CN111454748B - Waste mineral oil regeneration system and regeneration method - Google Patents

Waste mineral oil regeneration system and regeneration method Download PDF

Info

Publication number
CN111454748B
CN111454748B CN202010356708.6A CN202010356708A CN111454748B CN 111454748 B CN111454748 B CN 111454748B CN 202010356708 A CN202010356708 A CN 202010356708A CN 111454748 B CN111454748 B CN 111454748B
Authority
CN
China
Prior art keywords
oil
hydrogenation reaction
mineral oil
reaction
filtering
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010356708.6A
Other languages
Chinese (zh)
Other versions
CN111454748A (en
Inventor
王庆元
曹黎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Spang Technology Co ltd
Original Assignee
Spang Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Spang Technology Co ltd filed Critical Spang Technology Co ltd
Priority to CN202010356708.6A priority Critical patent/CN111454748B/en
Publication of CN111454748A publication Critical patent/CN111454748A/en
Application granted granted Critical
Publication of CN111454748B publication Critical patent/CN111454748B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C10G2300/1007—Used oils
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/205—Metal content

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention provides a waste mineral oil regeneration system and a regeneration method, wherein the regeneration system comprises a pretreatment unit, a hydrogenation reaction unit and a fractionation unit; the pretreatment unit comprises a first mixing device, a first filtering device, a light component removal device, a thermal cracking reactor, a second mixing device, a second filtering device and a first pressure reduction fractionation device which are connected in sequence; the hydrogenation reaction unit comprises a protection reaction device, a hydrofining reaction device and a dechlorination reaction device which are connected in sequence; the fractionation unit comprises a desulfurization device, an atmospheric fractionation device and a second reduced pressure fractionation device which are connected in sequence; a middle distillate oil outlet of a first vacuum fractionation device in the pretreatment unit is connected with a protection reactor in the hydrogenation reaction unit; the discharge hole of the dechlorination reactor in the hydrogenation unit is connected with the feed inlet of the desulphurization device in the fractionation unit. According to the invention, through the arrangement of the pretreatment unit and the hydrogenation reaction unit, the regeneration rate of the waste mineral oil is improved, and the regeneration system can stably operate.

