CN114425439A - A kind of waste catalytic cracking catalyst resurrection method - Google Patents

Abstract

The invention relates to a method for reactivating a waste catalytic cracking catalyst, which comprises the following steps: (1) treating the catalytic cracking waste catalyst in a reducing atmosphere; (2) properly contacting and carrying out oxygen treatment on the treated waste catalyst in an ammonia-ammonium solution; (3) and (6) heat treatment. The catalytic cracking catalyst reviving method provided by the invention has the advantages of less structural damage, high activity, high stability and capability of reducing hydrogen factors after reviving.

Description

A kind of waste catalytic cracking catalyst resurrection method

technical field

The present invention relates to a method for reviving the spent catalyst of catalytic cracking.

Background technique

Catalytic cracking (FCC) catalyst is the most widely used catalyst in oil refining process. At present, the amount of catalytic cracking catalyst used in my country is nearly 200,000 tons, about half of which is carried away with flue gas or catalytic oil slurry and cannot be recovered. About 100,000 tons of spent catalytic cracking catalyst are produced. Catalytic cracking catalyst waste treatment methods include reactivation, demetallization and building materials, among which the most valuable is reactivation as a catalyst for reuse.

One cause of deactivation of spent catalytic cracking catalysts is deactivation due to contamination of metals such as vanadium, iron and nickel. For spent catalysts with high contamination nickel content, the reactivation of catalysts requires de-nickel treatment. However, the study found that the nickel structure in the catalytic cracking waste catalyst is relatively stable and difficult to remove.

The methods for removing nickel from spent catalysts mainly include pyrotechnics and wet methods, among which pyrotechnics include sulfidation method and chlorination method, which have high energy consumption, easily generate polluting gas, and the removal rate of nickel is not high. Wet processes are usually acid processes, but studies have shown that nickel removal from catalytic cracking catalysts is very limited even at high acid concentrations.

The above nickel removal methods are usually mainly to obtain metals such as nickel, the structure of the catalyst is often destroyed, and the activity is difficult to recover.

Demetallization and resurrection method of waste catalytic cracking catalyst The method commonly used in foreign industries is the Demet method. Although the demetallization efficiency can reach 70%-80%, it requires a closed space to replace the use of three dangerous gases, harsh treatment conditions, and complex treatment processes. , which restricts the promotion of this technology, and the stability of the resurrection catalyst is poor.

CN100525917C Li Chunyi and others used reducing atmosphere to reduce nickel in catalytic cracking catalyst to nickel at high temperature, and then carried out acid leaching to remove metals such as nickel, vanadium and iron, and found that the removal rate of nickel could reach 70%-80%. However, when the metal removal reaches a high level, the acid strength is high, which has a great influence on the activity stability. Although the single-shot activity due to the activation of the surface acidity is high, the activity decreases rapidly after several cycles of use.

Invention content:

The technical problem to be solved by the present invention is to provide a method for reviving the spent catalytic cracking catalyst.

The inventors of the present invention have found that the nickel content of domestic crude oil is relatively high, and the spent catalytic cracking catalyst for processing domestic raw oil is generally high in nickel content. The damage is not large, and there is room for resurrection, but simply de-nicking cannot achieve a satisfactory resurrection effect.

The present invention provides a kind of revival method of spent catalytic cracking catalyst, comprising:

(1) Treat the spent catalytic cracking catalyst (hereinafter also referred to as spent catalyst) at 600-880° C. in a reducing atmosphere;

(2) first contact is carried out with the treated waste catalytic cracking catalyst in ammonia-ammonium solution at pH 9.5-11 and in the presence of oxygen-containing oxidant, and the spent catalytic cracking catalyst (referred to as the first contact for short) after the first contact is obtained by separation The spent catalyst after the catalyst), optionally washed; the ammonia-ammonium solution is a solution containing NH ₃ and NH ₄ ⁺ , and the total concentration of ammonium and ammonia in the ammonia-ammonium solution is 4-10 mol/L, and the first contact It can be carried out under normal pressure;

(3) subjecting the product of step (2) to heat treatment, such as drying and/or calcination.

