CN1552804A - Catalytic cracking catalyst demetallization and reactivation method - Google Patents

Abstract

A method for removing metals and reactivating catalytic cracking agent includes: 1) mixing acidifier composition liquid with catalytic cracking catalyst at liquid-solid ratio of (2 - 10): 1, stirring at atmosphere - 200degC for 1 - 24 hours; 2) filtering the slurry and beating the obtained cakes with deionized water at atmosphere - 100degC for 10 minutes to 6 hours under pH 3.0 - 7.0 controlled with ammonia, and filtering the obtained slurry; 3) beating the obtained cakes from the above step 2 with activated ion composition liquid at liquid-solid ratio of (2 - 10):1 at the same temperature above for 10 minutes to 5 hours, filtering the slurry and recovering the processed catalysts. Its advantages include simple procedure, less investment and short recovery period, to remove pollutant metals and to improve activity and selectivity of the products.

Description

Catalytic cracking catalyst demetallization and reactivation method

technical field

The invention belongs to the general regeneration or reactivation method of catalyst, more specifically, it is a demetallization reactivation method for catalytic cracking catalyst.

Background technique

During the catalytic cracking process, metals such as Ni, V, Fe, Cu, etc. in the raw oil are gradually deposited on the catalyst. With the increase of the amount of metal on the catalyst, the activity of the catalyst decreases and the selectivity becomes poor. In product distribution, the yields of hydrogen, dry gas, and coke increased, while the yields of target products such as liquefied gas and gasoline decreased. In industrial catalytic cracking production, there are two main methods to solve the problem of metal pollution, one is to reduce the level of metal pollution by discharging part of the balancer and replenishing fresh agent; the other is to use anti-metal catalysts and/or metal deactivators. As the crude oil becomes heavier, catalytic cracking develops rapidly towards heavy oil catalytic cracking, and the metal content in the raw material also increases significantly, so that the metal content of the equilibrium catalyst increases significantly, even if a new catalyst or passivator is used, the problem cannot be completely solved.

In actual industrial production, in order to maintain the activity and selectivity of the balance agent in the catalytic cracking unit, it is necessary to discharge part of the balance agent and replenish fresh agent frequently. This approach not only increases the operating cost of the device, but also the discharged waste agent is easy to cause environmental pollution. At present, the amount of waste catalyst (including waste catalyst recovered from the cyclone) is as high as 15,000 tons in China every year. These spent catalysts generally contain trace amounts of radioactive elements and cannot be disposed of at will. At home and abroad, the following methods are mainly used to deal with spent catalysts:

建池地埋，用半地下水泥池全封闭填埋。

Build the pool and bury it in the ground, and use a semi-underground cement pool to fully seal and fill it.

废催化剂作吸附剂，除去污水中氨离子和金属离子。

The spent catalyst is used as an adsorbent to remove ammonia ions and metal ions in sewage.

脱金属回收利用。

Demetallization and recycling.

采用磁分离的方法，将平衡剂中的高活性催化剂分离出来、再次使用。

Using the method of magnetic separation, the highly active catalyst in the balancing agent is separated and reused.

其它，如作水泥混合材料或作为新建装置的开工剂。

Others, such as cement mixing materials or as a start-up agent for new installations.

Among the above methods, building a pool to bury is not a long-term solution; the amount and use of the adsorbent are limited; although magnetic separation can recycle the highly active catalyst particles in the balancer, it does not fundamentally solve the problem of the outlet for industrial waste . Therefore, among the above methods, only demetallization recycling is the development direction. It can not only save fresh catalyst, reduce environmental pollution, but also reduce the metal content of the balancer, and improve the activity and selectivity of the catalyst.

As early as the 1960s, the chemical demetallization process of spent catalysts represented by MET-X and DEMET processes appeared, which is suitable for amorphous silica-alumina catalysts with low content of polluting metals. The catalyst is sulfurized and oxidized under certain conditions to convert the metal into a dispersible form, and then undergo reductive-oxidative washing to remove the metal. USP31501045 and USP3173882 use high-temperature chlorination to demetallize, USP3150103 and USP3147228 use high-temperature vulcanization and/or oxidative demetallization, and USP3178364 use high-temperature oxidation, vulcanization and chlorination to demetallize. The difference between these patents lies in the demetallization steps and reaction conditions. same.

