CN114479899A - Recycling treatment device and method for oil-containing and water-containing solid mixture - Google Patents
Recycling treatment device and method for oil-containing and water-containing solid mixture Download PDFInfo
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- CN114479899A CN114479899A CN202210174636.2A CN202210174636A CN114479899A CN 114479899 A CN114479899 A CN 114479899A CN 202210174636 A CN202210174636 A CN 202210174636A CN 114479899 A CN114479899 A CN 114479899A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/15—Treatment of sludge; Devices therefor by de-watering, drying or thickening by treatment with electric, magnetic or electromagnetic fields; by treatment with ultrasonic waves
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
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Abstract
The invention discloses a resource treatment device and a resource treatment method for an oil-containing water-containing solid mixture, wherein the resource treatment device comprises a raw material physical and chemical property analysis and control conveying unit, a raw material deep pretreatment unit, a high-efficiency oil extraction unit, a multi-effect separation and recovery unit and a two-stage deep pyrolysis coupling catalytic cleaning and incineration unit; the method has the advantages of remarkable recycling treatment effect, strong raw material adaptability, simple and efficient process flow, low device construction investment and environmental friendliness, and has wide application prospect in the field of recycling treatment of oil-containing water-containing solid mixtures.
Description
Technical Field
The invention belongs to the field of energy chemical industry, relates to a resource utilization technology of energy chemical industry wastes, and particularly relates to a resource treatment device and method of an oil-containing water-containing solid mixture.
Background
The oil-containing water-containing solid mixture is a muddy solid waste which is generated in the energy and chemical engineering process and consists of oil-in-water (O/W), water-in-oil (W/O) particles and ultrafine particle size solid (carbon-containing) and has extremely stable property, high viscosity and complex components, and is also called oil-containing sludge or tank bottom oil sludge and the like. The oil-containing water-containing solid mixture is rich in hydrocarbons, colloids and asphaltenes, and has high resource utilization value, but due to different factors such as mining areas, production processes, storage conditions, catalysts, additives and the like, the properties of the mixture are different, and the resource treatment is difficult to complete by a single treatment technology. Due to the fact that the water content is high, dehydration treatment is carried out in the first step of most of traditional technical schemes, but due to the hydration and the electrostatic property of the oil-containing water-containing solid mixture, the oil-containing water-containing solid mixture presents an extremely stable emulsification system, demulsification is difficult, energy consumption is extremely high, and the existing treatment technology is complex in device, high in energy consumption, large in waste water amount and difficult to operate for a long period.
In order to better solve the problem of the oil-containing water-containing solid mixture resource treatment technology, the existing treatment technology needs to be innovated, coupled and strengthened, and the practical requirements in the field are to develop a resource treatment technology of the oil-containing water-containing solid mixture, which is resource-based, reduced, low-cost and harmless, and to furthest improve the technical economy and environmental friendliness.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a recycling treatment device and a recycling treatment method for an oil-containing water-containing solid mixture, which are recycled, reduced, low in cost and harmless, and can realize high-efficiency recovery and separation of oil products in the oil-containing water-containing solid mixture and low-carbon, low-energy-consumption and clean treatment of solid residues.
In order to achieve the purpose, the invention adopts the following technical scheme:
a resource treatment device for an oil-containing water-containing solid mixture comprises a raw material physical and chemical property analysis and control conveying unit, a raw material deep pretreatment unit, a high-efficiency oil extraction unit, a multi-effect separation and recovery unit and a two-stage deep pyrolysis coupling catalytic cleaning incineration unit;
the raw material physical and chemical property analysis and control conveying unit comprises a first control conveying unit and a second control conveying unit which are connected with the raw material, the first control conveying unit is also connected with the clean conveying system, and the second control conveying unit is also connected with an inlet of the viscosity reduction demulsification settling separation tank; a raw material physical and chemical property analysis controller is arranged on a connecting pipeline between the raw material and the first control conveying unit and the second control conveying unit; the raw material physical and chemical property analysis controller is connected with the first control conveying unit and the second control conveying unit through signal lines;
the raw material deep pretreatment unit comprises a viscosity-reducing demulsification settling separation tank and a clean conveying system which are connected, and an outlet at the upper side of the viscosity-reducing demulsification settling separation tank is connected with the primary wastewater treatment system; the viscosity-reducing demulsification sedimentation separation tank is also connected with a demulsification viscosity-reducing agent storage tank;
the high-efficiency oil extraction unit comprises a primary oil extraction tank, a secondary oil extraction tank, an N-stage oil extraction tank, a first high-efficiency separator, a double-liquid-phase deep enhanced extraction tank and a second high-efficiency separator; the material outlet of the clean conveying system is connected with the solid inlet of the first-stage oil extraction tank, the outlets at the bottoms of the first-stage oil extraction tank, the second-stage oil extraction tank and the N-stage oil extraction tank are connected with the inlet of the first high-efficiency separator, and the solid outlet of the first high-efficiency separator is also connected with the solid inlets of the second-stage oil extraction tank, the N-stage oil extraction tank and the double-liquid-phase deep enhanced extraction tank; the discharge port of the double-liquid-phase deep enhanced extraction tank is also connected with the feed port of the high-efficiency separator II; the liquid outlets of the first high-efficiency separator and the second high-efficiency separator are also connected with an extract liquid storage tank;
the multi-effect separation and recovery unit comprises an extract storage tank, an enhanced flash separator inlet heat exchanger, an enhanced flash separator, a flash separator heat recovery system and a fractionating tower which are connected in sequence; the top outlet of the enhanced flash separator is also sequentially connected with an oil-water separator, a heat recoverer and an oil-water separation tank; the upper outlets of the light oil recovery system and the oil-water separation tank connected with the top of the fractionating tower are connected with the upper inlets of the sides of the primary oil extraction tank, the secondary oil extraction tank and the N-stage oil extraction tank;
the two-stage deep pyrolysis coupling catalysis cleaning incineration unit comprises a two-stage deep pyrolysis reactor and a catalysis strengthening cleaning incinerator which are sequentially connected with a solid outlet of the high-efficiency separator II, and top outlets of the two-stage deep pyrolysis reactor and the catalysis strengthening cleaning incinerator are sequentially connected with a high-efficiency gas-solid dust collector, a purification tower inlet heat exchanger and a purification tower.
Furthermore, a plurality of ultrasonic coupling electric field generators are radially and symmetrically distributed in the tank wall of the viscosity-reducing demulsification settling separation tank; the ultrasonic coupling electric field generator is one or a combination of an ultrasonic generator and an electric field generator; the diameter of the cylinder body part of the viscosity-reducing demulsification settling separation tank is D, and the height of the cylinder body part of the viscosity-reducing demulsification settling separation tank is H; the viscosity reducing demulsification sedimentation separation tank is internally provided with a guide cylinder which is axially arranged along the viscosity reducing demulsification sedimentation separation tank, the diameter D of the guide cylinder is 0.2-0.95D, the wall thickness Z is 0.001-0.3D, and the distance H between the lower edge of the guide cylinder and the bottom of the viscosity reducing demulsification sedimentation separation tank is 0.001-0.4H; the inside three-dimensional spiral stirring paddle that is equipped with of draft tube, three-dimensional spiral stirring paddle diameter K be 0.35 ~ 0.99d, high G be 0.35 ~ 1.3h, single spiral layer height P be 0.1 ~ 1G.
