CN115430465B - Regeneration method of anthraquinone hydrogenation catalyst - Google Patents
Regeneration method of anthraquinone hydrogenation catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 22
- 238000011069 regeneration method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 98
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000010926 purge Methods 0.000 claims abstract description 50
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 30
- 206010037544 Purging Diseases 0.000 claims abstract description 17
- 238000002791 soaking Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 17
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 13
- 238000011282 treatment Methods 0.000 claims abstract description 10
- 230000008929 regeneration Effects 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005336 cracking Methods 0.000 abstract description 15
- 230000001172 regenerating effect Effects 0.000 abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000006004 Quartz sand Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
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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
-
- 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
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- 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
- B01J23/90—Regeneration or reactivation
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the 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
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
-
- 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
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
-
- 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
- B01J38/56—Hydrocarbons
-
- 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)
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Abstract
The invention discloses a regeneration method of an anthraquinone hydrogenation catalyst. A method for regenerating an anthraquinone hydrogenation catalyst comprising: in a regeneration reactor or an anthraquinone hydrogenation reactor, the following steps are carried out: (1) Soaking an anthraquinone hydrogenation catalyst to be regenerated in heavy aromatic hydrocarbon; (2) purging with nitrogen; (3) carrying out purging treatment by using water vapor; (4) washing the catalyst with high temperature water; (5) purging with nitrogen. The method solves the problem of cracking of part of regenerated catalyst, reduces the loss of the catalyst in the regeneration process, and saves the cost and the working procedures.
Description
Technical Field
The invention relates to a method for regenerating a catalyst, in particular to a method for regenerating an anthraquinone hydrogenation catalyst.
Background
Hydrogen peroxide is an important inorganic chemical product, and is widely used in a plurality of fields of textile, papermaking, chemical synthesis, environmental protection and the like, and is closely related to improving the national life quality and level. At present, products are mainly classified into industrial grade, electronic grade and food grade, and the industrial grade is mainly applied to the fields of chemical synthesis, pulp bleaching, printing and dyeing, metallurgy, environmental protection and the like; the electronic grade is mainly used for cleaning silicon chips, etching printed circuit boards and processing semiconductor materials; food grade is mainly used for the production and processing of food.
The production method of hydrogen peroxide mainly comprises six methods of acidolysis peroxide method, electrolysis method, anthraquinone method, isopropanol method, oxygen cathode reduction method and hydrogen-oxygen direct oxidation method, wherein the anthraquinone method is the most main method for producing hydrogen peroxide at home and abroad at present.
The main industrial catalysts used for anthraquinone hydrogenation reactions are supported palladium-based catalysts. The deactivation of the anthraquinone hydrogenation palladium catalyst mainly comprises the following three reasons: firstly, the catalyst is deactivated by the blockage of surface organics. As the side reaction in the system proceeds, anthraquinone degradation products are increased gradually, and the generated degradation products cover the surface of the catalyst, so that the active sites capable of participating in the reaction are reduced, the catalyst is prevented from being contacted with alkylanthraquinone to generate hydrogenation reaction, and the hydrogenation efficiency is reduced. Secondly, the catalyst is deactivated by loss of surface metal. Thirdly, the catalyst loses activity due to poisoning, mainly referring to CO and CO in hydrogen 2 And H 2 S and other impurities. Wherein deactivation by reason one can restore the catalyst activity by catalyst regeneration.
At present, a common catalyst regeneration mode in industry is to desorb organic compounds on the surface of a catalyst by using high-temperature water washing, oxidize palladium particle crystals on the surface of a carrier, reduce the palladium particles by hydrogen, recover the activity, purge the catalyst by using nitrogen after the catalyst is regenerated, purge impurities, carbon deposit and the like in surface holes of the catalyst, and take away moisture on the surface of the catalyst.
However, cracking phenomenon of a part of regenerated catalyst is found in the regeneration process of the industrial catalyst, and the catalyst is crushed and reused, so that the bed pressure is reduced and the service life of the catalyst is influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a regeneration method of an anthraquinone hydrogenation catalyst. The method solves the problem of cracking of part of regenerated catalyst.