The method for reviving the spent catalytic cracking catalyst provided by the invention has high crystallinity retention, improved micro-activity index, higher activity stability, and can significantly reduce hydrogen yield and/or coke yield. In the method for reviving the spent catalytic cracking catalyst provided by the invention, ammonia and ammonium salts can be recovered and recycled, which is green and environmentally friendly. In a preferred case, when the removal rate of metallic nickel of the spent catalytic cracking catalyst is more than 80%, the molecular sieve structure is not damaged, and the micro-activity index is improved.

Detailed ways:

An embodiment of the method for reviving a spent catalytic cracking catalyst provided by the present invention, the mass fraction of silica of the spent catalytic cracking catalyst is 30-75 mass %, the mass fraction of aluminum oxide is 20-65 mass %, and the rare earth metal The mass fraction is 0-5 mass %, and the nickel mass fraction is >0.4 mass %, for example, 0.4-1.5 wt %. Preferably, the crystallinity of the spent catalytic cracking catalyst is ≥10%, such as ≥15%. The crystallinity can be analyzed with reference to SH/T 0340-1992 NaY molecular sieve crystallinity determination method. Preferably, the sum of the content of vanadium and iron in the spent catalytic cracking catalyst is not higher than 0.6% by mass. In one embodiment, the content of contaminated nickel in the spent catalytic cracking catalyst is significantly higher than the content of contaminated vanadium and iron.

The method for reviving the spent catalytic cracking catalyst provided by the invention enables the spent catalytic cracking catalyst to be reduced in a reducing atmosphere. The reducing atmosphere contains a gas that can reduce nickel, for example, contains one or more of hydrogen, CO, and hydrocarbons, but is not limited to the above-mentioned gases. The concentration of the reducing gas in the reducing atmosphere is 5% to 100% by volume. In one embodiment, the reducing atmosphere is hydrogen, carbon monoxide, refinery dry gas atmosphere, or an atmosphere containing a mixture of one or more of the above gases and optionally an inert gas, such as nitrogen, helium One or more of gas and neon gas.

According to the method for reviving the spent catalytic cracking catalyst provided by the present invention, in one embodiment, the spent catalytic cracking catalyst is reduced in a reducing atmosphere, and the reduction temperature is 600-880°C, preferably 650-850°C. The reduction time is, for example, 0.5-20 hours.

In the method for reviving the spent catalytic cracking catalyst provided by the present invention, the reduction of the spent catalytic cracking catalyst can be performed in a fixed bed mode or a fluidized mode, and is not limited thereto. Preferably, the reduction of the spent catalytic cracking catalyst is carried out in a fluidized manner, which is fast and uniform, and facilitates the loading and unloading of materials.

In the method for reviving the spent catalytic cracking catalyst provided by the present invention, the ammonia-ammonium solution is a mixed solution containing ammonia and ammonium salt, and contains NH ₃ and NH ₄ ⁺ . The ammonium salt can be one or more of ammonium carbonate and ammonium bicarbonate. The total concentration of NH ₃ and NH ₄ ⁺ in the ammonia-ammonium solution (called total ammonia concentration) is 4-10 mol/L. The ammonia-ammonium solution can be obtained by adding ammonia water and an ammonium salt or ammonium salt solution in a mixing vessel. In one embodiment, the molar ratio of NH ₃ to NH ₄ ⁺ added is 2:1-1:4. During the whole process of the first contact, the pH value of the mixed solution containing ammonia and ammonium salt is maintained between 9.5-11.

In order to make the total ammonia concentration 4-10 mol/L in the first contact process, the total ammonia concentration can be maintained by adding ammonia water, feeding ammonia gas, adding ammonium salt or ammonium salt solution, and can be recovered by condensation due to the volatilization of ammonia, or The absorption method recovers the volatilized ammonia gas for recycling, which is well known to those skilled in the art. One way to adjust the total ammonia concentration to remain constant is, for example, condensation reflux of ammonia.

