CN1552804A - Catalytic cracking catalyst demetallated reactivating process - Google Patents
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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
Technical Field
The invention belongs to a general regeneration or reactivation method of a catalyst, and particularly relates to a demetallization reactivation method for a catalytic cracking catalyst.
Background
In the catalytic cracking process, metals such as Ni, V, Fe, Cu, etc. in the feedstock oil are gradually deposited on the catalyst, and as the amount of metals on the catalyst increases, the catalyst activity decreases and the selectivity becomes poor. In the product distribution, the yield of hydrogen, dry gas and coke is increased, and the yield of target products such as liquefied gas and gasoline is reduced. In the industrial catalytic cracking production, two methods are mainly used for solving the problem of metal pollution, namely, a part of balancing agent is discharged and fresh agent is supplemented to reduce the metal pollution level; the second is the use of metal resistant catalysts and/or metal deactivators. As crude oil becomes heavier, catalytic cracking rapidly progresses to heavy oil catalytic cracking, and the metal content in the raw material is greatly increased, so that the pollution metal content of the equilibrium catalyst is greatly increased, and the problem cannot be completely solved even if a novel catalyst or a passivating agent is used.
In actual industrial production, in order to maintain the activity and selectivity of the balancing agent in a catalytic cracking unit, partial balancing agent needs to be frequently discharged and fresh agent needs to be supplemented. This not only increases the operating cost of the apparatus, but also the discharged waste agent is likely to cause environmental pollution. At present, the discharged waste agent (including the waste catalyst recovered from the cyclone) is up to 1.5 ten thousand tons every year in China. These spent catalysts generally contain trace amounts of radioactive elements and cannot be disposed of at will. The following methods are mainly adopted at home and abroad to treat the waste catalyst:
In the method, the underground construction of the pool is not a long-term measure; the dosage and the application of the adsorbent are limited; the magnetic separation can recycle the high-activity catalyst particles in the balancing agent, but the problem of the outlet of industrial waste agent is not fundamentally solved. Therefore, only demetallization recycling is a development in the above method. It can save fresh catalyst, reduce environmental pollution, reduce metal content in balancing agent and raise the activity and selectivity of catalyst.
As early as the sixties, a chemical demetallization process of a spent catalyst represented by the MET-X and DEMET processes has appeared, which is suitable for an amorphous silicon-aluminum catalyst having a low content of a contaminating metal. The catalyst is sulfided, oxidized under conditions to convert the metal to a dispersible form, and then reductively-oxidatively washed to remove the metal. USP31501045 and USP3173882 employ high temperature chlorination demetallization, USP3150103 and USP3147228 employ high temperature sulfidation and/or oxidative demetallization, and USP3178364 employs high temperature oxidation, sulfidation and chlorination demetallization, which differ in the demetallization step and the reaction conditions.
In the 70 s to 80 s, 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, sodium and the like on the molecular sieve catalysts is gradually increased, and the activity and selectivity of the catalysts are seriously affected. Patents on demetallization regeneration of deactivated molecular sieve catalysts can be divided mainly into two types. One is the improvement of DEMET process, such as USP4101444, USP4234452, USP4686197, USP4824814 and the like; another class is various solution treatment demetallization such as USP4787968, USP4280897, USP4814066, USP4929336, USP4954244, USP5021377, etc. In the DEME process modified by ARCO of America (jin.S.Y, et, J.I.E.C.Prod.rex.Dev.1986, 25, 549-553), the main steps include: hydrogen sulfide sulfides spent catalyst, air oxidation, and reductive, oxidative scrubbing. The Chemcat company modifies the DEMET process and comprises three steps, namely, firstly, introducing hydrogen sulfide gas and then introducing chlorine gas to change metal into soluble sulfide and chloride; secondly, oxidation-reduction washing; thirdly, ammonium sulfate ion exchange. These demetallization processes all have oxidation, sulfurization and/or chlorination steps, so that there are many equipments and large investment, and toxic 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 ammonium ion and rare earth ion content of the catalyst. USP4280897 uses ammonium citrate to form chelate with the contaminated metal on the catalyst, and the chelate is eluted to remove the contaminated metal. USP4814066, USP4929336, USP4954244 and USP5021377 disclose methods for exchanging, chelating and complexing citric acid, carboxylic acid and/or ammonium salt to treat the catalyst.