From the 1970s to the 1980s, with the development of heavy oil processing and the wide application of molecular sieve catalysts, the content of heavy metals such as iron, nickel, copper, vanadium, and sodium on molecular sieve catalysts gradually increased, and the activity and selectivity of the catalysts were seriously affected. Patents related to demetallization regeneration of deactivated molecular sieve catalysts can be mainly divided into two types. One is the improvement of DEMET process, such as USP4101444, USP4234452, USP4686197, USP4824814, etc.; In the DEMET process (Jin.S.Y, etal, J.I.E.C.Prod.rex.Dev.1986,25,549-553) improved by U.S. ARCO Company, its main steps include: hydrogen sulfide sulfides the spent catalyst, air oxidation, and reduction, Oxidative washing. Chemcat has made some modifications to the DEMET process, which also includes three steps, one is to pass hydrogen sulfide gas first, and then pass chlorine gas to make the metal become soluble sulfide and chloride; the second is redox washing; the third is sulfuric acid Ammonium ion exchange. These demetallization processes all have steps such as oxidation, sulfidation and/or chlorination. Therefore, there are many equipments and large investment, and poisonous gases such as hydrogen sulfide and chlorine may cause environmental pollution.

USP4787968 treats the catalyst with a solution containing ammonium ions and rare earth ions to increase the content of ammonium ions and rare earth ions in the catalyst. USP4280897 forms a chelate with ammonium citrate and the polluting metal on the catalyst, and the elution of the chelate removes the polluting metal. USP4814066, USP4929336, USP4954244, USP5021377 have introduced methods such as citric acid, carboxylic acid and/or ammonium salt exchange, chelation, complexation etc. to process catalyst.

USP5900383 introduces a metal-contaminated molecular sieve catalyst, which is beaten with a liquid composed of acid, detergent or surfactant, mixed at a certain temperature for a sufficient time, so that the contaminated metal is released from the pores of the molecular sieve, and then filtered and washed with water. The acid used in this patent is malic acid, acetic acid, citric acid, formic acid, hydrochloric acid, nitric acid or sulfuric acid, etc., and the combination liquid may also contain ammonium difluoride, enzyme compound, etc. The role of the detergent or surfactant is to suspend the pollutants removed from the pores of the molecular sieve to the surface layer of the liquid, extract a part of the liquid from the slurry, and return to the slurry after filtering to remove the pollutants.

USP6046125 introduces a method for improving catalyst activity, which can be applied to balancers and fresheners. The catalyst is contacted with a solution containing water, a chloride-free mineral acid and an aluminum source. The liquid-solid ratio is 1-10, the chloride ion content of the solution is less than 1000ppm, and the pH value of the solution is adjusted and maintained at 3-12 with ammonia water during the reaction. Suitable acids are sulfurous acid and sulfuric acid and suitable aluminum sources are gibbsite and alumina. The method is simple to operate, can reduce the heavy metal content of the catalyst, and increase the number of acidic active centers of the catalyst, but it is proved by experiments that the demetallization regeneration effect of the method is not ideal (see Comparative Example 1).

Contents of the invention

The purpose of the present invention is to provide a catalytic cracking catalyst demetallization and reactivation method on the basis of the prior art, so as to increase the activity of the catalyst and improve the product selectivity.

The catalytic cracking catalyst demetallization reactivation method provided by the invention comprises the following steps:

(1) The acidulant combination liquid and the catalytic cracking catalyst are mixed at a liquid-solid ratio of 2 to 10:1, and stirred and exchanged at room temperature to 200° C. for 1 to 24 hours;

(2) Filtrate the slurry, beat the obtained filter cake with deionized water, control the pH value of the slurry at 3.0 to 7.0 with ammonia water, wash the slurry at room temperature to 100° C. for 10 minutes to 6 hours, and filter the resulting slurry;

(3) The filter cake obtained in step (2) is beaten with an activated ion combination liquid, the liquid-solid ratio is 2 to 10: 1, the exchange temperature is room temperature to 100° C., and the exchange time is 10 minutes to 5 hours. Filter the slurry and recover the catalyst .

The demetallization and reactivation method of the catalytic cracking catalyst provided by the invention has simple process flow, less investment and short payback period; it can largely remove polluted metals, increase catalyst activity and improve product selectivity.

Detailed ways

Through a large number of experimental studies, it is found that strong or moderately strong acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and hydrofluoric acid can easily react with polluted metals on spent catalysts to form soluble salts, but because the reaction solution is too acidic, the cracking catalyst The acidic active centers are also destroyed. The invention adopts the acidifying agent combination liquid containing latent acid to gradually convert latent acid into strong acid under certain conditions. This way, the strong acid can slowly react with the contaminating metal without destroying the acidic active centers of the molecular sieve.

