CN117654995A - Ultrasonic pretreatment method for molybdenum-series spent catalyst - Google Patents
Ultrasonic pretreatment method for molybdenum-series spent catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 188
- 238000002203 pretreatment Methods 0.000 title claims abstract description 25
- 239000002699 waste material Substances 0.000 claims abstract description 88
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 80
- 239000011733 molybdenum Substances 0.000 claims abstract description 80
- 238000004140 cleaning Methods 0.000 claims abstract description 43
- 239000011247 coating layer Substances 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 238000001035 drying Methods 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 26
- 238000005237 degreasing agent Methods 0.000 claims description 23
- 239000013527 degreasing agent Substances 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 8
- 238000007667 floating Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 62
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 20
- 229910052759 nickel Inorganic materials 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 229910052720 vanadium Inorganic materials 0.000 description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 11
- 238000000605 extraction Methods 0.000 description 10
- 238000002386 leaching Methods 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 230000010355 oscillation Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000007158 vacuum pyrolysis Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses an ultrasonic pretreatment method of a molybdenum-based waste catalyst, which relates to the technical field of solid waste resource recovery treatment in petrochemical industry, and the ultrasonic pretreatment method of the molybdenum-based waste catalyst is used for cleaning the molybdenum-based waste catalyst through ultrasonic pretreatment, so that an oil content coating layer on the surface of the molybdenum-based waste catalyst can be effectively removed, the oil content of the molybdenum-based waste catalyst is thoroughly removed, and the oil removal rate is more than 99%; realizes harmless oil removal treatment of the molybdenum-series waste catalyst, avoids producing a large amount of harmful substances such as sulfur dioxide, nitrogen oxides, dioxin and the like which are seriously polluted by the atmosphere during high-temperature heating, is environment-friendly, and does not produce secondary pollution.
Description
Technical Field
The invention relates to the technical field of solid waste resource recovery treatment in petrochemical industry, in particular to an ultrasonic pretreatment method for molybdenum-series waste catalyst.
Background
Molybdenum is used as a strategic metal material, and the development and utilization of primary resources and secondary resources are increasingly important as the primary resources of molybdenum ore are reduced year by year due to the large-scale exploitation of molybdenum ore. The inactive molybdenum-series waste catalyst in petrochemical industry is characterized as dangerous waste in China, but is a secondary resource rich in valuable metals such as molybdenum, cobalt, nickel and the like, has higher recovery value, and even part of the waste catalyst has molybdenum content exceeding that of molybdenum ore. The recycling recovery treatment of the molybdenum-series spent catalyst not only carries out harmless treatment on dangerous wastes, but also reduces the harm to the environment; and the valuable metals such as molybdenum and the like are recycled, so that sustainable development of resources is realized. Therefore, the extraction of molybdenum metal from the molybdenum-series spent catalyst is particularly critical, and has remarkable environmental benefit, economic benefit and social benefit.
At present, the research on recovery of valuable metals from molybdenum-based spent catalysts at home and abroad is more, and the main leaching process of the molybdenum-based spent catalysts mainly comprises the following steps: oxidative roasting-alkaline leaching, sodium roasting-water leaching, direct acid leaching, composite leaching and the like. The catalyst which is inactive, such as nickel-molybdenum catalyst, vanadium-molybdenum catalyst and the like, is rich in oil residues, sulfides and carbides with the high content, and the surface of the catalyst is often coated with 10% -20% of oil, so that the catalyst is typical oily hazardous waste, and brings great difficulty to molybdenum recovery in the traditional technologies of oxidative roasting, sodium roasting and the like, and huge environmental protection pressure.
The pretreatment of the molybdenum-based dead catalyst aims at converting and separating harmful substances such as oil and the like on the surface of the dead catalyst, performing harmless treatment and reducing the threat to the environment and human health. The pretreatment method for removing the oil on the surface of the waste catalyst is improper, and harmful gas is easy to generate so as to pollute the atmospheric environment; if the oil on the surface of the waste catalyst is not completely removed, the chemical reaction activity of the waste catalyst in the recovery leaching process is directly affected, so that the recovery reaction efficiency and the recovery rate of valuable metals are adversely affected, and the reutilization capability of the waste catalyst is further affected. Therefore, pretreatment of the molybdenum-series spent catalyst before recovery and extraction is crucial, and is a key link in industrial recycling recovery of the spent catalyst.
