CN113004941B - Industrial purification method of waste engine oil - Google Patents
Industrial purification method of waste engine oil Download PDFInfo
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- CN113004941B CN113004941B CN202110353579.XA CN202110353579A CN113004941B CN 113004941 B CN113004941 B CN 113004941B CN 202110353579 A CN202110353579 A CN 202110353579A CN 113004941 B CN113004941 B CN 113004941B
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- 238000000034 method Methods 0.000 title claims abstract description 78
- 239000010705 motor oil Substances 0.000 title claims abstract description 33
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- 238000000746 purification Methods 0.000 title claims abstract description 20
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- 239000003054 catalyst Substances 0.000 claims abstract description 48
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- 239000007787 solid Substances 0.000 claims abstract description 6
- 230000016615 flocculation Effects 0.000 claims abstract description 3
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- 239000011148 porous material Substances 0.000 claims description 21
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 claims description 17
- 230000000694 effects Effects 0.000 claims description 17
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 16
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
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- 239000002245 particle Substances 0.000 claims description 15
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- 238000011084 recovery Methods 0.000 claims description 7
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- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 5
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- 238000009835 boiling Methods 0.000 claims description 5
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- 238000000748 compression moulding Methods 0.000 claims description 5
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
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- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
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- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract description 4
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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
- 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
- C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
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- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract
The invention provides an industrial purification method of waste engine oil, which comprises the following steps: standing and layering the waste engine oil constant-temperature oil tank into an upper oil layer, a middle oil layer and a lower layer; carrying out solid-liquid separation on the lower layer, blending and burning solid oil ash, and carrying out sewage treatment on the liquid; heating the upper oil layer and the middle oil layer at a high temperature to obtain a mixed oil and gas mixture, and collecting the gas mixture and then treating waste gas; introducing the mixed oil into a catalyst carrier bed for catalytic treatment, and then introducing the mixed oil into a three-stage distillation system to separate out first finished product oil; performing oil flocculation treatment on the residual oil to separate second product oil and oil residue, and enabling the oil residue to enter a blending combustion process; the method provided by the invention can rapidly reduce the viscosity and density of the used oil, greatly reduce secondary pollution caused by refining and purifying the used oil, reduce residual carbon and improve cetane index, thereby serving large-scale process production.
Description
Technical Field
The invention belongs to the technical field of waste engine oil purification, and particularly relates to an industrial purification method of waste engine oil.
Background
In the using process of the engine oil, various oxides are generated due to the oxidation action of high temperature and air, and in addition, moisture and dust which enter the engine oil due to the grinding action of a friction part and other reasons enter the engine oil, so that the color of the engine oil gradually becomes black, the viscosity is reduced, the quality is reduced, and impurities such as precipitates, oil sludge, paint films, hard paint films and the like generated in the using process can cause the damage of oil films, the corrosion of metal parts and the abrasion of moving devices, thereby causing the jamming and the malfunction of a speed regulating system and causing the damage of equipment, so the engine oil must be frequently replaced. The development of the regeneration technology of the used oil has important significance for saving resources and can generate good economic benefit.
In recent years, techniques for regenerating used oil mainly include: the method comprises an acid-base refining process, a solvent refining process, a hydrofining process, a molecular distillation process and a membrane treatment process, wherein the sulfuric acid-argil process is the most mature, but the process has high demand on white soil, can generate serious three wastes and has great pollution to the environment, so that the process is gradually replaced by the solvent refining and the hydrotreating; for example, in patent CN104004543A, a method for catalytically upgrading and regenerating used oil is provided, in which the used oil is subjected to reduced pressure distillation, then hydrogenated and upgraded by sulfide catalyst, and a gasoline-diesel oil and engine oil mixed oil with no peculiar smell and high quality is produced by desulfurization, denitrification, deoxidation and colloid removal, and then distilled to obtain gasoline, diesel oil and finished engine oil distillate oil; in the process of purifying the waste engine oil, the treatment process is complex, the energy consumption is increased, the environment is polluted, and the treatment of the oil residue is lacked, so that the oil residue cannot be effectively utilized.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides an industrial purification method of waste engine oil, through accurate temperature control and distillation technology, combined with a pre-distillation catalytic process in a link to accelerate purification and oil flocculation procedures, the viscosity and density of the waste engine oil can be rapidly reduced, residual carbon is reduced through innovative means, the cetane index is improved, the treatment process is simple, the waste oil recovery rate is high, and the requirement of large-scale process production can be met.
