CN111804311A - Method for continuously maintaining performance of catalyst for cyclohexene production - Google Patents

Method for continuously maintaining performance of catalyst for cyclohexene production Download PDF

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CN111804311A
CN111804311A CN202010586121.4A CN202010586121A CN111804311A CN 111804311 A CN111804311 A CN 111804311A CN 202010586121 A CN202010586121 A CN 202010586121A CN 111804311 A CN111804311 A CN 111804311A
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catalyst
amount
reactor
hydrogenation reactor
hydrogenation
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CN111804311B (en
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赵铎
史红军
陈聚良
张昌会
李晓峰
张乐
邹柯柯
卢磊
孟保勋
张磊磊
徐惠朋
杨莉
赵时超
孙维本
姜阅民
臧国亮
李润翊
赵雪山
周鹏飞
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HENAN SHENMA NYLON CHEMICAL CO Ltd
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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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/60—Platinum group metals with zinc, cadmium or mercury
    • 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
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/485—Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • C07C5/11—Partial hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/60—Platinum group metals with zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
    • 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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Abstract

The application discloses a method for continuously keeping the performance of a catalyst for cyclohexene production, which comprises the steps of firstly, reducing the feeding amount of a reactor, discharging a certain amount of low-activity catalyst, simultaneously adding a corresponding amount of zinc sulfate to maintain the concentration of slurry in a hydrogenation reactor, then adding a proper amount of new catalyst in batches, and adjusting the overall activity of the catalyst in the reactor, wherein the low-activity catalyst is an old catalyst which runs in the reactor for a long time and is close to the service life. The method uses two years as a replacement period to carry out quantitative replacement on the catalyst in the reactor, and the total replacement amount is 30-60Wt% of the total amount of the catalyst in the reactor. The method of the invention not only reduces the unit consumption of new catalyst, but also shortens the catalyst adjusting time, effectively reduces the cost and maintains the continuity of the production system.

Description

Method for continuously maintaining performance of catalyst for cyclohexene production
Technical Field
The invention belongs to the field of cyclohexene production, and particularly relates to a method for continuously maintaining the performance of a catalyst for cyclohexene production.
Background
When the catalyst applied to the traditional hydrogenation reactor is continuously operated, the activity of the catalyst in the reactor is influenced by factors such as the strength of the catalyst, the high flow of hydrogen during reaction, violent collision, partial skeleton metal precipitation during chemical reaction, mechanical transportation after catalyst regeneration, grain diameter change, catalyst poisoning and the like, partial abrasion, breakage, aging, inactivation and the like can occur, finally the activity of the catalyst in the hydrogenation reactor is deteriorated, and the yield of cyclohexene during reaction is obviously reduced. And affects subsequent separation systems, increasing operating costs.
The traditional method of maintaining catalyst performance in a reactor is:
in daily production, fresh catalyst is added into the reactor periodically, the fresh catalyst participates in reaction, the old catalyst is discharged, the catalyst is regenerated, and the fresh catalyst enters the reactor again.
After the operation reaches a certain period, the system is shut down, all the catalysts are removed, fresh catalysts are prepared and added into the system, the system is started, and the catalysts are adjusted to be in a reasonable state.
The application of the above-mentioned conventional process to maintain the activity of the catalyst in the reactor has the following problems:
(1) when the service life of the catalyst in the reactor is close to the service life, the reaction activity is obviously deteriorated, and even if a fresh catalyst is added periodically, the newly added catalyst is blocked by the original old catalyst in the reactor to prevent the effective contact area of the new catalyst and the benzene and hydrogen for reaction, so that the whole reaction activity of the catalyst in the system is still poor, the unit consumption of the catalyst is increased, and the production cost is increased;
(2) the catalyst is removed for replacement when the vehicle is stopped, the stability of the system is influenced, the replacement time is long, generally about 10 days, and the high-activity cyclohexene yield of the new catalyst is unstable;
(3) the fresh catalyst amount is large when the catalyst is completely replaced after the vehicle is stopped, and the mother liquor in the reactor is completely discharged and cannot be used continuously.
Disclosure of Invention
In view of the above problems of the prior art, the present invention provides a method for continuously maintaining the performance of a catalyst for cyclohexene production. The method changes the method of replacing the catalyst when the vehicle is stopped, thereby not only reducing the unit consumption of the fresh catalyst, but also shortening the catalyst adjusting time, effectively reducing the cost and maintaining the integral continuity of the production system.
