Industrial activation method of molecular sieve catalyst

Abstract

The present application discloses an industrial activation method for a molecular sieve catalyst, which belongs to the field of chemistry and chemical engineering, and specifically belongs to the technical field of catalysts for the carbonylation of dimethyl ether to produce methyl acetate. The industrial activation method of the present application uses nitrogen-containing heterocyclic compounds to perform high-pressure adsorption on molecular sieves, increases the adsorption amount of nitrogen-containing heterocyclic compounds at acidic sites in the pores of the molecular sieves, greatly improves the stability of the catalyst, and combines the intermittent feeding method of nitrogen-containing heterocyclic compounds to control the adsorption heat, thereby achieving the goal of activating the catalyst in an adiabatic reactor. The method can effectively reduce the activation cost and equipment complexity of the dimethyl ether carbonylation catalyst.

Description

Technical Field

[0001] The present application relates to an industrial activation method for a molecular sieve catalyst, and belongs to the field of chemistry and chemical engineering, and specifically to the technical field of catalysts for preparing methyl acetate by carbonylation of dimethyl ether. Background Art

[0002] As an important chemical raw material and organic solvent, ethanol is widely used in the chemical, pharmaceutical, pesticide, food, fragrance and cosmetic industries. The domestic demand for ethanol is increasing year by year. At the same time, ethanol can also be used as a clean vehicle fuel and gasoline additive, and it occupies an increasingly prominent position in the energy market. As the traditional production process is restricted by the shortage of crude oil and the rising prices of crops, new ethanol production processes with high economic benefits are increasingly attracting people's attention.

[0003] In 2006, Iglesia et al. first discovered that solid acid molecular sieve (MOR) can catalyze the carbonylation reaction of dimethyl ether to produce methyl acetate at lower temperature and pressure. Methyl acetate can be hydrogenated to produce ethanol. This process route has lower production cost and simpler process than other processes, and is expected to replace other ethanol production processes. The pore structure of solid acid molecular sieve (MOR) consists of twelve-membered ring pores and eight-membered ring pores. The target product methyl acetate is first synthesized in the eight-membered ring pores of the molecular sieve. As the reaction proceeds, the product diffuses into the twelve-membered ring and is desorbed on the molecular sieve with the help of the twelve-membered ring pores. However, the acid sites of the twelve-membered ring are prone to side reactions to form carbon deposits, which block the twelve-membered ring pores. The transmission channel of the product methyl acetate is cut off, causing the catalyst to deactivate quickly. At present, a more effective way is to modify the molecular sieve with a modifying substance to inhibit the side reactions of the twelve-membered ring acid sites to form carbon deposits.

[0004] The existing technology requires that the catalyst be uniformly loaded into each tube of the tube reactor before activation, and a complex heat exchange system is required to maintain the reaction temperature, which is complicated to operate, increases equipment investment and operating costs, and cannot guarantee the catalyst activation effect, seriously affecting the catalyst activity and life. Therefore, it is particularly important to develop a more efficient and lower-cost catalyst activation method. Summary of the invention

[0005] Patent CN101613274B uses pyridine organic amine to modify the MOR molecular sieve, modify the pore structure and acidity of the molecular sieve, effectively inhibit carbon deposition, and improve the stability of the catalyst. Patent CN 109985658B adds a desorption process in the modification process of the MOR molecular sieve, selectively poisons the strong adsorption sites of pyridine or methylpyridine, desorbs pyridine or methylpyridine on the weak adsorption sites, and maintains the stability and selectivity of the catalyst, but the dimethyl ether conversion rate is only about 41%, and the catalyst activity decreases significantly after 40 hours. When the applicant used in-situ infrared technology to conduct online detection of the molecular sieve carbonylation reaction after adsorption of pyridine, it was observed that the pyridine adsorbed by the molecular sieve would gradually desorb during the reaction process, which would lead to accelerated deactivation of the molecular sieve and affect the service life of the catalyst.