In the method provided by the present invention, the acidulant combination liquid mainly includes latent acid, acid, solvent and surfactant or tackifier, and their concentrations in the acidulant combination liquid are 1 to 30 wt. %, 0-10% by weight of acid, 0.001-0.04% by weight of surfactant or 0.02-0.2% by weight of tackifier and the balance of solvent. The composition of the acidifying agent combination preferably contains 3-15% by weight of latent acid, 0-3% by weight of acid, 0.001-0.04% by weight of surfactant or 0.02-0.2% by weight of tackifier and the balance of solvent.

Potential acids are mainly selected from: esters, halogenated hydrocarbons, halogen salts, acid halides, acid anhydrides, etc., as detailed below:

The low-molecular-weight esters formed by the reaction of low-molecular-weight carboxylic acids and low-molecular-weight alcohols are important latent acids, such as methyl formate and methyl acetate, which are hydrolyzed under certain conditions to produce corresponding low-molecular-weight carboxylic acids. Methyl formate is hydrolyzed at 54-82°C to produce formic acid, and methyl acetate is hydrolyzed at 88-138°C to produce acetic acid.

Halogenated hydrocarbons are also important potential acids. Halogenated hydrocarbons are hydrolyzed at 120-370°C to produce acids. According to the type of halogen, hydrochloric acid, hydrofluoric acid or their mixed acids can be produced after hydrolysis of halogenated hydrocarbons. A preferred halogenated hydrocarbon is carbon tetrachloride.

Halogen salts can produce corresponding acids under certain initiators. Among them, ammonium chloride and ammonium fluoride are the best. Ammonium chloride can produce hydrochloric acid when aldehyde (such as formaldehyde) is used as an initiator.

Low-molecular acid halides can be hydrolyzed to produce corresponding low-molecular carboxylic acids and halogen acids (hydrochloric acid or hydrofluoric acid). For example, hydrolysis of acetyl chloride produces acetic acid and hydrochloric acid.

Acid anhydrides can also be hydrolyzed to produce the corresponding acids, such as acetic anhydride to produce acetic acid.

In the acidulant combination liquid, only latent acid, surfactant or tackifier and solvent may be contained, but it is preferable to contain both latent acid and appropriate amount of strong acid or medium strong acid. The strong acid or medium strong acid is selected from any one or a mixture of more than one of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid and hydrofluoric acid; preferably: hydrochloric acid, sulfuric acid or sulfurous acid.

In order to control the reaction speed, a certain amount of retarder can be added during the reaction. There are two types of retarders, one is a surfactant and the other is a tackifier. After the surfactant is adsorbed on the surface of the catalyst, it can reduce the reaction rate of the acid and the catalyst. There are two types of most suitable surfactants, one is cationic surfactants, such as fatty amine hydrochloride, quaternary ammonium salt; the other is amphoteric surfactants, such as sulfonated polyoxyethylene alkylphenol ether . In the acidulant combination liquid of the present invention, the concentration of the surfactant is 0.001-0.04% by weight.

Viscosifiers control the reaction rate by thickening the solution and reducing the diffusion rate of hydrogen ions. Such as XC polymer, polyacrylamide, polyvinylpyrrolidone, etc. In the acidulant combination liquid of the present invention, the concentration of the thickener is 0.02-0.2% by weight.

The solvent used in the acidulant combination liquid can be an inorganic solvent or an organic solvent, for example, water, alcohols, esters, toluene, xylene, kerosene, diesel oil, etc. and mixtures thereof. Water and/or alcohols are preferred. The solvent should be used in an amount such that the liquid-solid ratio of the reaction reaches 2-10:1.

In the method provided by the present invention, the activator combination liquid uses a compound containing rare earth ions and/or elements such as Sb, Al, P, etc. as an activator. Rare earth mainly includes rare earth chloride, rare earth nitrate and rare earth oxides, preferably rare earth chloride; antimony compounds mainly include antimony trioxide, antimony pentoxide or other antimony-containing compounds; aluminum mainly includes aluminum hydroxide, aluminum sulfate Phosphorus mainly includes phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, etc. The concentration of the activator in the activated ion combination liquid is 1-10% by weight. The solvent in the activated ion combination liquid of the present invention is selected from one or more mixtures of water, alcohols and esters.

