WO2024092841A1 - Method and system for continuously producing base oil from waste mineral oil containing chlorine and silicon - Google Patents

Method and system for continuously producing base oil from waste mineral oil containing chlorine and silicon Download PDF

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WO2024092841A1
WO2024092841A1 PCT/CN2022/130151 CN2022130151W WO2024092841A1 WO 2024092841 A1 WO2024092841 A1 WO 2024092841A1 CN 2022130151 W CN2022130151 W CN 2022130151W WO 2024092841 A1 WO2024092841 A1 WO 2024092841A1
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oil
light
dechlorination
waste mineral
tank
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PCT/CN2022/130151
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French (fr)
Chinese (zh)
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王鸣
张帅
孟家平
侯东阳
王志忠
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宁波中循环保科技有限公司
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Publication of WO2024092841A1 publication Critical patent/WO2024092841A1/en

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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
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • 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
    • C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
    • C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/02—Working-up used lubricants to recover useful products ; Cleaning mineral-oil based
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes

Definitions

  • the invention relates to the technical field of comprehensive utilization of waste mineral oil, and in particular to a method and system for continuously producing base oil from chlorinated silicon-containing waste mineral oil.
  • Waste mineral oil is a high-value "urban mineral resource" in the recycling market. Domestic waste mineral oil recycling individuals and classification companies have not strictly followed the requirements of waste oil recycling standards and lack a clear classification awareness, resulting in a complex composition of recycled waste lubricating oils. Different waste mineral oils are mixed with each other, resulting in high chlorine and silicon content in waste mineral oils. Chlorine-silicon-containing waste mineral oils account for an increasing proportion of the market, causing many difficulties for companies in the disposal and reuse process.
  • Chlorine compounds in waste mineral oil can cause corrosion in distillation units and hydrogenation units, and the presence of organic chlorine can also cause poisoning and deactivation of hydrogenation catalysts.
  • Silicon in waste mineral oil increases the difficulty of subsequent hydrogenation refining treatment. Silicon will deposit on the surface of the hydrogenation catalyst, blocking the pores of the catalyst and causing the catalyst activity to decrease. After a long period of process operation, silicon will penetrate the hydrogenation catalyst bed, causing rapid poisoning and permanent deactivation of the catalyst.
  • Chinese patent CN105907452A discloses a combined process method for regenerating waste lubricating oil by heat treatment, comprising the following steps: heat treatment: waste lubricating oil raw material enters a heat treatment reactor for shallow thermal cracking reaction, and the material at the bottom of the heat treatment reactor enters an oil agent mixing unit; oil agent mixing: mixing with 120# solvent oil; centrifugation; steam stripping; membrane separation; atmospheric pressure fractionation: 120# solvent oil is recovered from the top of the tower, and a fraction ⁇ 300°C is obtained from the line, which can be used as a marine diesel product, and crude lubricating oil is obtained from the bottom of the tower and enters a vacuum distillation tower; vacuum distillation: the tower line and the bottom of the tower are cut into 4 fractions, which are respectively entered into a clay mixer for clay refining to obtain 4 lubricating oil products, namely, refined oil minus one, refined oil minus two, refined oil minus three and refined oil minus bottom.
  • Chinese patent CN109735391A discloses a method for improving the yield of solvent-refined regenerated lubricating oil base oil, the steps of which include first reducing the temperature of the waste lubricating oil extract after NMP refining to 25-30°C, standing for 5-15 minutes, separating the oil and solvent mixture parts precipitated by the temperature, and passing the obtained eluate through a desolventizing tower to produce a regenerated base oil product.
  • NMP solvent By adding NMP solvent to the adsorbent, its adsorption performance for waste lubricating oil is stronger than that of the adsorbent, and the oil adsorbed in the adsorbent can be effectively captured, further improving the yield of the regenerated base oil, and utilizing the different solubility of non-ideal components and ideal components in NMP solvent at low temperatures, the non-ideal components are precipitated from NMP, further improving the purity and recovery rate of the regenerated base oil.
  • Chinese patent CN104531328A discloses a fully hydrogenated waste lubricating oil hydrogenation regeneration process, which includes the following steps: extracting and stripping the waste lubricating oil to remove impurities and moisture in the waste lubricating oil; adding the obtained lubricating oil and new hydrogen into a heating furnace for heating and then adding them into a hydrogenation reactor; extracting and separating the materials after hydrogenation reaction to obtain high molecular weight compounds and low molecular weight compounds; desulfurizing the obtained high molecular weight compounds in a desulfurization tank and using them as raw materials; fractionating the obtained low molecular weight compounds through a fractionation tower to obtain white oil and lubricating oil base oil respectively.
  • the patented process is simple, easy to use, and can effectively recycle waste lubricating oil.
  • Chinese patent CN110577844A discloses a waste lubricating oil full hydrogenation regeneration process and a preparation method of a hydrogenation catalyst, the steps of which include waste lubricating oil pretreatment, hydrogenation demetallization, hydrogenation removal of heteroatoms and hydrogenation modification, and provides a matching hydrogenation catalyst for the above regeneration process.
  • the regeneration process has a high product yield and significantly improves the quality of the regenerated oil.
  • the quality of the regenerated lubricating oil product can meet the standard requirements of lubricating oil base oil.
  • the above patents only perform simple pretreatment on waste mineral oil, and do not specifically treat the chlorine and silicon in the waste mineral oil. They still do not fundamentally solve the problems of regenerating high-end base oil from waste mineral oil containing chlorine and silicon, and equipment corrosion and coking deposition caused by waste mineral oil containing chlorine and silicon. In addition, the above patents cannot continuously treat waste mineral oil containing chlorine and silicon for a long period of time. The equipment needs to be shut down for maintenance after running for 1-3 months, and even needs maintenance once every half a month, which significantly increases the difficulty of regenerating waste lubricating oil.
  • the purpose of the present invention is to provide a method for continuously producing base oil from waste mineral oil containing chlorine and silicon, which can effectively solve the problems of coking, corrosion, clogging and hydrogenation catalyst poisoning of the device during the regeneration process of the waste mineral oil containing chlorine and silicon, greatly reduce the secondary generation of hazardous waste, reduce production and maintenance costs, and at the same time extend the operation cycle of the waste mineral oil regeneration device to achieve continuous regeneration; the present invention also provides a system for continuously producing base oil from waste mineral oil containing chlorine and silicon.
  • the method for continuously producing base oil from chlorinated silicon-containing waste mineral oil comprises the following steps:
  • the waste mineral oil enters a heat settling device for heat settling, and the waste mineral oil after heat settling enters a flash evaporation device for flash evaporation to obtain light component oil and heavy component oil;
  • the heavy oil fraction and the heavy oil dechlorination agent enter the heavy oil dechlorination reactor for heavy oil dechlorination reaction, and then enter the demetallization reactor with the demetallization agent for demetallization reaction, and then undergo vacuum distillation to obtain distillate oil, light fraction and residual oil;
  • step (3) After the light component oil is separated from the water, it enters the light oil dechlorination reactor with the light oil dechlorination agent and the light fraction of step (2) to carry out a light oil dechlorination reaction to obtain light oil;
  • step (3) The light oil from step (3) is mixed with the residual oil from step (2) and then filtered through a membrane.
  • the resulting clear liquid and the distillate oil from step (2) are sent to an adsorption desiliconization tank for adsorption desiliconization reaction. After hydrogenation treatment, solvent oil, industrial white oil and base oil are obtained by distillation.
  • step (2) the temperature of the heavy oil dechlorination reaction is 200-350° C., the pressure is 0.2-4 MPa, the residence time is 15-60 min, and the mass ratio of the heavy oil dechlorination agent to the heavy oil fraction is 0.1-2:100.
  • the heavy oil dechlorination agent is prepared by compounding quaternary phosphonium salt, alcohol amine, ionic liquid and light white oil, wherein the mass composition ratio of quaternary phosphonium salt, alcohol amine, ionic liquid and light white oil is 10-30wt.%: 5-15wt.%: 5-10wt.%: 45-80wt.%;
  • the quaternary phosphonium salt is allyl triphenylphosphine hydroxide, hexadecyl triphenylphosphine acetate or ethyl triphenylphosphine acetate;
  • the alcohol amine is n-octyl diethanolamine, 1-hydroxypropanolamine or phosphatidylethanolamine;
  • the ionic liquid is didecyl dimethyl ammonium hydroxide or hexadecyl trimethyl ammonium hydroxide;
  • the light white oil is light white oil W1-130, light white oil W1-140 or light white oil W2-140.
  • the chlorine in the heavy oil is distributed in fractions at different temperatures.
  • the chlorine compounds in the heavy oil are dechlorinated by reaction under the action of alcohol amine, ionic liquid and light white oil.
  • the quaternary phosphonium salt used can play the role of emulsification and dispersion, thereby increasing the dechlorination effect.
  • step (2) the demetallization reaction temperature is 250-380° C.
  • the residence time is 10-60 min
  • the reaction pressure is 0.2-4 MPa
  • the mass ratio of the demetallization agent to the recombinant oil is 0.5-2:100.
  • the demetallizing agent is prepared by compounding histamine phosphate substances or phosphate ester substances and ethers; the mass composition ratio of histamine phosphate substances or phosphate ester substances and ethers is 30-50wt.%:50-70wt.%;
  • the histamine phosphate substance is phenyl tripropyl ammonium dihydrogen phosphate or phosphatidylethanolamine; the phosphate ester substance is lauric acid alkanolamide phosphate, n-dodecyl alcohol polyoxyethylene ether phosphate or octadecyl phosphate; the ether substance is tall oil acid polyoxyethylene polyoxypropylene ether, nonylphenol polyoxyethylene polyoxypropylene ether or glycerol polyoxyethylene polyoxypropylene ether.
  • step (3) the temperature of the light oil dechlorination reaction is 120-260° C., the pressure is 2-6 MPa, and the residence time is 15-60 min; the mass ratio of the light oil dechlorination agent to the light component is 0.1-2:100.
  • the light oil dechlorination agent is obtained by compounding copper alkoxide or copper alcoholamine substances, light oil and alcohols, wherein the mass composition ratio of copper alkoxide or copper alcoholamine substances, light oil and alcohols is 5-20wt.%:60-90wt.%:5-20wt.%;
  • the alcohol copper or alcohol amine copper substance is ethanolamine copper, dimethanol copper or ethanol copper; the light oil is 200# solvent oil or limonene; the alcohol is ethanol, propylene glycol, polyethylene glycol or diethylene glycol.
  • the light component oil contains more chlorine, but less impurities.
  • the light oil dechlorination agent uses alcohol amine copper substances to react with it. At the same time, the activity of alcohol amine copper substances is increased in the mutual dissolution environment of light oil and alcohols, which can remove most of the organic chlorine.
  • the mass ratio of residual oil to light oil is 0.5-1:1; a ceramic nanofiltration membrane or a silicon carbide tubular membrane is used as an ultrafiltration membrane for membrane filtration, the membrane filtration temperature is 120-200°C, the inlet pressure of the ultrafiltration membrane is 0.4-1.0MPa, the outlet pressure is 0.2-0.8MPa, and the pore size of the ultrafiltration membrane is 10-50nm.
  • the adsorbent during the adsorption desiliconization reaction is a chelating resin with active magnesium oxide attached to the surface.
  • the chelating resin is combined with magnesium oxide to improve the aggregation and adsorption effect of silicon;
  • the chelating resin is an iminodiacetic acid chelating resin, an iminodiacetaldehyde oxime chelating resin or a thiourea chelating resin, the pore size of the chelating resin is 5-12nm, and the loading concentration of active magnesium oxide is 0.05-0.5wt.%;
  • the temperature of the adsorption desiliconization reaction is 80-250°C.
  • the method for continuously producing base oil from chlorinated silicon-containing waste mineral oil of the present invention specifically comprises the following steps:
  • Waste mineral oil is pumped from the tank area into the heat settling device for heat settling.
  • the heat settling temperature is 60-120°C and the heat settling time is 2-6h.
  • Heat settling can preliminarily remove solid particles, sludge, water and other impurities in the waste mineral oil. After heat settling, the solid particles, sludge, water and other impurities enter the sludge recovery tank; the waste mineral oil after preliminary impurity removal enters the subsequent flash evaporation device.
  • the impurities removed by thermal sedimentation still contain a certain amount of waste mineral oil that can be recovered.
  • the utilization rate of the waste mineral oil is further improved through the sludge recovery tank.
  • the recovered waste mineral oil is sent to the subsequent flash evaporation device, and the impurities and water that cannot be used at all are sent outside the boundary for treatment.
  • the waste mineral oil obtained by thermal sedimentation and sludge recovery enters the flash evaporation device to completely remove the light component oil below 360°C and the remaining trace water.
  • the temperature of the flash evaporation device is 150-280°C and the pressure is 0.03-1.3KPa.
  • the material at the bottom of the flash evaporation device enters the heavy oil dechlorination reactor, and the light component oil and water at the top enter the oil-water separation tank.
  • the light component oil and water are separated in the oil-water separation tank, and the separated water is discharged into the wastewater tank, and the light component oil enters the light oil dechlorination reactor.
  • the heavy oil discharged from the bottom of the flash device is mixed with the heavy oil dechlorinating agent and then enters the heavy oil dechlorination reactor for dechlorination reaction.
  • the temperature of the heavy oil dechlorination reaction is 200-350°C
  • the pressure is 0.2-4MPa
  • the residence time is 15-60min
  • the mass ratio of the heavy oil dechlorinating agent to the heavy oil is 0.1-2:100
  • the dechlorinated heavy oil enters the subsequent demetallization reactor.
  • the dechlorinated heavy oil is mixed with a demetallizing agent and enters a demetallizing reactor for a demetallizing reaction.
  • the demetallizing reaction temperature is 250-380°C
  • the reaction time is 10-60min
  • the reaction pressure is 0.2-4MPa
  • the mass ratio of the demetallizing agent to the heavy oil is 0.5-2:100.
  • the demetallized heavy oil enters a subsequent vacuum distillation device.
  • the heavy oil after demetallization reaction treatment enters the vacuum distillation device for deep distillation to improve the quality of the raw materials before hydrogenation feeding;
  • the vacuum degree during vacuum distillation is 0.3-1.3KPa, and the distillate oil of 360-515°C is cut out under reduced pressure and enters the adsorption desiliconization unit;
  • the bottom residue oil of the vacuum distillation device (fraction>515°C) is the residual bottom oil of high-viscosity lubricating oil, which enters the intermediate residue oil storage tank for standby;
  • the light oil product (fraction ⁇ 360°C) condensed at the top of the tower, namely the light fraction is combined with the light component oil after oil-water separation from the top of the flash evaporation device, and enters the light oil dechlorination reactor for dechlorination.
  • the light component oil separated by the oil-water separation tank is mixed with the light oil dechlorinating agent, and then merged with the light oil product (fraction of ⁇ 360°C) condensed at the top of the vacuum distillation device, and dechlorination reaction is carried out in the light oil dechlorination reactor.
  • the temperature of the light oil dechlorination reaction is 120-260°C
  • the pressure is 2-6MPa
  • the residence time is 15-60min
  • the mass ratio of the light oil dechlorinating agent to the light component oil is 0.1-2:100
  • the dechlorinated light oil is stored in the light oil intermediate storage tank as extraction dilution oil.
  • the residual oil in the residual oil intermediate storage tank is mixed with the light oil in the light oil intermediate storage tank in proportion, and enters the deep membrane filtration device to obtain the clear liquid after membrane filtration.
  • the clear liquid after membrane filtration enters the adsorption desiliconization tank, and the remaining tailings enter the incinerator for incineration to provide heat source.
  • Light oil as a solvent can dissolve most of the high-viscosity saturated base oil hydrocarbons in the residual oil, but cannot dissolve impurities such as colloids and asphaltene. It dissolves the high-viscosity base oil and settles the solid impurities at the same time.
  • the mass ratio of residual oil to light oil is 0.5-1:1; the deep membrane filtration device is loaded with an ultrafiltration membrane, the ultrafiltration membrane is a ceramic nanofiltration membrane or a silicon carbide tubular membrane, the membrane filtration temperature is 120-200°C, the inlet and outlet pressure of the ultrafiltration membrane is 0.2-1MPa, the pore size of the ultrafiltration membrane is 10-50nm, a hydrophobic layer is attached to the surface of the ultrafiltration membrane, and a backwashing and constant pressure reflux system is set on the ceramic nanofiltration membrane.
  • multiple ultrafiltration membranes can be used in series for treatment.
  • the 360-515°C fraction oil after vacuum distillation is mixed with the clear liquid after membrane filtration and enters the adsorption desiliconization tank for adsorption desiliconization.
  • the adsorption desiliconization temperature is 80-250°C.
  • the oil after adsorption desiliconization enters the hydrogenation raw material buffer tank.
  • the chelate resin with large pores and active magnesium oxide on the surface of the random pile in the tank is used as an adsorbent.
  • the resin has excellent adsorption capacity, thereby adsorbing and removing silicon-containing impurities;
  • the chelate resin is an iminodiacetic acid chelate resin, an iminodiacetaldehyde oxime chelate resin or a thiourea chelate resin, and the active magnesium oxide loading concentration is 0.05-0.5wt.%.
  • the oil in the hydrogenation raw material buffer tank enters the three-stage hydrogenation reactor, and after hydrogenation refining reaction, isomerization decondensation reaction and supplementary refining reaction, it is distilled to obtain solvent oil, industrial white oil and base oil products.
  • the temperature of the hydrofining reaction is 350-400°C, the space velocity is 0.6-1.0h -1 , the hydrogen partial pressure is 12.0-16.0MPa, the hydrogen-oil ratio is 800-1200, and the active metal is a Mo-Ni catalyst; the catalyst uses Al 2 O 3 as a carrier, MoO 3 and NiO as active substances, wherein the loading amount of MoO 3 is 20-30wt.%, and the loading amount of NiO is 3-5wt.%.
  • the temperature of the isomerization decondensation reaction is 290-380°C
  • the space velocity is 1.2-1.6h -1
  • the hydrogen partial pressure is 14.0-16.0MPa
  • the hydrogen-oil ratio is 500-800
  • the catalyst with active metal as Pt-Pd is used;
  • the catalyst uses ZSM-5 molecular sieve as carrier and Pt and Pd as active substances, wherein the loading amount of Pt is 0.5-0.8wt.%, and the loading amount of Pd is 0.2-0.5wt.%.
  • the temperature of the supplementary refining reaction is 240-360°C, the space velocity is 0.4-0.8h -1 , the hydrogen partial pressure is 12.0-14.0MPa, the hydrogen-oil ratio is 500-800, and the catalyst with active metal as W-Mo-Ni is used; the catalyst uses Al 2 O 3 as a carrier, and uses WO 3 , MoO 3 and NiO as active substances, wherein the loading amount of WO 3 is 20-30wt.%, the loading amount of MoO 3 is 10-20wt.%, and the loading amount of NiO is 0.5-2wt.%.