[0006] In order to solve the problems of poor stability of dimethyl ether in the prior art of pyridine organic amine modified zeolite molecular sieves, and the high activation temperature caused by large adsorption heat during large-scale activation, which affects the activity and stability of the catalyst, the present application provides a new catalyst activation method, which uses nitrogen-containing heterocyclic compounds to perform high-pressure adsorption on molecular sieves, increases the adsorption amount of nitrogen-containing heterocyclic compounds on the twelve-membered ring acid sites in the molecular sieve, greatly improves the stability of the catalyst, and combines the intermittent feeding method of nitrogen-containing heterocyclic compounds to control the adsorption heat, and achieves the goal of catalyst activation in an adiabatic reactor. This method can effectively reduce the activation cost and equipment complexity of dimethyl ether carbonylation catalysts.

[0007] This application adopts the following technical solutions:

[0008] According to the first aspect of the present application, there is provided an industrial activation method for a molecular sieve catalyst, characterized in that it comprises the following steps:

[0009] S1, catalyst pretreatment: preheating the molecular sieve to a first constant temperature in an air atmosphere to obtain a dried molecular sieve;

[0010] S2, adsorption of nitrogen-containing heterocyclic compounds: cooling to a second constant temperature, and intermittently introducing nitrogen-containing heterocyclic compounds while continuously introducing an inert gas under a pressure of 1 to 4 MPa, so as to contact the dried molecular sieve, so that the molecular sieve adsorbs the nitrogen heterocyclic compounds until the adsorption is saturated, thereby obtaining a saturated molecular sieve;

[0011] S3, purging: cooling to a third constant temperature, using an inactive gas to purge the saturated adsorbed molecular sieve at a pressure of 0.1-0.5 MPa to obtain an activated molecular sieve catalyst;

[0012] The molecular sieve is at least one of HMFI molecular sieve, HFER molecular sieve, HMOR molecular sieve, HTON or HMTT molecular sieve.

[0013] Optionally, in step S2, the condition of intermittent introduction includes: the frequency of introducing the nitrogen-containing heterocyclic compound is to stop introducing the compound for 5 to 30 minutes after each introduction for 5 to 30 minutes.

[0014] Optionally, the nitrogen-containing heterocyclic compound is selected from at least one of pyridine and its derivatives.

[0015] Optionally, the industrial activation method of the molecular sieve catalyst is carried out in an adiabatic reactor. In the present application, the adiabatic reactor is an adiabatic fixed bed reactor, which refers to a reactor that does not exchange heat with the outside world and has the advantages of simple structure, low cost, and large catalyst processing capacity.

[0016] Optionally, in step S2, during the adsorption of the nitrogen-containing heterocyclic compound, the temperature of the molecular sieve is 200-300°C.

[0017] Optionally, in step S2, when the nitrogen-containing heterocyclic compound is introduced, the volume ratio of the nitrogen-containing heterocyclic compound introduced to the inert gas introduced is 1:20-200.

[0018] Optionally, in step S2, the conditions for introducing the inert gas include: a volume space velocity of 200 to 1000 h -1 .

[0019] Optionally, in step S2, the time for adsorbing the nitrogen-containing heterocyclic compound is 4 to 30 hours.

[0020] Optionally, in step S3, the purging conditions include: stopping the introduction of the nitrogen-containing heterocyclic compound while cooling to the third constant temperature, and adjusting the volume space velocity of the inert gas to 50 to 200 h -1 The purge time is 3 to 20 hours.

[0021] Optionally, the third constant temperature is 100-200°C.

[0022] Optionally, in step S1, the first constant temperature is 400-600°C.

[0023] Optionally, in step S2, the second constant temperature is 200-300°C.

[0024] The beneficial effects of this application include:

[0025] The industrial activation method of the molecular sieve catalyst provided in the present application uses nitrogen-containing heterocyclic compounds to perform high-pressure adsorption on the molecular sieve, increases the adsorption amount of the nitrogen-containing heterocyclic compounds on the acidic sites of the twelve-membered ring of the molecular sieve, greatly improves the stability of the catalyst, and combines the intermittent feeding of the nitrogen-containing heterocyclic compounds to control the adsorption heat, thereby achieving the goal of large-scale catalyst activation in an adiabatic reactor. The method can effectively reduce the activation cost and equipment complexity of the dimethyl ether carbonylation catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The curves of dimethyl ether conversion rate and product methyl acetate selectivity changing with time in the reaction of preparing methyl acetate by carbonylation of dimethyl ether when the molecular sieve catalyst is treated with different feeding methods in Comparative Example 1 and Example 1.

