CN102226103B - Method for producing gasoline and diesel by utilizing plastic oil - Google Patents
Method for producing gasoline and diesel by utilizing plastic oil Download PDFInfo
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- CN102226103B CN102226103B CN 201110134368 CN201110134368A CN102226103B CN 102226103 B CN102226103 B CN 102226103B CN 201110134368 CN201110134368 CN 201110134368 CN 201110134368 A CN201110134368 A CN 201110134368A CN 102226103 B CN102226103 B CN 102226103B
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Abstract
The invention discloses a method for producing gasoline and diesel by utilizing plastic oil, belonging to the technical field of environmental protection and energy. The method is characterized in that the plastic oil is used as the raw material and is subjected to distillation and hydrofining to produce the high-quality gasoline and diesel; firstly the plastic oil is distilled to obtain distillates at temperature being less than 300 DEG C and distillates at temperature being more than 300 DEG C; then the distillates at temperature being less than 300 DEG C are subjected to hydrofining reaction on a sulfide catalyst; monoene compounds are removed through monoolefine hydrogenation saturation reaction; sulfur, nitrogen and colloid are removed to produce the high-quality gasoline and diesel mixture free from extraneous odour; the gasoline and diesel mixture is distilled to obtain gasoline and diesel distillates; and the distillates at temperature being more than 300 DEG C are subjected to hydrofining or are mixed with the plastic oil to re-react after being subjected to reactive distillation, wherein the sulfide catalyst is prepared by selecting an appropriate carrier according to the composition and properties of the pyrolysis plastic oil and adopting a liquid phase method. The method has the advantages of simple process, high catalyst activity and selectivity and good economic benefits and industrial application prospect.
Description
Technical field
The invention belongs to environment protection and energy technology field, relate to a kind of new technology of utilizing plastics oil to produce petrol and diesel oil.
Background technology
Waste plastic and rubbish plastic waste that the fast development of plastics industry has brought people to be unwilling to see, a series of social concerns that cause.According to statistics, annual about 2,400,000～4,800,000 tons of the waste plastic total amount that produces of China.The plastic refuse that these can not be eliminated naturally increasing not only has a strong impact on and polluted environment, even will jeopardize human existence.Recovery and Utilization of Waste Plastics mainly contains landfill, burning, physical sepn processing and oiling technology.Wherein plastics in landfills can not be decomposed in the soil midium or long term, made soil compaction, reduced cultivated land resource; Plastics produce objectionable impuritiess such as HCl, HCN and polycyclic aromatic compound in burning process; It is poor that physically screening separates the plastic products quality that makes, the low and poor durability of intensity; Plastic waste oiling technology can be produced the clean fuel of urgent need owing to there is not secondary pollution, produces great economic benefit and receives much attention.
Plastic waste oiling technology is the technology that plastic waste is converted into fuel and chemical feedstocks under the effect of high temperature or catalyzer, and its action principle is that the macromolecular chain in the waste plastic product ruptures under the heat energy effect, becomes the low compound of molecular weight.Yet of poor quality by pyrolysis method, catalytic cracking solution, petrol and diesel oil that thermo-cracking-the catalytic reforming method obtains, inductive phase, weak point, frowziness, colloid and diene content height, condensation point of diesel oil height can not satisfy the quality standard of the petrol and diesel oil of increasingly stringent.The hydrogenation upgrading is effective technology and the method that plastics oil is produced high quality gasoline and diesel.
At abundant plastics oil recycling problem, according to chemical constitution and the character of plastics oil, we have successfully developed the new technology of plastics oil air distillation or catalytic distillation-hydrogenation upgrading-air distillation production petrol and diesel oil.Plastics oil obtains less than 300 through distillation
oC cut and greater than 300
oThe C cut next will be less than 300
oC cut hydrofining reaction on sulfide catalyst.And greater than 300
oThe C cut adopts the catalyzer with intellecture property, and the cut ratio by catalytic distillation transformation technology adjustment petrol and diesel oil reduces the gum level in the cut; Carry out hydrofining again and obtain distillate, distillate is produced the high-quality petrol and diesel oil of market in urgent need etc. through the normal pressure distillation.The no three wastes produce in air distillation or catalytic distillation-hydrogenation upgrading-air distillation, are a processes green, recycling.Following known technology all comes with some shortcomings:
Chinese patent, publication number: CN1174873 has introduced a kind of method with utilizing waste plastics to crack petroleum product, this method is that plastic waste is squeezed in the melting channel, adds hydrocarbon ils in 1～4 times ratio, through catalytic cracking, molecule is reformed and fractionation obtains liquefied petroleum gas (LPG), gasoline, diesel oil and kerosene.Gasoline, diesel number that this method is produced are low, purity difference.