Further, the two-stage deep pyrolysis reactor comprises a thermal desorption reactor and a catalytic pyrolysis reactor which are sequentially connected from bottom to top according to the incoming material direction; the thermal desorption reactor adopts an inert atmosphere operating environment, the temperature rise rate is 5-20 ℃/min, and the final reaction temperature is 320-570 ℃; the temperature rise rate of the catalytic pyrolysis reactor is 5-20 ℃/min, and the final reaction temperature is 610-900 ℃.
Furthermore, a conveying system formed by connecting a plurality of groups of screws in parallel is assembled in the clean conveying system; a heat preservation heat tracing system is arranged outside the clean conveying system; a discharge hole of the clean conveying system is provided with a flushing oil ejector, and the flushing oil ejector is also sequentially connected with a flushing oil control valve and a light oil recovery system; a plurality of jet ports are radially and symmetrically distributed on the flushing oil ejector; and a plurality of groups of flushing purging ports are arranged on the inner wall of each group of spiral of the clean conveying system, and flushing purging valves are connected between all the flushing purging ports and the flushing purging agent.
Further, an outlet at the bottom of the oil-water separation tank is also connected with a secondary wastewater treatment system; the middle part of the fractionating tower is also connected with a middle-section fraction product recovery system, and the bottom of the fractionating tower is also connected with a heavy oil recovery system; the bottom of the purification tower is connected with a secondary oil-water separation system, and the top of the purification tower is connected with a flue gas treatment system.
Further, the catalytic strengthening cleaning incinerator is respectively connected with a catalyst supply system and a blending agent supply system, and the bottom of the catalytic strengthening cleaning incinerator is also connected with a clean ash discharge system; the catalytic strengthening cleaning incinerator adopts one or a combination of a circulating fluidized bed, an entrained flow bed and a fixed bed; the incineration catalyst filled in the catalyst supply system is CaO and Fe2O3KCl, a supported catalyst and pyrolysis residue; the blended combustion agent filled in the blended combustion agent supply system is one or a mixture of a plurality of drying agents, forming agents, coal powder, semicoke, pyrolysis residues, biomass and fuel treatment agents.
A resource treatment method of an oil-containing water-containing solid mixture comprises the following steps:
the method comprises the following steps: analysis of physical and chemical properties of raw materials and controlled conveying
The physical and chemical properties of the raw materials are analyzed by the raw material physical and chemical property analysis controller, when the water content of the raw materials is more than 2-80%, the raw material physical and chemical property analysis controller operates the second conveying unit to start, and the raw materials enter the viscosity reduction demulsification sedimentation separation tank; when the water content of the raw materials is less than 2-80%, the raw material physical and chemical property analysis controller operates the control conveying unit to start, and the raw materials directly enter the clean conveying system;
step two: advanced pretreatment of raw materials
The raw material with the water content of more than 2-80% enters a viscosity-reducing demulsification settling separation tank, a demulsification viscosity-reducing agent storage tank adds a demulsification viscosity-reducing agent with the amount required by the process into the viscosity-reducing demulsification settling separation tank, the mixture is fully stirred by a three-dimensional spiral stirring paddle for 0.01-3 hours to form axial circulating liquid flow inside and outside a guide cylinder, and then an ultrasonic coupling electric field demulsification strengthening device sends one or more combinations of ultrasonic waves and an electric field to strengthen viscosity-reducing demulsification of the raw material for 0.01-24 hours; standing the raw materials subjected to the enhanced viscosity-reducing demulsification for 0.01-24 h in a viscosity-reducing demulsification settling separation tank for 0.1-72 h, removing a water layer from a primary wastewater treatment system, and conveying a solid layer to a primary oil extraction tank by a clean conveying system; the flushing oil control valve automatically controls a jet orifice assembled on the discharge port to spray flushing oil to lubricate the material; when the clean conveying system is blocked, the flushing and purging port is controlled by the flushing and purging valve to spray flushing and purging agent for dredging;
step three: multistage high-efficiency oil extraction
The raw materials pretreated in the second step enter a first-stage oil extraction tank, oil extraction is carried out for 0.01-3 h at the temperature of 20-100 ℃, then the raw materials enter an efficient separator for separating liquid and solid, the separated solid and recovered extraction liquid enter a second-stage oil extraction tank, and the separated liquid enters an extraction liquid storage tank; repeating the processes until the solid and the recovered extraction liquid in the Nth-1-stage oil extraction tank enter the Nth-stage oil extraction tank for extracting and extracting oil for 0.01-3 h at 20-100 ℃, then entering a first efficient separator for separation, enabling the separated liquid to enter an extraction liquid storage tank, enabling the separated solid to enter a double-liquid-phase deep enhanced extraction tank for extracting and extracting oil for 0.01-3 h through deep enhanced extraction liquid, then entering a second efficient separator for separation, enabling the separated extraction liquid to enter an extraction liquid storage tank, and enabling the separated solid to enter a two-stage deep pyrolysis reactor;
step four: multiple effect separation and recovery
Heating an extract in an extract storage tank by an inlet heat exchanger of a flash separator, then feeding the extract into an enhanced flash separator for flash separation at the temperature of 50-700 ℃ under the pressure of 0.001-3.0 Mpa, cooling a light component separated from a top product of the enhanced flash separator in an oil-water separator by a heat recovery device, feeding the light component into an oil-water separation tank for further separation, feeding a part of recovered extracting agent separated by the oil-water separation tank into a primary oil extraction tank, a secondary oil extraction tank and an N-stage oil extraction tank, and feeding water separated by the oil-water separation tank into a secondary wastewater treatment system for further treatment; heavy materials at the bottom of the enhanced flash separator enter a flash separator heat recovery system to recover heat and then enter a fractionating tower to carry out fraction cutting; the product at the top of the fractionating tower enters a light oil recovery system to separate light oil products; the middle product and the bottom product of the fractionating tower respectively enter a middle distillate product recovery system and a heavy oil recovery system to be separated to produce a middle distillate product and a heavy oil product;
step five: pyrolysis upgrading and clean incineration
Enabling the solid separated by the second efficient separator to enter a thermal desorption reactor to perform thermal desorption reaction at the temperature rise rate of 5-20 ℃/min under the inert atmosphere, wherein the final reaction temperature is 320-570 ℃; the reaction residues of the thermal desorption reactor enter a catalytic pyrolysis reactor, and a pyrolysis catalyst is adopted to carry out pyrolysis at the temperature rise rate of 5-20 ℃/min, wherein the final reaction temperature is 610-900 ℃; pyrolysis oil gas generated after two-stage deep pyrolysis is subjected to dust removal through a high-efficiency gas-solid dust remover, then enters a purification tower for purification and separation after heat exchange through a purification tower inlet heat exchanger, a product at the bottom of the purification tower enters a secondary oil-water separation system for continuous deep oil-water separation, and a product at the top of the purification tower enters a flue gas treatment system for environment-friendly treatment; after being deeply pyrolyzed by the two-stage deep pyrolysis reactor, the solid residue is mixed with an incineration catalyst and a blending agent and then is incinerated by the catalytic enhanced cleaning incinerator to generate steam and heat to be supplied to the whole system, the incineration residue at the bottom of the catalytic enhanced cleaning incinerator enters a clean ash discharge system, and flue gas generated by the catalytic enhanced cleaning incinerator is merged into a purification tower for further treatment.