[0027] Figure 2 The curves of dimethyl ether conversion rate and product methyl acetate selectivity changing with time in the reaction of preparing methyl acetate by carbonylation of dimethyl ether using molecular sieve catalysts treated with different feed frequencies in Comparative Example 2 and Example 1 are shown.

[0028] Figure 3 The curves of dimethyl ether conversion rate and product methyl acetate selectivity changing with time in the reaction of preparing methyl acetate by dimethyl ether carbonylation using molecular sieve catalysts treated with different adsorption pressures in Comparative Example 3 and Example 1 are shown.

[0029] Figure 4 The curves showing the change of dimethyl ether conversion rate and product methyl acetate selectivity over time for the long-term evaluation of the activated catalysts obtained in Comparative Example 3 and Example 1 are as follows.

[0030] Figure 5 The curves of dimethyl ether conversion rate and product methyl acetate selectivity changing with time in the reaction of preparing methyl acetate by dimethyl ether carbonylation using molecular sieve catalysts treated with different adsorption pressures in Comparative Example 4 and Example 1 are shown. DETAILED DESCRIPTION

[0031] The present application is described in detail below with reference to the accompanying drawings and embodiments, but the present application is not limited to these embodiments.

[0032] The MOR molecular sieve catalyst was purchased from Yanchang Zhongke (Dalian) Energy Technology Co., Ltd., and the silicon-aluminum atomic ratio of the molecular sieve was 3:1.

[0033] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0034] Unless otherwise specified, conventional methods were used for testing and instrument settings were those recommended by the manufacturer.

[0035] Catalyst reaction performance evaluation: Weigh 1.0g of activated molecular sieve catalyst and load it into a fixed bed reaction tube for evaluation. Evaluation conditions: the volume ratio of dimethyl ether: carbon monoxide: hydrogen in the feed gas is 1:15:4, and the volume space velocity is 3000mL / (g cat h), the reaction pressure was 2.0 MPa, the reaction temperature was 200° C., and the gas products after the reaction were analyzed online by gas chromatography.

[0036] In the examples of this application, the conversion rate and selectivity are calculated as follows:

[0037] Dimethyl ether conversion rate = [(molar number of dimethyl ether carbon in the feed gas) - (molar number of dimethyl ether carbon in the product)] ÷ (molar number of dimethyl ether carbon in the feed gas) × (100%);

[0038] Methyl acetate selectivity = (2 / 3) × (the number of moles of carbon of methyl acetate in the product) ÷ [(the number of moles of carbon of dimethyl ether in the feed gas) - (the number of moles of carbon of dimethyl ether in the product)] × (100%).

[0039] Example 1

[0040] 1000 kg of molecular sieve catalyst was loaded into an adiabatic fixed bed reactor with a height-to-diameter ratio of 5:1 and a volume of 2 m 3 The temperature of the catalyst bed in the reactor is controlled by heating the air and nitrogen in a heating furnace which burns natural gas.

[0041] First, in an air atmosphere, the heating furnace starts to heat up and heat the air. The hot air enters the reactor to slowly heat the catalyst bed to the first constant temperature of 580°C and is treated at this temperature for 6 hours to obtain a dried molecular sieve. Then the heating furnace temperature is lowered to slowly cool the catalyst bed to the second constant temperature of 260°C. At the same time, the air is switched to nitrogen, and the nitrogen volume space velocity is controlled to 500h -1 .

[0042] The catalyst bed is gradually pressurized by controlling the reactor inlet and outlet regulating valves until the catalyst bed pressure reaches 2.0 MPa. Pyridine is intermittently introduced into the activation gas mixing tank through a high-pressure constant flow pump. Nitrogen and pyridine are mixed in the mixing tank and then enter the reactor. The volume ratio of pyridine to nitrogen in the activation gas is controlled to be 1:200. The intermittent feeding frequency of pyridine is controlled to stop feeding for 10 minutes after every 10 minutes of feeding. During the adsorption process, the temperature of the molecular sieve is always monitored to be lower than 265°C. After 20 hours of high-pressure adsorption, the pyridine is stopped to obtain a saturated adsorbed molecular sieve. Then the catalyst bed is cooled to the third constant temperature of 200°C, the reactor inlet and outlet regulating valves are adjusted to release the pressure to normal pressure, and the nitrogen volume space velocity is adjusted to 100h -1 After purging the molecular sieve for 10 h, the temperature was lowered and samples were taken for activity analysis.