  • the system for continuously producing base oil from chlorinated silicon-containing waste mineral oil of the present invention comprises a waste mineral oil storage tank, a heat settling device, a flash evaporation device, a heavy oil dechlorination reactor, a demetallization reactor, a vacuum distillation device, an adsorption desiliconization tank, a hydrogenation raw material buffer tank, a hydrogenation reactor, a distillation tower and a product tank connected in sequence;
  • the bottom of the vacuum distillation device is also connected to the adsorption desiliconization tank through the residual oil intermediate storage tank and the deep membrane filtration device;
  • the flash evaporation device is also connected to the oil-water separation tank, the light oil dechlorination reactor, and the light oil intermediate storage tank in sequence, and the light oil intermediate storage tank is also connected to the residual oil intermediate storage tank;
  • the heat settling device is also connected to the sludge recovery tank, and the sludge recovery tank is further connected to the flash evaporation device;
  • the top of the vacuum distillation device is also connected to the light oil dechlorination reactor;
  • the pipeline between the oil-water separation tank and the light oil dechlorination reactor is connected to the light oil dechlorination agent storage tank, the pipeline between the flash evaporation device and the heavy oil dechlorination reactor is connected to the heavy oil dechlorination agent storage tank, and the pipeline between the heavy oil dechlorination reactor and the demetallization reactor is connected to the demetallization agent storage tank; the oil-water separation tank is also connected to the wastewater tank, and the deep membrane filtration device is also connected to the incinerator.
  • the waste mineral oil of the present invention enters a heat settling tank for heat settling, and the waste mineral oil after heat settling and the waste mineral oil obtained by recycling the oil sludge after heat settling enter a flash evaporation device together, and the light component oil below 360°C and the remaining trace water are completely removed.
  • the top light component oil is dehydrated and enters a light oil dechlorination reactor, and is mixed with a light oil dechlorination agent for dechlorination and enters a light oil intermediate storage tank.
  • the heavy oil obtained after flash evaporation enters a heavy oil dechlorination reactor, and is mixed with a heavy oil dechlorination agent for dechlorination.
  • the reaction After the reaction, it is mixed with a demetallization agent and enters a demetallization reactor.
  • the heavy oil after demetallization enters a vacuum distillation device for deep distillation to obtain a vacuum intermediate distillate, i.e., a distillate oil.
  • the residual oil at the bottom of the vacuum distillation device is a high-viscosity lubricating oil residual bottom oil, which enters a residual oil intermediate storage tank for standby.
  • the light oil product condensed at the top of the vacuum distillation device is combined with the light component oil separated from the top of the previous flash evaporation device and enters a light oil dechlorination reactor for dechlorination reaction, and enters a light oil intermediate storage tank after dechlorination.
  • the oil products in the intermediate storage tank of residual oil and the intermediate storage tank of light oil are mixed and enter the continuous deep membrane filtration device.
  • the clear liquid obtained after membrane filtration and the intermediate fraction of vacuum distillation enter the adsorption desiliconization tank for adsorption desiliconization.
  • the oil products after desiliconization enter the hydrogenation raw material buffer tank for storage.
  • the oil products in the hydrogenation raw material buffer tank enter the hydrogenation reactor for hydrogenation, and then distillation to obtain solvent oil and high-quality base oil and industrial white oil that meet the API (American Petroleum Institute) standard Class II + or above base oil specifications.
  • the waste mineral oil after thermal sedimentation in the present invention enters the flash evaporation device to completely remove the light component oil below 360°C and the remaining trace water.
  • the light component oil after the top light component is dehydrated enters the light oil dechlorination reactor, and the heavy component oil obtained after flash evaporation enters the heavy oil dechlorination reactor.
  • the light component oil and the heavy component oil are dechlorinated respectively by the two-stage dechlorination reactor, and the chlorine in the waste mineral oil is removed in a targeted manner, which greatly improves the chlorine removal rate.
  • the present invention innovatively mixes the residual oil obtained by dechlorination, demetallization and vacuum distillation of the heavy oil with the light oil obtained by dechlorination of the light oil.
  • the light oil as a solvent can dissolve most of the high-viscosity saturated base oil hydrocarbons in the residual oil, but cannot dissolve impurities such as colloids and asphaltene.
  • the high-viscosity base oil is dissolved and the solid impurities are precipitated. After the residual oil and the light oil are mixed, they are continuously treated with an ultrafiltration membrane without introducing a third added solvent, achieving self-sufficiency.
  • the lubricating oil in the residual oil is further extracted through an ultra-micro ultrafiltration membrane, solving the problem that the waste mineral oil utilization enterprises of the same industry cannot process the rear-end residual oil, greatly improving the overall process total recovery rate, and the oil product recovery rate can reach more than 92%.
  • the heavy oil yield can reach more than 88%, which is much higher than the average level of 70% in the industry.
  • the present invention adopts deep hydrogenation technology, has good product quality and strong light stability, and obtains solvent oil and high-quality base oil products and industrial white oil that meet the API (American Petroleum Institute) standard Class II+ or above base oil specifications.
  • API American Petroleum Institute
  • the present invention solves the problems of easy coking of the device, equipment corrosion, pipeline blockage, and easy poisoning and deactivation of the hydrogenation catalyst during the waste mineral oil regeneration process.
  • secondary dechlorination the chloride in the waste mineral oil is removed, the corrosion of the chloride to the equipment is reduced, the operation cycle of the waste mineral oil regeneration device is extended, the life of the equipment is increased, and the production and maintenance costs of the waste lubricating oil regeneration enterprise are reduced.
  • FIG1 is a schematic diagram of a system for continuously producing base oil from chlorinated silicon-containing waste mineral oil according to the present invention
  • Waste mineral oil storage tank 1. Heat sedimentation device; 3. Flash device; 4. Oil-water separation tank; 5. Wastewater tank; 6. Light oil dechlorination agent storage tank; 7. Light oil dechlorination reactor; 8. Light oil intermediate storage tank; 9. Residue oil intermediate storage tank; 10. Vacuum distillation device; 11. Demetallization reactor; 12. Demetallization agent storage tank; 13. Heavy oil dechlorination reactor; 14. Heavy oil dechlorination agent storage tank; 15. Distillation tower; 16. Hydrogenation reactor; 17. Hydrogenation raw material buffer tank; 18. Adsorption desiliconization tank; 19. Deep membrane filtration device; 20. Incinerator; 21. Sludge recovery tank; 22. Product tank.
  • Waste mineral oil is pumped from the tank area into the heat settling device for heat settling.
  • the heat settling temperature is 80°C and the heat settling time is 4h.
  • solid particles, sludge, water and other impurities enter the sludge recovery tank; the waste mineral oil after preliminary impurity removal enters the subsequent flash evaporation device.
  • the impurities removed by thermal sedimentation still contain a certain amount of waste mineral oil that can be recovered.
  • the utilization rate of the waste mineral oil is further improved through the sludge recovery tank, and the recovered waste mineral oil is sent to the subsequent flash evaporation device.
  • the waste mineral oil obtained by thermal sedimentation and sludge recovery enters the flash evaporation device to completely remove the light oil and water below 360°C.
  • the temperature of the flash evaporation device is 230°C and the pressure is 1KPa.
  • the material at the bottom of the flash evaporation device enters the heavy oil dechlorination reactor, and the light oil and water at the top enter the oil-water separation tank.
  • the light oil and water are separated in the oil-water separation tank.
  • the separated water is discharged into the wastewater tank, and the light oil enters the light oil dechlorination reactor.
  • the heavy oil discharged from the bottom of the flash device is mixed with the heavy oil dechlorination agent and then enters the heavy oil dechlorination reactor for dechlorination reaction.
  • the temperature of the heavy oil dechlorination reaction is 250°C
  • the pressure is 0.4MPa
  • the residence time is 60min
  • the mass ratio of the heavy oil dechlorination agent to the heavy oil is 2:100
  • the dechlorinated heavy oil enters the subsequent demetallization reactor.
  • the heavy oil dechlorination agent is obtained by compounding the following substances in percentage by mass: 10 wt.% of allyl triphenylphosphine hydroxide, 15 wt.% of n-octyl diethanolamine, 10 wt.% of didecyl dimethyl ammonium hydroxide, and 65 wt.% of light white oil W1-130.
  • the dechlorinated heavy oil is mixed with the demetallizing agent and enters the demetallizing reactor for demetallizing reaction.
  • the demetallizing reaction temperature is 330°C
  • the reaction time is 50min
  • the reaction pressure is 1MPa
  • the mass ratio of the demetallizing agent to the heavy oil is 0.5:100
  • the demetallized heavy oil enters the subsequent vacuum distillation device.
  • the demetallizing agent is prepared by compounding phenyl tripropyl ammonium dihydrogen phosphate and tall oil acid polyoxyethylene polyoxypropylene ether; wherein the mass composition ratio of phenyl tripropyl ammonium dihydrogen phosphate and tall oil acid polyoxyethylene polyoxypropylene ether is 30wt.%:70wt.%.
  • the heavy oil after demetallization reaction treatment enters the vacuum distillation device for deep distillation to improve the quality of the raw materials before hydrogenation feeding;
  • the vacuum degree during vacuum distillation is 0.5KPa, and the distillate oil of 360-515°C is cut out under reduced pressure and enters the adsorption desiliconization unit;
  • the bottom residue oil of the vacuum distillation device (fraction>515°C) is the residual bottom oil of high-viscosity lubricating oil, which enters the intermediate residue oil storage tank for standby;
  • the light oil product (fraction ⁇ 360°C) condensed at the top of the tower, namely the light fraction is combined with the light component oil after oil-water separation from the top of the flash evaporation device, and enters the light oil dechlorination reactor for dechlorination.
  • the light component oil separated by the oil-water separation tank is mixed with the light oil dechlorination agent, and then merged with the light oil product (fraction ⁇ 360°C) condensed at the top of the vacuum distillation device, and dechlorination reaction is carried out in the light oil dechlorination reactor.
  • the temperature of the light oil dechlorination reaction is 140°C
  • the pressure is 2.5MPa
  • the residence time is 55min
  • the mass ratio of the light oil dechlorination agent to the light component oil is 0.5:100
  • the dechlorinated light oil is stored in the light oil intermediate storage tank as extraction dilution oil.
  • the light oil dechlorination agent is prepared by compounding the following substances in percentage by mass: 6 wt.% of ethanolamine copper, 86 wt.% of 200# solvent oil, and 8 wt.% of ethanol.
  • the residual oil in the residual oil intermediate storage tank is mixed with the light oil in the light oil intermediate storage tank and enters the deep membrane filtration device to obtain the clear liquid after membrane filtration.
  • the clear liquid after membrane filtration enters the adsorption desiliconization tank, and the remaining tailings enter the incinerator for incineration to provide a heat source.
  • the mass ratio of residual oil to light oil is 0.7:1; the deep membrane filtration device is loaded with an ultrafiltration membrane, the ultrafiltration membrane is a silicon carbide tubular membrane, the membrane filtration temperature is 130°C, the inlet pressure of the ultrafiltration membrane is 0.6MPa, the outlet pressure is 0.2MPa, the pore size of the ultrafiltration membrane is 50nm, a hydrophobic layer is attached to the surface of the ultrafiltration membrane, and multi-stage ultrafiltration membranes are connected in series for treatment.
  • the 360-515°C fraction oil after vacuum distillation is mixed with the clear liquid after membrane filtration and enters the adsorption desiliconization tank for adsorption desiliconization.
  • the adsorption desiliconization temperature is 90°C.
  • the oil after adsorption desiliconization enters the hydrogenation raw material buffer tank.
  • the iminodiacetic acid-based chelating resin with large pores and active magnesium oxide on the surface is used as an adsorbent.
  • the active magnesium oxide loading concentration is 0.05wt.%, and the pore size of the iminodiacetic acid-based chelating resin is 8nm.
  • the oil in the hydrogenation raw material buffer tank enters the three-stage hydrogenation reactor, undergoes hydrogenation refining reaction, isomerization decondensation reaction and supplementary refining reaction, and then is distilled to obtain solvent oil fraction, industrial white oil and high-quality base oil that meets API Class II + standards.
  • the temperature of the hydrofining reaction is 350°C
  • the space velocity is 0.6h -1
  • the hydrogen partial pressure is 14.0MPa
  • the hydrogen-oil ratio is 1200
  • the catalyst uses Al 2 O 3 as the carrier and MoO 3 and NiO as the active substances; wherein the loading amount of MoO 3 is 30wt.%, and the loading amount of NiO is 5wt.%.
  • the temperature of the isomerization decondensation reaction is 290°C
  • the space velocity is 1.2h -1
  • the hydrogen partial pressure is 14.0MPa
  • the hydrogen-oil ratio is 500
  • a catalyst with ZSM-5 molecular sieve as carrier and Pt and Pd as active substances is used, wherein the Pt loading is 0.8wt.%, and the Pd loading is 0.2wt.%.
  • the temperature of the supplementary refining reaction is 240°C
  • the space velocity is 0.4h -1
  • the hydrogen partial pressure is 14.0MPa
  • the hydrogen -oil ratio is 500
  • the catalyst is supported by Al2O3 and active materials are WO3 , MoO3 and NiO, wherein the loading amount of WO3 is 20wt.%, the loading amount of MoO3 is 10wt.%, and the loading amount of NiO is 1wt.%.
  • Waste mineral oil is pumped from the tank area into the heat settling device for heat settling.
  • the heat settling temperature is 95°C and the heat settling time is 3 hours.
  • solid particles, sludge, water and other impurities enter the sludge recovery tank; the waste mineral oil after preliminary impurity removal enters the subsequent flash evaporation device.
  • the impurities removed by thermal sedimentation still contain a certain amount of waste mineral oil that can be recovered.
  • the utilization rate of the waste mineral oil is further improved through the sludge recovery tank, and the recovered waste mineral oil is sent to the subsequent flash evaporation device.
  • the waste mineral oil obtained by thermal sedimentation and sludge recovery enters the flash evaporation device to completely remove the light oil and water below 360°C.
  • the temperature of the flash evaporation device is 210°C and the pressure is 0.5KPa.
  • the material at the bottom of the flash evaporation device enters the heavy oil dechlorination reactor, and the light oil and water at the top enter the oil-water separation tank.
  • the light oil and water are separated in the oil-water separation tank.
  • the separated water is discharged into the wastewater tank, and the light oil enters the light oil dechlorination reactor.
  • the heavy oil discharged from the bottom of the flash device is mixed with the heavy oil dechlorination agent and then enters the heavy oil dechlorination reactor for dechlorination reaction.
  • the temperature of the heavy oil dechlorination reaction is 280°C
  • the pressure is 1MPa
  • the residence time is 30min
  • the mass ratio of the heavy oil dechlorination agent to the heavy oil is 1:100
  • the dechlorinated heavy oil enters the subsequent demetallization reactor.
  • the heavy oil dechlorination agent is obtained by compounding the following substances in percentage by mass: 20 wt.% of hexadecyl triphenylphosphine acetate, 10 wt.% of 1-hydroxypropanolamine, 8 wt.% of hexadecyl trimethylammonium hydroxide, and 62 wt.% of light white oil W1-140.
  • the dechlorinated heavy oil is mixed with the demetallizing agent and enters the demetallizing reactor for demetallizing reaction.
  • the demetallizing reaction temperature is 350°C
  • the reaction time is 20 min
  • the reaction pressure is 2 MPa
  • the mass ratio of the demetallizing agent to the heavy oil is 1:100
  • the demetallized heavy oil enters the subsequent vacuum distillation device.
  • the demetallizing agent is prepared by compounding lauric acid alkanolamide phosphate and nonylphenol polyoxyethylene polyoxypropylene ether; wherein the mass composition ratio of lauric acid alkanolamide phosphate and nonylphenol polyoxyethylene polyoxypropylene ether is 40wt.%:60wt.%.
  • the heavy oil after demetallization reaction treatment enters the vacuum distillation device for deep distillation to improve the quality of the raw materials before hydrogenation feeding;
  • the vacuum degree during vacuum distillation is 0.9KPa, and the distillate oil of 360-515°C is cut out under reduced pressure and enters the adsorption desiliconization unit;
  • the bottom residue oil of the vacuum distillation device (fraction>515°C) is the residual bottom oil of high-viscosity lubricating oil, which enters the intermediate residue oil storage tank for standby;
  • the light oil product (fraction ⁇ 360°C) condensed at the top of the tower, namely the light fraction is combined with the light component oil after oil-water separation from the top of the flash evaporation device, and enters the light oil dechlorination reactor for dechlorination.
  • the light component oil separated by the oil-water separation tank is mixed with the light oil dechlorination agent, and then merged with the light oil product (fraction ⁇ 360°C) condensed at the top of the vacuum distillation device, and dechlorination reaction is carried out in the light oil dechlorination reactor.
  • the temperature of the light oil dechlorination reaction is 180°C
  • the pressure is 3.5MPa
  • the residence time is 40min
  • the mass ratio of the light oil dechlorination agent to the light component oil is 1:100
  • the dechlorinated light oil is stored in the light oil intermediate storage tank as extraction dilution oil.
  • the light oil dechlorination agent is prepared by compounding the following substances in percentage by mass: 12 wt.% of copper dimethoxide, 75 wt.% of limonene, and 13 wt.% of propylene glycol.
  • the residual oil in the residual oil intermediate storage tank is mixed with the light oil in the light oil intermediate storage tank and enters the deep membrane filtration device to obtain the clear liquid after membrane filtration.
  • the clear liquid after membrane filtration enters the adsorption desiliconization tank, and the remaining tailings enter the incinerator for incineration to provide a heat source.
  • the mass ratio of residual oil to light oil is 0.6:1; the deep membrane filtration device is loaded with an ultrafiltration membrane, the ultrafiltration membrane is a silicon carbide tubular membrane, the membrane filtration temperature is 200°C, the inlet pressure of the ultrafiltration membrane is 0.9MPa, the outlet pressure is 0.6MPa, the pore size of the ultrafiltration membrane is 10nm, a hydrophobic layer is attached to the surface of the ultrafiltration membrane, and multi-stage ultrafiltration membranes are connected in series for treatment.
  • the 360-515°C fraction oil after vacuum distillation is mixed with the clear liquid after membrane filtration and enters the adsorption desiliconization tank for adsorption desiliconization.
  • the adsorption desiliconization temperature is 160°C.
  • the oil after adsorption desiliconization enters the hydrogenation raw material buffer tank.
  • the iminodiacetaldehyde oxime chelate resin with large pores and active magnesium oxide on the surface is used as an adsorbent.
  • the active magnesium oxide loading concentration is 0.2wt.%, and the pore size of the iminodiacetaldehyde oxime chelate resin is 5nm.
  • the oil in the hydrogenation raw material buffer tank enters the three-stage hydrogenation reactor, undergoes hydrogenation refining reaction, isomerization decondensation reaction and supplementary refining reaction, and then is distilled to obtain solvent oil fraction, industrial white oil and high-quality base oil that meets API Class II + standards.
  • the temperature of the hydrofining reaction is 400°C
  • the space velocity is 1.0h -1
  • the hydrogen partial pressure is 16.0MPa
  • the hydrogen-oil ratio is 800
  • the catalyst is Al 2 O 3 as the carrier and MoO 3 and NiO as the active substances; wherein the loading amount of MoO 3 is 20wt.%, and the loading amount of NiO is 5wt.%.
