Method and system for recycling waste mineral oil residues
阅读说明：本技术 废矿物油残渣再利用的方法及其系统 (Method and system for recycling waste mineral oil residues ) 是由 王鸣 刘然升 张帅 孟家平 侯东阳 周光林 于 2020-12-10 设计创作，主要内容包括：本发明涉及废矿物油深加工综合利用技术领域,具体涉及一种废矿物油残渣再利用的方法及其系统,包括萃取单元、电吸附单元、高效脱氯单元、膜分离单元、分馏单元和加氢精制单元。本发明不仅可以解决废矿物油残渣深加工利用的问题,提高了废矿物油再生装置的润滑油回收率；还可以解决再生过程中溶剂的环保问题,附产得到高粘度、品质佳、具有极高经济价值的高沸点润滑油基础油,为后续的加氢装置提供了最优质的原料。(The invention relates to the technical field of deep processing and comprehensive utilization of waste mineral oil, in particular to a method and a system for recycling waste mineral oil residues. The invention not only can solve the problem of deep processing and utilization of waste mineral oil residues, but also improves the recovery rate of the lubricating oil of the waste mineral oil regeneration device; the method can also solve the environmental protection problem of the solvent in the regeneration process, and the high-boiling-point lubricating oil base oil with high viscosity, good quality and extremely high economic value is obtained by the byproduct, thereby providing the best raw material for the subsequent hydrogenation device.)
1. A method for recycling waste mineral oil residues is characterized by comprising the following steps:
(1) extraction unit
Mixing the waste mineral oil residues after heat exchange with an extraction solvent, extracting in an extraction device, and separating in a three-phase separator to obtain an extract phase;
(2) electro-adsorption unit
The extraction phase enters an electric adsorption device for electric adsorption, an electrostatic generator is utilized to generate a high-voltage electrostatic field, the intensity of the high-voltage electrostatic field is controlled to enable charged impurity particles in the extraction phase to move towards respective opposite directions under the action of the electric field, so that the impurity particles suspended in the extraction phase are destabilized and collide with each other for adsorption, and waste mineral oil liquid is obtained;
(3) efficient dechlorination unit
Adding a dechlorinating agent into the waste mineral oil liquid, exchanging heat, and then entering a dechlorinating reaction tank for dechlorinating;
(4) membrane separation unit
The dechlorinated oil enters a membrane separation device for separation, and colloidal substances and particulate substances in the oil are separated by using a ceramic nanofiltration membrane to obtain a membrane clear solution;
(5) fractionation unit
After heat exchange, the membrane clear liquid enters a fractionating tower for reduced pressure fractionation, the upper fraction is condensed and then mixed with an extraction solvent for recycling, and the lower fraction is a high-viscosity lubricating oil raw material and enters a hydrofining unit;
(6) hydrorefining unit
And (3) feeding the high-viscosity lubricating oil raw material into a hydrofining reactor for hydrogenation reaction to obtain a lubricating oil base oil product.
2. The method of recycling waste mineral oil residues according to claim 1, characterized in that: in the step (1), the mass ratio of the waste mineral oil residue to the extraction solvent is 1: 0.5-2; the extraction solvent is a mixture of limonene and 200# solvent oil, wherein the mass ratio of the limonene to the 200# solvent oil is 1: 0.1-20; the extraction temperature is 60-120 ℃.
3. The method of recycling waste mineral oil residues according to claim 1, characterized in that: in the step (2), the working voltage of the positive plate and the negative plate in the electric adsorption process is 500-2400V, and the electric adsorption temperature is 60-120 ℃.
4. The method of recycling waste mineral oil residues according to claim 1, characterized in that: in the step (3), the temperature of the dechlorination reaction is 150-250 ℃, the pressure of the dechlorination reaction is 0.5-5 MPa, and the residence time of the dechlorination reaction is 5-10 min; the dosage of the dechlorinating agent is 0.01-1% of the mass of the waste mineral oil liquid.
5. The method of recycling waste mineral oil residues as claimed in claim 4, wherein: the dechlorinating agent is obtained by compounding glycerol, organic quaternary ammonium base and strong basic ionic liquid, wherein the mass ratio of the glycerol to the organic quaternary ammonium base to the strong basic ionic liquid is 40-60: 20-35: 15-25;
the organic quaternary ammonium base is cetyl trimethyl ammonium hydroxide or tetrabutyl ammonium hydroxide;
the strongly alkaline ionic liquid is polyethylene glycol functionalized bisimidazole type ionic liquid, 1-butyl-3-methylimidazole type ionic liquid or 1, 3-dimethyl imidazole type ionic liquid.
6. The method of recycling waste mineral oil residues according to claim 1, characterized in that: in the step (4), the aperture of the ceramic nanofiltration membrane is 30-200 nm, the inlet and outlet pressure of the ceramic nanofiltration membrane is 0.4-0.8 MPa, and the separation temperature is 80-120 ℃.
7. The method of recycling waste mineral oil residues according to claim 1, characterized in that: in the step (5), the pressure of the fractionating tower is 0.1-0.5 MPa, and the temperature of the upper part of the fractionating tower is 150-220 ℃.
8. The method of recycling waste mineral oil residues according to claim 1, characterized in that: in the step (6), the hydrogenation reaction pressure is 12-16 MPa, the hydrogenation reaction temperature is 340-360 ℃, and the volume hydrogen-oil ratio is 300-800: 1.