Description

Waste mineral oil regeneration system and regeneration method
Technical Field
The invention belongs to the technical field of waste treatment, relates to a treatment system and a treatment method of waste mineral oil, and particularly relates to a waste mineral oil regeneration system and a regeneration method.
Background
The waste mineral oil comprises various waste internal combustion engine oil, waste gear oil, waste hydraulic oil, waste transformer oil, waste compressor oil and waste turbine oil, is a complex mixture consisting of a plurality of substances, and mainly comprises C15-C39 alkane, polycyclic aromatic hydrocarbon, olefin and phenols, wherein a plurality of components have certain toxicity and harm effects on human bodies, so that serious environmental pollution is caused once the waste mineral oil enters the environment; moreover, the waste mineral oil can also destroy the normal living environment of organisms, and cause biological dysfunction.
From the analysis of mineral oil deterioration mechanism, most mineral oil is not really discarded, only part of hydrocarbons in the oil product are deteriorated and account for about 10-25% of the hydrocarbons in the mineral oil, and most of the hydrocarbons still form the main viscosity carriers and effective components of the mineral oil. The method is characterized in that the waste mineral oil can be regenerated into base oil meeting the requirements by removing deteriorated dirt and impurities in the waste oil through a physical and/or chemical method, so how to effectively remove the impurities in the waste mineral oil is the key for recycling and reusing the waste mineral oil. The method can recover and regenerate the polluted waste mineral oil, not only save petroleum resources, but also be a main measure for protecting the environment and preventing the pollution of the waste oil.
CN 105038849 a discloses a system for recycling waste mineral oil and a process thereof, the system comprises: the device comprises a solar heating device, a vacuum treatment device, a centrifugal circulation treatment device, a vibrating membrane separation device and a collection device. This regeneration processing system has reduced the temperature of separation processing through vacuum treatment device and vibrating membrane separator's setting, but the treatment effeciency is lower, and waste mineral oil edulcoration effect is not good.
CN 104560354 a discloses a method and a system for recovering and regenerating waste mineral oil, the method comprises the following steps: sequentially carrying out sedimentation, neutralization, alkaline washing delamination and dehydration on the waste mineral oil to form a clear liquid of the waste mineral oil after impurity removal; preheating the clear liquid to 160-180 ℃, entering a fractionating tower, and distilling and separating solvent oil components under the absolute pressure of 50-100 Pa; the residual components after the solvent oil separation enter a first-line short-path distiller to distill and separate first-line base oil at the absolute pressure of 5-10Pa and the temperature of 220-; the residual components after the first-line base oil separation enter a second-line short-path distiller to distill and separate second-line base oil at the absolute pressure of not more than 5Pa and the temperature of 220-240 ℃. This method not only produces a large amount of exhaust emissions, but also causes a problem of high cost because of the need for more short-range rectifiers.
The traditional process of distillation, solvent extraction and clay refining not only causes atmospheric pollution, but also the product can only reach the index of I-type base oil, and the added value of the product is low. In addition, secondary pollution of argil is caused in the process of regenerating the waste mineral oil, and the requirement of environmental protection is difficult to achieve. Meanwhile, in the traditional technology, a decompression tower used for pretreating the waste mineral oil is easy to block and coke, coke cleaning treatment needs to be carried out every two months, and the efficiency is low; the obtained product has high sulfur and chlorine content and cannot be used as a lubricating oil blending raw material.
Aiming at the defects in the prior art, a new regeneration system and a new regeneration method are provided for the regeneration of the waste mineral oil, and the regeneration system and the regeneration method have important significance for improving the utilization rate of the waste mineral oil and improving the quality of the obtained oil product.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a waste mineral oil regeneration system and a regeneration method, wherein the regeneration system can remove metal elements in the waste mineral oil, can also remove non-metal impurities in the waste mineral oil, and can recover and obtain diesel oil, asphalt and naphtha; the regeneration method is simple to operate, and high-quality mineral base oil can be obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a waste mineral oil regeneration system, which is characterized by comprising a pretreatment unit, a hydrogenation reaction unit and a fractionation unit which are connected in sequence.
The pretreatment unit comprises a first mixing device, a first filtering device, a light component removal device, a thermal cracking reactor, a second mixing device, a second filtering device and a first pressure reduction fractionation device which are sequentially connected.
The hydrogenation reaction unit comprises a protection reaction device, a hydrofining reaction device and a dechlorinating reaction device which are connected in sequence.
The fractionating unit comprises a desulfurization device, an atmospheric fractionating device and a second reduced pressure fractionating device which are connected in sequence.
A middle distillate oil outlet of a first vacuum fractionation device in the pretreatment unit is connected with a protection reaction device in the hydrogenation reaction unit; the discharge hole of the dechlorination reaction device in the hydrogenation reaction unit is connected with the feed hole of the desulphurization device in the fractionation unit.
The waste mineral oil is firstly mixed with a first medicament in a first mixing device, the mixture is filtered by a first filtering device to remove heavy metal impurities in the waste mineral oil and then flows into a light component removing device, dehydration and light component removal are carried out in the light component removing device, and oil components after dehydration and light component removal flow into a thermal cracking reactor to be thermally cracked. And mixing the oil component after the thermal cracking with a second medicament, filtering to remove floccules generated after the thermal cracking, and then flowing into a first reduced pressure fractionation device for reduced pressure fractionation to remove diesel oil and asphalt, thereby obtaining the middle distillate oil for the hydrogenation reaction unit. After the waste mineral oil is treated by the pretreatment unit, the metal removal rate can reach more than 95 percent, and the service life of a hydrogenation reaction catalyst in the hydrogenation reaction unit is prolonged.
The middle distillate oil sequentially flows through the protective reaction device, the hydrofining reaction device and the dechlorination reaction device, the reaction temperature in the protective reaction device is lower than that of the hydrofining reaction device, so that substances easy to coke are converted in the protective reaction device, and the substances easy to coke are prevented from condensing and forming coke in a high-temperature area; the dechlorination reaction device is used for removing HCl generated by hydrogenation reaction and preventing the HCl from corroding subsequent equipment.
The oil component after dechlorination sequentially flows through a desulfurization device, an atmospheric pressure fractionation device and a second reduced pressure fractionation device, wherein the desulfurization device is used for removing sulfur-containing rich gas, the atmospheric pressure fractionation device is used for removing naphtha and diesel oil, and the second reduced pressure fractionation device is used for completing product cutting of mineral oil base oil, so that the regeneration of the waste mineral oil is completed.
Preferably, the second vacuum fractionation device is a side-draw stripper.
Preferably, the first mixing device and the second mixing device are respectively independent mixing devices with stirring paddles.
Preferably, the first vacuum fractionation device is a vacuum fractionation tower; the desulfurization device is a desulfurization tower; the atmospheric fractionating device is an atmospheric fractionating tower.
Preferably, the first filter means has a filter fineness of 40-80 μm, for example 40 μm, 50 μm, 60 μm, 70 μm or 80 μm, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the second filter means has a filter fineness of 15 to 25 μm, for example 15 μm, 18 μm, 20 μm, 21 μm, 24 μm or 25 μm, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the waste mineral oil regeneration system further comprises an impurity removal device arranged before the first mixing device. The impurity removal device is an impurity removal device for removing solid impurities in waste mineral oil, and comprises but is not limited to a centrifuge, and a person skilled in the art can reasonably select the impurity removal device according to the content of the solid impurities in the waste mineral oil.
Preferably, the guard reaction means comprises at least 1 guard reactor. When the number of the protection reactors is at least 2, the protection reactors are connected in parallel, so that a plurality of protection reactors can be switched to use.
The protective reaction device, the hydrofining reaction device and the dechlorinating reaction device are reaction devices commonly used in hydrogenation reaction in the field, and the models of the protective reaction device, the hydrofining reaction device and the dechlorinating reaction device are not limited too much.
Preferably, an oil-gas-water three-phase separator is further arranged between the dechlorination reaction device and the desulfurization device, the separated hydrogen is reused for hydrogenation reaction, and the separated oil phase flows into the desulfurization device.
In a second aspect, the present invention provides a method for regenerating a waste mineral oil, the method being performed using the waste mineral oil regeneration system according to the first aspect, the method comprising the steps of:
(1) mixing the waste mineral oil with a first medicament, filtering, and then sequentially carrying out dehydration and light removal treatment and thermal cracking treatment;
(2) mixing the oil generated by the thermal cracking treatment in the step (1) with a second agent, filtering, heating the oil obtained after filtering, and performing reduced pressure fractionation to obtain middle distillate oil with the distillation range of 220-;
(3) sequentially carrying out a first hydrogenation reaction and a second hydrogenation reaction on the middle distillate oil obtained in the step (2), and carrying out a dechlorination reaction on the oil component obtained in the second hydrogenation reaction;
(4) and (3) carrying out desulfurization treatment, normal-pressure fractionation treatment and reduced-pressure cutting treatment on the oil component obtained after the dechlorination reaction in the step (3) in sequence, thereby completing the regeneration of the waste mineral oil.