Furthermore, the pyrolysis catalyst filled in the catalytic pyrolysis reactor is MnO2、CaO、CoCl2KCl, a supported catalyst, pyrolysis residue and biomass; the double-liquid-phase deep enhanced extraction tank is filled with deep enhanced extraction liquid, and the extraction phase state of the deep enhanced extraction tank is double liquid phases; the deep reinforcementThe extract is one or more of ionic liquid, microemulsion and supercritical fluid.
Further, the flushing and purging agent is one or a mixture of a plurality of low-pressure steam, nitrogen, a recovered extracting agent, desalted water, tar, coal tar and heavy oil; the raw material is one or a mixture of more of oil-containing sludge, coal-based oil sludge, coal chemical oil sludge, tower bottom oil sludge, oil field oil sludge, sand basin oil sludge, tank cleaning sludge, oil tank bottom sludge, ground oil sludge, oil sludge of a sewage treatment plant, refined oil sludge and oil sludge of a mail steamer.
Further, the demulsifying and viscosity reducing agent stored in the demulsifying and viscosity reducing agent storage tank is a mixture of one or more of ionic surfactant, nonionic surfactant, amphoteric surfactant, compound surfactant, hydroxy fat, organic acid, sodium silicate, carboxymethyl cellulose, naphtha, polyalcohol, polyester, low-carbon olefin and long-chain alkane. The invention has the beneficial effects that:
1) the invention discloses a novel oil-water-containing solid mixture recycling device which comprises a raw material physical and chemical property analysis and control conveying unit, a raw material deep pretreatment unit, a high-efficiency oil extraction unit, a multi-effect separation and recovery unit and a two-stage deep pyrolysis coupling catalytic clean incineration unit, optimizes the key technical link of resource utilization of the oil-water-containing solid mixture, and can treat the oil-water-containing solid mixture with high viscosity, complex components and extremely stable properties in a recycling, reducing, low-cost and harmless manner.
2) The invention discloses a viscosity-reducing demulsification sedimentation separation tank provided with an ultrasonic coupling electric field generator, which strengthens the pretreatment process of raw materials by the combination of one or more of ultrasonic waves and an electric field, so that a stable emulsification system caused by hydration and electrostatic properties is broken, an oil-containing water-containing solid mixture is easier to resolve, stratify and dehydrate, and the major problem which troubles the technical field of pretreatment of the oil-containing water-containing solid mixture is broken.
3) The efficient oil extraction unit is invented, mechanical centrifugal separation and N-level cross extraction are combined, the extraction efficiency is greatly improved compared with the traditional extraction process, and organic components in an oil-containing water-containing solid mixture can be efficiently recovered; meanwhile, a double-liquid-phase deep enhanced extraction technology is coupled, one or more mixtures of ionic liquid, microemulsion and supercritical fluid are used for deep extraction of the oil-containing water-containing solid mixture, oil-containing components are completely squeezed, and the extraction efficiency is fundamentally improved. Compared with the traditional extraction technology, the high-efficiency oil extraction unit has the advantages of greatly improved extraction efficiency, stronger raw material adaptability, lower solvent cost, simple and efficient process flow, simple and convenient process operation and lower investment, and can economically and efficiently realize the resource recycling of oil products in the oil-containing water-containing solid mixture.
4) The multi-effect separation and recovery unit is invented, and the efficient recovery of the extraction solvent and the multi-effect separation of the extraction product are realized by introducing key process units such as the enhanced flash separator, the flash separator heat recovery system, the fractionating tower, the light oil recovery system and the heavy oil recovery system.
5) The invention discloses a two-stage deep pyrolysis coupling catalytic cleaning incineration unit, which is used for further carrying out deep quality improvement on extracted residues through two-stage deep pyrolysis, mixing the pyrolyzed residues with an incineration catalyst and a doped combustion agent and then incinerating the mixed residues in a catalytic strengthening cleaning incinerator, so that pollutants in an oil-containing water-containing solid mixture can be efficiently removed and heat is provided for the whole system, and the incinerated residues almost do not contain organic matters and toxic substances and can be applied to the aspects of buildings, road and bridge construction and the like. Compared with the prior art, the method can solve the problem that the extraction residue of the oil-containing water-containing solid mixture cannot be treated in an environment-friendly manner in the prior art, and has remarkable beneficial effects.
Drawings
FIG. 1 is a schematic view of the overall structure of the present invention
FIG. 2 is a schematic structural diagram of the viscosity-reducing demulsification settling separation tank of the present invention
FIG. 3 is a schematic structural view of a two-stage deep pyrolysis reactor according to the present invention
FIG. 4 is a schematic view of a dual-liquid-phase deep enhanced extraction tank according to the present invention
FIG. 5a is a schematic side view of a clean delivery system according to the present invention
FIG. 5b is a schematic top view of the clean delivery system of the present invention
FIG. 6 is a schematic view showing the structure of a flushing oil ejector according to the present invention
FIG. 7 is a schematic view of the catalytic enhanced cleaning burner of the present invention
In the figure: 1. raw materials; 2. a raw material physical and chemical property analysis controller; 3. controlling the first conveying unit; 4. controlling a second conveying unit; 5. a viscosity-reducing demulsification settling separation tank; 6. a demulsifying and viscosity reducing agent storage tank; 7. a clean delivery system; 8. a primary wastewater treatment system; 9. a first-stage oil extraction tank; 10. a secondary oil extraction tank; 11. an N-stage oil extraction tank; 12. a first high-efficiency separator; 13. a double-liquid-phase deep enhanced extraction tank; 14. a second high-efficiency separator; 15. an extract liquid storage tank; 16. an enhanced flash separator inlet heat exchanger; 17. an intensified flash separator; 18. an oil-water separator; 19. a heat recoverer; 20. an oil-water separation tank; 21. a secondary wastewater treatment system; 22. a flash separator heat recovery system; 23. a fractionating column; 24. a light oil recovery system; 25. a middle distillate product recovery system; 26. a heavy oil recovery system; 27. a two-stage deep pyrolysis reactor; 28. catalyzing and strengthening the cleaning burner; 29. a clean ash discharge system; 30. a high-efficiency gas-solid dust remover; 31. a purge column inlet heat exchanger; 32. a purification tower; 33. a flue gas treatment system; 34. a secondary oil-water separation system; 35. a catalyst supply system; 36. a blending agent supply system; 37. an ultrasonic coupling electric field demulsification strengthening device; 38. a draft tube; 39. a three-dimensional spiral stirring paddle; 40. a thermal desorption reactor; 41. a catalytic pyrolysis reactor; 42. deeply strengthening the extract liquor; 43. a heat tracing and heat preservation system; 44. a discharge port; 45. a flush oil control valve; 46. flushing the purge valve; 47. a flushing oil jet; 48. flushing a purging agent; 49. flushing the purging port; 50. an ejection port; 51. demulsifying and viscosity reducing agent; 52. a pyrolysis catalyst; 53. incinerating the catalyst; 54. and (3) mixing a burning agent.
