CN112746170B - Treatment process of deactivated hydrogenation catalyst containing molecular sieve carrier - Google Patents

Treatment process of deactivated hydrogenation catalyst containing molecular sieve carrier Download PDF

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CN112746170B
CN112746170B CN201911035906.6A CN201911035906A CN112746170B CN 112746170 B CN112746170 B CN 112746170B CN 201911035906 A CN201911035906 A CN 201911035906A CN 112746170 B CN112746170 B CN 112746170B
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hydrogenation catalyst
treatment
molecular sieve
deactivated
deactivated hydrogenation
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CN112746170A (en
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朱慧红
刘铁斌
王永林
金浩
杨涛
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C22B21/0038—Obtaining aluminium by other processes
    • C22B21/0069—Obtaining aluminium by other processes from scrap, skimmings or any secondary source aluminium, e.g. recovery of alloy constituents
    • C22B21/0076—Obtaining aluminium by other processes from scrap, skimmings or any secondary source aluminium, e.g. recovery of alloy constituents from spent catalysts
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    • 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
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C22B23/026—Obtaining nickel or cobalt by dry processes from spent catalysts
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22B34/00—Obtaining refractory metals
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    • C22B34/345—Obtaining molybdenum from spent catalysts
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
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    • 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
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • 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
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Abstract

The invention discloses a treatment process of a deactivated hydrogenation catalyst containing a molecular sieve, which comprises the steps of firstly carrying out carbonization treatment and hydrothermal treatment on the deactivated hydrogenation catalyst containing the molecular sieve, crushing the treated catalyst, mixing the crushed catalyst with an alkaline solution for treatment, and further carrying out high-temperature heat treatment on the separated solid under the condition of hydrogen atmosphere. The treatment process does not need to deoil the deactivated catalyst, so that the deoiling treatment step in the existing process can be omitted, the energy consumption of a treatment device is greatly reduced, the process flow is shortened, high-value components such as tungsten, molybdenum, nickel, aluminum, silicon and the like in the deactivated catalyst can be effectively recovered, and the high-efficiency utilization of the deactivated hydrogenation catalyst containing the molecular sieve is realized.

Description

Treatment process of deactivated hydrogenation catalyst containing molecular sieve carrier
Technical Field
The invention relates to the field of petrochemical industry, relates to a treatment process of a deactivated hydrogenation catalyst containing a molecular sieve carrier, and particularly relates to a treatment process of an oil-containing deactivated hydrogenation catalyst containing a molecular sieve.
Background
With the aggravation of crude oil heaviness and deterioration and the continuous improvement of the clean standard of the petroleum fuel, the clean fuel and the deep processing technology of the crude oil will be further developed and become the key development direction of the oil refining technology in the world. Hydrocracking technology is a main process for deep processing of heavy oil, and is the only process technology capable of generating clean fuel and high-quality chemical raw materials while converting the raw materials into light weight. The hydrocracking technology has the advantages of strong raw material adaptability, flexible product scheme, high liquid product yield, good product quality and the like, so that the hydrocracking technology is widely applied. Hydrocracking catalysts are gaining increasing attention as their core technology.
The activity of the hydrogenation catalyst containing the molecular sieve is continuously reduced during the use process, and when the activity is reduced to a certain degree, the hydrogenation catalyst must be regenerated to restore the activity or be replaced by a new catalyst. The deactivation mechanism of the hydrogenation catalyst containing the molecular sieve is poisoning, coking and sintering. Poisoning generally refers to poisoning of acid sites, such as chemisorption of basic nitrogen onto acid sites, poisoning the catalyst. Coking is the formation of carbon deposits on the surface of the catalyst, covering the active center, and a large amount of coking causes the blockage of the orifice and prevents reactant molecules from entering the active center in the hole. Sintering can cause structural changes in the catalyst, leading to loss of active centers of the catalyst, manifested by aggregation or crystal enlargement of active metals, collapse of the framework of the molecular sieve, and the like. The deactivated and non-recyclable catalyst becomes a solid waste, which needs to be effectively disposed of.