  • the temperature of the isomerization decondensation reaction is 380°C
  • the space velocity is 1.6h -1
  • the hydrogen partial pressure is 16.0MPa
  • the hydrogen-oil ratio is 800
  • a catalyst with ZSM-5 molecular sieve as carrier and Pt and Pd as active substances is used, wherein the Pt loading is 0.5wt.%, and the Pd loading is 0.2wt.%.
  • the temperature of the supplementary refining reaction is 310°C
  • the space velocity is 0.8h -1
  • the hydrogen partial pressure is 14.0MPa
  • the hydrogen -oil ratio is 800
  • the catalyst is supported by Al2O3 and active materials are WO3 , MoO3 and NiO, wherein the loading amount of WO3 is 30wt.%, the loading amount of MoO3 is 20wt.%, and the loading amount of NiO is 2wt.%.
  • Waste mineral oil is pumped from the tank area into the heat settling device for heat settling.
  • the heat settling temperature is 110°C and the heat settling time is 2h.
  • solid particles, sludge, water and other impurities enter the sludge recovery tank; the waste mineral oil after preliminary impurity removal enters the subsequent flash evaporation device.
  • the impurities removed by thermal sedimentation still contain a certain amount of waste mineral oil that can be recovered.
  • the utilization rate of the waste mineral oil is further improved through the sludge recovery tank, and the recovered waste mineral oil is sent to the subsequent flash evaporation device.
  • the waste mineral oil obtained by thermal sedimentation and sludge recovery enters the flash evaporation device to completely remove the light oil and water below 360°C.
  • the temperature of the flash evaporation device is 225°C and the pressure is 0.3KPa.
  • the material at the bottom of the flash evaporation device enters the heavy oil dechlorination reactor, and the light oil and water at the top enter the oil-water separation tank.
  • the light oil and water are separated in the oil-water separation tank.
  • the separated water is discharged into the wastewater tank, and the light oil enters the light oil dechlorination reactor.
  • the heavy oil discharged from the bottom of the flash device is mixed with the heavy oil dechlorination agent and then enters the heavy oil dechlorination reactor for dechlorination reaction.
  • the temperature of the heavy oil dechlorination reaction is 330°C
  • the pressure is 2MPa
  • the residence time is 15min
  • the mass ratio of the heavy oil dechlorination agent to the heavy oil is 0.5:100
  • the dechlorinated heavy oil enters the subsequent demetallization reactor.
  • the heavy oil dechlorination agent is obtained by compounding the following substances in percentage by mass: 30 wt.% of ethyl triphenylphosphine acetate, 5 wt.% of phosphatidylethanolamine, 5 wt.% of hexadecyl trimethylammonium hydroxide, and 60 wt.% of light white oil W2-140.
  • the dechlorinated heavy oil is mixed with the demetallizing agent and enters the demetallizing reactor for demetallizing reaction.
  • the demetallizing reaction temperature is 370°C
  • the reaction time is 10 min
  • the reaction pressure is 3 MPa
  • the mass ratio of the demetallizing agent to the heavy oil is 2:100
  • the demetallized heavy oil enters the subsequent vacuum distillation device.
  • the demetallizing agent is prepared by compounding n-dodecyl alcohol polyoxyethylene ether phosphate and glycerol polyoxyethylene polyoxypropylene ether; wherein the mass composition ratio of n-dodecyl alcohol polyoxyethylene ether phosphate and glycerol polyoxyethylene polyoxypropylene ether is 45wt.%:55wt.%;
  • the heavy oil after demetallization reaction treatment enters the vacuum distillation device for deep distillation to improve the quality of the raw materials before hydrogenation feeding;
  • the vacuum degree during vacuum distillation is 1.2KPa, and the distillate oil of 360-515°C is cut out under reduced pressure and enters the adsorption desiliconization unit;
  • the bottom residue oil of the vacuum distillation device (fraction>515°C) is the residual bottom oil of high-viscosity lubricating oil, which enters the intermediate residue oil storage tank for standby;
  • the light oil product (fraction ⁇ 360°C) condensed at the top of the tower, namely the light fraction is combined with the light component oil after oil-water separation from the top of the flash evaporation device, and enters the light oil dechlorination reactor for dechlorination.
  • the light component oil separated by the oil-water separation tank is mixed with the light oil dechlorination agent, and then merged with the light oil product (fraction ⁇ 360°C) condensed at the top of the vacuum distillation device, and dechlorination reaction is carried out in the light oil dechlorination reactor.
  • the temperature of the light oil dechlorination reaction is 230°C
  • the pressure is 6MPa
  • the residence time is 20min
  • the mass ratio of the light oil dechlorination agent to the light component oil is 2:100
  • the dechlorinated light oil is stored in the light oil intermediate storage tank as extraction dilution oil.
  • the light oil dechlorination agent is prepared by compounding the following substances in percentage by mass: 20 wt.% of ethanol copper, 60 wt.% of 200# solvent oil and 20 wt.% of polyethylene glycol.
  • the residual oil in the residual oil intermediate storage tank is mixed with the light oil in the light oil intermediate storage tank and enters the deep membrane filtration device to obtain the clear liquid after membrane filtration.
  • the clear liquid after membrane filtration enters the adsorption desiliconization tank, and the remaining tailings enter the incinerator for incineration to provide a heat source.
  • the mass ratio of residual oil to light oil is 0.8:1; the deep membrane filtration device is loaded with an ultrafiltration membrane, the ultrafiltration membrane is a ceramic nanofiltration membrane, the membrane filtration temperature is 180°C, the inlet pressure of the ultrafiltration membrane is 10.MPa, the outlet pressure is 0.8MPa, the pore size of the ultrafiltration membrane is 30nm, a hydrophobic layer is attached to the surface of the ultrafiltration membrane, and multi-stage ultrafiltration membranes are connected in series for treatment.
  • the 360-515°C fraction oil after vacuum distillation is mixed with the clear liquid after membrane filtration and enters the adsorption desiliconization tank for adsorption desiliconization.
  • the adsorption desiliconization temperature is 230°C.
  • the oil after adsorption desiliconization enters the hydrogenation raw material buffer tank.
  • the thiourea-based chelating resin with large pores and active magnesium oxide on the surface is used as an adsorbent.
  • the loading concentration of active magnesium oxide is 0.4wt.%, and the pore size of the thiourea-based chelating resin is 12nm.
  • the oil in the hydrogenation raw material buffer tank enters the three-stage hydrogenation reactor, undergoes hydrogenation refining reaction, isomerization decondensation reaction and supplementary refining reaction, and then is distilled to obtain solvent oil fraction, industrial white oil and high-quality base oil that meets API Class II + standards.
  • the temperature of the hydrofining reaction is 380°C, the space velocity is 0.8h -1 , the hydrogen partial pressure is 15.0MPa, the hydrogen-oil ratio is 800, and the catalyst uses Al 2 O 3 as the carrier and MoO 3 and NiO as the active substances; the loading amount of MoO 3 is 20wt.%, and the loading amount of NiO is 3wt.%.
  • the temperature of the isomerization decondensation reaction is 330°C
  • the space velocity is 1.4h -1
  • the hydrogen partial pressure is 15.0MPa
  • the hydrogen-oil ratio is 800
  • a catalyst with ZSM-5 molecular sieve as carrier and Pt and Pd as active substances is used, wherein the loading amount of Pt is 0.5wt.%, and the loading amount of Pd is 0.5wt.%.
  • the temperature of the supplementary refining reaction is 350°C
  • the space velocity is 0.6h -1
  • the hydrogen partial pressure is 12.0MPa
  • the hydrogen -oil ratio is 800
  • the catalyst is supported by Al2O3 and active materials are WO3 , MoO3 and NiO, wherein the loading amount of WO3 is 30wt.%, the loading amount of MoO3 is 20wt.%, and the loading amount of NiO is 0.5wt.%.
  • the present invention not only solves a method for continuously producing base oil from mineral oil containing chlorine silicon waste, but also can improve the yield of base oil, the yield of heavy oil can reach more than 88%, the yield of total oil products can reach more than 92%, and the overall process total recovery rate can reach more than 98%; solvent oil and high-quality base oil products and industrial white oil that meet the API (American Petroleum Institute) standard Class II+ or above base oil specifications can be obtained.
  • API American Petroleum Institute
  • the system for continuously producing base oil from chlorinated silicon-containing waste mineral oil of the present invention comprises a waste mineral oil storage tank 1, a heat settling device 2, a flash evaporation device 3, a heavy oil dechlorination reactor 13, a demetallization reactor 11, a vacuum distillation device 10, an adsorption desiliconization tank 18, a hydrogenation raw material buffer tank 17, a hydrogenation reactor 16, a distillation tower 15 and a product tank 22 which are connected in sequence;
  • the bottom of the vacuum distillation device 10 is also connected to the adsorption desiliconization tank 18 through the residual oil intermediate storage tank 9 and the deep membrane filtration device 19;
  • the flash device 3 is also connected to the oil-water separation tank 4, the light oil dechlorination reactor 7, and the light oil intermediate storage tank 8 in sequence, and the light oil intermediate storage tank 8 is also connected to the residual oil intermediate storage tank 9;
  • the heat settling device 2 is also connected to the sludge recovery tank 21, and the sludge recovery tank 21 is further connected to the flash device 3;
  • the top of the vacuum distillation device 10 is also connected to the light oil dechlorination reactor 7;
  • the pipeline between the oil-water separation tank 4 and the light oil dechlorination reactor 7 is connected to the light oil dechlorination agent storage tank 6, the pipeline between the flash device 3 and the heavy oil dechlorination reactor 13 is connected to the heavy oil dechlorination agent storage tank 14, and the pipeline between the heavy oil dechlorination reactor 13 and the demetallization reactor 11 is connected to the demetallization agent storage tank 12; the oil-water separation tank 4 is also connected to the wastewater tank 5, and the deep membrane filtration device 19 is also connected to the incinerator 20.

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Abstract

A method and system for continuously producing base oil from waste mineral oil containing chlorine and silicon. Waste mineral oil is introduced into a thermal precipitation device (2) for thermal precipitation, the waste mineral oil subjected to thermal precipitation is introduced into a flash evaporation device (3), and the resulting light component oil and heavy component oil are subjected to a dechlorination reaction respectively; and after the dechlorination reaction, the heavy component oil is subjected to demetallization and distillation under reduced pressure, and then introduced into an adsorption desiliconization tank (18) for adsorption desiliconization, and the desiliconized oil product is subjected to a hydrogenation reaction and rectification to obtain solvent oil and high-quality base oil and industrial white oil with specifications meeting the standards for base oil of class II and above developed by American Petroleum Institute (API). By means of the method, the heavy oil yield can reach 88% or more, the total oil product yield can reach 92% or more, and the total recovery rate of the whole process can reach 98% or more. Moreover, the problems of device coking, corrosion, blockage, hydrogenation catalyst poisoning, etc., during the regeneration process of waste mineral oil containing chlorine and silicon can be effectively solved.

Description

含氯硅的废矿物油连续生产基础油的方法及系统Method and system for continuously producing base oil from waste mineral oil containing chlorine and silicon 技术领域Technical Field
本发明涉及废矿物油综合利用技术领域，具体涉及一种含氯硅的废矿物油连续生产基础油的方法及系统。The invention relates to the technical field of comprehensive utilization of waste mineral oil, and in particular to a method and system for continuously producing base oil from chlorinated silicon-containing waste mineral oil.
背景技术Background technique
废矿物油在回收市场属于高价值的“城市矿产资源”，国内废矿物油回收个人和分类企业未严格遵守废油回收标准的要求，缺少明确的分类意识，导致回收的废润滑油成分复杂，不同的废矿物油互相掺混，导致废矿物油中的氯和硅含量较高。含氯硅的废矿物油在市场中占比越来越大，给企业处置再利用过程造成诸多困难。Waste mineral oil is a high-value "urban mineral resource" in the recycling market. Domestic waste mineral oil recycling individuals and classification companies have not strictly followed the requirements of waste oil recycling standards and lack a clear classification awareness, resulting in a complex composition of recycled waste lubricating oils. Different waste mineral oils are mixed with each other, resulting in high chlorine and silicon content in waste mineral oils. Chlorine-silicon-containing waste mineral oils account for an increasing proportion of the market, causing many difficulties for companies in the disposal and reuse process.
废矿物油中的含氯化合物会引起蒸馏装置、加氢装置腐蚀，有机氯的存在还会导致加氢催化剂中毒失活。废矿物油中硅元素对后续的加氢精制处理增加难度，硅会沉积在加氢催化剂的表面，堵塞催化剂的孔道，引起催化剂活性下降；且经过长时间工艺运行，硅穿透加氢催化剂床层后，将导致催化剂的迅速中毒永久失活。Chlorine compounds in waste mineral oil can cause corrosion in distillation units and hydrogenation units, and the presence of organic chlorine can also cause poisoning and deactivation of hydrogenation catalysts. Silicon in waste mineral oil increases the difficulty of subsequent hydrogenation refining treatment. Silicon will deposit on the surface of the hydrogenation catalyst, blocking the pores of the catalyst and causing the catalyst activity to decrease. After a long period of process operation, silicon will penetrate the hydrogenation catalyst bed, causing rapid poisoning and permanent deactivation of the catalyst.
目前大多数企业处理废矿物油采用蒸馏-白土工艺、蒸馏-溶剂精制工艺等现有技术，少部分企业采用“溶剂萃取+加氢”或“二段加氢”、“丙烷萃取+加氢”的工艺。At present, most companies use existing technologies such as distillation-bleaching clay process and distillation-solvent refining process to treat waste mineral oil. A small number of companies use "solvent extraction + hydrogenation" or "two-stage hydrogenation" and "propane extraction + hydrogenation" processes.
中国专利CN105907452A公开一种通过热处理使废润滑油再生的组合工艺方法，包括以下步骤：热处理：废润滑油原料进入热处理反应器，进行浅度热裂化反应，热处理反应器底部物料进入油剂混合单元；油剂混合：与120#溶剂油混合；离心；汽提；膜分离；常压分馏：塔顶回收120#溶剂油，测线得到<300℃馏分，可作为船用柴油产品，塔底得到润滑油粗油，进入减压分馏塔；减压分馏：塔测线和塔底共切割成4个馏分，分别进入白土混合器进行白土精制，分别得到减一精制油、减二精制油、减三精制油和减底精制油4个润滑油产品。Chinese patent CN105907452A discloses a combined process method for regenerating waste lubricating oil by heat treatment, comprising the following steps: heat treatment: waste lubricating oil raw material enters a heat treatment reactor for shallow thermal cracking reaction, and the material at the bottom of the heat treatment reactor enters an oil agent mixing unit; oil agent mixing: mixing with 120# solvent oil; centrifugation; steam stripping; membrane separation; atmospheric pressure fractionation: 120# solvent oil is recovered from the top of the tower, and a fraction <300°C is obtained from the line, which can be used as a marine diesel product, and crude lubricating oil is obtained from the bottom of the tower and enters a vacuum distillation tower; vacuum distillation: the tower line and the bottom of the tower are cut into 4 fractions, which are respectively entered into a clay mixer for clay refining to obtain 4 lubricating oil products, namely, refined oil minus one, refined oil minus two, refined oil minus three and refined oil minus bottom.
中国专利CN109735391A公开一种提高溶剂精制再生润滑油基础油收率的方法，其步骤包括首先把经NMP精制后的废润滑油抽出液的温度降至25-30℃，静置5-15min，分离受温度影响而析出的油和溶剂混合物部分，得到的洗出液经脱溶剂塔制出再生基础油产品。通过在吸附剂中加入NMP溶剂，其对废润滑油的吸附性能强于吸附剂，可有效夺取吸附剂中吸附的油类，进一步提高再生基础油的产率，且利用低温下非理想组分与理想组分在NMP溶剂中的溶解度不同，将非理想组分从NMP中析出，进一步提高再生基础油的纯度及回收率。Chinese patent CN109735391A discloses a method for improving the yield of solvent-refined regenerated lubricating oil base oil, the steps of which include first reducing the temperature of the waste lubricating oil extract after NMP refining to 25-30°C, standing for 5-15 minutes, separating the oil and solvent mixture parts precipitated by the temperature, and passing the obtained eluate through a desolventizing tower to produce a regenerated base oil product. By adding NMP solvent to the adsorbent, its adsorption performance for waste lubricating oil is stronger than that of the adsorbent, and the oil adsorbed in the adsorbent can be effectively captured, further improving the yield of the regenerated base oil, and utilizing the different solubility of non-ideal components and ideal components in NMP solvent at low temperatures, the non-ideal components are precipitated from NMP, further improving the purity and recovery rate of the regenerated base oil.
中国专利CN104531328A公开一种全加氢型废润滑油加氢再生工艺，包括以下步骤：将得到的废旧润滑油通过萃取和反萃取操作，除去废旧润滑油中的杂质和水分；将得到的润滑油与新氢加入到加热炉中加热后加入到加氢反应器中；将经过加氢反应后的物料通过萃取分 离得到高分子化合物和低分子化合物；将得到的高分子化合物通过脱硫罐脱硫后作为原料使用；将得到的低分子化合物通过分馏塔进行分馏，分别得到白油料和润滑油基础油。该专利工艺简单，使用方便，能有效回收利用废旧润滑油。Chinese patent CN104531328A discloses a fully hydrogenated waste lubricating oil hydrogenation regeneration process, which includes the following steps: extracting and stripping the waste lubricating oil to remove impurities and moisture in the waste lubricating oil; adding the obtained lubricating oil and new hydrogen into a heating furnace for heating and then adding them into a hydrogenation reactor; extracting and separating the materials after hydrogenation reaction to obtain high molecular weight compounds and low molecular weight compounds; desulfurizing the obtained high molecular weight compounds in a desulfurization tank and using them as raw materials; fractionating the obtained low molecular weight compounds through a fractionation tower to obtain white oil and lubricating oil base oil respectively. The patented process is simple, easy to use, and can effectively recycle waste lubricating oil.
中国专利CN110577844A公开一种废润滑油全加氢再生工艺及加氢催化剂的制备方法，其步骤包括废润滑油预处理、加氢脱金属、加氢除杂原子和加氢改质，并且提供用于上述再生工艺的配套加氢催化剂。该再生工艺产品收率高，显著提高再生油的质量，再生后的润滑油产品质量能够达到润滑油基础油的标准要求。Chinese patent CN110577844A discloses a waste lubricating oil full hydrogenation regeneration process and a preparation method of a hydrogenation catalyst, the steps of which include waste lubricating oil pretreatment, hydrogenation demetallization, hydrogenation removal of heteroatoms and hydrogenation modification, and provides a matching hydrogenation catalyst for the above regeneration process. The regeneration process has a high product yield and significantly improves the quality of the regenerated oil. The quality of the regenerated lubricating oil product can meet the standard requirements of lubricating oil base oil.