9. A system for carrying out the method for recycling waste mineral oil residues according to any one of claims 1 to 8, wherein: the device comprises an extraction device (3), an electric adsorption device (5), a dechlorination reaction tank (8), a membrane separation device (9), a fractionating tower (11), a hydrofining reactor (12) and a product tank (13) which are sequentially connected, wherein the extraction device (3) is also connected with an extraction solvent tank (1) and a waste mineral oil residue raw material tank (2), and a three-phase separator (4) is arranged between the extraction device (3) and the electric adsorption device (5); the three-phase separator (4), the membrane separation device (9) and the fractionating tower (11) are all connected with the tail material tank (7), and the three-phase separator (4) and the fractionating tower (11) are also connected with the extraction solvent tank (1).
10. The system for recycling waste mineral oil residues as claimed in claim 9, wherein: a first heat exchanger (6) is arranged on a pipeline between the electro-adsorption device (5) and the dechlorination reaction tank (8), and a second heat exchanger (10) is arranged on a pipeline between the membrane separation device (9) and the fractionating tower (11).
Technical Field
The invention relates to the technical field of deep processing and comprehensive utilization of waste mineral oil, in particular to a method and a system for recycling waste mineral oil residues.
Background
With the gradual decrease of petroleum resources, the increasing emphasis on petroleum pollution and the increasing call for environmental protection, the understanding of the significance of waste mineral oil recovery and resource utilization is gradually improved in China, and the industrial support for the comprehensive utilization of waste mineral oil is continuously strengthened. The apparent consumption of lubricating oil in China reaches about 800 ten thousand tons, 50 percent of the lubricating oil can be recycled and reused after refining, and the output value can reach 500 hundred million.
The regeneration process of the waste mineral oil in China mainly comprises a distillation-acid washing-clay refining route and an acid washing-clay distillation refining route, and the pretreatment-thin film distillation-furfural refining and extraction-distillation-hydrogenation process is further developed at present. The method can be roughly divided into the following five steps: 1) removing mechanical impurities and carbon particles; 2) dehydrating and removing residual fuel oil; 3) deasphalting; 4) distilling; 5) and (5) refining. Some waste mineral oil regeneration process technologies not only have low product yield and poor quality, but also have serious secondary pollution. According to the data published by the China Committee for the regeneration of reclaimed oil, the process yield of the base oil regenerated by the waste mineral oil in China can only reach about 70 percent.
Taking a certain waste mineral oil comprehensive utilization enterprise as an example, in the standard of waste oil entering a factory, the water content and mechanical impurities generally account for 2-5%, and the contents of gasoline, diesel oil and light hydrocarbon are below 8%. And (3) removing a small part of deteriorated and particle components by mass balance calculation, wherein the recoverable mineral oil in the waste mineral oil is more than 80%. And the production enterprises can only recycle 70 percent of the lubricating oil base oil generally. Most of the unrecovered lubricating oil is left in the waste mineral oil vacuum residue oil, and a small part of the unrecovered lubricating oil is in mechanical impurities and oil sludge, and the unrecovered lubricating oil has a high boiling point and a distillation range of over 500 ℃, belongs to high-viscosity lubricating oil with good quality, and has extremely high utilization value.
Chinese patent CN110776989A discloses a method for refining waste lubricating oil by using waste lubricating oil residual oil, which comprises the steps of coking the waste lubricating oil residual oil at 400-500 ℃ to obtain a gas-phase product and a solid product, grinding the solid product, mixing the ground solid product with the waste lubricating oil, precipitating, and filtering to obtain a primary product of the lubricating oil, wherein the oil product has high chroma, clear oil and high viscosity. This patent adopts the high temperature coking to handle and cracks the green coke, has carried out structural destruction to the high viscosity lubricating oil component of residue, and the pyrolysis is micromolecular gasoline and diesel oil component, has lost the recoverable meaning of residue.
Due to the fact that purchasing of waste mineral oil has mixed diversity and complex properties, the waste mineral oil regeneration device still has the problem of continuous operation, shutdown maintenance is needed when the device is operated for 1-3 months, and some enterprises need to maintain once in half a month. Most recycling enterprises still examine the regeneration continuity of the waste mineral oil device, and do not deeply explore the waste mineral oil pressure-reducing residues, which has a large blank. Therefore, a set of complete comprehensive residue recycling process is formed, so that the regeneration yield of the lubricating oil can be increased, and the lubricating oil with high viscosity and high economic value can be produced by the process.
Disclosure of Invention
The invention aims to provide a method for recycling waste mineral oil residues, which can solve the problem of deep processing and utilization of the waste mineral oil residues and improve the recovery rate of lubricating oil of a waste mineral oil regeneration device; the method can also solve the environmental protection problem of the solvent in the regeneration process, and the high-boiling-point lubricating oil base oil with high viscosity, good quality and extremely high economic value is obtained by the byproduct, thereby providing the best raw material for the subsequent hydrogenation device. The invention also provides a system for recycling the waste mineral oil residues.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the method for recycling the waste mineral oil residues comprises the following steps:
(1) extraction unit
Mixing the waste mineral oil residues after heat exchange with an extraction solvent, extracting in an extraction device, and separating in a three-phase separator to obtain an extract phase;
(2) electro-adsorption unit
The extraction phase enters an electric adsorption device for electric adsorption, a high-voltage electrostatic field is generated by using an electrostatic generator, the charged impurity particles in the extraction phase move towards respective opposite directions under the action of the electric field by controlling the strength of the high-voltage electrostatic field, so that the impurity particles suspended in the extraction phase are destabilized and collide with each other for adsorption, the content of the waste mineral oil impurities in the extraction phase is further reduced, and the waste mineral oil liquid is obtained;
(3) efficient dechlorination unit
Adding a dechlorinating agent into the waste mineral oil liquid, performing heat exchange, then performing dechlorination in a dechlorination reaction tank, and converting organic chlorine into inorganic chlorine for removing;
(4) membrane separation unit
The dechlorinated oil enters a membrane separation device for separation, and colloidal substances and ultrafine particulate substances in the oil are separated by using a ceramic nanofiltration membrane to obtain a membrane clear solution;
(5) fractionation unit
After heat exchange, the membrane clear liquid enters a fractionating tower for reduced pressure fractionation, the upper fraction is condensed and then mixed with an extraction solvent for recycling, and the lower fraction is a high-viscosity lubricating oil raw material and enters a hydrofining unit;
(6) hydrorefining unit
And (3) feeding the high-viscosity lubricating oil raw material into a hydrofining reactor for hydrogenation reaction to obtain a lubricating oil base oil product.
