CN114763584A - Process for treating spent FCC catalyst - Google Patents
Process for treating spent FCC catalyst Download PDFInfo
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- CN114763584A CN114763584A CN202110049372.3A CN202110049372A CN114763584A CN 114763584 A CN114763584 A CN 114763584A CN 202110049372 A CN202110049372 A CN 202110049372A CN 114763584 A CN114763584 A CN 114763584A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0446—Leaching processes with an ammoniacal liquor or with a hydroxide of an alkali or alkaline-earth metal
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
Abstract
The invention relates to the technical field of waste chemical raw material recycling, and discloses a method for treating a waste FCC catalyst, which comprises the following steps: (1) roasting the waste FCC catalyst to obtain a roasted product; (2) mixing the roasted product with a solution containing an ammonia source for reaction, and carrying out solid-liquid separation on the obtained product to obtain a solution containing the nickel-ammonia complex; (3) and evaporating the solution containing the nickel-ammonia complex to obtain basic nickel carbonate, and then sequentially washing, drying and roasting the basic nickel carbonate to obtain nickel oxide. The invention can simplify the separation and purification process, realize the high-efficiency recovery of high-purity nickel oxide and realize the regeneration of the FCC catalyst by sequentially carrying out reduction roasting, ammonia leaching and ammonia distillation precipitation on the waste FCC catalyst.
Description
Technical Field
The invention relates to the technical field of waste chemical raw material recycling, in particular to a method for treating a waste FCC catalyst.
Background
Since the 21 st century, the demand for petroleum has increased with the development of economy, and China has become a world-wide petroleum consumption and import country. The data show that the total petroleum consumption amount of China in 2017 is about 5.9 hundred million tons, which is second only to the United states and second in the world, and accounts for 13.2 percent of the total petroleum consumption amount, and the petroleum is used as a non-renewable resource, but the reserves are gradually reduced.
Along with continuous exploitation of petroleum, the quality of crude oil is also continuously reduced, and the crude oil has the tendency of heaviness and deterioration; meanwhile, with the enhancement of the environmental protection concept of people and the increase of the demand of light oil, the catalytic cracking technology of crude oil is vigorously developed in various countries. As the most important link in the secondary processing process of the oil refining industry, the catalytic cracking (FCC) technology is rapidly developed and gradually becomes the core technology in the petroleum refining industry in China. The catalytic cracking (FCC) catalyst is also used as one of the most important raw materials in the oil product processing process, and the annual usage amount of the FCC catalyst is arranged at the head in the oil refining catalyst and accounts for 86 percent of the usage amount of the FCC catalyst in the oil refining industry. In 2011, the global FCC catalyst usage has reached 627kt/a and continues to increase at an increase of 18%. However, because crude oil contains a large amount of heavy metal elements, harmful elements such as nickel in the crude oil can be gradually deposited on the FCC catalyst during the oil refining process, resulting in the reduction of the activity of the catalyst, the deterioration of the selectivity of the product, and even the collapse of the molecular sieve structure, and the complete deactivation of the catalyst; meanwhile, due to the deposition of heavy metals, carbon deposition and the like, the deactivated waste catalyst is easily changed into dangerous waste.
At present, the common nickel recovery process mainly adopts a sodium hydroxide method or an acid method to leach the waste FCC catalyst, but in the leaching process, the sodium hydroxide or the acid can dissolve beneficial components such as nickel, more rare earth and the like, and also destroys the structure of the original molecular sieve, so that the recovery process can not realize the regeneration of the FCC catalyst, and can also cause the complex separation and purification of the recovered metal and large consumption of wastewater and acid.
Therefore, how to safely treat and utilize the waste FCC catalyst becomes an urgent problem to be solved.
Disclosure of Invention
The invention aims to solve the problems of complex separation and purification of recovered metal and incapability of regenerating an FCC catalyst in the conventional nickel recovery process, and provides a method for treating a waste FCC catalyst.