Detailed Description
The invention is described in further detail below with reference to the figures and the examples, but without limiting the invention.
Referring to fig. 1, the resource treatment device for the mixture of oil-containing water-containing solids comprises a raw material physical and chemical property analysis and control conveying unit, a raw material deep pretreatment unit, a high-efficiency oil extraction unit, a multi-effect separation and recovery unit and a two-stage deep pyrolysis coupling catalytic cleaning incineration unit.
Referring to fig. 1, the raw material physical and chemical property analysis and control conveying unit comprises a first control conveying unit 3 and a second control conveying unit 4 which are both connected with the raw material 1, the first control conveying unit 3 is also connected with a clean conveying system 7, the second control conveying unit 4 is also connected with an inlet of a viscosity reduction demulsification sedimentation separation tank 5, and a raw material physical and chemical property analysis controller 2 is also vertically connected to a connecting pipeline between the raw material 1 and the first control conveying unit 3 as well as the second control conveying unit 4; the raw material physical and chemical property analysis controller 2 is connected with the first control conveying unit 3 and the second control conveying unit 4 through signal lines, and operates and controls the actions of the first control conveying unit 3 and the second control conveying unit 4 according to the analysis result of the physical and chemical properties of the raw material 1.
Referring to fig. 1, the raw materials degree of depth pretreatment unit is including the visbreaking of viscosity reduction subsides knockout drum 5 and the clean conveying system 7 that are connected, and visbreaking of viscosity reduction subsides knockout drum 5 bottom solid outlet links to each other with clean conveying system 7, and the export connection in one-level effluent disposal system 8 of the side upper portion of visbreaking of viscosity reduction subsides knockout drum 5 still is connected with emulsion breaking viscidity agent storage tank 6 on the visbreaking of viscosity reduction subsides knockout drum 5.
Referring to fig. 1, the high-efficiency oil extraction unit comprises a primary oil extraction tank 9, a secondary oil extraction tank 10, an N-stage oil extraction tank 11, a first high-efficiency separator 12, a double-liquid-phase deep enhanced extraction tank 13 and a second high-efficiency separator 14; the material outlet of the clean conveying system 7 is connected with the solid inlet of the first-stage oil extraction tank 9, the bottom outlets of the first-stage oil extraction tank 9, the second-stage oil extraction tank 10 and the N-stage oil extraction tank 11 are connected with the inlet of the first high-efficiency separator 12, the solid outlet of the first high-efficiency separator 12 is also connected with the solid inlets of the second-stage oil extraction tank 10, the N-stage oil extraction tank 11 and the double-liquid-phase depth strengthening extraction tank 13, the outlet of the double-liquid-phase depth strengthening extraction tank 13 is connected with the material inlet of the second high-efficiency separator 14, and the liquid outlets of the first high-efficiency separator 12 and the second high-efficiency separator 14 are also connected with the extraction liquid storage tank 15.
Referring to fig. 1, the multi-effect separation and recovery unit comprises an extract storage tank 15, an enhanced flash separator inlet heat exchanger 16, an enhanced flash separator 17, a flash separator heat recovery system 22 and a fractionating tower 23 which are connected in sequence; an outlet of the extract storage tank 15 is communicated with an inlet of an enhanced flash separator 17 through an enhanced flash separator inlet heat exchanger 16, and an outlet at the top of the enhanced flash separator 17 is also sequentially connected with an oil-water separator 18, a heat recoverer 19 and an oil-water separation tank 20; the light oil recovery system 24 and the upper outlet of the oil-water separation tank 20 connected with the top of the fractionating tower 23 are connected with the side upper inlets of the primary oil extraction tank 9, the secondary oil extraction tank 10 and the N-stage oil extraction tank 11; the outlet at the bottom of the oil-water separation tank 20 is also connected with a secondary wastewater treatment system 21, the middle part of the fractionating tower 23 is also connected with a middle-stage fraction product recovery system 25, and the bottom of the fractionating tower 23 is also connected with a heavy oil recovery system 26.
As shown in fig. 1 and 7, the two-stage deep pyrolysis coupling catalytic cleaning incineration unit comprises a two-stage deep pyrolysis reactor 27 and a catalytic strengthening cleaning incinerator 28 which are sequentially connected with the solid outlet of the second high-efficiency separator 14. The top outlets of the two-stage deep pyrolysis reactor 27 and the catalytic strengthening cleaning incinerator 28 are sequentially connected with a high-efficiency gas-solid dust remover 30, a purification tower inlet heat exchanger 31 and a purification tower 32; the bottom of the purification tower 32 is connected with a secondary oil-water separation system 34, and the top of the purification tower 32 is connected with a flue gas treatment system 33; the catalytic strengthening cleaning burner 28 is respectively connected with a catalyst supply system 35 and a blending agent supply system 36, and the bottom of the catalytic strengthening cleaning burner 28 is also connected with a clean ash discharge system 29. The solid residue after the deep pyrolysis in the two-stage deep pyrolysis reactor 27 is mixed with the incineration catalyst 53 provided by the catalyst supply system 35 and the combustion improver 54 provided by the combustion improver supply system 36, and then is incinerated in the catalytic enhanced cleaning incinerator 28 to generate steam and heat to be supplied to the whole system.
Referring to FIG. 2, the viscosity-reducing demulsifying settling tank 7 of the present invention is described in further detail.