Chinese patent, publication number: CN101845323A has introduced a kind of technology of utilizing plastics oil to produce petrol and diesel oil, its two step of process need hydrogenation, complex operation, expense height.
Chinese patent, publication number: CN1337442A has introduced a kind of method with utilizing waste plastics to crack petroleum product, and its process need adds methyl alcohol, complex operation, expense height.
Chinese patent, publication number: CN114675A has introduced and has a kind ofly mixed its again with plastic waste or plastic waste and plant the method that oil is produced the oil plant oil of liquefied gas, gasoline, diesel oil and lubricant base, and its cracking process needs twice cracking, the process complexity, power consumption is high.
Chinese patent, publication number: CN1141331A has introduced and has a kind ofly transformed gasoline, diesel and hydrofining technology with plastic waste, and wherein the purity requirement to hydrogen is higher in the unifining process, and operate continuously is poor.
Chinese patent, publication number: CN101255343A has introduced a kind of method of utilizing plastic waste, waste oil or heavy oil and refining fuel diesel, and its operation will be refined under supercritical state, condition harshness, shortcoming such as waste water is many.
Summary of the invention
The invention provides that a kind of method of utilizing plastics oil to produce petrol and diesel oil is low at the product specification in the plastics oil conversion process, deficiency in economic performance and secondary pollution problems, be that target product realizes that plastics oil carries out recycling with the petrol and diesel oil, and waste residue and the combustion gas of comprehensive utilization process itself, make the energy-conservation and environmental protection of production process, avoided secondary pollution.Specifically, the present invention cuts distillate with plastics oil through the normal pressure distillation, less than 300
oThe direct hydrogenation of C distillate obtains petrol and diesel oil through fractionation again.And greater than 300
oThe C distillate need be through the upgrading of catalytic reaction distillation repeated hydrogenation or through air distillation recycle again.The present invention improved the transformation efficiency of balanced reaction and consecutive reaction selectivity, energy-conservation of consumption reduction, prolonged catalyst life, flow process is simple and reduce investment outlay.
Technical scheme of the present invention is as follows:
Plastics oil raw material among the present invention comprises that polyvinyl chloride (PVC) plastics, polyethylene (PE) plastics, polypropylene (PP) plastics, polystyrene (PS) plastics, ABS plastic are one or two or more kinds mixing wherein, also can select the waste rubber of rubber item as raw material.
Plastics oil enters distillation tower and cuts into 300 ℃ in distillate (＜300 ℃) and heavy oil (〉 through distillation according to recovered temperature).Distillate directly enters hydrogenator, and the control feeding temperature is at 200-350
oC, hydrogen partial pressure 1-6 MPa, volume space velocity 0.5-4.0 h
-1, hydrogen to oil volume ratio is 100-1000:1; Hydrogen recycles after separation and purification; The catalyzer that hydrogenation uses is the oxide carrier with two mesopore composite structures as loading type NiMo, NiW, CoMo, CoW, NiMoW or CoMoW sulfide catalyst, carrier, and oxide carrier is SiO
2, Al
2O
3, TiO
2, SiO
2-Al
2O
3Or Al
2O
3-TiO
2The gas phase catalysis cracking of heavy oil on molecular sieve/aluminium oxide catalyst.Heavy oil is injected the reaction fractionating tower that molecular sieve/aluminium oxide catalyst is housed carry out reactive distillation, distillate behind the reactive distillation can directly enter hydrogenator hydrofining, also can mix reaction again with converting plastic waste to oil, adopt the waste residue and the combustion gas that produce in the converting plastic waste to oil conversion process to heat.Distillate after the hydrofining distills through normal pressure, cuts into 180 ℃ of gasoline (＜180 ℃) and diesel oil (〉 according to recovered temperature).Technique scheme can continuous operation.Heavy oil enters to mix by the interchanger heating with hydrogen by feedstock pump through the cut of catalytic distillation and enters hydrogenator, and the control feeding temperature is at 250-350
oC; Hydrogen partial pressure 1-6 MPa, volume space velocity 0.5-4.0 h
-1, hydrogen to oil volume ratio is 100-1000:1; The catalyzer that hydrogenation uses is the oxide carrier with two mesopore composite structures as loading type NiMo, NiW, CoMo, CoW, NiMoW or CoMoW sulfide catalyst, carrier, and oxide carrier is SiO
2, Al
2O
3, TiO
2, SiO
2-Al
2O
3Or Al
2O
3-TiO
2
The catalyzer that catalytic distillation tower among the present invention uses is the molecular sieve of alumina load, and wherein molecular sieve comprises ZSM-5, y-type zeolite, mordenite and β zeolite or their mixture, and molecular sieve content is 0.5-95wt%.The size of preformed catalyst determines that according to the diameter of reaction fractionating tower the equivalent diameter of general granules of catalyst should be less than 0.1 with the diameter ratio of reaction fractionating tower.The main effect of catalyzer is the cracking macromole, and carries out isomerization reaction simultaneously.The catalyzer that the hydrogenation reaction tower uses is loading type NiMo, NiW, CoMo, CoW, NiMoW or CoMoW sulfide catalyst, and carrier is oxide carrier or the raw material of wood-charcoal material with two mesopore composite structures, and oxide carrier is SiO
2, Al
2O
3, TiO
2, SiO
2-Al
2O
3Or Al
2O
3-TiO
2
By method production of the present invention obtain gasoline fraction (＜180 ℃〉yield at 30-40%, octane value is 75-85, density 0.70-0.76g/cm
3, can be used as the blend component of gasoline.The yield of diesel oil distillate (180-360 ℃) is at 40-60%, and cetane value is 58, density 0.83-0.86g/cm
3, condensation point is lower than-10 ℃, can be used as low-coagulation diesel oil No. 10.Combustion gas and cinder productive rate are not higher than 7%.
The mode of operate continuously, flexible operation, easy are adopted in air distillation of the present invention, catalytic distillation and hydrofining.Adopt air distillation to combine with the gas phase catalysis cracking process, the combustion gas and the cinder that take full advantage of process have reduced energy consumption, non-secondary pollution; Improve the transformation efficiency of balanced reaction by air distillation and catalytic rectification process, improved the selectivity of reaction, prolonged the Hydrobon catalyst life-span, reduced catalyst levels simultaneously; Elder generation's fractionation repeated hydrogenation has reduced the hydrogen consumption; Product yield height, wide scope of material.
Description of drawings
Fig. 1 is process flow diagram of the present invention.
Among the figure: 1 atmospheric distillation tower; 2 reaction fractionating towers; 3 hydrogenators; 4 distillation towers.
Embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme and accompanying drawing.
Embodiment 1: raw material plastics oil is injected atmospheric distillation tower, adopt the waste residue and the combustion gas that produce in the converting plastic waste to oil conversion process to heat.Cut into 300 ℃ in distillate (＜300 ℃) and heavy oil (〉 according to recovered temperature).Distillate character before and after following table 1 air distillation.
Embodiment 2: the gas phase catalysis cracking of heavy oil on molecular sieve/aluminium oxide catalyst.Heavy oil is injected the reaction fractionating tower that molecular sieve/aluminium oxide catalyst is housed to react and the rectifying distillation tower, catalyzer is made up of the aluminum oxide that contains 30% ZSM-5 and 10% β zeolite, obtain the columnar product of 2.0-3.0 mm by molding bonded, length 3-8 mm, bulk density 0.65-0.80 g/mL, intensity is greater than 40 N/mm.Adopt the waste residue and the combustion gas that produce in the converting plastic waste to oil conversion process to heat, agent-oil ratio is controlled at 1-20.The combustion gas that produces is used for the heating of distillation tower.Following table 2 is seen catalytic distillation material balance test-results.
Following table 3 is seen catalytic distillation heavy oil oil nature
Embodiment 3: hydrogenation catalyst adopts load-type nickel molybdenum sulfur catalyst.Carrier adopts SiO
2-Al
2O
3, specific surface area is at 200-400 m
2/ g, pore volume is at 0.5-2.0 cm
3/ g, the most probable pore size distribution is at 2-4 nm and 10-15nm.Cobalt molybdenum sulphide precursor adopts Xiao Suangu or Cobaltous diacetate or acetylacetone cobalt and ammonium thiomolybdate.Adopt equi-volume impregnating to prepare supported cobalt molybdenum sulphide catalyzer through dipping-drying-steps such as roasting.Following table 4 is seen reaction process condition and product composition.
As shown in Table 4, oil distillate on supported cobalt molybdenum sulphide catalyzer in 300
oC hydrofining does not detect diolefine in the product that obtains, the content of colloid, sulphur and nitrogen reduces greatly, shows that supported cobalt molybdenum sulphide catalyzer has good desulfurization removing nitric deolefination efficient.The product water-white that obtains, free from extraneous odour, the petrol and diesel oil mixture that quality is high.
Embodiment 4: the product after the hydrofining enters atmospheric distillation tower and cuts into 180 ℃ of gasoline (＜180 ℃) and diesel oil (〉 according to recovered temperature).5 tables are seen petrol and diesel oil character down.
As shown in Table 5, oil distillate on supported cobalt molybdenum sulphide catalyzer in 300
oC hydrofining does not detect diolefine in the product that obtains, the content of colloid, sulphur and nitrogen reduces greatly, shows that supported cobalt molybdenum sulphide catalyzer has good desulfurization removing nitric deolefination efficient.The product water-white that obtains, free from extraneous odour, the gasoline that quality is high and diesel oil.
