CN213172500U

CN213172500U - Wet recovery device for oil-containing waste catalyst

Info

Publication number: CN213172500U
Application number: CN202020962750.8U
Authority: CN
Inventors: 康金星; 王亚运; 宋磊; 于传兵; 吕东; 郭素红; 刘志国; 王传龙; 王鑫; 仇云飞
Original assignee: China ENFI Engineering Corp
Current assignee: China ENFI Engineering Corp
Priority date: 2020-05-30
Filing date: 2020-05-30
Publication date: 2021-05-11
Anticipated expiration: 2030-05-30

Abstract

The utility model discloses a wet process recovery unit who contains oily useless catalyst, including rotating electrode electrolytic bath and oil water separator, set up rotatory anode in the middle of the rotating electrode electrolytic bath, set up fixed negative pole around the rotatory anode, be the electrochemical reaction room between rotatory anode and the negative pole, rotating electrode electrolytic bath upper portion sets up the profit discharge port, profit discharge port with oil water separator's access connection, oil water separator's aqueous phase export with rotating electrode electrolytic bath's electrolyte access connection. The device of the utility model synchronously realizes the deoiling and inorganic metal component separation and recovery of the wet oil-containing waste catalyst, does not need the fire deoiling and the material crushing, produces no waste slag, waste gas and waste water, and has obvious environmental effect.

Description

Wet recovery device for oil-containing waste catalyst

Technical Field

The utility model belongs to the technical field of electrochemistry hydrometallurgy, concretely relates to device that wet process of oily useless catalyst was retrieved.

Background

The oil-containing waste catalyst is generally existed in the industries of petrochemical industry, coal chemical industry, material synthesis, metallurgy, pharmacy and the like, and the waste catalyst is deactivated due to excessive oil compounds or metal compounds adsorbed or deposited on the surface. The surface of the waste catalyst is adsorbed with more organic compounds, and usually contains 5-20% of oily substances, such as hydrocarbon oil, organogel and the like, and is influenced by the large surface area and the carbon adsorption deposited on the surface of the waste catalyst, so that the deoiling of the waste catalyst is difficult. The waste catalyst is also an important secondary resource of metal elements, for example, the content of metals such as vanadium, nickel, cobalt, molybdenum, tungsten, aluminum and the like in the waste petroleum chemical catalyst is high, and before extracting the metal elements, oil components are generally required to be removed. Therefore, the inactivated waste catalyst is an important secondary solid waste resource, and the processing and recycling problems of the inactivated waste catalyst are hot problems in the fields of petrochemical industry, coal chemical industry, metallurgy, environmental engineering and the like for a long time. The components and structures of oil compounds and metal compounds in the oil-containing waste catalyst are complex, and the metal components are extracted after pre-deoiling treatment is usually adopted for recycling. The related technology for treating the waste catalyst has two modes of pyrometallurgy and wet extraction.

The typical process for treating waste oil-containing catalyst by pyrogenic process isRoasting at 900 ℃ at 600 ℃ for deoiling, then roasting at 1900 ℃ at 1200 ℃ for high temperature, melting and refining the metal-containing components in the waste catalyst into multi-metal alloy, fixing and recovering the metal elements, wherein SO is easily generated in the deoiling roasting and the high-temperature roasting in the process₂、CO、H₂S and the like, and the environmental hazard is relatively large. When the oil-containing waste catalyst is processed by a wet method, the subsequent wet smelting is obviously influenced by organic compounds contained in the oil-containing waste catalyst, and the oil is removed in advance and then the wet metal extraction is carried out. In order to obtain better pretreatment effect, the deoiling process is relatively effective in oxidation roasting pretreatment, and the deoiling can be realized through oxidation roasting, and simultaneously, the metal mineral original phase in the waste catalyst can be converted, so that the wet extraction is easier, and the pollution gas generated in the pyrogenic pretreatment process is still a treatment problem. However, the oxidation roasting process does not effectively recover or utilize the waste catalyst oils. For example, the method for extracting vanadium, molybdenum, nickel and aluminum from waste aluminum-based catalysts disclosed in CN185460A, the method for recovering vanadium and molybdenum from waste petroleum catalysts disclosed in CN105274344A, and the method for extracting tungsten and nickel from petroleum hydrogenation catalysts disclosed in CN105274343A, the waste catalysts are all decarbonized and deoiled by means of oxidation roasting, then roasted at high temperature, the metal mineral phase is converted into a fusible phase and then metal is extracted.