[0043] Comparative Example 1

[0044] 1000 kg of molecular sieve catalyst was loaded into an adiabatic fixed bed reactor with a height-to-diameter ratio of 5:1 and a volume of 2 m 3 The temperature of the catalyst bed in the reactor is controlled by heating the air and nitrogen in a heating furnace which burns natural gas.

[0045] First, in an air atmosphere, the heating furnace starts to heat up and heat the air. The hot air enters the reactor to slowly heat the catalyst bed to the first constant temperature of 580°C and is treated at this temperature for 6 hours to obtain a dried molecular sieve. Then the heating furnace temperature is lowered to slowly cool the catalyst bed to the second constant temperature of 260°C. At the same time, the air is switched to nitrogen, and the nitrogen volume space velocity is controlled to 500h -1 .

[0046] The catalyst bed is gradually pressurized by controlling the reactor inlet and outlet regulating valves until the catalyst bed pressure reaches 2.0 MPa. Pyridine is continuously introduced into the activation gas mixing tank through a high-pressure constant flow pump. Nitrogen and pyridine are mixed in the mixing tank and then enter the reactor. The volume ratio of pyridine to nitrogen in the activation gas is controlled to be 1:200. During the adsorption process, the temperature of the catalyst bed is monitored to reach 390°C after the accumulated adsorption heat. After 20 hours of high-pressure adsorption, the introduction of pyridine is stopped to obtain a saturated adsorbed molecular sieve. Then the catalyst bed is cooled to the third constant temperature of 200°C, the reactor inlet and outlet regulating valves are adjusted to release the pressure to normal pressure, and the nitrogen volume space velocity is adjusted to 100h -1 After purging the molecular sieve for 10 h, the temperature was lowered and samples were taken for activity analysis.

[0047] Comparative Example 2

[0048] 1000 kg of molecular sieve catalyst was loaded into an adiabatic fixed bed reactor with a height-to-diameter ratio of 5:1 and a volume of 2 m 3 The temperature of the catalyst bed in the reactor is controlled by heating the air and nitrogen in a heating furnace which burns natural gas.

[0049] First, in an air atmosphere, the heating furnace starts to heat up and heat the air. The hot air enters the reactor to slowly heat the catalyst bed to the first constant temperature of 580°C and is treated at this temperature for 6 hours to obtain a dried molecular sieve. Then the heating furnace temperature is lowered to slowly cool the catalyst bed to the second constant temperature of 260°C. At the same time, the air is switched to nitrogen, and the nitrogen volume space velocity is controlled to 500h -1 .

[0050] The catalyst bed is gradually pressurized by controlling the reactor inlet and outlet regulating valves until the catalyst bed pressure reaches 2.0MPa. Pyridine is intermittently introduced into the activation gas mixing tank through a high-pressure constant flow pump. Nitrogen and pyridine are mixed in the mixing tank and then enter the reactor. The volume ratio of pyridine to nitrogen in the activation gas is controlled to be 1:200. The intermittent feeding frequency of pyridine is controlled to stop feeding for 40 minutes after every 40 minutes of feeding. During the adsorption process, the maximum temperature of the molecular sieve is monitored to reach 320°C. After 20 hours of high-pressure adsorption, the pyridine is stopped to obtain a saturated adsorbed molecular sieve. Then the catalyst bed is cooled to the third constant temperature of 200°C, the reactor inlet and outlet regulating valves are adjusted to release the pressure to normal pressure, and the nitrogen volume space velocity is adjusted to 100h -1 After purging the molecular sieve for 10 h, the temperature was lowered and samples were taken for activity analysis.

[0051] Comparative Example 3

[0052] 1000 kg of molecular sieve catalyst was loaded into an adiabatic fixed bed reactor with a height-to-diameter ratio of 5:1 and a volume of 2 m 3 The temperature of the catalyst bed in the reactor is controlled by heating the air and nitrogen in a heating furnace which burns natural gas.

[0053] First, in an air atmosphere, the heating furnace starts to heat up and heat the air. The hot air enters the reactor to slowly heat the catalyst bed to the first constant temperature of 580°C and is treated at this temperature for 6 hours to obtain a dried molecular sieve. Then the heating furnace temperature is lowered to slowly cool the catalyst bed to the second constant temperature of 260°C. At the same time, the air is switched to nitrogen, and the nitrogen volume space velocity is controlled to 500h -1 .

