CN103555354B - Method for refining oil through depolymerizing and liquifying waste plastics and device used in method - Google Patents
Method for refining oil through depolymerizing and liquifying waste plastics and device used in method Download PDFInfo
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- CN103555354B CN103555354B CN201310502769.9A CN201310502769A CN103555354B CN 103555354 B CN103555354 B CN 103555354B CN 201310502769 A CN201310502769 A CN 201310502769A CN 103555354 B CN103555354 B CN 103555354B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention relates to a method for refining oil through depolymerizing and liquifying waste plastics and a device used in the method. The method comprises the following steps of (1) crushing the waste plastics; (2) carrying out depolymerization reaction on the crushed waste plastics; (3) neutralizing a depolymerized acidic product by using a sodium hydroxide solution; (4) further washing to obtain a plastic depolymerization chlorobenzene dissolved liquid; (5) carrying out reduced pressure distillation on the plastic depolymerization chlorobenzene dissolved liquid; (6) carrying out cracking reaction and condensing to obtain a cracked fuel oil mixture; (7) rectifying and catalyzing the cracked fuel oil. The method has the beneficial effects that the depolymerization and liquidation of the plastics are realized by using a solvent and acid catalysis technology on the basis of a liquifying technology for plastics such as polyurethane, polyester and the like used in the chemical fiber industry; the cracking temperature is controlled within 360 DEG C in heating and cracking, so that the coking phenomenon is avoided; a porous nickel and chromium salt loaded catalyst is used, and the catalyst is prepared by using a ceramic sintering method, so that the quality of a refined oil product is ensured.
Description
Technical field
The present invention relates to chemical field, particularly relate to a kind of plastic waste depolymerization liquefaction oil refining method and device thereof.
Background technology
Plastic waste has become the public hazards in the world, and the pollution that plastic waste environment causes is very serious.Domestic annual generation plastic waste total amount is not less than 2,500 ten thousand tons, and scale is very huge.And domestic import rubbish a large amount of in addition, average annual electronic waste, abandoned car etc. of developed country received as every in Zhaoqing Guangdong, plant resources in Wenling, Jinghai, Yingkou, Liaoning, Hong Kong and other places reaches tens tons, wherein plastic waste enormous amount causes environmental pollution important source of pollution.
Being recycled as renewable energy source by plastic waste is a good thinking, but due to technology imperfection, domestic waste plastic oil-refining technology has only run several years after being born the nineties in last century, just force by State Environmental Protection Administration (existing Chinese Ministry of Environmental Protection) and prohibit, major cause is, oil Refining Technologies at that time can not realize continuous prodution, therefore causes malignant pollution to surrounding enviroment in oil refining process, and within the scope of 500 meters, refinery periphery, not even a blade of grass grows.
After this, a large amount of contaminative waste plastic oil-refining technology is propagated by mode among the people, and make waste plastic oil-refining project be in illegal operation state all the time, the environmental problem brought is also increasing.
In recent years along with the progress of technology and the rapid increasing of plastic waste output, the technology of country in waste plastic oil-refining achieves new breakthrough, therefore the restriction to reclaiming the plastic waste energy is relaxed from policy aspect, but for environment protecting oil Refining Technologies not up to standard still in strict restriction.
For domestic, waste plastic oil-refining technology maturation fewer, chief reason is still the continuous prodution problem of refining oil and coking problem.
Summary of the invention
The object of this invention is to provide a kind of plastic waste depolymerization liquefaction oil refining method and device thereof, to solve the problem such as high energy consumption, coking that prior art exists.