The technical scheme adopted by the invention to solve the problems is as follows:
a method for continuously maintaining the performance of a catalyst for cyclohexene production comprises the following steps:
(1) calculating the total amount of the catalyst in the benzene hydrogenation reactor: m kg = ρCatalyst and process for preparing same×VIs effectiveReducing the feeding amount of raw material benzene of the hydrogenation reactor, discharging a certain amount of low-activity catalyst, and adding a certain amount of high-purity water into the hydrogenation reactor to maintain a certain slurry interface;
(2) adding a zinc sulfate solution into the hydrogenation reactor to maintain the concentration of zinc ions in the mother solution unchanged;
(3) then adding a proper amount of fresh catalyst in batches, adjusting the overall activity of the catalyst in the hydrogenation reactor, wherein the replacement period in the process is two years, and quantitatively replacing the catalyst in the reactor, wherein the single replacement amount is 30-60wt% of the total amount of the catalyst in the hydrogenation reactor.
Further, the specific process of step (1) is as follows: the feeding amount of the raw material benzene is reduced to 1/2m t/h from m t/h, the system is stably adjusted, the catalyst in the hydrogenation reactor is discharged to a catalyst regeneration system oil removal tank in batches, and the total discharged amount is 30-60wt% of the total amount of the catalyst in the hydrogenation reactor.
Further, the concentration of the zinc sulfate solution in the step (2) is 960kg/m for cultivation.
Further, the specific process of step (3) is as follows: addition amount M of the novel catalyst1=1/3M, according to new catalyst, dispersant ZrO2The mass ratio of 1 (5-8) is to add fresh catalyst, the fresh catalyst is added by 5 kg-10 kg each time, and hydrogenation is carried out according to the mass ratioThe reaction temperature and pressure of the reactor are stably adjusted, and after the system is stable, the system is added for the second time, and the process is repeated until the total adding amount M is reached1。
Further, the single displacement amount is 50wt% of the total amount of the catalyst in the hydrogenation reactor.
Further, the catalyst is a ruthenium-zinc catalyst.
The method ensures that the amount of the existing catalyst in the hydrogenation reactor is surplus, and then discharges the surplus catalyst to realize the taking out of the old catalyst in the reactor. Meanwhile, the discharge of the old catalyst can cause the loss of mother liquor zinc sulfate in the reactor system, further can influence the stable operation of the reactor, and the volume of the discharged liquid is calculated and the amount of the zinc sulfate solution to be supplemented is calculated by combining the analysis result of the discharged liquid. Adding a proper amount of fresh catalyst in batches according to the actual reaction condition to adjust the activity, collecting catalyst slurry in the reactor every day to perform component analysis and activity analysis, and finally realizing that the newly added fresh catalyst with overhigh activity and the residual old catalyst in the reactor reach a proper proportion and the reaction effect is optimal.
Mechanism of reaction
The partial hydrogenation of benzene is carried out in liquid by means of Ru-Zn ruthenium-zinc system catalyst slurry.
The reaction equation is as follows:
C6H6+2H2→C6H10
(BZ) PhenyleneHydroxycyclohexene (HE)
The reaction requirements are as follows: benzene conversion = 40-42%; the selectivity of cyclohexene =80-82%, the reaction is that hydrogen from benzene and hydrogen system is used as raw material, and cyclohexene and cyclohexane as by-product are prepared through partial hydrogenation reaction in the presence of ruthenium-zinc catalyst. The hydrogenation catalyst (main catalyst) is a catalyst for controlling the partial hydrogenation of BZ, and the catalyst in the Ru — Zn system is a particle formed of a metal Ru and a Zn salt. Since the hydrogenation catalyst has a low activity as the amount of hydrogen adsorbed increases, the activity is recovered by the hydrogenation catalyst regeneration step. When the activity of the catalyst decreases (the formation of the desired target product cyclohexene decreases), there are roughly three reasons:
(1) trace impurities poison the catalyst; (2) increase of the catalyst particle grain radius; (3) the adsorption of hydrogen on the catalyst surface increases.