Chinese patent CN107915256a discloses a method for preparing high-purity molybdic acid from spent catalyst, which can effectively extract molybdenum from residual oil hydrogenation spent catalyst by deoiling, sodium roasting, leaching, extraction, back extraction and other steps, and obtain molybdic acid with higher purity. The process residual oil hydrogenation catalyst adopts a deoiling furnace (1250-1375 ℃) to carry out deoiling treatment, but the process has the problems of larger energy consumption, long treatment time, low efficiency and easy sublimation and caking of materials under the high-temperature condition.
Chinese patent CN112646977B discloses a method for recovering vanadium, molybdenum, nickel and aluminum from petroleum refining waste catalyst, which adopts a vacuum pyrolysis method to pretreat the waste catalyst and obtain deoiling solid waste and heavy oil under the conditions of pyrolysis temperature of 250-550 ℃ and pyrolysis time of 1-4 hours, but the pretreatment method of the process has the problems of high vacuum equipment requirement, high energy consumption, long treatment time, low efficiency and high cost.
Chinese patent CN113293297B, title: the method does not pretreat the waste catalyst, adds a certain proportion of sodium carbonate into the catalyst, and directly feeds the catalyst into a rotary kiln for high-temperature roasting to generate sodium modification reaction. However, the process can generate a large amount of harmful substances such as sulfur dioxide, nitrogen oxides, dioxin and the like which are serious to atmosphere pollution by direct roasting, is difficult to effectively treat, and has the problems that deoiling is not thorough, and the alkali consumption is multiplied by direct roasting.
In summary, the method for improving the subsequent reuse capacity of the waste catalyst has important practical significance and value, and can ensure that no harmful gas is generated in the pretreatment process of the molybdenum-based waste catalyst.
Disclosure of Invention
The invention aims at: aiming at the problems, the invention provides an ultrasonic pretreatment method for the molybdenum-based waste catalyst, which is used for cleaning the molybdenum-based waste catalyst through ultrasonic pretreatment, so that an oil content coating layer on the surface of the molybdenum-based waste catalyst can be effectively removed, the oil content of the molybdenum-based waste catalyst is thoroughly removed, and the oil removal rate is more than 99%.
The technical scheme adopted by the invention is as follows:
an ultrasonic pretreatment method for molybdenum-series spent catalyst comprises the following steps:
raw material preparation: weighing a certain amount of molybdenum-series spent catalyst containing metallic element Mo as a raw material;
pretreatment preparation: opening an ultrasonic cleaner, injecting clear water into a cleaning tank of the ultrasonic cleaner, adding an ethyl acetate degreasing agent, uniformly stirring, and heating the clear water in the cleaning tank to a preset temperature;
ultrasonic pretreatment: placing the molybdenum-based spent catalyst into a cleaning tank, pretreating with ultrasonic waves, peeling a coating layer from the surface of the molybdenum-based spent catalyst, and adsorbing the coating layer into an oil removing agent; the molybdenum-based spent catalyst from which the coating layer was removed was obtained.
Further, also comprises
And (3) cleaning and rinsing: the ethyl acetate degreasing agent floats on the water surface after absorbing oil, so that floating oil is removed, the molybdenum-series waste catalyst pretreated by ultrasonic waves is transferred to a clean water tank for at least one rinsing, and the coating layer residue on the surface of the molybdenum-series waste catalyst is removed.
Further, also comprises
Drying and dehumidifying: and drying the rinsed molybdenum-series spent catalyst to obtain dry oil-free molybdenum-series spent catalyst particles.
Further, also comprises
Crushing: and crushing the molybdenum-series spent catalyst subjected to the drying treatment, and sieving the crushed molybdenum-series spent catalyst with a 60-mesh sieve to obtain the molybdenum-series spent catalyst pretreatment material which is fine and uniform in granularity and is dry and oil-free.
Further, the drying temperature is 60-80 ℃ and the drying time is 2-4 hours.
Further, in the pretreatment preparation step, the preset temperature is 50-60 degrees.
Further, in the pretreatment preparation step, when the water temperature is raised to 40 ℃, a certain amount of ethyl acetate degreasing agent is added according to the weighed amount of the molybdenum-based spent catalyst. Can effectively avoid the premature addition of the ethyl acetate degreasing agent and volatilize in the heating process.