The object of the invention is to be achieved through the following technical solutions:
A kind of plastic waste depolymerization liquefaction oil refining method, comprises the following steps:
1) plastic waste is pulverized;
2) use chlorobenzene as liquefaction solvent, the sulfuric acid of working concentration 1% is catalyzer, under 110-130 DEG C of conditions, carry out depolymerization reaction, 45 minutes to 1 hour depolymerization reaction time to the plastic waste after pulverizing;
3) acid product in aqueous sodium hydroxide solution and after depolymerization is used;
4) wash further, after washing, deviate from water in liquid and sodium sulfate through oily water separation, obtain plastics depolymerization chlorobenzene and dissolve liquid;
5) liquid is dissolved to plastics depolymerization chlorobenzene and carry out underpressure distillation, obtain plastics depolymerization liquid, be transported in preheating can;
6) the plastics depolymerization Liquid transfer being preheated to 90-110 DEG C is heated in heating pyrolyze stove, Heating temperature is not higher than 360 DEG C, depolymerization liquid adds catalyst for cracking after forming steam and carries out cracking, it is made to fragment into the small molecules chain composition of below 16 carbon by macromolecular chain composition, then after condensation, change liquid into, obtain Pyrolysis fuel oil PFO mixture; And
7) rectifying catalysis is carried out to Pyrolysis fuel oil PFO, use copper catalyst and ferronickel catalyzer to guide cut to be transformed into gasoline or diesel oil respectively.
Further, step 2) in, the input of solvent chlorobenzene is 50% of plastic waste weight, and sulphuric acid is 2% of solvent adding amount.
Further, in step 4), add industrial pure water and wash in solution, the add-on of industrial pure water is 10% of solution total amount.
Further, in step 5), collect the chlorobenzene steam after distillation, carry out cryogenic condensation to chlorobenzene steam while underpressure distillation obtains plastics depolymerization liquid, condensed liquid continues to use as solvent cycle.
Further, described catalyst for cracking is after pre-treatment, sinter the compound nickel salt chromic salts that particulate interspaces reaches 200-300 nanometer micropores into, main component is single nickel salt, chromium sulphate, nickelous carbonate, chromium carbonate, chromic oxide and nickel oxide, and the preparation method of described compound nickel salt chromic salts catalyst for cracking comprises the following steps:
1) compound nickel salt chromic salts catalyst for cracking is ground into a 300 object powder step of going forward side by side and makes lotion;
2) lotion is twisted into the spheroid that diameter is sizes between 0.5mm-4mm or right cylinder particle, then sinter molding under 800 DEG C of conditions;
3) when after catalyst failure, catalyzer is sent in sintering oven, under oxidizing atmosphere, under 800 DEG C of conditions, sinter 24 hours, recover catalyst function.
A kind of plastic waste depolymerization liquefaction oil refining apparatus, comprise the plastics depolymerization liquefaction subsystem and heatable catalytic cracking subsystem that are connected by service engineering subsystem controls, described plastics depolymerization liquefaction subsystem comprises liquefaction depolymerization reaction tank and underpressure distillation device, described liquefaction depolymerization reaction tank and underpressure distillation device are all connected with gas fired-boiler, liquefaction depolymerization reaction tank front end is connected with plastic crusher, liquefaction depolymerization reaction tank is communicated with sour hold-up vessel and solvent storage tank, solid-liquid separating machine is provided with below liquefaction depolymerization reaction tank, solid-liquid separating machine is connected with neutralization &washing tank and water-and-oil separator, water-and-oil separator connects described underpressure distillation device, underpressure distillation device is provided with water ring vacuum pump and subcooling condenser, subcooling condenser is connected with refrigerator and is connected with described solvent storage tank, be provided with depolymerization oil tank below described underpressure distillation device and connect described heatable catalytic cracking subsystem, described heatable catalytic cracking subsystem comprises pyrolyzer and rectifying tower, described pyrolyzer connects described plastics depolymerization liquefaction subsystem, below pyrolyzer, electric heater be installed and be connected with heavy oil storage tank, above pyrolyzer, catalyst channels be installed and be connected to the low-temp cooling tower of condensation withdrawing can, low-temp cooling tower is provided with refrigerator, described condensation withdrawing can connects fuel oil tank and described rectifying tower, and rectifying tower is connected to gasoline tank and diesel oil tank, described service engineering subsystem comprises pump, valve, pipeline, electrical control system and boiler exhaust gas treatment system.