Wherein
In the step (1), the mass ratio of the waste mineral oil residue to the extraction solvent is 1: 0.5-2; the extraction solvent is a mixture of limonene and 200# solvent oil, wherein the mass ratio of the limonene to the 200# solvent oil is 1: 0.1-20, and preferably 1: 05-10; the extraction temperature is 60-120 ℃; the extraction solvent can dissolve most of high-viscosity saturated base oil hydrocarbons but can not dissolve impurities such as colloid, asphaltene and the like, and the solid impurities are settled while the base oil is extracted. After the separation of the three-phase separator, the extracted base oil, namely an extraction phase, enters an electro-adsorption unit, solid impurities enter a tail material tank, and gas is condensed and then mixed with an extraction solvent for recycling.
In the step (2), the working voltage of the positive plate and the negative plate in the electric adsorption process is 500-2400V, and the electric adsorption temperature is 60-120 ℃.
In the step (3), the temperature of the dechlorination reaction is 150-250 ℃, the pressure of the dechlorination reaction is 0.5-5 MPa, and the residence time of the dechlorination reaction is 5-10 min; the dosage of the dechlorinating agent is 0.01-1% of the mass of the waste mineral oil liquid. The dechlorinating agent is obtained by compounding glycerol, organic quaternary ammonium base and strong basic ionic liquid, wherein the mass ratio of the glycerol to the organic quaternary ammonium base to the strong basic ionic liquid is 40-60: 20-35: 15-25;
the organic quaternary ammonium base is cetyl trimethyl ammonium hydroxide or tetrabutyl ammonium hydroxide;
the strongly alkaline ionic liquid is polyethylene glycol functionalized bisimidazole type ionic liquid, 1-butyl-3-methylimidazole type ionic liquid or 1, 3-dimethyl imidazole type ionic liquid.
The residence time is increased by adding the partition plates in the dechlorination reaction tank, so that the chlorine content in the waste mineral oil liquid is the lowest under the continuous working condition.
In the step (4), the aperture of the ceramic nanofiltration membrane is 30-200 nm, the inlet and outlet pressure of the ceramic nanofiltration membrane is 0.4-0.8 MPa, and the separation temperature is 80-120 ℃. The ceramic nanofiltration membrane is a mineral ceramic membrane, a hydrophobic layer is plated on the surface of the membrane, and a backwashing and pressure constant backflow system is arranged on the ceramic nanofiltration membrane.
In the step (5), the pressure of the fractionating tower is 0.1-0.5 MPa, and the temperature of the upper part of the fractionating tower is 150-220 ℃.
In the step (6), the high-viscosity lubricating oil raw material enters a hydrofining reactor to carry out hydrogenation reaction and reacts with H under the catalytic action of a catalyst2The function of the oil is to generate C-S, C-N and C-O bond breakage and saturation reaction of unsaturated hydrocarbons, change the performance of the waste mineral oil and ensure that the quality of the product is better and more stable. The hydrogenation reaction pressure is 12-16 MPa, the hydrogenation reaction temperature is 340-360 ℃, and the volume hydrogen-oil ratio is 300-800: 1.
The invention relates to a system for recycling waste mineral oil residues, which comprises the following steps: the device comprises an extraction device, an electric adsorption device, a dechlorination reaction tank, a membrane separation device, a fractionating tower, a hydrofining reactor and a product tank which are sequentially connected, wherein the extraction device is also connected with an extraction solvent tank and a waste mineral oil residue raw material tank, and a three-phase separator is arranged between the extraction device and the electric adsorption device; the three-phase separator, the membrane separation device and the fractionating tower are all connected with the tailing tank, and the three-phase separator and the fractionating tower are also connected with the extraction solvent tank.
A first heat exchanger is arranged on a pipeline between the electro-adsorption device and the dechlorination reaction tank, and a second heat exchanger is arranged on a pipeline between the membrane separation device and the fractionating tower.
The waste mineral oil residue is subjected to heat exchange and then is mixed and extracted with an extraction solvent consisting of limonene and 200# solvent oil, and an extraction phase enters an electric adsorption unit for adsorption operation, so that the impurity content in the extraction phase is further reduced. And then carrying out organochlorine conversion by an efficient dechlorination unit, separating most impurities and a small part of chloride salt in an extraction phase by using a ceramic nanofiltration membrane, carrying out heat exchange, then entering a fractionation unit, carrying out reduced pressure fractionation, condensing a fraction obtained at the upper part, mixing the condensed fraction with an extraction solvent for recycling, sending a high-viscosity lubricating oil raw material at the lower part to a hydrofining unit, and obtaining high-viscosity lubricating oil base oil with better quality and more stability by the hydrofining unit. The invention utilizes the environment-friendly extraction solvent to treat the waste mineral oil residue, and the extraction solvent can be recovered and does not pollute the environment; meanwhile, the invention introduces a process combining an electric adsorption unit, a membrane separation unit and a hydrofining unit for treatment, and high-quality high-viscosity high-boiling-point lubricating oil base oil is obtained by reduction, so that the recovery rate of comprehensive utilization of waste mineral oil is improved.