In the method for reviving the spent catalytic cracking catalyst provided by the present invention, the pH value of the first contact is 9.5-11. In order to make the pH value of the mixed solution of ammonia and ammonium salt between 9.5-11 in the whole process of the first contact, the spent catalytic cracking catalyst can be added to the ammonia-ammonium solution with a pH value of 9.5-11 to form the first The pH value of the first contacting mixed solution is adjusted to 9.5-11 by adding ammonia water or acid to the contacting mixed solution.

In the method for reviving the spent catalytic cracking catalyst provided by the present invention, preferably, the amount of the spent catalytic cracking catalyst added in the ammonia-ammonium solution, that is, the content of the spent catalytic cracking catalyst in the ammonia-ammonium solution, is 20-70 g/L ammonia-ammonium solution.

In the method for reviving the spent catalytic cracking catalyst provided by the present invention, the oxygen-containing oxidant is oxygen or a non-gas oxygen-containing oxidant. In one embodiment, a gas containing oxygen, such as oxygen and/or air and/or other gas containing oxygen, is passed into the ammonia-ammonium solution during the first contacting process. The introduction rate of oxygen can be 0.05-0.3 L/(min·g spent catalyst). ). In another embodiment, during the first contacting process, an oxygen-containing oxidant such as one or more of H ₂ O ₂ and K ₂ MnO ₄ is added to the ammonia-ammonium solution. In the present invention, the volume of oxygen and other gases is the volume under standard conditions.

In the method for reviving the spent catalytic cracking catalyst provided by the present invention, preferably, in the first contact process, the dissolved amount of oxygen or the oxygen production rate of the oxygen-containing oxidant makes the oxygen concentration in the contact solution not less than 0.005g/L (H ₂ 0).

In an embodiment of the method for reviving a spent catalytic cracking catalyst provided by the present invention, the contact temperature of the first contact is 10-100°C, preferably 10-70°C or 25-70°C or 25-60°C. The contact time of the first contact may be 10min-120min. There is no special requirement for the pressure of the first contact, and it can be carried out under normal pressure.

In the method for reviving the spent catalytic cracking catalyst provided by the present invention, the reduced spent catalytic cracking catalyst is first contacted in an ammonia-ammonium solution in the presence of an oxygen-containing oxidant, and then separated, such as by filtration, to obtain the spent catalytic cracking catalyst after the first contact. Cracking catalyst and mother liquor containing ammonia and ammonium. The mother liquor can recover ammonia, ammonium salts and nickel-containing substances. Ammonia and ammonium salts can be recycled, and nickel-containing substances can be used to prepare nickel or nickel compounds. The spent catalytic cracking catalyst after the first contact may be washed to remove ammonia-ammonium solution and nickel-containing species; such washing, for example, with water.

In the method for reviving the spent catalytic cracking catalyst provided by the present invention, the spent catalytic cracking catalyst after the first contact in step (2) is washed or not washed, and then treated with a treatment solution, wherein the treatment solution is a phosphorus-containing solution, a rare-earth salt-containing solution One or more of the solution and weak acid solution. The treatment generally involves mixing the washed or unwashed spent catalytic cracking catalyst after the first contact with the treatment solution for a second contact, stirring at the treatment temperature for a period of time called treatment time, and then filtering. The treatment temperature is, for example, 70-100° C., such as 75-95° C., and the treatment time is preferably 10-60 min. The weight ratio of the treatment liquid to the spent catalytic cracking catalyst after the first contact is, for example, 2-15:1 or 4-10:1. Preferably, the washed first contacted spent catalytic cracking catalyst is treated with a rare earth salt solution and/or a weakly acidic solution to enhance catalyst activity.

