CN114561229A - Energy-saving supercritical water oil product modifying method - Google Patents
Energy-saving supercritical water oil product modifying method Download PDFInfo
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- CN114561229A CN114561229A CN202210184677.XA CN202210184677A CN114561229A CN 114561229 A CN114561229 A CN 114561229A CN 202210184677 A CN202210184677 A CN 202210184677A CN 114561229 A CN114561229 A CN 114561229A
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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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
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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
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/06—Pressure conditions
- C02F2301/066—Overpressure, high pressure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses an energy-saving supercritical water oil modification method, which comprises the steps of heating, pressurizing and mixing oil and water, then transmitting the mixture to a supercritical water pyrolysis reactor, carrying out pyrolysis reaction on the oil in supercritical water, cooling and depressurizing outlet fluid, and then transmitting the fluid to a hot high-pressure separator to be separated into high-pressure gas and hot high-pressure oil; cooling the high-molecular gas and separating the high-molecular gas into cracked gas, cold high-molecular oil and high-molecular water; after being pressurized and heated, the high-moisture water and an oxygen supply agent are conveyed into a supercritical water oxidation reactor together, and organic matters in the high-moisture water are subjected to oxidation reaction to release a large amount of heat so as to raise the temperature of the water; the hot high-pressure oil is transmitted to the cold low-pressure separator for pressure reduction and then transmitted to the cold low-pressure separator, cracked gas is discharged from an upper outlet of the cold low-pressure separator, and modified oil is discharged from a lower outlet of the cold low-pressure separator. The method can realize the modification and viscosity reduction of oil products, adopts a continuous reaction form, has large treatment capacity, is suitable for industrial production, adopts a supercritical water oxidation process, and has remarkable energy-saving effect.
Description
Technical Field
The invention relates to the technical field of oil product modification, in particular to a method for modifying oil products by using supercritical water and reducing energy consumption by using a supercritical water oxidation technology.
Background
The supercritical fluid is fluid with temperature higher than critical temperature and critical pressure, no obvious gas-liquid interface, special physical property, low viscosity, high density, excellent flowing, mass transfer, heat transfer and dissolving performance. At present, the mature supercritical fluid technology includes supercritical water oxidation technology, supercritical fluid extraction technology, supercritical water liquefaction technology and the like. The technology for treating organic wastewater and solid hazardous waste which is difficult to treat by utilizing supercritical water oxidation is mature, and multiple sets of industrial production devices at home and abroad are utilized.
Supercritical water can be used for oil modification treatment, and belongs to an emerging research and development technology. Through a large amount of small-test research and mechanism research of scholars at home and abroad, the supercritical water modified oil product can obtain very good lightening and viscosity reduction effects.
Some patents disclose devices and processes for continuous supercritical water reactions.
CN106170532A discloses a method for upgrading petroleum raw material using supercritical water petroleum upgrading system, combining petroleum raw material and water to form mixed petroleum raw material, and introducing into the lower part of upflowing supercritical water reactor respectively and simultaneously. One embodiment of the method includes operating the supercritical water petroleum upgrading system that includes an upflowing supercritical water reactor and optionally a downflowing supercritical water reactor to introduce upflowing reactor product fluid into the upper portion of the downflowing supercritical water reactor. The temperature of the fluid contained in the downflow reactor is maintained at from 0 ℃ to 100 ℃ above the temperature of the fluid contained in the upflow reactor. This example of the process allows for an increase in API gravity of 11 for petroleum feedstocks and a decrease in asphaltene content from 4.88 wt% to 0.62 wt%. The process proposed in this patent increases the temperature in the reactor to some extent to increase upgrading, but increasing the temperature also increases the amount of coke formed and increases the risk of plugging the lines and reactor.
CN103920428A discloses a supercritical reaction device and a process method thereof, wherein the supercritical reaction device is adopted in the embodiment to carry out supercritical water gasification reaction of coal water slurry, the reaction temperature is 700 ℃, the reaction pressure is 25MPa, the reaction residence time is 4min, the reaction product is discharged from the supercritical reaction device and then enters a heat exchanger for preliminary cooling, the product after preliminary cooling enters a cyclone separation device for gas-liquid phase separation, and the conversion rate of 87.68% can be realized. The method proposed in the patent is not suitable for the reaction of supercritical water modified oil products, because the amount of cracked gas generated by the supercritical water modified oil products is relatively small, and after the supercritical water is converted into liquid water, the reaction products are difficult to have enough gas phase flow velocity to realize gas-liquid separation.