The invention provides the following technical scheme: an industrial purification method of used oil comprises the following steps:
1) Placing the waste engine oil in a constant-temperature oil tank at the temperature of 80-95 ℃, standing for 20-30 h, layering the waste engine oil to obtain an upper oil layer, a middle oil layer and a lower layer, wherein the lower layer comprises water and impurities, and performing coagulating sedimentation and filter pressing to complete solid-liquid separation.
2) Heating the upper oil layer and the middle oil layer obtained in the step 1) at the temperature of 150-190 ℃ to obtain a mixed oil and gas mixture, wherein the gas mixture comprises odor and water vapor, and the gas mixture is collected and enters a waste gas treatment process;
3) Introducing the mixed oil obtained after the heating treatment in the step 2) into a catalyst carrier bed, and performing catalytic treatment on the mixed oil by using a catalyst to obtain oil to be purified;
4) Introducing the oil to be purified obtained in the step 3) into a three-stage distillation tower, distilling three kinds of fraction mixtures with the boiling point of less than 300 ℃, and carrying out condensation separation to obtain first finished oil, wherein the yield of the first finished oil is 50-65%;
5) And (3) allowing the bottom oil of the distillation tower in the step 4) to enter a flocculation process, standing and precipitating for 2-4 h, and separating second product oil and oil residue, wherein the yield of the second product oil is 30-35%.
Preferably, the catalyst carrier bed in the step 3) comprises a carrier bed and nickel oxide particles loaded on the carrier bed, and the particle size of the nickel oxide is 1 mm-3 mm.
Preferably, the carrier bed consists of the following components in parts by weight: 30-40 parts of activated alumina, 10-20 parts of nano porous silicon dioxide, 8-15 parts of silicon carbide, 5-12 parts of kaolin, 3-6 parts of dolomite and 2-5 parts of sesbania powder;
the active alumina has a pore volume of 0.2-1.2 mL/g, a pore diameter of 2.0-11.0 nm, and a specific surface area of 200m 2 /g～380m 2 /g；
The nano-porous silicon dioxide has the pore volume of 0.2mL/g to 2.5mL/g, the pore diameter of 2nm to 100nm and the specific surface area of 220m 2 /g～450m 2 /g。
Preferably, the preparation method of the carrier bed comprises the following steps:
the method comprises the following steps: weighing the raw materials in proportion, mixing the raw materials with water accounting for 20-30% of the total weight of the raw materials, uniformly mixing, and then putting the mixture into a mixing roll for mixing for 30-120 min to prepare pug;
step two: placing the pug in a honeycomb steel mold, setting the pressure to be 10-15 MPa, and performing compression molding to obtain a honeycomb carrier blank;
step three: drying the honeycomb carrier blank at 110-130 ℃ for 20-24 h, heating the dried honeycomb carrier blank to 1200-1300 ℃ at the heating rate of 30-40 ℃/h, and sintering for 12-18 h to obtain the carrier bed with the honeycomb structure.
Preferably, the catalyst carrier bed in step 3) is subjected to an activity treatment before use, and the activity treatment method is as follows: treating the catalyst carrier in a dodecylbenzene soaking pool at 60-70 ℃ for 1-5 h, wherein the mass fraction of the dodecylbenzene is 15-27%, and then washing, separating and drying to obtain the required catalyst carrier bed, wherein the mass ratio of the dodecylbenzene to the nickel oxide catalyst is 1:0.1 to 0.25.
Preferably, the three-stage distillation tower in the step 4) is atmospheric distillation, and the temperature of the distillation tower is set to be 150-175 ℃, 175-260 ℃ and 260-300 ℃ from top to bottom in sequence.
Preferably, the flocculation process of step 5) is: adding a flocculant solution with the volume ratio of 10-20% into bottom oil of a distillation tower according to the ratio of 1-20-50 of solvent to oil, stirring for 8-20 min at the temperature of 60-90 ℃.
Preferably, the flocculant solution is prepared by dissolving a flocculant in toluene, and the flocculant is one or more of isophorone diamine, N- (2-hydroxyethyl) ethylene diamine, N-phenyl diethanol amine and diethylene triamine.