At present, the treatment of the waste hydrogenation catalyst mainly comprises the processes of pyrometallurgy, hydrometallurgy, biological metallurgy, combination of various metallurgical methods and the like. The problems of overhigh heating temperature, high energy consumption, incapability of separating metal independently and effectively and the like exist in pyrometallurgy. The wet method has the problem that the acid and alkaline treatment liquid is difficult to be recovered and treated. Meanwhile, for example, the deactivated cracking containing molecular sieve usually retains the complete structure of the molecular sieve and increases the difficulty of subsequent treatment, so a method for efficiently treating the hydrogenation catalyst containing the molecular sieve must be researched.
CN200780033953.6 is a process for recovering group VIB metals from spent catalyst by oxidizing one or more group VIB metals into one or more group VIB metal oxides; separating the one or more group VIB metal oxides from the one or more group VIII metals; dissolving the one or more group VIB metal oxides in water to obtain an aqueous solution of the one or more group VIB metal oxides; precipitating the one or more group VIB metal oxides from the aqueous solution by adding alkaline earth metal (group IIa) ions to the aqueous solution; optionally filtering and washing the precipitate, and converting the precipitate by adding an acid to form a solid metal compound comprising one or more group VIB metals. In yet another route, the spent sulfur-containing catalyst is oxidized by calcining with a basic compound, preferably an alkali metal carbonate (e.g., sodium carbonate), at a temperature of at least about 600 c, preferably at least about 800 c to about 1000 c, to form a group VIB alkali metal oxide solid and a group VIII metal sulfide liquid melt, which phase-seperate based on the difference in liquid density of the two liquid phases. And after the melt is cooled and solidified, physically separating the solid VIII group metal sulfide to obtain a solid VIB group alkali metal oxide. The solid group VIB metal oxides are then dissolved in an aqueous alkaline solution to produce an aqueous solution of one or more group VIB metal oxides. In the patent, the first route still has the problem of waste agent oxidizing roasting, and the second route has the problems that high-temperature alkali roasting can seriously corrode a roasting furnace and the density difference separation efficiency is not high.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a treatment process of a deactivated hydrogenation catalyst containing a molecular sieve, which does not need to deoil the deactivated catalyst, can save the deoiling treatment step in the prior art, greatly reduce the energy consumption of a treatment device, shorten the process flow, effectively recover high-value components such as tungsten, molybdenum, nickel, aluminum, silicon and the like in the deactivated catalyst, and realize the efficient utilization of the deactivated hydrogenation catalyst containing the molecular sieve.
The invention provides a treatment process of a deactivated hydrogenation catalyst containing a molecular sieve, which comprises the following steps:
(1) Carbonizing treatment: in the presence of nitrogen or inert gas, carrying out carbonization treatment on the deactivated hydrogenation catalyst containing the molecular sieve;
(2) Hydrothermal treatment: contacting the carbonized catalyst in the step (1) with vapor-containing gas to perform hydrothermal treatment, wherein the vapor-containing gas contains alkali and an auxiliary agent;
(3) Crushing the catalyst obtained after the treatment in the step (2), mixing the crushed catalyst with an alkaline solution for treatment, and further washing and drying the solid obtained after solid-liquid separation;
(4) And (4) carrying out high-temperature heat treatment on the material obtained after drying in the step (3) under the condition of hydrogen atmosphere.
In the above process for treating the deactivated hydrogenation catalyst containing molecular sieve, the deactivated hydrogenation catalyst containing molecular sieve in step (1) refers to a hydrogenation catalyst containing molecular sieve in a carrier which has not achieved the original reaction requirements, especially a deactivated hydrocracking catalyst.
In the above treatment process of the deactivated hydrogenation catalyst containing the molecular sieve, the oil content of the deactivated hydrogenation catalyst containing the molecular sieve in the step (1) is 10 to 40wt%, preferably 10 to 30wt%.
In the treatment process of the deactivated hydrogenation catalyst containing the molecular sieve, the liquid-phase material obtained by the solid-liquid separation in the step (3) can be used as a raw material for producing the silicon-containing aluminum hydroxide.
In the above treatment process of the deactivated hydrogenation catalyst containing molecular sieve, the inert gas in step (1) may be one or more of helium, neon and argon; the carbonization treatment temperature is 700-950 ℃, the preferable temperature is 700-900 ℃, the treatment time is 4-10 h, the preferable time is 3-8 h, and the volume space velocity of nitrogen or inert gas is 100-500 h -1 Preferably 100 to 300h -1 。
In the above processing technology of the deactivated hydrogenation catalyst containing the molecular sieve, the alkali in the step (2) is one or more of ammonia water, ammonium carbonate and ammonium bicarbonate, and the assistant is a high molecular polymer with hydroxyl, such as one or more of polyethylene glycol (with a molecular weight of 1000-6000) and polyvinyl alcohol, preferably polyethylene glycol.
In the treatment process of the deactivated hydrogenation catalyst containing the molecular sieve, the weight ratio of the alkali to the deactivated hydrogenation catalyst containing the molecular sieve in the step (2) is 2:1-1:5, preferably 1:1-1:3; the weight ratio of the auxiliary agent to the deactivated hydrogenation catalyst containing the molecular sieve is 1:1-1:5, preferably 1:3-1:5.
In the treatment process of the deactivated hydrogenation catalyst containing the molecular sieve, the vapor-containing gas in the step (2) is vapor or a mixed gas of vapor and a carrier gas, and the volume ratio of the vapor to the carrier gas in the mixed gas is 1:5-2:1, preferably 1:4-1:1; the carrier gas is nitrogen or inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.
In the treatment process of the deactivated hydrogenation catalyst containing the molecular sieve, the hydrothermal treatment conditions in the step (2) are as follows, and the treatment temperature is 550-900 ℃, preferably 650-850 ℃; the treatment time is 3-10 h, preferably 3-8 h, and the inlet temperature of the vapor-containing gas is 200-350 ℃, preferably 250-350 ℃; the water volume space velocity in the hydrothermal treatment process is 150-500 h -1 Preferably 200 to 450h -1 。
In the above method for treating a deactivated hydrogenation catalyst containing a molecular sieve, the catalyst after hydrothermal treatment in the step (2) in the step (3) is pulverized to a particle size of >150 mesh, preferably >200 mesh.
In the above treatment process of the deactivated hydrogenation catalyst containing the molecular sieve, the alkaline solution in step (3) is an inorganic alkaline solution, which may be one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, and is preferably sodium hydroxide. The concentration of the alkaline solution is 5 to 15mol/L, preferably 6.5 to 15mol/L, and more preferably 8 to 12mol/L. The molar ratio of the waste catalyst to the cations in the alkali in the treatment process of the alkaline solution is 1:0.008 to 0.04, preferably 1:0.01 to 0.03. The solid-liquid separation can be used for separating liquid and solid by adopting separation methods existing in the field, such as filtration, centrifugal separation and the like.
In the treatment process of the deactivated hydrogenation catalyst containing the molecular sieve, the washing in the step (3) is washed to be neutral by deionized water; the drying is carried out in the presence of nitrogen and/or inert gas, wherein the inert gas is one or more of helium, neon and argon; the drying temperature is 100-180 ℃, preferably 120-150 ℃, and the drying time is 2-8 hours, preferably 4-6 hours.
In the treatment process of the inactivated hydrogenation catalyst, the high-temperature treatment temperature in the step (4) is 600-900 ℃, preferably 700-850 ℃, and the treatment time is 3-10 h, preferably 3-8 h. The volume ratio of the catalyst to the hydrogen is 1:5 to 20, preferably 1:10 to 20.
Compared with the prior art, the treatment process of the deactivated hydrogenation catalyst containing the molecular sieve has the following advantages:
1. in the treatment process of the deactivated hydrogenation catalyst containing the molecular sieve, the deactivated hydrogenation catalyst containing the molecular sieve is carbonized firstly, the deactivated hydrogenation catalyst containing the molecular sieve does not need to be deoiled in advance, the deoiling step in the existing method is omitted, the deactivated hydrogenation catalyst containing the molecular sieve containing the oil is directly added as a raw material for treatment, and the treatment steps are greatly simplified.
2. According to the treatment process of the deactivated hydrogenation catalyst containing the molecular sieve, firstly, carbonization treatment is carried out, oil contained in the deactivated catalyst is converted into coke through carbonization treatment, and in combination with the high carbon deposit content of the raw material of the deactivated hydrogenation catalyst containing the molecular sieve, in the subsequent hydrothermal treatment, the carbon and water vapor are subjected to water-gas reaction to generate high value-added reducing gas, so that the upper surface metal of the catalyst is subjected to shallow reduction; meanwhile, the molecular sieve is subjected to skeleton destruction by using alkaline water vapor, and the solubility of aluminum and silicon in the molecular sieve is further enhanced under the action of the high molecular polymer, so that the subsequent treatment is facilitated, and the pollutant emission is reduced.
3. In the treatment process of the deactivated hydrogenation catalyst containing the molecular sieve, the catalyst after hydrothermal treatment is crushed and then treated by an alkaline solution, metal sulfides (molybdenum sulfide, nickel sulfide, vanadium sulfide and the like) in the catalyst are insoluble in the alkaline solution, alumina and silica except the molecular sieve in a carrier react with the alkaline solution to obtain an alkaline solution containing aluminum and silicon, and after solid-liquid separation, the alkaline solution containing aluminum and silicon can react with an acidic precipitator to prepare the silicon-containing pseudo-boehmite or serve as a raw material for synthesizing molecular sieve seed crystals. The solid phase material obtained by separation is further treated by hydrogen, so that sulfide in the solid phase material is converted from a vulcanization state to a reduction state to form a multi-metal alloy which can be used as a metallurgical raw material, and meanwhile, sulfur is uniformly recovered, so that secondary pollution is avoided, and the environment pollution is avoided.
4. The treatment process of the deactivated hydrogenation catalyst containing the molecular sieve can effectively recover high-value metal components such as molybdenum, tungsten, nickel, aluminum and the like in the deactivated catalyst, wherein the molybdenum, tungsten and nickel metal components finally form a multi-metal alloy, and the alkaline aluminum-containing solution and the alkaline solution are obtained after the aluminum and the silicon react with the alkaline solution.
Detailed Description
The following examples are provided to further illustrate the technical solutions of the present invention, but the present invention is not limited to the following examples. In the present invention, wt% is a mass fraction.
Example 1
The hydrocracking catalyst C-1 (containing 40% of Y molecular sieve) deactivated after the operation had an oil content of 15.3% by weight and the metal content thereof was as shown in Table 1. Weighing 150g of oil-containing catalyst sample, putting the oil-containing catalyst sample into an atmosphere furnace for carbonization reaction, wherein the volume space velocity of nitrogen is 200h under the nitrogen atmosphere -1 The reaction temperature is 700 ℃, and the reaction is carried out for 8 hours at constant temperature. Then 300g of ammonium carbonate and 30g of polyethylene glycol 1000 are added into water, stirred to be dissolved uniformly, mixed gas containing ammonium carbonate and polyethylene glycol 1000 water vapor and nitrogen in the volume ratio of 1:1 is introduced, the hydrothermal treatment temperature is 800 ℃, the treatment time is 5 hours, the inlet temperature of the gas containing the alkali vapor is 250 ℃, and the volume space velocity of the water is 400 hours -1 . The treated sample was removed and ground to 150 mesh using a colloid mill. And putting the crushed sample into a beaker, adding 390mL of 10mol/L sodium hydroxide solution, and stirring for sufficient reaction for 30min. And performing liquid-solid separation on the suspension after reaction by adopting a centrifugal machine, wherein the rotating speed of the centrifugal machine is 3500r/min, centrifuging for 10min, and taking out. The upper layer of liquid L-1 was decanted and sent to a sample coupled plasma emission spectrometer ICP for metal analysis, the results of which are shown in Table 2. The lower solid was washed to a pH of 7. The washed sample was dried for 4h at 120 ℃ under a nitrogen atmosphere. Weighing 10mL of the dried sample, filling the sample into an atmosphere furnace, and continuously introducing hydrogen for treatment at the treatment temperature of 80 DEG CAt 0 ℃, for 5h, wherein the volume ratio of the catalyst to the hydrogen is 1:20, the treated sample S-1 was obtained and sent for fluorescence analysis, the results of which are shown in Table 3.