Further, in the pretreatment preparation step, the molybdenum-based spent catalyst and the ethyl acetate degreasing agent are arranged according to a solid-liquid mass ratio of 20-25:1.
Further, in the pretreatment preparation step, the ultrasonic frequency of an ultrasonic cleaner is set to be 20-40KHz, the cleaning power is set to be 12-20KW, the cleaning power is too low, the ultrasonic energy is insufficient to thoroughly peel off the coating layer on the surface of the molybdenum-based spent catalyst, and the cleaning effect of the molybdenum-based spent catalyst is poor; the excessive cleaning power can lead to the rise of the temperature of clean water environment in a cleaning pool and accelerate the volatilization of the degreasing agent, thereby affecting the cleaning effect of the molybdenum-series dead catalyst, and on the other hand, the excessive power also causes unnecessary waste of energy sources; in the ultrasonic pretreatment step, the ultrasonic pretreatment time is 10-15min.
Further, a material washing net frame is arranged in the washing tank, and the mesh of the material washing net frame is smaller than the granularity of the molybdenum-series spent catalyst.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. the invention can effectively remove the oil content coating layer on the surface of the molybdenum-based waste catalyst by ultrasonic pretreatment, the oil content of the molybdenum-based waste catalyst is thoroughly removed, and the oil removal rate is more than 99%.
2. The invention realizes harmless oil removal treatment of the molybdenum-series dead catalyst, avoids a large amount of harmful substances such as sulfur dioxide, nitrogen oxides, dioxin and the like which are seriously polluted by the atmosphere during high-temperature heating, is environment-friendly, and does not produce secondary pollution.
3. The molybdenum-series spent catalyst pretreated by ultrasonic waves can be suitable for various subsequent recovery leaching processes. The selection of the recovery processes can be carried out according to the specific components and properties of the molybdenum-based spent catalyst, so that the comprehensive utilization of the molybdenum-based spent catalyst is realized.
4. The ultrasonic degreasing pretreatment method can also obviously reduce the alkali consumption in the subsequent extraction process, thereby greatly reducing the production cost of enterprises.
5. The invention has simple operation in the treatment process, strong practicability, low price of cleaning equipment and production lines and convenient purchase; the degreasing agent is low in price, safe and harmless, and can realize clean, low-consumption and high-efficiency production of the pretreatment of the molybdenum-series waste catalyst.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
An ultrasonic pretreatment method for molybdenum-series spent catalyst comprises the following steps:
raw material preparation: 200kg of molybdenum-series waste catalyst containing metallic element Mo is weighed as a raw material, the appearance of the molybdenum-series waste catalyst is black, cylindrical, the particle size phi is 1 multiplied by 2mm, the molybdenum-series waste catalyst contains 12.2% of oil, 30.98% of aluminum, 10.13% of molybdenum, 9.2% of vanadium and 6.2% of nickel, wherein the aluminum exists in the form of oxide, and the molybdenum, the vanadium and the nickel exist in the form of sulfide;
pretreatment preparation: opening an ultrasonic cleaner, setting the ultrasonic frequency of the ultrasonic cleaner to be 28KHz, the cleaning power to be 20KW, injecting clean water into a cleaning tank of the ultrasonic cleaner, heating the clean water in the cleaning tank to a preset temperature of 60 ℃ according to a solid-liquid mass ratio of 20:1, adding 10kg of ethyl acetate degreasing agent into the cleaning tank of the industrial ultrasonic cleaner when the water temperature is raised to 40 ℃, and uniformly stirring;
ultrasonic pretreatment: placing a plurality of stainless steel washing net frames with the same specification into a washing tank, then loading 200kg of molybdenum-series waste catalyst into the washing net frame once, wherein the mesh of the washing net frame is smaller than the granularity of the molybdenum-series waste catalyst, ensuring that the molybdenum-series waste catalyst does not fall off from the mesh, pretreating for 10min by ultrasonic waves, and breaking an oil-containing coating layer on the surface of the molybdenum-series waste catalyst by high-frequency oscillation of the ultrasonic waves, so that the coating layer is peeled off from the surface of the molybdenum-series waste catalyst and is adsorbed into an oil remover; on the other hand, the movement of water molecules on the surface of the molybdenum-based spent catalyst is accelerated, the separation of the water molecules and the coating layer is promoted, and the oil removal rate of the molybdenum-based spent catalyst is improved; obtaining a molybdenum-based spent catalyst from which the coating layer is removed;
and (3) cleaning and rinsing: the ethyl acetate degreasing agent floats on the water surface after absorbing oil, so that floating oil is removed, the molybdenum-series waste catalyst subjected to ultrasonic pretreatment is transferred to a clean water tank for primary rinsing, and the coating layer residue on the surface of the molybdenum-series waste catalyst is removed;
drying and dehumidifying: placing the rinsed molybdenum-series spent catalyst into a steam drying room for drying at the drying temperature of 70 ℃ for 3 hours to obtain dry oil-free molybdenum-series spent catalyst particles;
crushing: and (3) crushing the molybdenum-series spent catalyst subjected to the drying treatment by using a ball mill to 60 meshes, and sieving to obtain a molybdenum-series spent catalyst pretreatment material which is fine and uniform in granularity and is free of oil and is dried, and carrying out a molybdenum extraction process for the subsequent use. After ultrasonic pretreatment by the method, the oil content of the molybdenum-series waste catalyst is detected, and the oil removal rate of the molybdenum-series waste catalyst is 99.5%.
Example 2
An ultrasonic pretreatment method for molybdenum-series spent catalyst comprises the following steps:
raw material preparation: 200kg of molybdenum-series waste catalyst containing metallic element Mo is weighed as a raw material, the appearance is black, the strip shape, the grain diameter phi is 1.2 multiplied by 2cm, the waste catalyst contains 12.4 percent of oil, 27.4 percent of aluminum, 13.8 percent of molybdenum, 6.5 percent of vanadium and 4.3 percent of nickel, wherein the aluminum exists in the form of oxide, and the molybdenum, the vanadium and the nickel exist in the form of sulfide;
pretreatment preparation: opening an ultrasonic cleaner, setting the ultrasonic frequency of the ultrasonic cleaner to be 28KHz, the cleaning power to be 18KW, injecting clean water into a cleaning tank of the ultrasonic cleaner, heating clean water in the cleaning tank to a preset temperature of 55 ℃ according to a solid-liquid mass ratio of 22.2:1 by using a molybdenum-based dead catalyst to an ethyl acetate degreasing agent, adding 9kg of the ethyl acetate degreasing agent into the cleaning tank of the industrial ultrasonic cleaner when the water temperature is raised to 40 ℃, and uniformly stirring;
ultrasonic pretreatment: placing a stainless steel washing net frame into a washing tank, then loading 200kg of molybdenum-series waste catalyst into the washing net frame at a time, wherein the mesh size of the washing net frame is smaller than that of the molybdenum-series waste catalyst, ensuring that the molybdenum-series waste catalyst does not fall off from the mesh, pretreating for 12min by ultrasonic waves, and breaking an oil-containing coating layer on the surface of the molybdenum-series waste catalyst by high-frequency oscillation of the ultrasonic waves, so that the coating layer is peeled off from the surface of the molybdenum-series waste catalyst and is adsorbed into an oil remover; on the other hand, the movement of water molecules on the surface of the molybdenum-based spent catalyst is accelerated, the separation of the water molecules and the coating layer is promoted, and the oil removal rate of the molybdenum-based spent catalyst is improved; obtaining a molybdenum-based spent catalyst from which the coating layer is removed;
and (3) cleaning and rinsing: the ethyl acetate degreasing agent floats on the water surface after absorbing oil, so that floating oil is removed, the molybdenum-series waste catalyst subjected to ultrasonic pretreatment is transferred to a clean water tank for primary rinsing, and the coating layer residue on the surface of the molybdenum-series waste catalyst is removed;
drying and dehumidifying: placing the rinsed molybdenum-series spent catalyst into a steam drying room for drying at the drying temperature of 70 ℃ for 3 hours to obtain dry oil-free molybdenum-series spent catalyst particles;
crushing: and (3) crushing the molybdenum-series spent catalyst subjected to the drying treatment by using a ball mill to 60 meshes, and sieving to obtain a molybdenum-series spent catalyst pretreatment material which is fine and uniform in granularity and is free of oil and is dried, and carrying out a molybdenum extraction process for the subsequent use. After ultrasonic pretreatment by the method, the oil content of the molybdenum-series waste catalyst is detected, and the oil removal rate of the molybdenum-series waste catalyst is 99.3 percent.