The first agent provided by the invention has the function of interacting with heavy metal ions in the waste mineral oil so as to facilitate the removal of the heavy metal ions. Preferably, the first agent of step (1) comprises any one of or a combination of at least two of a polymer of a mono-alcohol and/or a diol, a quaternary ammonium salt, a quaternary phosphonium salt, a phosphate salt or a sulphate salt.
Preferably, the first agent in step (1) is 0.01-0.5% by mass of the waste mineral oil, for example, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4% or 0.5%, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the temperature of the mixing in step (1) is 60-90 ℃, for example 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the filtration precision of the filtration in step (1) is 40-80 μm, for example, 40 μm, 50 μm, 60 μm, 70 μm or 80 μm, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the thermal cracking treatment in step (1) is carried out at a temperature of 280-330 ℃, such as 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃ or 330 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
The second medicament of the invention has the function of polymerizing floccules generated by thermal cracking, thereby ensuring the filtering effect and further ensuring the subsequent hydrogenation reaction to be smoothly carried out.
Preferably, the second medicament of step (2) comprises, in parts by weight: SiO 2240-60 parts, for example 40 parts, 45 parts, 50 parts, 55 parts or 60 parts, but not limited to the cited values, and other values not listed in the numerical range are equally applicable; al (Al)2O315-30 parts, for example 15 parts, 18 parts, 20 parts, 25 parts or 30 parts, but not limited to the values listed, other values not listed in the numerical range also applying; fe2O35 to 10 parts, for example 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, but not limited to the cited values, and other values not listed in the numerical ranges are equally applicable; 1 to 5 parts, for example 1, 2, 3, 4 or 5 parts, of FeO, but not limited to the values listed, and other values not listed within the numerical range are equally applicable; 1 to 5 parts, for example, 1 part of MgO,2 parts, 3 parts, 4 parts or 5 parts, but are not limited to the values listed, and other values not listed in the numerical range are equally applicable; CaO in an amount of 1 to 5 parts, for example, 1 part, 2 parts, 3 parts, 4 parts or 5 parts, is not limited to the above-mentioned values, and other values not shown in the above-mentioned numerical ranges are also applicable.
Preferably, the second agent in step (2) is used in an amount of 0.5-2 wt% of the oil component produced by the thermal cracking process in step (1), for example, 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, or 2 wt%, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature of the mixing in step (2) is 100-150 ℃, for example, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, but not limited to the recited values, and other unrecited values within the range of values are equally applicable.
Preferably, the filtration precision of the filtration in step (2) is 15-25 μm, for example 15 μm, 18 μm, 20 μm, 21 μm, 24 μm or 25 μm, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the temperature of the oil component after heating in step (2) is 300-.
The temperature of the heated oil component is the temperature of the oil component entering the first vacuum fractionation device.
Preferably, the temperature of the first hydrogenation reaction in step (3) is 240-; gauge pressure is 10 to 12MPa, for example 10MPa, 10.5MPa, 11MPa, 11.5MPa or 12MPa, but is not limited to the values listed, and other values not listed in the numerical range are also applicable; the volume space velocity is 0.2-2h-1For example, it may be 0.2h-1、0.5h-1、1h-1、 1.5h-1Or 2h-1But are not limited to the recited values, and other values within the numerical range not recited are equally applicable.
Preferably, the temperature of the second hydrogenation reaction is 300-380 ℃, for example, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃ or 380 ℃ can be used, but not limited to the recited values, and other values not recited in the numerical range are also applicable; gauge pressure is 10 to 12MPa, for example 10MPa, 10.5MPa, 11MPa, 11.5MPa or 12MPa, but is not limited to the values listed, and other values not listed in the numerical range are also applicable; the volume space velocity is 0.5-2h-1For example, it may be 0.5h-1、 0.8h-1、1h-1、1.2h-1、1.5h-1、1.8h-1Or 2h-1But are not limited to the recited values, and other values within the numerical range not recited are equally applicable.
Preferably, the dechlorination temperature is 260-300 ℃, such as 260 ℃, 270 ℃, 280 ℃, 290 ℃ or 300 ℃, but not limited to the recited values, and other values not recited in the numerical range are equally applicable; gauge pressure is 10 to 12MPa, for example 10MPa, 10.5MPa, 11MPa, 11.5MPa or 12MPa, but is not limited to the values listed, and other values not listed in the numerical range are also applicable; the volume space velocity is 0.5-2h-1For example, it may be 0.5h-1、0.8h-1、1h-1、1.2h-1、1.5h-1、1.8h-1Or 2h-1But are not limited to the recited values, and other values within the numerical range not recited are equally applicable.
As a preferable embodiment of the regeneration method of the present invention, the regeneration method comprises the steps of:
(1) mixing the waste mineral oil and the first medicament at 60-90 ℃, and filtering, wherein the filtering precision of the filtering is 40-80 μm; then, dehydration and lightness removal treatment and thermal cracking treatment are sequentially carried out; the first agent is 0.01-0.5% of the waste mineral oil by mass; the temperature of thermal cracking treatment is 280-330 ℃;
(2) mixing the oil produced by the thermal cracking treatment in the step (1) with a second medicament, and filtering, wherein the filtering precision of the filtering is 15-25 mu m, and the dosage of the second medicament is 0.5-2 wt% of the oil produced by the thermal cracking treatment in the step (1); heating the oil component obtained after filtration to the temperature of 300-370 ℃ and then carrying out reduced pressure fractionation to obtain middle distillate oil with the distillation range of 220-520 ℃; the temperature of the mixing is 100-150 ℃;
(3) sequentially carrying out a first hydrogenation reaction and a second hydrogenation reaction on the middle distillate oil obtained in the step (2), and carrying out a dechlorination reaction on the oil component obtained in the second hydrogenation reaction; the temperature of the first hydrogenation reaction is 240-300 ℃, the gauge pressure is 10-12MPa, and the volume space velocity is 0.2-2h-1(ii) a The temperature of the second hydrogenation reaction is 300-380 ℃, the gauge pressure is 10-12MPa, and the volume space velocity is 0.5-2h-1(ii) a The temperature of the dechlorination reaction is 260-300 ℃, the gauge pressure is 10-12MPa, and the volume space velocity is 0.5-2h-1；
(4) And (3) carrying out desulfurization treatment, normal-pressure fractionation treatment and reduced-pressure cutting treatment on the oil component obtained after the dechlorination reaction in the step (3) in sequence, thereby completing the regeneration of the waste mineral oil.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, through the arrangement of the pretreatment unit, metal elements in the waste mineral oil can be removed, so that the metal removal rate reaches more than 95%, and the service life of the catalyst in the hydrogenation reaction unit is prolonged;
(2) according to the invention, through the arrangement of the protection reaction device in the hydrogenation reaction unit, the substance easy to coke is converted in the protection reaction device, and the substance easy to coke is prevented from condensing and coking in a high-temperature area; the dechlorination reaction device is used for removing HCl generated by hydrogenation reaction and preventing the HCl from corroding subsequent equipment.
Drawings
FIG. 1 is a schematic view showing the construction of a waste mineral oil recycling system according to example 1;
fig. 2 is a schematic structural view of a waste mineral oil recycling system provided in example 1.
Wherein: 1, a first stirring tank; 2, a first filter; 3, a light component removal tower; 4, a thermal cracking reactor; 5, a second stirring tank; 6, a second filter; 7, a vacuum fractionating tower; 8, protecting the reactor; 9, a hydrofining reactor; 10, a dechlorination reactor; 11, an oil-gas-water three-phase separator; 12, a desulfurizing tower; 13, an atmospheric fractionating tower; and 14, decompressing and fractionating the stripping tower.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a waste mineral oil regeneration system, and a schematic structural diagram of the waste mineral oil regeneration system is shown in fig. 1, and the waste mineral oil regeneration system comprises a pretreatment unit, a hydrogenation reaction unit and a fractionation unit which are connected in sequence.
The pretreatment unit comprises a first stirring tank 1, a first filter 2, a light component removal tower 3, a thermal cracking reactor 4, a second stirring tank 5, a second filter 6 and a reduced pressure fractionating tower 7 which are connected in sequence; the filtering precision of the first filter 2 is 40-80 μm, and the filtering precision of the second filter device is 15-25 μm.
The hydrogenation reaction unit comprises a protection reaction device, a hydrofining reactor 9 and a dechlorinating reactor 10 which are connected in sequence. The protection reaction device comprises 2 protection reactors 8 connected in parallel, and the 2 protection reactors 8 are switched for use.
The fractionating unit comprises a desulfurizing tower 12, an atmospheric fractionating tower 13 and a vacuum fractionating stripping tower 14 which are connected in sequence.
A middle distillate oil outlet of a vacuum fractionating tower 7 in the pretreatment unit is connected with a protective reactor 8 in the hydrogenation reaction unit; the discharge hole of the dechlorination reactor 10 in the hydrogenation unit is connected with the feed hole of the desulfurizing tower 12 in the fractionating unit. An oil-gas-water three-phase separator 11 is further arranged between the dechlorination reactor 10 and the desulfurizing tower 12, the separated hydrogen is reused for hydrogenation reaction, and the separated oil phase flows into the desulfurizing tower 12.
The waste mineral oil is firstly mixed with a first medicament in a first stirring tank 1, the mixture is filtered by a first filter 2 and flows into a lightness-removing tower 3, dehydration and lightness removal are carried out in the lightness-removing tower 3, and oil content after dehydration and lightness removal flows into a thermal cracking reactor 4 for thermal cracking. The oil after the thermal cracking and the second agent are mixed in the second stirring tank 5, then filtered in the second filter 6, and then flow into the reduced pressure fractionating tower 7 for reduced pressure fractionation to remove diesel oil and asphalt, and obtain middle distillate oil with the distillation range of 220-520 ℃ for the hydrogenation reaction unit. After the waste mineral oil is treated by the pretreatment unit, the metal removal rate can reach more than 95 percent, and the service life of a hydrogenation reaction catalyst in the hydrogenation reaction unit is prolonged.
The middle distillate oil sequentially flows through a protective reactor 8, a hydrofining reactor 9 and a dechlorinating reactor 10, the reaction temperature in the protective reactor 8 is lower than that of a hydrofining reactor, so that substances easy to coke are converted in the protective reactor 8, and the substances easy to coke are prevented from being condensed and coked in a high-temperature area; the dechlorination reactor 10 is used for removing HCl generated by hydrogenation reaction, and preventing the corrosion of HCl to subsequent equipment.