Therefore, it is urgently required to provide an environmentally friendly apparatus for treating the oil-containing spent catalyst.

SUMMERY OF THE UTILITY MODEL

The present invention is made based on the discovery and recognition by the inventors of the following facts and problems:

the disposal problem of the oil-containing waste catalyst is always a common problem of resource utilization and environmental protection. The waste catalyst has high oil component content and metal element content higher than that of conventional ore, and is important secondary organic energy and mineral resource.

In the related technology, when a wet process or a fire process device is adopted to treat the oil-containing waste catalyst, the difficult problems to be solved are mainly represented as two steps, one is effective separation of an oil-containing compound and an inorganic material, and the other is how to more simply, conveniently and effectively extract metals from the inorganic material after deoiling. The environmental protection problem caused by the smoke generated by pyrogenic process treatment or pretreatment of the waste hydrogenation catalyst is a bottleneck which is difficult to overcome. Wet degreasing is therefore a key finding for the utilization of oil-containing spent catalysts. The wet deoiling is realized by changing the oil-water interfacial tension essentially, and CN105498860A discloses a deoiling method for an oil-containing waste catalyst, wherein the surface tension of water is reduced by adding sodium dodecyl sulfate and caustic alkali, 95% of residual oil on the surface of the waste catalyst is removed at low temperature, but oil substances are not utilized after being co-dissolved with water, an oil-water mixed solution is difficult to dispose, resource waste is caused, and the added surfactant sodium dodecyl sulfate has certain toxicity and serious secondary pollution problem.

The present invention aims at solving at least one of the technical problems in the related art to a certain extent. Therefore, the embodiment of the utility model provides a wet process recovery unit of oily useless catalyst can realize wet process oily useless catalyst deoiling and inorganic metal component separation and recovery in step, need not pyrogenic process deoiling and comminuted, and no waste residue waste gas waste water produces, and environmental effect is showing.

According to the utility model provides a wet process recovery unit of oily spent catalyst, including rotating electrode electrolytic bath and oil water separator, set up rotatory anode in the middle of the rotating electrode electrolytic bath, set up fixed negative pole around the rotatory anode, be electrochemical reaction room between rotatory anode and the negative pole, rotating electrode electrolytic bath upper portion sets up oily water discharge port, oily water discharge port with oil water separator's access connection, oil water separator's aqueous phase export with rotating electrode electrolytic bath's electrolyte access connection.

According to the utility model discloses advantage and technological effect that have do: 1. the device provided by the embodiment of the utility model adopts the rotary electrode, and carries out the electrochemical reaction process through the relative high-speed movement of the electrolyte and the electrode, thereby avoiding the influence of low current efficiency, increased concentration polarization and other adverse factors on electrochemical separation caused by slow solution flow in the electrolysis process of the traditional flat frame type electrolytic cell; 2. the device provided by the embodiment of the utility model synchronously realizes the deoiling of the oil-containing waste catalyst in the wet process and the separation and recovery of inorganic metal components, reduces the extraction time and has high working efficiency; 3. the embodiment of the utility model provides a selective electrolysis is realized to the device, and the output treat that the separation retrieves liquid phase and solid phase component simple, has obtained oil product, hydrophobic nature inorganic particle product, dissolves soaks and negative pole sedimentary metal component product, electrolysis soaks sediment product etc. and the in-process does not have waste residue waste gas waste water discharge, and environmental effect is showing, and the follow-up wet process of product being convenient for is retrieved to oil and metal rate of recovery are high, have realized resource maximization and have utilized.