Compared with the prior art, the invention has the following beneficial effects:
compared with the traditional method for maintaining the performance of the catalyst in the reactor, the method disclosed by the invention is better applied to solving the problems of activity reduction, low reaction yield, high catalyst consumption and cost increase caused by long-period operation of the catalyst in continuous chemical production, and large system influence, overlong operation time and large fresh catalyst dosage caused by catalyst replacement in parking. And the problems of large difficulty in starting adjustment and increased production cost caused by long period due to the fact that fresh catalysts are added and used in the conventional method are solved. In addition, the application of the invention directly saves about 2/3M kg of fresh catalyst, saves about 5 days of operation time and has considerable economic benefit.
Drawings
FIG. 1 is a schematic diagram of the apparatus of the cyclohexene production process of the present invention; in the figure, 101, a benzene feeding pipeline, 102, a hydrogen feeding pipeline, 2, a hydrogenation reactor, 3, a catalyst settler, 4, an oil storage tank, 5, an aeration tank, 51, a heating coil, 6, a boiling tank, 7, a pressure regulating valve, 8, a catalyst circulating pump, 9, a first hydrogenation catalyst conveying pump and 10, a second hydrogenation catalyst conveying pump;
FIG. 2 is a graph showing the change in the benzene conversion, cyclohexene selectivity and yield ten months before and after the replacement of the hydrogenation catalyst, "-" indicates before the replacement.
Detailed Description
The present invention is described in detail with reference to the following embodiments, which are provided in the present invention as a premise of the technical solution of the present invention, and the detailed implementation manner and the specific operation process are provided in the present embodiment.
As shown in fig. 1, the device for producing cyclohexene is shown in fig. 1, and includes a hydrogenation reactor 2, a catalyst settler 3 and a hydrogenation catalyst regeneration system, a benzene feed pipeline 101 and a hydrogen feed pipeline 102 are arranged at the top of the hydrogenation reactor 2, a reactant outlet of the hydrogenation reactor 2 is connected with an inlet of the catalyst settler 3 through a pipeline, the catalyst settler 6 is provided with a reaction oil outlet 31 and a hydrogenation catalyst outlet, the reaction oil outlet 31 is connected with the next process, a first branch 103 and a second branch 104 are arranged in parallel at the hydrogenation catalyst outlet of the catalyst settler 3, the first branch 103 is communicated to the hydrogenation catalyst inlet of the hydrogenation reactor 2, the second branch 104 is connected with the hydrogenation catalyst regeneration system, the regenerated hydrogenation catalyst returns to the hydrogenation reactor 5, and a pressure regulating valve 7 is arranged at an inlet of the second branch 104;
hydrogenation catalyst regeneration system includes deoiling jar 4, aeration tank 5, the jar 6 of boiling that connects gradually through the pipeline, and the import of deoiling jar 4 links to each other with second branch road 104, and the export of boiling jar 6 passes through the pipeline and communicates to first branch road 103, is equipped with catalyst circulating pump 8 on the first branch road 103, is equipped with first hydrogenation catalyst delivery pump 9 on the pipeline between aeration tank 5 and the boiling jar 6, is equipped with second hydrogenation catalyst delivery pump 10 on boiling jar 6's the outlet pipeline.
When the device works, catalyst slurry is continuously discharged from a hydrogenation reaction system, flash evaporation is carried out through pressure conversion (the pressure of a hydrogenation reactor 2 is 4.0 MpaG-5.0 MpaG to the micro-positive pressure of a deoiling tank 4, the temperature is changed from 130-145 ℃ to about 90 ℃), meanwhile, 30-35 wt% of hydrogen peroxide in the deoiling tank 4 removes organic matters in the catalyst, the deoiled hydrogenation catalyst enters an aeration tank 5 through a potential difference, the temperature of the aeration tank 5 is 95 ℃ through adjusting steam in a heating coil 51, oxygen-poor air is introduced for aeration operation, the aeration operation time is 5 hours, the oxygen-poor air is mixed gas of air and nitrogen according to a certain proportion, the oxygen concentration in the mixed gas is 3vol%, hydrogen adsorbed on the aeration treatment catalyst is used, the aerated hydrogenation catalyst is supplied to a boiling tank 6 through a first hydrogenation catalyst delivery pump 9, the temperature of the boiling tank 6 is 145 ℃, the pressure is controlled at 0.4MpaG, boiling for 1 hour, and then continuously returning the catalyst to the hydrogenation reactor 2 by using a second hydrogenation catalyst delivery pump 10, so that the catalyst in the hydrogenation reactor 2 continuously enters a regeneration system for regeneration, and the regenerated new catalyst is continuously returned to the hydrogenation reactor to maintain the activity of the catalyst and ensure the temperature and pressure stability of the hydrogenation system.