2n (n is an integer greater than 1) ultrasonic coupling electric field generators 37 are radially and symmetrically distributed in the tank wall of the viscosity-reducing demulsification settling separation tank 5, and the ultrasonic coupling electric field generators 37 are one or a combination of more than one ultrasonic generator and one electric field generator; the diameter of the cylinder body part of the viscosity-reducing demulsification settling separation tank 5 is D, the height of the cylinder body part of the viscosity-reducing demulsification settling separation tank 5 is H, a guide cylinder 38 axially installed along the viscosity-reducing demulsification settling separation tank 5 is arranged, the diameter D of the guide cylinder 38 is 0.2-0.95D, the wall thickness Z is 0.001-0.3D, the distance H between the lower edge of the guide cylinder 38 and the bottom of the viscosity-reducing demulsification settling separation tank 5 is 0.001-0.4H, a three-dimensional spiral stirring paddle 39 is assembled in the guide cylinder, the diameter K of the three-dimensional spiral stirring paddle 39 is 0.35-0.99D, the height G is 0.35-1.3H, and the height P of a single spiral layer is 0.1-1G; the specially designed three-dimensional spiral stirring paddle 39 can fully stir the raw material 1 to form a circulating liquid flow which is convenient for demulsification inside and outside the guide cylinder 38. The demulsification viscosity-reducing agent storage tank 6 stores a demulsification viscosity-reducing agent 51, wherein the demulsification viscosity-reducing agent 51 is one or a mixture of more of ionic surfactant, nonionic surfactant, amphoteric surfactant, compound surfactant, hydroxy fat, organic acid, sodium silicate, carboxymethyl cellulose, naphtha, polyalcohol, polyester, low-carbon olefin and long-chain alkane, and can fully promote demulsification through surface interface effect and the like. Referring to FIG. 3, the two-stage deep pyrolysis reactor 27 of the present invention is described in further detail.
The two-stage deep pyrolysis reactor 27 comprises a thermal desorption reactor 40 and a catalytic pyrolysis reactor 41 which are sequentially connected from bottom to top according to the incoming material direction; the thermal desorption reactor 40 adopts an operating environment of inert atmosphere, the temperature rise rate is 5-20 ℃/min, and the final reaction temperature is 320-570 ℃; the temperature rise rate of the catalytic pyrolysis reactor 41 is 5-20 ℃/min, and the final reaction temperature is 610-900 ℃; the pyrolysis catalyst 52 filled in the catalytic pyrolysis reactor 41 is MnO2、CaO、CoCl2KCl, a supported catalyst, pyrolysis residue and biomass.
Referring to fig. 4, the dual liquid phase deep enhanced extraction tank 13 of the present invention will be described in further detail.
The deep enhanced extraction liquid 42 is filled in the double-liquid-phase deep enhanced extraction tank 13, and because the deep enhanced extraction liquid 42 has special properties, a double-liquid-phase extraction environment is formed in the double-liquid-phase deep enhanced extraction tank 13 and an extracted substance, so that the extraction strength is greatly improved; the depth enhancing extraction liquid 42 is a mixture of one or more of ionic liquids, microemulsions, and supercritical fluids.
Referring to fig. 5a, 5b and 6, the clean delivery system 7 of the present invention will be described in further detail.
The clean conveying system 7 is internally provided with a conveying system formed by connecting a plurality of groups of screws in parallel, and the M groups of screws are externally provided with a heat-preservation heat tracing system 43 heated by one or a plurality of combinations of low-pressure steam, hot water and electric heating so as to ensure that the raw material 1 can ensure certain temperature and fluidity in the conveying process and is not easy to block. A flushing oil injector 47 is annularly arranged on the discharge port 44 of the clean conveying system 7, and 2q (q is an integer larger than 1) injection ports 50 are radially symmetrically distributed around the discharge port 44 and controlled by a flushing oil control valve 45, and the flushing oil from the light oil recovery system 24 is uniformly sprayed to the discharge port 44. The inner walls of the M groups of screws are provided with a plurality of groups of flushing and purging ports 49, and the header pipes of all the flushing and purging ports 49 are provided with flushing and purging valves 46 connected with a flushing and purging agent 48. The flush purge agent 48 is a mixture of one or more of low pressure steam, nitrogen, recycled extractant, desalted water, tar, coal tar, and heavy oil.
The resource treatment method of the oil-containing water-containing solid mixture comprises the following steps:
the raw material 1 is one or a mixture of more of oil-containing sludge, coal-based oil sludge, coal chemical oil sludge, tower bottom oil sludge, oil field oil sludge, sand basin oil sludge, tank cleaning sludge, oil tank bottom sludge, ground oil sludge, oil sludge of a sewage treatment plant, refined oil sludge and oil sludge of a passenger liner. This example will be described by taking only the oily sludge as an example.
The method comprises the following steps: analysis of physical and chemical properties of raw materials and controlled conveying
The raw material physicochemical property analysis controller 2 analyzes the physicochemical properties of the raw material 1, when the water content of the raw material 1 is more than 2-80%, the raw material physicochemical property analysis controller 2 operates and controls the second conveying unit 4 to start, and the raw material 1 enters the viscosity reduction demulsification sedimentation separation tank 5; when the water content of the raw material 1 is less than 2-80%, the raw material physical and chemical property analysis controller 2 operates the first control conveying unit 3 to start, and the raw material 1 directly enters the clean conveying system 7.
Step two: advanced pretreatment of raw materials
The raw material 1 with the water content of more than 2-80% enters a viscosity-reducing demulsification settling separation tank 5, a demulsification viscosity-reducing agent storage tank 6 adds a demulsification viscosity-reducing agent 51 with a process requirement amount into the viscosity-reducing demulsification settling separation tank 5, and after the mixture is fully stirred for 0.01-3 hours by a three-dimensional spiral stirring paddle 39, an axial circulating liquid flow is formed inside and outside a guide cylinder 38, and the circulating liquid flow can greatly promote a demulsification process; then, the ultrasonic coupling electric field demulsification strengthening device 37 sends one or more combinations of ultrasonic waves and electric fields to carry out strengthened viscosity reduction demulsification on the raw material 1 for 0.01-24 h, and the oil-containing water-containing solid mixture is subjected to analytic layering dehydration under the action of the ultrasonic coupling electric field demulsification strengthening device 37; after the raw material 1 subjected to the enhanced viscosity-reducing demulsification for 0.01-24 h is placed in a viscosity-reducing demulsification settling separation tank 5 for settling for 0.1-72 h, a water layer is removed to a primary wastewater treatment system 8 for primary treatment, and a solid layer is conveyed to a primary oil extraction tank 9 by a clean conveying system 7; the flushing oil control valve 45 automatically controls 2q (q is an integer larger than 1) of injection ports 50 arranged on the discharge port 44 to inject flushing oil to lubricate the materials so as to prevent the materials from bridging at the discharge port 44; when the clean conveying system 7 is blocked, the flushing and purging valve 46 controls the flushing and purging port 49 to spray one or more of low-pressure steam, nitrogen, recovered extracting agent, desalted water, tar, coal tar and heavy oil for dredging.