Preferably, the residual heat of the flue gas generated in the step 2) is used for completing residual heat heating in the standing layering process and the catalyst carrier bed activity treatment process in the step 1), so that energy recovery is realized.
Preferably, the liquid obtained by solid-liquid separation in the step 1) is introduced into a sewage treatment process, the solid and the oil residue obtained by standing and precipitating in the step 5) are mixed and burnt, and the waste gas generated by mixed burning enters a tail gas treatment process.
The beneficial technical effects of the invention are as follows:
(1) The invention can quickly reduce the viscosity and density of the waste engine oil, reduce the carbon residue and improve the cetane index by an innovative means, has simple treatment process and high waste oil recovery rate which is not less than 80 percent, and can meet the requirement of large-scale process production by combining an accurate temperature control and distillation technology with a pre-distillation catalytic process in a link to accelerate the purification and oil flocculation processes.
(2) According to the invention, the aliphatic amine is used as the flocculating agent, on one hand, the amino group of the aliphatic amine can form a hydrogen bond with the oxidizing group in the waste engine oil and neutralize the acid group, and on the other hand, the crosslinking performance of the aliphatic amine can adsorb colloid particles, so that impurity particles in the waste engine oil are aggregated and settled, and thus the acid value, viscosity and density of bottom oil of the distillation tower are rapidly reduced, the settling speed of mechanical impurities is accelerated, and the quality of second finished product oil is further improved.
(3) The active components of the invention are active alumina and nano-porous silica, and due to the porous structures of the active alumina and the nano-porous silica, the active alumina and the nano-porous silica have large surface areas, and the microporous surfaces of the active alumina and the nano-porous silica have the characteristics required by catalytic action, such as adsorption performance, surface activity, excellent thermal stability and the like.
(4) The carrier bed of the invention adopts a honeycomb structure, the porosity of the honeycomb carrier is large, the adsorption capacity is strong, more catalytic active components can be loaded, and active alumina and nano-porous silica are selected as the active components, so that the catalyst carrier bed has micropores, mesopores, macropores or super-macropores at the same time, the contact area of the catalyst and the waste engine oil is increased, and the catalyst bed has higher catalytic effect in the same space.
(5) The invention adopts the dodecylbenzene to carry out the active treatment on the catalyst carrier bed, and mainly considers that the dodecylbenzene is taken as a surfactant, so that the surface tension of water can be reduced, the wetting angle of a solid-liquid interface is changed, more nickel oxide particles can be promoted to enter the pores in the catalyst carrier bed, and the catalytic capability of the catalyst carrier bed is effectively improved.
Drawings
FIG. 1 is a flow chart of an industrial purification method of used oil according to the present invention.
The present invention is described in detail below with reference to the attached drawings and embodiments, and it is obvious that the described embodiments are only a part of embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work based on the embodiments of the present invention belong to the protection scope of the present invention.
The method for industrially purifying used oil according to the present invention will be described in detail with reference to specific preferred embodiments.
Example 1:
the embodiment provides a method for industrially purifying waste engine oil, which comprises the following steps:
1) Placing the waste engine oil in a constant-temperature oil tank with the temperature of 95 ℃, standing for 20 hours, layering the waste engine oil to obtain an upper oil layer, a middle oil layer and a lower layer, wherein the lower layer comprises water and impurities, and performing solid-liquid separation through coagulating sedimentation and filter pressing procedures.
2) Heating the upper oil layer and the middle oil layer obtained in the step 1) at 150 ℃ to obtain a mixed oil and gas mixture, wherein the gas mixture comprises odor and water vapor, and the gas mixture is collected and enters a waste gas treatment process;
3) Introducing the mixed oil obtained after the heating treatment in the step 2) into a catalyst carrier bed, and performing catalytic treatment on the mixed oil by using a catalyst to obtain oil to be purified;
4) Introducing the oil to be purified obtained in the step 3) into a three-stage distillation tower, distilling three fraction mixtures with the boiling point of less than 300 ℃, and carrying out condensation separation to obtain first product oil, wherein the yield of the first product oil is 65%;
5) And (5) allowing the bottom oil of the distillation tower in the step 4) to enter a flocculation process, standing and precipitating for 2h, and separating second product oil and oil residues, wherein the yield of the second product oil is 30%.