In a preferred embodiment of the method for reviving spent catalytic cracking catalyst provided by the present invention, the treatment solution is a weakly acidic solution, and the method comprises: washing or not washing the spent catalytic cracking catalyst after the first contact, and then mixing the spent catalytic cracking catalyst with weak acid solution. The acidic solution is subjected to the second contact, the contact temperature of the second contact is 70-100 ° C, such as 75-95 ° C, and the contact time of the second contact is preferably 10-60 min; the weakly acidic solution contains hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid. , one or more solutions of ammonium sulfate, ammonium chloride, ammonium phosphate and ammonium hydrogen phosphate, the pH value of the weakly acidic solution is 3.5-5.

In the method for reviving the spent catalytic cracking catalyst provided by the present invention, in step (3), the product obtained in step (2) is subjected to heat treatment, and the temperature of the heat treatment is preferably 100-550° C. The heat treatment is, for example, drying and/or roasting.

The present invention will be further described below through specific examples. The basic chemical composition of the spent catalytic cracking catalyst used in this example is shown in Table 1, and the chemical composition is determined by X-ray fluorescence (XRF). Refer to ASTM D7085-04 (2010) Standard Guide for the Determination of Chemical Elements in Fluidized Catalytic Cracking Catalysts—Guide to the Determination of X-ray Fluorescence Spectrometry. The catalyst microreactivity was determined by NB/SH/T 0952-2017. . The crystallinity of the catalyst was tested by SH/T 0340-1992NaY molecular sieve crystallinity determination method. The ACE test was carried out by ASTMD7964/D7964M-14ACE evaluation method, and the evaluation test was carried out using Wuxian three raw material oil. The density at 20°C was 0.9044g/cm3, the initial boiling point was 243°C, and the 70% distillation temperature was 473°C. H ₂ /CH ₄ is the hydrogen index.

Table 1

Example 1

10 grams of spent catalytic cracking catalyst C1 was weighed and calcined in a hydrogen-helium atmosphere with a hydrogen content of 30% by volume at 800° C. for 3 hours to obtain a reduced spent catalytic cracking catalyst HCl. In a 1L three-necked flask, add 200ml of NH ₃ and NH ₄ ⁺ with a total concentration of 8 mol/L, NH ₃ : CO ₃ ² - being an ammonia-ammonium carbonate solution with a mass ratio of 135:86, turn on the water bath for heating, and use a condenser tube with The volatile matter was cooled by tap water (temperature 16°C), and the condensate was refluxed (hereinafter also referred to as condensation reflux of the volatile matter). The temperature was raised to 45° C., 10 g of the reduced waste catalytic cracking catalyst HCl was added, and oxygen was passed through at 1 L/min for 30 min to carry out the first contact. The pH throughout the first contacting process was 10.1-10.5. The spent catalytic cracking catalyst after the first contact is obtained after filtration. The spent catalytic cracking catalyst after the first contact is subjected to a second contact with a phosphoric acid solution having a pH of 4, wherein the weight ratio of the spent catalyst after the first contact to the phosphoric acid solution is 1:5, the temperature of the second contact is 80° C. The contact time of the second contact is 30 min, after filtration, rinse with 100 ml of distilled water at room temperature, and dry in a 150° C. desiccator to obtain a resurrection catalyst FC1-1.

The nickel mass fraction of the resurrection catalyst FC1-1 is 0.23%, the crystallinity is 13.9%, and the microreactivity is 65. ACE test hydrogen index of 0.32

The revived catalyst was regenerated and regenerated three times (the reaction temperature of each time was 550 ° C, the oil input was 1.5 g (the ratio of agent to oil was 6), the reaction time was 75 seconds, and the regeneration temperature was 700 ° C, the same below), and the micro-reaction was measured again. The activity is 63.