The oil component after dechlorination sequentially passes through a desulfurizing tower 12, an atmospheric fractionating tower 13 and a reduced pressure fractionating stripping tower 14, wherein the desulfurizing tower 12 is used for removing sulfur-containing rich gas, the atmospheric fractionating tower 13 is used for removing naphtha and diesel oil, and the reduced pressure fractionating stripping tower 14 is used for completing the product cutting of mineral oil base oil, so that the regeneration of the waste mineral oil is completed.
Example 2
This embodiment provides a waste mineral oil regeneration system, compared with embodiment 1, further including a centrifuge disposed before the first agitation tank 1.
The waste mineral oil with solid impurities removed by the centrifuge is firstly mixed with a first medicament in a first stirring tank 1, the mixture is filtered by a first filter 2 and then flows into a lightness-removing tower 3, dehydration and lightness removal are carried out in the lightness-removing tower 3, and oil content after dehydration and lightness removal flows into a thermal cracking reactor 4 for thermal cracking. The oil after the thermal cracking and the second agent are mixed in the second stirring tank 5, then filtered in the second filter 6, and then flow into the reduced pressure fractionating tower 7 for reduced pressure fractionation to remove diesel oil and asphalt, and obtain middle distillate oil with the distillation range of 220-520 ℃ for the hydrogenation reaction unit. After the waste mineral oil is treated by the pretreatment unit, the metal removal rate can reach more than 95 percent, and the service life of a hydrogenation reaction catalyst in the hydrogenation reaction unit is prolonged.
The middle distillate oil sequentially flows through a protective reactor 8, a hydrofining reactor 9 and a dechlorinating reactor 10, the reaction temperature in the protective reactor 8 is lower than that of a hydrofining reactor, so that substances easy to coke are converted in the protective reactor 8, and the substances easy to coke are prevented from being condensed and coked in a high-temperature area; the dechlorination reactor 10 is used for removing HCl generated by hydrogenation reaction, and preventing the corrosion of HCl to subsequent equipment.
The oil component after dechlorination sequentially passes through a desulfurizing tower 12, an atmospheric fractionating tower 13 and a reduced pressure fractionating stripping tower 14, wherein the desulfurizing tower 12 is used for removing sulfur-containing rich gas, the atmospheric fractionating tower 13 is used for removing naphtha and diesel oil, and the reduced pressure fractionating stripping tower 14 is used for completing the product cutting of mineral oil base oil, so that the regeneration of the waste mineral oil is completed.
Comparative example 1
This comparative example provides a system for regenerating a waste mineral oil, which has a schematic structural view as shown in fig. 2 and includes a pretreatment unit, a hydrogenation reaction unit, and a fractionation unit connected in sequence.
The pretreatment unit comprises a first stirring tank 1, a first filter 2, a light component removal tower 3, a thermal cracking reactor 4, a second stirring tank 5, a second filter 6 and a reduced pressure fractionating tower 7 which are connected in sequence; the filtering precision of the first filter 2 is 40-80 μm, and the filtering precision of the second filter device is 15-25 μm.
The hydrogenation reaction unit comprises a hydrofining reactor 9 and a dechlorinating reactor 10 which are sequentially connected.
The fractionating unit comprises a desulfurizing tower 12, an atmospheric fractionating tower 13 and a vacuum fractionating stripping tower 14 which are connected in sequence.
A middle distillate oil outlet of a vacuum fractionating tower 7 in the pretreatment unit and a hydrofining reactor 9; the discharge hole of the dechlorination reactor 10 in the hydrogenation reaction unit is connected with the feed hole of the desulfurizing tower 12 in the fractionating unit. An oil-gas-water three-phase separator 11 is further arranged between the dechlorination reactor 10 and the desulfurizing tower 12, the separated hydrogen is reused for hydrogenation reaction, and the separated oil phase flows into the desulfurizing tower 12.
The waste mineral oil is firstly mixed with a first medicament in a first stirring tank 1, the mixture is filtered by a first filter 2 and flows into a lightness-removing tower 3, dehydration and lightness removal are carried out in the lightness-removing tower 3, and oil content after dehydration and lightness removal flows into a thermal cracking reactor 4 for thermal cracking. The oil after the thermal cracking and the second agent are mixed in the second stirring tank 5, filtered by the second filter 6, and then flow into the reduced pressure fractionating tower 7 for reduced pressure fractionation to remove diesel oil and asphalt, and the middle distillate with the distillation range of 220-520 ℃ for the hydrogenation reaction unit is obtained. After the waste mineral oil is treated by the pretreatment unit, the metal removal rate can reach more than 95 percent, and the service life of a hydrogenation reaction catalyst in the hydrogenation reaction unit is prolonged.
The middle distillate oil sequentially flows through the hydrofining reactor 9 and the dechlorinating reactor 10, and as the hydrofining reactor 9 is directly used for treating the middle distillate oil in the comparative example, substances which are easy to coke in the middle distillate oil are condensed in the hydrofining reactor 9 to form coke, so that the use of the hydrofining reactor is influenced; the dechlorination reactor 10 is used for removing HCl generated by hydrogenation reaction, and preventing the corrosion of HCl to subsequent equipment.
The oil component after dechlorination sequentially passes through a desulfurizing tower 12, an atmospheric fractionating tower 13 and a reduced pressure fractionating stripping tower 14, wherein the desulfurizing tower 12 is used for removing sulfur-containing rich gas, the atmospheric fractionating tower 13 is used for removing naphtha and diesel oil, and the reduced pressure fractionating stripping tower 14 is used for completing the product cutting of mineral oil base oil, so that the regeneration of the waste mineral oil is completed.
Application example 1
The present application example provides a method for regenerating a waste mineral oil, which is a waste internal combustion engine oil having an ash content of 1.3 wt% and a metal content of 4000mg/Kg, using the waste mineral oil regeneration system provided in application example 1, and the method includes the steps of:
(1) mixing the waste mineral oil and diammonium hydrogen phosphate at 75 ℃, and filtering, wherein the filtering precision of the filtering is 60 mu m; then, dehydration and lightness removal treatment and thermal cracking treatment are sequentially carried out; the using amount of diammonium phosphate is 0.3 percent of the mass of the waste mineral oil; the temperature of the thermal cracking treatment is 310 ℃;
(2) mixing the oil produced by the thermal cracking treatment in the step (1) with a second medicament at 120 ℃, and filtering, wherein the filtering precision of the filtering is 20 mu m, and the dosage of the second medicament is 1 wt% of the oil produced by the thermal cracking treatment in the step (1); heating the oil component obtained after filtration to 350 ℃, and then carrying out reduced pressure fractionation to obtain middle distillate oil with the distillation range of 220-520 ℃;
(3) sequentially carrying out a first hydrogenation reaction and a second hydrogenation reaction on the middle distillate oil obtained in the step (2), and carrying out a dechlorination reaction on the oil component obtained in the second hydrogenation reaction; the temperature of the first hydrogenation reaction is 270 ℃, the gauge pressure is 11MPa, and the volume space velocity is 1h-1(ii) a The temperature of the second hydrogenation reaction is 350 ℃, the gauge pressure is 11MPa, and the volume space velocity is 1h-1(ii) a The temperature of the dechlorination reaction is 280 ℃, the gauge pressure is 11MPa, and the volume space velocity is 1h-1；
(4) And (3) carrying out desulfurization treatment, normal-pressure fractionation treatment and reduced-pressure cutting treatment on the oil component obtained after the dechlorination reaction in the step (3) in sequence, thereby completing the regeneration of the waste mineral oil.
The second medicament comprises 50 parts of SiO by weight221 parts of Al2O38 parts of Fe2O33 parts of FeO, 3 parts of MgO and 3 parts of CaO.
The method in RIPP124ICP-AES is adopted for testing, the ash content in the middle distillate oil obtained in the step (2) is 0.12 wt%, and the metal removal rate is 99.5% when the metal content is 20 mg/Kg; and through the arrangement of the first hydrogenation reaction and the second hydrogenation reaction, the easily-coked substance is converted in the first hydrogenation reaction, the easily-coked substance is prevented from coking and condensing in a high-temperature region, and the sulfur content in the oil component obtained after the reduced pressure cutting treatment is less than or equal to 50ug/g and the chromaticity is less than or equal to 0.5.
Application example 2
The present application example provides a method for regenerating waste mineral oil by using the waste mineral oil regeneration system provided in application example 1, where the waste mineral oil is waste hydraulic oil having a metal content of 900mg/kg, and the method includes the steps of:
(1) mixing the waste mineral oil and ammonium bisulfate at 70 ℃, and filtering, wherein the filtering precision of the filtering is 50 mu m; then dehydration and lightness removal treatment and thermal cracking treatment are sequentially carried out; the ammonium bisulfate accounts for 0.1 percent of the mass of the waste mineral oil; the temperature of thermal cracking treatment is 300 ℃;
(2) mixing the oil produced by the thermal cracking treatment in the step (1) with a second medicament at the temperature of 110 ℃, and filtering, wherein the filtering precision of the filtering is 18 mu m, and the dosage of the second medicament is 0.8 wt% of the oil produced by the thermal cracking treatment in the step (1); heating the oil component obtained after filtration to 320 ℃, and then carrying out reduced pressure fractionation to obtain middle distillate oil with the distillation range of 220-520 ℃;
(3) sequentially carrying out a first hydrogenation reaction and a second hydrogenation reaction on the middle distillate oil obtained in the step (2), and carrying out a dechlorination reaction on the oil component obtained in the second hydrogenation reaction; the temperature of the first hydrogenation reaction is 250 ℃, the gauge pressure is 11.5MPa, and the volume space velocity is 1.5h-1(ii) a The temperature of the second hydrogenation reaction is 320 ℃, the gauge pressure is 11.5MPa, and the volume space velocity is 1.5h-1(ii) a The temperature of the dechlorination reaction is 270 ℃, the gauge pressure is 11.5MPa, and the volume space velocity is 1.5h-1；
(4) And (3) carrying out desulfurization treatment, normal-pressure fractionation treatment and reduced-pressure cutting treatment on the oil component obtained after the dechlorination reaction in the step (3) in sequence, thereby completing the regeneration of the waste mineral oil.
The second medicament comprises 45 parts of SiO by weight227 parts of Al2O39 parts of Fe2O32 parts of FeO, 4 parts of MgO and 2 parts of CaO.