国际专利GR3030648T3和国际专利EP3098290A1分别公开了一种对废油进行再精炼的方法和一种再生废油的方法。International patent GR3030648T3 and international patent EP3098290A1 disclose a method for re-refining waste oil and a method for regenerating waste oil, respectively.
上述专利都只是对废矿物油进行简单的预处理，未对针性的对废矿物油中的氯硅进行特殊处理，仍未从根本上解决含氯硅的废矿物油再生高端基础油、含氯硅的废矿物油对设备腐蚀和结焦沉积等问题。另外，上述专利无法对含氯硅的废矿物油进行长周期连续处理，装置运转1-3个月的时间需要进行停工检修，甚至半个月就需要检修一次，显著增加了废润滑油的再生难度。The above patents only perform simple pretreatment on waste mineral oil, and do not specifically treat the chlorine and silicon in the waste mineral oil. They still do not fundamentally solve the problems of regenerating high-end base oil from waste mineral oil containing chlorine and silicon, and equipment corrosion and coking deposition caused by waste mineral oil containing chlorine and silicon. In addition, the above patents cannot continuously treat waste mineral oil containing chlorine and silicon for a long period of time. The equipment needs to be shut down for maintenance after running for 1-3 months, and even needs maintenance once every half a month, which significantly increases the difficulty of regenerating waste lubricating oil.
发明内容Summary of the invention
本发明的目的是提供一种含氯硅的废矿物油连续生产基础油的方法，能够有效解决含氯硅废矿物油再生过程中装置结焦、腐蚀、堵塞和加氢催化剂中毒等问题，大大减少了危废的二次产生，降低了生产和检修成本，同时可以延长废矿物油再生装置的运转周期，实现连续再生；本发明同时提供一种含氯硅的废矿物油连续生产基础油的系统。The purpose of the present invention is to provide a method for continuously producing base oil from waste mineral oil containing chlorine and silicon, which can effectively solve the problems of coking, corrosion, clogging and hydrogenation catalyst poisoning of the device during the regeneration process of the waste mineral oil containing chlorine and silicon, greatly reduce the secondary generation of hazardous waste, reduce production and maintenance costs, and at the same time extend the operation cycle of the waste mineral oil regeneration device to achieve continuous regeneration; the present invention also provides a system for continuously producing base oil from waste mineral oil containing chlorine and silicon.
本发明解决其技术问题所采取的技术方案是：The technical solution adopted by the present invention to solve the technical problem is:
所述的含氯硅的废矿物油连续生产基础油的方法，包括以下步骤：The method for continuously producing base oil from chlorinated silicon-containing waste mineral oil comprises the following steps:
(1)废矿物油进入热沉降装置中进行热沉降，热沉降后的废矿物油进入闪蒸装置进行闪蒸，得到轻组分油和重组分油；(1) The waste mineral oil enters a heat settling device for heat settling, and the waste mineral oil after heat settling enters a flash evaporation device for flash evaporation to obtain light component oil and heavy component oil;
(2)重组分油与重油脱氯剂进入重油脱氯反应器进行重油脱氯反应，之后与脱金属剂进入脱金属反应器进行脱金属反应，再经减压蒸馏，得到馏分油、轻馏分和渣油；(2) the heavy oil fraction and the heavy oil dechlorination agent enter the heavy oil dechlorination reactor for heavy oil dechlorination reaction, and then enter the demetallization reactor with the demetallization agent for demetallization reaction, and then undergo vacuum distillation to obtain distillate oil, light fraction and residual oil;
(3)轻组分油经油水分离后，与轻油脱氯剂、步骤(2)的轻馏分进入轻油脱氯反应器进行轻油脱氯反应，得到轻油；(3) After the light component oil is separated from the water, it enters the light oil dechlorination reactor with the light oil dechlorination agent and the light fraction of step (2) to carry out a light oil dechlorination reaction to obtain light oil;
(4)步骤(3)的轻油与步骤(2)渣油混合后进行膜过滤，得到的清液与步骤(2)的馏分油一起进入吸附脱硅罐进行吸附脱硅反应，经加氢处理后，精馏得到溶剂油、工业白油和基础油。(4) The light oil from step (3) is mixed with the residual oil from step (2) and then filtered through a membrane. The resulting clear liquid and the distillate oil from step (2) are sent to an adsorption desiliconization tank for adsorption desiliconization reaction. After hydrogenation treatment, solvent oil, industrial white oil and base oil are obtained by distillation.
其中：in:
步骤(2)中，重油脱氯反应的温度为200-350℃，压力为0.2-4MPa，停留时间为15-60min，重油脱氯剂与重组分油的质量比为0.1-2:100。In step (2), the temperature of the heavy oil dechlorination reaction is 200-350° C., the pressure is 0.2-4 MPa, the residence time is 15-60 min, and the mass ratio of the heavy oil dechlorination agent to the heavy oil fraction is 0.1-2:100.
所述的重油脱氯剂由季膦盐、醇胺、离子液体和轻质白油复配得到，其中季膦盐、醇胺、离子液体和轻质白油的质量组成配比为10-30wt.％:5-15wt.％:5-10wt.％:45-80wt.％；The heavy oil dechlorination agent is prepared by compounding quaternary phosphonium salt, alcohol amine, ionic liquid and light white oil, wherein the mass composition ratio of quaternary phosphonium salt, alcohol amine, ionic liquid and light white oil is 10-30wt.％: 5-15wt.％: 5-10wt.％: 45-80wt.％;
所述的季膦盐为烯丙基三苯基氢氧化膦、十六烷基三苯基醋酸膦或乙基三苯基醋酸膦；所述的醇胺为正辛基二乙醇胺、1-羟基丙醇胺或磷酯酰乙醇胺；所述的离子液体为双十烷基二甲基氢氧化铵或十六烷基三甲基氢氧化铵；所述的轻质白油为轻质白油W1-130、轻质白油W1-140或轻质白油W2-140。The quaternary phosphonium salt is allyl triphenylphosphine hydroxide, hexadecyl triphenylphosphine acetate or ethyl triphenylphosphine acetate; the alcohol amine is n-octyl diethanolamine, 1-hydroxypropanolamine or phosphatidylethanolamine; the ionic liquid is didecyl dimethyl ammonium hydroxide or hexadecyl trimethyl ammonium hydroxide; the light white oil is light white oil W1-130, light white oil W1-140 or light white oil W2-140.
重组分油中氯分布在不同温度的馏分中，重组分油中的氯化合物在醇胺、离子液体和轻质白油的作用下反应脱氯，采用的季膦盐能够起到乳化分散的作用，增加了脱氯的效果。The chlorine in the heavy oil is distributed in fractions at different temperatures. The chlorine compounds in the heavy oil are dechlorinated by reaction under the action of alcohol amine, ionic liquid and light white oil. The quaternary phosphonium salt used can play the role of emulsification and dispersion, thereby increasing the dechlorination effect.
步骤(2)中，脱金属反应温度为250-380℃，停留时间为10-60min，反应压力为0.2-4MPa；脱金属剂与重组分油的质量比为0.5-2:100。In step (2), the demetallization reaction temperature is 250-380° C., the residence time is 10-60 min, the reaction pressure is 0.2-4 MPa, and the mass ratio of the demetallization agent to the recombinant oil is 0.5-2:100.
所述的脱金属剂由磷酸组胺类物质或磷酸酯类物质、醚类复配而成；磷酸组胺类物质或磷酸酯类物质、醚类的质量组成配比为30-50wt.％:50-70wt.％；The demetallizing agent is prepared by compounding histamine phosphate substances or phosphate ester substances and ethers; the mass composition ratio of histamine phosphate substances or phosphate ester substances and ethers is 30-50wt.%:50-70wt.%;
所述的磷酸组胺类物质为苯基三丙基磷酸二氢铵或磷酯酰乙醇胺；所述的磷酸酯类物质为月桂酸烷醇酰胺磷酸酯、正十二醇聚氧乙烯醚磷酸酯或十八烷基磷酸酯；所述的醚类为妥尔油酸聚氧乙烯聚氧丙烯醚、壬基酚聚氧乙烯聚氧丙烯醚或丙三醇聚氧乙烯聚氧丙烯醚。The histamine phosphate substance is phenyl tripropyl ammonium dihydrogen phosphate or phosphatidylethanolamine; the phosphate ester substance is lauric acid alkanolamide phosphate, n-dodecyl alcohol polyoxyethylene ether phosphate or octadecyl phosphate; the ether substance is tall oil acid polyoxyethylene polyoxypropylene ether, nonylphenol polyoxyethylene polyoxypropylene ether or glycerol polyoxyethylene polyoxypropylene ether.
在醚类物质的作用下，采用磷酸组胺类物质或磷酸酯类物质与金属进行反应，能够大大减少胶质聚集。Under the action of ether substances, the use of phosphoric acid histamine substances or phosphate substances to react with metals can greatly reduce colloid aggregation.
步骤(3)中，轻油脱氯反应的温度为120-260℃，压力为2-6MPa，停留时间为15-60min；轻油脱氯剂与轻组分的质量比为0.1-2:100。In step (3), the temperature of the light oil dechlorination reaction is 120-260° C., the pressure is 2-6 MPa, and the residence time is 15-60 min; the mass ratio of the light oil dechlorination agent to the light component is 0.1-2:100.
所述的轻油脱氯剂由醇铜类或醇胺铜类物质、轻质油与醇类复配得到，其中醇铜类或醇胺铜类物质、轻质油与醇类的质量组成配比为5-20wt.％:60-90wt.％:5-20wt.％；The light oil dechlorination agent is obtained by compounding copper alkoxide or copper alcoholamine substances, light oil and alcohols, wherein the mass composition ratio of copper alkoxide or copper alcoholamine substances, light oil and alcohols is 5-20wt.％:60-90wt.％:5-20wt.％;
所述的醇铜类或醇胺铜类物质为乙醇胺铜、二甲醇铜或乙醇铜；所述的轻质油为200#溶剂油或柠檬烯；所述的醇类为乙醇、丙二醇、聚乙二醇或二甘醇。The alcohol copper or alcohol amine copper substance is ethanolamine copper, dimethanol copper or ethanol copper; the light oil is 200# solvent oil or limonene; the alcohol is ethanol, propylene glycol, polyethylene glycol or diethylene glycol.
轻组分油中氯含量较多，但轻油中杂质较少，轻油脱氯剂采用醇胺铜类物质与其反应，同时在轻油和醇类的互溶环境中增加了醇胺铜类物质的活性，能够脱除大部分有机氯。The light component oil contains more chlorine, but less impurities. The light oil dechlorination agent uses alcohol amine copper substances to react with it. At the same time, the activity of alcohol amine copper substances is increased in the mutual dissolution environment of light oil and alcohols, which can remove most of the organic chlorine.
步骤(4)中，渣油与轻油的质量比为0.5-1:1；采用陶瓷纳滤膜或碳化硅管式膜作为超滤膜进行膜过滤，膜过滤的温度为120-200℃，超滤膜的进口压力为0.4-1.0MPa，出口压力为0.2-0.8MPa，超滤膜的孔径为10-50nm。In step (4), the mass ratio of residual oil to light oil is 0.5-1:1; a ceramic nanofiltration membrane or a silicon carbide tubular membrane is used as an ultrafiltration membrane for membrane filtration, the membrane filtration temperature is 120-200°C, the inlet pressure of the ultrafiltration membrane is 0.4-1.0MPa, the outlet pressure is 0.2-0.8MPa, and the pore size of the ultrafiltration membrane is 10-50nm.
步骤(4)中，吸附脱硅反应时的吸附剂为表面附载活性氧化镁的螯合树脂，螯合树脂与 氧化镁结合，能够提高硅的聚集吸附效果；所述的螯合树脂为亚胺二乙酸基螯合树脂、亚氨基二乙醛肟螯合树脂或硫脲基螯合树脂，螯合树脂的孔径为5-12nm，活性氧化镁的附载浓度为0.05-0.5wt.％；吸附脱硅反应的温度为80-250℃。In step (4), the adsorbent during the adsorption desiliconization reaction is a chelating resin with active magnesium oxide attached to the surface. The chelating resin is combined with magnesium oxide to improve the aggregation and adsorption effect of silicon; the chelating resin is an iminodiacetic acid chelating resin, an iminodiacetaldehyde oxime chelating resin or a thiourea chelating resin, the pore size of the chelating resin is 5-12nm, and the loading concentration of active magnesium oxide is 0.05-0.5wt.%; the temperature of the adsorption desiliconization reaction is 80-250°C.
本发明所述的含氯硅的废矿物油连续生产基础油的方法具体包括以下步骤：The method for continuously producing base oil from chlorinated silicon-containing waste mineral oil of the present invention specifically comprises the following steps:
(1)热沉降(1) Heat sinking
废矿物油自罐区经泵进入热沉降装置中进行热沉降，热沉降温度为60-120℃，热沉降时间为2-6h。热沉降可以初步除去废矿物油中的固体颗粒、油泥、水等杂质。经过热沉降后的固体颗粒、油泥、水等杂质进入油泥回收罐；初步除杂后的废矿物油进入后续闪蒸装置。Waste mineral oil is pumped from the tank area into the heat settling device for heat settling. The heat settling temperature is 60-120℃ and the heat settling time is 2-6h. Heat settling can preliminarily remove solid particles, sludge, water and other impurities in the waste mineral oil. After heat settling, the solid particles, sludge, water and other impurities enter the sludge recovery tank; the waste mineral oil after preliminary impurity removal enters the subsequent flash evaporation device.
(2)油泥回收(2) Oil sludge recovery
经过热沉降脱除后的杂质中还含有一定量可以回收的废矿物油，通过油泥回收罐进一步提高废矿物油的利用率，回收后的废矿物油送至后续闪蒸装置，彻底无法利用的杂质和水则送至界外进行处理。The impurities removed by thermal sedimentation still contain a certain amount of waste mineral oil that can be recovered. The utilization rate of the waste mineral oil is further improved through the sludge recovery tank. The recovered waste mineral oil is sent to the subsequent flash evaporation device, and the impurities and water that cannot be used at all are sent outside the boundary for treatment.
(3)闪蒸(3) Flash evaporation
由热沉降及油泥回收得到的废矿物油进入闪蒸装置，彻底脱除360℃以下轻组分油和剩余的微量水，闪蒸装置的温度为150-280℃，压力为0.03-1.3KPa。闪蒸装置底部物料进入重油脱氯反应器，顶部轻组分油和水进入油水分离罐，轻组分油和水在油水分离罐中进行分离，分离后的水排入废水罐，轻组分油进入轻油脱氯反应器。The waste mineral oil obtained by thermal sedimentation and sludge recovery enters the flash evaporation device to completely remove the light component oil below 360°C and the remaining trace water. The temperature of the flash evaporation device is 150-280°C and the pressure is 0.03-1.3KPa. The material at the bottom of the flash evaporation device enters the heavy oil dechlorination reactor, and the light component oil and water at the top enter the oil-water separation tank. The light component oil and water are separated in the oil-water separation tank, and the separated water is discharged into the wastewater tank, and the light component oil enters the light oil dechlorination reactor.
(4)重组分油脱氯(4) Dechlorination of heavy oil
闪蒸装置底部出料的重组分油与重油脱氯剂混合后，进入重油脱氯反应器进行脱氯反应，重油脱氯反应的温度为200-350℃，压力为0.2-4MPa，停留时间为15-60min，重油脱氯剂与重组分油的质量比为0.1-2:100，脱氯后的重组分油进入后续的脱金属反应器。The heavy oil discharged from the bottom of the flash device is mixed with the heavy oil dechlorinating agent and then enters the heavy oil dechlorination reactor for dechlorination reaction. The temperature of the heavy oil dechlorination reaction is 200-350°C, the pressure is 0.2-4MPa, the residence time is 15-60min, the mass ratio of the heavy oil dechlorinating agent to the heavy oil is 0.1-2:100, and the dechlorinated heavy oil enters the subsequent demetallization reactor.
(5)重组分油脱金属(5) Recombinant oil demetallization
脱氯后的重组分油与脱金属剂混合后进入脱金属反应器进行脱金属反应，脱金属反应温度为250-380℃，反应时间为10-60min，反应压力为0.2-4MPa，脱金属剂与重组分油的质量配比为0.5-2:100，脱金属后的重组分油进入后续减压蒸馏装置。The dechlorinated heavy oil is mixed with a demetallizing agent and enters a demetallizing reactor for a demetallizing reaction. The demetallizing reaction temperature is 250-380°C, the reaction time is 10-60min, the reaction pressure is 0.2-4MPa, and the mass ratio of the demetallizing agent to the heavy oil is 0.5-2:100. The demetallized heavy oil enters a subsequent vacuum distillation device.
(6)减压蒸馏(6) Vacuum distillation
经过脱金属反应处理后的重组分油进入减压蒸馏装置中进行深度蒸馏，提高加氢进料前原料的品质；减压蒸馏时的真空度为0.3-1.3KPa，减压切割出360-515℃的馏分油进入吸附脱硅单元；减压蒸馏装置塔底渣油(＞515℃的馏分)为高粘度润滑油残余底油，进入渣油中间储罐备用；塔顶冷凝的轻质油品(＜360℃的馏分)即轻馏分，则与闪蒸装置顶部脱出的经油水分离后的轻组分油汇合，进入轻油脱氯反应器进行脱氯。The heavy oil after demetallization reaction treatment enters the vacuum distillation device for deep distillation to improve the quality of the raw materials before hydrogenation feeding; the vacuum degree during vacuum distillation is 0.3-1.3KPa, and the distillate oil of 360-515℃ is cut out under reduced pressure and enters the adsorption desiliconization unit; the bottom residue oil of the vacuum distillation device (fraction>515℃) is the residual bottom oil of high-viscosity lubricating oil, which enters the intermediate residue oil storage tank for standby; the light oil product (fraction<360℃) condensed at the top of the tower, namely the light fraction, is combined with the light component oil after oil-water separation from the top of the flash evaporation device, and enters the light oil dechlorination reactor for dechlorination.
(7)轻组分油脱氯(7) Dechlorination of light component oil
经油水分离罐分离后的轻组分油与轻油脱氯剂混合后，与减压蒸馏装置顶部冷凝的轻质油品(＜360℃的馏分)汇合，在轻油脱氯反应器中进行脱氯反应，轻油脱氯反应的温度为120-260℃，压力为2-6MPa，停留时间为15-60min，轻油脱氯剂与轻组分油的质量比为0.1-2:100，脱氯后的轻油作为萃取稀释油储存在轻油中间储罐中。The light component oil separated by the oil-water separation tank is mixed with the light oil dechlorinating agent, and then merged with the light oil product (fraction of <360°C) condensed at the top of the vacuum distillation device, and dechlorination reaction is carried out in the light oil dechlorination reactor. The temperature of the light oil dechlorination reaction is 120-260°C, the pressure is 2-6MPa, the residence time is 15-60min, the mass ratio of the light oil dechlorinating agent to the light component oil is 0.1-2:100, and the dechlorinated light oil is stored in the light oil intermediate storage tank as extraction dilution oil.