Further, below described solid-liquid separating machine, be provided with solid residue tank, below described water-and-oil separator, Sewage treatment systems be installed.
Further, described low-temp cooling tower and rectifying tower are all connected described gas fired-boiler by combustion gas withdrawing can.
Beneficial effect of the present invention is: on the basis of the plastics liquefaction technology such as urethane, polyester of chemical fibre industry use, uses solvent+acid catalysis technology, achieves the depolymerization liquefaction of plastics; In heating pyrolyze, have employed strict temperature limitation, controlled by cracking temperature within 360 DEG C, make not produce coking phenomenon in heating pyrolyze, residual components is liquid double distilled composition, can use as industrial heavy oil; Use porous nickel salt chromic salts load catalyzer, utilize ceramic post sintering means to make catalyzer, ensure that oil refining oil quality.
Accompanying drawing explanation
With reference to the accompanying drawings the present invention is described in further detail below.
Fig. 1 is the structural representation of plastic waste depolymerization liquefaction oil refining apparatus described in the embodiment of the present invention;
Fig. 2 is the structural representation of plastic waste depolymerization liquefaction oil refining apparatus plastics depolymerization liquefaction subsystem described in the embodiment of the present invention;
Fig. 3 is the structural representation of plastic waste depolymerization liquefaction oil refining apparatus heatable catalytic cracking subsystem described in the embodiment of the present invention.
In figure:
1, plastic crusher; 2, liquefy depolymerization reaction tank; 3, solid-liquid separating machine; 4, neutralization &washing tank; 5, underpressure distillation device; 6, water ring vacuum pump; 7, subcooling condenser; 8, refrigerator one; 9, water-and-oil separator; 10, gas fired-boiler; 11, solvent storage tank; 12, sour hold-up vessel; 13, solid residue tank; 14, depolymerization oil tank; 15, Sewage treatment systems; 16, pyrolyzer; 17, catalyst channels; 18, low-temp cooling tower; 19, condensation withdrawing can; 20, rectifying tower; 21, combustion gas withdrawing can; 22, gasoline tank; 23, diesel oil tank; 24, fuel oil tank; 25, heavy oil storage tank; 26, electric heater; 27, refrigerator two; 28, plastics depolymerization liquefaction subsystem; 29, heatable catalytic cracking subsystem; 30, service engineering subsystem.
Embodiment
A kind of plastic waste depolymerization liquefaction oil refining method described in the embodiment of the present invention, comprises the following steps:
1) use chlorobenzene as liquefaction solvent, the sulfuric acid of working concentration 1% is catalyzer, under 110-130 DEG C of conditions, carry out depolymerization reaction, and the depolymerization reaction time is about 45 minutes to 1 hour.
2) product after depolymerization is acid, aqueous sodium hydroxide solution is used to neutralize, then wash, water in liquid and sodium sulfate is deviate from through oily water separation after washing, obtain plastics depolymerization chlorobenzene and dissolve liquid, liquid is dissolved to plastics depolymerization chlorobenzene and carries out underpressure distillation, reclaim chlorobenzene solvent, solvent recovering rate is not less than 90%, continues on for liquefaction solvent.
3) after underpressure distillation, obtain plastics depolymerization liquid, be transported in preheating can, prepare to supply raw material to heating pyrolyze.
4) the plastics depolymerization Liquid transfer of hot (90-110 DEG C) is heated in heating pyrolyze stove, Heating temperature is not higher than 360 DEG C, depolymerization liquid vapour is produced from 200 DEG C, steam is by cleaved after catalyst for cracking passage, fragmented into the small molecules chain composition of below 16 carbon by macromolecular chain composition, then after condensation, change liquid into.
5) rectifying catalysis is carried out to Pyrolysis fuel oil PFO, use copper catalyst and ferronickel catalyzer to guide cut to be transformed into gasoline or diesel oil respectively.
In cracking process, main two classes that occur are reacted, and one is scission reaction, generate small molecules hydro carbons and get final product the materials such as combustion gas body, petrol hydrocarbon types, diesel oil hydro carbons, the small molecules hydrocarbons mainly below 16 carbon; Another kind of is that aromatic hydrocarbons, alkene etc. in condensation reaction and raw material and intermediate product is condensed into larger molecular product, exists with Residual oil form.Thermo-cracking is according to radical reaction mechanism, and C-C key place fracture that bond energy is lower first in the molecule, generates two free radicals:
（R—R）n ——→ nR+nR
The small molecules free radical generated captures hydrogen from raw material, itself becomes alkane or alkene, and raw material is become free radical, and when two combined with radical, chain reaction stops.Catalytic cracking reaction is under certain temperature condition, the cracking occurred when having catalyzer to exist, hydrogen transference, lock and etc. characteristic reaction, and catalyst requirement must have isomerization function, and isomeric hydrocarbon content in product is increased.The catalyzer that we adopt is the nickel salt catalyzer of nanometer micropore, can promote that cracking chain reaction and condensation chain reaction are carried out continuously, and provide a large amount of hydrogen by condensation reaction to scission reaction.Due to coking reaction adjoint in reaction, carbon distribution can be produced at catalyst surface after working long hours, make catalyst deactivation, now Regenrable catalyzed dose of process be burnt to catalyzer.
Scission reaction resultant enters condensate recycling device condensation with steam form through after catalyst channels, and condensation reaction resultant flows back in scission reaction still.
After scission reaction, plastics depolymerization liquid rotating becomes three kinds of compositions, and one is uncondensable gas, and main component is the hydro carbons of below four carbon, is inflammable gas; The second is condensable liquid, and main component is the hydro carbons of five carbon to ten six carbon, has the hydro carbons of below 20 a small amount of carbon, is the mixture of gasoline, diesel oil, kerosene composition, namely our target product oil fuel; The third is double distilled composition, stays in scission reaction still with raffinate form, as industrial heavy oil product, can have certain recovery value.
The Pyrolysis fuel oil PFO that scission reaction obtains itself can be directly used in industrial circle, as purposes such as the oil engines such as boats and ships, boiler, if need to obtain gasoline, diesel oil, then need to carry out rectifying catalysis to Pyrolysis fuel oil PFO, copper catalyst conventional in petrochemical industry and ferronickel catalyzer is used to guide cut to be transformed into gasoline or diesel oil, for automobile-used market respectively.
The catalyst for cracking that the present invention uses is nickel salt and chromic salts composite catalyst, catalyzer principle is as follows: nickel salt catalyzer is compound nickel salt chromic salts mainly, main component is single nickel salt, chromium sulphate, nickelous carbonate, chromium carbonate, chromic oxide and nickel oxide, cracking reaction and condensation reaction is there is in plastic cracking oil vapour on this nickel salt surface, the hydrogen ion that condensation reaction is deviate from adds in cracking reaction, completes the internal recycle of goods and materials.
In order to ensure that condensation reaction resultant completely by catalyst channels, and can be tackled in heating pyrolyze tank by the product after cracking, need nickel salt catalyzer to be made into the porous small ball that hole is 200-300 nanometers, concrete manufacture craft is as follows:
Nickel salt catalyst powder is broken into the powder (about 300 orders) of 50 microns, nickel salt powder is modulated into lotion, be twisted into spheroid or right cylinder particle that diameter is sizes between 0.5mm-4mm again, then sinter molding under 800 DEG C of conditions, make granules of catalyst, the minimum hole that particle made by catalyzer is about 200-300 nanometers.
In using, after catalyst pores is reached 60% by area carbon covering, catalyst failure.After catalyst failure, sent into by catalyzer in sintering oven, under oxidizing atmosphere, under 800 DEG C of conditions, sinter 24 hours, area carbon oxidation disappears, catalyst regeneration restore funcitons.
In oil refining system of waste plastics; basic reaction guarantee condition is anoxybiotic; the means that we realize anoxybiotic are: before system works first; protective gas such as argon gas, nitrogen etc. is used to be full of system space; avoid air residual; need the stopping property of keeping system in subsequent production, be full of system space with oil gas, prevent cracked gas from leaking.