Example 2
The other conditions were the same as in example 1 except that the catalyst C-1 (containing 40wt% of Y molecular sieve) was changed to C-2 (containing 80wt% of ZSM-5 molecular sieve), the oil content was 11.6wt%, the amount of ammonium carbonate added was 150g, the hydrothermal treatment temperature was 850 deg.C, the amount of sodium hydroxide solution added was 600mL, the hydrogen reduction temperature was 700 deg.C, and the time was 8 hours, to obtain supernatant liquid L-2, and the results are shown in Table 2, and the treated sample S-2 was sent for fluorescence analysis and the results are shown in Table 3.
Example 3
The other conditions were the same as in example 1 except that C-1 (containing 40wt% of Y molecular sieve) was changed to C-3 (containing 45wt% of beta molecular sieve), the oil content was 16.4wt%, the carbonization temperature was changed to 800 ℃ for 3 hours, the hydrothermal treatment temperature was 700 ℃ for 8 hours, the concentration of sodium hydroxide added was changed to 4.5mol/L, and 390mL of the solution was added to obtain an upper layer liquid L-3, the results are shown in Table 2, and the treated sample S-3 was subjected to fluorescence analysis, and the results are shown in Table 3.
Example 4
The hydrocracking catalyst C-4 (containing 35wt% of Y molecular sieve) deactivated after the operation had an oil content of 28.3wt% and its metal content was as shown in Table 1. Weighing 100g of oil-containing catalyst sample, putting the oil-containing catalyst sample into an atmosphere furnace for carbonization treatment, wherein the volume space velocity of nitrogen is 300h under the nitrogen atmosphere -1 The reaction temperature is 850 ℃, and the reaction is carried out for 5 hours at constant temperature. Then adding 120g of ammonia water (density 0.95 g/mL) and 50g of polyethylene glycol 2000 into water, stirring to dissolve the ammonia water and the polyethylene glycol 2000 uniformly, introducing mixed gas of vapor containing ammonia water and the polyethylene glycol 2000 and nitrogen in a volume ratio of 1:2, carrying out hydrothermal treatment at the temperature of 600 ℃ for 10h, carrying out hydrothermal treatment at the vapor-containing gas inlet temperature of 350 ℃, and carrying out water volume space velocity of 450h -1 . The treated sample was removed and ground to 150 mesh with colloidal powder. And putting the crushed sample into a beaker, adding 300mL of 8.5mol/L sodium hydroxide solution, and stirring for sufficient reaction for 30min. Performing liquid-solid separation on the reacted suspension by adopting a centrifugal machine, wherein the rotating speed of the centrifugal machine is 3500rAnd (5) centrifuging for 10min, and taking out. The upper layer of liquid L-4 was decanted and sample fed for metal analysis by coupled plasma emission spectroscopy ICP, the results of which are shown in Table 2. The lower solid was washed to a pH of 7. The washed sample was dried for 6h at 120 ℃ under a nitrogen atmosphere. Weighing 10mL of the dried sample, filling the sample into an atmosphere furnace, continuously introducing hydrogen for treatment, wherein the treatment temperature is 850 ℃, the treatment time is 6h, and the volume ratio of the catalyst to the hydrogen is 1:15, the treated sample S-4 was obtained and sent for fluorescence analysis, the results of which are shown in Table 3.
Example 5
The procedure is otherwise the same as in example 1 except that C-4 (35 wt% of Y-containing molecular sieve) is changed to C-5 (40 wt% of Y-containing molecular sieve), the oil content is 24.1wt%, and the metal contents are shown in Table 1. The addition of ammonia water was changed to 200g, polyethylene glycol 2000 was changed to 3000 g, the hydrothermal treatment temperature was 800 ℃ and the treatment time was 5 hours, to obtain supernatant liquid L-5, the results are shown in Table 2, and the results of fluorescence analysis of the treated sample S-5 were shown in Table 3.
