WO2023130454A1

WO2023130454A1 - Method and system for recovering metals from heavy oil

Info

Publication number: WO2023130454A1
Application number: PCT/CN2022/071044
Authority: WO
Inventors: 唐全红; 何伟民; 张强; 倪伟权; 赖少伟; 舒程
Original assignee: 广东赛瑞新能源有限公司
Priority date: 2022-01-10
Filing date: 2022-01-10
Publication date: 2023-07-13

Abstract

The present invention discloses a method and system for recovering metals from heavy oil. The method comprises: stirring and mixing a heavy component oil and a solvent oil to obtain a mixed oil; separating the mixed oil into a solvent-enriched insoluble substance and a light oil component; heating the solvent-enriched insoluble substance, wherein the dry distillation temperature is lower than the sublimation temperature of metals and metal compounds thereof; and crushing and sorting solid carbon components obtained from the dry distillation to obtain various solid particle components that are uniform and consistent in granularity and rich in different metals. By means of the process route consisting of mixing with the solvent oil, separation in a sedimentation or centrifugation mode, oxygen-isolated dry distillation at a relatively low temperature, and smashing and sorting, the method is in accordance with the industrial direction of developing clean and low-carbon fuels, and the energy consumption and pollution are relatively low; and compared with a traditional combustion mode, the process route of the system is low in terms of the recovery cost and more environmentally friendly, and also does not drastically change the form of existence of the heavy metals or even generate some alloys, thereby greatly reducing the complexity of subsequent treatments.

Description

A method and system for recovering metals from heavy oil

technical field

The invention relates to the field of heavy oil treatment, in particular to a method and system for recovering metals from heavy oil.

Background technique

With the development of science and technology and the expansion of the petrochemical industry, environmental issues have increasingly become the focus of attention. The heavy oil produced by coal chemical and petrochemical processing contains a large amount of metals. If these metals are not effectively treated and utilized, it will gradually increase the environmental impact. Natural environmental pollution; at the same time, in order to mine and refine these metals from nature for industrial use, people have also caused huge damage to the natural environment, as well as huge carbon emissions and water pollution.

The traditional metal recovery technology from heavy oil mostly uses heavy oil as fuel for combustion, and then recovers heavy metal oxides in flue gas or combustion tailings; however, this traditional recovery method is not in line with clean fuel and the direction of low-carbon industry, the second is that the existence form of heavy metals has undergone tremendous changes, and some alloys have been produced, which increases the complexity of subsequent processing. The third is that the energy consumption, material consumption and pollutant emissions of recycling are high. Recycling is costly and not environmentally friendly.

technical problem

In order to solve the above technical problems, the present invention provides a method and system for recovering metals from heavy oil, which is in line with the industrial direction of fuel cleanliness and low carbonization, and has low energy consumption and pollution.

technical solution

The technical scheme of the present invention is as follows: a method for recovering metal from heavy oil, comprising the following steps:

Step C, fully stirring and mixing heavy component oil S2 and solvent oil R according to the ratio of 1:0.01~4, and controlling the temperature during mixing between 60-240°C to obtain mixed oil H1;

Step D, input the mixed oil H1 into a settler or centrifuge, after settling or centrifuging for a predetermined period of time, separate the mixed oil H1 into bottom and top two parts, the bottom is rich in solvent insolubles or solid-liquid rich in particles Mixing component HZ, the top is light oil component or liquid phase component HQ;

Step F, heat up the solid-liquid mixed component HZ enriched in solvent insolubles or rich in particulate matter HZ at the bottom and perform oxygen-barrier dry distillation to obtain solid carbon component G1, light components and coking gas, and the dry distillation temperature is lower than that recovered The sublimation temperature of metals and their metal compounds;

Step H, after crushing and sorting the dry-distilled solid carbon component G1, various solid particle components (Ki, i=1, 2, 3.... .).

The method for recovering metal from heavy oil, wherein, before step C, also includes:

Step A, distilling and cutting the heavy oil S1 containing metal elements and raising the temperature.

Step B. Filter the heavy oil S1 by means of inorganic membrane filtration or extract the heavy oil S1 by solvent deasphalting, and divide the heavy oil S1 into two shares after filtering or extracting, one is heavy component oil S2, and the other is Light component oil S3.