Example 2

10 grams of spent catalytic cracking catalyst C1 was weighed and calcined in a fluidized state at 800° C. under a hydrogen-helium atmosphere with a hydrogen content of 30% by volume for 3 hours to obtain a reduced spent catalytic cracking catalyst HC2. In a 1L three-necked flask, add 200ml of NH ₃ and NH ₄ ⁺ the total concentration of 8mol/L, NH ₃ : CO ₃ ² - is an ammonia-ammonium carbonate solution with a mass ratio of 135:86, turn on the water bath to heat and use a condenser to make Volatile material condenses to reflux. The temperature was raised to 45° C., 10 g of the reduced waste catalytic cracking catalyst HC2 was added, and oxygen was passed through at 1 L/min for 30 min to carry out the first contact. The pH value of the whole first contacting process is 10.1-10.5. After filtration, the spent catalytic cracking catalyst after the first contact was obtained after being rinsed twice with 100 ml of distilled water at room temperature. It was dried in a desiccator at 150°C to obtain a resurrected catalyst FC1-2.

The nickel mass fraction of the resurrection catalyst FC1-2 is 0.26%, the crystallinity is 14.1%, and the microreactive activity is 62. ACE test hydrogen index of 0.37

The revived catalyst was regenerated and regenerated three times, and the microreaction activity was determined to be 59 again.

Example 3

10 grams of spent catalytic cracking catalyst C1 was weighed and calcined at 750°C in a carbon monoxide-N2 atmosphere with a carbon monoxide content of 60% for 6 hours in a fixed bed manner to obtain a reduced spent catalytic cracking catalyst HC3. In a 1L three-necked flask, add 200ml of NH ₃ and a mixed solution of ammonium bicarbonate, the ammonia and ammonium total concentration of the mixed solution is 10mol/L, and NH ₃ : CO ₃ ² - is an ammonia-ammonium bicarbonate solution with a mass ratio of 100:65 , turn on the water bath to heat and use the condenser tube to condense the volatiles to reflux. The temperature was raised to 40° C. and 10 g of the spent catalyst after reduction and roasting was added to conduct the first contact with oxygen at 1.5 L/min for 20 min. The pH value of the whole first contact process is 9.8-10.3, and the spent catalytic cracking catalyst after the first contact is obtained by filtration, and washed with water (with deionized water at a temperature of 60 ℃, water and the spent catalytic cracking catalyst after the first contact) The weight ratio of the catalyst is 10:1); the spent catalytic cracking catalyst after the first contact after washing is treated with an ammonium phosphate solution with pH of 4, wherein the weight ratio of the spent catalyst after the first contact and the ammonium phosphate solution is 1: 8. The treatment temperature is 80°C, the treatment time is 50min, filtered, and dried in a 120°C desiccator to obtain the resurrection catalyst FC1-3.

The nickel mass fraction of the resurrection catalyst FC1-3 was 0.23%, the crystallinity was 13.7%, and the microreactivity was 65. The ACE test hydrogen index is 0.34.

The revived catalyst was regenerated and regenerated three times, and the microreactivity was determined to be 64 again.

Comparative Example 1

In a 1L three-necked flask, add 200ml of NH ₃ and NH ₄ ⁺ the total concentration of 8mol/L, NH ₃ : CO ₃ ² - is an ammonia-ammonium carbonate solution with a mass ratio of 135:86, turn on the water bath to heat and use a condenser to make Volatile material condenses to reflux. The temperature was raised to 45° C., 10 g of the reduced waste catalytic cracking catalyst C1 was added, and oxygen was passed through at 1 L/min for 30 min. The pH throughout the first contacting process was 10.1-10.5. The spent catalytic cracking catalyst after the first contact is obtained after filtration. The spent catalytic cracking catalyst after the contact is treated with a phosphoric acid solution with a pH of 4, wherein the weight ratio of the spent catalyst after the first contact to the phosphoric acid solution is 1:5, the treatment temperature is 80 ° C, the treatment time is 30 min, and 100 ml of The distilled water was rinsed at room temperature and dried in a desiccator at 150 °C to obtain a resurrected catalyst FC1-4.