Step three: multi-stage high-efficiency oil extraction
The raw material 1 pretreated in the second step enters a first-stage oil extraction tank 9, is subjected to oil extraction at the temperature of 20-100 ℃ for 0.01-3 h, then enters a high-efficiency separator I12 to separate liquid and solid, the separated solid and recovered extraction liquid enter a second-stage oil extraction tank 10, and the separated liquid enters an extraction liquid storage tank 15; the process is repeated until the solid and the recovered extraction liquid in the Nth-1-stage oil extraction tank enter the Nth-stage oil extraction tank 11, the oil is extracted at the temperature of 20-100 ℃ for 0.01-3 h and then enters the high-efficiency separator I12 for separation, and the mechanical centrifugal separation and the N-stage cross extraction are combined in the process, so that the extraction efficiency is greatly improved compared with the traditional extraction process, and the organic components in the oil-containing water-containing solid mixture can be efficiently recovered; liquid separated by the high-efficiency separator I12 enters an extraction liquid storage tank 15, and separated solid enters a double-liquid-phase deep enhanced extraction tank 13 to form a double-liquid-phase extraction environment with an extracted substance in the double-liquid-phase deep enhanced extraction tank 13 under the action of one or more of ionic liquid, microemulsion and supercritical fluid, so that the extraction strength is greatly improved; due to the double-liquid-phase extraction environment, the separation after extraction is more complete, and the separation of the extraction mixture can be promoted by small change of reaction conditions. After the double-liquid-phase deep enhanced extraction oil extraction lasts for 0.01-3 hours, the materials enter a second high-efficiency separator 14 for separation, the separated extraction liquid enters an extraction liquid storage tank 15, and the separated solids enter a two-stage deep pyrolysis reactor 27.
Step four: multiple effect separation and recovery
Heating the extract liquor in the extract liquor storage tank 15 through a flash separator inlet heat exchanger 16, then entering an enhanced flash separator 17 for flash separation at the temperature of 50-700 ℃ under the pressure of 0.001-3.0 MPa, cooling a light component separated from a top product of the enhanced flash separator 17 in an oil-water separator 18 through a heat recoverer 19, then entering an oil-water separation tank 20 for further separation, allowing a part of recovered extracting agent separated from the oil-water separation tank 20 to enter a primary oil extraction tank 9, a secondary oil extraction tank 10 and an N-level oil extraction tank 11, and allowing water separated from the oil-water separation tank 20 to enter a secondary wastewater treatment system 21 for further treatment; heavy materials at the bottom of the enhanced flash separator 17 enter a flash separator heat recovery system 22 to recover heat and then enter a fractionating tower 23 to carry out distillate cut; the top product of the fractionating tower 23 enters a light oil recovery system 24 to separate light oil products; the middle product and the bottom product of the fractionating tower 23 enter a middle distillate product recovery system 25 and a heavy oil recovery system 26 respectively to be separated to produce a middle distillate product and a heavy oil product; by the steps, the extraction agent can be efficiently recycled, the solvent consumption is reduced, a heat exchange network is established, and the energy utilization efficiency of the device is greatly improved.
Step five: pyrolysis upgrading and clean incineration
The solid separated by the second high-efficiency separator 14 enters a thermal desorption reactor 38 to carry out a first-stage thermal desorption reaction at a temperature rise rate of 5-20 ℃/min under an inert atmosphere, the final reaction temperature is 320-570 ℃, and the desorption process of deep-layer volatile components of the solid material occurs in the reactor; the reaction residue of the thermal desorption reactor 40 enters the catalystPyrolysis reactor 41 using MnO2、CaO、CoCl2Performing catalytic pyrolysis on a mixture of one or more of KCl, a supported catalyst, pyrolysis residues and biomass at the temperature rise rate of 5-20 ℃/min, wherein the final reaction temperature is 610-900 ℃, deep pyrolysis is performed on solid materials in the reactor under the promotion of the catalyst, and the oil-containing components are fully upgraded; pyrolysis oil gas generated after the two-stage deep pyrolysis is subjected to dust removal through the high-efficiency gas-solid dust remover 30, then enters the purification tower 32 for purification and separation after heat exchange through the purification tower inlet heat exchanger 31, a product at the bottom of the purification tower 32 enters the secondary oil-water separation system 34 for continuous deep oil-water separation, and a product at the top of the purification tower 32 enters the flue gas treatment system 33 for environment-friendly treatment.
After the solid residue after the deep pyrolysis in the two-stage deep pyrolysis reactor 27 is mixed with the incineration catalyst and the doped combustion agent, the solid residue is incinerated in the catalytic enhanced cleaning incinerator 28 to generate steam and heat to be supplied to the whole system; the incineration process after the solid residue is mixed with the incineration catalyst and the doped incineration agent can efficiently remove pollutants in the oil-containing water-containing solid mixture and provide heat for the whole system; the incineration residues at the bottom of the catalytic strengthening cleaning incinerator 28 are discharged out through the clean ash discharge system 29, the incineration residues almost do not contain organic matters and toxic substances, and the method can be applied to the aspects of buildings, road and bridge construction and the like; the flue gas generated by the catalytic enhanced cleaning burner 28 is merged into the purifying tower 32 for environmental protection treatment.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (10)
1. A resourceful treatment device for oil-containing and water-containing solid mixtures is characterized in that: the system comprises a raw material physical and chemical property analysis and control conveying unit, a raw material deep pretreatment unit, a high-efficiency oil extraction unit, a multi-effect separation and recovery unit and a two-stage deep pyrolysis coupling catalytic cleaning incineration unit;
the raw material physical and chemical property analysis and control conveying unit comprises a first control conveying unit (3) and a second control conveying unit (4) which are connected with the raw material (1), the first control conveying unit (3) is also connected with a clean conveying system (7), and the second control conveying unit (4) is also connected with an inlet of the viscosity reduction demulsification sedimentation separation tank (5); a raw material physical and chemical property analysis controller (2) is arranged on a connecting pipeline between the raw material (1) and the first control conveying unit (3) and the second control conveying unit (4); the raw material physical and chemical property analysis controller (2) is connected with the first control conveying unit (3) and the second control conveying unit (4) through signal lines;
the raw material deep pretreatment unit comprises a viscosity-reducing demulsification settling separation tank (5) and a clean conveying system (7) which are connected, and an outlet at the upper side of the viscosity-reducing demulsification settling separation tank (5) is connected with a primary wastewater treatment system (8); the viscosity-reducing demulsification sedimentation separation tank (5) is also connected with a demulsification viscosity-reducing agent storage tank (6);
the high-efficiency oil extraction unit comprises a primary oil extraction tank (9), a secondary oil extraction tank (10), an N-stage oil extraction tank (11), a first high-efficiency separator (12), a double-liquid-phase deep enhanced extraction tank (13) and a second high-efficiency separator (14); a material outlet of the clean conveying system (7) is connected with a solid inlet of the first-stage oil extraction tank (9), outlets at the bottoms of the first-stage oil extraction tank (9), the second-stage oil extraction tank (10) and the N-stage oil extraction tank (11) are connected with inlets of a first high-efficiency separator (12), and a solid outlet of the first high-efficiency separator (12) is also connected with solid inlets of the second-stage oil extraction tank (10), the N-stage oil extraction tank (11) and the double-liquid-phase depth strengthening extraction tank (13); the discharge port of the double-liquid-phase deep enhanced extraction tank (13) is also connected with the feed port of the high-efficiency separator II (14); the liquid outlets of the first efficient separator (12) and the second efficient separator (14) are also connected with an extract liquid storage tank (15);
the multi-effect separation and recovery unit comprises an extract liquid storage tank (15), an enhanced flash separator inlet heat exchanger (16), an enhanced flash separator (17), a flash separator heat recovery system (22) and a fractionating tower (23) which are connected in sequence; the top outlet of the enhanced flash separator (17) is also sequentially connected with an oil-water separator (18), a heat recoverer (19) and an oil-water separation tank (20); the upper outlets of the light oil recovery system (24) and the oil-water separation tank (20) connected with the top of the fractionating tower (23) are respectively connected with the upper inlets at the sides of the primary oil extraction tank (9), the secondary oil extraction tank (10) and the N-stage oil extraction tank (11);
the two-stage deep pyrolysis coupling catalysis cleaning incineration unit comprises a two-stage deep pyrolysis reactor (27) and a catalysis strengthening cleaning incinerator (28) which are sequentially connected with a solid outlet of the two-stage deep pyrolysis separator (14), and top outlets of the two-stage deep pyrolysis reactor (27) and the catalysis strengthening cleaning incinerator (28) are sequentially connected with a high-efficiency gas-solid dust collector (30), a purification tower inlet heat exchanger (31) and a purification tower (32).