The method for recovering metals from heavy oil, wherein, the solvent oil R in the step C adopts ethylene oxide, propylene oxide, butylene oxide, alkane with carbon six to carbon twenty, cycloalkane, methanol , ethanol and one or several components in the single-ring aromatic hydrocarbon-based component oil.

The method for recovering metal from heavy oil, wherein:

Step E is also included after step D, sending the light oil component HQ into the solvent recovery tower for distillation and separation to obtain solvent oil R and heavy oil components, and the heavy oil component removal device is used for other purposes, and solvent oil R is returned to step C recycle;

After step F, step G is also included. After cooling and gas-liquid separation of light components and coking gas from dry distillation, the gas phase component removal device is used for other purposes, and the liquid phase components are treated as solvent oil R Return to step C for recycling.

A system for recovering metals from heavy oil, including a solvent mixing unit, a solid-liquid separation unit, an oxygen barrier dry distillation unit and a solid crushing and sorting unit, wherein:

The solvent mixing unit is used to fully stir and mix the heavy component oil S2 and solvent oil R according to the ratio of 1:0.01~4, and the temperature during mixing is controlled between 60-240°C to obtain the mixed oil H1;

The solid-liquid separation unit is used to input the mixed oil H1 into a settler or a centrifuge. After settling or centrifuging for a predetermined period of time, the mixed oil H1 is separated into two parts, the bottom and the top. The solid-liquid mixed component HZ containing particulate matter, the top is light oil component or liquid phase component HQ;

The oxygen barrier dry distillation unit is used to send the solid-liquid mixed component HZ rich in solvent insolubles or particles rich in the bottom into the oxygen barrier dry distillation device for heating, and the dry distillation temperature is lower than the sublimation of recovered metals and their metal compounds temperature;

The solid crushing and sorting unit is used for crushing and sorting the dry-distilled solid carbon component G1 to obtain various solid particle components with uniform particle size and enriched in different metals (Ki, i=1,2 ,3.....).

The system for recovering metals from heavy oil also includes:

Concentration unit, used to filter heavy oil S1 by means of inorganic membrane filtration or extract heavy oil S1 by solvent deasphalting, divide heavy oil S1 into two streams after filtration or extraction, one is heavy component oil S2, One is light component oil S3.

The system for recovering metals from heavy oil, wherein: the solvent oil R in the solvent mixing unit adopts ethylene oxide, propylene oxide, butylene oxide, alkanes with six to twenty carbons, naphthenes, Methanol, ethanol, and one or more components in the component oil mainly composed of single-ring aromatic hydrocarbons are mixed.

The system for recovering metals from heavy oil also includes a solvent recovery unit and a cooling and gas-liquid separation unit, wherein:

The solvent recovery unit is used to send the light oil component HQ separated by the solid-liquid separation unit into the solvent recovery tower for distillation and separation to obtain solvent oil R and heavy oil components. The heavy oil component extraction device is used for other purposes, solvent oil R is returned to the solvent mixing unit for recycling;

The cooling and gas-liquid separation unit is used for cooling and gas-liquid separation of light components and coking gas from the oxygen barrier dry distillation unit, and the gas phase component separation device is used for other purposes. , as solvent oil R returned to the solvent mixing unit for recycling.

The system for recovering metals from heavy oil also includes:

Specific metal recycling mixing unit, used to grind part of the solid particle components separated by the solid crushing and sorting unit to between 0.1-10um, and mix them into the light component oil S3 obtained in the concentration unit for full dispersion, It is used as a recycling oil return device.

Beneficial effect

The method and system for recovering metals from heavy oil provided by the present invention adopts a process route of mixing with solvent oil and then separating by sedimentation or centrifugation, and then adopting relatively low-temperature oxygen-barrier dry distillation followed by crushing and sorting, which meets the requirements of The industrial direction of fuel cleanliness and low-carbonization, and low energy consumption and pollution; compared with traditional combustion methods, the process route recovery cost of this system is low and more environmentally friendly, and it does not have a huge change in the existence of heavy metals. Some alloys are not produced, which greatly reduces the complexity of subsequent processing.

Description of drawings

The drawings described here are only for the purpose of explanation, and are not intended to limit the scope of the disclosure of the present invention in any way; the shapes and proportions of the components in the drawings are only schematic, and are used to help the understanding of the present invention. The shapes and proportional dimensions of the components in the present invention are not specifically limited; those skilled in the art can implement the present invention by selecting various possible shapes and proportional dimensions under the teaching of the present invention.