Testing by adopting a method in RIPP124ICP-AES, wherein the metal content in the middle distillate oil obtained in the step (2) is less than or equal to 20mg/Kg, and the metal removal rate is more than or equal to 97.8%; and through the arrangement of the first hydrogenation reaction and the second hydrogenation reaction, the easily-coked substance is converted in the first hydrogenation reaction, the easily-coked substance is prevented from coking and condensing in a high-temperature region, the sulfur content in the oil component obtained after the reduced pressure cutting treatment is less than or equal to 10ug/g, and the chromaticity is less than or equal to 0.5.
Application example 3
The application example provides a method for regenerating waste mineral oil by using the waste mineral oil regeneration system provided in the application example 2, wherein the waste mineral oil is waste gear oil with the returned powder content of 1.89% and the metal content of 480mg/kg, and the method comprises the following steps:
(1) mixing the waste mineral oil with solid impurities removed by a centrifuge and a first medicament at 80 ℃, and filtering, wherein the filtering precision of the filtering is 70 mu m; then, dehydration and lightness removal treatment and thermal cracking treatment are sequentially carried out; the first agent accounts for 0.4 percent of the mass of the waste mineral oil; the temperature of thermal cracking treatment is 320 ℃; the first agent is a mixture formed by mixing ammonium sulfate and ammonium bisulfate according to the mass ratio of 1: 1;
(2) mixing the oil component produced by the thermal cracking treatment in the step (1) with a second medicament at 140 ℃, and filtering, wherein the filtering precision of the filtering is 22 mu m, and the dosage of the second medicament is 1.5 wt% of the oil component produced by the thermal cracking treatment in the step (1); heating the oil component obtained after filtration to 360 ℃, and then carrying out reduced pressure fractionation to obtain middle distillate oil with the distillation range of 220-520 ℃;
(3) sequentially carrying out a first hydrogenation reaction and a second hydrogenation reaction on the middle distillate oil obtained in the step (2), and carrying out a dechlorination reaction on the oil component obtained in the second hydrogenation reaction; the temperature of the first hydrogenation reaction is 240 ℃, the gauge pressure is 10MPa, and the volume space velocity is 2h-1(ii) a The temperature of the second hydrogenation reaction is 300 ℃, the gauge pressure is 10MPa, and the volume space velocity is 2h-1(ii) a The temperature of the dechlorination reaction is 260 ℃, the gauge pressure is 10MPa, and the volume space velocity is 2h-1；
(4) And (3) carrying out desulfurization treatment, normal-pressure fractionation treatment and reduced-pressure cutting treatment on the oil component obtained after the dechlorination reaction in the step (3) in sequence, thereby completing the regeneration of the waste mineral oil.
The second medicament comprises 40 parts of SiO by weight215 parts of Al2O310 parts of Fe2O31 part of FeO, 5 parts of MgO and 5 parts of CaO.
The method in RIPP124ICP-AES is adopted for testing, the ash content in the middle distillate oil obtained in the step (2) is 0.009 wt%, the metal content is less than or equal to 18mg/Kg, and the metal removal rate is more than or equal to 96.3%; and through the arrangement of the first hydrogenation reaction and the second hydrogenation reaction, the easily-coked substance is converted in the first hydrogenation reaction, the easily-coked substance is prevented from coking and condensing in a high-temperature region, the sulfur content in the oil component obtained after the reduced pressure cutting treatment is less than or equal to 10ug/g, and the chromaticity is less than or equal to 0.5.
Application example 4
The application example provides a method for regenerating waste mineral oil by using the waste mineral oil regeneration system provided in the embodiment 2, wherein the waste mineral oil is waste compressor oil with ash content of 0.052% and metal content of 1056mg/kg, and the method comprises the following steps:
(1) mixing the waste mineral oil with solid impurities removed by a centrifuge and a first medicament at 60 ℃, and filtering, wherein the filtering precision of the filtering is 80 mu m; then, dehydration and lightness removal treatment and thermal cracking treatment are sequentially carried out; the first agent accounts for 0.01 percent of the mass of the waste mineral oil; the temperature of thermal cracking treatment is 280 ℃; the first medicament is a combination of glycerol and diammonium hydrogen phosphate in a mass ratio of 1: 1;
(2) mixing the oil component generated by the thermal cracking treatment in the step (1) with a second medicament at 100 ℃, and filtering, wherein the filtering precision of the filtering is 15 mu m, and the dosage of the second medicament is 0.5 wt% of the oil component generated by the thermal cracking treatment in the step (1); heating the oil component obtained after filtration to 300 ℃, and then carrying out reduced pressure fractionation to obtain the middle distillate with the distillation range of 220-520 ℃;
(3) sequentially carrying out a first hydrogenation reaction and a second hydrogenation reaction on the middle distillate oil obtained in the step (2), and carrying out a dechlorination reaction on the oil component obtained in the second hydrogenation reaction; the temperature of the first hydrogenation reaction is 280 ℃, the gauge pressure is 10.5MPa, and the volume space velocity is 0.2h-1(ii) a The temperature of the second hydrogenation reaction is 360 ℃, the gauge pressure is 10.5MPa, and the volume space velocity is 0.5h-1(ii) a The temperature of the dechlorination reaction is 300 ℃, the gauge pressure is 10.5MPa, and the volume space velocity is 0.5h-1；
(4) And (3) carrying out desulfurization treatment, normal-pressure fractionation treatment and reduced-pressure cutting treatment on the oil component obtained after the dechlorination reaction in the step (3) in sequence, thereby completing the regeneration of the waste mineral oil.
The second medicament comprises 55 parts of SiO by weight218 parts of Al2O36 parts of Fe2O34 parts of FeO, 2 parts of MgO and 4 parts of CaO.
The method in RIPP124ICP-AES is adopted for testing, the ash content in the middle distillate oil obtained in the step (2) is 0.02 percent, the metal content is less than or equal to 15mg/Kg, and the metal removal rate is more than or equal to 98.6 percent; and through the arrangement of the first hydrogenation reaction and the second hydrogenation reaction, the easily-coked substance is converted in the first hydrogenation reaction, the easily-coked substance is prevented from coking and condensing in a high-temperature region, the sulfur content in the oil component obtained after the reduced pressure cutting treatment is less than or equal to 10ug/g, and the chromaticity is less than or equal to 0.5.
Application example 5
The application example provides a method for regenerating waste mineral oil by using the waste mineral oil regeneration system provided in the application example 2, wherein the waste mineral oil is waste wash oil with ash content of 1.76% and metal content of 3680mg/Kg, and the method comprises the following steps:
(1) mixing the waste mineral oil from which solid impurities are removed by a centrifugal machine with ammonium phosphate at 90 ℃, and filtering, wherein the filtering precision of the filtering is 40 mu m; then dehydration and lightness removal treatment and thermal cracking treatment are sequentially carried out; ammonium phosphate accounts for 0.51 percent of the mass of the waste mineral oil; the temperature of the thermal cracking treatment is 330 ℃;
(2) mixing the oil produced by the thermal cracking treatment in the step (1) with a second medicament at the temperature of 150 ℃, and filtering, wherein the filtering precision of the filtering is 25 mu m, and the dosage of the second medicament is 2 wt% of the oil produced by the thermal cracking treatment in the step (1); heating the oil component obtained after filtration to 370 ℃, and then carrying out reduced pressure fractionation to obtain middle distillate oil with the distillation range of 220-520 ℃;
(3) sequentially carrying out a first hydrogenation reaction and a second hydrogenation reaction on the middle distillate oil obtained in the step (2), and carrying out a dechlorination reaction on the oil component obtained in the second hydrogenation reaction; the temperature of the first hydrogenation reaction is 300 ℃, the gauge pressure is 12MPa, and the volume space velocity is 0.5h-1(ii) a The temperature of the second hydrogenation reaction is 380 ℃, the gauge pressure is 12MPa, and the volume space velocity is 0.2h-1(ii) a The temperature of the dechlorination reaction is 290 ℃, the gauge pressure is 12MPa, and the volume space velocity is 0.8h-1；
(4) And (3) carrying out desulfurization treatment, normal-pressure fractionation treatment and reduced-pressure cutting treatment on the oil component obtained after the dechlorination reaction in the step (3) in sequence, thereby completing the regeneration of the waste mineral oil.
In parts by weightThe second agent comprises 60 parts of SiO230 parts of Al2O35 parts of Fe2O35 parts of FeO, 1 part of MgO and 1 part of CaO.
The method in RIPP124ICP-AES is adopted for testing, the ash content in the middle distillate oil obtained in the step (2) is 0.27 percent, the metal content is less than or equal to 25mg/kg, and the metal removal rate is more than or equal to 99.3 percent; and through the arrangement of the first hydrogenation reaction and the second hydrogenation reaction, the easily-coked substance is converted in the first hydrogenation reaction, the easily-coked substance is prevented from coking and condensing in a high-temperature region, the sulfur content in the oil component obtained after the reduced pressure cutting treatment is less than or equal to 20ug/g, and the chromaticity is less than or equal to 0.5.
Application example 6
The application example provides a method for regenerating waste mineral oil by using the waste mineral oil regeneration system provided in the application example 1, wherein the waste mineral oil is waste internal combustion engine oil with ash content of 1.3 wt% and metal content of 4000 mg/Kg.
Compared with application example 1, the second medicament is prepared from 50 parts of SiO221 parts of Al2O38 parts of Fe2O3The composition was the same as in application example 1 except for 4.5 parts of FeO and 4.5 parts of MgO.
The method in RIPP124ICP-AES is adopted for testing, the ash content in the middle distillate oil obtained in the step (2) is more than or equal to 0.18 wt%, and the metal removal rate of the metal content of more than or equal to 46mg/Kg is less than or equal to 98.8%; and through the arrangement of the first hydrogenation reaction and the second hydrogenation reaction, the easily-coked substance is converted in the first hydrogenation reaction, the easily-coked substance is prevented from coking and condensing in a high-temperature region, and the sulfur content in the oil component obtained after the reduced pressure cutting treatment is less than or equal to 50ug/g and the chromaticity is less than or equal to 0.5.
Application example 7
The present application example provides a method for regenerating waste mineral oil, which is waste internal combustion engine oil having an ash content of 1.3 wt% and a metal content of 4000mg/Kg, using the waste mineral oil regeneration system provided in example 1.
Compared with application example 1, the second medicament is prepared from 50 parts of SiO by weight221 parts of Al2O38 parts of Fe2O3The composition was the same as in application example 1 except that the composition was changed to 4.5 parts of FeO and 4.5 parts of CaO.