Example 3
An ultrasonic pretreatment method for molybdenum-series spent catalyst comprises the following steps:
raw material preparation: 200kg of molybdenum-series waste catalyst containing metallic element Mo is weighed as a raw material, the appearance is black, spherical, the grain diameter phi is 1.3 multiplied by 5mm, the waste catalyst contains 11.8 percent of oil, 28.6 percent of aluminum, 13.5 percent of molybdenum, 7.5 percent of vanadium and 6.2 percent of nickel, wherein the aluminum exists in the form of oxide, and the molybdenum, the vanadium and the nickel exist in the form of sulfide;
pretreatment preparation: opening an ultrasonic cleaner, setting the ultrasonic frequency of the ultrasonic cleaner to be 28KHz, the cleaning power to be 16KW, injecting clean water into a cleaning tank of the ultrasonic cleaner, heating clean water in the cleaning tank to a preset temperature of 58 ℃ according to a solid-liquid mass ratio of 23.5:1, adding 8.5kg of ethyl acetate degreasing agent into the cleaning tank of the industrial ultrasonic cleaner when the water temperature is raised to 40 ℃, and uniformly stirring;
ultrasonic pretreatment: placing a stainless steel washing net frame into a washing tank, then loading 200kg of molybdenum-series waste catalyst into the washing net frame at a time, wherein the mesh size of the washing net frame is smaller than that of the molybdenum-series waste catalyst, ensuring that the molybdenum-series waste catalyst does not fall off from the mesh, pretreating for 14min by ultrasonic waves, and breaking an oil-containing coating layer on the surface of the molybdenum-series waste catalyst by high-frequency oscillation of the ultrasonic waves, so that the coating layer is peeled off from the surface of the molybdenum-series waste catalyst and is adsorbed into an oil remover; on the other hand, the movement of water molecules on the surface of the molybdenum-based spent catalyst is accelerated, the separation of the water molecules and the coating layer is promoted, and the oil removal rate of the molybdenum-based spent catalyst is improved; obtaining a molybdenum-based spent catalyst from which the coating layer is removed;
and (3) cleaning and rinsing: the ethyl acetate degreasing agent floats on the water surface after absorbing oil, so that floating oil is removed, the molybdenum-series waste catalyst subjected to ultrasonic pretreatment is transferred to a clean water tank for primary rinsing, and the coating layer residue on the surface of the molybdenum-series waste catalyst is removed;
drying and dehumidifying: placing the rinsed molybdenum-series spent catalyst into a steam drying room for drying at the drying temperature of 70 ℃ for 3 hours to obtain dry oil-free molybdenum-series spent catalyst particles;
crushing: and (3) crushing the molybdenum-series spent catalyst subjected to the drying treatment by using a ball mill to 60 meshes, and sieving to obtain a molybdenum-series spent catalyst pretreatment material which is fine and uniform in granularity and is free of oil and is dried, and carrying out a molybdenum extraction process for the subsequent use. After ultrasonic pretreatment by the method, the oil content of the molybdenum-series waste catalyst is detected, and the oil removal rate of the molybdenum-series waste catalyst is 99.6%.