The gas generated by the separation of the three-phase separator and the upper fraction generated by the reduced pressure fractionation of the fractionating tower contain light hydrocarbon with the temperature of less than 200 ℃, and after the light hydrocarbon is respectively condensed, the obtained liquid enters an extraction solvent tank and is mixed with the extraction solvent for recycling; the uncondensed gases enter the vent system.
The invention has the following beneficial effects:
(1) the invention treats the waste mineral oil residue by using the limonene and the No. 200 solvent oil as extraction solvents, does not use toxic organic solvents such as dimethylbenzene, NMP or furfural and the like, and does not pollute the environment. The limonene mainly plays a role in dissolution, and the No. 200 mineral oil serves as a blending dilution and solvent dispersion component, so that the dissolution problem in the waste mineral oil residue treatment process is solved, and the environmental protection problem of the solvent is also solved.
(2) In the electric adsorption unit, the electrostatic generator is used for generating a high-voltage electrostatic field, and the intensity of the high-voltage electrostatic field is controlled to enable the impurity particles charged in the extraction phase to move towards respective opposite directions under the action of the electric field, so that the impurity particles suspended in the extraction phase are destabilized and collide with each other for adsorption. The separation is carried out in the simplest and most efficient mode, the content of the waste mineral oil impurities in the extraction phase is further reduced, and the impurities are prevented from coking in a subsequent flow unit.
(3) According to the invention, the oil-soluble dechlorinating agent is added into the high-efficiency dechlorinating unit, and the retention time is increased by adding the partition plate, so that the chlorine content in the waste mineral oil liquid is minimized under the continuous working condition, and the problems of corrosion of a subsequent device, catalyst poisoning of a hydrofining unit and the like can be reduced.
(4) In the membrane separation unit, the ceramic nanofiltration membrane is used for separating out colloidal substances and ultrafine particle substances in the oil liquid, so that the metal content and dechlorinated small particles are greatly reduced, and the coking pressure of the fractionating tower is delayed.
(5) The fractionation unit and the hydrofining unit are used together, the lower fraction high-viscosity lubricating oil raw material is obtained by fractionation, and meanwhile, the upper fraction is mixed with the extraction solvent for recycling after being condensed; the high-viscosity lubricating oil raw material is subjected to hydrotreating, hydrodewaxing and complementary isomerization refining in a three-stage hydrofining reactor, and is reduced to obtain a high-quality high-viscosity high-boiling point lubricating oil base oil product.
Drawings
FIG. 1 is a process flow diagram of the present invention;
wherein: 1. an extraction solvent tank; 2. a waste mineral oil residue feed tank; 3. an extraction device; 4. a three-phase separator; 5. an electro-adsorption device; 6. a first heat exchanger; 7. a tail material tank; 8. a dechlorination reaction tank; 9. a membrane separation device; 10. a second heat exchanger; 11. a fractionating column; 12. a hydrofining reactor; 13. and (5) a product tank.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
(1) Extraction unit
After the waste mineral oil residue from the waste mineral oil residue raw material tank 2 reaches 70 ℃ through heat exchange, the waste mineral oil residue is mixed with an extraction solvent from an extraction solvent tank 1 and then enters an extraction device 3, extraction is carried out at 85 ℃, and after extraction, an extraction phase is obtained through separation by a three-phase separator 4 and then enters an electric adsorption unit; solid impurities generated by three-phase separation enter a tail material tank 7, liquid obtained by condensing gas enters an extraction solvent tank 1 to be mixed with an extraction solvent, the liquid is recycled, and uncondensed gas enters an emptying system. Wherein the mass ratio of the waste mineral oil residue to the extraction solvent is 1: 1; the extraction solvent is a mixture of limonene and 200# solvent oil, and the mass ratio of the limonene to the 200# solvent oil is 1: 0.5; the extraction solvent can dissolve most of high-viscosity saturated base oil hydrocarbons, but can not dissolve impurities such as colloid, asphaltene and the like, and the solid impurities are settled while the base oil is extracted.
(2) Electro-adsorption unit
The extract phase obtained by separation enters an electro-adsorption device 5 for electro-adsorption, the working voltage of the positive plate and the negative plate in the electro-adsorption process is controlled to be 2200V, and the electro-adsorption temperature is controlled to be 85 ℃; the electrostatic generator is utilized to generate a high-voltage electrostatic field, and the intensity of the high-voltage electrostatic field is controlled to enable charged impurity particles in the extraction phase to move towards respective opposite directions under the action of the electric field, so that the impurity particles suspended in the extraction phase are destabilized and collide with each other to be adsorbed, the content of waste mineral oil impurities in the extraction phase is further reduced, and the waste mineral oil liquid is obtained.
(3) Efficient dechlorination unit
Adding a dechlorinating agent into the waste mineral oil liquid, performing heat exchange by a first heat exchanger 6, then performing dechlorination in a dechlorination reaction tank 8, converting organic chlorine into inorganic chlorine for removing, controlling the dechlorination temperature at 200 ℃, the dechlorination pressure at 3.5MPa, and the residence time of the dechlorination reaction at 8 min. The residence time is increased by adding a partition plate in the dechlorination reaction tank 8 so as to ensure that the chlorine content in the waste mineral oil liquid is lowest under the continuous working condition.
Wherein the dosage of the dechlorinating agent is 0.8 percent of the mass of the waste mineral oil liquid; the dechlorinating agent is obtained by compounding glycerol, organic quaternary ammonium base and strong basic ionic liquid, wherein the mass ratio of the glycerol to the organic quaternary ammonium base to the strong basic ionic liquid is 40:35: 25;
the organic quaternary ammonium base is cetyl trimethyl ammonium hydroxide; the strongly alkaline ionic liquid is polyethylene glycol functionalized bisimidazole type ionic liquid.