In order to achieve the above object, the present invention provides a method for treating a spent FCC catalyst, the method comprising:
(1) roasting the waste FCC catalyst to obtain a roasted product;
(2) mixing the roasted product with a solution containing an ammonia source for reaction, and carrying out solid-liquid separation on the obtained product to obtain a solution containing the nickel-ammonia complex;
(3) evaporating the solution containing the nickel-ammonia complex to obtain basic nickel carbonate, and then sequentially washing, drying and roasting the basic nickel carbonate to obtain nickel oxide.
Through the technical scheme, the waste FCC catalyst is subjected to reduction roasting, ammonia leaching and ammonia distillation precipitation in sequence, so that the separation and purification process can be simplified, high-efficiency recovery of high-purity nickel oxide can be realized, and the regeneration of the FCC catalyst can be realized.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the prior art, the nickel on the waste FCC catalyst is usually recovered by sodium hydroxide leaching or acid leaching, but the method can dissolve nickel and more beneficial elements such as rare earth in the leaching process, also destroys the structure of the original molecular sieve, cannot realize the regeneration of the FCC catalyst, and has complex separation and purification of the recovered nickel, so that the purity and yield of nickel oxide are lower, and the consumption of wastewater and acid is high. In order to solve the above problems, the inventors of the present invention have found in their research that, by sequentially subjecting the spent FCC catalyst to reduction roasting, ammonia leaching and ammonia evaporation precipitation, the process flow is simplified, nickel can be selectively complexed and dissolved, beneficial elements such as rare earth and the like are not dissolved, and the structure of the original molecular sieve is not destroyed, so that the regeneration of the FCC catalyst can be achieved, and at the same time, nickel oxide with higher purity and yield can be obtained, and high-efficiency recovery of high-purity nickel oxide can be achieved.
As previously described, the present invention provides a method for treating a spent FCC catalyst, the method comprising:
(1) roasting the waste FCC catalyst to obtain a roasted product;
(2) mixing the roasted product with a solution containing an ammonia source for reaction, and carrying out solid-liquid separation on the obtained product to obtain a solution containing the nickel-ammonia complex;
(3) evaporating the solution containing the nickel-ammonia complex to obtain basic nickel carbonate, and then sequentially washing, drying and roasting the basic nickel carbonate to obtain nickel oxide.
The method for treating the waste FCC catalyst can be summarized as that the waste FCC catalyst is sequentially subjected to reduction roasting, ammonia leaching and ammonia distillation precipitation to obtain the regenerated FCC catalyst and nickel oxide. The prior art generally recovers nickel from spent FCC catalyst by either sodium hydroxide leaching or acid leaching, but fails to achieve FCC catalyst regeneration.
The source of the spent FCC catalyst in the step (1) is not particularly limited in the present invention, and it can be used in any existing process, and preferably, the spent FCC catalyst has a carbon content of 20 to 30 wt% and a nickel oxide content of 1 to 5 wt% in terms of Ni element.
In some embodiments of the present invention, the spent FCC catalyst is calcined by step (1), on the one hand, the soot can be used as a reducing agent to reduce nickel oxide to metallic nickel, and on the other hand, the soot can be removed, preferably, the calcination conditions include: the temperature is between 450 ℃ and 650 ℃, and more preferably between 500 ℃ and 600 ℃; the time is 30-150 min. In the present invention, the heating rate of the calcination in the step (1) is not particularly limited, but is preferably (1 to 5) ° c/min.
In some embodiments of the present invention, selective complex dissolution of nickel without dissolving other beneficial elements such as rare earth elements can be achieved by mixing the calcined product with the solution containing the ammonia source, so that on one hand, difficulty in nickel metal separation can be avoided, and on the other hand, the regeneration of the FCC catalyst can be achieved, and preferably, in step (2), the mass/volume ratio of the calcined product to the solution containing the ammonia source is 1 g: (2.5-7) mL, more preferably 1 g: (2.5-5) mL.
In some embodiments of the present invention, preferably, the solution containing ammonia source is ammonia water and/or ammonium salt solution, more preferably a mixed solution of ammonia water and ammonium salt solution. In this preferred case, selective complex dissolution of nickel is more facilitated.