CN103013550A discloses a system and a method for preparing fuel oil by modifying tar residue with supercritical water, wherein materials and an oxygen source are respectively conveyed into a supercritical water reactor, a heating device in the reactor is started, the reaction temperature is 370-800 ℃, the reaction pressure is 22-32 MPa, and tar residue is subjected to modification reaction in supercritical water. The reacted solid residue enters a residue storage tank from a residue discharge port at the bottom of the reactor through a back pressure valve, and the reacted fluid is condensed by a heat exchanger and then enters a high-pressure gas-liquid separator. This patent proposes to set up heating device inside supercritical water reactor, need heat up several hundred degrees behind the mixed material input reactor of tar sediment and water, and heating time is long, and this will lead to this system's handling capacity to be low, and simultaneously, near local high temperature of heating device, the easy coke that grows of tar sediment blocks up reactor inner space.
CN106513421 discloses an energy-saving and consumption-reducing method for treating oil-based drilling cuttings in oil and gas fields by supercritical water oxidation, which comprises the steps of eluting organic matters in the oil-based drilling cuttings in a leaching kettle by using high-temperature fluid generated by supercritical water oxidation organic wastewater, transferring the organic matters into water to form organic wastewater, pressurizing and preheating the organic wastewater, mixing the organic wastewater with an oxidant, introducing the mixture into a supercritical water oxidation reactor, completely oxidizing and degrading organic pollutants, introducing gas-liquid products into the leaching kettle, and starting the next cycle. The cooling water required for cooling the high-temperature fluid is saved.
The device of supercritical water modified oil needs to bear high pressure, high temperature and corrosion resistance, the supercritical water reaction is carried out in batch type reaction device mostly, some reported supercritical water continuous reaction device functions are not perfect enough, in addition, there are easy coking, jam and energy consumption height problems.
Disclosure of Invention
The invention aims to provide a method for modifying oil products by supercritical water, in particular to a method for performing energy-saving supercritical water modification on oil products by a supercritical water oxidation process. The method leads supercritical water and oil products to generate pyrolysis reaction in the supercritical water pyrolysis reactor, and leads macromolecules such as asphaltene, colloid and the like in the oil products to generate chain scission reaction of alkyl side chains, condensation reaction of polycyclic aromatic hydrocarbon and the like, thereby realizing the light transformation of the oil products and promoting the quality of the oil products to be improved. The generated organic wastewater is treated by supercritical water oxidation, so that the purification problem of the organic wastewater is solved, the self-sufficiency of heat is realized, and the energy consumption of the device is reduced.