Example 1
A method for continuously maintaining the performance of a catalyst for cyclohexene production comprises the following steps:
(1) calculating the total amount of the catalyst in the benzene hydrogenation reactor:
M =ρcatalyst and process for preparing sameVIs effective
Reducing the raw material supply of a hydrogenation reactor, reducing the supply amount of raw material benzene from M t/h to 1/2M t/h, stably adjusting a system, discharging a catalyst in the hydrogenation reactor to a catalyst regeneration system, treating the catalyst by an oil removal tank, wherein a zinc-ruthenium catalyst exists in a zinc sulfate aqueous solution and circularly operates in the hydrogenation reaction system along with the catalyst, certain high-purity water is added to the system in the catalyst discharge process to maintain a certain slurry interface, so that the phenomenon that the oil is carried in catalyst slurry with too low circulation of the interface and the reaction activity is influenced is prevented, and the catalyst is discharged from the oil removal tank, if 1/2M catalyst is discharged, the concentration of zinc ions in the slurry is ensured to be unchanged, and the same amount of ZnSO needs to be supplemented4·7H2O; the catalyst needing to be discharged is divided into four times (the discharged catalyst amount can be reached by calculating four times according to the volume of the oil removal tank = 1/2M), the interval time of each time is determined according to the stability of the catalyst interface of the hydrogenation catalyst settler (the interval time is 4h generally),
(2) calculating the amount of zinc sulfate to be supplemented, and preparing 960kg/m zinc sulfate solution; the vat prepared to collect the old catalyst is drained for collection of the old catalyst slurry. After the catalyst is discharged each time, corresponding amount of zinc sulfate solution for 960kg/m plantation is supplemented to the hydrogenation reactor in time to adjust the slurry concentration in the hydrogenation reactor,
(3) addition of fresh catalyst: adding new catalyst immediately after the fourth discharge, wherein the addition amount M of the new catalyst1=1/3M, as new catalyst/ZrO2(dispersant) mass ratio = 1/(5-8) the two were mixed to carry the new catalyst on ZrO2Adding 8kg of new catalyst each time (8 kg is calculated according to the activity analysis of the old catalyst and the activity analysis of the new catalyst which are quitted each time), stably adjusting the pressure according to the reaction temperature of the hydrogenation reactor, and after the system is stabilizedAnd then adding for the second time, repeatedly performing the above operations until the total amount of the added materials is 1/2M1kg, adjusting the system to be stable, and then adding 1/2M in sequence1kg；
The catalyst slurry in the reactor is collected every day in the whole process for component analysis and activity analysis, so that the concentration of the catalyst is ensured, and the composition of the catalyst is in a normal range.
In a workshop, the addition amount of raw material benzene is reduced to 25 t/h from 50 t/h, the primary addition amount of the catalyst is 250kg, the average addition amount of the catalyst is 30kg per month, after the system runs for two years, the old catalyst needs to be replaced, the specific withdrawal amount of the catalyst is 500kg, the catalyst is withdrawn for four times, the interval time is 4h each time, 960kg/m zinc sulfate solution is prepared, after the catalyst is discharged each time, 960kg/m zinc sulfate solution is added into a hydrogenation reactor to maintain the normal concentration of mother liquor, and 8kg new catalyst (the new catalyst is loaded on ZrO according to the mass ratio of 1 (5-8)) is added each time according to the calculation of the cyclohexene yield2The method comprises the following steps of (1) stabilizing the temperature and pressure of a reaction system, adding for the second time after the system is stabilized until the addition amount is 328kg, after the catalyst replacement is finished, testing the conversion rate, the selectivity and the yield of cyclohexene within ten months before and after the catalyst replacement, wherein the flow rate of benzene at the inlet of a hydrogenation reactor is 1.3 m/s, the flow rate of benzene at the outlet of the hydrogenation reactor is 0.98m/s, and the generation amount of cyclohexene at the outlet of the hydrogenation reactor is 16.6t/h, and concretely, the detailed figure 2 shows that the conversion rate is increased to 42.02% from the minimum value of 36.05%; the selectivity is increased from the lowest value of 76.05% to 83.25%; the cyclohexene yield (yield = conversion selectivity) increased from a minimum of 28.16% to 35%.