Fig. 1 is the block flow diagram of the method for recovering metal from heavy oil of the present invention;

Fig. 2 is a schematic diagram of the composition principle of the metal recovery system from heavy oil composed of pre-inorganic membrane separation and subsequent sedimentation separation in the present invention;

Fig. 3 is a schematic diagram of the composition principle of the system for recovering metals from heavy oil by adopting pre-solvent deasphalting separation and post-sedimentation separation in the present invention;

Fig. 4 is a schematic diagram of the composition principle of the system for recovering metals from heavy oil by using pre-inorganic membrane separation and centrifugal separation after distribution in the present invention;

Fig. 5 is a schematic diagram of the composition principle of the system for recovering metals from heavy oil by adopting pre-solvent deasphalt separation and centrifugal separation after blending in the present invention;

Fig. 6 is the raw material composition table of certain heavy oil that the present invention reclaims metal specific embodiment from heavy oil;

Fig. 7 is the component property analysis table of the permeate oil and concentrated oil that inorganic membrane separation Fig. 6 heavy oil obtains of the present invention;

Summary of each label in the figure: heavy oil S1, heavy component oil S2, light component oil S3, solvent oil R, mixed oil H1, solid-liquid mixed component rich in solvent insolubles or rich in particles HZ, light oil Component or liquid phase component HQ relatively free of particles, solid carbon component G1, particle K, solid particle component (Ki, i=1,2,3...);

Concentration unit 210, stirring tank 220, solid-liquid separation unit 230, separator 231, separation tower 232, solvent recovery unit 240, insoluble matter delivery unit 250, oxygen barrier dry distillation unit 260, cooler 271, gas-liquid separation equipment 272, Solid crushing and sorting unit 280, solid-liquid mixer 290.

Embodiments of the present invention

The specific embodiments and examples of the present invention will be described in detail below in conjunction with the accompanying drawings. The described specific embodiments are only used to explain the present invention, and are not intended to limit the specific embodiments of the present invention.

As shown in Figure 1, Fig. 1 is the flowchart of the method for recovering metal from heavy oil of the present invention, and this method for recovering metal from heavy oil comprises the following steps:

Optional step 100, distilling and cutting the heavy oil S1 containing metal elements and increasing the temperature to increase the initial boiling point of the heavy oil S1, reduce the proportion of light components with lower metal content in the heavy oil S1, and reduce the Viscosity of heavy oil S1;

Optional step 110: filter the heavy oil S1 by means of inorganic membrane filtration or extract the heavy oil S1 by means of solvent deasphalting, divide the heavy oil S1 into two strands after filtration or extraction, one strand is rich in asphaltenes and contains large The heavy component oil S2 with relatively more particles (that is, the heavy component in Figure 1), and one is the light component oil S3 with relatively few large particles;

Step 120, thoroughly stir and mix the asphaltene-enriched heavy component oil S2 (that is, the concentrated component in Fig. 1 ) and solvent oil R according to the ratio of 1:0.01~4 , the temperature during mixing is controlled between 60-240°C to obtain mixed oil H1 (that is, the solution in Figure 1); solvent oil R can be ethylene oxide, propylene oxide, butylene oxide, carbon six to carbon Twenty alkanes, cycloalkanes, methanol, ethanol and (one or more) one or more components of single-ring aromatic hydrocarbons are mixed;

Step 130: Input the miscella H1 into a separation device such as a settler or a centrifuge, and after settling or centrifuging for a predetermined period of time, separate the miscella H1 into two parts, the bottom and the top, and the bottom is rich in solvent insolubles or rich in particles The solid-liquid mixing component HZ (that is, the solvent-insoluble matter in Fig. 1), the top is the light oil component or the liquid phase component HQ (that is, the oil phase solution in Fig. 1 ) that does not contain particles relatively;

Step 140, sending the top light oil component HQ (i.e. the oil phase solution in Figure 1) into a solvent recovery tower for distillation and separation to obtain solvent oil R and heavy oil components, wherein the recovered solvent oil R (i.e. in Figure 1 The solvent) can be returned to step 120 for recycling, and the heavy oil components that do not contain or contain a small amount of metal can be used for other purposes;