According to the invention, in the mixed solution, ammonia water and ammonium salt solution are mixed in a proper proportion, if the proportion of ammonia water is too high relative to that of ammonium salt solution, nickel hydroxide precipitate is generated, and the subsequent nickel dissolution and the regeneration of FCC catalyst are affected, preferably, the volume ratio of ammonia water to ammonium salt solution is 1: 1-10, more preferably 1: 2-4. In this preferred case, it is more advantageous to achieve efficient recovery of high purity nickel oxide and regeneration of the FCC catalyst.
In the mixed solution, the concentration selection range of the ammonia water and the ammonium salt solution is wide, preferably, the concentration of the ammonia water is 25 to 27.5 weight percent, and the concentration of the ammonium salt solution is 10 to 27.5 weight percent.
In some embodiments of the present invention, the selection range of the ammonium salt solution is wide, and preferably, the ammonium salt solution is at least one selected from the group consisting of an ammonium bicarbonate solution, an ammonium carbonate solution, and an ammonium sulfate solution, and more preferably, an ammonium carbonate solution.
In some embodiments of the present invention, preferably, in the step (2), the conditions of the mixing reaction include: the temperature is 50-90 ℃, preferably 65-75 ℃; the time is 30-120min, preferably 30-45 min.
The solid-liquid separation mode in step (2) is not particularly limited in the present invention, and may be a conventional choice in the art, including, but not limited to, pressure filtration, centrifugal separation, and the like.
The number of times of the water washing in step (2) is not particularly limited in the present invention, and may be selected by those skilled in the art as required according to the actual situation, and may be, for example, 2 or 3 times.
The drying in step (2) is not particularly limited in the present invention, and a drying manner conventional in the art can be adopted, preferably, the drying temperature is 100-120 ℃, and the drying time is 90-120 min.
In some embodiments of the present invention, the evaporation of the solution containing nickel ammine complex in step (3) can precipitate out basic nickel carbonate in the solution, while other elements such as potassium and sodium in the solution are not precipitated out, and at the same time, NH can be recovered3And CO2Preferably, the conditions of evaporation include: the temperature is 70-100 ℃, and more preferably 80-90 ℃; the time is 30-120min, more preferably 90-120 min. The invention is realized by volatilizing NH3Absorbing with water to obtain ammonia water for recycling.
The number of times of the water washing in step (3) is not particularly limited in the present invention, and may be selected by those skilled in the art as needed according to the actual situation.
The drying in step (3) is not particularly limited in the present invention, and a drying manner conventional in the art may be adopted, preferably, the drying temperature is 90-120 ℃, and the drying time is 90-120 min.
In the present invention, the drying temperature and the drying time involved in the step (2) and the step (3) may be the same or different, and can be determined by those skilled in the art according to the actual situation.
In some embodiments of the invention, step (3) is carried out with the purpose of converting the basic nickel carbonate into high purity nickel oxide, preferably under conditions comprising: the temperature is 230-450 ℃, and the temperature is more preferably 300-350 ℃; the time is 30-150 min. In the present invention, the heating rate of the calcination in the step (3) is not particularly limited, but is preferably (1 to 5) ° c/min.
In some embodiments of the present invention, in order to increase the reaction efficiency, the contact of the solution containing the ammonia source with the roasted product is increased, thereby rapidly achieving the selective complex leaching of nickel, preferably, the method further comprises: and (3) adding a penetrant into the mixed reaction in the step (2).
Preferably, the mass/volume ratio of the penetrant to the solution containing the source of ammonia is (0.005-0.01) g: 1 mL.
The selection range of the penetrant is wide, and preferably, the penetrant is selected from at least one of a nonionic surfactant JFC, a nonionic surfactant JFC-1, a nonionic surfactant JFC-2, a nonionic surfactant JFC-E, a rapid penetrant T, an alkali-resistant penetrant OEP-70, an alkali-resistant penetrant AEP and a high-temperature penetrant JFC-M.