Comparative example 1 (No carbonation reaction)
After the operation, the deactivated hydrocracking catalyst C-1 (containing 40wt% of Y molecular sieve) discharged oil content of 15.3wt%, and its metal content is shown in Table 1. 150g of an oil-containing catalyst sample is weighed and placed into an atmosphere furnace for hydrothermal treatment. Then 300g of ammonium carbonate and 30g of polyethylene glycol 1000 are added into water, stirred to be dissolved uniformly, mixed gas of water vapor and nitrogen with the volume ratio of 1:1 containing ammonium carbonate and polyethylene glycol 1000 is introduced, the hydrothermal treatment temperature is 800 ℃, the treatment time is 5h, the inlet temperature of the gas containing water vapor is 250 ℃, and the volume space velocity of water is 400h -1 . The treated sample was removed and ground to 150 mesh with colloidal powder. And putting the crushed sample into a beaker, adding 390mL of 10mol/L sodium hydroxide solution, and stirring for sufficient reaction for 30min. And performing liquid-solid separation on the suspension after reaction by adopting a centrifugal machine, wherein the rotating speed of the centrifugal machine is 3500r/min, centrifuging for 10min, and taking out. The upper layer of liquid L-F1 was decanted and sent to a sample coupled plasma emission spectrometer ICP for metal analysis, the results of which are shown in Table 2. The lower solid was washed to a pH of 7. The washed sample was dried at 120 ℃ under a nitrogen atmosphere 4h. Weighing 10mL of the dried sample, filling the sample into an atmosphere furnace, continuously introducing hydrogen for treatment, wherein the treatment temperature is 800 ℃, the treatment time is 5h, and the volume ratio of the catalyst to the hydrogen is 1:20, the treated sample S-F1 was obtained and sent for fluorescence analysis, the results of which are shown in Table 3.
Comparative example 2 (without steam treatment)
After the operation, the deactivated hydrocracking catalyst C-1 (containing 40wt% of Y molecular sieve) discharged oil content of 15.3wt%, and its metal content is shown in Table 1. Weighing 150g of oil-containing catalyst sample, putting the oil-containing catalyst sample into an atmosphere furnace for carbonization reaction, wherein the volume space velocity of nitrogen is 200h under the nitrogen atmosphere -1 The reaction temperature is 700 ℃, and the reaction is carried out for 8 hours at constant temperature. The treated sample was removed and ground to 150 mesh with colloidal powder. And putting the crushed sample into a beaker, adding 390mL of 10mol/L sodium hydroxide solution, and stirring for sufficient reaction for 30min. And performing liquid-solid separation on the suspension after reaction by adopting a centrifugal machine, wherein the rotating speed of the centrifugal machine is 3500r/min, centrifuging for 10min, and taking out. The upper layer of liquid L-F2 was decanted and sent to a sample coupled plasma emission spectrometer ICP for metal analysis, the results of which are shown in Table 2. The lower solid was washed to a pH of 7. The washed sample was dried for 4h at 120 ℃ under a nitrogen atmosphere. Weighing 10mL of the dried sample, filling the sample into an atmosphere furnace, continuously introducing hydrogen for treatment, wherein the treatment temperature is 800 ℃, the treatment time is 5h, and the volume ratio of the catalyst to the hydrogen is 1:20, treated sample S-F2 was obtained and submitted for fluorescence analysis, the results of which are shown in Table 3.
Comparative example 3 (without Hydrogen reduction)
After the operation, the deactivated hydrocracking catalyst C-1 (containing 40wt% of Y molecular sieve) discharged oil content of 15.3wt%, and its metal content is shown in Table 1. Weighing 150g of oil-containing catalyst sample, putting the oil-containing catalyst sample into an atmosphere furnace for carbonization reaction, wherein the volume space velocity of nitrogen is 200h under the nitrogen atmosphere -1 The reaction temperature is 700 ℃, and the reaction is carried out for 8 hours at constant temperature. Then 300g ammonium carbonate and 30g polyethylene glycol 1000 are added into water, stirred to be dissolved evenly, mixed gas of water vapor and nitrogen with the volume ratio of 1:1 containing ammonium carbonate and polyethylene glycol 1000 is introduced, the hydrothermal treatment temperature is 800 ℃, and the treatment time is5h, the inlet temperature of the acid-containing water vapor gas is 250 ℃, and the volume space velocity of water is 400h -1 . The treated sample was removed and ground to 150 mesh with colloidal powder. And putting the crushed sample into a beaker, adding 390mL of 10mol/L sodium hydroxide solution, and stirring for sufficient reaction for 30min. And performing liquid-solid separation on the suspension after reaction by adopting a centrifugal machine, wherein the rotating speed of the centrifugal machine is 3500r/min, centrifuging for 10min, and taking out. The upper layer of liquid L-3 was decanted and sent to a sample coupled plasma emission spectrometer ICP for metal analysis, the results of which are shown in Table 2. The lower solid was washed so that the pH of the washing solution was 7. The washed sample was dried at 120 ℃ for 4 hours in a nitrogen atmosphere to obtain a treated sample S-F3, which was subjected to fluorescence analysis, and the results are shown in Table 3.