2. The apparatus for recycling treatment of oil-containing water-containing solid mixture according to claim 1, wherein: a plurality of ultrasonic coupling electric field generators (37) are radially and symmetrically distributed in the tank wall of the viscosity-reducing demulsification settling separation tank (5); the ultrasonic coupling electric field generator (37) is one or a combination of an ultrasonic generator and an electric field generator; the diameter of the cylinder body part of the viscosity-reducing demulsification settling separation tank (5) is D, and the height of the cylinder body part is H; the viscosity reducing demulsification sedimentation separation tank (5) is internally provided with a guide cylinder (38) which is axially installed along the viscosity reducing demulsification sedimentation separation tank (5), the diameter D of the guide cylinder (38) is 0.2-0.95D, the wall thickness Z is 0.001-0.3D, and the distance H between the lower edge of the guide cylinder (38) and the tank bottom of the viscosity reducing demulsification sedimentation separation tank (5) is 0.001-0.4H; the three-dimensional spiral stirring paddle (39) is assembled in the guide cylinder (38), the diameter K of the three-dimensional spiral stirring paddle (39) is 0.35-0.99 d, the height G is 0.35-1.3 h, and the height P of a single spiral layer is 0.1-1G.
3. The apparatus for recycling an oil-containing aqueous solid mixture according to claim 1, wherein: the two-stage deep pyrolysis reactor (27) comprises a thermal desorption reactor (40) and a catalytic pyrolysis reactor (41) which are sequentially connected from bottom to top according to the incoming material direction; the thermal desorption reactor (40) adopts an inert atmosphere operating environment, the temperature rise rate is 5-20 ℃/min, and the final reaction temperature is 320-570 ℃; the temperature rise rate of the catalytic pyrolysis reactor (41) is 5-20 ℃/min, and the final reaction temperature is 610-900 ℃.
4. The apparatus for recycling an oil-containing aqueous solid mixture according to claim 1, wherein: a conveying system formed by connecting a plurality of groups of screws in parallel is assembled in the clean conveying system (7); a heat preservation heat tracing system (43) is arranged outside the clean conveying system (7); a flushing oil ejector (47) is assembled on a discharge hole (44) of the clean conveying system (7), and the flushing oil ejector (47) is also sequentially connected with a flushing oil control valve (45) and a light oil recovery system (24); a plurality of spray nozzles (50) are radially and symmetrically distributed on the flushing oil sprayer (47); each group of spiral inner walls of the clean conveying system (7) is provided with a plurality of groups of flushing and purging ports (49), and flushing and purging valves (46) are connected between all the flushing and purging ports (49) and flushing and purging agents (48).
5. The apparatus for recycling an oil-containing aqueous solid mixture according to any one of claims 1 to 4, wherein: the outlet at the bottom of the oil-water separation tank (20) is also connected with a secondary wastewater treatment system (21); the middle part of the fractionating tower (23) is also connected with a middle-stage fraction product recovery system (25), and the bottom of the fractionating tower (23) is also connected with a heavy oil recovery system (26); the bottom of the purification tower (32) is connected with a secondary oil-water separation system (34), and the top of the purification tower (32) is connected with a flue gas treatment system (33).
6. The apparatus for recycling an oil-containing aqueous solid mixture according to claim 5, wherein: the catalytic strengthening cleaning incinerator (28) is respectively connected with a catalyst supply system (35) and a blending agent supply system (36), and the bottom of the catalytic strengthening cleaning incinerator (28) is also connected with a clean ash discharge system (29); the catalytic strengthening cleaning incinerator (28) adopts one or more of a circulating fluidized bed, an entrained flow bed and a fixed bed; the incineration catalyst (53) loaded in the catalyst supply system (35) is CaO or Fe2O3KCl, a supported catalyst and pyrolysis residue; the blending agent (54) filled in the blending agent supply system (36) is a drying agent, a forming agent, coal powder, semicoke, pyrolysis residue,A mixture of one or more of biomass and a fueling treatment agent.