[0054] The catalyst bed pressure is controlled to 0.5MPa by the reactor inlet and outlet regulating valves, and pyridine is intermittently introduced into the activated gas mixing tank through a high-pressure constant flow pump. Nitrogen and pyridine are mixed in the mixing tank and then enter the reactor. The volume ratio of pyridine to nitrogen in the activated gas is controlled to be 1:200, and the intermittent feeding frequency of pyridine is controlled to stop feeding for 10 minutes after every 10 minutes of feeding. During the adsorption process, the temperature of the molecular sieve is always monitored to be lower than 265°C. After 20 hours of adsorption, the pyridine is stopped to obtain a saturated adsorbed molecular sieve. Then the catalyst bed is cooled to the third constant temperature of 200°C, and the nitrogen volume space velocity is adjusted to 100h -1 After purging the molecular sieve for 10 h, the temperature was lowered and samples were taken for activity analysis.

[0055] Comparative Example 4

[0056] 1000 kg of molecular sieve catalyst was loaded into an adiabatic fixed bed reactor with a height-to-diameter ratio of 5:1 and a volume of 2 m 3The temperature of the catalyst bed in the reactor is controlled by heating the air and nitrogen in a heating furnace which burns natural gas.

[0057] First, in an air atmosphere, the heating furnace starts to heat up and heat the air. The hot air enters the reactor to slowly heat the catalyst bed to the first constant temperature of 580°C and is treated at this temperature for 6 hours to obtain a dried molecular sieve. Then the heating furnace temperature is lowered to slowly cool the catalyst bed to the second constant temperature of 260°C. At the same time, the air is switched to nitrogen, and the nitrogen volume space velocity is controlled to 500h -1 .

[0058] The catalyst bed is gradually pressurized by controlling the reactor inlet and outlet regulating valves until the catalyst bed pressure reaches 5.0 MPa. Pyridine is intermittently introduced into the activation gas mixing tank through a high-pressure constant flow pump. Nitrogen and pyridine are mixed in the mixing tank and then enter the reactor. The volume ratio of pyridine to nitrogen in the activation gas is controlled to be 1:200. The intermittent feeding frequency of pyridine is controlled to stop feeding for 10 minutes after every 10 minutes of feeding. During the adsorption process, the temperature of the molecular sieve is always monitored to be lower than 265°C. After 20 hours of high-pressure adsorption, the pyridine is stopped to obtain a saturated adsorbed molecular sieve. Then the catalyst bed is cooled to the third constant temperature of 200°C, the reactor inlet and outlet regulating valves are adjusted to release the pressure to normal pressure, and the nitrogen volume space velocity is adjusted to 100h -1 After purging the molecular sieve for 10 h, the temperature was lowered and samples were taken for activity analysis.

[0059] Figure 1 The following is a curve showing changes in dimethyl ether conversion and product methyl acetate selectivity over time in the dimethyl ether carbonylation reaction to produce methyl acetate by treating molecular sieve catalysts in different feeding methods in Comparative Example 1 and Example 1: By comparing the dimethyl ether conversion rate, it can be seen that in Comparative Example 1, a continuous feeding activation method is adopted. Due to the large amount of heat adsorbed by the catalyst, the reactor cannot quickly remove the heat, the catalyst bed temperature in the reactor is much higher than the optimal adsorption temperature of the catalyst, and the catalyst activity and stability are significantly reduced.

[0060] Figure 2 The following is a curve showing changes in dimethyl ether conversion and product methyl acetate selectivity over time in the dimethyl ether carbonylation reaction to produce methyl acetate using molecular sieve catalysts treated with different feed frequencies in Comparative Example 2 and Example 1: By comparing the dimethyl ether conversion, it can be seen that after the intermittent feeding frequency is reduced in Comparative Example 2, the catalyst activity and stability decrease because the catalyst bed temperature in the reactor is higher than the optimal adsorption temperature of the catalyst.