The method in RIPP124ICP-AES is adopted for testing, the ash content in the middle distillate oil obtained in the step (2) is more than or equal to 0.25 wt%, and the metal removal rate of the metal content of more than or equal to 42mg/Kg is less than or equal to 99.2%; and through the arrangement of the first hydrogenation reaction and the second hydrogenation reaction, the easily-coked substance is converted in the first hydrogenation reaction, the easily-coked substance is prevented from coking and condensing in a high-temperature region, and the sulfur content in the oil component obtained after the reduced pressure cutting treatment is less than or equal to 50ug/g and the chromaticity is less than or equal to 0.5.
Application example 8
The present application example provides a method for regenerating waste mineral oil, which is waste internal combustion engine oil having an ash content of 1.3 wt% and a metal content of 4000mg/Kg, using the waste mineral oil regeneration system provided in example 1.
Compared with application example 1, the second medicament is prepared from 50 parts of SiO221 parts of Al2O38 parts of Fe2O3The composition was the same as in application example 1 except that the composition was changed to 4.5 parts of MgO and 4.5 parts of CaO.
The method in RIPP124ICP-AES is adopted for testing, the ash content in the middle distillate oil obtained in the step (2) is more than or equal to 0.34 wt%, and the metal removal rate of the metal content of more than or equal to 38mg/Kg is less than or equal to 99.0%; and through the arrangement of the first hydrogenation reaction and the second hydrogenation reaction, the easily-coked substance is converted in the first hydrogenation reaction, the easily-coked substance is prevented from coking and condensing in a high-temperature region, and the sulfur content in the oil component obtained after the reduced pressure cutting treatment is less than or equal to 50ug/g and the chromaticity is less than or equal to 0.5.
Application example 9
The present application example provides a method for regenerating waste mineral oil, which is waste internal combustion engine oil having an ash content of 1.3 wt% and a metal content of 4000mg/Kg, using the waste mineral oil regeneration system provided in example 1.
Compared with application example 1, the second medicament is prepared from 53 parts of SiO223 parts of Al2O3The same as in application example 1, except that the composition was changed to 4 parts of FeO, 4 parts of MgO, and 4 parts of CaO.
The method in RIPP124ICP-AES is adopted for testing, the ash content in the middle distillate oil obtained in the step (2) is more than or equal to 0.41 wt%, and the metal removal rate of the metal content of more than or equal to 52mg/Kg is less than or equal to 98.7%; and through the arrangement of the first hydrogenation reaction and the second hydrogenation reaction, the easily-coked substance is converted in the first hydrogenation reaction, the easily-coked substance is prevented from coking and condensing in a high-temperature region, and the sulfur content in the oil component obtained after the reduced pressure cutting treatment is less than or equal to 50ug/g and the chromaticity is less than or equal to 0.5.
Application example 10
The present application example provides a method for regenerating waste mineral oil, which is waste internal combustion engine oil having an ash content of 1.3 wt% and a metal content of 4000mg/Kg, using the waste mineral oil regeneration system provided in example 1.
Compared with application example 1, except that the second medicament consists of 64 parts of SiO by weight 212 parts of Fe2O3The composition was the same as in application example 1 except for the composition of 4 parts of FeO, 4 parts of MgO and 4 parts of CaO.
Testing by adopting a method in RIPP124ICP-AES, wherein the ash content in the middle distillate oil obtained in the step (2) is more than or equal to 0.48 wt%, and the metal removal rate of the metal content of more than or equal to 69mg/Kg is less than or equal to 98.3%; and through the arrangement of the first hydrogenation reaction and the second hydrogenation reaction, the easily-coked substance is converted in the first hydrogenation reaction, the easily-coked substance is prevented from coking and condensing in a high-temperature region, and the sulfur content in the oil component obtained after the reduced pressure cutting treatment is less than or equal to 50ug/g and the chromaticity is less than or equal to 0.5.
Application example 11
The application example provides a method for regenerating waste mineral oil by using the waste mineral oil regeneration system provided in the application example 1, wherein the waste mineral oil is waste internal combustion engine oil with ash content of 1.3 wt% and metal content of 4000 mg/Kg.
Compared with application example 1, except that the second medicament consists of 42 parts of Al by weight2O318 parts of Fe2O3The same as in application example 1, except that the composition was changed to 9 parts of FeO, 9 parts of MgO, and 10 parts of CaO.
The method in RIPP124ICP-AES is adopted for testing, the ash content in the middle distillate oil obtained in the step (2) is more than or equal to 0.45 wt%, and the metal removal rate of the metal content of more than or equal to 66mg/Kg is less than or equal to 98.3%; and through the arrangement of the first hydrogenation reaction and the second hydrogenation reaction, the easily-coked substance is converted in the first hydrogenation reaction, the easily-coked substance is prevented from coking and condensing in a high-temperature region, and the sulfur content in the oil component obtained after the reduced pressure cutting treatment is less than or equal to 50ug/g and the chromaticity is less than or equal to 0.5.
Comparative application example 1
This comparative application example provides a method for regenerating a waste mineral oil, which is a waste internal combustion engine oil having an ash content of 1.3 wt% and a metal content of 4000mg/Kg, using the waste mineral oil regeneration system provided in comparative example 1, the method including the steps of:
(1) mixing the waste mineral oil and diammonium hydrogen phosphate at 75 ℃ and filtering, wherein the filtering precision of the filtering is 60 mu m; then, dehydration and lightness removal treatment and thermal cracking treatment are sequentially carried out; the using amount of diammonium phosphate is 0.3 percent of the mass of the waste mineral oil; the temperature of thermal cracking treatment is 310 ℃;
(2) mixing the oil produced by the thermal cracking treatment in the step (1) with a second medicament at 120 ℃, and filtering, wherein the filtering precision of the filtering is 20 mu m, and the dosage of the second medicament is 1 wt% of the oil produced by the thermal cracking treatment in the step (1); heating the oil component obtained after filtration to 350 ℃, and then carrying out reduced pressure fractionation to obtain middle distillate oil with the distillation range of 220-520 ℃;
(3) carrying out hydrogenation reaction on the middle distillate oil obtained in the step (2), and carrying out dechlorination reaction on the oil component obtained in the hydrogenation reaction; the temperature of the hydrogenation reaction is 270 ℃, the gauge pressure is 11MPa, and the volume space velocity is 1h-1(ii) a The temperature of the dechlorination reaction is 280 ℃, the gauge pressure is 11MPa, and the volume space velocity is 1h-1；
(4) And (3) carrying out desulfurization treatment, normal-pressure fractionation treatment and reduced-pressure cutting treatment on the oil component obtained after the dechlorination reaction in the step (3) in sequence, thereby completing the regeneration of the waste mineral oil.
The second medicament comprises 50 parts of SiO by weight221 parts of Al2O38 parts of Fe2O33 parts of FeO, 3 parts of MgO and 3 parts of CaO.
The ash content in the middle distillate oil obtained in the step (2) is 0.12 wt%, and the metal removal rate is 99.5% when the metal content is 20 mg/Kg; but only carrying out one-time hydrogenation reaction, and the temperature of the hydrogenation reaction is lower, the hydrogenation reaction is incomplete, and the quality of the oil component obtained by finally carrying out reduced pressure cutting treatment is lower, the sulfur content is more than or equal to 0.31 percent, the nitrogen content is more than or equal to 0.12 percent, and the organic chlorine is more than or equal to 1541 mg/kg; moreover, the hydrofinishing reactor 9 cannot operate stably due to the presence of coke-prone condensation species in the middle distillate.
Comparative application example 2
This comparative application example provides a method for regenerating a waste mineral oil, which is a waste internal combustion engine oil having an ash content of 1.3 wt% and a metal content of 4000mg/Kg, using the waste mineral oil regeneration system provided in comparative example 1, the method including the steps of:
(1) mixing the waste mineral oil and diammonium hydrogen phosphate at 75 ℃, and filtering, wherein the filtering precision of the filtering is 60 mu m; then, dehydration and lightness removal treatment and thermal cracking treatment are sequentially carried out; the using amount of diammonium phosphate is 0.3 percent of the mass of the waste mineral oil; the temperature of thermal cracking treatment is 310 ℃;
(2) mixing the oil produced by the thermal cracking treatment in the step (1) with a second medicament at 120 ℃, and filtering, wherein the filtering precision of the filtering is 20 mu m, and the dosage of the second medicament is 1 wt% of the oil produced by the thermal cracking treatment in the step (1); heating the oil component obtained after filtration to 350 ℃, and then carrying out reduced pressure fractionation to obtain middle distillate oil with the distillation range of 220-520 ℃;
(3) sequentially carrying out hydrogenation reaction on the middle distillate oil obtained in the step (2), and carrying out dechlorination reaction on the oil component obtained in the hydrogenation reaction; the temperature of the hydrogenation reaction is 270 ℃, the gauge pressure is 11MPa, and the volume space velocity is 1h-1(ii) a The temperature of the dechlorination reaction is 280 ℃, the gauge pressure is 11MPa, and the volume space velocity is 1h-1；
(4) And (3) carrying out desulfurization treatment, normal-pressure fractionation treatment and reduced-pressure cutting treatment on the oil component obtained after the dechlorination reaction in the step (3) in sequence, thereby completing the regeneration of the waste mineral oil.
The second medicament comprises 50 parts of SiO by weight221 parts of Al2O38 parts of Fe2O33 parts of FeO, 3 parts of MgO and 3 parts of CaO.
The ash content in the middle distillate oil obtained in the step (2) is 0.12 wt%, and the metal removal rate is 99.5% when the metal content is 20 mg/Kg; however, since only one hydrogenation reaction is carried out and the hydrogenation reaction temperature is high, a large amount of easily coked substances are coked and condensed in the hydrofining reactor, so that the hydrofining reactor 9 cannot stably operate.
In conclusion, the pretreatment unit can remove metal elements in the waste mineral oil, so that the metal removal rate reaches over 95 percent, and the service life of the catalyst in the hydrogenation reaction unit is prolonged; according to the invention, through the arrangement of the protection reaction device in the hydrogenation reaction unit, the substance easy to coke is converted in the protection reaction device, and the substance easy to coke is prevented from condensing and coking in a high-temperature area; the dechlorination reaction device is used for removing HCl generated by hydrogenation reaction and preventing the HCl from corroding subsequent equipment.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (17)