(8)膜过滤(8) Membrane filtration
渣油中间储罐中的渣油与轻油中间储罐的轻油进行比例混合，进入深度膜过滤装置，得到膜过滤后的清液，膜过滤后的清液进入吸附脱硅罐，剩余尾渣进入焚烧炉焚烧，提供热源。轻油作为溶剂能够溶解渣油中大部分的高粘度饱和基础油烃类，但不能溶解胶质、沥青质等杂质，将高粘度基础油溶解出来的同时将固体杂质沉降下来。The residual oil in the residual oil intermediate storage tank is mixed with the light oil in the light oil intermediate storage tank in proportion, and enters the deep membrane filtration device to obtain the clear liquid after membrane filtration. The clear liquid after membrane filtration enters the adsorption desiliconization tank, and the remaining tailings enter the incinerator for incineration to provide heat source. Light oil as a solvent can dissolve most of the high-viscosity saturated base oil hydrocarbons in the residual oil, but cannot dissolve impurities such as colloids and asphaltene. It dissolves the high-viscosity base oil and settles the solid impurities at the same time.
渣油与轻油的质量比为0.5-1:1；深度膜过滤装置中装载有超滤膜，所述的超滤膜为陶瓷纳滤膜或碳化硅管式膜，膜过滤的温度为120-200℃，超滤膜的进出口压力为0.2-1MPa，超滤膜的孔径为10-50nm，所述的超滤膜表面附着一层疏水层，且陶瓷纳滤膜上设置反冲洗和压力恒定回流系统。优选地，可采用多级超滤膜串联进行处理。The mass ratio of residual oil to light oil is 0.5-1:1; the deep membrane filtration device is loaded with an ultrafiltration membrane, the ultrafiltration membrane is a ceramic nanofiltration membrane or a silicon carbide tubular membrane, the membrane filtration temperature is 120-200°C, the inlet and outlet pressure of the ultrafiltration membrane is 0.2-1MPa, the pore size of the ultrafiltration membrane is 10-50nm, a hydrophobic layer is attached to the surface of the ultrafiltration membrane, and a backwashing and constant pressure reflux system is set on the ceramic nanofiltration membrane. Preferably, multiple ultrafiltration membranes can be used in series for treatment.
(9)吸附脱硅(9) Adsorption desiliconization
经过减压蒸馏的360-515℃馏分油与膜过滤后的清液混合，进入吸附脱硅罐中进行吸附脱硅，吸附脱硅温度为80-250℃，吸附脱硅后的油品进入加氢原料缓冲罐。罐中散堆大孔径的表面附载活性氧化镁的螯合树脂作为吸附剂，该树脂具备优秀的吸附能力，从而吸附脱除含硅杂质；所述的螯合树脂为亚胺二乙酸基螯合树脂、亚氨基二乙醛肟螯合树脂或硫脲基螯合树脂，活性氧化镁的附载浓度为0.05-0.5wt.％。The 360-515℃ fraction oil after vacuum distillation is mixed with the clear liquid after membrane filtration and enters the adsorption desiliconization tank for adsorption desiliconization. The adsorption desiliconization temperature is 80-250℃. The oil after adsorption desiliconization enters the hydrogenation raw material buffer tank. The chelate resin with large pores and active magnesium oxide on the surface of the random pile in the tank is used as an adsorbent. The resin has excellent adsorption capacity, thereby adsorbing and removing silicon-containing impurities; the chelate resin is an iminodiacetic acid chelate resin, an iminodiacetaldehyde oxime chelate resin or a thiourea chelate resin, and the active magnesium oxide loading concentration is 0.05-0.5wt.%.
(10)加氢处理+精馏(10) Hydrotreatment + distillation
加氢原料缓冲罐中的油品进入三段式加氢反应器，经加氢精制反应、异构降凝反应和补充精制反应后、精馏得到溶剂油、工业白油和基础油产品。The oil in the hydrogenation raw material buffer tank enters the three-stage hydrogenation reactor, and after hydrogenation refining reaction, isomerization decondensation reaction and supplementary refining reaction, it is distilled to obtain solvent oil, industrial white oil and base oil products.
加氢精制反应的温度为350-400℃，空速为0.6-1.0h -1，氢分压为12.0-16.0MPa，氢油比为800-1200，采用活性金属为Mo-Ni的催化剂；所述的催化剂以Al 2O 3为载体，以MoO 3、NiO为活性物质，其中MoO 3的负载量为20-30wt.％，NiO的负载量为3-5wt.％。 The temperature of the hydrofining reaction is 350-400°C, the space velocity is 0.6-1.0h -1 , the hydrogen partial pressure is 12.0-16.0MPa, the hydrogen-oil ratio is 800-1200, and the active metal is a Mo-Ni catalyst; the catalyst uses Al 2 O 3 as a carrier, MoO 3 and NiO as active substances, wherein the loading amount of MoO 3 is 20-30wt.%, and the loading amount of NiO is 3-5wt.%.
异构降凝反应的温度为290-380℃，空速为1.2-1.6h -1，氢分压为14.0-16.0MPa，氢油比为500-800，采用活性金属为Pt-Pd的催化剂；所述的催化剂以ZSM-5分子筛为载体，以Pt、Pd为活性物质，其中Pt的负载量为0.5-0.8wt.％，Pd的负载量为0.2-0.5wt.％。 The temperature of the isomerization decondensation reaction is 290-380°C, the space velocity is 1.2-1.6h -1 , the hydrogen partial pressure is 14.0-16.0MPa, the hydrogen-oil ratio is 500-800, and the catalyst with active metal as Pt-Pd is used; the catalyst uses ZSM-5 molecular sieve as carrier and Pt and Pd as active substances, wherein the loading amount of Pt is 0.5-0.8wt.%, and the loading amount of Pd is 0.2-0.5wt.%.
补充精制反应的温度为240-360℃，空速为0.4-0.8h -1，氢分压为12.0-14.0MPa，氢油比为500-800，采用活性金属为W-Mo-Ni的催化剂；所述的催化剂以Al 2O 3为载体，以WO 3、 MoO 3和NiO为活性物质，其中WO 3的负载量为20-30wt.％，MoO 3的负载量为10-20wt.％，NiO的负载量为0.5-2wt.％。 The temperature of the supplementary refining reaction is 240-360°C, the space velocity is 0.4-0.8h -1 , the hydrogen partial pressure is 12.0-14.0MPa, the hydrogen-oil ratio is 500-800, and the catalyst with active metal as W-Mo-Ni is used; the catalyst uses Al 2 O 3 as a carrier, and uses WO 3 , MoO 3 and NiO as active substances, wherein the loading amount of WO 3 is 20-30wt.%, the loading amount of MoO 3 is 10-20wt.%, and the loading amount of NiO is 0.5-2wt.%.
本发明所述的含氯硅的废矿物油连续生产基础油的系统：包括依次相连的废矿物油储罐、热沉降装置、闪蒸装置、重油脱氯反应器、脱金属反应器、减压蒸馏装置、吸附脱硅罐、加氢原料缓冲罐、加氢反应器、精馏塔和产品罐；The system for continuously producing base oil from chlorinated silicon-containing waste mineral oil of the present invention comprises a waste mineral oil storage tank, a heat settling device, a flash evaporation device, a heavy oil dechlorination reactor, a demetallization reactor, a vacuum distillation device, an adsorption desiliconization tank, a hydrogenation raw material buffer tank, a hydrogenation reactor, a distillation tower and a product tank connected in sequence;
所述的减压蒸馏装置底部还通过渣油中间储罐、深度膜过滤装置与吸附脱硅罐连接；所述的闪蒸装置还与油水分离罐、轻油脱氯反应器、轻油中间储罐依次相连，轻油中间储罐还与渣油中间储罐连接；所述的热沉降装置还连接油泥回收罐，油泥回收罐再与闪蒸装置连接；减压蒸馏装置的顶部还连接轻油脱氯反应器；The bottom of the vacuum distillation device is also connected to the adsorption desiliconization tank through the residual oil intermediate storage tank and the deep membrane filtration device; the flash evaporation device is also connected to the oil-water separation tank, the light oil dechlorination reactor, and the light oil intermediate storage tank in sequence, and the light oil intermediate storage tank is also connected to the residual oil intermediate storage tank; the heat settling device is also connected to the sludge recovery tank, and the sludge recovery tank is further connected to the flash evaporation device; the top of the vacuum distillation device is also connected to the light oil dechlorination reactor;
所述的油水分离罐与轻油脱氯反应器之间的管路连接轻油脱氯剂储罐，闪蒸装置与重油脱氯反应器之间的管路连接重油脱氯剂储罐，重油脱氯反应器与脱金属反应器之间的管路连接脱金属剂储罐；油水分离罐还连接废水罐，深度膜过滤装置还连接焚烧炉。The pipeline between the oil-water separation tank and the light oil dechlorination reactor is connected to the light oil dechlorination agent storage tank, the pipeline between the flash evaporation device and the heavy oil dechlorination reactor is connected to the heavy oil dechlorination agent storage tank, and the pipeline between the heavy oil dechlorination reactor and the demetallization reactor is connected to the demetallization agent storage tank; the oil-water separation tank is also connected to the wastewater tank, and the deep membrane filtration device is also connected to the incinerator.
本发明废矿物油进入热沉降储罐中进行热沉降，热沉降后的废矿物油与热沉降后的油泥经回收处理得到的废矿物油一起进入闪蒸装置，彻底脱除360℃以下轻组分油和剩余的微量水，顶部轻组分油脱水后进入轻油脱氯反应器，与轻油脱氯剂混合反应脱氯后进入轻油中间储罐中。闪蒸后得到的重组分油进入重油脱氯反应器，与重油脱氯剂混合反应脱氯，反应后与脱金属剂混合后进入脱金属反应器，经过脱金属后的重组分油进入减压蒸馏装置中进行深度蒸馏，得到减压中间馏分即馏分油。减压蒸馏装置塔底渣油为高粘度润滑油残余底油，进入渣油中间储罐备用。减压蒸馏装置塔顶冷凝的轻质油品则与前序闪蒸装置顶部脱出的经油水分离的轻组分油汇合进入轻油脱氯反应器中进行脱氯反应，脱氯后进入轻油中间储罐。渣油中间储罐与轻油中间储罐的油品进行混合，进入连续化深度膜过滤装置，得到的膜过滤后的清液与减压蒸馏的中间馏分进入吸附脱硅罐中进行吸附脱硅，脱硅后的油品进入加氢原料缓冲罐中储存。加氢原料缓冲罐的油品进入加氢反应器中加氢，之后精馏，得到溶剂油和满足API(美国石油协会)标准的II类+以上基础油规格的高品质的基础油和工业白油。The waste mineral oil of the present invention enters a heat settling tank for heat settling, and the waste mineral oil after heat settling and the waste mineral oil obtained by recycling the oil sludge after heat settling enter a flash evaporation device together, and the light component oil below 360°C and the remaining trace water are completely removed. The top light component oil is dehydrated and enters a light oil dechlorination reactor, and is mixed with a light oil dechlorination agent for dechlorination and enters a light oil intermediate storage tank. The heavy oil obtained after flash evaporation enters a heavy oil dechlorination reactor, and is mixed with a heavy oil dechlorination agent for dechlorination. After the reaction, it is mixed with a demetallization agent and enters a demetallization reactor. The heavy oil after demetallization enters a vacuum distillation device for deep distillation to obtain a vacuum intermediate distillate, i.e., a distillate oil. The residual oil at the bottom of the vacuum distillation device is a high-viscosity lubricating oil residual bottom oil, which enters a residual oil intermediate storage tank for standby. The light oil product condensed at the top of the vacuum distillation device is combined with the light component oil separated from the top of the previous flash evaporation device and enters a light oil dechlorination reactor for dechlorination reaction, and enters a light oil intermediate storage tank after dechlorination. The oil products in the intermediate storage tank of residual oil and the intermediate storage tank of light oil are mixed and enter the continuous deep membrane filtration device. The clear liquid obtained after membrane filtration and the intermediate fraction of vacuum distillation enter the adsorption desiliconization tank for adsorption desiliconization. The oil products after desiliconization enter the hydrogenation raw material buffer tank for storage. The oil products in the hydrogenation raw material buffer tank enter the hydrogenation reactor for hydrogenation, and then distillation to obtain solvent oil and high-quality base oil and industrial white oil that meet the API (American Petroleum Institute) standard Class II + or above base oil specifications.
本发明的有益效果如下：The beneficial effects of the present invention are as follows:
(1)全馏分连续脱氯。本发明热沉降后的废矿物油进入闪蒸装置，彻底脱除360℃以下轻组分油和剩余的微量水，顶部轻组分脱水后的轻组分油进入轻油脱氯反应器，闪蒸后得到的重组分油进入重油脱氯反应器。通过两级脱氯反应器分别对轻组分油和重组分油进行脱氯，对废矿物油的氯进行了针对性的脱除，大大提高了氯的脱除率。(1) Continuous dechlorination of the whole fraction. The waste mineral oil after thermal sedimentation in the present invention enters the flash evaporation device to completely remove the light component oil below 360°C and the remaining trace water. The light component oil after the top light component is dehydrated enters the light oil dechlorination reactor, and the heavy component oil obtained after flash evaporation enters the heavy oil dechlorination reactor. The light component oil and the heavy component oil are dechlorinated respectively by the two-stage dechlorination reactor, and the chlorine in the waste mineral oil is removed in a targeted manner, which greatly improves the chlorine removal rate.
(2)提高基础油收率。本发明创新性将重组分油经脱氯、脱金属、减压蒸馏得到的渣油与轻组分油经脱氯得到的轻油混合，轻油作为溶剂能够溶解渣油中大部分的高粘度饱和基础 油烃类，但不能溶解胶质、沥青质等杂质，将高粘度基础油溶解出来的同时将固体杂质沉降下来。渣油与轻油混合后，采用超滤膜对其连续处理，不引入第三种添加溶剂，实现自给自足，将渣油中的润滑油通过极微超滤膜进一步的提取，解决了同行废矿物油利用企业不能处理后端渣油的困局，极大提高了整体工艺总回收率，油品回收率可达92％以上。重质油收率可达88％以上，远高于行业内70％的平均水平。(2) Improve the base oil yield. The present invention innovatively mixes the residual oil obtained by dechlorination, demetallization and vacuum distillation of the heavy oil with the light oil obtained by dechlorination of the light oil. The light oil as a solvent can dissolve most of the high-viscosity saturated base oil hydrocarbons in the residual oil, but cannot dissolve impurities such as colloids and asphaltene. The high-viscosity base oil is dissolved and the solid impurities are precipitated. After the residual oil and the light oil are mixed, they are continuously treated with an ultrafiltration membrane without introducing a third added solvent, achieving self-sufficiency. The lubricating oil in the residual oil is further extracted through an ultra-micro ultrafiltration membrane, solving the problem that the waste mineral oil utilization enterprises of the same industry cannot process the rear-end residual oil, greatly improving the overall process total recovery rate, and the oil product recovery rate can reach more than 92%. The heavy oil yield can reach more than 88%, which is much higher than the average level of 70% in the industry.
(3)产品高品质。本发明采用深度加氢技术，产品质量好，光稳定性强，得到溶剂油和满足API(美国石油协会)标准的II类+以上基础油规格的高品质的基础油产品和工业白油。(3) High product quality. The present invention adopts deep hydrogenation technology, has good product quality and strong light stability, and obtains solvent oil and high-quality base oil products and industrial white oil that meet the API (American Petroleum Institute) standard Class II+ or above base oil specifications.
(4)工艺连续再生。本发明解决了废矿物油再生过程中装置易结焦、设备腐蚀、管路堵塞、加氢催化剂易中毒失活等问题。通过二级脱氯，脱除了废矿物油中氯化物，减小了氯化物对设备的腐蚀，延长了废矿物油再生装置的运行周期，增加了设备的寿命，降低了废润滑油再生企业的生产和检修成本。(4) Continuous regeneration process. The present invention solves the problems of easy coking of the device, equipment corrosion, pipeline blockage, and easy poisoning and deactivation of the hydrogenation catalyst during the waste mineral oil regeneration process. Through secondary dechlorination, the chloride in the waste mineral oil is removed, the corrosion of the chloride to the equipment is reduced, the operation cycle of the waste mineral oil regeneration device is extended, the life of the equipment is increased, and the production and maintenance costs of the waste lubricating oil regeneration enterprise are reduced.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明的含氯硅的废矿物油连续生产基础油的系统示意图；FIG1 is a schematic diagram of a system for continuously producing base oil from chlorinated silicon-containing waste mineral oil according to the present invention;
其中：1、废矿物油储罐；2、热沉降装置；3、闪蒸装置；4、油水分离罐；5、废水罐；6、轻油脱氯剂储罐；7、轻油脱氯反应器；8、轻油中间储罐；9、渣油中间储罐；10、减压蒸馏装置；11、脱金属反应器；12、脱金属剂储罐；13、重油脱氯反应器；14、重油脱氯剂储罐；15、精馏塔；16、加氢反应器；17、加氢原料缓冲罐；18、吸附脱硅罐；19、深度膜过滤装置；20、焚烧炉；21、油泥回收罐；22、产品罐。Among them: 1. Waste mineral oil storage tank; 2. Heat sedimentation device; 3. Flash device; 4. Oil-water separation tank; 5. Wastewater tank; 6. Light oil dechlorination agent storage tank; 7. Light oil dechlorination reactor; 8. Light oil intermediate storage tank; 9. Residue oil intermediate storage tank; 10. Vacuum distillation device; 11. Demetallization reactor; 12. Demetallization agent storage tank; 13. Heavy oil dechlorination reactor; 14. Heavy oil dechlorination agent storage tank; 15. Distillation tower; 16. Hydrogenation reactor; 17. Hydrogenation raw material buffer tank; 18. Adsorption desiliconization tank; 19. Deep membrane filtration device; 20. Incinerator; 21. Sludge recovery tank; 22. Product tank.
具体实施方式Detailed ways
以下结合实施例对本发明做进一步描述。The present invention is further described below with reference to the embodiments.
实施例1Example 1
(1)热沉降(1) Heat sinking
废矿物油自罐区经泵进入热沉降装置中进行热沉降，热沉降温度为80℃，热沉降时间为4h。经过热沉降后的固体颗粒、油泥、水等杂质进入油泥回收罐；初步除杂后的废矿物油进入后续闪蒸装置。Waste mineral oil is pumped from the tank area into the heat settling device for heat settling. The heat settling temperature is 80℃ and the heat settling time is 4h. After heat settling, solid particles, sludge, water and other impurities enter the sludge recovery tank; the waste mineral oil after preliminary impurity removal enters the subsequent flash evaporation device.
(2)油泥回收(2) Oil sludge recovery
经过热沉降脱除后的杂质中还含有一定量可以回收的废矿物油，通过油泥回收罐进一步提高废矿物油的利用率，回收后的废矿物油送至后续闪蒸装置。The impurities removed by thermal sedimentation still contain a certain amount of waste mineral oil that can be recovered. The utilization rate of the waste mineral oil is further improved through the sludge recovery tank, and the recovered waste mineral oil is sent to the subsequent flash evaporation device.
(3)闪蒸(3) Flash evaporation
由热沉降及油泥回收得到的废矿物油进入闪蒸装置，彻底脱除360℃以下轻组分油和水，闪蒸装置的温度为230℃，压力为1KPa。闪蒸装置底部物料进入重油脱氯反应器，顶部轻组 分油和水进入油水分离罐，轻组分油和水在油水分离罐中进行分离，分离后的水排入废水罐，轻组分油进入轻油脱氯反应器。The waste mineral oil obtained by thermal sedimentation and sludge recovery enters the flash evaporation device to completely remove the light oil and water below 360°C. The temperature of the flash evaporation device is 230°C and the pressure is 1KPa. The material at the bottom of the flash evaporation device enters the heavy oil dechlorination reactor, and the light oil and water at the top enter the oil-water separation tank. The light oil and water are separated in the oil-water separation tank. The separated water is discharged into the wastewater tank, and the light oil enters the light oil dechlorination reactor.
(4)重组分油脱氯(4) Dechlorination of heavy oil
闪蒸装置底部出料的重组分油与重油脱氯剂混合后，进入重油脱氯反应器进行脱氯反应，重油脱氯反应的温度为250℃，压力为0.4MPa，停留时间为60min，重油脱氯剂与重组分油质量配比为2:100，脱氯后的重组分油进入后续的脱金属反应器。The heavy oil discharged from the bottom of the flash device is mixed with the heavy oil dechlorination agent and then enters the heavy oil dechlorination reactor for dechlorination reaction. The temperature of the heavy oil dechlorination reaction is 250°C, the pressure is 0.4MPa, the residence time is 60min, the mass ratio of the heavy oil dechlorination agent to the heavy oil is 2:100, and the dechlorinated heavy oil enters the subsequent demetallization reactor.
所述的重油脱氯剂由以下质量百分比的物质复配得到：烯丙基三苯基氢氧化膦10wt.％、正辛基二乙醇胺15wt.％、双十烷基二甲基氢氧化铵10wt.％、轻质白油W1-130 65wt.％。The heavy oil dechlorination agent is obtained by compounding the following substances in percentage by mass: 10 wt.% of allyl triphenylphosphine hydroxide, 15 wt.% of n-octyl diethanolamine, 10 wt.% of didecyl dimethyl ammonium hydroxide, and 65 wt.% of light white oil W1-130.
(5)重组分油脱金属(5) Recombinant oil demetallization
脱氯后的重组分油与脱金属剂混合后进入脱金属反应器进行脱金属反应，脱金属反应温度为330℃，反应时间为50min，反应压力为1MPa，脱金属剂与重组分油质量配比为0.5:100，脱金属后的重组分油进入后续减压蒸馏装置。The dechlorinated heavy oil is mixed with the demetallizing agent and enters the demetallizing reactor for demetallizing reaction. The demetallizing reaction temperature is 330°C, the reaction time is 50min, the reaction pressure is 1MPa, the mass ratio of the demetallizing agent to the heavy oil is 0.5:100, and the demetallized heavy oil enters the subsequent vacuum distillation device.
所述的脱金属剂由苯基三丙基磷酸二氢铵、妥尔油酸聚氧乙烯聚氧丙烯醚复配得到；其中苯基三丙基磷酸二氢铵、妥尔油酸聚氧乙烯聚氧丙烯醚的质量组成配比为30wt.％:70wt.％。The demetallizing agent is prepared by compounding phenyl tripropyl ammonium dihydrogen phosphate and tall oil acid polyoxyethylene polyoxypropylene ether; wherein the mass composition ratio of phenyl tripropyl ammonium dihydrogen phosphate and tall oil acid polyoxyethylene polyoxypropylene ether is 30wt.%:70wt.%.
(6)减压蒸馏(6) Vacuum distillation
经过脱金属反应处理后的重组分油进入减压蒸馏装置中进行深度蒸馏，提高加氢进料前原料的品质；减压蒸馏时的真空度为0.5KPa，减压切割出360-515℃的馏分油进入吸附脱硅单元；减压蒸馏装置塔底渣油(＞515℃的馏分)为高粘度润滑油残余底油，进入渣油中间储罐备用；塔顶冷凝的轻质油品(＜360℃的馏分)即轻馏分，则与闪蒸装置顶部脱出的经油水分离后的轻组分油汇合，进入轻油脱氯反应器进行脱氯。The heavy oil after demetallization reaction treatment enters the vacuum distillation device for deep distillation to improve the quality of the raw materials before hydrogenation feeding; the vacuum degree during vacuum distillation is 0.5KPa, and the distillate oil of 360-515℃ is cut out under reduced pressure and enters the adsorption desiliconization unit; the bottom residue oil of the vacuum distillation device (fraction>515℃) is the residual bottom oil of high-viscosity lubricating oil, which enters the intermediate residue oil storage tank for standby; the light oil product (fraction<360℃) condensed at the top of the tower, namely the light fraction, is combined with the light component oil after oil-water separation from the top of the flash evaporation device, and enters the light oil dechlorination reactor for dechlorination.
(7)轻组分油脱氯(7) Dechlorination of light component oil
经油水分离罐分离后的轻组分油与轻油脱氯剂混合后，与减压蒸馏装置顶部冷凝的轻质油品(＜360℃的馏分)汇合，在轻油脱氯反应器中进行脱氯反应，轻油脱氯反应的温度为140℃，压力为2.5MPa，停留时间为55min，轻油脱氯剂与轻组分油质量配比为0.5:100，脱氯后的轻油作为萃取稀释油储存在轻油中间储罐中。The light component oil separated by the oil-water separation tank is mixed with the light oil dechlorination agent, and then merged with the light oil product (fraction <360°C) condensed at the top of the vacuum distillation device, and dechlorination reaction is carried out in the light oil dechlorination reactor. The temperature of the light oil dechlorination reaction is 140°C, the pressure is 2.5MPa, the residence time is 55min, the mass ratio of the light oil dechlorination agent to the light component oil is 0.5:100, and the dechlorinated light oil is stored in the light oil intermediate storage tank as extraction dilution oil.
所述的轻油脱氯剂由以下质量百分比的物质复配得到：乙醇胺铜6wt.％、200#溶剂油86wt.％、乙醇8wt.％。The light oil dechlorination agent is prepared by compounding the following substances in percentage by mass: 6 wt.% of ethanolamine copper, 86 wt.% of 200# solvent oil, and 8 wt.% of ethanol.
(8)膜过滤(8) Membrane filtration
渣油中间储罐中的渣油与轻油中间储罐的轻油进行混合，进入深度膜过滤装置，得到膜过滤后的清液，膜过滤后的清液进入吸附脱硅罐，剩余尾渣进入焚烧炉焚烧，提供热源。The residual oil in the residual oil intermediate storage tank is mixed with the light oil in the light oil intermediate storage tank and enters the deep membrane filtration device to obtain the clear liquid after membrane filtration. The clear liquid after membrane filtration enters the adsorption desiliconization tank, and the remaining tailings enter the incinerator for incineration to provide a heat source.
渣油与轻油的质量比为0.7:1；深度膜过滤装置中装载有超滤膜，所述的超滤膜为碳化硅 管式膜，膜过滤的温度为130℃，超滤膜的进口压力为0.6MPa，出口压力为0.2MPa，超滤膜的孔径为50nm，所述的超滤膜表面附着一层疏水层，采用多级超滤膜串联进行处理。The mass ratio of residual oil to light oil is 0.7:1; the deep membrane filtration device is loaded with an ultrafiltration membrane, the ultrafiltration membrane is a silicon carbide tubular membrane, the membrane filtration temperature is 130°C, the inlet pressure of the ultrafiltration membrane is 0.6MPa, the outlet pressure is 0.2MPa, the pore size of the ultrafiltration membrane is 50nm, a hydrophobic layer is attached to the surface of the ultrafiltration membrane, and multi-stage ultrafiltration membranes are connected in series for treatment.
(9)吸附脱硅(9) Adsorption desiliconization
经过减压蒸馏的360-515℃馏分油与膜过滤后的清液混合，进入吸附脱硅罐中进行吸附脱硅，吸附脱硅温度为90℃，吸附脱硅后的油品进入加氢原料缓冲罐。罐中散堆大孔径的表面附载活性氧化镁的亚胺二乙酸基螯合树脂作为吸附剂，活性氧化镁的附载浓度为0.05wt.％，亚胺二乙酸基螯合树脂的孔径为8nm。The 360-515℃ fraction oil after vacuum distillation is mixed with the clear liquid after membrane filtration and enters the adsorption desiliconization tank for adsorption desiliconization. The adsorption desiliconization temperature is 90℃. The oil after adsorption desiliconization enters the hydrogenation raw material buffer tank. The iminodiacetic acid-based chelating resin with large pores and active magnesium oxide on the surface is used as an adsorbent. The active magnesium oxide loading concentration is 0.05wt.%, and the pore size of the iminodiacetic acid-based chelating resin is 8nm.
(10)加氢处理+精馏(10) Hydrotreatment + distillation
加氢原料缓冲罐中的油品进入三段式加氢反应器，经加氢精制反应、异构降凝反应和补充精制反应，再经精馏后得到溶剂油馏分、工业白油和符合APIⅡ类+标准的高品质的基础油。The oil in the hydrogenation raw material buffer tank enters the three-stage hydrogenation reactor, undergoes hydrogenation refining reaction, isomerization decondensation reaction and supplementary refining reaction, and then is distilled to obtain solvent oil fraction, industrial white oil and high-quality base oil that meets API Class II + standards.
加氢精制反应的温度为350℃，空速为0.6h -1，氢分压为14.0MPa，氢油比为1200，采用以Al 2O 3为载体，以MoO 3、NiO为活性物质的催化剂；其中MoO 3的负载量为30wt.％，NiO的负载量为5wt.％。 The temperature of the hydrofining reaction is 350°C, the space velocity is 0.6h -1 , the hydrogen partial pressure is 14.0MPa, the hydrogen-oil ratio is 1200, and the catalyst uses Al 2 O 3 as the carrier and MoO 3 and NiO as the active substances; wherein the loading amount of MoO 3 is 30wt.%, and the loading amount of NiO is 5wt.%.
异构降凝反应的温度为290℃，空速为1.2h -1，氢分压为14.0MPa，氢油比为500，采用以ZSM-5分子筛为载体，以Pt、Pd为活性物质的催化剂，其中Pt的负载量为0.8wt.％，Pd的负载量为0.2wt.％。 The temperature of the isomerization decondensation reaction is 290°C, the space velocity is 1.2h -1 , the hydrogen partial pressure is 14.0MPa, the hydrogen-oil ratio is 500, and a catalyst with ZSM-5 molecular sieve as carrier and Pt and Pd as active substances is used, wherein the Pt loading is 0.8wt.%, and the Pd loading is 0.2wt.%.
补充精制反应的温度为240℃，空速为0.4h -1，氢分压为14.0MPa，氢油比为500，采用以Al 2O 3为载体，以WO 3、MoO 3和NiO为活性物质的催化剂，其中WO 3的负载量为20wt.％，MoO 3的负载量为10wt.％，NiO的负载量为1wt.％。 The temperature of the supplementary refining reaction is 240℃, the space velocity is 0.4h -1 , the hydrogen partial pressure is 14.0MPa, the hydrogen -oil ratio is 500, and the catalyst is supported by Al2O3 and active materials are WO3 , MoO3 and NiO, wherein the loading amount of WO3 is 20wt.%, the loading amount of MoO3 is 10wt.%, and the loading amount of NiO is 1wt.%.
实施例2Example 2
(1)热沉降(1) Heat sinking
废矿物油自罐区经泵进入热沉降装置中进行热沉降，热沉降温度为95℃，热沉降时间为3h。经过热沉降后的固体颗粒、油泥、水等杂质进入油泥回收罐；初步除杂后的废矿物油进入后续闪蒸装置。Waste mineral oil is pumped from the tank area into the heat settling device for heat settling. The heat settling temperature is 95°C and the heat settling time is 3 hours. After heat settling, solid particles, sludge, water and other impurities enter the sludge recovery tank; the waste mineral oil after preliminary impurity removal enters the subsequent flash evaporation device.
(2)油泥回收(2) Oil sludge recovery
经过热沉降脱除后的杂质中还含有一定量可以回收的废矿物油，通过油泥回收罐进一步提高废矿物油的利用率，回收后的废矿物油送至后续闪蒸装置。The impurities removed by thermal sedimentation still contain a certain amount of waste mineral oil that can be recovered. The utilization rate of the waste mineral oil is further improved through the sludge recovery tank, and the recovered waste mineral oil is sent to the subsequent flash evaporation device.
(3)闪蒸(3) Flash evaporation
由热沉降及油泥回收得到的废矿物油进入闪蒸装置，彻底脱除360℃以下轻组分油和水，闪蒸装置的温度为210℃，压力为0.5KPa。闪蒸装置底部物料进入重油脱氯反应器，顶部轻 组分油和水进入油水分离罐，轻组分油和水在油水分离罐中进行分离，分离后的水排入废水罐，轻组分油进入轻油脱氯反应器。The waste mineral oil obtained by thermal sedimentation and sludge recovery enters the flash evaporation device to completely remove the light oil and water below 360°C. The temperature of the flash evaporation device is 210°C and the pressure is 0.5KPa. The material at the bottom of the flash evaporation device enters the heavy oil dechlorination reactor, and the light oil and water at the top enter the oil-water separation tank. The light oil and water are separated in the oil-water separation tank. The separated water is discharged into the wastewater tank, and the light oil enters the light oil dechlorination reactor.
(4)重组分油脱氯(4) Dechlorination of heavy oil
闪蒸装置底部出料的重组分油与重油脱氯剂混合后，进入重油脱氯反应器进行脱氯反应，重油脱氯反应的温度为280℃，压力为1MPa，停留时间为30min，重油脱氯剂与重组分油质量配比为1:100，脱氯后的重组分油进入后续的脱金属反应器。The heavy oil discharged from the bottom of the flash device is mixed with the heavy oil dechlorination agent and then enters the heavy oil dechlorination reactor for dechlorination reaction. The temperature of the heavy oil dechlorination reaction is 280°C, the pressure is 1MPa, the residence time is 30min, the mass ratio of the heavy oil dechlorination agent to the heavy oil is 1:100, and the dechlorinated heavy oil enters the subsequent demetallization reactor.
所述的重油脱氯剂由以下质量百分比的物质复配得到：十六烷基三苯基醋酸膦20wt.％、1-羟基丙醇胺10wt.％、十六烷基三甲基氢氧化铵8wt.％、轻质白油W1-140 62wt.％。The heavy oil dechlorination agent is obtained by compounding the following substances in percentage by mass: 20 wt.% of hexadecyl triphenylphosphine acetate, 10 wt.% of 1-hydroxypropanolamine, 8 wt.% of hexadecyl trimethylammonium hydroxide, and 62 wt.% of light white oil W1-140.
(5)重组分油脱金属(5) Recombinant oil demetallization
脱氯后的重组分油与脱金属剂混合后进入脱金属反应器进行脱金属反应，脱金属反应温度为350℃，反应时间为20min，反应压力为2MPa，脱金属剂与重组分油质量配比为1:100，脱金属后的重组分油进入后续减压蒸馏装置。The dechlorinated heavy oil is mixed with the demetallizing agent and enters the demetallizing reactor for demetallizing reaction. The demetallizing reaction temperature is 350°C, the reaction time is 20 min, the reaction pressure is 2 MPa, the mass ratio of the demetallizing agent to the heavy oil is 1:100, and the demetallized heavy oil enters the subsequent vacuum distillation device.
所述的脱金属剂由月桂酸烷醇酰胺磷酸酯、壬基酚聚氧乙烯聚氧丙烯醚复配得到；其中月桂酸烷醇酰胺磷酸酯、壬基酚聚氧乙烯聚氧丙烯醚的质量组成配比为40wt.％:60wt.％。The demetallizing agent is prepared by compounding lauric acid alkanolamide phosphate and nonylphenol polyoxyethylene polyoxypropylene ether; wherein the mass composition ratio of lauric acid alkanolamide phosphate and nonylphenol polyoxyethylene polyoxypropylene ether is 40wt.%:60wt.%.
(6)减压蒸馏(6) Vacuum distillation
经过脱金属反应处理后的重组分油进入减压蒸馏装置中进行深度蒸馏，提高加氢进料前原料的品质；减压蒸馏时的真空度为0.9KPa，减压切割出360-515℃的馏分油进入吸附脱硅单元；减压蒸馏装置塔底渣油(＞515℃的馏分)为高粘度润滑油残余底油，进入渣油中间储罐备用；塔顶冷凝的轻质油品(＜360℃的馏分)即轻馏分，则与闪蒸装置顶部脱出的经油水分离后的轻组分油汇合，进入轻油脱氯反应器进行脱氯。The heavy oil after demetallization reaction treatment enters the vacuum distillation device for deep distillation to improve the quality of the raw materials before hydrogenation feeding; the vacuum degree during vacuum distillation is 0.9KPa, and the distillate oil of 360-515℃ is cut out under reduced pressure and enters the adsorption desiliconization unit; the bottom residue oil of the vacuum distillation device (fraction>515℃) is the residual bottom oil of high-viscosity lubricating oil, which enters the intermediate residue oil storage tank for standby; the light oil product (fraction<360℃) condensed at the top of the tower, namely the light fraction, is combined with the light component oil after oil-water separation from the top of the flash evaporation device, and enters the light oil dechlorination reactor for dechlorination.
(7)轻组分油脱氯(7) Dechlorination of light component oil
经油水分离罐分离后的轻组分油与轻油脱氯剂混合后，与减压蒸馏装置顶部冷凝的轻质油品(＜360℃的馏分)汇合，在轻油脱氯反应器中进行脱氯反应，轻油脱氯反应的温度为180℃，压力为3.5MPa，停留时间为40min，轻油脱氯剂与轻组分油质量配比为1:100，脱氯后的轻油作为萃取稀释油储存在轻油中间储罐中。The light component oil separated by the oil-water separation tank is mixed with the light oil dechlorination agent, and then merged with the light oil product (fraction <360°C) condensed at the top of the vacuum distillation device, and dechlorination reaction is carried out in the light oil dechlorination reactor. The temperature of the light oil dechlorination reaction is 180°C, the pressure is 3.5MPa, the residence time is 40min, the mass ratio of the light oil dechlorination agent to the light component oil is 1:100, and the dechlorinated light oil is stored in the light oil intermediate storage tank as extraction dilution oil.
所述的轻油脱氯剂由以下质量百分比的物质复配得到：二甲醇铜12wt.％、柠檬烯75wt.％、丙二醇13wt.％。The light oil dechlorination agent is prepared by compounding the following substances in percentage by mass: 12 wt.% of copper dimethoxide, 75 wt.% of limonene, and 13 wt.% of propylene glycol.
(8)膜过滤(8) Membrane filtration
渣油中间储罐中的渣油与轻油中间储罐的轻油进行混合，进入深度膜过滤装置，得到膜过滤后的清液，膜过滤后的清液进入吸附脱硅罐，剩余尾渣进入焚烧炉焚烧，提供热源。The residual oil in the residual oil intermediate storage tank is mixed with the light oil in the light oil intermediate storage tank and enters the deep membrane filtration device to obtain the clear liquid after membrane filtration. The clear liquid after membrane filtration enters the adsorption desiliconization tank, and the remaining tailings enter the incinerator for incineration to provide a heat source.
渣油与轻油的质量比为0.6:1；深度膜过滤装置中装载有超滤膜，所述的超滤膜为碳化硅 管式膜，膜过滤的温度为200℃，超滤膜的进口压力为0.9MPa，出口压力为0.6MPa，超滤膜的孔径为10nm，所述的超滤膜表面附着一层疏水层，采用多级超滤膜串联进行处理。The mass ratio of residual oil to light oil is 0.6:1; the deep membrane filtration device is loaded with an ultrafiltration membrane, the ultrafiltration membrane is a silicon carbide tubular membrane, the membrane filtration temperature is 200°C, the inlet pressure of the ultrafiltration membrane is 0.9MPa, the outlet pressure is 0.6MPa, the pore size of the ultrafiltration membrane is 10nm, a hydrophobic layer is attached to the surface of the ultrafiltration membrane, and multi-stage ultrafiltration membranes are connected in series for treatment.
(9)吸附脱硅(9) Adsorption desiliconization
经过减压蒸馏的360-515℃馏分油与膜过滤后的清液混合，进入吸附脱硅罐中进行吸附脱硅，吸附脱硅温度为160℃，吸附脱硅后的油品进入加氢原料缓冲罐。罐中散堆大孔径的表面附载活性氧化镁的亚氨基二乙醛肟螯合树脂作为吸附剂，活性氧化镁的附载浓度为0.2wt.％，亚氨基二乙醛肟螯合树脂的孔径为5nm。The 360-515℃ fraction oil after vacuum distillation is mixed with the clear liquid after membrane filtration and enters the adsorption desiliconization tank for adsorption desiliconization. The adsorption desiliconization temperature is 160℃. The oil after adsorption desiliconization enters the hydrogenation raw material buffer tank. The iminodiacetaldehyde oxime chelate resin with large pores and active magnesium oxide on the surface is used as an adsorbent. The active magnesium oxide loading concentration is 0.2wt.%, and the pore size of the iminodiacetaldehyde oxime chelate resin is 5nm.
(10)加氢处理+精馏(10) Hydrotreatment + distillation
加氢原料缓冲罐中的油品进入三段式加氢反应器，经加氢精制反应、异构降凝反应和补充精制反应，再经精馏后得到溶剂油馏分、工业白油和符合APIⅡ类+标准的高品质的基础油。The oil in the hydrogenation raw material buffer tank enters the three-stage hydrogenation reactor, undergoes hydrogenation refining reaction, isomerization decondensation reaction and supplementary refining reaction, and then is distilled to obtain solvent oil fraction, industrial white oil and high-quality base oil that meets API Class II + standards.
加氢精制反应的温度为400℃，空速为1.0h -1，氢分压为16.0MPa，氢油比为800，采用以Al 2O 3为载体，以MoO 3、NiO为活性物质的催化剂；其中MoO 3的负载量为20wt.％，NiO的负载量为5wt.％。 The temperature of the hydrofining reaction is 400°C, the space velocity is 1.0h -1 , the hydrogen partial pressure is 16.0MPa, the hydrogen-oil ratio is 800, and the catalyst is Al 2 O 3 as the carrier and MoO 3 and NiO as the active substances; wherein the loading amount of MoO 3 is 20wt.%, and the loading amount of NiO is 5wt.%.
异构降凝反应的温度为380℃，空速为1.6h -1，氢分压为16.0MPa，氢油比为800，采用以ZSM-5分子筛为载体，以Pt、Pd为活性物质的催化剂，其中Pt的负载量为0.5wt.％，Pd的负载量为0.2wt.％。 The temperature of the isomerization decondensation reaction is 380°C, the space velocity is 1.6h -1 , the hydrogen partial pressure is 16.0MPa, the hydrogen-oil ratio is 800, and a catalyst with ZSM-5 molecular sieve as carrier and Pt and Pd as active substances is used, wherein the Pt loading is 0.5wt.%, and the Pd loading is 0.2wt.%.
补充精制反应的温度为310℃，空速为0.8h -1，氢分压为14.0MPa，氢油比为800，采用以Al 2O 3为载体，以WO 3、MoO 3和NiO为活性物质的催化剂，其中WO 3的负载量为30wt.％，MoO 3的负载量为20wt.％，NiO的负载量为2wt.％。 The temperature of the supplementary refining reaction is 310℃, the space velocity is 0.8h -1 , the hydrogen partial pressure is 14.0MPa, the hydrogen -oil ratio is 800, and the catalyst is supported by Al2O3 and active materials are WO3 , MoO3 and NiO, wherein the loading amount of WO3 is 30wt.%, the loading amount of MoO3 is 20wt.%, and the loading amount of NiO is 2wt.%.
实施例3Example 3
(1)热沉降(1) Heat sinking
废矿物油自罐区经泵进入热沉降装置中进行热沉降，热沉降温度为110℃，热沉降时间为2h。经过热沉降后的固体颗粒、油泥、水等杂质进入油泥回收罐；初步除杂后的废矿物油进入后续闪蒸装置。Waste mineral oil is pumped from the tank area into the heat settling device for heat settling. The heat settling temperature is 110℃ and the heat settling time is 2h. After heat settling, solid particles, sludge, water and other impurities enter the sludge recovery tank; the waste mineral oil after preliminary impurity removal enters the subsequent flash evaporation device.
(2)油泥回收(2) Oil sludge recovery
经过热沉降脱除后的杂质中还含有一定量可以回收的废矿物油，通过油泥回收罐进一步提高废矿物油的利用率，回收后的废矿物油送至后续闪蒸装置。The impurities removed by thermal sedimentation still contain a certain amount of waste mineral oil that can be recovered. The utilization rate of the waste mineral oil is further improved through the sludge recovery tank, and the recovered waste mineral oil is sent to the subsequent flash evaporation device.
(3)闪蒸(3) Flash evaporation
由热沉降及油泥回收得到的废矿物油进入闪蒸装置，彻底脱除360℃以下轻组分油和水，闪蒸装置的温度为225℃，压力为0.3KPa。闪蒸装置底部物料进入重油脱氯反应器，顶部轻 组分油和水进入油水分离罐，轻组分油和水在油水分离罐中进行分离，分离后的水排入废水罐，轻组分油进入轻油脱氯反应器。The waste mineral oil obtained by thermal sedimentation and sludge recovery enters the flash evaporation device to completely remove the light oil and water below 360°C. The temperature of the flash evaporation device is 225°C and the pressure is 0.3KPa. The material at the bottom of the flash evaporation device enters the heavy oil dechlorination reactor, and the light oil and water at the top enter the oil-water separation tank. The light oil and water are separated in the oil-water separation tank. The separated water is discharged into the wastewater tank, and the light oil enters the light oil dechlorination reactor.
(4)重组分油脱氯(4) Dechlorination of heavy oil
闪蒸装置底部出料的重组分油与重油脱氯剂混合后，进入重油脱氯反应器进行脱氯反应，重油脱氯反应的温度为330℃，压力为2MPa，停留时间为15min，重油脱氯剂与重组分油质量配比为0.5:100，脱氯后的重组分油进入后续的脱金属反应器。The heavy oil discharged from the bottom of the flash device is mixed with the heavy oil dechlorination agent and then enters the heavy oil dechlorination reactor for dechlorination reaction. The temperature of the heavy oil dechlorination reaction is 330°C, the pressure is 2MPa, the residence time is 15min, the mass ratio of the heavy oil dechlorination agent to the heavy oil is 0.5:100, and the dechlorinated heavy oil enters the subsequent demetallization reactor.
所述的重油脱氯剂由以下质量百分比的物质复配得到：乙基三苯基醋酸膦30wt.％、磷酯酰乙醇胺5wt.％、十六烷基三甲基氢氧化铵5wt.％、轻质白油W2-140 60wt.％。The heavy oil dechlorination agent is obtained by compounding the following substances in percentage by mass: 30 wt.% of ethyl triphenylphosphine acetate, 5 wt.% of phosphatidylethanolamine, 5 wt.% of hexadecyl trimethylammonium hydroxide, and 60 wt.% of light white oil W2-140.
(5)重组分油脱金属(5) Recombinant oil demetallization
脱氯后的重组分油与脱金属剂混合后进入脱金属反应器进行脱金属反应，脱金属反应温度为370℃，反应时间为10min，反应压力为3MPa，脱金属剂与重组分油质量配比为2:100，脱金属后的重组分油进入后续减压蒸馏装置。The dechlorinated heavy oil is mixed with the demetallizing agent and enters the demetallizing reactor for demetallizing reaction. The demetallizing reaction temperature is 370°C, the reaction time is 10 min, the reaction pressure is 3 MPa, the mass ratio of the demetallizing agent to the heavy oil is 2:100, and the demetallized heavy oil enters the subsequent vacuum distillation device.
所述的脱金属剂由正十二醇聚氧乙烯醚磷酸酯、丙三醇聚氧乙烯聚氧丙烯醚复配得到；其中正十二醇聚氧乙烯醚磷酸酯、丙三醇聚氧乙烯聚氧丙烯醚的质量组成配比为45wt.％:55wt.％；The demetallizing agent is prepared by compounding n-dodecyl alcohol polyoxyethylene ether phosphate and glycerol polyoxyethylene polyoxypropylene ether; wherein the mass composition ratio of n-dodecyl alcohol polyoxyethylene ether phosphate and glycerol polyoxyethylene polyoxypropylene ether is 45wt.%:55wt.%;
(6)减压蒸馏(6) Vacuum distillation
经过脱金属反应处理后的重组分油进入减压蒸馏装置中进行深度蒸馏，提高加氢进料前原料的品质；减压蒸馏时的真空度为1.2KPa，减压切割出360-515℃的馏分油进入吸附脱硅单元；减压蒸馏装置塔底渣油(＞515℃的馏分)为高粘度润滑油残余底油，进入渣油中间储罐备用；塔顶冷凝的轻质油品(＜360℃的馏分)即轻馏分，则与闪蒸装置顶部脱出的经油水分离后的轻组分油汇合，进入轻油脱氯反应器进行脱氯。The heavy oil after demetallization reaction treatment enters the vacuum distillation device for deep distillation to improve the quality of the raw materials before hydrogenation feeding; the vacuum degree during vacuum distillation is 1.2KPa, and the distillate oil of 360-515℃ is cut out under reduced pressure and enters the adsorption desiliconization unit; the bottom residue oil of the vacuum distillation device (fraction>515℃) is the residual bottom oil of high-viscosity lubricating oil, which enters the intermediate residue oil storage tank for standby; the light oil product (fraction<360℃) condensed at the top of the tower, namely the light fraction, is combined with the light component oil after oil-water separation from the top of the flash evaporation device, and enters the light oil dechlorination reactor for dechlorination.
(7)轻组分油脱氯(7) Dechlorination of light component oil
经油水分离罐分离后的轻组分油与轻油脱氯剂混合后，与减压蒸馏装置顶部冷凝的轻质油品(＜360℃的馏分)汇合，在轻油脱氯反应器中进行脱氯反应，轻油脱氯反应的温度为230℃，压力为6MPa，停留时间为20min，轻油脱氯剂与轻组分油质量配比为2:100，脱氯后的轻油作为萃取稀释油储存在轻油中间储罐中。The light component oil separated by the oil-water separation tank is mixed with the light oil dechlorination agent, and then merged with the light oil product (fraction <360°C) condensed at the top of the vacuum distillation device, and dechlorination reaction is carried out in the light oil dechlorination reactor. The temperature of the light oil dechlorination reaction is 230°C, the pressure is 6MPa, the residence time is 20min, the mass ratio of the light oil dechlorination agent to the light component oil is 2:100, and the dechlorinated light oil is stored in the light oil intermediate storage tank as extraction dilution oil.
所述的轻油脱氯剂由以下质量百分比的物质复配得到：乙醇铜20wt.％、200#溶剂油60wt.％、聚乙二醇20wt.％。The light oil dechlorination agent is prepared by compounding the following substances in percentage by mass: 20 wt.% of ethanol copper, 60 wt.% of 200# solvent oil and 20 wt.% of polyethylene glycol.
(8)膜过滤(8) Membrane filtration
渣油中间储罐中的渣油与轻油中间储罐的轻油进行混合，进入深度膜过滤装置，得到膜过滤后的清液，膜过滤后的清液进入吸附脱硅罐，剩余尾渣进入焚烧炉焚烧，提供热源。The residual oil in the residual oil intermediate storage tank is mixed with the light oil in the light oil intermediate storage tank and enters the deep membrane filtration device to obtain the clear liquid after membrane filtration. The clear liquid after membrane filtration enters the adsorption desiliconization tank, and the remaining tailings enter the incinerator for incineration to provide a heat source.
渣油与轻油的质量比为0.8:1；深度膜过滤装置中装载有超滤膜，所述的超滤膜为陶瓷纳滤膜，膜过滤的温度为180℃，超滤膜的进口压力为10.MPa，出口压力为0.8MPa，超滤膜的孔径为30nm，所述的超滤膜表面附着一层疏水层，采用多级超滤膜串联进行处理。The mass ratio of residual oil to light oil is 0.8:1; the deep membrane filtration device is loaded with an ultrafiltration membrane, the ultrafiltration membrane is a ceramic nanofiltration membrane, the membrane filtration temperature is 180°C, the inlet pressure of the ultrafiltration membrane is 10.MPa, the outlet pressure is 0.8MPa, the pore size of the ultrafiltration membrane is 30nm, a hydrophobic layer is attached to the surface of the ultrafiltration membrane, and multi-stage ultrafiltration membranes are connected in series for treatment.
(9)吸附脱硅(9) Adsorption desiliconization
经过减压蒸馏的360-515℃馏分油与膜过滤后的清液混合，进入吸附脱硅罐中进行吸附脱硅，吸附脱硅温度为230℃，吸附脱硅后的油品进入加氢原料缓冲罐。罐中散堆大孔径的表面附载活性氧化镁的硫脲基螯合树脂作为吸附剂，活性氧化镁的附载浓度为0.4wt.％，硫脲基螯合树脂的孔径为12nm。The 360-515℃ fraction oil after vacuum distillation is mixed with the clear liquid after membrane filtration and enters the adsorption desiliconization tank for adsorption desiliconization. The adsorption desiliconization temperature is 230℃. The oil after adsorption desiliconization enters the hydrogenation raw material buffer tank. The thiourea-based chelating resin with large pores and active magnesium oxide on the surface is used as an adsorbent. The loading concentration of active magnesium oxide is 0.4wt.%, and the pore size of the thiourea-based chelating resin is 12nm.
(10)加氢处理+精馏(10) Hydrotreatment + distillation
加氢原料缓冲罐中的油品进入三段式加氢反应器，经加氢精制反应、异构降凝反应和补充精制反应，再经精馏后得到溶剂油馏分、工业白油和符合APIⅡ类+标准的高品质的基础油。The oil in the hydrogenation raw material buffer tank enters the three-stage hydrogenation reactor, undergoes hydrogenation refining reaction, isomerization decondensation reaction and supplementary refining reaction, and then is distilled to obtain solvent oil fraction, industrial white oil and high-quality base oil that meets API Class II + standards.
加氢精制反应的温度为380℃，空速为0.8h -1，氢分压为15.0MPa，氢油比为800，采用以Al 2O 3为载体，以MoO 3、NiO为活性物质的催化剂；其中MoO 3的负载量为20wt.％，NiO的负载量为3wt.％。 The temperature of the hydrofining reaction is 380°C, the space velocity is 0.8h -1 , the hydrogen partial pressure is 15.0MPa, the hydrogen-oil ratio is 800, and the catalyst uses Al 2 O 3 as the carrier and MoO 3 and NiO as the active substances; the loading amount of MoO 3 is 20wt.%, and the loading amount of NiO is 3wt.%.
异构降凝反应的温度为330℃，空速为1.4h -1，氢分压为15.0MPa，氢油比为800，采用以ZSM-5分子筛为载体，以Pt、Pd为活性物质的催化剂，其中Pt的负载量为0.5wt.％，Pd的负载量为0.5wt.％。 The temperature of the isomerization decondensation reaction is 330°C, the space velocity is 1.4h -1 , the hydrogen partial pressure is 15.0MPa, the hydrogen-oil ratio is 800, and a catalyst with ZSM-5 molecular sieve as carrier and Pt and Pd as active substances is used, wherein the loading amount of Pt is 0.5wt.%, and the loading amount of Pd is 0.5wt.%.
补充精制反应的温度为350℃，空速为0.6h -1，氢分压为12.0MPa，氢油比为800，采用以Al 2O 3为载体，以WO 3、MoO 3和NiO为活性物质的催化剂，其中WO 3的负载量为30wt.％，MoO 3的负载量为20wt.％，NiO的负载量为0.5wt.％。 The temperature of the supplementary refining reaction is 350℃, the space velocity is 0.6h -1 , the hydrogen partial pressure is 12.0MPa, the hydrogen -oil ratio is 800, and the catalyst is supported by Al2O3 and active materials are WO3 , MoO3 and NiO, wherein the loading amount of WO3 is 30wt.%, the loading amount of MoO3 is 20wt.%, and the loading amount of NiO is 0.5wt.%.
(1)对实施例1-3废矿物油在连续生产过程中的物料平衡进行检测，数据如表1。(1) The material balance of the waste mineral oil of Examples 1-3 during the continuous production process was tested, and the data are shown in Table 1.
表1实施例1-3的物料平衡数据表Table 1 Material balance data table of Examples 1-3
Figure PCTCN2022130151-appb-000001
Figure PCTCN2022130151-appb-000001
Figure PCTCN2022130151-appb-000002
Figure PCTCN2022130151-appb-000002
(2)对实施例1-3废矿物油中氯硅含量见表2。(2) The chlorine and silicon contents in the waste mineral oils of Examples 1-3 are shown in Table 2.
表2实施例1-3废矿物油中氯硅含量Table 2 Chlorine and silicon content in waste mineral oil of Examples 1-3
Figure PCTCN2022130151-appb-000003
Figure PCTCN2022130151-appb-000003
(3)实施例2中废矿物油、加氢原料及加氢产品的性质见表3。(3) The properties of the waste mineral oil, hydrogenation feedstock and hydrogenation product in Example 2 are shown in Table 3.
表2实施例2中废矿物油、加氢原料及加氢产品的性质数据Table 2 Property data of waste mineral oil, hydrogenation feedstock and hydrogenation product in Example 2
Figure PCTCN2022130151-appb-000004
Figure PCTCN2022130151-appb-000004
Figure PCTCN2022130151-appb-000005
Figure PCTCN2022130151-appb-000005
Figure PCTCN2022130151-appb-000006
Figure PCTCN2022130151-appb-000006
(4)实施例1中加氢分馏切割后工业白油、基础油产品的性质数据如表4。(4) The property data of the industrial white oil and base oil products after hydrofractionation and cutting in Example 1 are shown in Table 4.