Step 150, heat up the solvent-insoluble matter at the bottom or the solid-liquid mixed component HZ rich in particles (that is, the solvent-insoluble matter in Fig. 1 ) and carry out dry distillation with oxygen insulation, and the dry distillation temperature is lower than the recovered metal and its metal compound sublimation temperature, such as 450, 500, 550°C, etc.; it is preferable to take a moderate decompression operation on the retort to further strengthen the retort effect; the product of retort includes solid carbon component G1, distilled light components and Coking gas reacted at high temperature;

Step 160: After cooling and gas-liquid separation of light components and coking gas from dry distillation, the gas phase component extraction device can be used for other purposes, and the liquid phase components can be used as solvent oil R after treatment, or can be exported The device is used for other purposes;

Step 170, the dry-distilled solid carbon component G1 (that is, the solid phase component in Figure 1) is pulverized to obtain a particle K with a moderate particle size (such as a diameter less than 2 cm);

Step 180: Sorting the particles K repeatedly to obtain solid particle powders with relatively uniform particle size but different densities, that is, various solid particle components enriched with different metals (Ki, i=1, 2, 3... .), and process and utilize them separately according to the needs;

Step 190. For the solid particle components with high carbon content, they can be used as fuel or hydrogen production components, and part of the metal-containing carbon particle components can also be used as gasification raw materials to recover the metal in an oxidized state, that is, use oxidation Remove carbon by means of a method to obtain relatively pure metals and their oxides;

For specific metals, such as vanadium, nickel, molybdenum, chromium, etc., some of the separated solid particle components (Ki, i=1, 2, 3...) can be crushed to a diameter between 0.1-10um , and mixed into the liquid phase oil to fully disperse, and then return to the device for use as recycled oil.

Based on the above-mentioned method for recovering metals from heavy oil, the system for recovering metals from heavy oil in the present invention includes: a concentration unit, a solvent mixing unit, a solid-liquid separation unit, a solvent recovery unit, an insoluble matter delivery unit, an oxygen barrier dry distillation unit, cooling and Gas-liquid separation unit, solid crushing and separation unit, specific metal recycling mixing unit; specifically,

The concentration unit can be either an inorganic membrane separation device or a solvent deasphalting device; the concentration unit is used in the above step 110 to divide the heavy oil S1 into heavy component oil S2 and light component oil S3;

The solvent mixing unit can directly adopt the pipeline online mixing mode, or can adopt the pipeline mixing first and then the stirring tank mixing mode, and can also adopt the mixing mode of injecting solvent oil R in the stirring tank; the solvent mixing unit is used in the above step 120 to obtain the mixed Oil H1;

The solid-liquid separation unit can either use a separation device that relies on gravity sedimentation or a disc centrifugal separation device; the separation unit is used in the above step 130 to separate the mixed oil H1 into solids that are rich in solvent insolubles or rich in particles. Two parts: liquid mixed component HZ and light oil component or liquid phase component HQ relatively free of particles; if the separation unit adopts separation equipment relying on gravity settling, such as a settler, it is preferable to add a coagulant to accelerate the settling; If the separation unit adopts disc centrifugal separation equipment, such as a centrifuge, it is preferably a centrifuge with independent separator and separation tower;

The solvent recovery unit can be composed of a distillation tower or a rectification tower under normal pressure or reduced pressure, and is used in the above step 140 to decompose the light oil component HQ into solvent oil R and heavy oil components; wherein the solvent oil R is returned to the solvent The mixing unit is reused, and the heavy oil components can be used for other purposes, or mixed into the light component oil S3 produced by the heavy oil concentration unit, which contains relatively few large particles, for the next step of processing and utilization;

The insoluble material conveying unit can adopt equipment suitable for conveying high-viscosity materials such as screw pumps, screw conveyors or screw feeders; the oxygen-barrier carbonization unit can adopt either a vertical retort furnace capable of intermittent operation, or a horizontal continuous feed retort equipment, and a gas-phase discharge pipeline is set on the furnace roof or upper part of the furnace, and the temperature and time of the oxygen barrier dry distillation unit are adjustable and the time is controllable; the insoluble matter delivery unit is used in the above step 150 to enrich the solvent insoluble matter or rich in particulate matter The solid-liquid mixed component HZ is sent into the oxygen barrier dry distillation unit; the oxygen barrier dry distillation unit is also used in the above step 150 to dry out the solid carbon component G1, the steamed light gas-liquid component and the high-temperature reaction coking gas;