USP5900383 describes metal contaminated molecular sieve catalysts, slurried with a liquid comprising an acid, a detergent or a surfactant, mixing at a temperature and for a time sufficient to remove the contaminating metal from the molecular sieve channels, filtering, and washing with water. The acid used in the patent is malic acid, acetic acid, citric acid, formic acid, hydrochloric acid, nitric acid or sulfuric acid, etc., and the combined solution may also contain ammonium difluoride, an enzymatic compound, etc. The cleaning agent or surfactant functions to suspend the contaminants removed from the channels of the molecular sieve in the surface layer of the liquid, to withdraw a portion of the liquid from the slurry, to remove the contaminants by filtration, and to return the slurry.
USP6046125 describes a process for increasing the activity of a catalyst, which can be applied both to a balancing agent and to a rejuvenating agent. The catalyst is contacted with a solution containing water, a chloride ion-free inorganic 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 to be 3-12 by ammonia water in the reaction process. Suitable acids are sulfurous and sulfuric acids and suitable aluminium sources are gibbsite and alumina. The method is simple to operate, the heavy metal content of the catalyst can be reduced, and the acid activity center number of the catalyst is increased, but the demetallization regeneration effect of the method is not ideal through tests (see comparative example 1).
Disclosure of Invention
The invention aims to provide a catalytic cracking catalyst demetalization reactivation method based on the prior art, so as to improve the activity of the catalyst and improve the product selectivity.
The catalytic cracking catalyst demetalization reactivation method provided by the invention comprises the following steps:
(1) mixing the acidulant combination liquid with a catalytic cracking catalyst according to a liquid-solid ratio of 2-10: 1, and stirring and exchanging for 1-24 hours at room temperature-200 ℃;
(2) filtering the slurry, pulping the obtained filter cake by using deionized water, controlling the pH value of the slurry to be 3.0-7.0 by using ammonia water, carrying out slurry washing for 10 minutes-6 hours at the room temperature-100 ℃, and filtering the obtained slurry;
(3) pulping the filter cake obtained in the step (2) by using an activated ion combined liquid, wherein the liquid-solid ratio is 2-10: 1, the exchange temperature is room temperature-100 ℃, the exchange time is 10 minutes-5 hours, and filtering the slurry and recovering the catalyst.
The catalytic cracking catalyst demetalization reactivation method provided by the invention has simple process flow; the investment is low, and the recovery period is short; can greatly remove the polluted metal, improve the activity of the catalyst and improve the selectivity of the product.
Detailed Description
Through a large number of experimental studies, it is found that: strong or medium acids such as hydrochloric acid, sulfuric acid, phosphoric acid and hydrofluoric acid are easy to react with the polluted metal on the waste catalyst to generate soluble salts, but the acidic active center of the cracking catalyst is damaged due to the strong acidity of the reaction solution. The invention adopts acidifier combined liquid containing potential acid to gradually convert the potential acid into strong acid under certain conditions. Thus, the strong acid can slowly react with the contaminant metal without destroying the acidic active sites of the molecular sieve.
In the method provided by the invention, the acidulant combination liquid mainly comprises latent acid, solvent and surfactant or tackifier, and the concentrations of the latent acid, the surfactant and the surfactant or the tackifier in the acidulant combination liquid are respectively 1-30 wt%, 0-10 wt%, 0.001-0.04 wt% or 0.02-0.2 wt% of the surfactant and the balance of the solvent. The acidifying agent composition liquid preferably contains 3 to 15 wt% of latent acid, 0 to 3 wt% of acid, 0.001 to 0.04 wt% of surfactant, 0.02 to 0.2 wt% of tackifier, and the balance of solvent.