According to the utility model discloses wet process recovery unit of oily dead catalyst, wherein, still include filtration equipment, filtration equipment's import with oil phase exit linkage of oil water separator.

According to the utility model discloses wet process recovery unit of oily spent catalyst, wherein, rotatory electrode electrolytic cell bottom sets up and soaks the sediment discharge port.

According to the utility model discloses wet process recovery unit of oily spent catalyst, wherein, rotatory anode is the inertia rotatory anode.

According to the utility model discloses wet process recovery unit of oily spent catalyst, wherein, set up the acidimeter on the upper reaches pipeline of the electrolyte import of rotating electrode electrolytic cell.

According to the utility model discloses wet process recovery unit of oily useless catalyst, wherein, set up the flowmeter on the upper reaches pipeline of the electrolyte import of rotating electrode electrolytic cell.

According to the utility model discloses wet process recovery unit of oily spent catalyst, wherein, still include lower floor's electrolyte dashpot, the import of this electrolyte dashpot with oil water separator's water phase exit linkage, the export with the electrolyte access connection of rotating electrode electrolytic cell.

According to the utility model discloses wet process recovery unit of oily spent catalyst, wherein, still include electrolyte recovery unit, this electrolyte recovery unit's import pass through the three-way valve with the exit linkage of lower floor's electrolyte dashpot.

Drawings

Fig. 1 is a schematic view of a wet recovery device for oil-containing spent catalyst according to an embodiment of the present invention.

Reference numerals: 1-rotating electrode electrolytic cell; 2-an electrochemical reaction chamber; 3-a cathode; 4-rotating the anode; 5-a power transmission cabinet; 6-a rotary power unit; 7-an electrolyte inlet; 8-oil water discharge port; 9-a residue leaching discharge port; 10-a shut-off valve; 11-a shut-off valve; 12-oil-water separation device; 13-a shut-off valve; 14-lower electrolyte buffer tank; 15-three-way valve; 16-acidimeters; 17-an electrolyte circulation pump; 18-a flow meter; 19-electrolyte recovery means; 20-a shut-off valve; 21-upper oil collecting equipment; 22-a shut-off valve; 23-a filter pressing delivery pump; 24-a filtration device; 25-an oil collecting tank; 26-a hydrophobic inorganic particle collection box; 27-a shut-off valve; 28-a leaching residue collection box; 29-electrolyte reservoir.

Detailed Description

Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are exemplary and intended to be used for explaining the present invention, and should not be construed as limiting the present invention.

As shown in fig. 1, according to the embodiment of the present invention, a wet recovery device for oil-containing waste catalyst is provided, which includes a rotary electrode electrolytic cell 1 and an oil-water separation device 12, a rotary anode 4, preferably an inert rotary anode, is disposed in the middle of the rotary electrode electrolytic cell 1, a fixed cathode 3 is disposed around the rotary anode 4, an electrochemical reaction chamber 2 is disposed between the rotary anode 4 and the cathode 3, an oil-water discharge port 8 is disposed on the upper portion of the rotary electrode electrolytic cell 1, the oil-water discharge port 8 is connected to the inlet of the oil-water separation device 12, and the water phase outlet of the oil-water separation device 12 is connected to the electrolyte inlet 7 of the rotary electrode electrolytic cell.

According to the utility model discloses wet recovery unit of oily dead catalyst, wherein, still include filtration equipment 24, filtration equipment 24's import with oil phase exit linkage of oil water separator 12. The embodiment of the utility model provides an in, through setting up filtration equipment, with the further filtration separation of the oily compound that contains granule that oil water separator 12 separation obtained, retrieved the hydrophobic inorganic granule of difficult electrolysis, can be used for follow-up processing to refine, the filtrating then is the oily compound product of recovery.

According to the utility model discloses wet process recovery unit of oily spent catalyst, wherein, 1 bottom of rotary electrode electrolytic cell sets up and soaks sediment discharge port 9. In the device of the embodiment of the utility model, the difficult electrolytic metallic compound remains in the sediment phase among the oily spent catalyst, discharges through soaking the sediment discharge port and retrieves, returns and is used for among the catalyst preparation system.