The cooling and gas-liquid separation unit can adopt a water-cooled heat exchanger or a heat exchanger that is first air-cooled and then water-cooled, followed by a gas-liquid separation device, and used in the above step 160 to divide the gas-liquid product from dry distillation into gas components and Liquid components; Among them, the gas phase discharge pipeline connected to the top of the gas-liquid separation equipment tank is used for other purposes after being pressurized by the compressor, and the liquid phase discharge pipeline connected to the tank bottom of the gas-liquid separation equipment is used for other purposes through the external delivery device of the pump For other purposes, it can be used as supplementary solvent oil R, and can also be used as other oil products;

The solid crushing and sorting unit can be composed of different types of crushers, pulverizers, mineral flotation machines, sorting water shakers, etc., and used in the above steps 170 and 180 to crush the solid carbon component G1 After that, various solid particle components enriched with different metals (Ki, i=1, 2, 3.....) are obtained;

The specific metal recycling mixing unit is composed of a particle nano pulverizer and a solid-liquid mixer, and is used in the above-mentioned step 190 to grind some of the selected solid particle components to a suitable value between 0.1-10um, and then in the solid The liquid phase oil (such as light component oil S3) is mixed into the liquid mixer, and after being fully dispersed, it is used as recycled oil and then returned to the device.

As shown in Figure 2, Figure 2 is a schematic diagram of the composition principle of the system for recovering metals from heavy oil by adopting the pre-inorganic membrane separation method and the subsequent sedimentation separation method in the present invention. The concentration unit 210 in this system uses an inorganic membrane separation device, and S1 is divided into two streams after being filtered by an inorganic membrane separation device, one is heavy component oil S2 rich in asphaltene and relatively more large particles, and the other is light component oil S3 containing relatively few large particles The heavy component oil S2 and the solvent oil R are mixed in the pipeline and enter the stirring tank 220 for further stirring and mixing to form the mixed oil H1; what the solid-liquid separation unit 230 in this system uses is a settler, and the mixed oil H1 enters the sedimentation through the pipeline After adding coagulant and settling for a period of time, mixed oil H1 is separated into light oil component HQ and enriched solvent insoluble matter HZ; light oil component HQ is located at the top of the settler and transported through pipelines and pumps The solvent recovery unit 240 is decomposed into solvent oil R and heavy oil components, wherein the solvent oil R is returned to the solvent mixing unit for reuse, and the heavy oil components are sent out of the system for other purposes or returned to the device for reuse; and the enriched solvent The insoluble matter HZ is sent to the oxygen barrier dry distillation unit 260 through the insoluble matter delivery unit 250 for dry distillation, and the distilled light gas-liquid components and the coking gas reacted at high temperature are cooled by the cooler 271 and then enter the gas-liquid separation device 272, and the dry distillation The gas-liquid product is divided into a gas component and a liquid component. The gas component is sent out of the system after being pressurized by a compressor through the top of the gas-liquid separation device 272, and the liquid component is sent out of the system through the tank bottom of the gas-liquid separation device 272. sent out to the system; and the solid carbon component G1 from the dry distillation enters the solid crushing and sorting unit 280, and after crushing, various solid particle components enriched in different metals are obtained according to different densities (Ki, i=1, 2, 3. ....), for solid particle components with high carbon content, the carbon is removed by oxidation to obtain relatively pure metals and their oxides; for specific metals, such as vanadium, nickel, molybdenum, chromium, etc., use The particles are further ground by the nano pulverizer, and the liquid phase oil is mixed into the solid-liquid mixer 290 and fully dispersed, and then returned to the device as recycled oil.

As shown in Figure 3, Figure 3 is a schematic diagram of the composition principle of the system for recovering metals from heavy oil by using pre-solvent deasphalting, separation, and subsequent sedimentation and separation. The difference from Figure 2 is that the enrichment in the system shown in Figure 3 Unit 210 uses a solvent deasphalting device. After the metal-containing heavy oil S1 passes through the solvent deasphalting device, it is divided into deasphalted oil and deoiled asphalt. The deasphalted oil is the light component oil S3, and the deoiled asphalt is the heavy component. Separation of oil S2.