The latent acid is selected from the group consisting essentially of: esters, halogenated hydrocarbons, halogen salts, acid halides, acid anhydrides, and the like, as specifically described below:
low molecular esters generated by the reaction of low molecular carboxylic acid and low molecular alcohol are important potential acids, such as methyl formate and methyl acetate,and the low molecular esters are hydrolyzed under certain conditions to generate corresponding low molecular carboxylic acid. Methyl formate is hydrolyzed at 54-82 ℃ to generate formic acid, and methyl acetate is hydrolyzed at 88-138 ℃ to generate acetic acid.
The halogenated hydrocarbon is also an important potential acid, the halogenated hydrocarbon is hydrolyzed at 120-370 ℃ to generate acid, and according to the type of halogen, the halogenated hydrocarbon can generate hydrochloric acid, hydrofluoric acid or a mixed acid of the hydrochloric acid and the hydrofluoric acid after being hydrolyzed. The preferred halogenated hydrocarbon is carbon tetrachloride.
The halogen salt can generate corresponding acid under certain initiator. Among them, ammonium chloride and ammonium fluoride are preferred. Ammonium chloride can generate hydrochloric acid with aldehydes (such as formaldehyde) as initiators.
The low-molecular acyl halide can produce corresponding low-molecular carboxylic acid and halogen acid (hydrochloric acid or hydrofluoric acid) by hydrolysis. Such as hydrolysis of acetyl chloride to produce acetic acid and hydrochloric acid.
Anhydrides can also be hydrolyzed to produce the corresponding acids, such as acetic anhydride to produce acetic acid.
The acidulant composition may contain only the latent acid, the surfactant or the tackifier, and the solvent, but it is preferable to contain both the latent acid and a suitable amount of the strong or medium-strong acid. The strong or medium acid is selected from: any one or more 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 in the reaction process. Retarders are of two types, surfactants and tackifiers. After the surface active agent is adsorbed on the surface of the catalyst, the reaction speed of the acid and the catalyst can be reduced. The most suitable surfactants are of two classes, one class being cationic surfactants such as fatty amine hydrochlorides, quaternary ammonium salts; one class is amphoteric surfactants such as sulfonated polyoxyethylene alkylphenol ethers. In the acidulant composition liquid of the present invention, the concentration of the surfactant is 0.001 to 0.04% by weight.
The tackifier is used for controlling the reaction speed by thickening the solution and reducing the diffusion speed of hydrogen ions. Such as XC polymer, polyacrylamide, polyvinylpyrrolidone, etc. In the acidulant combination liquid, the concentration of the tackifier is 0.02-0.2 wt%.
The solvent used in the acidulant composition may be an inorganic solvent, or an organic solvent, such as water, alcohols, esters, toluene, xylene, kerosene, diesel oil, and the like, and a mixture thereof. Water and/or alcohols are preferred. The dosage of the solvent is based on the condition that the liquid-solid ratio of the reaction reaches 2-10: 1.
In the method provided by the invention, the activator composition liquid takes a compound containing rare earth ions and/or elements such as Sb, Al, P and the like as an activator. The rare earth mainly comprises rare earth chloride, rare earth nitrate and rare earth oxide, preferably rare earth chloride; the antimony compound mainly comprises antimony trioxide, antimony pentoxide or other antimony-containing compounds; the aluminum mainly comprises aluminum hydroxide, aluminum sulfate and the like; the phosphorus mainly comprises phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate and the like. The concentration of the activating agent in the activated ion combined liquid is 1-10 wt%. The solvent in the activated ion combined liquid is selected from the following solvents: one or more of water, alcohols and esters.