Preferably, the catalyst carrier bed in the step 3) comprises a carrier bed and nickel oxide particles supported on the carrier bed, wherein the particle size of the nickel oxide is 1mm.
Preferably, the carrier bed consists of the following components in parts by weight: 40 parts of activated alumina, 20 parts of nano porous silicon dioxide, 8 parts of silicon carbide, 5 parts of kaolin, 6 parts of dolomite and 5 parts of sesbania powder;
the active alumina has a pore volume of 0.2mL/g, a pore diameter of 2.0nm and a specific surface area of 380m 2 /g；
The pore volume of the nano porous silicon dioxide is 0.2mL/g, the pore diameter is 2nm, and the specific surface area is 450m 2 /g。
Preferably, the preparation method of the carrier bed comprises the following steps:
the method comprises the following steps: weighing the raw materials in proportion, mixing the raw materials with water accounting for 30% of the total weight of the raw materials, uniformly mixing, and then putting into a mixing roll for mixing for 120min to prepare pug;
step two: placing the pug into a honeycomb steel mold, setting the pressure to be 10MPa, and performing compression molding to obtain a honeycomb carrier blank;
step three: drying the honeycomb carrier green body at 130 ℃ for 20h, heating the dried honeycomb carrier green body to 1300 ℃ at the heating rate of 40 ℃/h, and firing for 12h to obtain the carrier bed with the honeycomb structure.
Preferably, the catalyst carrier bed in step 3) is subjected to an activity treatment before use, and the activity treatment method comprises the following steps: treating the catalyst carrier in a dodecyl benzene soaking pool at 60 ℃ for 5 hours, wherein the mass fraction of the dodecyl benzene is 15%, and then washing, separating and drying to obtain the required catalyst carrier bed, wherein the mass ratio of the dodecyl benzene to the nickel oxide catalyst is 1:0.25.
preferably, the three-stage distillation tower of the step 4) is an atmospheric distillation tower, and the temperature of the distillation tower is set to 150 ℃, 175 ℃ and 260 ℃ from top to bottom in sequence.
Preferably, the flocculation process of step 5) is: firstly adding 10% by volume of isophorone diamine flocculant solution into distillation tower bottom oil according to the ratio of solvent to oil volume being 1.
Preferably, the residual heat of the flue gas generated in the step 2) is used for completing residual heat heating in the standing layering process and the catalyst carrier bed activity treatment process in the step 1), so that energy recovery is realized.
Preferably, the liquid obtained by solid-liquid separation in the step 1) is introduced into a sewage treatment process, the solid and the oil residue obtained by standing and precipitating in the step 5) are mixed and burned, and the waste gas generated by burning is introduced into a tail gas treatment process.
Example 2:
the embodiment provides an industrial purification method of waste engine oil, which comprises the following steps:
1) Placing the waste engine oil in a constant-temperature oil tank with the temperature of 80 ℃, standing for 30h, layering the waste engine oil to obtain an upper oil layer, a middle oil layer and a lower layer, wherein the lower layer comprises water and impurities, and performing solid-liquid separation through coagulating sedimentation and filter pressing procedures.
2) Heating the upper oil layer and the middle oil layer obtained in the step 1) at 190 ℃ to obtain a mixed oil and gas mixture, wherein the gas mixture comprises odor and water vapor, and the gas mixture is collected and enters a waste gas treatment process;
3) Introducing the mixed oil obtained after the heating treatment in the step 2) into a catalyst carrier bed, and performing catalytic treatment on the mixed oil by using a catalyst to obtain oil to be purified;
4) Introducing the oil to be purified obtained in the step 3) into a three-stage distillation tower, distilling three kinds of fraction mixtures with the boiling point of less than 300 ℃, and carrying out condensation separation to obtain a first finished oil, wherein the yield of the first finished oil is 50%;
5) And (3) allowing the bottom oil of the distillation tower in the step 4) to enter a flocculation process, standing and precipitating for 2-4 h, and separating second product oil and oil residue, wherein the yield of the second product oil is 35%.
Preferably, the catalyst carrier bed in the step 3) comprises a carrier bed and nickel oxide particles supported on the carrier bed, wherein the nickel oxide particles have a particle size of 3mm.