The regeneration method of the anthraquinone hydrogenation catalyst comprises the following steps: in a regeneration reactor or an anthraquinone hydrogenation reactor, the following steps are carried out: (1) Soaking an anthraquinone hydrogenation catalyst to be regenerated in heavy aromatic hydrocarbon; (2) purging with nitrogen or an inert gas; (3) carrying out purging treatment by using water vapor; (4) washing the catalyst with high temperature water; (5) purging with nitrogen or an inert gas.
In the method, heavy aromatic hydrocarbon in the step (1) is a common working solvent in the technical process of producing hydrogen peroxide by an anthraquinone method, the soaking time is 24-72 hours, and the liquid-solid mass ratio of the heavy aromatic hydrocarbon to the catalyst is 3-5:1. the process dissolves a portion of the organics adsorbed on the catalyst into the heavy aromatics.
In the method, the purging treatment time in the step (2) is 8-24 hours, and the liquid on the surface of the catalyst is dried.
In the method, the water vapor purging treatment in the step (3) adopts water vapor purging at the temperature of 100-110 ℃ in a proportion of 5% -100% for 0.5-24 hours; wherein the ratio refers to the ratio of the steam inlet amount per hour to the catalyst mass.
In the method of the present invention, the steam purge treatment in step (3) is preferably performed as follows: the temperature of the reactor is raised to 100 ℃, one or more than one of the proportions of 5% -50% are treated in a combined way, steam at 100% -110 ℃ is introduced to purge for 0.5-5 hours, preferably 1-3 hours, so that the surfaces of all the catalysts are fully wetted, and then steam is introduced to purge for 5-24 hours according to the proportion of 55% -100%, preferably 70% -100%; wherein the multiple combined treatments are respectively purged according to the proportion from small to large; further preferably, the process is performed as follows: firstly, 100-110 ℃ water vapor is introduced according to the proportion of 10% for 0.5-1h, then 100-110 ℃ water vapor is introduced according to the proportion of 20% for 0.5-1h, then 100-110 ℃ water vapor is introduced according to the proportion of 50% for 0.5-1h, then 100-110 ℃ water vapor is introduced according to the proportion of 80% for 0.5-1h, and then 100-110 ℃ water vapor is introduced according to the proportion of 100% for 5-24 h for purging; wherein the ratio refers to the ratio of the steam inlet amount per hour to the catalyst mass.
In the method, the temperature of the high-temperature water in the step (4) is 100-120 ℃, the flow of the high-temperature water is t/h, t is 1/3-1/2 of the mass of the catalyst, and the washing time is 12-48 hours.
In the method of the invention, the purging treatment time in the step (5) is 8-24 hours.
In the method of the invention, the anthraquinone hydrogenation catalyst is a supported metal catalyst commonly used in industry, generally inorganic porous materials are used as carriers, such as alumina or modified alumina, and noble metals or Ni are used as active components.
The inventor finds that the anthraquinone hydrogenation catalyst belongs to a porous material with a large specific surface, and has a plurality of micropores, when the catalyst is directly put into water, the pore canal is rapidly filled with water and a large amount of adsorption heat is instantaneously discharged, and the water in the pore canal rapidly expands to cause cracking of catalyst particles. According to the invention, part of organic matters are dissolved by heavy aromatic hydrocarbon, the catalyst is purged by steam before washing, the steam amount is gradually increased, the catalyst is fully wetted, and then the catalyst is washed by high temperature water, so that the possibility of instantaneous heat release of the catalyst pore canal is reduced, the probability of rapid expansion of the catalyst pore canal is reduced, the catalyst is ensured to be intact after regeneration, and the problem of cracking is avoided.
Drawings
FIG. 1 is a photograph of the regenerated catalyst of comparative example 1.
FIG. 2 is a photograph of the regenerated catalyst of example 1.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way. The catalyst to be regenerated adopted in the embodiment is an anthraquinone hydrogenation catalyst which takes modified alumina pellets as a carrier and palladium as active metal, and the diameter of the catalyst is 1-3 mm; and unloading the catalyst, randomly taking 100 catalysts, observing whether the appearance is cracked, representing the cracking condition of the catalyst by using the cracking rate, repeating the process for three times, and taking an average value, wherein the cracking rate is 100 percent.