The nickel mass fraction of the resurrection catalyst FC1-4 is 0.88%, the crystallinity is 14.0%, and the micro-reactivity is 62. The ACE test hydrogen index is 0.83.

The revived catalyst was regenerated and regenerated three times, and the microreaction activity was determined to be 56 again.

Comparative Example 2

10 grams of spent catalytic cracking catalyst C1 was weighed and calcined for 3 hours in a hydrogen-helium atmosphere with a hydrogen content of 30% by volume at 500° C. to obtain a reduced spent catalytic cracking catalyst HC5. In a 1L three-necked flask, add 200ml of NH ₃ and NH ₄ ⁺ the total concentration of 8mol/L, NH ₃ : CO ₃ ² - is an ammonia-ammonium carbonate solution with a mass ratio of 135:86, turn on the water bath to heat and use a condenser to make Volatile material condenses to reflux. The temperature was raised to 45° C., 10 g of the reduced waste catalytic cracking catalyst HC5 was added, and oxygen was passed through at 1 L/min for 30 min. The pH throughout the contact process was 10.1-10.5. After filtration, the contacted spent catalytic cracking catalyst is obtained. The spent catalytic cracking catalyst after the contact is treated with a phosphoric acid solution with a pH of 4 for the second treatment, wherein the weight ratio of the spent catalyst after the first contact to the phosphoric acid solution is 1:5, the treatment temperature is 80° C., and the treatment time is 30min. Filter , and dried in a desiccator at 150 °C to obtain a resurrection catalyst FC1-5.

The nickel mass fraction of the resurrection catalyst FC1-5 was 0.82%, the crystallinity was 13.9%, and the microreactivity was 61. The ACE test hydrogen index is 0.79.

The revived catalyst was regenerated and regenerated three times, and the microreactivity was determined to be 54 again.

Comparative Example 3

10 grams of spent catalytic cracking catalyst C1 was weighed and calcined for 3 hours in a hydrogen-helium atmosphere with a hydrogen content of 30% by volume at 800° C. to obtain a reduced spent catalytic cracking catalyst HC6. In a 1L three-necked flask, add 200ml of NH ₃ and NH ₄ ⁺ with a total concentration of 8mol/L, NH ₃ : CO ₃ ² - being an ammonia-ammonium carbonate solution with a mass ratio of 135:86, turn on the water bath to heat and use a condenser to make Volatile material condenses to reflux. The temperature was raised to 45° C. and 10 g of the reduced waste catalytic cracking catalyst HC6 was added, and the pH of the entire contact process was 10.5-11.0. After filtration, the contacted spent catalytic cracking catalyst is obtained. The spent catalytic cracking catalyst after the contact is treated with a phosphoric acid solution with a pH of 4 for the second contact treatment, wherein the weight ratio of the spent catalyst after the first contact with the phosphoric acid solution is 1:5, the treatment temperature is 80 ° C, and the treatment time is 30min , filtered, and dried in a desiccator at 150 °C to obtain a resurrected catalyst FC1-6.

The nickel mass fraction of the resurrection catalyst FC1-6 is 0.59%, the crystallinity is 13.8%, and the micro-reactivity is 62. The ACE test hydrogen index is 0.68.

The revived catalyst was regenerated and regenerated three times, and the microreaction activity was determined to be 55 again.

Comparative Example 4

10 grams of spent catalytic cracking catalyst C1 were weighed and calcined at 800 °C for 6 h in a hydrogen atmosphere. Then wash with 0.5% nitric acid solution 3 times at 90°C for 1 h each time, each time the mass ratio of acid solution to catalyst is 4,. The acid-washed catalyst was washed with deionized water three times, 10 ml each time, and fully dried in a 120° C. desiccator to obtain a resurrected catalyst FC1-7.

The nickel mass fraction of the resurrection catalyst FC1-7 is 0.22%, the crystallinity is 11.6%, and the microreactive activity is 63. The ACE test hydrogen index is 0.31.

The revived catalyst was regenerated and regenerated three times, and the microreaction activity was determined to be 50 again.

Comparative Example 5

10 grams of spent catalytic cracking catalyst C1 was weighed and calcined in a fluidized state at 800° C. under a hydrogen-helium atmosphere with a hydrogen content of 30% by volume for 3 hours to obtain a reduced spent catalytic cracking catalyst HC8. In a 1L three-necked flask, add 200ml of pure ammonia solution with a total concentration of 8mol/L of NH ₃ and NH ₄ ⁺ , turn on the water bath to heat and use a condenser to condense and reflux volatile substances. The temperature was raised to 45° C., 10 g of the reduced waste catalytic cracking catalyst HC8 was added, and oxygen was passed through at 1 L/min for 30 min. The pH throughout the contact process was 10.2-11.0. The spent catalytic cracking catalyst after the first contact is obtained after filtration. The spent catalytic cracking catalyst after the first contact is treated with a phosphoric acid solution with a pH of 4 for the second contact treatment, wherein the weight ratio of the spent catalyst after the first contact to the phosphoric acid solution is 1:5, the treatment temperature is 80 ° C, and the treatment time is 30min, filtered and dried in a desiccator at 150°C to obtain a resurrection catalyst FC1-8.

The nickel mass fraction of the resurrection catalyst FC1-8 is 0.38%, the crystallinity is 12.9%, and the microreactive activity is 62. The ACE test hydrogen index is 0.67.

The revived catalyst was regenerated and regenerated three times, and the microreactivity was determined to be 54 again.

Comparative Example 6

10 grams of spent catalytic cracking catalyst C1 was weighed and calcined for 3 hours in a hydrogen-helium atmosphere with a hydrogen content of 30% by volume at 800° C. to obtain a reduced spent catalytic cracking catalyst HC9. In a 1L three-necked flask, add 200ml of NH ₃ ^and NH ₄ The total concentration of 8mol/L, NH ₃ : CO ₃ ² - is an ammonia-ammonium carbonate solution with a mass ratio of 135:86, open a water bath to heat and condense the volatile matter backflow. The temperature was raised to 45° C., 10 g of the reduced waste catalytic cracking catalyst HC9 was added, and oxygen was passed through at 1 L/min for 30 min. The pH throughout the first contacting process was 10.1-10.5. The spent catalytic cracking catalyst after the first contact is obtained after filtration. The waste catalytic cracking catalyst after the first contact adopts the hydrochloric acid solution of pH 2 to carry out the second contact treatment, wherein the weight ratio of the waste catalyst after the first contact to the hydrochloric acid solution is 1:5, the treatment temperature is 80 ° C, and the treatment time is 30min, filtered and dried in a desiccator at 150°C to obtain a resurrected catalyst FC1-9.

The nickel mass fraction of the resurrection catalyst FC1-9 is 0.21%, the crystallinity is 12.5%, and the microreactive activity is 62. The ACE test hydrogen index is 0.35.

The revived catalyst was regenerated and regenerated three times, and the microreactive activity was determined to be 49 again.

The properties of the revived catalysts obtained in Examples 1-3 and Comparative Examples 1-6 are listed in Table 2.

Table 2

It can be seen from Table 2 that the resurrection method provided by the present invention can make the removal rate of nickel reach more than 70%, can greatly reduce the nickel content, and reduce the hydrogen index. The resurrection method provided by the present invention can better maintain the crystallinity of the catalyst. The method of the invention can improve the stability of the resurrection catalyst, and the catalyst activity loss of the resurrection catalyst after three reactions is small. Although the activity of the resurrected catalyst obtained by the method of the comparative example is improved, the crystallinity decreases more and the activity stability is poor.

The preferred embodiments of the present disclosure are described above in detail, however, the present disclosure is not limited to the specific details of the above-mentioned embodiments. Within the scope of the technical idea of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure. These simple modifications All belong to the protection scope of the present disclosure.