Example 4
An ultrasonic pretreatment method for molybdenum-series spent catalyst comprises the following steps:
raw material preparation: 200kg of molybdenum-series waste catalyst containing metallic element Mo is weighed as a raw material, the appearance is black, the cylinder shape and the grain diameter phi 1.5 multiplied by 2cm, the waste catalyst contains 15.2 percent of oil, 26.8 percent of aluminum, 10.5 percent of molybdenum, 8.7 percent of vanadium and 5.4 percent of nickel, wherein the aluminum exists in the form of oxide, and the molybdenum, the vanadium and the nickel exist in the form of sulfide;
pretreatment preparation: opening an ultrasonic cleaner, setting the ultrasonic frequency of the ultrasonic cleaner to be 28KHz and the cleaning power to be 12KW, injecting clean water into a cleaning tank of the ultrasonic cleaner, heating clean water in the cleaning tank to a preset temperature of 50 ℃ according to a solid-liquid mass ratio of 25:1 by using a molybdenum-based dead catalyst to an ethyl acetate degreasing agent, adding 8kg of the ethyl acetate degreasing agent into the cleaning tank of the industrial ultrasonic cleaner when the water temperature is raised to 40 ℃, and uniformly stirring;
ultrasonic pretreatment: placing a stainless steel washing net frame into a washing tank, then loading 200kg of molybdenum-series waste catalyst into the washing net frame at a time, wherein the mesh size of the washing net frame is smaller than that of the molybdenum-series waste catalyst, ensuring that the molybdenum-series waste catalyst does not fall off from the mesh, pretreating for 15min by ultrasonic waves, and breaking an oil-containing coating layer on the surface of the molybdenum-series waste catalyst by high-frequency oscillation of the ultrasonic waves, so that the coating layer is peeled off from the surface of the molybdenum-series waste catalyst and is adsorbed into an oil remover; on the other hand, the movement of water molecules on the surface of the molybdenum-based spent catalyst is accelerated, the separation of the water molecules and the coating layer is promoted, and the oil removal rate of the molybdenum-based spent catalyst is improved; obtaining a molybdenum-based spent catalyst from which the coating layer is removed;
and (3) cleaning and rinsing: the ethyl acetate degreasing agent floats on the water surface after absorbing oil, so that floating oil is removed, the molybdenum-series waste catalyst subjected to ultrasonic pretreatment is transferred to a clean water tank for primary rinsing, and the coating layer residue on the surface of the molybdenum-series waste catalyst is removed;
drying and dehumidifying: placing the rinsed molybdenum-series spent catalyst into a steam drying room for drying at the drying temperature of 70 ℃ for 3 hours to obtain dry oil-free molybdenum-series spent catalyst particles;
crushing: and (3) crushing the molybdenum-series spent catalyst subjected to the drying treatment by using a ball mill to 60 meshes, and sieving to obtain a molybdenum-series spent catalyst pretreatment material which is fine and uniform in granularity and is free of oil and is dried, and carrying out a molybdenum extraction process for the subsequent use. After ultrasonic pretreatment by the method, the oil content of the molybdenum-series waste catalyst is detected, and the oil removal rate of the molybdenum-series waste catalyst is 99.2%.
Example 5
An ultrasonic pretreatment method for molybdenum-series spent catalyst comprises the following steps:
raw material preparation: 200kg of molybdenum-series waste catalyst containing metallic element Mo is weighed as a raw material, the appearance is black, the cylinder shape and the grain diameter phi 2.0 multiplied by 3cm, the waste catalyst contains 13.1 percent of oil, 21.8 percent of aluminum, 12.2 percent of molybdenum, 6.7 percent of vanadium and 5.7 percent of nickel, wherein the aluminum exists in the form of oxide, and the molybdenum, the vanadium and the nickel exist in the form of sulfide;
pretreatment preparation: opening an ultrasonic cleaner, setting the ultrasonic frequency of the ultrasonic cleaner to be 28KHz, the cleaning power to be 14KW, injecting clean water into a cleaning tank of the ultrasonic cleaner, heating the clean water in the cleaning tank to a preset temperature of 53 ℃ according to a solid-liquid mass ratio of 25:1, adding 8kg of ethyl acetate degreasing agent into the cleaning tank of the industrial ultrasonic cleaner when the water temperature is raised to 40 ℃, and uniformly stirring;
ultrasonic pretreatment: placing a stainless steel washing net frame into a washing tank, then loading 200kg of molybdenum-series waste catalyst into the washing net frame at a time, wherein the mesh size of the washing net frame is smaller than that of the molybdenum-series waste catalyst, ensuring that the molybdenum-series waste catalyst does not fall off from the mesh, pretreating for 15min by ultrasonic waves, and breaking an oil-containing coating layer on the surface of the molybdenum-series waste catalyst by high-frequency oscillation of the ultrasonic waves, so that the coating layer is peeled off from the surface of the molybdenum-series waste catalyst and is adsorbed into an oil remover; on the other hand, the movement of water molecules on the surface of the molybdenum-based spent catalyst is accelerated, the separation of the water molecules and the coating layer is promoted, and the oil removal rate of the molybdenum-based spent catalyst is improved; obtaining a molybdenum-based spent catalyst from which the coating layer is removed;
and (3) cleaning and rinsing: the ethyl acetate degreasing agent floats on the water surface after absorbing oil, so that floating oil is removed, the molybdenum-series waste catalyst subjected to ultrasonic pretreatment is transferred to a clean water tank for primary rinsing, and the coating layer residue on the surface of the molybdenum-series waste catalyst is removed;
drying and dehumidifying: placing the rinsed molybdenum-series spent catalyst into a steam drying room for drying at the drying temperature of 70 ℃ for 3 hours to obtain dry oil-free molybdenum-series spent catalyst particles;
crushing: and (3) crushing the molybdenum-series spent catalyst subjected to the drying treatment by using a ball mill to 60 meshes, and sieving to obtain a molybdenum-series spent catalyst pretreatment material which is fine and uniform in granularity and is free of oil and is dried, and carrying out a molybdenum extraction process for the subsequent use. After ultrasonic pretreatment by the method, the oil content of the molybdenum-series waste catalyst is detected, and the oil removal rate of the molybdenum-series waste catalyst is 99.4%.