1. The waste mineral oil regeneration system is characterized by comprising a pretreatment unit, a hydrogenation reaction unit and a fractionation unit which are sequentially connected;
the pretreatment unit comprises a first mixing device, a first filtering device, a light component removal device, a thermal cracking reactor, a second mixing device, a second filtering device and a first pressure reduction fractionation device which are connected in sequence;
the hydrogenation reaction unit comprises a protection reaction device, a hydrofining reaction device and a dechlorination reaction device which are connected in sequence;
the fractionation unit comprises a desulfurization device, an atmospheric fractionation device and a second reduced pressure fractionation device which are connected in sequence;
a middle distillate oil outlet of a first vacuum fractionation device in the pretreatment unit is connected with a protection reaction device in the hydrogenation reaction unit; a discharge hole of a dechlorination reaction device in the hydrogenation reaction unit is connected with a feed hole of a desulphurization device in the fractionation unit;
the protection reaction device comprises at least 1 protection reactor;
the reaction temperature in the protection reaction device is lower than that of the hydrofining reaction device, so that the substance easy to coke is converted in the protection reaction device, and the substance easy to coke is prevented from condensing and coking in a high-temperature area.
2. The waste mineral oil recycling system of claim 1, wherein the first filtering means has a filtering accuracy of 40-80 μm.
3. The used mineral oil recycling system of claim 1, wherein the second filtering means has a filtering accuracy of 15-25 μm.
4. The waste mineral oil recovery system of claim 1, further comprising an impurity removal device disposed before the first mixing device.
5. A method for regenerating waste mineral oil, characterized in that it is carried out using a waste mineral oil regenerating system according to any one of claims 1 to 4, said regenerating method comprising the steps of:
(1) mixing the waste mineral oil with a first medicament, filtering, and then sequentially carrying out dehydration and light removal treatment and thermal cracking treatment;
(2) mixing the oil generated by the thermal cracking treatment in the step (1) with a second agent, filtering, heating the oil component obtained after filtering, and then carrying out reduced pressure fractionation to obtain middle distillate with the distillation range of 220-520 ℃;
(3) sequentially carrying out a first hydrogenation reaction and a second hydrogenation reaction on the middle distillate oil obtained in the step (2), and carrying out a dechlorination reaction on the oil component obtained in the second hydrogenation reaction;
(4) carrying out desulfurization treatment, normal-pressure fractionation treatment and reduced-pressure cutting treatment on the oil component obtained after the dechlorination reaction in the step (3) in sequence, thereby completing the regeneration of the waste mineral oil;
the temperature of the first hydrogenation reaction in the step (3) is 240-300 ℃, the gauge pressure is 10-12MPa, and the volume space velocity is 0.2-2h-1；
The temperature of the second hydrogenation reaction is 300-380 ℃, the gauge pressure is 10-12MPa, and the volume space velocity is 0.5-2h-1。
6. The regeneration method of claim 5, wherein the first agent of step (1) comprises any one of or a combination of at least two of a polymer of a mono-alcohol and/or a diol, a quaternary ammonium salt, a quaternary phosphonium salt, a phosphate salt, or a sulfate salt.
7. The regeneration method according to claim 5, wherein the first chemical in step (1) is 0.01-0.5% by mass of the waste mineral oil.
8. The regeneration process of claim 5, wherein the temperature of the mixing of step (1) is 60-90 ℃.
9. The regeneration method according to claim 5, wherein the filtration precision of the filtration of step (1) is 40 to 80 μm.
10. The regeneration method as claimed in claim 5, wherein the temperature of the thermal cracking process in step (1) is 280-330 ℃.
11. The regeneration method of claim 5, wherein the second medicament of step (2) comprises, in parts by weight:
Figure FDA0003447563290000031
12. the regeneration method according to claim 5, wherein the amount of the second chemical used in step (2) is 0.5 to 2 wt% of the oil component produced by the thermal cracking process in step (1).
13. The regeneration method as claimed in claim 5, wherein the temperature of the mixing in step (2) is 100-150 ℃.
14. The regeneration method according to claim 5, wherein the filtration precision of the filtration of step (2) is 15 to 25 μm.
15. The regeneration method according to claim 5, wherein the temperature of the oil component after heating in step (2) is 300-370 ℃.
16. The regeneration method as claimed in claim 5, wherein the dechlorination reaction is carried out at a temperature of 260 ℃ and 300 ℃, a gauge pressure of 10-12MPa and a volume space velocity of 0.5-2h-1。
17. Regeneration method according to claim 5, characterized in that it comprises the following steps:
(1) mixing the waste mineral oil and the first medicament at 60-90 ℃, and filtering, wherein the filtering precision of the filtering is 40-80 μm; then, dehydration and lightness removal treatment and thermal cracking treatment are sequentially carried out; the first agent is 0.01-0.5% of the waste mineral oil by mass; the temperature of thermal cracking treatment is 280-330 ℃;
(2) mixing the oil produced by the thermal cracking treatment in the step (1) with a second medicament, and filtering, wherein the filtering precision of the filtering is 15-25 mu m, and the dosage of the second medicament is 0.5-2 wt% of the oil produced by the thermal cracking treatment in the step (1); heating the oil component obtained after filtration to the temperature of 300-370 ℃ and then carrying out reduced pressure fractionation to obtain middle distillate oil with the distillation range of 220-520 ℃; the temperature of the mixing is 100-150 ℃;
(3) sequentially carrying out the middle distillate oil obtained in the step (2)The first hydrogenation reaction and the second hydrogenation reaction, and the oil component obtained by the second hydrogenation reaction is subjected to dechlorination reaction; the temperature of the first hydrogenation reaction is 240-300 ℃, the gauge pressure is 10-12MPa, and the volume space velocity is 0.2-2h-1(ii) a The temperature of the second hydrogenation reaction is 300-380 ℃, the gauge pressure is 10-12MPa, and the volume space velocity is 0.5-2h-1(ii) a The temperature of the dechlorination reaction is 260-300 ℃, the gauge pressure is 10-12MPa and the volume space velocity is 0.5-2h-1；
(4) And (3) carrying out desulfurization treatment, normal-pressure fractionation treatment and reduced-pressure cutting treatment on the oil component obtained after the dechlorination reaction in the step (3) in sequence, thereby completing the regeneration of the waste mineral oil.
CN202010356708.6A 2020-04-29 2020-04-29 Waste mineral oil regeneration system and regeneration method Active CN111454748B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010356708.6A CN111454748B (en) 2020-04-29 2020-04-29 Waste mineral oil regeneration system and regeneration method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010356708.6A CN111454748B (en) 2020-04-29 2020-04-29 Waste mineral oil regeneration system and regeneration method