When the method provided by the invention is adopted, attention should be paid to the following steps: the dosage of acid and potential acid is too low, the acid content of the solution is insufficient, the contact chance with trace metal oxide on the catalyst is less, the reaction is incomplete, and the demetallization effect is poor; the use amount of acid and potential acid is increased, the demetallization rate is increased, but the dealumination and rare earth removal effects are increased at the same time, so that the use amount of acid and potential acid cannot be too high, otherwise the structure of the catalyst is damaged. Suitable acid concentrations are 0 to 10 wt.%, preferably 0 to 3 wt.%; the concentration of the latent acid is 1 to 30 wt%, preferably 3 to 15 wt%.
The reaction temperature in the step (1) is too low, the potential acid cannot be fully hydrolyzed into the corresponding acid, the reaction speed and the reaction depth are limited, and the demetallization effect is poor; the reaction temperature is increased, the reaction of acid and metal is accelerated, and the demetallization efficiency is improved. The reaction temperature is usually between room temperature and 200 ℃, preferably between 50 and 150 ℃, and most preferably between 70 and 120 ℃.
In the step (2) of the present invention, if the pH is higher than 7.5, the alkalinity is increased, and the catalyst particles are destroyed; at pH values below 2.0, the acidity is too strong, which has an effect on the acidic sites of the molecular sieve. Therefore, the pH of the slurry is preferably 3.0 to 7.0, and more preferably 3.5 to 5.0. The pulp washing temperature is between room temperature and 100 ℃, and the time is between 10min and 6 h.
In the step (3), when an ion exchange method is adopted, the liquid-solid ratio is 2: 1-10: 1, the temperature is room temperature-100 ℃, and the time is 10 min-6 h. When the dipping method is adopted, rinsing dipping is mainly adopted.
The following examples will further illustrate the process provided by the present invention, but the invention is not limited thereto.
Example 1
This example illustrates: the invention provides the implementation effect of the method for demetallizing and reactivating the FCC catalyst.
The test was carried out using ZCM-7 equilibria (ultrastable Y-type molecular sieve catalyst, industrially produced by catalyst works of the Qilu petrochemical company). The heavy metal content of the agent is 0.47 wt% for Ni, 0.02 wt% for V, 0.39 wt% for Fe, and 0.31 wt% for Na. 200 g of the balancing agent is put into a 1500ml three-port glass reaction kettle (a bite thermometer controls the reaction temperature, a bite stirrer, a bite reflux condenser), 1000 g of the acidifying agent combination liquid A (containing 1.0 wt% of hydrochloric acid, 7.0 wt% of ammonium chloride, 3.0 wt% of glacial acetic acid, 0.03 wt% of sodium polyoxyethylene alkylphenol ether sulfonate and the balance of water) is added, and reflux stirring is carried out for 3h at the temperature of 90 ℃. Then cooling to room temperature, and carrying out vacuum filtration byusing a Buchner funnel; pulping the filter cake with 1000ml deionized water, controlling pH to 5.0 with ammonia water, washing at 60 deg.C for 30min, and vacuum filtering; RECl for secondary filter cake3Aqueous solution exchange treatment of (1), RECl3At a concentration of 30 g RE2O3The solution/L has a liquid-solid ratio of 3: 1, a temperature of 60 ℃ and a time of 1 h. And (3) carrying out suction filtration on the exchanged slurry, drying a filter cake for 4h under an infrared lamp, and roasting in a muffle furnace for 2h at 600 ℃ to obtain the ZCM-7 treating agent.
The ZCM-7 balancing agent is also roasted in a muffle furnace at 600 ℃ for 2h to obtain the ZCM-7 balancing agent. And (3) carrying out physical and chemical performance analysis on the treating agent and the balancing agent, and carrying out a fixed fluid catalytic cracking test. The raw oil for the fixed fluidized bed test is pipe wax oil mixed with residual oil, and the carbon residue is 2.8 wt%. The catalyst loading is 160 g, the reaction temperature is 500 ℃, the catalyst-oil ratio is 5, and the space velocity is 8h-1. The analysis and test results are shown in tables 1 and 2.
Example 2
This example illustrates: the invention provides the implementation effect of the method for demetallizing and reactivating the FCC catalyst.
A RAG-1 equilibrium catalyst was used for the experiment (composite molecular sieve catalyst, containing REHY, USY, ZSM-5 molecular sieves, produced by catalyst factories of Qilu petrochemical company). The heavy metal content of the agent is 0.95 wt% Ni, 0.24 wt% V, 0.63 wt% Fe and 0.28 wt% Na. 200 g of balancing agent is taken and put into a 1500ml three-port glass reaction kettle, 1000 g of balancing agent is addedAcidulant combination liquid B (containing H)2SO40.5 percent of carbon tetrachloride, 7.0percent of carbon tetrachloride, 0.1 percent of polyacrylamide and the balance of water) and stirring for 3 hours at the temperature of 130 ℃. However, the device is not suitable for use in a kitchenCooling to 60 deg.c, vacuum filtering in Buchner funnel; pulping the filter cake with 1000ml deionized water, controlling the pH value to 5.0 with ammonia water, washing for 1h at 70 ℃, and performing vacuum filtration; exchanging the secondary filter cake with an activating agent combined liquid B (the activating agent combined liquid contains rare earth and metal, RE)2O3The content of RE is 30 g2O3Solution/l of Sb2O5The content is 10 g/l solution, the rest is deionized water), the liquid-solid ratio is 4: 1, the temperature is 80 ℃, and the time is 45 min. And (3) carrying out suction filtration on the exchanged slurry, drying a filter cake for 4h under an infrared lamp, and roasting in a muffle furnace at 600 ℃ for 2h to obtain the RAG-1 treating agent.
The RAG-1 equilibrium reagent is also roasted in a muffle furnace at 600 ℃ for 2h to obtain the RAG-1 equilibrium reagent. Physicochemical properties of the treating agent and the balancing agent were analyzed, and a fixed fluid catalytic cracking test was conducted (test conditions were the same as in example 1). The analysis and test results are shown in tables 1 and 2.
As can be seen from Table 1, after ZCM-7 and RAG-1 equilibrium agents are treated by the method of the invention, the contents of Ni, V, Fe, Na and the like which are pollution metals are greatly reduced, the specific surface and pore volume are increased, and the micro-inverse activity is greatly improved.
As can be seen from Table 2, the cracking performance of the treated catalyst is significantly improved, the conversion rate is increased, the yields of liquefied gas and gasoline are increased, the yield of dry gas is decreased, and the hydrogen/methane ratio is greatly reduced.
Comparative example
RAG-1 equilibrium treatment was performed according to the method described in USP 6046125. 1600ml of distilled water are placed in a beaker, the temperature is controlled at 50 ℃ and 324ml of sulfurous acid (6% strength) and 14 g of gibbsite are added with stirring. After 5 minutes, 200 g of RAG-1 balancing agent is added, stirring is carried out continuously, and the pH value of the solution is adjusted to 4.7-5.3 by ammonia water in the reaction process. After reacting for 45min, performing vacuum filtration by using a Buchner funnel; the filter cake is pulped with 1000ml of deionized water twice, washed for 1h at 70 ℃ and filtered in vacuum. Drying the filter cake under an infrared lamp for 4 hours, and roasting the filter cake in a muffle furnace at 600 ℃ for 2 hours to obtain the RAG-1 treating agent. The physicochemical property analysis results are shown in table 1, and it can be seen that when the equilibrium agent is treated by the method provided by USP6046125, the metal removal rate is low, the catalyst activity is not obviously increased, and the demetalization reactivation effect is not ideal.
TABLE 1
| Numbering | Reference 1 | Example 1 | Reference 2 | Example 2 | Comparative example |
| Catalyst and process for preparing same | ZCM-7 Balancing agent | ZCM-7 Treating agent | RAG-1 Balancing agent | RAG-1 Treating agent | RAG-1 Treating agent |
| Processing method | Without treatment | The invention | Without treatment | The invention | Comparative example 1 |
| Metal content, wt% | |||||
| 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 |
| Micro-reverse activity MA | 55 | 68 | 65 | 73 | 64 |
| Specific surface area, m2/g | 93 | 146 | 98 | 131 | 101 |
| Pore volume, g/ml | 0.119 | 0.235 | 0.131 | 0.156 | 0.137 |
TABLE 2
| Numbering | Reference 1 | Example 1 | Reference 2 | Example 2 |
| Catalyst and process for preparing same | ZCM-7 balancing agents | ZCM-7 treating agent | RAG-1 equilibria | RAG-1 treatment agents |
| Conversion, weight% | 70.31 | 73.96 | 74.84 | 78.98 |
| The materials are balanced and heavy | ||||
| H2-C2 | 2.08 | 2.11 | 2.35 | 2.42 |
| Liquefied gas | 13.87 | 14.15 | 19.25 | 24.37 |
| C5 +Gasoline (gasoline) | 47.07 | 51.52 | 44.98 | 45.61 |
| Diesel oil | 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 ratio | 0.197 | 0.191 | 0.257 | 0.309 |
| Gasoline/conversion ratio | 0.669 | 0.697 | 0.601 | 0.577 |
| Coke/conversion ratio | 0.104 | 0.084 | 0.110 | 0.083 |
| Hydrogen yield, wt.% | 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 by comprising the following steps:
(1) mixing the acidulant combination liquid with a catalytic cracking catalyst according to a liquid-solid ratio of 2-10: 1, and stirring and exchanging for 1-24 hours at room temperature-200 ℃;
(2) filtering the slurry, pulping the obtained filter cake by using deionized water, controlling the pH value of the slurry to be 3.0-7.0 by using ammonia water, carrying out slurry washing for 10 minutes-6 hours at the room temperature-100 ℃, and filtering the obtained slurry;
(3) pulping the filter cake obtained in the step (2) by using an activated ion combined liquid, wherein the liquid-solid ratio is 2-10: 1, the exchange temperature is room temperature-100 ℃, the exchange time is 10 minutes-5 hours, and filtering the slurry and recovering the catalyst.
2. The method according to claim 1, wherein the acidulant combination liquid in step (1) comprises a latent acid, an acid, a solvent, and a surfactant or a tackifier, and the concentrations thereof in the acidulant combination liquid are 1 to 30 wt% of the latent acid, 0 to 10 wt% of the acid, 0.001 to 0.04 wt% of the surfactant, or 0.02 to 0.2 wt% of the tackifier, respectively, and the balance of the solvent.
3. The method according to claim 2, characterized in that the acidulant combination liquid contains 3 to 15 wt.% latent acid, 0 to 3 wt.% acid, 0.001 to 0.04 wt.% surfactant, or 0.02 to 0.2 wt.% tackifier, and the balance solvent.
4. The method according to claim 2, characterized in that the latent acid is selected from the group consisting of: esters, halogenated hydrocarbons, halogen salts, acid halides, and acid anhydrides.
5. A process according to any one of claims 2, 3 or 4, characterised in that the latent acid is selected from the group consisting of: one or more of methyl formate, methyl acetate, carbon tetrachloride, ammonium chloride, ammonium fluoride, acetyl chloride and acetic anhydride.
6. A process according to claim 2, characterized in that the acid is selected from: any one or more of hydrochloric acid, sulfuric acid, sulfurous acid, phosphoric acid and hydrofluoric acid.
7. A process according to any one of claims 2, 3 or 6, characterised in that the acid is selected from: one or more of hydrochloric acid, sulfuric acid and sulfurous acid.
8. A process according to claim 2, characterized in that the surfactant is selected from: cationic surfactants or amphoteric surfactants.
9. A process according to any one of claims 2, 3 or 8, characterised in that the surfactant is selected from: any one of fatty amine hydrochloride, quaternary ammonium salt and sulfonated polyoxyethylene alkylphenol ether.
10. A process according to claim 2 or 3, characterized in that the adhesion promoter is selected from: XC polymer, polyacrylamide and polyvinylpyrrolidone.
11. A process according to claim 2, characterized in that the solvent is selected from: any one or more than one mixture of water, alcohols, esters, toluene, xylene, kerosene and diesel oil.
12. A process according to claim 3 or 11, characterized in that the solvent is water and/or an alcohol.
13. A method according to claim 1, characterized in that the activating ionic composition comprises as activating agent rare earth ions and/or compounds containing Sb, Al, P elements.
14. The process according to claim 13, characterized in that the activator is selected from the group consisting of: the activating agent comprises one or more of rare earth chloride, rare earth nitrate, rare earth oxide, antimony trioxide, antimony pentoxide, aluminum hydroxide, aluminum sulfate, phosphoric acid, ammonium phosphate and ammonium hydrogen phosphate, and the concentration of the activating agent in the activating ion combined liquid is 1-10 wt%.
15. The method according to claim 1, characterized in that the acidulant combination liquid in step (1) is exchanged with the catalyst under stirring at 50-150 ℃.
16. The method according to claim 15, characterized in that the acidulant combination liquid in step (1) is exchanged with the catalyst under stirring at 70-120 ℃.
17. The method according to claim 1, wherein the pH of the slurry in the step (2) is controlled to 3.5 to 5.0.
18. The method of claim 1, wherein during the filtering of the slurry in step (2), the filter cake is rinsed with deionized water.
19. The method of claim 1, wherein said process of step (2) is repeated as necessary.
20. A method according to claim 1, characterized in that step (3) uses the following operations: directly spraying the activated ion combined liquid to the wet filter cake or the dried demetallization catalyst, and then recovering the treated catalyst.
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| CN101168137A (en) * | 2007-12-10 | 2008-04-30 | 北京立诚石化技术有限公司 | System and method for regenerating reactivating and recovering FCC balance catalyst |
| CN101612590B (en) * | 2009-07-16 | 2011-02-02 | 浙江新和成股份有限公司 | Method for recovering pyridines debromination catalyst |
| CN102764675A (en) * | 2011-05-05 | 2012-11-07 | 中国科学院城市环境研究所 | Formula for coal-fired flue gas denitrification catalyst activity regeneration |
| CN104815702B (en) * | 2015-04-10 | 2018-08-31 | 于向真 | The rejuvenation method of catalytic cracking spent catalyst |
| CN104815702A (en) * | 2015-04-10 | 2015-08-05 | 于向真 | Revivification method for catalytic cracking waste catalyst |
| CN104815704B (en) * | 2015-04-15 | 2017-02-01 | 中国石油大学(华东) | Revivification method of catalytic cracking waste catalyst by exchange with rear earth chloride |
| CN104815704A (en) * | 2015-04-15 | 2015-08-05 | 中国石油大学(华东) | Revivification method of catalytic cracking waste catalyst by exchange with rear earth chloride |
| CN104815703A (en) * | 2015-04-15 | 2015-08-05 | 中国石油大学(华东) | Method for resuscitating spent catalytic cracking catalyst through gas-solid reaction with SiCl4 |
| CN110732349A (en) * | 2018-07-19 | 2020-01-31 | 中国石油化工股份有限公司 | Demetallization reactivation method for waste catalytic cracking catalyst |
| CN110732350A (en) * | 2018-07-19 | 2020-01-31 | 中国石油化工股份有限公司 | Demetallization reactivation method for waste catalytic cracking catalyst |
| CN110732349B (en) * | 2018-07-19 | 2022-11-01 | 中国石油化工股份有限公司 | Demetalization reactivation method for waste catalytic cracking catalyst |
| CN110732350B (en) * | 2018-07-19 | 2022-11-01 | 中国石油化工股份有限公司 | Demetallization reactivation method for waste catalytic cracking catalyst |
| CN111905841A (en) * | 2020-09-16 | 2020-11-10 | 延安大学 | Regeneration method of FCC spent catalyst |
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