Preferably, the carrier bed consists of the following components in parts by weight: 30 parts of activated alumina, 10 parts of nano porous silicon dioxide, 15 parts of silicon carbide, 12 parts of kaolin, 3 parts of dolomite and 2 parts of sesbania powder;
the active alumina has the pore volume of 1.2mL/g, the pore diameter of 11.0nm and the specific surface area of 200m 2 /g；
The nano porous silicon dioxide has the pore volume of 2.5mL/g, the pore diameter of 100nm and the specific surface area of 220m 2 /g。
Preferably, the preparation method of the carrier bed comprises the following steps:
the method comprises the following steps: weighing the raw materials in proportion, mixing the raw materials with water accounting for 20% of the total weight of the raw materials, uniformly mixing, and then putting into a mixing roll for mixing for 30min to prepare pug;
step two: placing the pug into a honeycomb steel mold, setting the pressure to be 15MPa, and performing compression molding to obtain a honeycomb carrier blank;
step three: drying the honeycomb carrier green body at 110 ℃ for 24h, heating the dried honeycomb carrier green body to 1200 ℃ at the heating rate of 30 ℃/h, and sintering for 18h to obtain the carrier bed with the honeycomb structure.
Preferably, the catalyst carrier bed in step 3) is subjected to an activity treatment before use, and the activity treatment method comprises the following steps: treating the catalyst carrier in a dodecylbenzene soaking pool at 70 ℃ for 1h, wherein the mass fraction of the dodecylbenzene is 27%, and then washing, separating and drying to obtain the required catalyst carrier bed, wherein the mass ratio of the dodecylbenzene to the nickel oxide catalyst is 1:0.1.
preferably, the three-stage distillation tower of the step 4) is an atmospheric distillation tower, and the temperature of the distillation tower is set to 175 ℃, 260 ℃ and 300 ℃ from top to bottom in sequence.
Preferably, the flocculation process of step 5) is: adding 20% by volume of N- (2-hydroxyethyl) ethylenediamine flocculant solution into bottom oil of a distillation tower according to the volume ratio of the solvent to the oil of 1 to 50, stirring for 20min at the temperature of 90 ℃, adding 10% by volume of N-phenyldiethanolamine solution into the bottom oil of the distillation tower according to the volume ratio of the solvent to the oil of 1 to 20, and stirring for 8min at the temperature of 60 ℃.
Preferably, the residual heat of the flue gas generated in the step 2) is used for completing residual heat heating in the standing layering process and the catalyst carrier bed activity treatment process in the step 1), so that energy recovery is realized.
Preferably, the liquid obtained by solid-liquid separation in the step 1) is introduced into a sewage treatment process, the solid and the oil residue obtained by standing and precipitating in the step 5) are mixed and burnt, and the waste gas generated by mixed burning enters a tail gas treatment process.
Example 3:
the embodiment provides an industrial purification method of waste engine oil, which comprises the following steps:
1) Placing the waste engine oil in a constant-temperature oil tank with the temperature of 85 ℃, standing for 25h, layering the waste engine oil to obtain an upper oil layer, a middle oil layer and a lower layer, wherein the lower layer comprises water and impurities, and performing solid-liquid separation through coagulating sedimentation and filter pressing procedures.
2) Heating the upper oil layer and the middle oil layer obtained in the step 1) at 165 ℃ to obtain a mixed oil and gas mixture, wherein the gas mixture comprises odor and water vapor, and the gas mixture is collected and enters a waste gas treatment process;
3) Introducing the mixed oil obtained after the heating treatment in the step 2) into a catalyst carrier bed, and performing catalytic treatment on the mixed oil by using a catalyst to obtain oil to be purified;
4) Introducing the oil to be purified obtained in the step 3) into a three-stage distillation tower, distilling three kinds of fraction mixtures with the boiling point of less than 300 ℃, and carrying out condensation separation to obtain a first finished oil product, wherein the yield of the first finished oil product is 60%;
5) And (3) allowing the bottom oil of the distillation tower in the step 4) to enter a flocculation process, standing and precipitating for 3h, and separating second product oil and oil residues, wherein the yield of the second product oil is 34%.
Preferably, the catalyst carrier bed in the step 3) comprises a carrier bed and nickel oxide particles supported on the carrier bed, wherein the nickel oxide particles have a particle size of 2mm.
