CN111112295A - Pretreatment method and system for waste catalyst containing precious metal - Google Patents
Pretreatment method and system for waste catalyst containing precious metal Download PDFInfo
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- CN111112295A CN111112295A CN201911377326.5A CN201911377326A CN111112295A CN 111112295 A CN111112295 A CN 111112295A CN 201911377326 A CN201911377326 A CN 201911377326A CN 111112295 A CN111112295 A CN 111112295A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 239000002699 waste material Substances 0.000 title claims abstract description 31
- 238000002203 pretreatment Methods 0.000 title claims abstract description 18
- 239000010970 precious metal Substances 0.000 title abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 39
- 239000007795 chemical reaction product Substances 0.000 claims description 76
- 239000007788 liquid Substances 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- 238000006243 chemical reaction Methods 0.000 claims description 57
- 230000009467 reduction Effects 0.000 claims description 43
- 239000002893 slag Substances 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 40
- 238000000926 separation method Methods 0.000 claims description 37
- 238000009284 supercritical water oxidation Methods 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 21
- 239000000498 cooling water Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- 239000007791 liquid phase Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 238000004080 punching Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 238000000605 extraction Methods 0.000 abstract description 12
- 238000011084 recovery Methods 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000003860 storage Methods 0.000 description 9
- 239000006200 vaporizer Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
-
- 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
-
- 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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- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention provides a pretreatment method and a pretreatment system for a waste catalyst containing noble metals, belonging to the technical field of waste catalyst treatment. The pretreatment method can be carried out by a pretreatment system of a spent catalyst containing a noble metal. The pretreatment method and the system for the waste catalyst containing the precious metals improve the extraction amount of ash, are beneficial to improving the recovery rate of the following precious metals, and simultaneously have cleaner emissions.
Description
Technical Field
The invention belongs to the technical field of waste catalyst treatment, and particularly relates to a pretreatment method and a pretreatment system for a waste catalyst containing precious metals.
Background
In the preparation process of the catalyst, in order to ensure the performance of the catalyst such as activity, selectivity, toxicity resistance, service life and the like, some noble metals are often added as active components. Common noble metals include gold (Au), silver (Ag), ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (I t), with the platinum group metals (Pt, Pd, Rh) being widely used in catalysts for hydrogenation, oxidation, dehydrogenation, hydrogenolysis, ammonia synthesis, methanol synthesis, hydrocarbon synthesis, hydroformylation, and carbonylation, among others. Although the morphology, structure and amount of certain components of the catalyst change during the use process, the waste catalyst still contains a considerable amount of noble metals, and if the noble metals are recovered, the resource utilization rate is improved, and the environmental problems caused by the catalyst are reduced.
At present, before the recovery of a waste catalyst containing noble metals such as silver, platinum and rhodium, the waste catalyst needs to be pretreated to obtain an organic mixture containing the noble metals, and the organic mixture is treated to extract the noble metals. The prior method adopts methods such as a high-temperature volatilization method, a pyrogenic process smelting method, a combustion method and the like to pretreat the waste catalyst and extract noble metals. In the three methods, high-temperature flue gas and dust are generated in the pretreatment process of the waste catalyst, part of precious metals in the waste catalyst are carried out of the system by the flue gas, the subsequent precious metal recovery rate is low, and the generated dust can cause adverse effects on the environment.
Disclosure of Invention
The invention aims to provide a pretreatment method and a pretreatment system for a waste catalyst containing precious metals, and aims to solve the problems that the recovery rate of the precious metals is low and dust generated in the reaction process causes adverse effects on the environment in the conventional method.
In order to achieve the purpose, the invention adopts the technical scheme that: provided are a pretreatment method and a system for a waste catalyst containing noble metal, comprising the following steps:
mixing the waste catalyst with an oxygen source, and then sending the mixture into a reactor filled with supercritical water to carry out supercritical water oxidation reaction, wherein the temperature of a reaction zone of the reactor is controlled to be 600-750 ℃, and the pressure in the reaction zone is more than or equal to 23 MPa;
cooling reaction products of the supercritical water oxidation reaction and then discharging the reaction products out of the reactor, wherein the reaction products of the supercritical water oxidation reaction are divided into a first group of reaction products and a second group of reaction products, the first group of reaction products comprise solid particles and a part of slag water, the second group of reaction products comprise gas and the other part of slag water, the settled first group of reaction products are periodically collected, and the second group of reaction products are subjected to gas-liquid separation;
and carrying out solid-liquid separation on the solid-liquid mixture obtained by gas-liquid separation of the first group of reaction products and the second group of reaction products.
As a further embodiment of the present application, the temperature in the reaction zone of the reactor is controlled between 600 ℃ and 750 ℃ by means of a temperature-regulating substance.
As another embodiment of the present application, the temperature regulating substance is cold water and methanol, and when the temperature of the reaction zone is higher than 750 ℃, the cold water is added into the reaction zone; when the temperature in the reaction zone is below 600 ℃, methanol is added to the reaction zone.
As another example of the present application, the spent catalyst is ground and mixed with water to form a slurry, and the slurry is mixed with an oxygen source, which is liquid oxygen, and then fed into the reactor.
In another embodiment of the present invention, the slurry and the liquid oxygen are mixed together after the pressure is increased, and the pressure of the slurry and the pressure of the liquid oxygen are both increased to 25MPa or more.
As another embodiment of the application, the reaction product of the supercritical water oxidation reaction is chilled by cooling water to be cooled, the temperature is lower than 300 ℃, and the pressure is reduced to 20-23 MPa.
As another embodiment of the present application, the second group of reaction products are subjected to gas-liquid separation by depressurization treatment.
As another embodiment of the present application, the depressurization treatment includes a first depressurization treatment and a second depressurization treatment, the pressure of the second group of reaction products is reduced to 5.5-6.5MPa after the first depressurization treatment, and the second group of reaction products are separated to obtain a first gas-phase mixture and a liquid-phase mixture; and (3) carrying out secondary pressure reduction treatment on the liquid phase mixture, reducing the pressure of the liquid phase mixture to be below 0.3MPa after the secondary pressure reduction treatment, and separating to obtain a solid-liquid mixture.
The technical scheme adopted by the invention is as follows: the pretreatment system comprises a reactor, a temperature adjusting part, a slag water discharging part, a temperature reducing part and a pressure reducing part, wherein the reactor is used for carrying out supercritical water oxidation reaction on the waste catalyst, the reactor is connected with a nozzle, and slurry prepared from the waste catalyst and an oxygen source are mixed by the nozzle and then enter the reactor; the temperature adjusting part is provided with a temperature adjusting pipeline which is connected with the nozzle and used for conveying cold water or methanol to the reactor; the slag water removing part is provided with a lock hopper and a slag water tank, the slag water removing part is used for collecting the first group of reaction products, one end of the lock hopper is connected with the reactor, and the other end of the lock hopper is connected with the slag water tank; the cooling part is provided with a water-cooling protection pipeline for conveying cooling water, and the water-cooling protection pipeline is connected with the reactor and is used for controlling the temperature of the shell of the reactor and cooling reaction products of the supercritical water oxidation reaction; the pressure reduction part is connected with the reactor and is used for carrying out pressure reduction treatment on the cooled second group of reaction products.
As another embodiment of this application, sediment water gets rid of the portion and includes the punching press pipeline, and punching press pipeline and water-cooling protection pipeline all link to each other with the lock fill, and punching press pipeline and water-cooling protection pipeline cooperation are to lock fill pressure boost, and the punching press pipeline is used for to lock fill transport nitrogen gas pressure boost, and lock fill one end links to each other with the reactor through first control valve, and the other end passes through the second control valve and links to each other with the sediment water tank.
The pretreatment method of the waste catalyst containing the noble metal has the beneficial effects that: compared with the prior art, the pretreatment method of the waste catalyst containing noble metal utilizes supercritical water oxidation reaction to carry out oxidation treatment on the waste catalyst containing noble metal, the temperature of a reaction zone of a reactor is controlled to be 600-750 ℃, the pressure in the reaction zone is more than or equal to 23MPa, a reaction product after the supercritical water oxidation reaction falls to the bottom of the reactor, in order to ensure that the shell of the reactor is in a safe temperature range, the temperature of the shell of the reactor is lower, the reaction product is cooled at the bottom of the reactor, the reaction product comprises a solid shell, slag water mixed with slag ash and gas mixed with partial slag ash, the noble metal is contained in the slag ash, solid particles are separated from the gas mixed with partial slag ash through the weight effect to form a first group of reaction products and a second group of reaction products, the first group of reaction products can obtain the slag ash through direct solid-liquid separation, the second group of reaction products can extract slag ash after gas-liquid separation and solid-liquid separation in sequence, and the slag ash has large recovery amount and high purity, so that the purity of noble metal can be directly extracted from the slag ash in the subsequent step. Obtain the lime-ash through supercritical water oxidation reaction to accurate control reaction temperature, supercritical water oxidation reaction carry out the progress separation to the reaction product, make the extraction volume of lime-ash rise, more be favorable to the improvement of noble metal extraction rate, have protected the environment.
The pretreatment system of the waste catalyst containing the precious metal has the beneficial effects that: compared with the prior art, set up the reactor and carry out supercritical water oxidation reaction, control reaction temperature through the portion that adjusts the temperature, set up sediment water discharge portion, cooling portion, step-down portion, further separate the reaction product of supercritical water oxidation reaction for the extraction volume of lime-ash rises, is favorable to the noble metal extraction rate to rise, and the gas of simultaneously discharging is cleaner, is favorable to the protection of environment.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed for the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic structural view of a pretreatment system for a spent catalyst containing a noble metal according to an embodiment of the present invention.
In the figure: 1. a slurry storage tank; 2. a high pressure diaphragm pump; 3. a reactor; 4. a slag discharge lock hopper; 5. a slag water tank; 6. a first pressure reducing orifice plate; 7. a high pressure separation tank; 8. a gas phase pressure reducing valve; 9. a second pressure reducing orifice plate; 10. a low pressure knockout drum; 11. a cooling water tank; 12. a high pressure water pump; 13. a calorific value adjusting tank; 14. a high pressure pump; 15. a liquid oxygen tank; 16. a liquid oxygen pump; 17. a liquid oxygen vaporizer; 18. a liquid nitrogen tank; 19. a liquid nitrogen pump; 20. a liquid nitrogen vaporizer.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The supercritical water oxidation technology is a novel oxidation technology which can thoroughly destroy the structure of organic pollutants. Under the supercritical state (temperature > 374.3 deg.C and pressure > 22.1MPa), the interface between liquid phase and gas phase disappears, oxygen can be dissolved in any proportion, and the problem of substance movement between gas phase and liquid phase interface does not exist, so that an ideal oxidation reaction environment is provided. The reactor 3 is a core device in the supercritical water oxidation technology, the reactor 3 comprises a shell and a reaction furnace, and the reaction area of the reactor 3 is the reaction furnace.
Example 1
A catalyst containing noble metal Pt, wherein the weight percentage of Pt in the catalyst is 25%.
Grinding catalyst particles, mixing the ground catalyst particles with water to form slurry with the mass concentration of 10%, stirring a slurry storage tank 1 for storing the slurry, placing the particles for sedimentation, raising the pressure of the slurry in the slurry storage tank 1 to 25MPa through a high-pressure diaphragm pump 2, raising the pressure of liquid oxygen to 25MPa through a high-pressure liquid oxygen pump 16 and a vaporizer, and mixing the slurry and high-pressure oxygen at a nozzle to enter a supercritical water oxidation reactor 3. And detecting the temperature in the hearth of the reaction furnace, and controlling the temperature at 680 ℃.
The supercritical water oxidation reaction is an exothermic reaction, when the reaction temperature is detected to exceed 680 ℃, cold water is sent to a hearth of the reactor 3 through a high-pressure pump 14, and the temperature of the hearth is reduced to 680 ℃; when the reaction temperature is detected to be less than 680 ℃, the methanol water is sent to the furnace of the reactor 3 by the high-pressure pump 14.
Reaction products of the supercritical water oxidation reaction enter the shell of the reactor 3 from the discharge hole of the hearth, cooling water is conveyed to the reactor 3 in the shell of the reactor 3 to control the temperature of the reactor 3, the chilling temperature of the reaction products at the bottom of the reactor 3 is reduced to 260 ℃ through the cooling water, and the pressure is 22 MPa. The first group of reaction products are discharged out of the reactor 3 and directly collected due to the action of gravity, and the second group of reaction products are subjected to gas-liquid separation.
The second group of reaction products are firstly subjected to first pressure reduction treatment, the pressure is reduced to 6MPa, and a first gas phase mixture obtained by the first pressure reduction treatment contains CO2And water vapor and small amounts of O2The first gas phase mixture is directly discharged after being depressurized. The liquid phase mixture obtained after the first pressure reduction treatment contains most of water and a small part of CO dissolved in water2And a small amount of ash and slag carried out in the reaction system.
Subjecting the liquid phase mixture to a second pressure reduction treatment to reduce the pressure to 0.3MPa, thereby reducing the pressure of water vapor and CO2And separating the slag water from the gas, directly discharging the gas, wherein the slag water is a solid-liquid mixture obtained by the second pressure reduction treatment.
And carrying out solid-liquid separation on the solid-liquid mixture obtained by gas-liquid separation of the first group of reaction products and the second group of reaction products.
The first group of reaction products and the solid-liquid mixture are subjected to solid-liquid separation through sedimentation, suspended particles floating on the liquid are subjected to solid-liquid separation through filtration, and clear liquid obtained through solid-liquid separation can be recycled and mixed with the catalyst.
The ash obtained after the pretreatment is subjected to the noble metal extraction by methods such as a chemical displacement method, and the recovery rate of the noble metal reaches 92%. The extraction amount of the ash slag is increased, so that the extraction rate of the precious metals is improved, the other discharged materials do not contain the entrained precious metals, the environmental protection is facilitated, the clear liquid of the solid-liquid separation is recycled, and the waste of resources is avoided.
Example 2
A catalyst containing noble metal Pd, wherein the weight percentage of Pd in the catalyst is 20%.
Grinding catalyst particles, mixing the ground catalyst particles with water to form slurry with the mass concentration of 15%, stirring a slurry storage tank 1 for storing the slurry, placing the particles for sedimentation, raising the pressure of the slurry in the slurry storage tank 1 to 27MPa through a high-pressure diaphragm pump 2, raising the pressure of liquid oxygen to 27MPa through a high-pressure liquid oxygen pump 16 and a vaporizer, and mixing the slurry and high-pressure oxygen at a nozzle to enter a supercritical water oxidation reactor 3. Detecting the temperature in the hearth of the reaction furnace, and controlling the temperature at 600 ℃.
Reaction products of the supercritical water oxidation reaction enter the shell of the reactor 3 from a discharge hole of the hearth, the temperature of the shell of the reactor 3 is controlled by cooling water through conveying the cooling water to the reactor 3, the chilling temperature of the reaction products at the bottom of the reactor 3 is reduced to 300 ℃ through the cooling water, and the pressure is 21 MPa.
The second group of reaction products are firstly subjected to first pressure reduction treatment, the pressure is reduced to 5.5MPa, and the first gas-phase mixture is directly discharged after being subjected to pressure reduction. The liquid phase mixture obtained by the first pressure reduction treatment is subjected to second pressure reduction treatment, and the pressure is reduced to 0.2MPa, so that the water vapor and the CO are removed2And separating the slag water from the gas, directly discharging the gas, wherein the slag water is a solid-liquid mixture obtained by the second pressure reduction treatment.
And carrying out solid-liquid separation on the solid-liquid mixture obtained by gas-liquid separation of the first group of reaction products and the second group of reaction products.
The first group of reaction products and the solid-liquid mixture are subjected to solid-liquid separation through sedimentation, suspended particles floating on the liquid are subjected to solid-liquid separation through filtration, and clear liquid obtained through solid-liquid separation can be recycled and mixed with the catalyst.
The ash obtained after the pretreatment is subjected to the noble metal extraction by methods such as chemical displacement means, and the recovery rate of the noble metal reaches 85 percent.
Example 3
A catalyst comprising a noble metal Rh, Ph being 20% by weight of the catalyst.
Grinding catalyst particles, mixing the ground catalyst particles with water to form slurry with the mass concentration of 8%, stirring a slurry storage tank 1 for storing the slurry, placing the particles for sedimentation, raising the pressure of the slurry in the slurry storage tank 1 to 26MPa through a high-pressure diaphragm pump 2, raising the pressure of liquid oxygen to 26MPa through a high-pressure liquid oxygen pump 16 and a vaporizer, and mixing the slurry and high-pressure oxygen at a nozzle to enter a supercritical water oxidation reactor 3. Detecting the temperature in the hearth of the reaction furnace, and controlling the temperature at 750 ℃.
Reaction products of the supercritical water oxidation reaction enter the shell of the reactor 3 from a discharge hole of the hearth, the temperature of the shell of the reactor 3 is controlled by cooling water through conveying the cooling water to the reactor 3, the temperature of the reaction products at the bottom of the reactor 3 is reduced to 270 ℃ through cooling water chilling, and the pressure is 22.5 MPa.
The second group of reaction products are firstly subjected to first pressure reduction treatment, the pressure is reduced to 6.5MPa, and the first gas-phase mixture is directly discharged after being subjected to pressure reduction.The liquid phase mixture obtained by the first pressure reduction treatment is subjected to second pressure reduction treatment, and the pressure is reduced to 0.3MPa, so that the water vapor and the CO are removed2And separating the slag water from the gas, directly discharging the gas, wherein the slag water is a solid-liquid mixture obtained by the second pressure reduction treatment.
And carrying out solid-liquid separation on the solid-liquid mixture obtained by gas-liquid separation of the first group of reaction products and the second group of reaction products.
The first group of reaction products and the solid-liquid mixture are subjected to solid-liquid separation through sedimentation, suspended particles floating on the liquid are subjected to solid-liquid separation through filtration, and clear liquid obtained through solid-liquid separation can be recycled and mixed with the catalyst.
The ash obtained after the pretreatment is subjected to the noble metal extraction by methods such as chemical displacement means, and the recovery rate of the noble metal reaches 90 percent.
Referring to fig. 1, a system for pretreating a spent catalyst containing a noble metal according to the present invention will now be described. The pretreatment system of the precious metal-containing waste catalyst comprises a reactor 3, a temperature adjusting part, a slag water discharging part, a temperature reducing part and a pressure reducing part, wherein the reactor 3 is used for carrying out supercritical water oxidation reaction on the waste catalyst, the reactor 3 is connected with a nozzle, and slurry prepared by the waste catalyst and an oxygen source enter the reactor 3 after being mixed through the nozzle; the temperature adjusting part is provided with a temperature adjusting pipeline which is connected with the nozzle and is used for conveying cold water or methanol to the reactor 3; the slag water removing part is provided with a lock hopper 4 and a slag water tank 5, the slag water removing part is used for collecting the first group of reaction products, one end of the lock hopper 4 is connected with the reactor 3, and the other end is connected with the slag water tank 5; the cooling part is provided with a water-cooling protection pipeline for conveying cooling water, and the water-cooling protection pipeline is connected with the reactor 3 and is used for controlling the shell temperature of the reactor 3 and cooling reaction products of the supercritical water oxidation reaction; the pressure reduction part is connected with the reactor 3 and is used for carrying out pressure reduction treatment on the second group of reaction products after temperature reduction.
Compared with the prior art, the pretreatment method and the pretreatment system for the waste catalyst containing the precious metals have the advantages that the reactor 3 is arranged for carrying out supercritical water oxidation reaction, the temperature regulation part is used for controlling the reaction temperature, the slag water discharge part, the temperature reduction part and the pressure reduction part are arranged, reaction products of the supercritical water oxidation reaction are further separated, the extraction amount of ash and slag is increased, the precious metal extraction rate is increased, the discharged gas is cleaner, and the environment is protected.
In this embodiment, set up thick liquids storage tank 1, liquid oxygen jar 15, thick liquids storage tank 1 is used for storing thick liquids, and liquid oxygen jar 15 is used for depositing liquid oxygen, and thick liquids step up through high-pressure diaphragm pump 2, and liquid oxygen steps up through liquid oxygen pump 16 and liquid oxygen vaporizer 17, and the hydraulic pressure after stepping up mixes with thick liquids atomizing in nozzle department, sends into reactor 3 after mixing and carries out oxidation reaction. The temperature adjusting part is provided with a heat value adjusting tank 13, the heat value adjusting tank 13 is connected with a temperature adjusting pipeline and is used for adjusting the temperature of cold water or methanol in the temperature adjusting pipeline, and the reaction temperature is controlled by sending the cold water or methanol with the adjusted temperature into the reactor 3. The product of the oxidation reaction is chilled with cooling water conveyed by a water-cooling protection pipeline at the bottom of the reactor 3 and then cooled. The water-cooling protection pipeline is provided with a cooling water tank 11 and a high-pressure water pump 12, and cooling water flows into the reactor 3 from the cooling water tank 11 under the action of the high-pressure water pump 12. And a first group of reaction products in the reaction products after temperature reduction are collected through a slag water removing part, and a second group of reaction products are subjected to pressure reduction treatment through a pressure reduction part, so that a generated solid-liquid mixture is collected.
Referring to fig. 1, the slag water removing part includes a stamping pipeline, the stamping pipeline and a water cooling protection pipeline are both connected to the lock hopper 4, the stamping pipeline and the water cooling protection pipeline cooperate to pressurize the lock hopper 4, the stamping pipeline is used to deliver nitrogen gas to the lock hopper 4 for pressurization, one end of the lock hopper 4 is connected to the reactor 3 through a first control valve, and the other end is connected to the slag water tank 5 through a second control valve.
In this embodiment, the first control valve is opened, and the first group reaction product falls into lock 4 by reactor 3 and collects, and lock 4 and 3 pressure balance of reactor collect the first control valve after a period of time and close, carries out the pressure release to lock 4, opens second control valve and sediment water jar 5 after succeeding in the pressure release, and the first group reaction product is collected and is got into sediment water jar 5. And then the second control valve is closed, and a liquid nitrogen tank 18, a liquid nitrogen pump 19 and a liquid nitrogen vaporizer 20 are arranged on the punching pipeline. Firstly, the lock hopper 4 is stamped through a water-cooling protection pipeline, then liquid nitrogen is converted into nitrogen through a liquid nitrogen pump 19 and a liquid nitrogen vaporizer 20 to stamp the lock hopper 4, the pressure of the lock hopper 4 is balanced with that of the reactor 3, and a first control valve is opened.
Referring to fig. 1, a pressure reduction part includes a first pressure reduction orifice 6, a high pressure separation tank 7, a second pressure reduction orifice 9, and a low pressure separation tank 10. The second group of reaction products are subjected to first pressure reduction treatment by a first pressure reduction pore plate 6 and then sent into a high-pressure separation tank 7, and the first gas-phase mixture is directly discharged from the high-pressure separation tank 7 through a gas-phase pressure reduction valve 8. And the liquid phase mixture is sent to a second pressure reduction pore plate 9 from the high-pressure separation tank 7 for secondary pressure reduction treatment, the liquid phase mixture subjected to the secondary pressure reduction treatment is sent to a low-pressure separation tank 10, the generated gas is directly discharged, and the generated solid-liquid mixture is collected. And carrying out settling solid-liquid separation on the collected solid-liquid mixture and the first group of reaction products.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A pretreatment method of a waste catalyst containing noble metal, which is characterized by comprising the following steps:
mixing a waste catalyst and an oxygen source, and then sending the mixture into a reactor filled with supercritical water to carry out supercritical water oxidation reaction, wherein the temperature of a reaction zone of the reactor is controlled to be 600-750 ℃, and the pressure in the reaction zone is more than or equal to 23 MPa;
cooling reaction products of the supercritical water oxidation reaction and then discharging the reaction products out of the reactor, wherein the reaction products of the supercritical water oxidation reaction are divided into a first group of reaction products and a second group of reaction products, the first group of reaction products comprise solid particles and a part of slag water, the second group of reaction products comprise gas and the other part of slag water, the settled first group of reaction products are collected, and the second group of reaction products are subjected to gas-liquid separation;
and carrying out solid-liquid separation on the solid-liquid mixture obtained by gas-liquid separation of the first group of reaction products and the second group of reaction products.
2. The pretreatment method for a spent catalyst containing a noble metal according to claim 1, wherein the temperature of the reaction zone of said reactor is controlled to 600 ℃ to 750 ℃ by a temperature adjusting substance.
3. The pretreatment method and system for a spent catalyst containing a noble metal according to claim 2, wherein the temperature adjusting substance is cold water, methanol, and cold water is added to the reaction zone when the temperature of the reaction zone is higher than 750 ℃; when the temperature of the reaction zone is below 600 ℃, methanol is added to the reaction zone.
4. The method of pretreating a spent catalyst containing a noble metal according to claim 1, wherein said spent catalyst is ground and mixed with water to form a slurry, and said slurry is mixed with an oxygen source, and then fed into said reactor, and said oxygen source is liquid oxygen.
5. The method for pretreating a spent catalyst containing a noble metal according to claim 4, wherein said slurry and liquid oxygen are mixed with each other after being pressurized, and the pressure of each of said slurry and liquid oxygen is raised to 25MPa or more.
6. The pretreatment method and system for a spent catalyst containing noble metals according to claim 1, wherein the reaction product of the supercritical water oxidation reaction is chilled in cooling water to a temperature lower than 300 ℃ and the pressure is reduced to 20 to 23 MPa.
7. The method for pretreating a spent catalyst containing a noble metal according to claim 1, wherein said second group of reaction products is subjected to gas-liquid separation by pressure reduction treatment.
8. The pretreatment method for a spent catalyst containing a noble metal according to claim 7, wherein the depressurization treatment comprises:
carrying out first pressure reduction treatment, reducing the pressure of the second group of reaction products to 5.5-6.5MPa after the first pressure reduction treatment, and separating the second group of reaction products to obtain a first gas-phase mixture and a liquid-phase mixture;
and (3) carrying out secondary pressure reduction treatment on the liquid phase mixture, reducing the pressure of the liquid phase mixture to be below 0.3MPa after the secondary pressure reduction treatment on the liquid phase mixture, and separating to obtain the solid-liquid mixture.
9. The system for the pretreatment method of a spent catalyst containing a noble metal according to any one of claims 1 to 8, comprising:
the reactor is used for carrying out supercritical water oxidation reaction on the waste catalyst, the reactor is connected with a nozzle, and slurry prepared by the waste catalyst and an oxygen source enter the reactor after being mixed by the nozzle;
the temperature adjusting part is provided with a temperature adjusting pipeline, and the temperature adjusting pipeline is connected with the nozzle and is used for conveying cold water or methanol to the reactor;
the slag water discharge part is provided with a lock hopper and a slag water tank and is used for collecting the first group of reaction products, one end of the lock hopper is connected with the reactor, and the other end of the lock hopper is connected with the slag water tank;
the cooling part is provided with a water-cooling protection pipeline for conveying cooling water, and the water-cooling protection pipeline is connected with the reactor and is used for controlling the temperature of the shell of the reactor and cooling reaction products of the supercritical water oxidation reaction; and
and the pressure reduction part is connected with the reactor and is used for carrying out pressure reduction treatment on the cooled second group of reaction products.
10. The system for the pretreatment method of a spent catalyst containing a noble metal according to claim 9, wherein the slag water removing part comprises a punching line, the punching line and the water-cooling protection line are connected to the lock hopper, the punching line and the water-cooling protection line cooperate to pressurize the lock hopper, the punching line is used to supply nitrogen gas to the lock hopper, and the lock hopper is connected at one end to the reactor through a first control valve and at the other end to the slag water tank through a second control valve.
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