The invention relates to an energy-saving supercritical water oil modifying method, which comprises the following treatment steps:
1) pressurizing the deionized water to 14-16 MPa, mixing the deionized water with high-split water from a cold high-pressure separator to form mixed water flow, pressurizing the mixed water flow to 23-40 MPa, heating to 60-300 ℃, and conveying the mixed water flow to an inlet of a supercritical water oxidation reactor, wherein the mass content of organic matters in the high-split water is not less than 1%;
2) pressurizing an oxygen supply agent to 23-40 MPa, conveying the oxygen supply agent to an inlet of a supercritical water oxidation reactor, generating a supercritical water oxidation reaction on the mixed water flow and the oxygen supply agent in the step 1) in the supercritical water oxidation reactor, and conveying the effluent of the supercritical water oxidation reactor to an inlet of a mixer;
3) heating an oil raw material to 50-90 ℃, pressurizing to 23-40 MPa, conveying the oil raw material to an inlet of a mixer, mixing the oil raw material with the effluent of the supercritical water oxidation reactor in the step 2) to obtain a mixed solution, controlling the mass content of organic matters in high-moisture water in the step 1) and the addition amount of an oxygen supply agent in the step 2) according to the different properties of the oil raw material and the requirement of the supercritical water pyrolysis reaction temperature, so that the temperature of the mixed solution reaches 380-500 ℃, and conveying the mixed solution to the inlet of the supercritical water pyrolysis reactor;
4) carrying out pyrolysis reaction on an oil raw material in a supercritical water pyrolysis reactor, wherein the retention time of the oil raw material in the supercritical water pyrolysis reactor is 1-40 min, the fluid discharged from the supercritical water pyrolysis reactor exchanges heat with the mixed water flow in the step 1), then cooling to 240-260 ℃, reducing the pressure to 14-16 MPa, transmitting to a thermal high-pressure separator, and separating into high-pressure gas and thermal high-pressure oil through the thermal high-pressure separator;
5) cooling the high-molecular gas obtained in the step 4) to 40-60 ℃, then transferring the high-molecular gas to a cold high-pressure separator, separating the high-molecular gas into cracked gas, cold high-molecular oil and high-molecular water, reducing the pressure of the hot high-molecular oil to 2-4 MPa, then transferring the hot high-molecular oil to a cold low-pressure separator, reducing the pressure of the cold high-molecular oil to 2-4 MPa, then transferring the cold high-molecular oil to a cold low-pressure separator, discharging the cracked gas from an upper outlet of the cold low-pressure separator, and discharging the modified oil from a lower outlet of the cold low-pressure separator.
In the energy-saving supercritical water oil modifying method, preferably, the pressure of the mixed water flow after pressurization in the step 1), the pressure of the oxygen supply agent after pressurization in the step 2) and the pressure of the oil raw material after pressurization in the step 3) are 23-30 MPa.
In the energy-saving supercritical water oil modifying method, the mass content of the organic matters in the high-moisture in the step 1) is preferably 1-3%.
In the energy-saving supercritical water oil modifying method, preferably, the mass flow rate of the oil raw material in the step 2) is 1-2 times of the mass flow rate of the mixed water flow in the step 1).
In the above energy-saving supercritical water oil modifying method, preferably, the oxygen supplying agent in step 2) is one or two of air and oxygen.
In the energy-saving method for modifying oil product by supercritical water, preferably, the temperature of the mixed liquor conveyed to the supercritical water pyrolysis reactor in the step 3) is 380-420 ℃.
In the energy-saving method for modifying an oil product by supercritical water, preferably, the oil product raw material in the step 4) stays in the supercritical water pyrolysis reactor for 5-10 min.
Compared with the prior art, the method has the beneficial effects that: the invention adopts a continuous reaction form, has large treatment capacity, solves the problem of small treatment capacity of an intermittent reaction device, and can realize industrial scale-up production. Through supercritical water pyrolysis reaction, oil products such as thickened oil, super-thickened oil and the like can be greatly modified and reduced in viscosity, and the viscosity reduction rate is higher than 80%. Meanwhile, by utilizing the supercritical water oxidation process, the organic wastewater generated by supercritical water thermal modification is treated and recycled, and meanwhile, the oxidation heat release is effectively utilized, so that the energy-saving effect is achieved.
Drawings
FIG. 1 is a schematic process flow diagram of an embodiment of the energy-saving supercritical water oil upgrading method of the present invention.
In the figure, 1 is a raw material heater, 2 is a raw material booster pump, 3 is a mixer, 4 is a supercritical water pyrolysis reactor, 5 is a heat exchanger, 6 is a compressor, 7 is a supercritical water oxidation reactor, 8 is a water heater, 9 is a water booster pump, 10 is a cooler, 11 is a back pressure valve, 12 is a hot high-pressure separator, 13 is a high-pressure air cooler, 14 is a cold high-pressure separator, 15 is an angle valve, and 16 is a cold low-pressure separator;
101 is oil raw material, 102 is oxygen donor, 103 is high-molecular gas, 104 is hot high-molecular oil, 105 and 108 are cracked gas, 106 is cold high-molecular oil, 107 is high-molecular water, 109 is modified oil and 110 is deionized water.
Detailed Description
The invention provides an energy-saving supercritical water oil product modifying method, which comprises the following steps:
1) pressurizing the deionized water to 14-16 MPa, mixing the deionized water with high-split water from a cold high-pressure separator to form mixed water flow, pressurizing the mixed water flow to 23-40 MPa, heating to 60-300 ℃, and conveying to an inlet of a supercritical water oxidation reactor, wherein the mass content of organic matters in the high-split water is not lower than 1%;
2) pressurizing an oxygen supply agent to 23-40 MPa, wherein the oxygen supply agent is one or more of air, oxygen and hydrogen peroxide, the oxygen supply agent is conveyed to an inlet of a supercritical water oxidation reactor, the mixed water flow and the oxygen supply agent in the step 1) generate a supercritical water oxidation reaction in the supercritical water oxidation reactor, and the effluent of the supercritical water oxidation reactor is conveyed to an inlet of a mixer;
3) heating an oil raw material to 50-90 ℃, pressurizing to 23-40 MPa, conveying the oil raw material to an inlet of a mixer, mixing the oil raw material with the effluent of the supercritical water oxidation reactor in the step 2) to obtain a mixed solution, controlling the mass content of organic matters in high-water-content water in the step 1) and the addition amount of an oxygen supply agent in the step 2) according to the different properties of the oil and the requirement of the supercritical water pyrolysis reaction temperature, so that the temperature of the mixed solution reaches 380-500 ℃, and conveying the mixed solution to the inlet of the supercritical water pyrolysis reactor;
4) carrying out pyrolysis reaction on an oil raw material in a supercritical water pyrolysis reactor, wherein the retention time of the oil raw material in the supercritical water pyrolysis reactor is 1-40 min, the fluid discharged from the supercritical water pyrolysis reactor exchanges heat with the mixed water flow in the step 1), then cooling to 240-260 ℃, reducing the pressure to 14-16 MPa, transmitting to a thermal high-pressure separator, and separating into high-pressure gas and thermal high-pressure oil through the thermal high-pressure separator;
5) cooling the high-molecular gas obtained in the step 4) to 40-60 ℃, then transferring the high-molecular gas to a cold high-pressure separator, separating the high-molecular gas into cracked gas, cold high-molecular oil and high-molecular water, reducing the pressure of the hot high-molecular oil to 2-4 MPa, then transferring the hot high-molecular oil to a cold low-pressure separator, reducing the pressure of the cold high-molecular oil to 2-4 MPa, then transferring the cold high-molecular oil to a cold low-pressure separator, discharging the cracked gas from an upper outlet of the cold low-pressure separator, and discharging the modified oil from a lower outlet of the cold low-pressure separator.
In the energy-saving supercritical water oil modifying method, preferably, the pressure of the mixed water flow after pressurization in the step 1), the pressure of the oxygen supply agent after pressurization in the step 2) and the pressure of the oil raw material after pressurization in the step 3) are 23-30 MPa.
In the energy-saving supercritical water oil modifying method, the mass content of the organic matters in the high-moisture in the step 1) is preferably 1-3%.
In the energy-saving supercritical water oil modifying method, preferably, the mass flow rate of the oil raw material in the step 2) is 1-2 times of the mass flow rate of the mixed water flow in the step 1).
In the above energy-saving supercritical water oil modifying method, preferably, the oxygen supplying agent in step 2) is one or two of air and oxygen.
In the energy-saving method for modifying oil product by supercritical water, preferably, the temperature of the mixed liquor conveyed to the supercritical water pyrolysis reactor in the step 3) is 380-420 ℃.
In the energy-saving method for modifying an oil product by supercritical water, preferably, the oil product raw material in the step 4) stays in the supercritical water pyrolysis reactor for 5-10 min.
The present invention will be further described in the following detailed description with reference to the drawings, but the invention is not limited thereto.
As shown in figure 1, deionized water 110 is pressurized to 14-16 MPa, and forms a mixed water flow with high-pressure water separation 107 from a cold high-pressure separator 14, the mixed water flow is pressurized to 23-40 MPa by a water booster pump 9, is heated to 60-300 ℃ by a water heater 8, passes through a heat exchanger 5 and is conveyed to an inlet of a supercritical water oxidation reactor 7, and the mass content of organic matters in the high-pressure water separation 107 is not lower than 1%. Pressurizing the oxygen supply agent 102 to 23-40 MPa by the compressor 6, wherein the oxygen supply agent 102 is one or more of air, oxygen and hydrogen peroxide, the oxygen supply agent 102 is conveyed to the inlet of the supercritical water oxidation reactor 7, the mixed water flow and the oxygen supply agent 102 generate a supercritical water oxidation reaction in the supercritical water oxidation reactor 7, and the effluent of the supercritical water oxidation reactor 7 is conveyed to the inlet of the mixer 3. Heating an oil raw material 101 to 50-90 ℃ through a raw material heater 1, pressurizing the oil raw material to 23-40 MPa through a raw material booster pump 2, conveying the oil raw material 101 to an inlet of a mixer 3, mixing the oil raw material 101 and the effluent of a supercritical water oxidation reactor 7 in the mixer 3 to obtain a mixed solution, controlling the mass content of organic matters in high-water-distribution 107 and the addition of an oxygen supply agent according to the different properties of the oil raw material and the requirement of the supercritical water pyrolysis reaction temperature to enable the temperature of the mixed solution to reach 380-500 ℃, and conveying the mixed solution to an inlet of a supercritical water pyrolysis reactor 4. The oil raw materials are subjected to pyrolysis reaction in the supercritical water pyrolysis reactor 4, the retention time of the oil raw materials in the supercritical water pyrolysis reactor 4 is 1-40 min, fluid discharged from the supercritical water pyrolysis reactor 4 and mixed water flow exchange heat in the heat exchanger 5, the temperature of the fluid and mixed water flow is reduced to 240-260 ℃ through the cooler 10, the fluid and the mixed water flow are reduced to 14-16 MPa through the back pressure valve 11, and the fluid and the mixed water flow are transmitted to the hot high-pressure separator 12 to be separated into high-pressure gas 103 and hot high-pressure oil 104. The high-pressure gas 103 is cooled to 40-60 ℃ by a high-pressure air cooler 13 and then transferred to a cold high-pressure separator 14 to be separated into cracked gas 105, cold high-pressure oil 106 and high-pressure water 107, the hot high-pressure oil 104 is depressurized to 2-4 MPa and then transferred to a cold low-pressure separator 16, the cold high-pressure oil 106 is depressurized to 2-4 MPa by an angle valve 15 and then transferred to the cold low-pressure separator 16, the cracked gas 108 is discharged from the upper outlet of the cold low-pressure separator 16, and the modified oil 109 is discharged from the lower outlet.
The present invention will be described in detail below by way of examples, but the present invention is not limited thereto.
Example 1
Heavy oil upgrading is carried out on a device provided with a supercritical water thermal cracking reactor and a supercritical water oxidation reactor. The mixed water flow consists of deionized water and high-split water from the cold high-pressure separator, the mass flow of the mixed water flow is 8kg/h, the mixed water flow is pressurized to 23MPa, the mixed water flow is heated to 200 ℃, and the mixed water flow is conveyed to the supercritical water oxidation reactor after passing through the heat exchanger. The mass content of organic matters in the high-moisture water is 2 percent. The oxygen supply agent selects air, the air is pressurized to 23MPa, the air is conveyed to the inlet of the supercritical water oxidation reactor, and the mixed water flow and the air generate the supercritical water oxidation reaction in the supercritical water oxidation reactor. Oil sand bitumen is used as a raw material, and the properties of the oil product are shown in a table 1. The mass flow of the oil product raw material is 16 kg/h. Heating the oil raw material to 90 ℃, pressurizing to 23MPa, conveying the oil raw material to an inlet of a mixer, mixing the oil raw material with the effluent of the supercritical water oxidation reactor in the mixer to obtain a mixed solution, wherein the temperature of the mixed solution reaches 380 ℃, and then conveying the mixed solution to the supercritical water pyrolysis reactor. The retention time of the oil raw material in the supercritical water pyrolysis reactor is 21 min. And cooling, depressurizing and separating the supercritical water pyrolysis reaction product to obtain cracked gas, cold high-fraction oil, high-fraction water and modified oil. The viscosity reduction rate can be calculated by detecting the viscosity of the oil product raw material and the modified oil. The product analysis results are shown in Table 3.
Example 2
Upgrading of heavy oil is carried out on a plant equipped with a supercritical water thermal cracking reactor and a supercritical water oxidation reactor. The mixed water flow consists of deionized water and high-split water from the cold high-pressure separator, the mass flow of the mixed water flow is 18kg/h, the mixed water flow is pressurized to 30MPa, the mixed water flow is heated to 150 ℃, and the mixed water flow is conveyed to the supercritical water oxidation reactor after passing through the heat exchanger. The mass content of organic matters in the high-moisture water is 1.4 percent. Oxygen is selected for use as the oxygen supply agent, oxygen is pressurized to 30MPa, oxygen is conveyed to the inlet of the supercritical water oxidation reactor, and mixed water flow and oxygen generate supercritical water oxidation reaction in the supercritical water oxidation reactor. Oil sand bitumen is used as a raw material, and the properties of the oil product are shown in a table 1. The mass flow of the oil product raw material is 18 kg/h. Heating the oil raw material to 80 ℃, pressurizing to 30MPa, conveying the oil raw material to an inlet of a mixer, mixing the oil raw material with the effluent of the supercritical water oxidation reactor in the mixer to obtain a mixed solution, wherein the temperature of the mixed solution reaches 420 ℃, and then conveying the mixed solution to the supercritical water pyrolysis reactor. The retention time of the oil raw materials in the supercritical water pyrolysis reactor is 7 min. And cooling, depressurizing and separating the supercritical water pyrolysis reaction product to obtain cracked gas, cold high-fraction oil, high-fraction water and modified oil. The viscosity reduction rate can be calculated by detecting the viscosity of the oil product raw material and the modified oil. The product analysis results are shown in Table 3.
Example 3
Heavy oil upgrading is carried out on a device provided with a supercritical water thermal cracking reactor and a supercritical water oxidation reactor. The mixed water flow consists of deionized water and high-split water from the cold high-pressure separator, the mass flow of the mixed water flow is 15kg/h, the mixed water flow is pressurized to 40MPa, the mixed water flow is heated to 80 ℃, and the mixed water flow is conveyed to the supercritical water oxidation reactor after passing through the heat exchanger. The mass content of organic matters in the high-moisture water is 2 percent. The oxygen supply agent selects air, the air is pressurized to 40MPa, the air is conveyed to the inlet of the supercritical water oxidation reactor, and the mixed water flow and the air generate the supercritical water oxidation reaction in the supercritical water oxidation reactor. The properties of the oil product are shown in Table 1. The mass flow of the oil product raw material is 3 kg/h. Heating the oil raw material to 70 ℃, pressurizing to 40MPa, conveying the oil raw material to an inlet of a mixer, mixing the oil raw material with the effluent of the supercritical water oxidation reactor in the mixer to obtain a mixed solution, wherein the temperature of the mixed solution reaches 500 ℃, and then conveying the mixed solution to the supercritical water pyrolysis reactor. The retention time of the oil raw materials in the supercritical water pyrolysis reactor is 30 min. And (3) cooling, depressurizing and separating the supercritical water pyrolysis reaction product to obtain cracked gas, cold high-molecular oil, high-molecular water and modified oil. The viscosity reduction rate can be calculated by detecting the viscosity of the oil product raw material and the modified oil. The product analysis results are shown in Table 3.
TABLE 1 oil feedstock Properties
TABLE 2 operating conditions
| Item | Example 1 | Example 2 | Example 3 |
| Reaction temperature, deg.C | 380 | 420 | 500 |
| Pressure, MPa | 23 | 30 | 40 |
| Reaction time, min | 21 | 7 | 30 |
| Weight ratio of deionized water to oil raw material | 1:2 | 1:1 | 5:1 |
TABLE 3 oil modified data
| Item | Example 1 | Example 2 | Example 3 |
| Viscosity reduction rate of% | 87.3 | 95.7 | 98.7 |
| Distribution of the product, weight% | |||
| Pyrolysis gas | 2.1 | 3.2 | 4.0 |
| Light oil | 22.5 | 28.6 | 38.2 |
| Heavy oil | 75.4 | 68.2 | 57.8 |
| Total up to | 100 | 100 | 100 |
It should be understood that the above-mentioned embodiments are only illustrative of the technical concepts and features of the present invention, and the purpose of the present invention is to enable people to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the main technical scheme of the invention are covered in the protection scope of the invention.
Claims (7)
1. An energy-saving supercritical water oil modifying method, which comprises the following steps:
1) pressurizing the deionized water to 14-16 MPa, mixing the deionized water with high-split water from a cold high-pressure separator to form mixed water flow, pressurizing the mixed water flow to 23-40 MPa, heating to 60-300 ℃, and conveying to an inlet of a supercritical water oxidation reactor, wherein the mass content of organic matters in the high-split water is not lower than 1%;
2) pressurizing an oxygen supply agent to 23-40 MPa, conveying the oxygen supply agent to an inlet of a supercritical water oxidation reactor, generating a supercritical water oxidation reaction on the mixed water flow and the oxygen supply agent in the step 1) in the supercritical water oxidation reactor, and conveying the effluent of the supercritical water oxidation reactor to an inlet of a mixer;
3) heating an oil raw material to 50-90 ℃, pressurizing to 23-40 MPa, conveying the oil raw material to an inlet of a mixer, mixing the oil raw material with the effluent of the supercritical water oxidation reactor in the step 2) to obtain a mixed solution, controlling the mass content of organic matters in high-moisture water in the step 1) and the addition amount of an oxygen supply agent in the step 2) according to the different properties of the oil raw material and the requirement of the supercritical water pyrolysis reaction temperature, so that the temperature of the mixed solution reaches 380-500 ℃, and conveying the mixed solution to the inlet of the supercritical water pyrolysis reactor;
4) carrying out pyrolysis reaction on an oil raw material in a supercritical water pyrolysis reactor, wherein the retention time of the oil raw material in the supercritical water pyrolysis reactor is 1-40 min, the fluid discharged from the supercritical water pyrolysis reactor exchanges heat with the mixed water flow in the step 1), then cooling to 240-260 ℃, reducing the pressure to 14-16 MPa, transmitting to a thermal high-pressure separator, and separating into high-pressure gas and thermal high-pressure oil through the thermal high-pressure separator;
5) cooling the high-pressure gas obtained in the step 4) to 40-60 ℃, transferring the high-pressure gas to a cold high-pressure separator, separating the high-pressure gas into cracked gas, cold high-pressure oil and high-pressure water, reducing the pressure of the hot high-pressure oil to 2-4 MPa, transferring the hot high-pressure oil to a cold low-pressure separator, reducing the pressure of the cold high-pressure oil to 2-4 MPa, transferring the cold high-pressure oil to the cold low-pressure separator, discharging the cracked gas from an upper outlet of the cold low-pressure separator, and discharging the modified oil from a lower outlet.
2. The energy-saving supercritical water oil upgrading method of claim 1, characterized in that the pressure after the mixed water flow of step 1) is pressurized, the pressure after the oxygen supply agent of step 2) is pressurized, and the pressure after the oil raw material of step 3) is pressurized is 23-30 MPa.
3. The energy-saving supercritical water oil upgrading method of claim 1, characterized in that the mass content of organic matters in the high-moisture in step 1) is 1-3%.
4. The energy-saving supercritical water oil upgrading method of claim 1, characterized in that the mass flow of the oil raw material in step 2) is 1-2 times of the mass flow of the mixed water flow in step 1).
5. The energy-saving supercritical water oil upgrading method of claim 1, characterized in that the oxygen supply agent in step 2) is one or two of air and oxygen.
6. The energy-saving supercritical water oil upgrading method of claim 1, characterized in that the temperature of the mixed liquor delivered to the supercritical water pyrolysis reactor in step 3) is 380-420 ℃.
7. The energy-saving supercritical water oil upgrading method of claim 1, characterized in that the oil raw material in step 4) stays in the supercritical water pyrolysis reactor for 5-10 min.
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