According to the utility model discloses wet process recovery unit of oily spent catalyst, wherein, set up acidimeter 16 on the upstream pipeline of the electrolyte import 7 of rotatory electrode electrolytic cell 1 for control the required acidity of electrochemical reaction.

According to the utility model discloses wet process recovery unit of oily useless catalyst, wherein, set up flowmeter 18 on the upstream pipeline of the electrolyte import 7 of rotary electrode electrolytic cell 1 for control electrolyte circulation flow's speed.

According to the utility model discloses wet process recovery unit of oily spent catalyst, wherein, still include lower floor's electrolyte dashpot 14, this electrolyte dashpot 14 import with oil water separator 12's water phase exit linkage, the export with the electrolyte import 7 of rotating electrode electrolytic cell 1 is connected.

According to the utility model discloses wet process recovery unit of oily spent catalyst, wherein, still include electrolyte recovery unit 19, this electrolyte recovery unit's import through three-way valve 15 with the exit linkage of lower floor's electrolyte dashpot 14. After the electrolyte is enriched with a certain concentration of metal components, the electrolyte may be introduced into the electrolyte collecting device 19, and the electrolytic components leached but not deposited at the cathode are recovered by a wet process.

The operation of the wet recovery device for oil-containing spent catalyst according to the embodiment of the present invention will be described in detail with reference to fig. 1.

Filling oil-containing waste catalyst particles into an electrochemical reaction chamber 2 between a cathode 3 and a rotary anode 4 of a rotary electrode electrolytic cell 1, wherein oil compounds in the waste catalyst contain 2-25% of oil compounds which are adsorbed on the surface of the waste catalyst, and more multi-metal compound components are adsorbed on the surface of the waste catalyst. An acid electrolyte solution is prepared in an electrolyte storage tank 29, a stop valve 11 is opened, the stop valve 20 is closed, a stop valve 27 at the upstream of a residue immersion collecting box 28 is closed, the electrolyte passes through an oil-water separation device 12 and a lower-layer electrolyte buffer tank 14, is added into an electrochemical reaction chamber 2 through an electrolyte inlet 7 by an electrolyte circulating pump 17, gradually immerses oily waste catalyst particles filled in the electrochemical reaction chamber 2 from bottom to top, and finally enough electrolyte is introduced to circularly flow out of an electrolytic cell 1 through an oil-water discharge port 8 and enter the oil-water separation device 12 through the stop valve 10, so that the electrolyte is circulated in the electrochemical reaction chamber in advance. The circulation flow speed of the electrolyte is realized by controlling the speed of an electrolyte circulation pump 17 through a flow meter 18, and the acidity required by the electrochemical reaction is regulated and controlled by an acidity meter 16, so that the acidity of the electrolyte is at a constant level.

After the electrolyte circulates and stabilizes in the electrochemical reaction chamber 2, the rotary power device 6 is started to rotate the rotary anode 4, the power transmission cabinet 5 is adopted to supply power, catalytic electrolysis separation is carried out on the oil-containing waste catalyst, and electrochemical reactions such as deoiling reaction, metal component leaching reaction, metal component cathodic deposition and the like are completed in the electrochemical reaction chamber 2.

The oil substances on the surface of the waste catalyst and the electrolyte have obvious polarization difference and are gradually extruded from the surface of the waste catalyst to form fine oil drops, the fine oil drops have relatively low density and gradually float up to the surface of the reaction chamber 2 under the influence of upward rotary buoyancy of the rotary electrode, the oil drops are merged to form an oil film layer and are circularly introduced into the oil-water separation device 12 along with the electrolyte, the oil compounds containing particles are distributed on the upper layer after standing, and the oil compounds on the upper layer are automatically discharged and flow into the upper-layer oil collection device 21 through the stop valve 20 to obtain the oil mixture containing hydrophobic inorganic particles. The oil mixture contains surface adsorbed hydrophobic finely particulate metal components which are partially difficult to be electrolytically leached in the spent catalyst, such as MoS contained in the spent catalyst₂And C or electrolytic separation of substances such as simple substance S, and the like, wherein an oil mixture collected on the upper layer enters a filtering device 24 through a stop valve 22 and a filter pressing conveying pump 23 to separate hydrophobic inorganic particles carried by oil, a filtering slag phase is the mixed hydrophobic inorganic particles, the separated hydrophobic inorganic particles are collected in a hydrophobic inorganic particle collecting box 26 and can be recovered through a wet method or a fire method, and oil components are collected by an oil collecting box 25 to realize the separation of oil and hydrophobic products.