Embodiment 5: be raw material with the catalytic distillation diesel oil distillate, on the basis of embodiment 5 in 4.0MPa and 300
oC carries out stability experiment, and following table 6 is seen the reaction process condition of operation in 200 hours and the product property that obtains at last.
200 hours experimental result as shown in Table 6, on load-type nickel molybdenum sulphide catalyzer in 300
oC hydrofining does not detect diolefine in the petrol and diesel oil product that air distillation obtains, reach 2 mg 100mL for gasoline gum content
-1, also be reduced to 20 mg 100mL for the diesel oil gum level
-1, containing with beginning test of sulphur and nitrogen compared constantly substantially, meets national petrol and diesel oil standard, shows the product free from extraneous odour that this technology obtains, and has good stability the petrol and diesel oil that quality is high.The above results shows that technology of the present invention has satisfactory stability.
Claims (3)
1. method of utilizing plastics oil to produce petrol and diesel oil is characterized in that: plastics oil enter distillation tower through distillation according to recovered temperature cut into＜300 ℃ of distillates and 300 ℃ of heavy oil; Distillate directly enters hydrogenator, and the control feeding temperature is at 200-350
oC, hydrogen partial pressure 1-6 MPa, volume space velocity 0.5-4.0 h
-1, hydrogen to oil volume ratio is 100-1000:1; Hydrogen recycles after separation and purification; The sulfide catalyst that hydrogenation uses, carrier is the oxide carrier with two mesopore composite structures; The gas phase catalysis cracking of heavy oil on molecular sieve/aluminium oxide catalyst; Heavy oil is injected the reaction fractionating tower that molecular sieve/aluminium oxide catalyst is housed carry out reactive distillation, distillate behind the reactive distillation directly enters hydrogenator hydrofining or mixes reaction again with converting plastic waste to oil, adopts the waste residue and the combustion gas that produce in the converting plastic waste to oil conversion process to heat; Distillate after the hydrofining distills through normal pressure, cuts into gasoline and diesel oil according to recovered temperature; Described sulfide catalyst is NiMo, NiW, CoMo, CoW, NiMoW or CoMoW.
2. method according to claim 1, be further characterized in that: described oxide carrier with two mesopore composite structures is SiO
2, Al
2O
3, TiO
2, SiO
2-Al
2O
3Or Al
2O
3-TiO
2
3. method according to claim 1 and 2 is further characterized in that: plastics oil raw material comprises lumarith Vn., vinyon, acrylic plastering, polystyrene plastic, ABS plastic, is one or two or more kinds mixing wherein.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110134368 CN102226103B (en) | 2011-05-23 | 2011-05-23 | Method for producing gasoline and diesel by utilizing plastic oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110134368 CN102226103B (en) | 2011-05-23 | 2011-05-23 | Method for producing gasoline and diesel by utilizing plastic oil |
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| CN102226103B true CN102226103B (en) | 2013-08-07 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676220A (en) * | 2012-05-15 | 2012-09-19 | 大连理工大学 | Method for producing gasoline and diesel by waste rubber oil |
| CN102839020A (en) * | 2012-07-27 | 2012-12-26 | 大连理工大学 | Method for producing gasoline and diesel oil by mixing and refining plastic oil, coal tar, ethylene tar or tire oil |
| CN102786985B (en) * | 2012-07-27 | 2015-01-07 | 大连理工大学 | Resource utilization method for waste lubricating oil |
| CN104004543A (en) * | 2014-05-05 | 2014-08-27 | 大连理工大学 | Method for catalysis upgrading regeneration of waste engine oil |
| US11473016B2 (en) * | 2019-12-23 | 2022-10-18 | Chevron U.S.A. Inc. | Circular economy for plastic waste to polyethylene and lubricating oil via crude and isomerization dewaxing units |
| KR20230031464A (en) | 2021-08-27 | 2023-03-07 | 에스케이이노베이션 주식회사 | Preparation method of Lube base oil from atmospheric residue in pyrolysis oil derived from waste plastic |
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| JP4382552B2 (en) * | 2004-03-26 | 2009-12-16 | 株式会社ジャパンエナジー | Processing method of plastic decomposition oil |
| CN101845323B (en) * | 2010-05-14 | 2013-01-30 | 大连理工大学 | Process for producing petrol and diesel oil by plastic oil |
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Effective date of registration: 20171116 Address after: 057750 New Chemical Industrial Park in Handan, Hebei province (the north side of the 309 State Road of Shoushan temple, Guantao county) Patentee after: Hebei Rong of environmental protection science and technology limited company Address before: 116100 No. 2 Ling Road, Ganjingzi District, Liaoning, Dalian Patentee before: Dalian University of Technology |