TABLE 1 deactivated catalyst Metal content (inorganic analysis)
Figure DEST_PATH_IMAGE001
TABLE 2 centrifugal supernatant liquid ICP results
Figure 370188DEST_PATH_IMAGE002
TABLE 3 results of fluorescence analysis of samples
Figure DEST_PATH_IMAGE003
From the above data it can be seen that: after the treatment method is adopted for the deactivated hydrocracking catalyst containing the molecular sieve, the molecular sieve structure is effectively destroyed, aluminum and silicon are effectively recovered, and other metals on the catalyst are also effectively treated to be used as raw materials in the metallurgical industry, so that the discharge of hazardous wastes is reduced, and the deactivated catalyst is changed into valuables.

Claims (28)

1. A treatment process for deactivated hydrogenation catalyst containing molecular sieve, which comprises the following steps:
(1) Carbonizing treatment: in the presence of nitrogen or inert gas, carrying out carbonization treatment on the deactivated hydrogenation catalyst containing the molecular sieve;
(2) Hydrothermal treatment: contacting the carbonized catalyst in the step (1) with vapor-containing gas to perform hydrothermal treatment, wherein the vapor-containing gas simultaneously contains alkali and an auxiliary agent, the alkali is one or more of ammonia water, ammonium carbonate and ammonium bicarbonate, and the auxiliary agent is a high molecular polymer with hydroxyl;
(3) Crushing the catalyst obtained after the treatment in the step (2), mixing the crushed catalyst with an alkaline solution for treatment, further washing and drying the solid obtained after solid-liquid separation, wherein the alkaline solution is an inorganic alkaline solution;
(4) And (4) carrying out high-temperature heat treatment on the material obtained after drying in the step (3) under the condition of hydrogen atmosphere, wherein the temperature of the high-temperature heat treatment is 600-900 ℃, and the treatment time is 3-10 h.
2. The process of claim 1 wherein the deactivated hydrogenation catalyst comprises: the deactivated hydrogenation catalyst containing the molecular sieve in the step (1) refers to a hydrogenation catalyst containing the molecular sieve in a carrier which can not meet the requirements of the original reaction.
3. The process of claim 1 wherein the deactivated hydrogenation catalyst comprises: the deactivated hydrogenation catalyst containing the molecular sieve in the step (1) is a deactivated hydrocracking catalyst.
4. A process according to any one of claims 1 to 3 for the treatment of deactivated hydrogenation catalyst containing molecular sieve, characterized in that: the oil content of the deactivated hydrogenation catalyst containing the molecular sieve in the step (1) is 10-40 wt%.
5. The process according to claim 4, wherein the deactivated hydrogenation catalyst comprises: the oil content of the deactivated hydrogenation catalyst containing the molecular sieve in the step (1) is 10-30 wt%.
6. According to the rightThe process for treating a deactivated hydrogenation catalyst containing a molecular sieve according to claim 1, which comprises the steps of: the carbonization treatment temperature in the step (1) is 700-950 ℃, the treatment time is 4-10 h, and the volume space velocity of nitrogen or inert gas is 100-500 h -1 。
7. The process according to claim 1 or 6, wherein the molecular sieve-containing deactivated hydrogenation catalyst comprises: the carbonization treatment temperature in the step (1) is 700-900 ℃, the treatment time is 3-8 h, and the volume space velocity of nitrogen or inert gas is 100-300 h -1 。
8. The process of claim 1 wherein the molecular sieve-containing deactivated hydrogenation catalyst is prepared by: the auxiliary agent in the step (2) is one or more of polyethylene glycol and polyvinyl alcohol.
9. The process according to claim 1 or 8, wherein the molecular sieve-containing deactivated hydrogenation catalyst comprises: the auxiliary agent in the step (2) is polyethylene glycol, and the molecular weight is 1000-6000.
10. The process of claim 1 wherein the deactivated hydrogenation catalyst comprises: in the step (2), the weight ratio of the alkali to the deactivated hydrogenation catalyst containing the molecular sieve is 2:1-1:5, and the weight ratio of the auxiliary agent to the deactivated hydrogenation catalyst containing the molecular sieve is 1:1-1:5.
11. The process according to claim 1 or 10, wherein the deactivated hydrogenation catalyst comprises: the weight ratio of the alkali to the deactivated hydrogenation catalyst containing the molecular sieve in the step (2) is 1:1-1:3; the weight ratio of the auxiliary agent to the deactivated hydrogenation catalyst containing the molecular sieve is 1:3-1:5.
12. The process of claim 1 wherein the deactivated hydrogenation catalyst comprises: in the step (2), the gas containing water vapor is water vapor or a mixed gas of water vapor and a carrier gas, the carrier gas is nitrogen or an inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.
13. The process of claim 1 wherein the deactivated hydrogenation catalyst comprises: the hydrothermal treatment conditions in the step (2) are that the treatment temperature is 550-900 ℃, the treatment time is 3-10 h, the inlet temperature of the vapor-containing gas is 200-350 ℃, and the water volume space velocity in the hydrothermal treatment process is 150-500 h -1 。
14. The process according to claim 1 or 13, wherein the deactivated hydrogenation catalyst comprises: the hydrothermal treatment conditions in the step (2) are that the treatment temperature is 650-850 ℃, the treatment time is 3-8 h, the inlet temperature of the vapor-containing gas is 250-350 ℃, and the water volume space velocity in the hydrothermal treatment process is 200-450 h -1 。
15. The process of claim 1 wherein the deactivated hydrogenation catalyst comprises: and (3) crushing the catalyst subjected to the hydrothermal treatment in the step (2) to a particle size of more than 150 meshes.
16. The process of claim 1 wherein the deactivated hydrogenation catalyst comprises: and (3) crushing the catalyst subjected to the hydrothermal treatment in the step (2) to a particle size of more than 200 meshes.
17. The process of claim 1 wherein the deactivated hydrogenation catalyst comprises: in the step (3), the alkaline solution is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.
18. A process according to claim 1 or 17 for the treatment of deactivated hydrogenation catalyst containing molecular sieve, characterized in that: and (3) the alkaline solution is sodium hydroxide.
19. The process of claim 1 wherein the molecular sieve-containing deactivated hydrogenation catalyst is prepared by: the concentration of the alkaline solution is 5-15 mol/L.
20. The process according to claim 1 or 19, wherein the molecular sieve-containing deactivated hydrogenation catalyst comprises: the concentration of the alkaline solution is 6.5-15 mol/L.
21. A process according to claim 1 or 19 for the treatment of deactivated hydrogenation catalyst comprising molecular sieve, characterized in that: the concentration of the alkaline solution is 8-12 mol/L.
22. The process of claim 1 wherein the deactivated hydrogenation catalyst comprises: the molar ratio of the waste catalyst to the cations in the alkali in the treatment process of the alkaline solution is 1:0.008 to 0.04.
23. A process according to claim 1 or 22 for the treatment of deactivated hydrogenation catalyst containing molecular sieve, characterized in that: the molar ratio of the waste catalyst to the cations in the alkali in the treatment process of the alkaline solution is 1:0.01 to 0.03.
24. The process of claim 1 wherein the deactivated hydrogenation catalyst comprises: the washing in the step (3) is washing to be neutral by deionized water; the drying is carried out in the presence of nitrogen and/or inert gas, wherein the inert gas is one or more of helium, neon and argon; the drying temperature is 100-180 ℃, and the drying time is 2-8 h.
25. The process according to claim 24, wherein the deactivated hydrogenation catalyst comprises: in the step (3), the drying temperature is 120-150 ℃, and the drying time is 4-6 h.
26. The process of claim 1 wherein the deactivated hydrogenation catalyst comprises: the high-temperature heat treatment temperature in the step (4) is 700-850 ℃, and the treatment time is 3-8 h.
27. The process of claim 1 wherein the deactivated hydrogenation catalyst comprises: the volume ratio of the catalyst to the hydrogen is 1:5 to 20.
28. The process of claim 1 wherein the deactivated hydrogenation catalyst comprises: the volume ratio of the catalyst to the hydrogen is 1:10 to 20.
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