The components to be leached or electrolyzed adsorbed on the surface of the waste catalyst, such as metal compounds containing V, Ni, Co, Al and the like, is preferentially dissolved into the electrolytic aqueous phase solution by the electrolyte leaching under the influence of electric field force in the electrochemical reaction chamber 2, then the electrolyte directionally moves to the cathode 3 to deposit under the action of electric field force, after the electrolyte circularly flows out from the oil-water discharge port 8 from bottom to top, the electrolyte solution enters an oil-water separation device 12, is in the lower layer after standing separation and enters a lower layer electrolyte buffer tank 14 through a stop valve 13, electrolyte in the buffer tank controls the flow of the electrolyte to go through a three-way valve 15, the electrolyte returns to the rotary electrode electrolytic cell 1 through an acidimeter 16 and a flowmeter 17 to circulate, the electrolyte solution can be introduced into the electrolyte solution collecting device 19 after being enriched with a certain concentration of metal components, and the electrolytic components leached but not deposited at the cathode are recovered by a wet method.

After the oil compounds and the cathode deposited metal are recovered, the non-leached waste catalyst leaching residue can enter a leaching residue collection box 28 from a leaching residue discharge port 9 through a stop valve 27 for further recovery and utilization. The embodiment of the utility model provides an in can adopt traditional method recycle cathode deposition's metal and the difficult electrolytic metal in the slag phase.

Example 1

The mass percentage of oil components in a certain desulfurization hydrogenation waste catalyst is 12 percent, the mass percentage of vanadium, nickel, molybdenum, cobalt, aluminum and sulfur are respectively 5.4 percent, 3.3 percent, 0.9 percent, 1.2 percent, 27.3 percent and 8.3 percent, and the mass percentage of other metals is less; the catalyst has high contents of oil compounds and sulfur. Adopt the embodiment of the utility model provides an in the device to 5% sulphuric acid solution is as acid electrolyte aqueous solution, input voltage, and the negative and positive potential difference is 3V, can dissolve and soak vanadium, nickel, cobalt, after the normal atmospheric temperature electrochemical reaction separation 120min, obtains 98% oil compound and collects in the oil sump tank, and molybdenum compound and S more than 90% are with simple substance form enrichment in hydrophobic inorganic granule, and the rate of recovery of the sedimentary vanadium of negative pole, nickel, cobalt, aluminium all reaches more than 98%.

Example 2

The waste aluminum-based platinum-palladium catalyst contains 2.5% of oil. Adopt the embodiment of the utility model provides an in the device to 3.5% concentration's hydrochloric acid is as acid electrolyte aqueous solution, input voltage, and the negative and positive potential difference is 2V, and electrochemical dissolution in electrochemical reaction chamber selectively degreases and soaks negative pole deposit platinum palladium, and platinum palladium extraction rate is more than 99%, and the aluminium leaching rate is less than 20%, and remaining high-alumina products are discharged as leaching residue, are used as high-purity alumina raw materials, and oily compound rate of recovery reaches 95%.

Example 3

The oil component of the waste SCR catalyst was 4.5%. Adopt the embodiment of the utility model provides an in the device to 5% nitric acid is as acid electrolyte aqueous solution, under 40 ℃, input voltage, and the negative and positive potential difference is 1.5V, carries out electrochemical catalysis leaching, and the rate of recovery of vanadium and nickel reaches more than 97%, and the rate of recovery of oil class compound is more than 96%.