[0061] Figure 3The following is a curve showing the change in dimethyl ether conversion rate and product methyl acetate selectivity over time in the dimethyl ether carbonylation reaction to produce methyl acetate using molecular sieve catalysts treated with different adsorption pressures in Comparative Example 3 and Example 1: By comparing the dimethyl ether conversion rate, it can be seen that the activity of the catalyst activated by atmospheric pressure adsorption is slightly lower than that of the catalyst activated by high pressure adsorption.

[0062] Figure 4 The curves of the dimethyl ether conversion rate and product methyl acetate selectivity over time for the long-term evaluation of the activated catalyst obtained in Comparative Example 3 and Example 1 are as follows: By comparing the dimethyl ether conversion rate, it can be seen that when the reaction is carried out to 1000h, the catalyst activated by high-pressure adsorption still maintains a high activity, while the activity of the catalyst activated by normal pressure adsorption has a significant downward trend. This indicates that the desorption rate of pyridine adsorbed by high pressure slows down during the reaction process, and side reactions such as carbon deposition at the acidic sites of the twelve-membered ring of the molecular sieve are suppressed, and the stability of the catalyst is greatly improved.

[0063] Figure 5 The following is a curve showing the change in dimethyl ether conversion rate and product methyl acetate selectivity over time in the dimethyl ether carbonylation reaction to produce methyl acetate by treating molecular sieve catalysts with different adsorption pressures in Comparative Example 4 and Example 1: By comparing the dimethyl ether conversion rate, it can be seen that when the adsorption pressure is too high, the catalyst activity decreases instead, indicating that when the adsorption pressure is too high, excessive adsorption of pyridine by the molecular sieve is likely to block the twelve-membered ring pores of the molecular sieve, affecting the mass transfer effect and reducing the activity of the catalyst.

[0064] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. An industrial activation method for a molecular sieve catalyst, characterized in that: The steps include: S1. Catalyst pretreatment: preheating the molecular sieve to a first constant temperature in an air atmosphere to obtain a dried molecular sieve; S2, adsorption of nitrogen-containing heterocyclic compounds: cooling to a second constant temperature, and intermittently introducing nitrogen-containing heterocyclic compounds while continuously introducing an inert gas under a pressure of 1 to 4 MPa, so as to contact the dried molecular sieve, so that the molecular sieve adsorbs the nitrogen heterocyclic compounds until the adsorption is saturated, thereby obtaining a saturated molecular sieve; S3, purging: cooling to a third constant temperature, using an inactive gas to purge the saturated adsorbed molecular sieve at a pressure of 0.1-0.5 MPa to obtain an activated molecular sieve catalyst; The molecular sieve is at least one selected from HMFI molecular sieve, HFER molecular sieve, HMOR molecular sieve, HTON or HMTT molecular sieve.

2. The industrial activation method according to claim 1, characterized in that In step S2, the intermittent introduction conditions include: the frequency of introducing the nitrogen-containing heterocyclic compound is to stop introducing the nitrogen-containing heterocyclic compound for 5 to 30 minutes after each introduction for 5 to 30 minutes.

3. The industrial activation method according to claim 1, characterized in that In step S2, during the adsorption of the nitrogen-containing heterocyclic compound, the temperature of the molecular sieve is 200-300°C.

4. The industrial activation method according to claim 1, characterized in that In step S2, when the nitrogen-containing heterocyclic compound is introduced, the volume ratio of the nitrogen-containing heterocyclic compound introduced to the inert gas introduced is 1:20-200.

5. The industrial activation method according to claim 1, characterized in that In step S2, the conditions for introducing the inert gas include: a volume space velocity of 200 to 1000 h -1 .

6. The industrial activation method according to claim 1, characterized in that In step S2, the time for adsorbing the nitrogen-containing heterocyclic compound is 4 to 30 hours.

7. The industrial activation method according to claim 1, characterized in that In step S3, the purging conditions include: stopping the introduction of the nitrogen-containing heterocyclic compound while cooling to the third constant temperature, and adjusting the volume space velocity of the inert gas to 50 to 200 h -1 The purge time is 3 to 20 hours.

8. The industrial activation method according to claim 7, characterized in that In step S3, the third constant temperature is 100-200°C.

9. The industrial activation method according to claim 1, characterized in that In step S1, the first constant temperature is 400-600°C.

10. The industrial activation method according to claim 1, characterized in that In step S2, the second constant temperature is 200-300°C.

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