In some embodiments of the present invention, preferably, the method further comprises: adding hydrogen peroxide into the mixed reaction in the step (2). According to the invention, hydrogen peroxide is added into the mixed reaction, so that on one hand, compared with other oxidants needing purification and impurity removal, a small amount of hydrogen peroxide does not influence the subsequent purification of nickel, and the process steps can be simplified; on the other hand, the decomposition of the hydrogen peroxide can generate a micro oxygen-rich environment, thereby improving the activity of ammonia leaching and effectively promoting the complexation of nickel under the conditions of oxygen enrichment and ammonia enrichment.
Preferably, the mass/volume ratio of the hydrogen peroxide solution to the solution containing the ammonia source is (0.01-0.05) g: 1 mL.
The invention has wider selection range of the concentration of the hydrogen peroxide, and preferably, the concentration of the hydrogen peroxide is 25 to 27.5 weight percent.
In some embodiments of the present invention, preferably, the method further comprises: and (3) carrying out ultrasonic treatment on the product before the solid-liquid separation in the step (2).
Preferably, the conditions of the sonication include: the ultrasonic frequency is 28-40kHz, the power is 30-100W/L, and the time is 15-60 min. According to the invention, the product is subjected to ultrasonic treatment under a closed condition, so that the leaching rate and the specific surface area of the FCC catalyst can be effectively improved.
In some embodiments of the present invention, preferably, the method further comprises: and (3) carrying out solid-liquid separation on the product obtained in the step (2) to obtain solid, and sequentially washing and drying the solid to obtain the regenerated FCC catalyst. In the prior art, the regeneration of the FCC catalyst cannot be realized by adopting the sodium hydroxide leaching or acid leaching process.
In order to clearly describe the process for the treatment of spent FCC catalyst according to the present invention, a preferred embodiment is provided as follows:
(1) roasting the waste FCC catalyst at the temperature of 500-600 ℃ for 30-150min to obtain a roasted product;
(2) mixing the roasted product with a solution containing an ammonia source according to a ratio of 1 g: (2.5-5) mL, adding a penetrant and hydrogen peroxide, and then mixing and reacting at 65-75 ℃ for 30-45min, wherein the mass/volume ratio of the penetrant to the solution containing the ammonia source is (0.005-0.01) g: 1mL, the mass/volume ratio of the hydrogen peroxide to the solution containing the ammonia source is (0.01-0.05) g: 1 mL; carrying out ultrasonic treatment on the obtained product, and then carrying out solid-liquid separation to obtain a solid and a solution containing the nickel-ammonia complex;
(3) evaporating the solution containing the nickel-ammonia complex for 90-120min at 80-90 ℃ to obtain basic nickel carbonate, washing the basic nickel carbonate with water, drying at 90-120 ℃ for 90-120min, and roasting at 300-350 ℃ for 30-150min to obtain nickel oxide; and (3) washing the solid with water, and drying at the temperature of 100-120 ℃ for 90-120min to obtain the regenerated FCC catalyst.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available without specific description.
Spent FCC catalyst: the content of carbon deposit is 21.2 wt%, and the content of nickel oxide calculated by Ni element is 1.23 wt%;
the specific surface area and the pore volume of the FCC catalyst are measured by a BET method;
the purity of the nickel oxide was determined by X-ray fluorescence spectroscopy (XRF).
Example 1
(1) Roasting the waste FCC catalyst for 90min at 550 ℃ (the heating rate is 5 ℃/min) to obtain a roasted product;
(2) mixing 18.5g of the roasted product with 92.5mL of solution containing an ammonia source (comprising 20mL of ammonia water with the concentration of 25 wt% and 50mL of ammonium carbonate solution with the concentration of 12 wt%), 0.5g of nonionic surfactant JFC and 2.5g of hydrogen peroxide with the concentration of 27.5 wt% at 70 ℃ for reaction for 40min, carrying out ultrasonic treatment on the obtained product for 45min under the conditions that the ultrasonic frequency is 40kHz and the power is 50W/L, and then carrying out centrifugal separation to obtain a solid and a solution containing nickel-ammonia complex;
(3) evaporating the solution containing the nickel-ammonia complex at 90 ℃ for 100min to obtain basic nickel carbonate, then washing the basic nickel carbonate with water for 2 times, drying at 90 ℃ for 90min, and roasting at 350 ℃ (the temperature rise rate is 5 ℃/min) for 90min to obtain nickel oxide; and (3) washing the solid for 2 times, and drying at 120 ℃ for 90min to obtain the regenerated FCC catalyst.