As shown in Figure 4, Figure 4 is a schematic diagram of the composition principle of the system for recovering metals from heavy oil by adopting the pre-inorganic membrane separation and centrifugal separation after the preparation of the present invention. The difference from Figure 2 is that the solid-liquid separation in the system shown in Figure 4 Unit 230 uses disc centrifugal separation equipment. In the separator 231, the mixed oil H1 is separated into two parts: the solid-liquid mixed component HZ rich in particulate matter and the liquid phase component HQ relatively free of particulate matter. The liquid phase component HQ is transported to the solvent recovery unit 240 through pipelines and pumps to be decomposed, and the solid-liquid mixed component HZ rich in particulate matter enters the separation tower 232 and is transported to the oxygen barrier dry distillation unit 260 through the insoluble matter delivery unit 250 for dry distillation.

As shown in Figure 5, Figure 5 is a schematic diagram of the composition principle of the system for recovering metals from heavy oil by using pre-solvent deasphalting, separation, and centrifugal separation after blending. The difference from Figure 4 is that the enrichment in the system shown in Figure 5 Unit 210 uses a solvent deasphalting device. After the metal-containing heavy oil S1 passes through the solvent deasphalting device, it is divided into deasphalted oil and deoiled asphalt. The deasphalted oil is the light component oil S3, and the deoiled asphalt is the heavy component. Separation of oil S2.

A refinery in southern China has a total of 100,000 tons of heavy oil that needs to be processed. As shown in Figure 6, Figure 6 is a raw material composition table for a certain heavy oil used in the specific embodiment of metal recovery from heavy oil in the present invention, wherein, non-ferrous metal A, heavy metal B. The content of heavy metal C refers to the total content of one or two or more of vanadium, nickel, copper, molybdenum, chromium, and iron. The unit price is about 200,000/ton after weighted average. Calculated by the total amount, the content of non-ferrous metal A is 80 tons, the content of heavy metal B is 210 tons, and the content of heavy metal C is 280 tons. The total theoretical value of the recovery of the three metals is about 114 million yuan.

Taking the system shown in Figure 2 as an example, the enrichment unit 210 in this system adopts a complete set of inorganic membrane separation device. In the environment of 200-380°C, the heavy oil S1 is filtered with an inorganic membrane to obtain permeated oil (i.e. light Heavy component oil S3) and concentrated oil (heavy component oil S2); the permeated oil permeates through the inorganic membrane, and basically does not contain tetrahydrofuran insolubles, particles, and ash, while the concentrated oil is intercepted and concentrated by the inorganic membrane, and the permeated oil and The ratio of concentrated oil is about 4:6; considering 8,000 hours/year, permeate oil is about 5 tons/hour, 40,000 tons/year, and concentrated oil is about 7.5 tons/hour, 60,000 tons/year.

As shown in Fig. 7, Fig. 7 is an analysis table of the components and properties of the permeated oil and concentrated oil obtained by separating the heavy oil in Fig. 6 with the inorganic membrane of the present invention. It can be clearly seen from this table that most of the metals in the heavy oil are concentrated In the concentrated oil, this is also in line with the distribution of metals in heavy oil; after the concentrated oil comes out of the enrichment unit 210, it is re-mixed with solvent oil R in the pipeline according to the ratio of 1:1 and enters the stirring tank 220 for full stirring; considering the concentrated The oil has relatively high residual carbon content and aromatics content. The solvent oil R in this example is made by mixing alkanes from C6 to C20 and component oils mainly composed of single-ring aromatics, and the mixed oil H1 The temperature is controlled at about 180° C., and after being fully mixed and uniform, the mixed oil H1 is input into a tower-type gravity settling device (ie, solid-liquid separation unit 230 ) for separation.