Preferably, the carrier bed consists of the following components in parts by weight: 35 parts of activated alumina, 15 parts of nano porous silica, 12 parts of silicon carbide, 8 parts of kaolin, 5 parts of dolomite and 4 parts of sesbania powder;
the active alumina has a pore volume of 0.8mL/g, a pore diameter of 6.0nm and a specific surface area of 280m 2 /g；
The nano porous silicon dioxide has the pore volume of 1.2mL/g, the pore diameter of 50nm and the specific surface area of 320m 2 /g。
Preferably, the preparation method of the carrier bed comprises the following steps:
the method comprises the following steps: weighing the raw materials in proportion, mixing the raw materials with water accounting for 25% of the total weight of the raw materials, uniformly mixing, and then putting into a mixing roll for mixing for 60min to prepare pug;
step two: placing the pug in a honeycomb steel mold, setting the pressure to be 12MPa, and performing compression molding to obtain a honeycomb carrier blank;
step three: drying the honeycomb carrier green body at 120 ℃ for 22h, heating the dried honeycomb carrier green body to 1250 ℃ at the heating rate of 35 ℃/h, and firing for 15h to obtain the carrier bed with the honeycomb structure.
Preferably, the catalyst carrier bed in step 3) is subjected to an activity treatment before use, and the activity treatment method is as follows: treating the catalyst carrier in a dodecylbenzene soaking pool at 65 ℃ for 3 hours, wherein the mass fraction of the dodecylbenzene is 20%, and then washing, separating and drying to obtain the required catalyst carrier bed, wherein the mass ratio of the dodecylbenzene to the nickel oxide catalyst is 1:0.15.
preferably, the three-stage distillation tower of the step 4) is an atmospheric distillation tower, and the temperature of the distillation tower is sequentially set to 160 ℃, 215 ℃ and 280 ℃ from top to bottom.
Preferably, the flocculation process of step 5) is: adding an isophorone diamine flocculant solution with a volume ratio of 15% into distillation tower bottom oil according to a ratio of agent oil to volume ratio of 1.
Preferably, the residual heat of the flue gas generated in the step 2) is used for the residual heat heating of the standing layering process and the catalyst carrier bed activity treatment process in the step 1), so that energy recovery is realized.
Preferably, the liquid obtained by solid-liquid separation in the step 1) is introduced into a sewage treatment process, the solid and the oil residue obtained by standing and precipitating in the step 5) are mixed and burnt, and the waste gas generated by mixed burning enters a tail gas treatment process.
Test example 1
The first finished oils prepared in examples one to three were subjected to a performance test, and the following performance data were obtained in comparison with standard "B5 diesel" (GB 25199-2017):
and (3) measuring results: the physicochemical property indexes of the first finished oil obtained by the regeneration technology, such as viscosity, flash point, acid value, cetane number and the like all meet the requirements of the standard B5 diesel (GB 25199-2017).
Test example 2
The second finished oils prepared in examples one to three were subjected to performance testing, and the used motor oil was used as a comparative example, and the following performance data were obtained in comparison with standard "universal lubricant base oil" (QSY 44-2009):
and (3) measuring results: the second finished oil obtained by the regeneration technology has physicochemical property indexes such as chroma, appearance, acid value, carbon residue and the like which reach the standard of general lubricating oil base oil (QSY 44-2009).
While the embodiments of the invention have been described above, it is not limited to the applications listed in the description and the embodiments, but is fully applicable in various fields of application of the invention, and it will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in the embodiments without departing from the principles of the invention, and therefore the invention is not limited to the details given herein, without departing from the general concept defined by the claims and their equivalents.