(4) Membrane separation unit
The dechlorinated oil enters a membrane separation device 9 for separation, and colloidal substances and ultrafine particulate substances in the oil are separated by using a ceramic nanofiltration membrane with the aperture of 100nm to obtain a membrane clear solution; the separated colloidal substances and ultrafine particulate substances enter a tailing tank 7. The inlet and outlet pressure of the ceramic nanofiltration membrane is 0.6MPa, and the separation temperature is 100 ℃. The ceramic nanofiltration membrane is a mineral ceramic membrane, a hydrophobic layer is plated on the surface of the ceramic nanofiltration membrane, and a backwashing and pressure constant backflow system is arranged on the ceramic nanofiltration membrane.
(5) Fractionation unit
And (3) after heat exchange of the membrane clear liquid is carried out by a second heat exchanger 10, the membrane clear liquid enters a fractionating tower 11 for reduced pressure fractionation, the pressure of the fractionating tower is 0.5MPa, and the extraction temperature of the upper part of the fractionation is converted into the actual temperature of the normal pressure of 200 ℃. The upper fraction is condensed and then enters an extraction solvent tank 1 to be mixed with an extraction solvent for recycling, and the lower fraction is a high-viscosity lubricating oil raw material and enters a hydrofining unit; the solid impurities produced by fractionation enter a tail material tank 7.
(6) Hydrorefining unit
The high-viscosity lubricating oil raw material enters a hydrofining reactor 12 to be subjected to hydrogenation reaction, wherein the hydrogenation reaction pressure is controlled to be 16MPa, the hydrogenation reaction temperature is 350 ℃, and the volume hydrogen-oil ratio is 800: 1. Under the catalytic action of catalyst, high-viscosity lubricating oil raw material and H2The C-S, C-N and C-O bond are broken and the unsaturated hydrocarbons are saturated to obtain the high-quality lubricating oil base oil product with high viscosity and high boiling point, which enters the product tank 13.
Example 2
(1) Extraction unit
After the waste mineral oil residue from the waste mineral oil residue raw material tank 2 reaches 85 ℃ through heat exchange, the waste mineral oil residue is mixed with an extraction solvent from an extraction solvent tank 1 and then enters an extraction device 3, extraction is carried out at 90 ℃, and after extraction, an extraction phase is obtained through separation by a three-phase separator 4 and then enters an electric adsorption unit; solid impurities generated by three-phase separation enter a tail material tank 7, liquid obtained by condensing gas enters an extraction solvent tank 1 to be mixed with an extraction solvent, the liquid is recycled, and uncondensed gas enters an emptying system. Wherein the mass ratio of the waste mineral oil residue to the extraction solvent is 1: 1.5; the extraction solvent is a mixture of limonene and 200# solvent oil, and the mass ratio of the limonene to the 200# solvent oil is 1: 1; the extraction solvent can dissolve most of high-viscosity saturated base oil hydrocarbons, but can not dissolve impurities such as colloid, asphaltene and the like, and the solid impurities are settled while the base oil is extracted.
(2) Electro-adsorption unit
The extract phase obtained by separation enters an electric adsorption device 5 for electric adsorption, the working voltage of the positive plate and the negative plate in the electric adsorption process is controlled to be 1800V, and the electric adsorption temperature is controlled to be 90 ℃; the electrostatic generator is utilized to generate a high-voltage electrostatic field, and the intensity of the high-voltage electrostatic field is controlled to enable charged impurity particles in the extraction phase to move towards respective opposite directions under the action of the electric field, so that the impurity particles suspended in the extraction phase are destabilized and collide with each other to be adsorbed, the content of waste mineral oil impurities in the extraction phase is further reduced, and the waste mineral oil liquid is obtained.
(3) Efficient dechlorination unit
Adding a dechlorinating agent into the waste mineral oil liquid, performing heat exchange by a first heat exchanger 6, then performing dechlorination in a dechlorination reaction tank 8, converting organic chlorine into inorganic chlorine for removing, controlling the dechlorination temperature at 250 ℃, the dechlorination pressure at 5MPa and the residence time of the dechlorination at 6 min. The residence time is increased by adding a partition plate in the dechlorination reaction tank 8 so as to ensure that the chlorine content in the waste mineral oil liquid is lowest under the continuous working condition.
Wherein the dosage of the dechlorinating agent is 0.2 percent of the mass of the waste mineral oil liquid; the dechlorinating agent is obtained by compounding glycerol, organic quaternary ammonium base and strong basic ionic liquid, wherein the mass ratio of the glycerol to the organic quaternary ammonium base to the strong basic ionic liquid is 50:25: 25;
the organic quaternary ammonium base is tetrabutyl ammonium hydroxide; the strongly alkaline ionic liquid is 1-butyl-3-methylimidazole ionic liquid.
(4) Membrane separation unit
The dechlorinated oil enters a membrane separation device 9 for separation, and colloidal substances and ultrafine particulate substances in the oil are separated by using a ceramic nanofiltration membrane with the aperture of 50nm to obtain a membrane clear solution; the separated colloidal substances and ultrafine particulate substances enter a tailing tank 7. The inlet and outlet pressure of the ceramic nanofiltration membrane is 0.7MPa, and the separation temperature is 120 ℃. The ceramic nanofiltration membrane is a mineral ceramic membrane, a hydrophobic layer is plated on the surface of the ceramic nanofiltration membrane, and a backwashing and pressure constant backflow system is arranged on the ceramic nanofiltration membrane.