After standing still for a period of time, the liquid phase component HQ is extracted from the middle and upper layers of the tower gravity settling equipment and pumped into the solvent recovery tower (i.e. the solvent recovery unit 240) for decomposition, wherein the solvent oil R is recycled, and the heavy oil group The points are returned to the device for reuse; and the enriched solvent insolubles HZ located at the bottom of the tower gravity settling equipment are input into the oxygen barrier dry distillation unit 260 through the screw conveyor (that is, the insolubles delivery unit 250) for dry distillation; after calculation, the mixed oil H1 is In the case of an input of 2.5 tons/hour, the output of the enriched solvent insoluble matter HZ located at the bottom of the tower gravity settling equipment is about 1.5 tons/hour; In 260, after a period of reaction, most of the solvents and solvent insolubles will undergo coking reactions, and the light components and coking gases produced will enter the gas-liquid separation equipment 272 for gas-liquid separation after being cooled by the cooler 271. The output of the obtained gas phase components and liquid phase components is also about 1.5 tons/hour, and the solid carbon component G1 after dry distillation is mostly carbon particles, and contains a small amount of volatile components, also known as dry distillation coke, dry distillation coke The output is also about 1 ton/hour; since the carbonization temperature of 550°C used is lower than the sublimation temperature of metals and metal compounds, most of the metal compounds remain in the carbonization coke. After calculation, the total metal content is about 7.1%. , of which the contents of non-ferrous metal A, heavy metal B, and heavy metal C are 1%, 2.6%, and 3.5%, respectively.

After cooling the retorted coke to normal temperature, it is input into the solid crushing and sorting unit 280 for crushing. Firstly, the retorted coke is crushed into particles K smaller than 2cm by a crusher, and then the particles K are ground into fine particles of 0.005mm-1mm by a mill. After sieving, classify according to the particle size, and return the large particles to the mill until the fine particles with a relatively uniform particle size are obtained, and then use the sorting water shaker to repeatedly sort the fine particles of the same level to obtain different densities The solid particle components (Ki, i=1, 2, 3.....), due to the different densities of enriched carbon, non-ferrous metal A, heavy metal B, and heavy metal C compounds, can respectively obtain enriched carbon, Four kinds of solid particle components enriched in non-ferrous metal A, enriched in heavy metal B, and enriched in heavy metal C; after calculation, the output of particle components enriched in carbon is 0.6 tons/hour, and the output of particle components enriched in nonferrous metal A 0.056 tons/hour, and the content purity of non-ferrous metal A is about 14%, the output of particle components enriched in heavy metal B is 0.15 tons/hour, and the content purity of heavy metal B is about 15%, and the particle concentration of heavy metal C is 0.15 tons/hour. The component output is 0.194 tons/hour, and the content purity of heavy metal C is about 16%.

In the above example, since the non-ferrous metal A and heavy metal B are utilized to obtain their oxidized metals, carbon can be further removed by oxidation to obtain relatively pure or higher-purity non-ferrous metal A and heavy metal B. and the utilization of heavy metal C is to maintain its original compound form, which needs to be sent back to the device for use, so the particles enriched in heavy metal C can be further pulverized. In the above-mentioned embodiment, a supersonic gas nano pulverizer is used , pulverize the particle component enriched in heavy metal C to the nanometer level as fine as possible, and add light component oil S3 or organic acid solvent into the solid-liquid mixer 290 to fully disperse, and then use the fluid pump to return to the device Utilize or send out the system for other purposes; in addition, the carbon-enriched particle components can be used as coal water slurry hydrogen production or raw materials for boilers, and the water used in the sorting water shaker can also be recycled to reduce environmental impact pollute.

The contents not described in detail in this specification belong to the prior art known to those skilled in the art.

It should be understood that the above descriptions are only preferred embodiments of the present invention, and are not sufficient to limit the technical solutions of the present invention. For those of ordinary skill in the art, within the spirit and principles of the present invention, they can Additions, substitutions, transformations or improvements are described, and all technical solutions after such additions, substitutions, transformations or improvements shall belong to the protection scope of the appended claims of the present invention.

Claims

A method for recovering metal from heavy oil, comprising the following steps:

Step C, fully stirring and mixing heavy component oil S2 and solvent oil R according to the ratio of 1:0.01~4, and controlling the temperature during mixing between 60-240°C to obtain mixed oil H1;

Step D, input the mixed oil H1 into a settler or centrifuge, after settling or centrifuging for a predetermined period of time, separate the mixed oil H1 into bottom and top two parts, the bottom is rich in solvent insolubles or solid-liquid rich in particles Mixing component HZ, the top is light oil component or liquid phase component HQ;

Step F, heat up the solid-liquid mixed component HZ enriched in solvent insolubles or rich in particulate matter HZ at the bottom and perform oxygen-barrier dry distillation to obtain solid carbon component G1, light components and coking gas, and the dry distillation temperature is lower than that recovered The sublimation temperature of metals and their metal compounds;