As Figure 1-3, the plastic waste depolymerization liquefaction oil refining apparatus described in the embodiment of the present invention, comprises the plastics depolymerization liquefaction subsystem 28 by service engineering subsystem 30 control linkage and heatable catalytic cracking subsystem 29.
Described plastics depolymerization liquefaction subsystem 28 comprises liquefaction depolymerization reaction tank 2 and underpressure distillation device 5, described liquefaction depolymerization reaction tank 2 and underpressure distillation device 5 are all connected with gas fired-boiler 10, liquefaction depolymerization reaction tank 2 front end is connected with plastic crusher 1, liquefaction depolymerization reaction tank 2 is communicated with sour hold-up vessel 12 and solvent storage tank 11, solid-liquid separating machine 3 is provided with below liquefaction depolymerization reaction tank 2, solid-liquid separating machine 3 is connected with neutralization &washing tank 4 and water-and-oil separator 9, water-and-oil separator 9 connects described underpressure distillation device 5, underpressure distillation device 5 is provided with water ring vacuum pump 6 and subcooling condenser 7, subcooling condenser 7 is connected with refrigerator 1 and is connected with described solvent storage tank 11, be provided with depolymerization oil tank 14 below described underpressure distillation device 5 and connect described heatable catalytic cracking subsystem 29, solid residue tank 13 is provided with below described solid-liquid separating machine 3, below described water-and-oil separator 9, Sewage treatment systems 15 is installed.
Described heatable catalytic cracking subsystem 29 comprises pyrolyzer 16 and rectifying tower 20, described pyrolyzer 16 connects described plastics depolymerization liquefaction subsystem 28, electric heater 26 is installed below pyrolyzer 16 and is connected with heavy oil storage tank 25, catalyst channels 17 is installed above pyrolyzer 16 and is connected to the low-temp cooling tower 18 of condensation withdrawing can 19, low-temp cooling tower 18 is provided with refrigerator 2 27, described condensation withdrawing can 19 is connected with fuel oil tank 24 and described rectifying tower 20, and rectifying tower 20 is connected to gasoline tank 22 and diesel oil tank 23; Described service engineering subsystem 30 comprises pump, valve, pipeline, electrical control system and boiler exhaust gas treatment system; Described low-temp cooling tower 18 and rectifying tower 20 are all connected described gas fired-boiler 10 by combustion gas withdrawing can 21.
During concrete use, plastic waste is directly pulverized in plastic crusher 1, plastic waste after pulverizing is rendered in liquefaction depolymerization reaction tank 2, in depolymerization reaction tank 2, solvent chlorobenzene is inputted by solvent storage tank 11, input is 50% of plastic waste weight, so dissolving poly-retort 2 by gas-steam boiler 10 feeding supplies saturated 140 DEG C of steam heating, the whipping appts in liquefaction depolymerization reaction tank 2 is started at the whole post liquefaction of plastics, in liquefaction depolymerization reaction tank 2, instill the sulfuric acid that concentration is 1% by sour hold-up vessel 12 simultaneously, add-on is 2% of quantity of solvent, when in liquefaction depolymerization reaction tank 2, fluid temperature reaches 110-130 DEG C, keep temperature about 30 minutes, depolymerization reaction completes, obtain plastics depolymerization and dissolve liquid.