(5) Fractionation unit
And (3) after heat exchange of the membrane clear liquid is carried out by a second heat exchanger 10, the membrane clear liquid enters a fractionating tower 11 for reduced pressure fractionation, the pressure of the fractionating tower is 0.3MPa, and the extraction temperature of the upper part of the fractionation is converted into the actual temperature of the normal pressure of 210 ℃. The upper fraction is condensed and then enters an extraction solvent tank 1 to be mixed with an extraction solvent for recycling, and the lower fraction is a high-viscosity lubricating oil raw material and enters a hydrofining unit; the solid impurities produced by fractionation enter a tail material tank 7.
(6) Hydrorefining unit
The high-viscosity lubricating oil raw material enters a hydrofining reactor 12 to be subjected to hydrogenation reaction, wherein the hydrogenation reaction pressure is controlled to be 15MPa, the hydrogenation reaction temperature is 360 ℃, and the volume hydrogen-oil ratio is 300: 1. Under the catalytic action of catalyst, high-viscosity lubricating oil raw material and H2The C-S, C-N and C-O bond are broken and the unsaturated hydrocarbons are saturated to obtain the high-quality lubricating oil base oil product with high viscosity and high boiling point, which enters the product tank 13.
Example 3
(1) Extraction unit
After the waste mineral oil residue from the waste mineral oil residue raw material tank 2 reaches 95 ℃ through heat exchange, the waste mineral oil residue is mixed with an extraction solvent from an extraction solvent tank 1, the mixture enters an extraction device 3, extraction is carried out at 100 ℃, an extraction phase is obtained through separation by a three-phase separator 4 after extraction, and the extraction phase enters an electric adsorption unit; solid impurities generated by three-phase separation enter a tail material tank 7, liquid obtained by condensing gas enters an extraction solvent tank 1 to be mixed with an extraction solvent, the liquid is recycled, and uncondensed gas enters an emptying system. Wherein the mass ratio of the waste mineral oil residue to the extraction solvent is 1: 2; the extraction solvent is a mixture of limonene and 200# solvent oil, and the mass ratio of the limonene to the 200# solvent oil is 1: 3; the extraction solvent can dissolve most of high-viscosity saturated base oil hydrocarbons, but can not dissolve impurities such as colloid, asphaltene and the like, and the solid impurities are settled while the base oil is extracted.
(2) Electro-adsorption unit
The extract phase obtained by separation enters an electric adsorption device 5 for electric adsorption, the working voltage of the positive plate and the negative plate in the electric adsorption process is controlled to be 2000V, and the electric adsorption temperature is controlled to be 100 ℃; the electrostatic generator is utilized to generate a high-voltage electrostatic field, and the intensity of the high-voltage electrostatic field is controlled to enable charged impurity particles in the extraction phase to move towards respective opposite directions under the action of the electric field, so that the impurity particles suspended in the extraction phase are destabilized and collide with each other to be adsorbed, the content of waste mineral oil impurities in the extraction phase is further reduced, and the waste mineral oil liquid is obtained.
(3) Efficient dechlorination unit
Adding a dechlorinating agent into the waste mineral oil liquid, performing heat exchange by a first heat exchanger 6, then performing dechlorination in a dechlorination reaction tank 8, converting organic chlorine into inorganic chlorine for removing, controlling the dechlorination temperature at 160 ℃, the dechlorination pressure at 3MPa and the residence time of the dechlorination at 10 min. The residence time is increased by adding a partition plate in the dechlorination reaction tank 8 so as to ensure that the chlorine content in the waste mineral oil liquid is lowest under the continuous working condition.
Wherein the dosage of the dechlorinating agent is 0.1 percent of the mass of the waste mineral oil liquid; the dechlorinating agent is obtained by compounding glycerol, organic quaternary ammonium base and strong-base ionic liquid, wherein the mass ratio of the glycerol to the organic quaternary ammonium base to the strong-base ionic liquid is 60:20: 20;
the organic quaternary ammonium base is cetyl trimethyl ammonium hydroxide; the strong-alkaline ionic liquid is 1, 3-dimethyl imidazole ionic liquid.
(4) Membrane separation unit
The dechlorinated oil enters a membrane separation device 9 for separation, and colloidal substances and ultrafine particulate substances in the oil are separated by using a ceramic nanofiltration membrane with the aperture of 150nm to obtain a membrane clear solution; the separated colloidal substances and ultrafine particulate substances enter a tailing tank 7. The inlet and outlet pressure of the ceramic nanofiltration membrane is 0.7MPa, and the separation temperature is 110 ℃. The ceramic nanofiltration membrane is a mineral ceramic membrane, a hydrophobic layer is plated on the surface of the ceramic nanofiltration membrane, and a backwashing and pressure constant backflow system is arranged on the ceramic nanofiltration membrane.
(5) Fractionation unit
And (3) after heat exchange of the membrane clear liquid is carried out by a second heat exchanger 10, the membrane clear liquid enters a fractionating tower 11 for reduced pressure fractionation, the pressure of the fractionating tower is 0.3MPa, and the extraction temperature of the upper part of the fractionation is converted into the actual temperature of the normal pressure of 210 ℃. The upper fraction is condensed and then enters an extraction solvent tank 1 to be mixed with an extraction solvent for recycling, and the lower fraction is a high-viscosity lubricating oil raw material and enters a hydrofining unit; the solid impurities produced by fractionation enter a tail material tank 7.
(6) Hydrorefining unit
The high-viscosity lubricating oil raw material enters a hydrofining reactor 12 to be subjected to hydrogenation reaction, wherein the hydrogenation reaction pressure is controlled to be 16MPa, the hydrogenation reaction temperature is 350 ℃, and the volume hydrogen-oil ratio is 500: 1. Under the catalytic action of catalyst, high-viscosity lubricating oil raw material and H2The C-S, C-N and C-O bond are broken and the unsaturated hydrocarbons are saturated to obtain the high-quality lubricating oil base oil product with high viscosity and high boiling point, which enters the product tank 13.