Comparative example 1

The same apparatus as that used in example 1 was used except that a rotary electrode was not used as the anode, but a stationary anode was used. The recovery rate of the oil-based compound obtained by recovering the oil-containing spent catalyst using the apparatus of comparative example 1 was 76%, the recovery rate of vanadium, nickel, cobalt, and aluminum deposited at the cathode was 90%, and the recovery rate of the molybdenum compound and S was 72%.

Comparative example 2

The same as the apparatus of example 1 except that the rotating electrode in the middle of the electrolytic cell was the cathode and the anode was a stationary electrode disposed around the rotating cathode. With the apparatus of comparative example 2, the recovery rate of oil compounds was 70%, the recovery rate of vanadium, nickel, cobalt, and aluminum deposited at the cathode was 51%, and the recovery rate of molybdenum compounds and S was 63%. In comparative example 2 where the cathode and the anode were switched, the recovery rates of the oil-based compound and the inorganic metal component were seriously decreased because, on the one hand, the metal deposition reaction occurred on the cathode and a large specific surface area was required, but the specific surface area of the rotary electrode was not so large as to affect the deposition of the metal; on the other hand, the polarization of the water phase in the electrochemical reaction chamber is from the cathode to the anode, and after the cathode and the anode are switched, the water molecules can extrude the oil molecules inwards, and the oil molecules can move close to the rotating electrode, so that the rapid floating separation of the oil substances in the waste catalyst is not facilitated.

In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," and "fixed" are to be construed broadly and may, for example, be fixedly connected, detachably connected, or integrally formed; may be mechanically coupled, may be electrically coupled or may be in communication with each other; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meaning of the above terms in the present invention can be understood according to specific situations by those skilled in the art.

In the present application, unless expressly stated or limited otherwise, the first feature may be directly on or directly under the second feature or indirectly via intermediate members. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.

In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.

Although embodiments of the present invention have been shown and described, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art without departing from the scope of the present invention.

Claims

1. The wet recovery device for the oily waste catalyst is characterized by comprising a rotary electrode electrolytic cell and an oil-water separation device, wherein a rotary anode is arranged in the middle of the rotary electrode electrolytic cell, a fixed cathode is arranged around the rotary anode, an electrochemical reaction chamber is arranged between the rotary anode and the cathode, an oil-water discharge port is formed in the upper part of the rotary electrode electrolytic cell, the oil-water discharge port is connected with an inlet of the oil-water separation device, and a water phase outlet of the oil-water separation device is connected with an electrolyte inlet of the rotary electrode electrolytic cell.

2. The apparatus for wet recovery of an oily spent catalyst according to claim 1, further comprising a filtering device, wherein an inlet of the filtering device is connected to an oil phase outlet of the oil-water separating device.

3. The wet recovery apparatus of oil-containing spent catalyst according to claim 1, wherein a residue leaching discharge port is provided at the bottom of the rotary electrode electrolytic cell.

4. The apparatus for wet recovery of oil-containing spent catalyst according to claim 1, wherein the rotary anode is an inert rotary anode.

5. The apparatus for wet recovery of oil-containing spent catalyst according to claim 1, wherein an acidimeter is provided on the upstream line of the electrolyte inlet of the rotary electrode electrolytic cell.

6. The apparatus for wet recovery of oil-containing spent catalyst according to claim 1, wherein a flow meter is provided on an upstream line of an electrolyte inlet of the rotary electrode electrolytic cell.

7. The apparatus for wet recovery of oily spent catalyst according to claim 1, further comprising a lower electrolyte buffer tank, an inlet of which is connected to the aqueous phase outlet of the oil-water separation device and an outlet of which is connected to the electrolyte inlet of the rotary electrode electrolytic cell.

8. The apparatus for wet recovery of oil-containing spent catalyst according to claim 7, further comprising an electrolyte recovery unit, an inlet of which is connected to an outlet of the lower electrolyte buffer tank through a three-way valve.