Example 1
(1) Catalyst loading
30g of the catalyst after the test is measured, the catalyst is filled into a micro-reaction constant temperature section of a fixed bed, and the upper part and the lower part of the reactor are filled with quartz sand;
(2) Heavy aromatic soaking
Injecting heavy aromatic hydrocarbon into the reactor at the rate of 30g/h, wherein the injection time is 3 hours, and the soaking time is 72 hours;
(3) Nitrogen purge
After the soaking is finished, the catalyst bed is purged by nitrogen, the nitrogen amount is 100mL/min, and the purging is performed for 8 hours;
(4) Introducing water vapor
After the nitrogen purging is finished, the temperature of the reactor is raised to 100 ℃, firstly, 100-110 ℃ water vapor is introduced for 0.5h according to the proportion of 10 percent (water vapor flow rate of 3 g/h), then 100-110 ℃ water vapor is introduced for 0.5h according to the proportion of 20 percent (water vapor flow rate of 6 g/h), then 100-110 ℃ water vapor is introduced for 0.5h according to the proportion of 50 percent (water vapor flow rate of 15 g/h), then 100-110 ℃ water vapor is introduced for 0.5h according to the proportion of 80 percent (water vapor flow rate of 24 g/h), and then 100-110 ℃ water vapor is introduced for 5h according to the proportion of 100 percent (water vapor flow rate of 30 g/h);
(5) Washing with water
After the introduction of the water vapor is finished, the temperature of the reactor is adjusted to 100 ℃, and the reactor is washed by hot water at 100 ℃ for 48 hours at the speed of 10 g/h;
(6) Nitrogen purge
After the water washing is finished, introducing nitrogen to cool and blow the water, wherein the nitrogen amount is 100mL/min, and purging the water for 8 hours. And discharging the catalyst after the temperature of the reactor is reduced to below 30 ℃, wherein the cracking rate of the catalyst is less than 1%.
Example 2
(1) Catalyst loading
30g of the catalyst after the test is measured, the catalyst is filled into a micro-reaction constant temperature section of a fixed bed, and the upper part and the lower part of the reactor are filled with quartz sand;
(2) Heavy aromatic soaking
Injecting heavy aromatic hydrocarbon into the reactor at the rate of 30g/h, wherein the injection time is 5 hours, and the soaking time is 24 hours;
(3) Nitrogen purge
After the soaking is finished, the catalyst bed is purged by nitrogen, the nitrogen amount is 100mL/min, and the purging is carried out for 24 hours;
(4) Introducing water vapor
After the nitrogen purging is finished, the temperature of the reactor is raised to 100 ℃, firstly, 100-110 ℃ water vapor is introduced for 1h according to the proportion of 10% (water vapor flow rate of 3 g/h), then 100-110 ℃ water vapor is introduced for 1h according to the proportion of 20% (water vapor flow rate of 6 g/h), then 100-110 ℃ water vapor is introduced for 1h according to the proportion of 50% (water vapor flow rate of 15 g/h), then 100-110 ℃ water vapor is introduced for 1h according to the proportion of 80% (water vapor flow rate of 24 g/h), and then 100-110 ℃ water vapor is introduced for 24 h according to the proportion of 100% (water vapor flow rate of 30 g/h).
(5) Washing with water
After the introduction of the water vapor is finished, the temperature of the reactor is adjusted to 100 ℃, and the reactor is washed for 12 hours by 15g/h of hot water at 100 ℃;
(6) Nitrogen purge
After the water washing is finished, introducing nitrogen to cool and blow the water, wherein the nitrogen amount is 100mL/min, and purging the water for 8 hours. And discharging the catalyst after the temperature of the reactor is reduced to below 30 ℃, wherein the cracking rate of the catalyst is less than 1%.
Example 3
(1) Catalyst loading
30g of the catalyst after the test is measured, the catalyst is filled into a micro-reaction constant temperature section of a fixed bed, and the upper part and the lower part of the reactor are filled with quartz sand;
(2) Heavy aromatic soaking
Injecting heavy aromatic hydrocarbon into the reactor at the rate of 30g/h, wherein the injection time is 4 hours, and the soaking time is 48 hours;
(3) Nitrogen purge
After the soaking is finished, nitrogen is used for purging the catalyst bed, the nitrogen amount is 100mL/min, and the purging is carried out for 16 hours;
(4) Introducing water vapor
After the nitrogen purging is finished, the temperature of the reactor is raised to 100 ℃, firstly, 100-110 ℃ water vapor is introduced for 1h according to the proportion of 10% (water vapor flow rate of 3 g/h), then 100-110 ℃ water vapor is introduced for 1h according to the proportion of 20% (water vapor flow rate of 6 g/h), then 100-110 ℃ water vapor is introduced for 1h according to the proportion of 50% (water vapor flow rate of 15 g/h), then 100-110 ℃ water vapor is introduced for 1h according to the proportion of 80% (water vapor flow rate of 24 g/h), and then 100-110 ℃ water vapor is introduced for 18 h according to the proportion of 100% (water vapor flow rate of 30 g/h).
(5) Washing with water
After the introduction of the water vapor, the temperature of the reactor was raised to 120℃and the reactor was washed with 10g/h of hot water at 120℃for 24 hours;
(6) Nitrogen purge
After the water washing is finished, introducing nitrogen to cool and blow the water, wherein the nitrogen amount is 100mL/min, and purging the water for 24 hours. And discharging the catalyst after the temperature of the reactor is reduced to below 30 ℃, wherein the cracking rate of the catalyst is less than 0.5%.
Example 4
The procedure of example 1 is followed except that step (4) is performed as follows: after the nitrogen purging is finished, the temperature of the reactor is raised to 100 ℃, firstly 10 percent (water vapor flow rate 3 g/h) of water vapor at 100-110 ℃ is introduced for 1h, 80 percent (water vapor flow rate 24 g/h) of water vapor at 100-110 ℃ is introduced for 1h, and then 100 percent (water vapor flow rate 30 g/h) of water vapor at 100-110 ℃ is introduced for 16 h. Discharging the catalyst, wherein the cracking rate of the catalyst is less than 1%.
Comparative example 1
(1) Catalyst loading
30g of the catalyst after the test is measured, the catalyst is filled into a micro-reaction constant temperature section of a fixed bed, and the upper part and the lower part of the reactor are filled with quartz sand;
(2) Washing with water
The temperature of the reactor is raised to 120 ℃, and the reactor is washed for 24 hours by 15g/h of hot water at about 120 ℃;
(3) Nitrogen purge
After the water washing is finished, introducing nitrogen to cool and blow the water, wherein the nitrogen amount is 100mL/min, and purging the water for 8 hours. When the temperature of the reactor is reduced to below 30 ℃, the catalyst is discharged, 30% of the catalyst has cracking phenomenon, and white pellets are taken as cracking catalysts in the picture of figure 1.
Comparative example 2
(1) Catalyst loading
30g of the catalyst after the test is measured, the catalyst is filled into a micro-reaction constant temperature section of a fixed bed, and the upper part and the lower part of the reactor are filled with quartz sand;
(2) Heavy aromatic soaking
Injecting heavy aromatic hydrocarbon into the reactor at the rate of 30g/h, wherein the injection time is 4 hours, and the soaking time is 48 hours;
(3) Nitrogen purge
After the soaking is finished, nitrogen is used for purging the catalyst bed, the nitrogen amount is 100mL/min, and the purging is carried out for 16 hours;
(4) Introducing water vapor
After the nitrogen purging is finished, the temperature of the reactor is raised to 100 ℃, and steam with the temperature of 100-110 ℃ is introduced for 6 hours according to the proportion of 100% (steam flow rate 30 g/h);
(5) Washing with water
After the water vapor is introduced, the temperature of the reactor is raised to 120 ℃, and the reactor is washed for 24 hours by hot water at about 120 ℃ with the concentration of 10 g/h;
(6) Nitrogen purge
After the water washing is finished, introducing nitrogen to cool and blow the water, wherein the nitrogen amount is 100mL/min, and purging the water for 24 hours. When the reactor temperature was reduced to below 30 ℃, the catalyst was discharged and about 10% of the catalyst had cracking.