7. A method for recycling an aqueous solid mixture containing oil based on the apparatus for recycling an aqueous solid mixture containing oil according to claims 1 to 6, comprising the steps of:
the method comprises the following steps: analysis of physical and chemical properties of raw materials and controlled conveying
The raw material physical and chemical property analysis controller (2) analyzes the physical and chemical properties of the raw material (1), when the water content of the raw material (1) is more than 2-80%, the raw material physical and chemical property analysis controller (2) operates and controls the second conveying unit (4) to start, and the raw material (1) enters the viscosity-reducing demulsification sedimentation separation tank (5); when the water content of the raw material (1) is less than 2-80%, the raw material physical and chemical property analysis controller (2) operates and controls the first conveying unit (3) to start, and the raw material (1) directly enters the clean conveying system (7);
step two: advanced pretreatment of raw materials
The raw material (1) with the water content of more than 2-80% enters a viscosity-reducing demulsification settling separation tank (5), a demulsification viscosity-reducing agent storage tank (6) adds a demulsification viscosity-reducing agent (51) with the amount required by the process into the viscosity-reducing demulsification settling separation tank (5), and after fully stirring for 0.01-3 h by a three-dimensional spiral stirring paddle (39), axial circulating liquid flow is formed inside and outside a guide cylinder (38), and then an ultrasonic coupling electric field demulsification strengthening device (37) sends out one or more combinations of ultrasonic waves and electric fields to strengthen viscosity-reducing demulsification for 0.01-24 h on the raw material (1); standing the raw material (1) subjected to enhanced viscosity-reducing demulsification for 0.01-24 h in a viscosity-reducing demulsification settling separation tank (5) for 0.1-72 h, removing a water layer from a primary wastewater treatment system (8), and conveying a solid layer to a primary oil extraction tank (9) through a clean conveying system (7); the flushing oil control valve (45) automatically controls a jet orifice (50) assembled on the discharge hole (44) to spray flushing oil to lubricate the materials; when the clean conveying system (7) is blocked, the flushing purging valve (46) controls the flushing purging port (49) to spray a flushing purging agent (48) for dredging;
step three: multistage high-efficiency oil extraction
The raw material (1) pretreated in the second step enters a first-stage oil extraction tank (9) and is extracted at the temperature of 20-100 ℃ for 0.01-3 h, then enters a high-efficiency separator I (12) to separate liquid and solid, the separated solid and recovered extraction liquid enter a second-stage oil extraction tank (10), and the separated liquid enters an extraction liquid storage tank (15); repeating the processes until the solid and the recovered extraction liquid in the Nth-1-stage oil extraction tank enter the Nth-stage oil extraction tank (11) for extracting oil at 20-100 ℃ for 0.01-3 h, then entering a high-efficiency separator I (12) for separation, entering the separated liquid into an extraction liquid storage tank (15), entering the separated solid into a double-liquid-phase deep enhanced extraction tank (13), extracting the oil by a deep enhanced extraction liquid (42) for 0.01-3 h, then entering a high-efficiency separator II (14) for separation, entering the separated extraction liquid storage tank (15), and removing the separated solid into a two-stage deep pyrolysis reactor (27);
step four: multiple effect separation and recovery
Heating extract liquor in an extract liquor storage tank (15) through a flash separator inlet heat exchanger (16), then entering an enhanced flash separator (17) for flash separation at the temperature of 50-700 ℃ under the pressure of 0.001-3.0 Mpa, cooling light components separated from a top product of the enhanced flash separator (17) in an oil-water separator (18) through a heat recoverer (19), then entering an oil-water separation tank (20) for further separation, feeding part of recovered extracting agent separated by the oil-water separation tank (20) into a primary oil extraction tank (9), a secondary oil extraction tank (10) and an N-level oil extraction tank (11), and further processing water separated by the oil-water separation tank (20) in a secondary wastewater treatment system (21); heavy materials at the bottom of the enhanced flash separator (17) enter a flash separator heat recovery system (22) to recover heat and then enter a fractionating tower (23) to carry out distillate cut; the top product of the fractionating tower (23) enters a light oil recovery system (24) to separate light oil products; the middle product and the bottom product of the fractionating tower (23) respectively enter a middle distillate product recovery system (25) and a heavy oil recovery system (26) to be separated to produce a middle distillate product and a heavy oil product;
step five: pyrolysis upgrading and clean incineration
The solid separated by the second efficient separator (14) enters a thermal desorption reactor (38) to perform thermal desorption reaction at the temperature rising rate of 5-20 ℃/min under inert atmosphere, and the final reaction temperature is 320-570 ℃; reaction residues of the thermal desorption reactor (40) enter a catalytic pyrolysis reactor (41), pyrolysis is carried out by adopting a pyrolysis catalyst (52) at the temperature rise rate of 5-20 ℃/min, and the final reaction temperature is 610-900 ℃; pyrolysis oil gas generated after two-stage deep pyrolysis enters a purification tower (32) for purification and separation after being dedusted by a high-efficiency gas-solid deduster (30) and heat exchanged by a purification tower inlet heat exchanger (31), a product at the bottom of the purification tower (32) enters a secondary oil-water separation system (34) for continuous deep oil-water separation, and a product at the top of the purification tower (32) enters a flue gas treatment system (33) for environment-friendly treatment; after solid residues subjected to deep pyrolysis in the two-stage deep pyrolysis reactor (27) are mixed with an incineration catalyst (53) and a combustion admixture (54), steam and heat are generated after incineration in the catalytic strengthening cleaning incinerator (28) and are supplied to the whole system, the incineration residues at the bottom of the catalytic strengthening cleaning incinerator (28) enter a clean ash discharge system (29), and flue gas generated by the catalytic strengthening cleaning incinerator (28) is merged into a purification tower (32) for further treatment.
8. A method of resource utilization of the oil-containing aqueous solids mixture according to claim 7, wherein: the pyrolysis catalyst (52) filled in the catalytic pyrolysis reactor (41) is MnO2、CaO、CoCl2KCl, a supported catalyst, pyrolysis residue and biomass; the double-liquid-phase deep enhanced extraction tank (13) is filled with deep enhanced extraction liquid (42), and the extraction phase state of the deep enhanced extraction tank (13) is double liquid phase; the deep reinforcing extraction liquid (42) is one or a mixture of ionic liquid, microemulsion and supercritical fluid.
9. A method of resource utilization of the oil-containing aqueous solids mixture according to claim 7, wherein: the flushing and purging agent (48) is one or a mixture of a plurality of low-pressure steam, nitrogen, a recovered extracting agent, desalted water, tar, coal tar and heavy oil; the raw material (1) is one or a mixture of more of oily sludge, coal-based oil sludge, coal chemical oil sludge, oil sludge at the bottom of a tower, oil sludge in an oil field, oil sludge in a sand basin, tank cleaning sludge, oil tank bottom sludge, oil sludge on the ground, oil sludge in a sewage treatment plant, refined oil sludge and oil sludge in a passenger liner.
10. A method of resource utilization of the oil-containing aqueous solids mixture according to claim 7, wherein: the demulsification viscosity-reducing agent (51) stored in the demulsification viscosity-reducing agent storage tank (6) is one or a mixture of more of ionic surfactant, nonionic surfactant, amphoteric surfactant, compound surfactant, hydroxy fat, organic acid, sodium silicate, carboxymethyl cellulose, naphtha, polyalcohol, polyester, low-carbon olefin and long-chain alkane.
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| CN115475487A (en) * | 2022-09-11 | 2022-12-16 | 昆明理工大学 | System and method for absorbing organic matters in waste tire waste gas through pyrolysis |
| CN115475487B (en) * | 2022-09-11 | 2024-01-16 | 昆明理工大学 | System and method for absorbing organic matters in waste gas generated by pyrolysis of waste tires |
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| CN114479899B (en) | 2023-06-27 |
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