Example 2
(1) Roasting the waste FCC catalyst for 100min at 500 ℃ (the heating rate is 5 ℃/min) to obtain a roasted product;
(2) mixing 18.5g of roasted product with 85mL of solution containing ammonia source (comprising 20mL of 25 wt% ammonia water and 65mL of 12.5 wt% ammonium carbonate solution), 0.6g of rapid penetrant T and 2.5g of 27.5 wt% hydrogen peroxide at 65 ℃ for 45min, carrying out ultrasonic treatment on the obtained product for 45min under the conditions of ultrasonic frequency of 40kHz and power of 50W/L, and then carrying out centrifugal separation to obtain solid and solution containing nickel-ammonia complex;
(3) evaporating the solution containing the nickel-ammonia complex for 90min at 85 ℃ to obtain basic nickel carbonate, then washing the basic nickel carbonate with water for 2 times, drying at 90 ℃ for 120min, and roasting at 300 ℃ (the temperature rise rate is 5 ℃/min) for 60min to obtain nickel oxide; and (3) washing the solid for 2 times, and drying at 120 ℃ for 90min to obtain the regenerated FCC catalyst.
Example 3
(1) Roasting the waste FCC catalyst for 90min at 600 ℃ (the temperature rise rate is 5 ℃/min) to obtain a roasted product;
(2) mixing 18.5g of the roasted product with 55mL of solution containing an ammonia source (comprising 12mL of ammonia water with the concentration of 25 wt% and 43mL of ammonium carbonate solution with the concentration of 17.5 wt%), 0.4g of nonionic surfactant JFC and 1.5g of hydrogen peroxide with the concentration of 27.5 wt% at 75 ℃ for reaction for 30min, carrying out ultrasonic treatment on the obtained product for 45min under the conditions that the ultrasonic frequency is 40kHz and the power is 50W/L, and then carrying out centrifugal separation to obtain a solid and a solution containing nickel-ammonia complex;
(3) evaporating the solution containing the nickel-ammonia complex at 80 ℃ for 120min to obtain basic nickel carbonate, washing the basic nickel carbonate with water for 2 times, drying at 100 ℃ for 90min, and roasting at 330 ℃ (the heating rate is 5 ℃/min) for 60min to obtain nickel oxide; and (3) washing the solid for 2 times, and drying at 120 ℃ for 90min to obtain the regenerated FCC catalyst.
Example 4
The procedure of example 1 was followed except that, in the step (1), the calcination temperature was changed to 450 ℃ to obtain a regenerated FCC catalyst and nickel oxide, respectively.
Example 5
The method of example 1 was followed except that, in step (2), the volume of the solution containing the ammonia source was changed to 125mL so that the mass/volume ratio of the roast product to the solution containing the ammonia source was 1 g: 6.75mL, respectively, to obtain regenerated FCC catalyst and nickel oxide.
Example 6
A regenerated FCC catalyst and nickel oxide were obtained by the method of example 1 except that in step (2), 20mL of 25 wt% strength aqueous ammonia and 50mL of 12 wt% strength ammonium carbonate solution were replaced with 30mL of 25 wt% strength aqueous ammonia and 30mL of 25 wt% strength ammonium carbonate solution, respectively.
Example 7
The procedure of example 1 was followed except that, in the step (2), the temperature of the mixing reaction was changed to 80 ℃ and the time was changed to 60min, to obtain a regenerated FCC catalyst and nickel oxide, respectively.
Example 8
The procedure of example 1 was followed except that, in the step (3), the temperature of the vaporization was changed to 70 ℃ and the time was changed to 70min, to obtain a regenerated FCC catalyst and nickel oxide, respectively.