表4实施例1中加氢分馏切割后工业白油、基础油的性质数据表Table 4 Property data of industrial white oil and base oil after hydrofractionation cutting in Example 1
Figure PCTCN2022130151-appb-000007
Figure PCTCN2022130151-appb-000007
(5)实施例1中溶剂油性质数据如表5。(5) The property data of solvent oil in Example 1 are shown in Table 5.
表5实施例1中溶剂油性质Table 5 Solvent oil properties in Example 1
项目project 数据data 数据data
产品名称product name 溶剂油1Solvent oil 1 溶剂油2 Solvent oil 2
馏分/℃Fraction/℃ <150<150 150-275150-275
密度(20℃)/kg.m -3 Density (20℃)/kg.m -3 0.6600.660 0.7780.778
硫含量/μg.g -1 Sulfur content/μg.g -1 <1.0<1.0 <1.0<1.0
芳烃，％Aromatics, % <0.2<0.2 <0.20<0.20
溴指数/mgBr.(100g) -1 Bromine index/mgBr.(100g) -1 <100<100 <100<100
颜色(赛氏)/号Color(Saybolt)/No. +30+30 +30+30
(6)实施例1-3中的收率如表6。(6) The yields in Examples 1-3 are shown in Table 6.
表6实施例1-3收率计算Table 6 Calculation of yield of Example 1-3
Figure PCTCN2022130151-appb-000008
Figure PCTCN2022130151-appb-000008
通过表4、表5和表6数据可以看出，本发明不仅解决了一种含氯硅废的矿物油连续生产基础油的方法，还可以提高基础油的收率，重质油收率可达88％以上，总油品收率可达92％以上，整体工艺总回收率可达98％以上；得到溶剂油和满足API(美国石油协会)标准的II类+以上基础油规格的高品质的基础油产品和工业白油。同时能延长废矿物油再生装置的运转周期，实现连续再生，有效解决含氯硅的废矿物油再生过程中装置结焦、腐蚀、堵塞和加氢催化剂中毒等问题，大大减少了危废的二次产生，降低了生产和检修成本。It can be seen from the data in Tables 4, 5 and 6 that the present invention not only solves a method for continuously producing base oil from mineral oil containing chlorine silicon waste, but also can improve the yield of base oil, the yield of heavy oil can reach more than 88%, the yield of total oil products can reach more than 92%, and the overall process total recovery rate can reach more than 98%; solvent oil and high-quality base oil products and industrial white oil that meet the API (American Petroleum Institute) standard Class II+ or above base oil specifications can be obtained. At the same time, it can extend the operation cycle of the waste mineral oil regeneration device, realize continuous regeneration, effectively solve the problems of coking, corrosion, clogging and hydrogenation catalyst poisoning of the device during the regeneration process of chlorine silicon waste mineral oil, greatly reduce the secondary generation of hazardous waste, and reduce production and maintenance costs.
本发明所述含氯硅的废矿物油连续生产基础油的系统：包括依次相连的废矿物油储罐1、热沉降装置2、闪蒸装置3、重油脱氯反应器13、脱金属反应器11、减压蒸馏装置10、吸附脱硅罐18、加氢原料缓冲罐17、加氢反应器16、精馏塔15和产品罐22；The system for continuously producing base oil from chlorinated silicon-containing waste mineral oil of the present invention comprises a waste mineral oil storage tank 1, a heat settling device 2, a flash evaporation device 3, a heavy oil dechlorination reactor 13, a demetallization reactor 11, a vacuum distillation device 10, an adsorption desiliconization tank 18, a hydrogenation raw material buffer tank 17, a hydrogenation reactor 16, a distillation tower 15 and a product tank 22 which are connected in sequence;
所述的减压蒸馏装置10底部还通过渣油中间储罐9、深度膜过滤装置19与吸附脱硅罐18连接；所述的闪蒸装置3还与油水分离罐4、轻油脱氯反应器7、轻油中间储罐8依次相连，轻油中间储罐8还与渣油中间储罐9连接；所述的热沉降装置2还连接油泥回收罐21，油泥回收罐21再与闪蒸装置3连接；减压蒸馏装置10的顶部还连接轻油脱氯反应器7；The bottom of the vacuum distillation device 10 is also connected to the adsorption desiliconization tank 18 through the residual oil intermediate storage tank 9 and the deep membrane filtration device 19; the flash device 3 is also connected to the oil-water separation tank 4, the light oil dechlorination reactor 7, and the light oil intermediate storage tank 8 in sequence, and the light oil intermediate storage tank 8 is also connected to the residual oil intermediate storage tank 9; the heat settling device 2 is also connected to the sludge recovery tank 21, and the sludge recovery tank 21 is further connected to the flash device 3; the top of the vacuum distillation device 10 is also connected to the light oil dechlorination reactor 7;
所述的油水分离罐4与轻油脱氯反应器7之间的管路连接轻油脱氯剂储罐6，闪蒸装置3与重油脱氯反应器13之间的管路连接重油脱氯剂储罐14，重油脱氯反应器13与脱金属反应器11之间的管路连接脱金属剂储罐12；油水分离罐4还连接废水罐5，深度膜过滤装置19还连接焚烧炉20。The pipeline between the oil-water separation tank 4 and the light oil dechlorination reactor 7 is connected to the light oil dechlorination agent storage tank 6, the pipeline between the flash device 3 and the heavy oil dechlorination reactor 13 is connected to the heavy oil dechlorination agent storage tank 14, and the pipeline between the heavy oil dechlorination reactor 13 and the demetallization reactor 11 is connected to the demetallization agent storage tank 12; the oil-water separation tank 4 is also connected to the wastewater tank 5, and the deep membrane filtration device 19 is also connected to the incinerator 20.

Claims (10)

  1. 一种含氯硅的废矿物油连续生产基础油的方法，其特征在于包括以下步骤：A method for continuously producing base oil from chlorinated silicon-containing waste mineral oil, characterized by comprising the following steps:
    (1)废矿物油进入热沉降装置中进行热沉降，热沉降后的废矿物油进入闪蒸装置进行闪蒸，得到轻组分油和重组分油；(1) The waste mineral oil enters a heat settling device for heat settling, and the waste mineral oil after heat settling enters a flash evaporation device for flash evaporation to obtain light component oil and heavy component oil;
    (2)重组分油与重油脱氯剂进入重油脱氯反应器进行重油脱氯反应，之后与脱金属剂进入脱金属反应器进行脱金属反应，再经减压蒸馏，得到馏分油、轻馏分和渣油；(2) the heavy oil fraction and the heavy oil dechlorinating agent enter the heavy oil dechlorinating reactor for heavy oil dechlorination reaction, and then enter the demetallizing reactor with the demetallizing agent for demetallizing reaction, and then undergo vacuum distillation to obtain distillate oil, light fraction and residual oil;
    (3)轻组分油经油水分离后，与轻油脱氯剂、步骤(2)的轻馏分进入轻油脱氯反应器进行轻油脱氯反应，得到轻油；(3) After the light component oil is separated from the water, it enters the light oil dechlorination reactor with the light oil dechlorination agent and the light fraction of step (2) to carry out a light oil dechlorination reaction to obtain light oil;
    (4)步骤(3)的轻油与步骤(2)渣油混合后进行膜过滤，得到的清液与步骤(2)的馏分油一起进入吸附脱硅罐进行吸附脱硅反应，经加氢处理后，精馏得到溶剂油、工业白油和基础油。(4) The light oil of step (3) is mixed with the residual oil of step (2) and then subjected to membrane filtration. The resulting clear liquid and the distillate oil of step (2) are sent into an adsorption desiliconization tank for adsorption desiliconization reaction. After hydrogenation treatment, solvent oil, industrial white oil and base oil are obtained by distillation.
  2. 根据权利要求1所述的含氯硅的废矿物油连续生产基础油的方法，其特征在于：步骤(2)中，重油脱氯反应的温度为200-350℃，压力为0.2-4MPa，停留时间为15-60min，重油脱氯剂与重组分油的质量比为0.1-2:100。The method for continuously producing base oil from chlorinated silicon-containing waste mineral oil according to claim 1, characterized in that: in step (2), the temperature of the heavy oil dechlorination reaction is 200-350° C., the pressure is 0.2-4 MPa, the residence time is 15-60 min, and the mass ratio of the heavy oil dechlorination agent to the heavy oil fraction is 0.1-2:100.
  3. 根据权利要求2所述的含氯硅的废矿物油连续生产基础油的方法，其特征在于：所述的重油脱氯剂由季膦盐、醇胺、离子液体和轻质白油复配得到，其中季膦盐、醇胺、离子液体和轻质白油的质量组成配比为10-30wt.％:5-15wt.％:5-10wt.％:45-80wt.％；The method for continuously producing base oil from chlorinated silicon-containing waste mineral oil according to claim 2, characterized in that: the heavy oil dechlorinating agent is obtained by compounding quaternary phosphonium salt, alcohol amine, ionic liquid and light white oil, wherein the mass composition ratio of quaternary phosphonium salt, alcohol amine, ionic liquid and light white oil is 10-30wt.％: 5-15wt.％: 5-10wt.％: 45-80wt.％;
    所述的季膦盐为烯丙基三苯基氢氧化膦、十六烷基三苯基醋酸膦或乙基三苯基醋酸膦；所述的醇胺为正辛基二乙醇胺、1-羟基丙醇胺或磷酯酰乙醇胺；所述的离子液体为双十烷基二甲基氢氧化铵或十六烷基三甲基氢氧化铵；所述的轻质白油为轻质白油W1-130、轻质白油W1-140或轻质白油W2-140。The quaternary phosphonium salt is allyl triphenylphosphine hydroxide, hexadecyl triphenylphosphine acetate or ethyl triphenylphosphine acetate; the alcohol amine is n-octyl diethanolamine, 1-hydroxypropanolamine or phosphatidylethanolamine; the ionic liquid is didecyl dimethyl ammonium hydroxide or hexadecyl trimethyl ammonium hydroxide; the light white oil is light white oil W1-130, light white oil W1-140 or light white oil W2-140.
  4. 根据权利要求1所述的含氯硅的废矿物油连续生产基础油的方法，其特征在于：步骤(2)中，脱金属反应温度为250-380℃，停留时间为10-60min，反应压力为0.2-4MPa；脱金属剂与重组分油的质量比为0.5-2:100。The method for continuously producing base oil from chlorinated silicon-containing waste mineral oil according to claim 1, characterized in that: in step (2), the demetallization reaction temperature is 250-380°C, the residence time is 10-60 min, the reaction pressure is 0.2-4 MPa; and the mass ratio of the demetallization agent to the recombinant oil is 0.5-2:100.
  5. 根据权利要求4所述的含氯硅的废矿物油连续生产基础油的方法，其特征在于：所述的脱金属剂由磷酸组胺类物质或磷酸酯类物质、醚类复配而成；磷酸组胺类物质或磷酸酯类物质、醚类的质量组成配比为30-50wt.％:50-70wt.％；The method for continuously producing base oil from chlorinated silicon-containing waste mineral oil according to claim 4, characterized in that: the demetallizing agent is compounded from phosphate histamine substances or phosphate ester substances and ethers; the mass composition ratio of phosphate histamine substances or phosphate ester substances and ethers is 30-50wt.%:50-70wt.%;
    所述的磷酸组胺类物质为苯基三丙基磷酸二氢铵或磷酯酰乙醇胺；所述的磷酸酯类物质为月桂酸烷醇酰胺磷酸酯、正十二醇聚氧乙烯醚磷酸酯或十八烷基磷酸酯；所述的醚类为妥尔油酸聚氧乙烯聚氧丙烯醚、壬基酚聚氧乙烯聚氧丙烯醚或丙三醇聚氧乙烯聚氧丙烯醚。The histamine phosphate substance is phenyl tripropyl ammonium dihydrogen phosphate or phosphatidylethanolamine; the phosphate ester substance is lauric acid alkanolamide phosphate, n-dodecyl alcohol polyoxyethylene ether phosphate or octadecyl phosphate; the ether substance is tall oil acid polyoxyethylene polyoxypropylene ether, nonylphenol polyoxyethylene polyoxypropylene ether or glycerol polyoxyethylene polyoxypropylene ether.
  6. 根据权利要求1所述的含氯硅的废矿物油连续生产基础油的方法，其特征在于：步骤(3)中，轻油脱氯反应的温度为120-260℃，压力为2-6MPa，停留时间为15-60min；轻油 脱氯剂与轻组分油的质量比为0.1-2:100。The method for continuously producing base oil from chlorinated silicon-containing waste mineral oil according to claim 1 is characterized in that: in step (3), the temperature of the light oil dechlorination reaction is 120-260°C, the pressure is 2-6MPa, and the residence time is 15-60min; the mass ratio of the light oil dechlorinating agent to the light component oil is 0.1-2:100.
  7. 根据权利要求6所述的含氯硅的废矿物油连续生产基础油的方法，其特征在于：所述的轻油脱氯剂由醇铜类或醇胺铜类物质、轻质油与醇类复配得到，其中醇铜类或醇胺铜类物质、轻质油与醇类的质量组成配比为5-20wt.％:60-90wt.％:5-20wt.％；The method for continuously producing base oil from chlorinated silicon-containing waste mineral oil according to claim 6, characterized in that: the light oil dechlorinating agent is obtained by compounding copper alkoxide or copper amine substances, light oil and alcohols, wherein the mass composition ratio of copper alkoxide or copper amine substances, light oil and alcohols is 5-20wt.%:60-90wt.%:5-20wt.%;
    所述的醇铜类或醇胺铜类物质为乙醇胺铜、二甲醇铜或乙醇铜；所述的轻质油为200#溶剂油或柠檬烯；所述的醇类为乙醇、丙二醇、聚乙二醇或二甘醇。The alcohol copper or alcohol amine copper substance is ethanolamine copper, dimethanol copper or ethanol copper; the light oil is 200# solvent oil or limonene; the alcohol is ethanol, propylene glycol, polyethylene glycol or diethylene glycol.
  8. 根据权利要求1所述的含氯硅的废矿物油连续生产基础油的方法，其特征在于：步骤(4)中，渣油与轻油的质量比为0.5-1:1；采用陶瓷纳滤膜或碳化硅管式膜作为超滤膜进行膜过滤，膜过滤的温度为120-200℃，超滤膜的进口压力为0.4-1.0MPa，出口压力为0.2-0.8MPa，超滤膜的孔径为10-50nm。The method for continuously producing base oil from chlorinated silicon-containing waste mineral oil according to claim 1, characterized in that: in step (4), the mass ratio of residual oil to light oil is 0.5-1:1; a ceramic nanofiltration membrane or a silicon carbide tubular membrane is used as an ultrafiltration membrane for membrane filtration, the membrane filtration temperature is 120-200°C, the inlet pressure of the ultrafiltration membrane is 0.4-1.0MPa, the outlet pressure is 0.2-0.8MPa, and the pore size of the ultrafiltration membrane is 10-50nm.
  9. 根据权利要求1所述的含氯硅的废矿物油连续生产基础油的方法，其特征在于：步骤(4)中，吸附脱硅反应时的吸附剂为表面附载活性氧化镁的螯合树脂，所述的螯合树脂为亚胺二乙酸基螯合树脂、亚氨基二乙醛肟螯合树脂或硫脲基螯合树脂，活性氧化镁的附载浓度为0.05-0.5wt.％；吸附脱硅反应的温度为80-250℃。The method for continuously producing base oil from chlorosilicon-containing waste mineral oil according to claim 1 is characterized in that: in step (4), the adsorbent during the adsorption desiliconization reaction is a chelating resin with active magnesium oxide attached to the surface, the chelating resin is an iminodiacetic acid chelating resin, an iminodiacetaldehyde oxime chelating resin or a thiourea chelating resin, and the loading concentration of active magnesium oxide is 0.05-0.5wt.%; the temperature of the adsorption desiliconization reaction is 80-250°C.
  10. 一种实现权利要求1-9任一所述方法的含氯硅的废矿物油连续生产基础油的系统，其特征在于：包括依次相连的废矿物油储罐(1)、热沉降装置(2)、闪蒸装置(3)、重油脱氯反应器(13)、脱金属反应器(11)、减压蒸馏装置(10)、吸附脱硅罐(18)、加氢原料缓冲罐(17)、加氢反应器(16)、精馏塔(15)和产品罐(22)；A system for continuously producing base oil from chlorinated silicon-containing waste mineral oil according to any one of claims 1 to 9, characterized in that it comprises a waste mineral oil storage tank (1), a heat settling device (2), a flash evaporation device (3), a heavy oil dechlorination reactor (13), a demetallization reactor (11), a vacuum distillation device (10), an adsorption desiliconization tank (18), a hydrogenation raw material buffer tank (17), a hydrogenation reactor (16), a distillation tower (15) and a product tank (22) connected in sequence;
    所述的减压蒸馏装置(10)底部还通过渣油中间储罐(9)、深度膜过滤装置(19)与吸附脱硅罐(18)连接；所述的闪蒸装置(3)还与油水分离罐(4)、轻油脱氯反应器(7)、轻油中间储罐(8)依次相连，轻油中间储罐(8)还与渣油中间储罐(9)连接；所述的热沉降装置(2)还连接油泥回收罐(21)，油泥回收罐(21)再与闪蒸装置(3)连接；减压蒸馏装置(10)的顶部还连接轻油脱氯反应器(7)；The bottom of the vacuum distillation device (10) is also connected to the adsorption desiliconization tank (18) through the residual oil intermediate storage tank (9) and the deep membrane filtration device (19); the flash evaporation device (3) is also connected to the oil-water separation tank (4), the light oil dechlorination reactor (7), and the light oil intermediate storage tank (8) in sequence, and the light oil intermediate storage tank (8) is also connected to the residual oil intermediate storage tank (9); the heat settling device (2) is also connected to the sludge recovery tank (21), and the sludge recovery tank (21) is further connected to the flash evaporation device (3); the top of the vacuum distillation device (10) is also connected to the light oil dechlorination reactor (7);
    所述的油水分离罐(4)与轻油脱氯反应器(7)之间的管路连接轻油脱氯剂储罐(6)，闪蒸装置(3)与重油脱氯反应器(13)之间的管路连接重油脱氯剂储罐(14)，重油脱氯反应器(13)与脱金属反应器(11)之间的管路连接脱金属剂储罐(12)；油水分离罐(4)还连接废水罐(5)，深度膜过滤装置(19)还连接焚烧炉(20)。The pipeline between the oil-water separation tank (4) and the light oil dechlorination reactor (7) is connected to the light oil dechlorination agent storage tank (6), the pipeline between the flash device (3) and the heavy oil dechlorination reactor (13) is connected to the heavy oil dechlorination agent storage tank (14), and the pipeline between the heavy oil dechlorination reactor (13) and the demetallization reactor (11) is connected to the demetallization agent storage tank (12); the oil-water separation tank (4) is also connected to the wastewater tank (5), and the deep membrane filtration device (19) is also connected to the incinerator (20).
PCT/CN2022/130151 2022-11-03 2022-11-05 Method and system for continuously producing base oil from waste mineral oil containing chlorine and silicon WO2024092841A1 (en)

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