The principles and embodiments of the present invention have been described herein with reference to specific examples, which are intended to be merely illustrative of the methods of the present invention and their core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (10)
1. The ultrasonic pretreatment method of the molybdenum-series spent catalyst is characterized by comprising the following steps:
raw material preparation: weighing a certain amount of molybdenum-series spent catalyst containing metallic element Mo as a raw material;
pretreatment preparation: opening an ultrasonic cleaner, injecting clear water into a cleaning tank of the ultrasonic cleaner, adding an ethyl acetate degreasing agent, uniformly stirring, and heating the clear water in the cleaning tank to a preset temperature;
ultrasonic pretreatment: placing the molybdenum-based spent catalyst into a cleaning tank, pretreating with ultrasonic waves, peeling a coating layer from the surface of the molybdenum-based spent catalyst, and adsorbing the coating layer into an oil removing agent; the molybdenum-based spent catalyst from which the coating layer was removed was obtained.
2. The ultrasonic pretreatment method for the molybdenum-based spent catalyst according to claim 1, further comprising
And (3) cleaning and rinsing: the ethyl acetate degreasing agent floats on the water surface after absorbing oil, so that floating oil is removed, the molybdenum-series waste catalyst pretreated by ultrasonic waves is transferred to a clean water tank for at least one rinsing, and the coating layer residue on the surface of the molybdenum-series waste catalyst is removed.
3. The ultrasonic pretreatment method for the molybdenum-based spent catalyst according to claim 2, further comprising
Drying and dehumidifying: and drying the rinsed molybdenum-series spent catalyst to obtain dry oil-free molybdenum-series spent catalyst particles.
4. The ultrasonic pretreatment method for molybdenum-based spent catalyst as defined in claim 3, further comprising
Crushing: and crushing the molybdenum-series spent catalyst subjected to the drying treatment to 60 meshes, and sieving to obtain the molybdenum-series spent catalyst pretreatment material which is fine and uniform in granularity and is dry and oil-free.
5. The ultrasonic pretreatment method of the molybdenum-series spent catalyst as defined in claim 3, wherein the drying temperature is 60-80 ℃ and the drying time is 2-4h.
6. The ultrasonic pretreatment method for molybdenum-based spent catalyst according to claim 1, wherein the preset temperature is 50 to 60 degrees in the pretreatment preparation step.
7. The ultrasonic pretreatment method for a molybdenum-based spent catalyst according to claim 6, wherein a certain amount of ethyl acetate degreasing agent is added according to the weighed amount of the molybdenum-based spent catalyst when the water temperature is raised to 40 ℃ in the pretreatment preparation step.
8. The ultrasonic pretreatment method for molybdenum-based spent catalyst according to claim 7, wherein in the pretreatment preparation step, the molybdenum-based spent catalyst and the ethyl acetate degreasing agent are provided at a solid-liquid mass ratio of 20-25:1.
9. The ultrasonic pretreatment method of molybdenum-based spent catalyst according to claim 1, characterized in that in the pretreatment preparation step, the ultrasonic frequency of an ultrasonic cleaner is set to be 20-40KHz and the cleaning power is set to be 12-20KW; in the ultrasonic pretreatment step, the ultrasonic pretreatment time is 10-15min.
10. The ultrasonic pretreatment method for the molybdenum-based spent catalyst according to claim 1, wherein a material washing net frame is arranged in the washing tank, and the mesh of the material washing net frame is smaller than the granularity of the molybdenum-based spent catalyst.
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