Depolymerization solution is input in solid-liquid separating machine 3, leach in liquid is dissolved impurity, impurity enters in solid residue tank 13 and processes, liquid after filtration directly enters in neutralization &washing tank 4, start the whipping appts of neutralization &washing tank 4, sodium hydroxide saturated aqueous solution is used to be titrated in depolymerization solution, in and depolymerization solution in acid, after pH value reaches 7, the industrial pure water of solution total amount 10% is added in solution, sodium sulfate compositions all in eluting liquid, then whipping appts is stopped, liquid left standstill after 30 minutes, liquid is entered in water-and-oil separator 9, the moisture be separated sends into process in Sewage treatment systems 15, oil component enters in underpressure distillation device 5, water ring vacuum pump 6 pairs of underpressure distillation devices 5 are used to vacuumize decompression, use gas fired-boiler 10 to supply saturated 140 DEG C of steam heating to underpressure distillation tank 5 simultaneously, the target of distillation is chlorobenzene solvent, chlorobenzene steam after distillation is condensed into liquid after subcooling condenser 7 condensation, be transported in solvent storage tank 11 and recycle, subcooling condenser 7 supplies water at low temperature (2-5 DEG C) by refrigerator 1, to guarantee the reliable recovery of chlorobenzene solvent.
After underpressure distillation completes, in underpressure distillation device 5, residuum is plastics depolymerization liquefaction oil, is input to by this part plastics depolymerization liquefaction oil in depolymerization oil tank 14 and stores, for cracking.Depolymerization oil tank 14 must keep 60-80 DEG C of temperature, to keep the mobility of depolymerization liquefaction oil, ensures that follow-up use conveying is smooth, by gas fired-boiler 10 heat supply.Plastics depolymerization liquefaction ratio is not less than 90%.
Depolymerization liquefaction oil exports from depolymerization oil tank 14, enters in pyrolyzer 16, and pyrolyzer 16 is by electric heater 26 heat supply, and Oil-temperature control is within 360 DEG C; The oil vapour that liquefaction oil produces after being heated and seething with excitement is directed through catalyst channels 17, the scission reaction of high polymer long chain hydrocarbon is there is under the effect of catalyzer, produce condensation reaction simultaneously, the small molecules chain hydrocarbon steam that cracking produces is by entering low-temp cooling tower 18 after catalyst channels 17, the macromole long chain hydrocarbon that condensation reaction generates then condenses into liquid and falls back in pyrolyzer 16 and become raffinate, can be recovered in heavy oil storage tank 25 sell as industrial heavy oil; Fall into condensation withdrawing can 19 after entering the oil vapour condensation of low-temp cooling tower 18, low-temp cooling tower 18 supplies water at low temperature by refrigerator 2 27; In condensation withdrawing can 19, regenerant is oil fuel, can enter direct marketing in fuel oil tank 24, also can enter refining vapour, diesel oil in rectifying tower 20, and the vapour obtained after refining, diesel oil enter direct marketing in gasoline tank 22 and diesel oil tank 23 respectively; In the condensation of catalytic pyrolysis gas and refining, a certain amount of uncondensable combustion gas is produced respectively by low-temp cooling tower 18 and rectifying tower 20, combustion gas is unified to be recovered in combustion gas withdrawing can 21, then is transported to burning in gas fired-boiler 10, steam required in production technique.
Again in this process, the service engineering subsystem be made up of pump, valve, pipeline, electrical control system, boiler exhaust gas treatment system etc. mainly requires to perform fixing action according to technical process.
The light-weight fuel oil changing cracking generation is not less than 70%, and generator yield is about 7-9%, and being born in composition is raffinate industry heavy oil.Containing a small amount of chlorine, sulphur composition in partly plastic, merge in oil refining process in heavy oil composition, the lightweight oil therefore obtained is substantially not chloride, sulphur.
The present invention is not limited to above-mentioned preferred forms; anyone can draw other various forms of products under enlightenment of the present invention; no matter but any change is done in its shape or structure; every have identical with the application or akin technical scheme, all drops within protection scope of the present invention.