Publications (2)

Publication Number Publication Date
CN111454748A CN111454748A (en) 2020-07-28
CN111454748B true CN111454748B (en) 2022-06-17

Family

ID=71676032

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010356708.6A Active CN111454748B (en) 2020-04-29 2020-04-29 Waste mineral oil regeneration system and regeneration method

Country Status (1)

Country Link
CN (1) CN111454748B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112607981B (en) * 2020-12-10 2022-07-08 宁波中循环保科技有限公司 Method and system for recycling waste mineral oil sludge
CN115305143B (en) * 2022-09-14 2023-04-07 重庆中吉达环保科技有限公司 Method for refining waste mineral oil

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101307271B (en) * 2007-05-18 2010-12-22 中国石油化工股份有限公司 Recovering and regenerating method for waste lubrication oil
CN107892990B (en) * 2017-11-14 2020-11-13 新疆聚力环保科技有限公司 Method for producing high-grade lubricating oil base oil by full-hydrogen regeneration of waste mineral oil
CN108251156B (en) * 2018-01-31 2020-01-31 新疆聚力环保科技有限公司 Method for two-stage hydrotreating regeneration process of full-fraction waste mineral oil

Also Published As

Publication number Publication date
CN111454748A (en) 2020-07-28

Similar Documents

Publication Publication Date Title
CN103205271B (en) Hydrogenation of high temperature coal tar produces the method for mesophase pitch
CN106753742B (en) Regeneration method of waste lubricating oil
CN1100854C (en) Process and plant for purifying spent oil
CN111454748B (en) Waste mineral oil regeneration system and regeneration method
RU2099397C1 (en) Method of treating exhausted lubricating oils
CN102604732A (en) Static mixed rotational flow separation and extraction process of regenerative base oil N-methyl pyrrolidone
CN103205272A (en) Method for production of purified coal tar pitch from high temperature coal tar
CN105316018B (en) A kind of coal tar deep processing preprocess method
CN110194966A (en) A kind of demetallated method and apparatus of residual oil
JP4481567B2 (en) Quench water pretreatment process
CN1686977A (en) Method for refining environmental protection type carbonized benzene
MX2014011361A (en) Process for removing nitrogen from fuel streams with caprolactamium ionic liquids.
CN105907452B (en) A kind of combined technical method making waste lubricant oil regeneration by being heat-treated
CA2367207C (en) Method of removing contaminants from petroleum distillates
DK3098291T3 (en) PROCEDURE FOR REGULATING WASTE OILS
CN111607430A (en) Comprehensive treatment system and method for waste mineral oil
CN104212489B (en) Processing method of heavy oil product with high nitrogen content
CN105001892A (en) Method for co-production of refined maltha through fixed bed-based coal-tar hydrogenation process
CN108315052B (en) FCC (fluid catalytic cracking) oil slurry de-solidification process, equipment and application
CN106753542B (en) Inferior heavy oil desalting processing method
CN106336906A (en) Low-rank coal treating system and method
CN106000478A (en) Recycling method of slurry-bed hydrocracking catalyst for heavy oil
CN106318430B (en) A kind of system and method using low-order coal
CN105733666B (en) Method for treating catalytic cracking slurry oil
CN206279155U (en) A kind of system of utilization low-order coal

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant