 ℃, placing the catalyst on the filter screen, and erecting the catalyst above the magneton stirring, wherein the catalyst is strictly prevented from contacting with the magneton. Introducing H under the stirring state 2 ，H 2 Inserted below the filter screen, the stirring speed is 800r/min, and the hydrogen flow rate is 20 mL/min. Continuously introducing H 2 After sufficient adsorption, Ni (NO) is added in the same amount as the noble metal in the waste catalyst 3 ) 2 ·6H 2 And O, stirring is continued for 0.5 h. Then, suction filtration is carried out, and the solid after suction filtration is washed to be neutral. The filtrate is retained for the next use.
(3) And (3) carrying out vacuum drying treatment on the neutral solid washed in the step (2), wherein the vacuum drying procedure is as follows: the temperature is kept at 30 ℃ for 1h, 70 ℃ for 1h and 100 ℃ for 2 h.
(4) The dried catalyst is loaded into a tubular reactor, and H is introduced 2 The hydrogen flow rate is kept at 20mL/min, the reaction temperature is 300 ℃, the hydrogen pressure is 1.0MPa, and the reaction is carried out for 2 h.
(5) The reacted catalyst was washed with 0.1mol/L dilute hydrochloric acid and the temperature was maintained at 20 ℃. And detecting by using an AAS test method, and when the nickel ions cannot be detected, washing to be neutral by using deionized water. Then filtering and vacuum drying are carried out, and the vacuum drying procedure is as follows: keeping the temperature at 30 ℃ for 1h, keeping the temperature at 70 ℃ for 1h, and keeping the temperature at 100 ℃ for 2h to finally obtain the regenerated catalyst.
Example 2
The embodiment provides a regeneration method of a carbon-supported metal catalyst, which specifically comprises the following steps:
(1) fully mixing methanol and water in the dosage ratio of 1:5 to prepare the required mixed solution. 2g of the waste catalyst is taken and washed by 4mL of mixed liquor, the temperature is set to be 55 ℃ during washing, and the washing is repeated for 10 times, and each washing time is 30 min. After the cleaning, the powdered carbon is filtered by a sieve.
(2) And (3) placing the washed waste catalyst into 4mL of deionized water with a filter screen, keeping the temperature at 25 ℃, placing the catalyst on the filter screen, and erecting the catalyst above the magneton stirring, wherein the catalyst is strictly prevented from contacting with the magneton. Introducing H under the stirring state 2 ，H 2 Inserted below the filter screen, the stirring speed is 800r/min, and the hydrogen flow rate is 20 mL/min. Continuously introducing H 2 After sufficient adsorption, Ni (NO) is added in the same amount as the noble metal in the waste catalyst 3 ) 2 ·6H 2 And O, stirring is continued for 0.5 h. Then, suction filtration is carried out, and the solid after suction filtration is washed to be neutral. The filtrate is retained for the next use.
(3) And (3) carrying out vacuum drying treatment on the neutral solid washed in the step (2), wherein the vacuum drying procedure is as follows: the temperature is kept at 30 ℃ for 1h, 70 ℃ for 1h and 100 ℃ for 2 h.
(4) The dried catalyst is loaded into a tubular reactor, and H is introduced 2 The hydrogen flow rate is kept at 20mL/min, the reaction temperature is 300 ℃, the hydrogen pressure is 1.0MPa, and the reaction is carried out for 2 h.
(5) The reacted catalyst was washed with 0.1mol/L dilute hydrochloric acid and the temperature was maintained at 20 ℃. And detecting by using an AAS test method, and continuously washing by using deionized water to be neutral after nickel ions are not detected. Then filtering and vacuum drying are carried out, wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2h, and finally the regenerated catalyst is obtained.
Example 3
The embodiment provides a regeneration method of a carbon-supported metal catalyst, which specifically comprises the following steps:
(1) fully mixing methanol and water in the dosage ratio of 1:1 to prepare the required mixed solution. And (3) taking 2g of the waste catalyst, washing with 4mL of mixed liquor, setting the temperature to be 35 ℃ during washing, repeatedly washing for 5 times, washing for 10min each time, and filtering out the powdered carbon by using a sieve after washing is finished.
(2) And (3) placing the washed waste catalyst into 10mL of deionized water with a filter screen, keeping the temperature at 90 ℃, placing the catalyst on the filter screen, and erecting the catalyst above the magneton stirring, wherein the catalyst is strictly prevented from contacting with the magneton. Introducing H under the stirring state 2 ，H 2 Inserted below the filter screen, the stirring speed is 1000r/min, and the hydrogen flow rate is 40 mL/min. Continuously introducing H 2 After sufficient adsorption, Ni (NO) is added in the same amount as the noble metal in the waste catalyst 3 ) 2 ·6H 2 And O, stirring for 3 hours. Then, suction filtration is carried out, and the solid after suction filtration is washed to be neutral. The filtrate is retained for the next use.
(3) And (3) carrying out vacuum drying treatment on the neutral solid washed in the step (2), wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2 h.
(4) The dried catalyst is loaded into a tubular reactor, and H is introduced 2 The hydrogen flow rate is kept at 20mL/min, the reaction temperature is 300 ℃, the hydrogen pressure is 1.0MPa, and the reaction is carried out for 2 h.
(5) The reacted catalyst was washed with 0.1mol/L dilute hydrochloric acid and the temperature was maintained at 20 ℃. And detecting by using an AAS test method, and continuously washing by using deionized water to be neutral after nickel ions are not detected. Then filtering and vacuum drying are carried out, wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2h, and finally the regenerated catalyst is obtained.
Example 4
The embodiment provides a regeneration method of a carbon-supported metal catalyst, which specifically comprises the following steps:
(1) fully mixing methanol and water in the dosage ratio of 1:1 to prepare the required mixed solution. And (3) taking 2g of the waste catalyst, washing with 4mL of mixed liquor, setting the temperature to be 35 ℃ during washing, repeatedly washing for 5 times, washing for 10min each time, and filtering out the powdered carbon by using a sieve after washing is finished.
(2) And (3) placing the washed waste catalyst into 4mL of deionized water with a filter screen, keeping the temperature at 25 ℃, placing the catalyst on the filter screen, and erecting the catalyst above the magneton stirring, wherein the catalyst is strictly prevented from contacting with the magneton. Introducing H under the stirring state 2 ，H 2 Inserted below the filter screen, the stirring speed is 800r/min, and the hydrogen flow rate is 20 mL/min. Continuously introducing H 2 After sufficient adsorption, Ni (NO) is added in the same amount as the noble metal in the waste catalyst 3 ) 2 ·6H 2 And O, stirring is continued for 0.5 h. Then, suction filtration is carried out, and the solid after suction filtration is washed to be neutral. The filtrate is retained for the next use.
(3) And (3) carrying out vacuum drying treatment on the neutral solid washed in the step (2), wherein the vacuum drying procedure comprises the steps of keeping at 50 ℃ for 2h, keeping at 80 ℃ for 2h and keeping at 120 ℃ for 3 h.
(4) The dried catalyst is loaded into a tubular reactor, and H is introduced 2 The hydrogen flow rate is kept at 20mL/min, the reaction temperature is 300 ℃, the hydrogen pressure is 1.0MPa, and the reaction is carried out for 2 h.
(5) The reacted catalyst was washed with 0.1mol/L dilute hydrochloric acid and the temperature was maintained at 20 ℃. And detecting by using an AAS test method, and continuously washing by using deionized water to be neutral after nickel ions are not detected. Then filtering and vacuum drying are carried out, wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2h, and finally the regenerated catalyst is obtained.
Example 5
The embodiment provides a regeneration method of a carbon-supported metal catalyst, which specifically comprises the following steps:
(1) fully mixing methanol and water in the dosage ratio of 1:1 to prepare the required mixed solution. And (3) taking 2g of the waste catalyst, washing with 4mL of mixed liquor, setting the temperature to be 35 ℃ during washing, repeatedly washing for 5 times, washing for 10min each time, and filtering out the powdered carbon by using a sieve after washing is finished.
(2) The washed waste catalyst is put into 4mL deionized water with a filter screen, the temperature is kept at 25 ℃, and the catalyst is catalyzedThe catalyst is placed on a filter screen and is erected above the magneton stirring, and the catalyst is strictly prevented from contacting the magneton. Introducing H under the stirring state 2 ，H 2 Inserted below the filter screen, the stirring speed is 800r/min, and the hydrogen flow rate is 20 mL/min. Continuously introducing H 2 After sufficient adsorption, Ni (NO) is added in the same amount as the noble metal in the waste catalyst 3 ) 2 ·6H 2 And O, stirring is continued for 0.5 h. And then carrying out suction filtration, and washing the solid after suction filtration to be neutral. The filtrate is retained for the next use.
(3) And (3) carrying out vacuum drying treatment on the neutral solid washed in the step (2), wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2 h.
(4) The dried catalyst is loaded into a tubular reactor, and H is introduced 2 The hydrogen flow rate is kept at 20mL/min, the reaction temperature is 500 ℃, the hydrogen pressure is 3.0MPa, and the reaction is carried out for 5 hours.
(5) The reacted catalyst was washed with 0.1mol/L dilute hydrochloric acid and the temperature was maintained at 20 ℃. And detecting by using an AAS test method, and continuously washing by using deionized water to be neutral after nickel ions are not detected. Then filtering and vacuum drying are carried out, wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2h, and finally the regenerated catalyst is obtained.
Example 6
The embodiment provides a regeneration method of a carbon-supported metal catalyst, which specifically comprises the following steps:
(1) fully mixing methanol and water in the dosage ratio of 1:1 to prepare the required mixed solution. And (3) taking 2g of the waste catalyst, washing with 4mL of mixed liquor, setting the temperature to be 35 ℃ during washing, repeatedly washing for 5 times, washing for 10min each time, and filtering out the powdered carbon by using a sieve after washing is finished.
(2) And (3) placing the washed waste catalyst into 4mL of deionized water with a filter screen, keeping the temperature at 25 ℃, placing the catalyst on the filter screen, and erecting the catalyst above the magneton stirring, wherein the catalyst is strictly prevented from contacting with the magneton. Introducing H under the stirring state 2 ，H 2 Inserted below the filter screen, the stirring speed is 800r/min, and the hydrogen flow rate is 20 mL/min. Continuously introducing H 2 After sufficient adsorption, adding noble metal to the waste catalystMetal loading of Ni (NO) 3 ) 2 ·6H 2 And O, stirring is continued for 0.5 h. Then, suction filtration is carried out, and the solid after suction filtration is washed to be neutral. The filtrate is retained for the next use.
(3) And (3) carrying out vacuum drying treatment on the neutral solid washed in the step (2), wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2 h.
(4) The dried catalyst is loaded into a tubular reactor, and H is introduced 2 The hydrogen flow rate is kept at 20mL/min, the reaction temperature is 300 ℃, the hydrogen pressure is 1.0MPa, and the reaction is carried out for 2 h.
(5) The reacted catalyst was washed with 0.5mol/L dilute hydrochloric acid and the temperature was kept at 50 ℃. And detecting by using an AAS test method, and continuously washing by using deionized water to be neutral after nickel ions are not detected. Then filtering and vacuum drying are carried out, wherein the vacuum drying procedure comprises the steps of keeping the temperature of 50 ℃ for 2h, keeping the temperature of 80 ℃ for 2h and keeping the temperature of 120 ℃ for 3h, and finally the regenerated catalyst is obtained.
Example 7
The embodiment provides a regeneration method of a carbon-supported metal catalyst, which specifically comprises the following steps:
(1) fully mixing methanol and water in the dosage ratio of 1:1 to prepare the required mixed solution. And (3) taking 4g of the waste catalyst, washing with 8mL of mixed liquor, setting the temperature to be 35 ℃ during washing, repeatedly washing for 5 times, washing for 10min each time, and filtering out the powdered carbon by using a sieve after washing is finished.
(2) And (3) placing the washed waste catalyst into 4mL of deionized water with a filter screen, keeping the temperature at 25 ℃, placing the catalyst on the filter screen, and erecting the catalyst above the magneton stirring, wherein the catalyst is strictly prevented from contacting with the magneton. Introducing H under the stirring state 2 ，H 2 Inserted below the filter screen, the stirring speed is 800r/min, and the hydrogen flow rate is 20 mL/min. Continuously introducing H 2 After sufficient adsorption, Ni (NO) is added in the same amount as the noble metal in the waste catalyst 3 ) 2 ·6H 2 And O, stirring is continued for 0.5 h. Then, suction filtration is carried out, and the solid after suction filtration is washed to be neutral. The filtrate is retained for the next use.
(3) And (3) carrying out vacuum drying treatment on the neutral solid washed in the step (2), wherein the vacuum drying procedure is to keep the temperature at 30 ℃ for 1h, keep the temperature at 70 ℃ for 1h and keep the temperature at 100 ℃ for 2 h.
(4) The dried catalyst is loaded into a tubular reactor, and H is introduced 2 The hydrogen flow rate is kept at 20mL/min, the reaction temperature is 300 ℃, the hydrogen pressure is 1.0MPa, and the reaction is carried out for 2 h.
(5) The reacted catalyst was washed with 0.1mol/L dilute hydrochloric acid and the temperature was maintained at 20 ℃. And detecting by using an AAS test method, and continuously washing by using deionized water to be neutral after nickel ions are not detected. Then filtering and vacuum drying are carried out, wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2h, and finally the regenerated catalyst is obtained.
Example 8
The embodiment provides a regeneration method of a carbon-supported metal catalyst, which specifically comprises the following steps:
(1) fully mixing methanol and water in the dosage ratio of 1:1 to prepare the required mixed solution. And (3) taking 2g of the waste catalyst, washing with 4mL of mixed liquor, setting the temperature to be 35 ℃ during washing, repeatedly washing for 5 times, washing for 10min each time, and filtering out the powdered carbon by using a sieve after washing is finished.
(2) And (3) placing the washed waste catalyst into 4mL of deionized water with a filter screen, keeping the temperature at 25 ℃, placing the catalyst on the filter screen, and erecting the catalyst above the magneton stirring, wherein the catalyst is strictly prevented from contacting with the magneton. Introducing H under the stirring state 2 ，H 2 Inserted below the filter screen, the stirring speed is 800r/min, and the hydrogen flow rate is 20 mL/min. Continuously introducing H 2 After full adsorption, NiSO with the same loading as the noble metal in the waste catalyst is added 4 ·6H 2 And O, stirring is continued for 0.5 h. Then, suction filtration is carried out, and the solid after suction filtration is washed to be neutral. The filtrate is retained for the next use.
(3) And (3) carrying out vacuum drying treatment on the neutral solid washed in the step (2), wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2 h.
(4) The dried catalyst is loaded into a tubular reactor, H is introduced 2 The hydrogen flow rate is kept at 20mL/min, the reaction temperature is 300 ℃, the hydrogen pressure is 1.0MPa, and the reaction is carried out for 2 h.
(5) The reacted catalyst was washed with 0.1mol/L dilute hydrochloric acid and the temperature was maintained at 20 ℃. And detecting by using an AAS test method, and when nickel ions cannot be detected, continuously washing by using deionized water until the nickel ions are neutral. Then filtering and vacuum drying are carried out, wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2h, and finally the regenerated catalyst is obtained.
Example 9
The embodiment provides a regeneration method of a carbon-supported metal catalyst, which specifically comprises the following steps:
(1) fully mixing methanol and water in the dosage ratio of 1:3 to prepare the required mixed solution. And (3) taking 2g of the waste catalyst, washing with 4mL of mixed liquor, setting the temperature to be 40 ℃ during washing, repeatedly washing for 8 times, washing for 20min each time, and filtering out the powdered carbon by using a sieve after washing is finished.
(2) And (3) placing the washed waste catalyst into 4mL of deionized water with a filter screen, keeping the temperature at 25 ℃, placing the catalyst on the filter screen, and erecting the catalyst above the magneton stirring, wherein the catalyst is strictly prevented from contacting with the magneton. Introducing H under the stirring state 2 ，H 2 Inserted below the filter screen, the stirring speed is 800r/min, and the hydrogen flow rate is 20 mL/min. Continuously introducing H 2 After sufficient adsorption, Ni (NO) is added in the same amount as the noble metal in the waste catalyst 3 ) 2 ·6H 2 And O, stirring is continued for 0.5 h. Then, suction filtration is carried out, and the solid after suction filtration is washed to be neutral. The filtrate is retained for the next use.
(3) And (3) carrying out vacuum drying treatment on the neutral solid washed in the step (2), wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2 h.
(4) The dried catalyst is loaded into a tubular reactor, and H is introduced 2 The hydrogen flow rate is kept at 20mL/min, the reaction temperature is 300 ℃, the hydrogen pressure is 1.0MPa, and the reaction is carried out for 2 h.
(5) The reacted catalyst was washed with 0.1mol/L dilute hydrochloric acid and the temperature was maintained at 20 ℃. And detecting by using an AAS test method, and continuously washing by using deionized water to be neutral after nickel ions are not detected. Then filtering and vacuum drying are carried out, wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2h, and finally the regenerated catalyst is obtained.
Example 10
The embodiment provides a regeneration method of a carbon-supported metal catalyst, which specifically comprises the following steps:
(1) fully mixing methanol and water in the dosage ratio of 1:1 to prepare the required mixed solution. And (3) taking 2g of the waste catalyst, washing with 4mL of mixed liquor, setting the temperature to be 35 ℃ during washing, repeatedly washing for 5 times, washing for 10min each time, and filtering out the powdered carbon by using a sieve after washing is finished.
(2) And (3) placing the washed waste catalyst into 8mL of deionized water with a filter screen, keeping the temperature at 50 ℃, placing the catalyst on the filter screen, and erecting the catalyst above the magneton stirring, wherein the catalyst is strictly prevented from contacting with the magneton. Introducing H under the stirring state 2 ，H 2 Inserted below the filter screen, the stirring speed is 1000r/min, and the hydrogen flow rate is 20 mL/min. Continuously introducing H 2 After sufficient adsorption, Ni (NO) is added in the same amount as the noble metal in the waste catalyst 3 ) 2 ·6H 2 And O, stirring for 1 hour. Then, suction filtration is carried out, and the solid after suction filtration is washed to be neutral. The filtrate is retained for the next use.
(3) And (3) carrying out vacuum drying treatment on the neutral solid washed in the step (2), wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2 h.
(4) The dried catalyst is loaded into a tubular reactor, and H is introduced 2 The hydrogen flow rate is kept at 20mL/min, the reaction temperature is 300 ℃, the hydrogen pressure is 1.0MPa, and the reaction is carried out for 2 h.
(5) The reacted catalyst was washed with 0.1mol/L dilute hydrochloric acid and the temperature was maintained at 20 ℃. And detecting by using an AAS test method, and continuously washing by using deionized water to be neutral after nickel ions are not detected. Then filtering and vacuum drying are carried out, wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2h, and finally the regenerated catalyst is obtained.
Example 11
The embodiment provides a regeneration method of a carbon-supported metal catalyst, which specifically comprises the following steps:
(1) fully mixing methanol and water in the dosage ratio of 1:1 to prepare the required mixed solution. And (3) taking 2g of the waste catalyst, washing with 4mL of mixed liquor, setting the temperature to be 35 ℃ during washing, repeatedly washing for 5 times, washing for 10min each time, and filtering out the powdered carbon by using a sieve after washing is finished.
(2) And (3) placing the washed waste catalyst into 4mL of deionized water with a filter screen, keeping the temperature at 25 ℃, placing the catalyst on the filter screen, and erecting the catalyst above the magneton stirring, wherein the catalyst is strictly prevented from contacting with the magneton. Introducing H under the stirring state 2 ，H 2 Inserted below the filter screen, the stirring speed is 800r/min, and the hydrogen flow rate is 20 mL/min. Continuously introducing H 2 After sufficient adsorption, Ni (NO) is added in the same amount as the noble metal in the waste catalyst 3 ) 2 ·6H 2 And O, stirring is continued for 0.5 h. Then, suction filtration is carried out, and the solid after suction filtration is washed to be neutral. The filtrate is retained for the next use.
(3) And (3) carrying out vacuum drying treatment on the neutral solid washed in the step (2), wherein the vacuum drying procedure comprises the steps of keeping at 40 ℃ for 2h, keeping at 75 ℃ for 2h and keeping at 110 ℃ for 3 h.
(4) The dried catalyst is loaded into a tubular reactor, and H is introduced 2 The hydrogen flow rate is kept at 20mL/min, the reaction temperature is 300 ℃, the hydrogen pressure is 1.0MPa, and the reaction is carried out for 2 h.
(5) The reacted catalyst was washed with 0.1mol/L dilute hydrochloric acid and the temperature was maintained at 20 ℃. And detecting by using an AAS test method, and continuously washing by using deionized water to be neutral after nickel ions are not detected. Then filtering and vacuum drying are carried out, wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2h, and finally the regenerated catalyst is obtained.
Example 12
The embodiment provides a regeneration method of a carbon-supported metal catalyst, which specifically comprises the following steps:
(1) fully mixing methanol and water in the dosage ratio of 1:1 to prepare the required mixed solution. And (3) taking 2g of the waste catalyst, washing with 4mL of mixed liquor, setting the temperature to be 35 ℃ during washing, repeatedly washing for 5 times, washing for 10min each time, and filtering out the powdered carbon by using a sieve after washing is finished.
(2) The washed waste catalyst is placed in a filterThe temperature was maintained at 25 ℃ in 4mL of deionized water on a mesh, the catalyst was placed on a filter mesh and set on top of the magneton stirrer, and the catalyst was kept strictly in contact with the magneton. Introducing H under the stirring state 2 ，H 2 Inserted below a filter screen, the stirring speed is 800r/min, and the hydrogen flow rate is 20 mL/min. Continuously introducing H 2 After sufficient adsorption, Ni (NO) is added in the same amount as the noble metal in the waste catalyst 3 ) 2 ·6H 2 And O, stirring is continued for 0.5 h. Then, suction filtration is carried out, and the solid after suction filtration is washed to be neutral. The filtrate is retained for the next use.
(3) And (3) carrying out vacuum drying treatment on the neutral solid washed in the step (2), wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2 h.
(4) The dried catalyst is loaded into a tubular reactor, and H is introduced 2 The hydrogen flow rate is kept at 20mL/min, the reaction temperature is 400 ℃, the hydrogen pressure is 2.0MPa, and the reaction is carried out for 3 hours.
(5) The reacted catalyst was washed with 0.1mol/L dilute hydrochloric acid and the temperature was maintained at 20 ℃. And detecting by using an AAS test method, and continuously washing by using deionized water to be neutral after nickel ions are not detected. Then filtering and vacuum drying are carried out, wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2h, and finally the regenerated catalyst is obtained.
Example 13
The embodiment provides a regeneration method of a carbon-supported metal catalyst, which specifically comprises the following steps:
(1) fully mixing methanol and water in the dosage ratio of 1:1 to prepare the required mixed solution. And (3) taking 2g of the waste catalyst, cleaning with 4mL of mixed liquor, setting the temperature to be 35 ℃ during cleaning, repeating the cleaning for 5 times, cleaning for 10min each time, and filtering out the powdered carbon by using a sieve after the cleaning is finished.
(2) And (3) placing the washed waste catalyst into 4mL of deionized water with a filter screen, keeping the temperature at 25 ℃, placing the catalyst on the filter screen, and erecting the catalyst above the magneton stirring, wherein the catalyst is strictly prevented from contacting with the magneton. Introducing H under the stirring state 2 ，H 2 Inserted below a filter screen, the stirring speed is 800r/min, and the hydrogen flow rate is 20 mL/min. Continuously introducing H 2 After sufficient adsorption, Ni (NO) is added in the same amount as the noble metal in the waste catalyst 3 ) 2 ·6H 2 And O, stirring is continued for 0.5 h. Then, suction filtration is carried out, and the solid after suction filtration is washed to be neutral. The filtrate is retained for the next use.
(3) And (3) carrying out vacuum drying treatment on the neutral solid washed in the step (2), wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2 h.
(4) The dried catalyst is loaded into a tubular reactor, and H is introduced 2 The hydrogen flow rate is kept at 20mL/min, the reaction temperature is 300 ℃, the hydrogen pressure is 1.0MPa, and the reaction is carried out for 2 h.
(5) The reacted catalyst was washed with 0.3mol/L dilute hydrochloric acid and the temperature was maintained at 40 ℃. And detecting by using an AAS test method, and continuously washing by using deionized water to be neutral after nickel ions are not detected. Then filtering and vacuum drying are carried out, wherein the vacuum drying procedure comprises the steps of keeping the temperature of 50 ℃ for 2h, keeping the temperature of 80 ℃ for 2h and keeping the temperature of 120 ℃ for 3h, and finally the regenerated catalyst is obtained.
Example 14
The embodiment provides a regeneration method of a carbon-supported metal catalyst, which specifically comprises the following steps:
(1) fully mixing methanol and water in the dosage ratio of 1:1 to prepare the required mixed solution. And (3) taking 4g of the waste catalyst, washing with 8mL of mixed liquor, setting the temperature to be 35 ℃ during washing, repeatedly washing for 5 times, washing for 10min each time, and filtering out the powdered carbon by using a sieve after washing is finished.
(2) And (3) placing the washed waste catalyst into 4mL of deionized water with a filter screen, keeping the temperature at 25 ℃, placing the catalyst on the filter screen, and erecting the catalyst above the magneton stirring, wherein the catalyst is strictly prevented from contacting with the magneton. Introducing H under the stirring state 2 ，H 2 Inserted below the filter screen, the stirring speed is 800r/min, and the hydrogen flow rate is 20 mL/min. Continuously introducing H 2 After sufficient adsorption, Ni (NO) is added in the same amount as the noble metal in the waste catalyst 3 ) 2 ·6H 2 And O, stirring is continued for 0.5 h. Then, suction filtration is carried out, and the solid after suction filtration is washed to be neutral. The filtrate is retained for the next use.
(3) And (3) carrying out vacuum drying treatment on the neutral solid washed in the step (2), wherein the vacuum drying procedure comprises the steps of keeping at 30 ℃ for 1h, keeping at 70 ℃ for 1h and keeping at 100 ℃ for 2 h.
(4) The dried catalyst is loaded into a tubular reactor, and H is introduced 2 The hydrogen flow rate is kept at 20mL/min, the reaction temperature is 300 ℃, the hydrogen pressure is 1.0MPa, and the reaction is carried out for 2 h.
(5) The reacted catalyst was washed with 0.1mol/L dilute hydrochloric acid and the temperature was maintained at 20 ℃. And detecting by using an AAS test method, and continuously washing by using deionized water to be neutral after nickel ions are not detected. Then filtering and vacuum drying are carried out, wherein the vacuum drying procedure comprises the steps of keeping at 40 ℃ for 1h, keeping at 75 ℃ for 1h and keeping at 110 ℃ for 2h, and finally the regenerated catalyst is obtained.
Comparative example 1
This comparative example is compared with example 1 to show the procedure (2) to H 2 Importance for the performance of the regenerated catalyst. Comparative example 1 procedure of the regeneration process:
step (1) is the same as step (1) of example 1.
Step (2), stopping H in the adsorption process 2 Otherwise, the procedure was the same as in step (2) of example 1.
Step (3) is the same as step (3) of example 1.
Step (4) is the same as step (4) of example 1.
Step (5) is the same as step (5) of example 1.
Comparative example 2
This comparative example is compared with example 1 to show the case of the introduction of H in step (4) 2 Importance for the performance of the regenerated catalyst. Comparative example 2 procedure of regeneration process:
step (1) is the same as step (1) of example 1.
Step (2) is the same as step (2) of example 1.
Step (3) is the same as step (3) of example 1.
Step (4) is the same as step (5) of example 1.
Comparative example 3
This comparative example is compared with example 1 to show the importance of the reaction temperature in step (4) for the performance of the regenerated catalyst. Comparative example 3 procedure of the regeneration process:
step (1) is the same as step (1) of example 1.
Step (2) is the same as step (2) of example 1.
Step (3) is the same as step (3) of example 1.
Step (4), the reaction temperature was 290 ℃, and the rest was the same as in step (4) of example 1.
Step (5) is the same as step (5) of example 1.
Comparative example 4
This comparative example is compared with example 1 to show the importance of the reaction temperature in step (4) for the performance of the regenerated catalyst. Comparative example 4 procedure of the regeneration process:
step (1) is the same as step (1) of example 1.
Step (2) is the same as step (2) of example 1.
Step (3) is the same as step (3) of example 1.
Step (4), the reaction temperature was 510 ℃, and the rest was the same as in step (4) of example 1.
Step (5) is the same as step (5) of example 1.
Comparative example 5
This comparative example is compared with example 1 to show the importance of the ratio of methanol to water in the mixed liquor of step (1) on the performance of the regenerated catalyst. Comparative example 5 procedure of the regeneration process:
step (1), the ratio of methanol to water was 1:0.5, and the rest was the same as in step (1) of example 1.
Step (2) is the same as step (2) of example 1.
Step (3) is the same as step (3) of example 1.
Step (4) is the same as step (4) of example 1.
Step (5) is the same as step (5) of example 1.
Comparative example 6
This comparative example is compared with example 1 to show the importance of the ratio of methanol to water in the mixed liquor of step (1) on the performance of the regenerated catalyst. Comparative example 6 procedure of regeneration process:
step (1), methanol to water ratio 1:6, otherwise the same as in step (1) of example 1.
Step (2) is the same as step (2) of example 1.
Step (3) is the same as step (3) of example 1.
Step (4) is the same as step (4) of example 1.
Step (5) is the same as step (5) of example 1.
Comparative example 7
This comparative example is compared to example 1 to show the importance of the cleaning conditions of step (1) on the performance of the regenerated catalyst. Comparative example 7 procedure of the regeneration process:
and (1) washing at 30 ℃ for 5 times for 5min, wherein the rest is the same as the step (1) in the example 1.
Step (2) is the same as step (2) of example 1.
Step (3) is the same as step (3) of example 1.
Step (4) is the same as step (4) of example 1.
Step (5) is the same as step (5) of example 1.
Comparative example 8
This comparative example is compared with example 1 to show the importance of the step (1) cleaning conditions on the performance of the regenerated catalyst. Comparative example 8 procedure of the regeneration process:
and (1) washing at 60 ℃ for 2 times, wherein each washing time is 5min, and the rest is the same as the step (1) in the example 1.
Step (2) is the same as step (2) of example 1.
Step (3) is the same as step (3) of example 1.
Step (4) is the same as step (4) of example 1.
Step (5) is the same as step (5) of example 1.
Comparative example 9
This comparative example is compared to example 1 to show the importance of the nickel salt species in step (2) for the performance of the regenerated catalyst. Comparative example 9 procedure of regeneration process:
step (1) is the same as step (1) of example 1.
Step (2), selecting the nickel salt as NiBr 2 Otherwise, the procedure was the same as in step (2) of example 1.
Step (3) is the same as step (3) of example 1.
Step (4) is the same as step (4) of example 1.
Step (5) is the same as step (5) of example 1.
Comparative example 10
This comparative example is compared to example 1 to show the importance of the vacuum drying ramp in step (3) for the performance of the regenerated catalyst. Comparative example 10 procedure of the regeneration process:
step (1) is the same as step (1) of example 1.
Step (2) is the same as step (2) of example 1.
And (3) carrying out vacuum drying and temperature rising procedures of keeping at 25 ℃ for 1h, keeping at 65 ℃ for 2h, and keeping at 95 ℃ for 2 h. The rest is the same as in step (3) of example 1.
Step (4) is the same as step (4) of example 1.
Step (5) is the same as step (5) of example 1.
Comparative example 11
This comparative example is compared to example 1 to show the importance of the vacuum drying ramp in step (3) for the performance of the regenerated catalyst. Comparative example 11 procedure of the regeneration process:
step (1) is the same as step (1) of example 1.
Step (2) is the same as step (2) of example 1.
And (3) carrying out vacuum drying and temperature rising procedures of keeping at 55 ℃ for 2h, keeping at 85 ℃ for 2h, and keeping at 125 ℃ for 3 h. The rest is the same as in step (3) of example 1.
Step (4) is the same as step (4) of example 1.
Step (5) is the same as step (5) of example 1.
Comparative example 12
This comparative example is compared to example 1 to show the importance of the vacuum drying ramp in step (3) for the performance of the regenerated catalyst. Comparative example 12 procedure of the regeneration process:
step (1) is the same as step (1) of example 1.
Step (2) is the same as step (2) of example 1.
And (3) carrying out vacuum drying and temperature rising procedures for keeping at 50 ℃ for 4 h. The rest is the same as in step (3) of example 1.
Step (4) is the same as step (4) of example 1.
Step (5) is the same as step (5) of example 1.
Comparative example 13
This comparative example is compared to example 1 to show the importance of the vacuum drying ramp in step (3) for the performance of the regenerated catalyst. Comparative example 13 procedure of regeneration process:
step (1) is the same as step (1) of example 1.
Step (2) is the same as step (2) of example 1.
And (3) carrying out vacuum drying and temperature rising procedures of keeping at 50 ℃ for 2h and keeping at 120 ℃ for 3 h. The rest is the same as in step (3) of example 1.
Step (4) is the same as step (4) of example 1.
Step (5) is the same as step (5) of example 1.
Comparative example 14
This comparative example is compared with example 1 to show the importance of the dilute hydrochloric acid concentration in step (5) for the performance of the regenerated catalyst. Comparative example 14 procedure of the regeneration process:
step (1) is the same as step (1) of example 1.
Step (2) is the same as step (2) of example 1.
Step (3) is the same as step (3) of example 1.
Step (4) is the same as step (4) of example 1.
Step (5), the dilute hydrochloric acid concentration was 0.05mol/L, which was the same as in step (5) of example 1.
Comparative example 15
This comparative example is compared with example 1 to show the importance of the dilute hydrochloric acid concentration in step (5) for the performance of the regenerated catalyst. Comparative example 15 procedure of the regeneration process:
step (1) is the same as step (1) of example 1.
Step (2) is the same as step (2) of example 1.
Step (3) is the same as step (3) of example 1.
Step (4) is the same as step (4) of example 1.
Step (5), the dilute hydrochloric acid concentration was 0.6mol/L, which was the same as in step (5) of example 1.
Application embodiment 1
The fresh Pd/AC catalyst is applied to the reaction of preparing CTFE by R113 hydrodechlorination, the final conversion rate is reduced to be less than 55 percent, the catalyst after the reaction is regenerated by adopting the regeneration methods of examples 1-14 and comparative examples 1-15, and the obtained regenerated catalyst is continuously put into the reaction system for preparing CTFE by R113 hydrodechlorination for trial. The space velocity in the reaction process is 60h -1 The reaction temperature was 300 ℃ (i.e., the aforementioned reaction method), and the initial activity performance of the regenerated catalyst was observed, and the results are shown in table 1 below:
TABLE 1 initial Activity of regenerated catalysts obtained in examples and comparative examples
| Catalyst and process for preparing same | CTFE yield/% |
| Example 1 | 98.5 |
| Example 2 | 98.6 |
| Example 3 | 98.5 |
| Example 4 | 98.7 |
| Example 5 | 97.9 |
| Example 6 | 98.6 |
| Example 7 | 98.4 |
| Example 8 | 98.4 |
| Example 9 | 98.2 |
| Example 10 | 98.2 |
| Example 11 | 98.6 |
| Example 12 | 98.3 |
| Example 13 | 99.5 |
| Example 14 | 98.4 |
| Comparative example 1 | 60.2 |
| Comparative example 2 | 55.6 |
| Comparative example 3 | 75.4 |
| Comparative example 4 | 68.5 |
| Comparative example 5 | 45.2 |
| Comparative example 6 | 54.9 |
| Comparative example 7 | 66.3 |
| Comparative example 8 | 78.5 |
| Comparative example 9 | 56.2 |
| Comparative example 10 | 63.3 |
| Comparative example 11 | 75.2 |
| Comparative example 12 | 69.3 |
| Comparative example 13 | 65.3 |
| Comparative example 14 | 59.6 |
| Comparative example 15 | 58.0 |
Application example two
The activity test was carried out under the following conditions using as a reaction system chlorotrifluoroethylene prepared by hydrodechlorination of R113, the fresh catalyst mentioned in the preparation of the above spent catalyst test sample and the regenerated catalyst regenerated by the method of example 1: in the reaction process, the space velocity is 1000h -1 The reaction temperature was 300 ℃.
FIG. 1 shows the conversion of the starting materials at different reaction times for fresh and regenerated catalyst, from which the catalytic activity is evaluated. As can be seen from fig. 1, the catalytic activity of the regenerated catalyst is substantially consistent with that of the fresh catalyst, and the catalyst life is slightly smaller than that of the fresh catalyst but is not much different.
Claims (10)
1. A method for regenerating a carbon-supported metal catalyst, characterized by comprising the steps of:
step (1), cleaning the waste catalyst by using a mixed solution of an organic solvent and water, and washing away hydrocarbon compounds and powdered carbon deposition;
step (2), the cleaned waste catalyst is placed in deionized water, and H is introduced into the waste catalyst under the stirring state 2 Adding nickel salt after full adsorption, and continuously stirring to load nickel on the waste catalyst, wherein the load of the nickel is 0.8-1.5 times of that of noble metal in the waste catalyst; then carrying out suction filtration, and washing the solid after suction filtration to be neutral;
step (3), carrying out vacuum drying treatment on the neutral solid washed in the step (2);
step (4), loading the dried catalyst into a tubeIn the reactor, H is introduced 2 Carrying out reaction;
washing the reacted catalyst with dilute hydrochloric acid until no nickel ions can be detected in the filtrate; then, continuously washing the mixture by deionized water to be neutral; finally, vacuum drying is carried out to obtain the regenerated catalyst.
2. The method for regenerating a carbon-supported metal catalyst according to claim 1, wherein: in the step (1), the spent catalyst is washed with a mixed solution of methanol and water.
3. The method for regenerating a carbon-supported metal catalyst as claimed in claim 2, wherein: in the step (1), the ratio of methanol to water in the mixed solution is 1 (1-5), and the dosage ratio of the waste catalyst to the mixed solution is 1 (2-7).
4. The method for regenerating a carbon-supported metal catalyst according to claim 1, wherein: in the step (1), the cleaning temperature is 35-55 ℃, and the cleaning is carried out for 5-10 times, 10-30min each time; the powdered carbon was removed by filtration through a sieve.
5. The method for regenerating a carbon-supported metal catalyst according to claim 1, wherein: in the step (2), the volume usage ratio of the waste catalyst to the deionized water is 1 (2-5), and the temperature is 25-90 ℃; the waste catalyst is arranged on the filter screen, is erected above the magneton stirring and is not contacted with the magneton, the stirring speed is 800-1000r/min, the hydrogen is inserted below the filter screen, and the flow rate is 20-40 mL/min.
6. The method for regenerating a carbon-supported metal catalyst according to claim 1, wherein: the nickel salt is Ni (NO) 3 ) 2 ·6H 2 O、NiCl 2 (H 2 O)·6H 2 O or NiSO 4 ·6H 2 And O is one of the compounds.
7. The method for regenerating a carbon-supported metal catalyst according to claim 1, wherein: in the step (3) and the step (5), programmed heating is adopted for vacuum drying, and the temperature-raising program is sequentially that the temperature is kept at 30-50 ℃ for 1-2h, the temperature is kept at 70-80 ℃ for 1-2h, and the temperature is kept at 100-120 ℃ for 2-3 h.
8. The method for regenerating a carbon-supported metal catalyst according to claim 1, wherein: in the step (4), the reaction temperature is 300-.
9. The method for regenerating a carbon-supported metal catalyst according to claim 1, wherein: in the step (5), the concentration of dilute hydrochloric acid is 0.1-0.5mol/L, and the washing temperature is 20-50 ℃; and (3) combining and collecting the washed metal and the metal in the step (2), and supplementing a proper amount of nickel to be used in the step (2).
10. The method for regenerating a carbon-supported metal catalyst according to claim 1, wherein: the detection method for nickel ions in the step (5) is an AAS test method.
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| JPH09117665A (en) * | 1995-10-25 | 1997-05-06 | Mitsubishi Gas Chem Co Inc | Catalyst regeneration |
| US20020115554A1 (en) * | 2000-12-22 | 2002-08-22 | Hydrocarbon Technologies, Inc. | Regeneration of used supported noble metal catalysts |
| CN102658171A (en) * | 2012-05-09 | 2012-09-12 | 杭州凯大催化金属材料有限公司 | Regeneration method of catalyst for preparing DSD acid by catalytic hydrogenation |
| CN104588094A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Regeneration method for deactivated catalyst |
| CN105689013A (en) * | 2016-03-14 | 2016-06-22 | 辽宁石油化工大学 | Regeneration method and application of low-alkane dehydrogenation catalyst |
| WO2020121287A1 (en) * | 2018-12-14 | 2020-06-18 | Pixel Voltaic Lda | Catalytic methane decomposition and catalyst regeneration, methods and uses thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09117665A (en) * | 1995-10-25 | 1997-05-06 | Mitsubishi Gas Chem Co Inc | Catalyst regeneration |
| US20020115554A1 (en) * | 2000-12-22 | 2002-08-22 | Hydrocarbon Technologies, Inc. | Regeneration of used supported noble metal catalysts |
| CN102658171A (en) * | 2012-05-09 | 2012-09-12 | 杭州凯大催化金属材料有限公司 | Regeneration method of catalyst for preparing DSD acid by catalytic hydrogenation |
| CN104588094A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Regeneration method for deactivated catalyst |
| CN105689013A (en) * | 2016-03-14 | 2016-06-22 | 辽宁石油化工大学 | Regeneration method and application of low-alkane dehydrogenation catalyst |
| WO2020121287A1 (en) * | 2018-12-14 | 2020-06-18 | Pixel Voltaic Lda | Catalytic methane decomposition and catalyst regeneration, methods and uses thereof |
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