Claims (8)
1. An industrial purification method of used oil is characterized by comprising the following steps:
1) Placing the waste engine oil in a constant-temperature oil tank with the temperature of 80-95 ℃, standing for 20-30 h, layering the waste engine oil to obtain an upper oil layer, a middle oil layer and a lower layer, wherein the lower layer comprises water and impurities, and performing coagulating sedimentation and filter pressing to complete solid-liquid separation of the lower layer;
2) Heating the upper oil layer and the middle oil layer obtained in the step 1) at the temperature of 150-190 ℃ to obtain a mixed oil and gas mixture, wherein the gas mixture comprises odor and water vapor, and the gas mixture is collected and enters a waste gas treatment process;
3) Introducing the mixed oil obtained after the heating treatment in the step 2) into a catalyst carrier bed, and performing catalytic treatment on the mixed oil by using a catalyst to obtain oil to be purified, wherein the catalyst carrier bed comprises a carrier bed and nickel oxide particles loaded on the carrier bed, and the particle size of the nickel oxide is 1-3 mm;
4) Introducing the oil to be purified obtained in the step 3) into a three-stage distillation tower, distilling three kinds of fraction mixtures with the boiling point of less than 300 ℃, and carrying out condensation separation to obtain first finished oil, wherein the yield of the first finished oil is 50-65%;
5) Enabling the bottom oil of the distillation tower in the step 4) to enter a flocculation process, standing and precipitating for 2-4 h, and separating second product oil and oil residue, wherein the yield of the second product oil is 30-35%;
wherein, the catalyst carrier bed in the step 3) needs to be subjected to activity treatment before use, and the activity treatment method comprises the following steps: placing the catalyst carrier in a dodecyl benzene soaking pool at 60-70 ℃ for treatment for 1-5 h, wherein the mass fraction of the dodecyl benzene is 15-27%, and then washing, separating and drying to obtain the required catalyst carrier bed, wherein the mass ratio of the dodecyl benzene to the nickel oxide catalyst is 1:0.1 to 0.25.
2. The industrial purification process of claim 1, wherein the support bed consists of, in parts by weight: 30-40 parts of activated alumina, 10-20 parts of nano porous silicon dioxide, 8-15 parts of silicon carbide, 5-12 parts of kaolin, 3-6 parts of dolomite and 2-5 parts of sesbania powder;
the active alumina has a pore volume of 0.2-1.2 mL/g, a pore diameter of 2.0-11.0 nm, and a specific surfaceProduct of 200m 2 /g～380m 2 /g；
The pore volume of the nano porous silicon dioxide is 0.2mL/g to 2.5mL/g, the pore diameter is 2nm to 100nm, and the specific surface area is 220m 2 /g～450m 2 /g。
3. Industrial purification process according to claim 2, characterized in that the support bed is prepared by:
the method comprises the following steps: weighing the raw materials in proportion, mixing the raw materials with water accounting for 20-30% of the total weight of the raw materials, uniformly mixing, and then putting the mixture into a mixing roll for mixing for 30-120 min to prepare pug;
step two: placing the pug in a honeycomb steel mold, setting the pressure to be 10-15 MPa, and performing compression molding to obtain a honeycomb carrier blank;
step three: drying the honeycomb carrier blank at 110-130 ℃ for 20-24 h, heating the dried honeycomb carrier blank to 1200-1300 ℃ at the heating rate of 30-40 ℃/h, and sintering for 12-18 h to obtain the carrier bed with the honeycomb structure.
4. The industrial purification method according to claim 1, wherein the three-stage distillation column of step 4) is an atmospheric distillation, and the temperature of the distillation column is set to 150 ℃ to 175 ℃, 175 ℃ to 260 ℃, and 260 ℃ to 300 ℃ from top to bottom.
5. The industrial purification method according to claim 1, wherein the flocculation step of step 5) is: adding a flocculant solution with the volume ratio of 10-20% into bottom oil of a distillation tower according to the ratio of 1-20-50 of solvent to oil, stirring for 8-20 min at the temperature of 60-90 ℃.
6. The industrial purification process of claim 5, wherein the flocculant solution is prepared by dissolving a flocculant in toluene, and the flocculant is one or more of isophoronediamine, N- (2-hydroxyethyl) ethylenediamine, N-phenyldiethanolamine, and diethylenetriamine.
7. The industrial purification method according to claim 1, wherein the gas mixture residual temperature generated in the step 2) is used for completing residual temperature heating in the standing and layering process in the step 1) and the catalyst carrier bed activity treatment process in the step 3), so as to realize energy recovery.
8. The industrial purification method according to claim 1, wherein the liquid obtained by solid-liquid separation in step 1) enters a sewage treatment process, the solid and the oil residue obtained by standing and precipitation in step 5) are mixed and burned, and the waste gas generated by burning is introduced into a tail gas treatment process.
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