After the method is applied, the activity of the catalyst in the hydrogenation reactor is obviously improved through operation detection, the conversion rate is increased back to 42%, the selectivity is as high as 83%, and compared with the prior art, the conversion rate is increased by 4%, and the selectivity is increased by 5% (the yield of the cyclohexene is increased from 29% to 35%). And after the replacement is finished, the fresh catalyst is periodically replenished, the reaction effect is obvious, and the conversion rate and the selectivity can be maintained to be operated at a higher level.
Note: calculation of conversion
The conversion is the ratio (in moles) of the amount of any reaction substance converted to the product substance.
For example, the Benzene (BZ) conversion of a hydrogenation reactor represents the ratio of BZ at the reactor inlet reacted in the reactor.
If the BZ flow rate is A (mol/h) at the reactor inlet and B (mol/h) at the reactor outlet, the BZ conversion is expressed as follows:
BZ conversion (%) = (a-B)/a 100%
Calculation of the selection Rate
The selectivity is a ratio of the amount (mol number) of the target component among the amounts of the reaction substances converted into the product substances.
For example, the selectivity to cyclohexene (HE) is an indication of how much HE is produced in the amount of BZ converted in the hydrogenation reactor.
If the HE flow at the reactor outlet is C (mol/h) and the above conversion is the flow used, the HE selectivity is expressed as follows:
HE selectivity (%) = C/(a-B) × 100
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited to the embodiments, and various changes and modifications can be made by one skilled in the art without departing from the scope of the invention.

Claims (6)

1. A method for continuously maintaining the performance of a catalyst for cyclohexene production is characterized by comprising the following steps:
(1) calculating the total amount of the catalyst in the benzene hydrogenation reactor: m kg = ρCatalyst and process for preparing same×VIs effectiveReducing the feeding amount of raw material benzene of the hydrogenation reactor, discharging a certain amount of low-activity catalyst, and adding a certain amount of high-purity water into the hydrogenation reactor to maintain a certain slurry interface;
(2) adding a zinc sulfate solution into the hydrogenation reactor to maintain the concentration of zinc ions in the slurry unchanged;
(3) then adding a proper amount of fresh catalyst in batches, adjusting the overall activity of the catalyst in the hydrogenation reactor, wherein the replacement period in the process is two years, and quantitatively replacing the catalyst in the reactor, wherein the single replacement amount is 30-60wt% of the total amount of the catalyst in the hydrogenation reactor.
2. The method for continuously maintaining the performance of a catalyst for cyclohexene production according to claim 1, wherein the step (1) comprises the following steps: the feeding amount of the raw material benzene is reduced to 1/2m t/h from m t/h, the system is stably adjusted, the catalyst in the hydrogenation reactor is discharged to a catalyst regeneration system oil removal tank in batches, and the total discharged amount is 30-60wt% of the total amount of the catalyst in the hydrogenation reactor.
3. The method for continuously maintaining the performance of the catalyst for cyclohexene production according to claim 1, wherein the concentration of the zinc sulfate solution in step (2) is obtained by high pressure swing chromatography (adopted) at 960 kg/m.
4. The method for continuously maintaining the performance of the catalyst for cyclohexene production according to claim 1, wherein the step (3) comprises the following steps: addition amount M of the novel catalyst1=1/3M, according to new catalyst, ZrO2The mass ratio of (5-8) is that a new catalyst is added, 5 kg-10 kg of the new catalyst is added each time, the stable adjustment is carried out according to the reaction temperature and the pressure of the hydrogenation reactor, the second addition is carried out after the system is stable, and the steps are repeated until the total addition amount M is reached1。
5. The method for continuously maintaining the performance of a catalyst for cyclohexene production according to claim 1 or 2, wherein the single replacement amount is 50wt% of the total amount of the catalyst in the hydrogenation reactor.
6. The method for continuously maintaining the performance of a catalyst for cyclohexene production according to any of claims 1 to 4, wherein the catalyst is a ruthenium-zinc catalyst.
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