When adopting the method provided by the invention, attention should be paid to: the consumption of acid and latent acid is too low, the amount of acid in the solution is insufficient, and the chance of contact with trace metal oxides on the catalyst is small, the reaction is not complete, and the demetallization effect is poor; When the amount of acid increases, the demetallization rate increases, but the effects of dealumination and rare earth removal also increase accordingly, so the amount of acid and latent acid should not be too high, otherwise the structure of the catalyst will be destroyed. The suitable acid concentration is 0-10% by weight, preferably 0-3% by weight; the concentration of latent acid is 1-30% by weight, preferably 3-15% by weight.

The reaction temperature of step (1) is too low, potential acid can not be fully hydrolyzed into corresponding acid, reaction speed and depth of reaction are all restricted, and demetallization effect is relatively poor; Reaction temperature increases, the reaction of acid and metal accelerates, and demetallization efficiency improves . Usually the reaction temperature is from room temperature to 200°C, preferably from 50 to 150°C, most preferably from 70 to 120°C.

In the step (2) of the present invention, if the pH value is higher than 7.5, the alkalinity will increase and the catalyst particles will be destroyed; if the pH value is lower than 2.0, the acidity will be too strong, which will affect the acid center of the molecular sieve. Therefore, the pH value of the slurry is more suitable from 3.0 to 7.0, preferably from 3.5 to 5.0. The washing temperature is from room temperature to 100°C, and the washing time is from 10 minutes to 6 hours.

In the step (3) of the present invention, when the ion exchange method is used, the liquid-solid ratio is 2:1-10:1, the temperature is room temperature-100°C, and the time is 10min-6h. When using the impregnation method, it is mainly rinse impregnation.

The following examples will further illustrate the method provided by the present invention, but the present invention is not thereby limited in any way.

Example 1

This example illustrates: the implementation effect of the FCC catalyst demetallization and reactivation method provided by the present invention.

The test was carried out with ZCM-7 balancer (ultra-stable Y-type molecular sieve catalyst, industrially produced by Qilu Petrochemical Company Catalyst Factory). The heavy metal content of this agent was Ni=0.47% by weight, V=0.02% by weight, Fe=0.39% by weight, and Na=0.31% by weight. Get 200 grams of balancing agent, pack in the three-port glass reaction kettle of 1500ml (one port inserts the thermometer to control the reaction temperature, one port inserts the stirrer, and the other port connects the reflux condenser), adds 1000 grams of acidulant combination liquid A (containing hydrochloric acid 1.0% by weight, 7.0% by weight of ammonium chloride, 3.0% by weight of glacial acetic acid, 0.03% by weight of sodium polyoxyethylene alkylphenol ether sulfonate, and the rest is water), and stirred under reflux at 90°C for 3 hours. Then cool to room temperature, vacuum filter with Buchner funnel; filter cake with 1000ml deionized water, control pH value to 5.0 with ammonia water, wash at 60°C for 30min, vacuum filter; secondary filter cake with RECl ₃ aqueous solution For exchange treatment, the concentration of RECl ₃ is 30 grams of RE ₂ O ₃ /L solution, the liquid-solid ratio is 3:1, the temperature is 60° C., and the time is 1 h. The exchanged slurry was suction-filtered, the filter cake was dried under an infrared lamp for 4 hours, and calcined in a muffle furnace at 600°C for 2 hours to obtain the ZCM-7 treatment agent.

The ZCM-7 balancer was also calcined in a muffle furnace at 600° C. for 2 hours to obtain the ZCM-7 balancer. The physical and chemical properties of the treatment agent and balance agent are analyzed, and the fixed fluidized bed catalytic cracking test is carried out. The feedstock oil used in the fixed fluidized bed test was wax oil mixed with residual oil, and its carbon residue was 2.8% by weight. The catalyst loading is 160g, the reaction temperature is 500°C, the catalyst-to-oil ratio is 5, and the space velocity is 8h ^-1 . Analysis and test results are shown in Table 1 and Table 2.

Example 2

This example illustrates: the implementation effect of the FCC catalyst demetallization and reactivation method provided by the present invention.

RAG-1 equilibrium catalyst was used for the test (composite molecular sieve catalyst, containing REHY, USY, ZSM-5 molecular sieve, industrially produced by Qilu Petrochemical Company Catalyst Factory). The heavy metal content of this agent is Ni=0.95 wt%, V=0.24 wt%, Fe=0.63 wt%, Na=0.28 wt%. Get 200 grams of balancing agent, put it into a 1500ml three-necked glass reactor, add 1000 grams of acidulant combination solution B (containing _{H2SO4 0.5} % by weight, carbon tetrachloride 7.0% by weight, polyacrylamide 0.1% by weight, the rest water), reflux and stir at 130°C for 3h. Then cool to about 60°C, vacuum filter the Buchner funnel; beat the filter cake with 1000ml deionized water, control the pH value to 5.0 with ammonia water, wash it at a temperature of 70°C for 1 hour, and vacuum filter; use an activator for the secondary filter cake _Combination solution B exchange treatment (activator combination _solution contains rare earth and metal, _RE2O3 content is 30 g _RE2O3 /l solution, _Sb2O5 content is 10 g/l solution, the rest is deionized _water ) , the liquid-solid ratio is 4:1, the temperature is 80°C, and the time is 45min. The exchanged slurry was suction-filtered, the filter cake was dried under an infrared lamp for 4 hours, and roasted in a muffle furnace at 600°C for 2 hours to obtain the RAG-1 treatment agent.

The RAG-1 balancer was also calcined in a muffle furnace at 600°C for 2 hours to obtain the RAG-1 balancer. The treatment agent and balance agent were analyzed for physical and chemical properties, and a fixed fluidized bed catalytic cracking test was carried out (the test conditions were the same as in Example 1). Analysis and test results are shown in Table 1 and Table 2.

As can be seen from Table 1, after ZCM-7 and RAG-1 balancing agent are treated with the method of the present invention, the contents of polluting metals Ni, V, Fe, Na etc. are greatly reduced, the specific surface and pore volume increase, and the micro-reaction activity is large increase in magnitude.

It can be seen from Table 2 that the cracking performance of the treated catalyst is significantly improved, the conversion rate is increased, the yield of liquefied gas and gasoline is increased, the dry gas yield is decreased, and the hydrogen/methane ratio is greatly reduced.

Comparative ratio

RAG-1 balancer treatment was performed according to the method described in USP6046125. Add 1600ml distilled water in the beaker, control temperature is 50 ℃, add 324ml sulfurous acid (concentration 6%) and 14 grams gibbsite under stirring. After 5 minutes, add 200 grams of RAG-1 balancing agent, stir continuously, and adjust the pH value of the solution to 4.7-5.3 with ammonia water during the reaction. After reacting for 45 minutes, use a Buchner funnel to vacuum filter; the filter cake is beaten twice with 1000 ml of deionized water, washed at a temperature of 70° C. for 1 hour, and vacuum filtered. The filter cake was dried under an infrared lamp for 4 hours, and roasted in a muffle furnace at 600°C for 2 hours to obtain the RAG-1 treatment agent. The analysis results of physical and chemical properties are shown in Table 1. It can be seen that the method provided by USP6046125 to treat the balancer has a low metal removal rate, the catalyst activity does not increase significantly, and the demetallization and reactivation effect is not ideal.

Table 1 serial number Benchmark 1 Example 1 Benchmark 2 Example 2 comparative example catalyst ZCM-7 Balancer ZCM-7 treatment agent RAG-1 Balancer RAG-1 treatment agent RAG-1 treatment agent Approach No treatment this invention No treatment this invention Comparative example 1 Metal content, weight % Ni 0.47 0.25 0.95 0.55 0.89 V 0.02 0.02 0.24 0.16 0.22 Fe 0.39 0.33 0.63 0.43 0.52 Na 0.31 0.11 0.28 0.15 0.21 Sb 0.11 0.11 0.00 0.21 0.00 microreactive MA 55 68 65 73 64 Specific surface, m ² /g 93 146 98 131 101 Pore volume, g/ml 0.119 0.235 0.131 0.156 0.137

Table 2 serial number Benchmark 1 Example 1 Benchmark 2 Example 2 catalyst ZCM-7 Balancer ZCM-7 treatment agent RAG-1 Balancer RAG-1 treatment agent Conversion rate, weight % 70.31 73.96 74.84 78.98 Material balance, weight % H ₂ -C ₂ 2.08 2.11 2.35 2.42 liquefied gas 13.87 14.15 19.25 24.37 C ₅ ⁺ petrol 47.07 51.52 44.98 45.61 diesel fuel 17.24 16.68 16.65 15.78 heavy oil 12.45 9.36 8.51 5.24 Coke 7.29 6.18 8.26 6.58 Product selectivity: dry gas/conversion 0.030 0.029 0.031 0.031 Liquefied gas/conversion rate 0.197 0.191 0.257 0.309 gasoline/conversion 0.669 0.697 0.601 0.577 coke/conversion 0.104 0.084 0.110 0.083 Hydrogen yield, weight % 0.33 0.17 0.52 0.22 Hydrogen/methane, v/v 3.57 1.82 4.52 2.05

Claims (20)

1. A catalytic cracking catalyst demetallization reactivation method is characterized in that the method comprises the following steps: (1) The acidulant combination liquid and the catalytic cracking catalyst are mixed at a liquid-solid ratio of 2 to 10:1, and stirred and exchanged at room temperature to 200° C. for 1 to 24 hours; (2) Filtrate the slurry, beat the obtained filter cake with deionized water, control the pH value of the slurry at 3.0 to 7.0 with ammonia water, wash the slurry at room temperature to 100° C. for 10 minutes to 6 hours, and filter the resulting slurry; (3) The filter cake obtained in step (2) is beaten with an activated ion combination liquid, the liquid-solid ratio is 2 to 10: 1, the exchange temperature is room temperature to 100° C., and the exchange time is 10 minutes to 5 hours. Filter the slurry and recover the catalyst . 2, according to the method for claim 1, it is characterized in that step (1) said acidulant combination liquid comprises latent acid, acid, solvent and surfactant or tackifier, and their concentration in acidulant combination liquid is respectively 1-30% by weight of latent acid, 0-10% by weight of acid, 0.001-0.04% by weight of surfactant or 0.02-0.2% by weight of tackifier and the balance of solvent. 3. The method according to claim 2, characterized in that the acidifying agent combination liquid contains 3-15 wt% of latent acid, 0-3 wt% of acid, 0.001-0.04 wt% of surfactant or 0.02-0.2 wt% of tackifier % and the balance of solvent. 4. The method according to claim 2, characterized in that said latent acid is selected from the group consisting of: esters, halogenated hydrocarbons, halogen salts, acid halides, acid anhydrides. 5. A method according to claim 2, 3 or 4, characterized in that said latent acid is selected from the group consisting of: methyl formate, methyl acetate, carbon tetrachloride, ammonium chloride, ammonium fluoride, acetyl chloride, acetyl chloride, One or more mixtures of acid anhydrides. 6. The method according to claim 2, characterized in that said acid is selected from any one of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid and hydrofluoric acid or a mixture of more than one. 7. The method according to any one of claims 2, 3 or 6, characterized in that said acid is selected from one or a mixture of more than one of hydrochloric acid, sulfuric acid or sulfurous acid. 8. A method according to claim 2, characterized in that said surfactant is selected from the group consisting of cationic surfactants or amphoteric surfactants. 9. The method according to one of claims 2, 3 or 8, characterized in that said surfactant is selected from the group consisting of fatty amine hydrochloride, quaternary ammonium salt, sulfonated polyoxyethylene alkylphenol ether any kind. 10. The method according to claim 2 or 3, characterized in that said tackifier is selected from any one of XC polymer, polyacrylamide and polyvinylpyrrolidone. 11. The method according to claim 2, characterized in that said solvent is selected from any one or a mixture of more than one of water, alcohols, esters, toluene, xylene, kerosene and diesel. 12. Process according to claim 3 or 11, characterized in that said solvent is water and/or alcohols. 13. The method according to claim 1, characterized in that said activated ion combination liquid uses rare earth ions and/or compounds containing Sb, Al and P elements as activators. 14. The method according to claim 13, characterized in that said activator is selected from the group consisting of: rare earth chloride, rare earth nitrate, rare earth oxide, antimony trioxide, antimony pentoxide, aluminum hydroxide, aluminum sulfate, phosphoric acid, phosphoric acid One or more mixtures of ammonium and ammonium hydrogen phosphate, and in the activated ion combination liquid, the concentration of the activator is 1-10% by weight. 15. The method according to claim 1, characterized in that in the step (1), the acidifying agent combination liquid and the catalyst are stirred and exchanged at 50-150°C. 16. The method according to claim 15, characterized in that in the step (1), the acidifying agent combination liquid and the catalyst are stirred and exchanged at 70-120°C. 17. The method according to claim 1, characterized in that the pH value of the slurry in the step (2) is controlled at 3.5-5.0. 18. The method according to claim 1, characterized in that in the process of filtering the slurry in step (2), the filter cake is rinsed with deionized water. 19. The method according to claim 1, characterized in that the process in step (2) can be repeated as needed. 20. The method according to claim 1, characterized in that the step (3) adopts the following operation: directly spray the activated ion combination liquid on the wet filter cake or the dried demetallization catalyst, and then recover the treated catalyst.