Example 9
The procedure of example 1 was followed except that, in the step (3), the calcination temperature was changed to 450 ℃ to obtain a regenerated FCC catalyst and nickel oxide, respectively.
Example 10
A regenerated FCC catalyst and nickel oxide were obtained by the method of example 1 except that in step (2), 20mL of 25 wt% strength aqueous ammonia and 50mL of 12 wt% strength ammonium carbonate solution were replaced with 50mL of 25 wt% strength aqueous ammonia and 20mL of 12 wt% strength ammonium carbonate solution, respectively.
Example 11
According to the method of the embodiment 1, except that in the step (2), the penetrating agent and the hydrogen peroxide are not added, and ultrasonic treatment is not carried out, the regenerated FCC catalyst and the nickel oxide are respectively obtained.
Comparative example 1
The method for recovering Ni from waste FCC catalyst is disclosed in CN103343232A, and comprises the following steps:
the method comprises the following steps: after the waste FCC catalyst is leached by hydrochloric acid, removing residues and recycling aluminum compounds;
step two: acidifying the residual FCC residues by hydrochloric acid to convert into metal chloride, extracting the P507 mixed solution to obtain a quenched residual solution, wherein the P507 mixed solution is a P507-kerosene-nitric acid system, the concentration of P507 is 2.0mol/L, kerosene is used as a diluent, the acidity pH of the solution is between 2.00 and 2.50, and the extraction ratio is 2: 1, the extraction time is 30min, and the leaching solubility of the enriched nickel solution is the maximum;
step three: adding a small amount of hydrogen peroxide into the raffinate, and boiling for 5-10min, low-valence Fe is completely converted into Fe3+；
Step four: mixing the raffinate with sufficient ammonia to cause Fe3+Etc. are completely precipitated, and Ni2+Complexing with ammonia water completely, and filtering the precipitate to obtain filtrate;
step five: adding NaF solution into the filtrate, heating and stirring at 80 deg.C for 30min, cooling, and filtering to remove CaF2；
Step six: adding NaOH solution into the nickel ammonia solution from which impurities such as Fe, Ca and the like are removed to convert nickel ammonia complex ions into Ni (OH)2Precipitating, and washing the precipitate with pure water for 3-5 times;
step seven: the obtained Ni (OH)2Dissolving the precipitate with 1/1 vol% hydrochloric acid to obtain nickel chloride solution, concentrating and crystallizing to obtain NiCl2·6H2And (4) O crystals. The method can not realize the regeneration of the waste FCC catalyst, the recovery rate of the obtained nickel chloride product is 72.7 percent, and the product purity reaches the chemical industry standard HG/T2771-1996.
The specific surface area and pore volume of the regenerated FCC catalyst prepared in the above examples, and the spent FCC catalyst and the fresh FCC catalyst were measured, respectively, and the results are shown in table 1.
TABLE 1
Note: "-" indicates that it was impossible to measure, since the catalyst support structure was destroyed after the hydrochloric acid reaction, and it was not reproducible.
As can be seen from the results in table 1, the differences between the specific surface areas and pore volumes of the regenerated FCC catalysts prepared in examples 1 to 10 and the fresh FCC catalysts are not great, which indicates that the treatment method of the spent FCC catalyst provided by the present invention can realize the regeneration of the FCC catalyst and the regeneration performance of the FCC catalyst is good.
The purity of the nickel oxide prepared in the above examples was measured by XRF, respectively, and the recovery rate of nickel was calculated according to the following formula:
η＝(mfront side-mRear end)/mFront side×100％
Wherein the content of the first and second substances,
eta represents the recovery of nickel in%;
mfront sideRepresents the nickel oxide content of the spent FCC catalyst in wt%;
mrear endThe nickel oxide content of the regenerated FCC catalyst is expressed in wt% and the results are shown in table 2.