Claims (8)
1. A regeneration method of an anthraquinone hydrogenation catalyst is characterized in that: in a regeneration reactor or an anthraquinone hydrogenation reactor, the following steps are carried out: (1) Soaking an anthraquinone hydrogenation catalyst to be regenerated in heavy aromatic hydrocarbon; (2) purging with nitrogen or an inert gas; (3) carrying out purging treatment by using water vapor; (4) washing the catalyst with high temperature water; (5) purging with nitrogen or an inert gas; the water vapor purging treatment process in the step (3) comprises the following steps: the temperature of the reactor is raised to 100 ℃, one or more than one of the proportions of 5 to 50 percent are treated, steam at 100 to 110 ℃ is introduced to purge for 0.5 to 5 hours, and then steam at 55 to 100 percent is introduced to purge for 5 to 24 hours; wherein the multiple combined treatments are respectively purged according to the proportion from small to large; wherein the ratio refers to the ratio of the steam inlet amount per hour to the catalyst mass.
2. The regeneration method according to claim 1, characterized in that: the soaking time in the step (1) is 24-72 hours, and the liquid-solid mass ratio of heavy aromatic hydrocarbon to catalyst is 3-5:1.
3. the regeneration method according to claim 1, characterized in that: and (3) the nitrogen purging time in the step (2) is 8-24 hours.
4. The regeneration method according to claim 1, characterized in that: the water vapor purging process is as follows: the temperature of the reactor is raised to 100 ℃, firstly 100-110 ℃ water vapor is introduced according to the proportion of 10% for 0.5-1 hour, then 100-110 ℃ water vapor is introduced according to the proportion of 20% for 0.5-1 hour, then 100-110 ℃ water vapor is introduced according to the proportion of 50% for 0.5-1 hour, then 100-110 ℃ water vapor is introduced according to the proportion of 80% for 0.5-1 hour, and then 100-110 ℃ water vapor is introduced according to the proportion of 100% for 5-24 hours.
5. The regeneration method according to claim 1, characterized in that: the temperature of the high-temperature water in the step (4) is 100-120 ℃, and the washing time is 12-48 hours.
6. The regeneration method according to claim 1, characterized in that: the flow rate of the high-temperature water in the step (4) is t/h, and t is 1/3-1/2 of the mass of the catalyst.
7. The regeneration method according to claim 1, characterized in that: and (5) the nitrogen purging time is 8-24 hours.
8. The regeneration method according to claim 1, characterized in that: the anthraquinone hydrogenation catalyst is a load type metal catalyst commonly used in industry, an inorganic porous material is used as a carrier, and noble metal or Ni is used as an active component.
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| CN202110607007.XA CN115430465B (en) | 2021-06-01 | 2021-06-01 | Regeneration method of anthraquinone hydrogenation catalyst |
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| GB1455030A (en) * | 1974-04-25 | 1976-11-10 | British Petroleum Co | Regeneration of support nickel catalysts |
| CN104475175A (en) * | 2014-12-17 | 2015-04-01 | 烟台百川汇通科技有限公司 | Method for generating palladium catalyst for producing hydrogen peroxide by using anthraquinone process |
| CN105057006A (en) * | 2015-08-17 | 2015-11-18 | 浙江巴陵恒逸己内酰胺有限责任公司 | Method for regenerating palladium catalyst for production of hydrogen peroxide solution through anthraquinone process |
| CN110652984A (en) * | 2018-06-28 | 2020-01-07 | 中国石油化工股份有限公司 | Methane dry reforming catalyst, preparation method thereof and methane dry reforming method |
| CN111437889A (en) * | 2020-04-01 | 2020-07-24 | 安徽泉盛化工有限公司 | Regeneration method of catalyst of hydrogenation system for producing hydrogen peroxide by anthraquinone process |
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| GB1455030A (en) * | 1974-04-25 | 1976-11-10 | British Petroleum Co | Regeneration of support nickel catalysts |
| CN104475175A (en) * | 2014-12-17 | 2015-04-01 | 烟台百川汇通科技有限公司 | Method for generating palladium catalyst for producing hydrogen peroxide by using anthraquinone process |
| CN105057006A (en) * | 2015-08-17 | 2015-11-18 | 浙江巴陵恒逸己内酰胺有限责任公司 | Method for regenerating palladium catalyst for production of hydrogen peroxide solution through anthraquinone process |
| CN110652984A (en) * | 2018-06-28 | 2020-01-07 | 中国石油化工股份有限公司 | Methane dry reforming catalyst, preparation method thereof and methane dry reforming method |
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