Example 4
(1) Extraction unit
After the waste mineral oil residue from the waste mineral oil residue raw material tank 2 reaches 105 ℃ through heat exchange, the waste mineral oil residue is mixed with the extraction solvent from the extraction solvent tank 1 and enters an extraction device 3, extraction is carried out at 110 ℃, and after extraction, an extraction phase is obtained through separation by a three-phase separator 4 and enters an electric adsorption unit; solid impurities generated by three-phase separation enter a tail material tank 7, liquid obtained by condensing gas enters an extraction solvent tank 1 to be mixed with an extraction solvent, the liquid is recycled, and uncondensed gas enters an emptying system. Wherein the mass ratio of the waste mineral oil residue to the extraction solvent is 1: 1; the extraction solvent is a mixture of limonene and 200# solvent oil, and the mass ratio of the limonene to the 200# solvent oil is 1: 5; the extraction solvent can dissolve most of high-viscosity saturated base oil hydrocarbons, but can not dissolve impurities such as colloid, asphaltene and the like, and the solid impurities are settled while the base oil is extracted.
(2) Electro-adsorption unit
The extract phase obtained by separation enters an electric adsorption device 5 for electric adsorption, the working voltage of the positive plate and the negative plate in the electric adsorption process is controlled to be 1000V, and the electric adsorption temperature is 110 ℃; the electrostatic generator is utilized to generate a high-voltage electrostatic field, and the intensity of the high-voltage electrostatic field is controlled to enable charged impurity particles in the extraction phase to move towards respective opposite directions under the action of the electric field, so that the impurity particles suspended in the extraction phase are destabilized and collide with each other to be adsorbed, the content of waste mineral oil impurities in the extraction phase is further reduced, and the waste mineral oil liquid is obtained.
(3) Efficient dechlorination unit
Adding a dechlorinating agent into the waste mineral oil liquid, performing heat exchange by a first heat exchanger 6, then performing dechlorination in a dechlorination reaction tank 8, converting organic chlorine into inorganic chlorine for removing, controlling the dechlorination temperature at 240 ℃, the dechlorination pressure at 4.5MPa, and the residence time of the dechlorination at 9 min. The residence time is increased by adding a partition plate in the dechlorination reaction tank 8 so as to ensure that the chlorine content in the waste mineral oil liquid is lowest under the continuous working condition.
Wherein the dosage of the dechlorinating agent is 0.05 percent of the mass of the waste mineral oil liquid; the dechlorinating agent is obtained by compounding glycerol, organic quaternary ammonium base and strong basic ionic liquid, wherein the mass ratio of the glycerol to the organic quaternary ammonium base to the strong basic ionic liquid is 60:35: 15;
the organic quaternary ammonium base is tetrabutyl ammonium hydroxide; the strongly alkaline ionic liquid is polyethylene glycol functionalized bisimidazole type ionic liquid.
(4) Membrane separation unit
The dechlorinated oil enters a membrane separation device 9 for separation, and colloidal substances and ultrafine particulate substances in the oil are separated by using a ceramic nanofiltration membrane with the pore diameter of 80nm to obtain a membrane clear solution; the separated colloidal substances and ultrafine particulate substances enter a tailing tank 7. The inlet and outlet pressure of the ceramic nanofiltration membrane is 0.5MPa, and the separation temperature is 90 ℃. The ceramic nanofiltration membrane is a mineral ceramic membrane, a hydrophobic layer is plated on the surface of the ceramic nanofiltration membrane, and a backwashing and pressure constant backflow system is arranged on the ceramic nanofiltration membrane.
(5) Fractionation unit
And (3) after heat exchange of the membrane clear liquid is carried out by a second heat exchanger 10, the membrane clear liquid enters a fractionating tower 11 for reduced pressure fractionation, the pressure of the fractionating tower is 0.2MPa, and the extraction temperature of the upper part of the fractionation is converted into the actual temperature of the normal pressure of 210 ℃. The upper fraction is condensed and then enters an extraction solvent tank 1 to be mixed with an extraction solvent for recycling, and the lower fraction is a high-viscosity lubricating oil raw material and enters a hydrofining unit; the solid impurities produced by fractionation enter a tail material tank 7.
(6) Hydrorefining unit
The high-viscosity lubricating oil raw material enters a hydrofining reactor 12 to be subjected to hydrogenation reaction, the hydrogenation reaction pressure is controlled to be 14MPa, the hydrogenation reaction temperature is 340 ℃, and the volume hydrogen-oil ratio is 400: 1. Under the catalytic action of catalyst, high-viscosity lubricating oil raw material and H2The C-S, C-N and C-O bond are broken and the unsaturated hydrocarbons are saturated to obtain the high-quality lubricating oil base oil product with high viscosity and high boiling point, which enters the product tank 13.
Example 5
(1) Extraction unit
After the waste mineral oil residue from the waste mineral oil residue raw material tank 2 reaches 115 ℃ through heat exchange, the waste mineral oil residue is mixed with an extraction solvent from an extraction solvent tank 1, the mixture enters an extraction device 3, extraction is carried out at 120 ℃, an extraction phase is obtained through separation by a three-phase separator 4 after extraction, and the extraction phase enters an electric adsorption unit; solid impurities generated by three-phase separation enter a tail material tank 7, liquid obtained by condensing gas enters an extraction solvent tank 1 to be mixed with an extraction solvent, the liquid is recycled, and uncondensed gas enters an emptying system. Wherein the mass ratio of the waste mineral oil residue to the extraction solvent is 1: 0.5; the extraction solvent is a mixture of limonene and 200# solvent oil, and the mass ratio of the limonene to the 200# solvent oil is 1: 10; the extraction solvent can dissolve most of high-viscosity saturated base oil hydrocarbons, but can not dissolve impurities such as colloid, asphaltene and the like, and the solid impurities are settled while the base oil is extracted.