In addition, it should be noted that, the specific technical features described in the above-mentioned specific embodiments can be combined in any suitable manner unless they are inconsistent. In order to avoid unnecessary repetition, the present disclosure provides The combination method will not be specified otherwise.

In addition, the various embodiments of the present disclosure can also be arbitrarily combined, as long as they do not violate the spirit of the present disclosure, they should also be regarded as the contents disclosed in the present disclosure.

Claims (13)

1. a revival method of spent catalytic cracking catalyst, comprises the following steps: (1) treating the spent catalytic cracking catalyst in a reducing atmosphere at 600-880° C. to obtain a treated spent catalyst; (2) first contacting the treated waste catalyst in ammonia-ammonium solution in the presence of pH 9.5-11 and oxygen-containing oxidant, and separating and obtaining the waste catalyst after the first contact, wherein ammonia in the ammonia-ammonium solution The total concentration of ammonium and ammonium is 4-10mol/L; optional washing; (3) heat-treating the product of step (2). 2. according to the described method of claim 1, it is characterized in that, in step (2), the waste catalyst after the first contact is washed or not washed, with a kind of phosphorus-containing solution, rare-earth-containing solution, weakly acidic solution or more processing. 3. according to the described method of claim 1 or 2, it is characterized in that, in step (2), the spent catalyst after the first contact is washed or not washed, and the second contact is carried out with weak acid solution, and the temperature of the second contact is 70 ℃ -100°C, the contact time of the second contact is preferably 10-60min; the weakly acidic solution contains one or more of hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, ammonium sulfate, ammonium chloride, ammonium phosphate and ammonium hydrogen phosphate The pH value of the weakly acidic solution is 3.5-5. 4. The method according to claim 1, characterized in that, in the spent catalytic cracking catalyst, the mass fraction of silica is 30-75%, the mass fraction of aluminum oxide is 20-65%, and the fraction of rare earth metals is 0% -5.0 wt%, nickel mass fraction>0.4%, molecular sieve crystallinity ≥10%, for example ≥15%. 5 . The method according to claim 1 , wherein the spent catalytic cracking catalyst in step (1) is treated in a reducing atmosphere at a temperature of 650° C.-880° C. and a treatment time of 0.5-20 hours. 6 . 6. The method according to claim 1 or 5, characterized in that, the spent catalytic cracking catalyst is reduced in a fixed bed mode or in a fluidized mode; the reducing atmosphere contains hydrogen, carbon monoxide, and hydrogen in the refinery dry gas. One or more, the concentration of the reducing gas in the reducing atmosphere is 5-100% by volume. 7. The method according to claim 1, wherein the ammonia-ammonium solution is a solution containing ammonia and an ammonium salt, and the ammonium salt is one or more of ammonium carbonate and ammonium bicarbonate. 8. method according to claim 1 is characterized in that, the content of spent catalytic cracking catalyst in ammonia-ammonium solution is 20-70g spent catalytic cracking catalyst/L ammonia-ammonium solution. 9 . The method according to claim 1 , wherein the oxygen-containing oxidant is oxygen or a non-gaseous oxygen-containing oxidant; the non-gaseous oxygen-containing oxidant is, for example, in H ₂ O ₂ , K ₂ MnO ₄ . one or more of. 10. according to the described method of claim 1, it is characterized in that, described oxygen-containing oxidant is oxygen, the introduction rate of oxygen is 0.05-0.3L/(min.g spent catalytic cracking catalyst), wherein oxygen volume refers to standard volume in state. 11. The method according to claim 1 or 10, wherein the temperature of the first contact in step (2) is 10-70°C, preferably 25-60°C. 12. The method according to claim 1 or 11, wherein the contact time of the first contact is 10min-120min. 13. according to the described method of claim 1, it is characterized in that, also comprise the ammonia-ammonium solution recovery ammonia and ammonium salt of the waste catalyst after the first contact after the first contact in the described step (2), Ammonia and ammonium salt recycling.