Step H, after crushing and sorting the dry-distilled solid carbon component G1, various solid particle components (Ki, i=1, 2, 3.... .).
The method for recovering metals from heavy oil according to claim 1, characterized in that before the step C, it also includes: step A, distilling and cutting the heavy oil S1 containing metal elements and raising the temperature.
The method for recovering metals from heavy oil according to claim 1, characterized in that, before step C, it also includes: step B, filtering heavy oil S1 by inorganic membrane filtration or deasphalting heavy oil S1 by solvent For extraction, the heavy oil S1 is filtered or extracted and divided into two stocks, one is the heavy component oil S2, and the other is the light component oil S3.
The method for recovering metals from heavy oil according to claim 1, characterized in that: the solvent oil R in the step C adopts ethylene oxide, propylene oxide, butylene oxide, carbon six to carbon twenty It is a mixture of one or more components of alkanes, naphthenes, methanol, ethanol and component oils mainly composed of single-ring aromatic hydrocarbons.
The method for recovering metal from heavy oil according to claim 1, characterized in that:

Step E is also included after step D, sending the light oil component HQ into the solvent recovery tower for distillation and separation to obtain solvent oil R and heavy oil components, and the heavy oil component removal device is used for other purposes, and solvent oil R is returned to step C Recycling; after step F, step G is also included, after cooling and gas-liquid separation of the light components and coking gas from dry distillation, the gas phase component separation device is used for other purposes, and the liquid phase components are treated as Solvent oil R is returned to step C for recycling.
A system for recovering metals from heavy oil, characterized in that it includes a solvent mixing unit, a solid-liquid separation unit, an oxygen barrier dry distillation unit and a solid crushing and sorting unit, wherein:

The solvent mixing unit is used to fully stir and mix the heavy component oil S2 and solvent oil R according to the ratio of 1:0.01~4, and the temperature during mixing is controlled between 60-240°C to obtain the mixed oil H1;

The solid-liquid separation unit is used to input the mixed oil H1 into a settler or centrifuge, and after settling or centrifuging for a predetermined period of time, the mixed oil H1 is separated into two parts, the bottom and the top, and the bottom is enriched with solvent insolubles or enriched The solid-liquid mixed component HZ containing particulate matter, the top is light oil component or liquid phase component HQ;

The oxygen barrier dry distillation unit is used to send the solid-liquid mixed component HZ rich in solvent insolubles or particles rich in the bottom into the oxygen barrier dry distillation device for heating, and the dry distillation temperature is lower than the sublimation of recovered metals and their metal compounds temperature; the solid crushing and sorting unit is used for crushing and sorting the solid carbon component G1 from dry distillation to obtain various solid particle components with uniform particle size and enrichment of different metals (Ki, i=1 ,2,3.....).
The system for recovering metals from heavy oil according to claim 6, wherein the system further comprises:

Concentration unit, used to filter heavy oil S1 by means of inorganic membrane filtration or extract heavy oil S1 by solvent deasphalting, divide heavy oil S1 into two streams after filtration or extraction, one is heavy component oil S2, One is light component oil S3.
The system for recovering metals from heavy oil according to claim 6, characterized in that: the solvent oil R in the solvent mixing unit adopts ethylene oxide, propylene oxide, butylene oxide, carbon six to carbon twenty It is formed by mixing one or several components of alkanes, naphthenes, methanol, ethanol and single-ring aromatics-based component oils.
The system for recovering metals from heavy oil according to claim 6, wherein the system also includes a solvent recovery unit and a cooling and gas-liquid separation unit, wherein:

The solvent recovery unit is used to send the light oil component HQ separated by the solid-liquid separation unit into the solvent recovery tower for distillation and separation to obtain solvent oil R and heavy oil components. The heavy oil component extraction device is used for other purposes, solvent oil R is returned to the solvent mixing unit for recycling; the cooling and gas-liquid separation unit is used for cooling and gas-liquid separation of the light components and coking gas from the oxygen barrier dry distillation unit, and the gas phase component separation device is another After the liquid phase components are processed, they are returned to the solvent mixing unit as solvent oil R for recycling.
The system for recovering metals from heavy oil according to claim 6, characterized in that the system also includes: a specific metal recycling mixing unit, which is used to grind part of the solid particle components separated by the solid crushing and sorting unit to Between 0.1-10um, and mixed with the light component oil S3 obtained in the enrichment unit to fully disperse it, and use it as a recycled oil return device.