TABLE 2
As can be seen from the results in table 2, the treatment method of the spent FCC catalyst according to the present invention can achieve high recovery rate of nickel and high purity of nickel oxide; the traditional method for treating the waste FCC catalyst has lower recovery rate of nickel and purity of nickel oxide. Further, as can be seen from the results of comparative examples 1 and 10, the recovery rate of nickel and the purity of nickel oxide are significantly reduced when the amount of ammonia is too high, because the ammonia is too high, nickel hydroxide precipitate is easily generated, and the subsequent dissolution of nickel is affected, so that the recovery rate of nickel and the purity of nickel oxide become small.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A method for treating spent FCC catalyst, the method comprising:
(1) roasting the waste FCC catalyst to obtain a roasted product;
(2) mixing the roasted product with a solution containing an ammonia source for reaction, and carrying out solid-liquid separation on the obtained product to obtain a solution containing the nickel-ammonia complex;
(3) evaporating the solution containing the nickel-ammonia complex to obtain basic nickel carbonate, and then sequentially washing, drying and roasting the basic nickel carbonate to obtain nickel oxide.
2. The method of claim 1, wherein in step (1), the roasting conditions comprise: the temperature is 450-650 ℃, preferably 500-600 ℃; the time is 30-150 min.
3. The method according to claim 1 or 2, wherein in step (2), the mass/volume ratio of the roasted product to the solution containing the ammonia source is 1 g: (2.5-7) mL, preferably 1 g: (2.5-5) mL;
preferably, the solution containing the ammonia source is ammonia water and/or ammonium salt solution, and more preferably is mixed solution of ammonia water and ammonium salt solution;
further preferably, the volume ratio of the ammonia water to the ammonium salt solution is 1: 1-10, more preferably 1: 2-4.
4. The method according to claim 3, wherein in the mixed solution, the concentration of ammonia water is 25-27.5 wt%, and the concentration of ammonium salt solution is 10-27.5 wt%;
preferably, the ammonium salt solution is selected from at least one of an ammonium bicarbonate solution, an ammonium carbonate solution and an ammonium sulfate solution, more preferably an ammonium carbonate solution.
5. The method according to any one of claims 1 to 4, wherein in step (2), the conditions of the mixing reaction comprise: the temperature is 50-90 ℃, preferably 65-75 ℃; the time is 30-120min, preferably 30-45 min.
6. The method according to any one of claims 1 to 5, wherein in step (3), the evaporation conditions comprise: the temperature is 70-100 ℃, preferably 80-90 ℃; the time is 30-120min, preferably 90-120 min;
preferably, the roasting conditions in step (3) include: the temperature is 230-450 ℃, and the temperature is more preferably 300-350 ℃; the time is 30-150 min.
7. The method of any of claims 1-6, wherein the method further comprises: adding a penetrant into the mixed reaction in the step (2);
preferably, the mass/volume ratio of the penetrant to the solution containing the source of ammonia is (0.005-0.01) g: 1 mL.
8. The method according to claim 7, wherein the penetrant is selected from at least one of a nonionic surfactant JFC, a nonionic surfactant JFC-1, a nonionic surfactant JFC-2, a nonionic surfactant JFC-E, a fast penetrant T, an alkali-resistant penetrant OEP-70, an alkali-resistant penetrant AEP, and a high-temperature penetrant JFC-M.
9. The method of any one of claims 1-8, wherein the method further comprises: adding hydrogen peroxide into the mixed reaction in the step (2);
preferably, the mass/volume ratio of the hydrogen peroxide solution to the solution containing the ammonia source is (0.01-0.05) g: 1 mL;
further preferably, the concentration of the hydrogen peroxide is 25-27.5 wt%.
10. The method of any one of claims 1-9, wherein the method further comprises: performing ultrasonic treatment on the product obtained in the step (2) before solid-liquid separation;
preferably, the conditions of the ultrasonic treatment include: the ultrasonic frequency is 28-40kHz, the power is 30-100W/L, and the time is 15-60 min.
11. The method of any one of claims 1-10, wherein the method further comprises: and (3) carrying out solid-liquid separation on the product obtained in the step (2) to obtain solid, and sequentially washing and drying the solid to obtain the regenerated FCC catalyst.
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