(2) Electro-adsorption unit
The extract phase obtained by separation enters an electric adsorption device 5 for electric adsorption, the working voltage of the positive plate and the negative plate in the electric adsorption process is controlled to be 1500V, and the electric adsorption temperature is controlled to be 120 ℃; the electrostatic generator is utilized to generate a high-voltage electrostatic field, and the intensity of the high-voltage electrostatic field is controlled to enable charged impurity particles in the extraction phase to move towards respective opposite directions under the action of the electric field, so that the impurity particles suspended in the extraction phase are destabilized and collide with each other to be adsorbed, the content of waste mineral oil impurities in the extraction phase is further reduced, and the waste mineral oil liquid is obtained.
(3) Efficient dechlorination unit
Adding a dechlorinating agent into the waste mineral oil liquid, performing heat exchange by a first heat exchanger 6, then performing dechlorination in a dechlorination reaction tank 8, converting organic chlorine into inorganic chlorine for removing, controlling the dechlorination temperature at 190 ℃, the dechlorination pressure at 3MPa, and the residence time of the dechlorination reaction at 7 min. The residence time is increased by adding a partition plate in the dechlorination reaction tank 8 so as to ensure that the chlorine content in the waste mineral oil liquid is lowest under the continuous working condition.
Wherein the dosage of the dechlorinating agent is 0.5 percent of the mass of the waste mineral oil liquid; the dechlorinating agent is obtained by compounding glycerol, organic quaternary ammonium base and strong basic ionic liquid, wherein the mass ratio of the glycerol to the organic quaternary ammonium base to the strong basic ionic liquid is 53:30: 17;
the organic quaternary ammonium base is tetrabutyl ammonium hydroxide; the strong-alkaline ionic liquid is 1, 3-dimethyl imidazole ionic liquid.
(4) Membrane separation unit
The dechlorinated oil enters a membrane separation device 9 for separation, and colloidal substances and ultrafine particulate substances in the oil are separated by using a ceramic nanofiltration membrane with the aperture of 200nm to obtain a membrane clear solution; the separated colloidal substances and ultrafine particulate substances enter a tailing tank 7. The inlet and outlet pressure of the ceramic nanofiltration membrane is 0.8MPa, and the separation temperature is 80 ℃. The ceramic nanofiltration membrane is a mineral ceramic membrane, a hydrophobic layer is plated on the surface of the ceramic nanofiltration membrane, and a backwashing and pressure constant backflow system is arranged on the ceramic nanofiltration membrane.
(5) Fractionation unit
And (3) after heat exchange of the membrane clear liquid is carried out by a second heat exchanger 10, the membrane clear liquid enters a fractionating tower 11 for reduced pressure fractionation, the pressure of the fractionating tower is 0.1MPa, and the extraction temperature of the upper part of the fractionation is converted into the actual temperature of the normal pressure of 200 ℃. The upper fraction is condensed and then enters an extraction solvent tank 1 to be mixed with an extraction solvent for recycling, and the lower fraction is a high-viscosity lubricating oil raw material and enters a hydrofining unit; the solid impurities produced by fractionation enter a tail material tank 7.
(6) Hydrorefining unit
The high-viscosity lubricating oil raw material enters a hydrofining reactor 12 to be subjected to hydrogenation reaction, wherein the hydrogenation reaction pressure is controlled to be 13MPa, the hydrogenation reaction temperature is 360 ℃, and the volume hydrogen-oil ratio is 700: 1. Under the catalytic action of catalyst, high-viscosity lubricating oil raw material and H2The C-S, C-N and C-O bond are broken and the unsaturated hydrocarbons are saturated to obtain the high-quality lubricating oil base oil product with high viscosity and high boiling point, which enters the product tank 13.
The results of examining the material balance in the whole process of recycling the waste mineral oil residues of examples 1 to 5 are shown in Table 1 below.
TABLE 1 tables of material balance data for examples 1-5
The properties of the waste mineral oils and the waste mineral oil residues of examples 1 to 5 were analyzed, and the data are shown in Table 2.
TABLE 2 data of the properties of the waste mineral oils and the waste mineral oil residues of examples 1 to 5
The products obtained in examples 1 to 5 were subjected to property testing, and the data are shown in Table 3.
TABLE 3 tables of data on the measurement of properties of the products obtained in examples 1 to 5
The data show that the invention has high utilization rate of deep processing and recycling of waste mineral oil residue oil, and the obtained lubricating oil is high-quality API II lubricating oil base oil with high added value and has high light stability.
The system for recycling the waste mineral oil residues comprises an extraction device 3, an electric adsorption device 5, a dechlorination reaction tank 8, a membrane separation device 9, a fractionating tower 11, a hydrofining reactor 12 and a product tank 13 which are sequentially connected, wherein the extraction device 3 is also connected with an extraction solvent tank 1 and a waste mineral oil residue raw material tank 2, and a three-phase separator 4 is arranged between the extraction device 3 and the electric adsorption device 5; the three-phase separator 4, the membrane separation device 9 and the fractionating tower 11 are all connected with the tailing tank 7, and the three-phase separator 4 and the fractionating tower 11 are also connected with the extraction solvent tank 1.
A first heat exchanger 6 is arranged on a pipeline between the electro-adsorption device 5 and the dechlorination reaction tank 8, and a second heat exchanger 10 is arranged on a pipeline between the membrane separation device 9 and the fractionating tower 11.