Claims (9)
1. a plastic waste depolymerization liquefaction oil refining method, is characterized in that, comprise the following steps:
1) plastic waste is pulverized;
2) use chlorobenzene as liquefaction solvent, the sulfuric acid of functional quality concentration 1% is catalyzer, under 110-130 DEG C of condition, carry out depolymerization reaction, 45 minutes to 1 hour depolymerization reaction time to the plastic waste after pulverizing;
3) acid product in aqueous sodium hydroxide solution and after depolymerization is used;
4) wash further, after washing, deviate from water in liquid and sodium sulfate through oily water separation, obtain plastics depolymerization chlorobenzene and dissolve liquid;
5) liquid is dissolved to plastics depolymerization chlorobenzene and carry out underpressure distillation, obtain plastics depolymerization liquid, be transported in preheating can;
6) the plastics depolymerization Liquid transfer being preheated to 90-110 DEG C is heated in heating pyrolyze stove, Heating temperature is not higher than 360 DEG C, depolymerization liquid adds catalyst for cracking after forming steam and carries out cracking, it is made to fragment into the small molecules chain composition of below 16 carbon by macromolecular chain composition, then after condensation, change liquid into, obtain Pyrolysis fuel oil PFO mixture; And
7) rectifying catalysis is carried out to Pyrolysis fuel oil PFO, use copper catalyst and ferronickel catalyzer to guide cut to be transformed into gasoline or diesel oil respectively.
2. plastic waste depolymerization liquefaction oil refining method according to claim 1, is characterized in that: step 2) in, the input of solvent chlorobenzene is 50% of plastic waste quality, and sulphuric acid is that solvent adds 2% of quality.
3. plastic waste depolymerization liquefaction oil refining method according to claim 1, it is characterized in that: in step 4), add industrial pure water and wash in solution, the add-on of industrial pure water is 10% of solution total amount.
4. plastic waste depolymerization liquefaction oil refining method according to claim 1, it is characterized in that: in step 5), collect the chlorobenzene steam after distillation while underpressure distillation obtains plastics depolymerization liquid, carry out cryogenic condensation to chlorobenzene steam, condensed liquid continues to use as solvent cycle.
5. according to the plastic waste depolymerization liquefaction oil refining method described in claim 1, it is characterized in that: described catalyst for cracking is after pre-treatment, sinter the compound nickel salt chromic salts that particulate interspaces reaches 200-300 nanometer micropore into, and main component is single nickel salt, chromium sulphate, nickelous carbonate, chromium carbonate, chromic oxide and nickel oxide.
6. plastic waste depolymerization liquefaction oil refining method according to claim 5, is characterized in that: the preparation method of described compound nickel salt chromic salts catalyst for cracking comprises the following steps:
1) compound nickel salt chromic salts catalyst for cracking is ground into a 300 object powder step of going forward side by side and makes lotion;
2) lotion is twisted into the spheroid that diameter is sizes between 0.5mm-4mm or right cylinder particle, then sinter molding under 800 DEG C of conditions;
3) when after catalyst failure, catalyzer is sent in sintering oven, under oxidizing atmosphere, under 800 DEG C of conditions, sinter 24 hours, recover catalyst function.
7. a plastic waste depolymerization liquefaction oil refining apparatus, comprise plastics depolymerization liquefaction subsystem (28) by service engineering subsystem (30) control linkage and heatable catalytic cracking subsystem (29), it is characterized in that: described plastics depolymerization liquefaction subsystem (28) comprises liquefaction depolymerization reaction tank (2) and underpressure distillation device (5), described liquefaction depolymerization reaction tank (2) and underpressure distillation device (5) are all connected with gas fired-boiler (10), liquefaction depolymerization reaction tank (2) front end is connected with plastic crusher (1), liquefaction depolymerization reaction tank (2) is communicated with sour hold-up vessel (12) and solvent storage tank (11), liquefaction depolymerization reaction tank (2) below is provided with solid-liquid separating machine (3), solid-liquid separating machine (3) is connected with neutralization &washing tank (4) and water-and-oil separator (9), water-and-oil separator (9) connects described underpressure distillation device (5), underpressure distillation device (5) is provided with water ring vacuum pump (6) and subcooling condenser (7), subcooling condenser (7) is connected with refrigerator one (8) and is connected with described solvent storage tank (11), described underpressure distillation device (5) below is provided with depolymerization oil tank (14) and connects described heatable catalytic cracking subsystem (29), described heatable catalytic cracking subsystem (29) comprises pyrolyzer (16) and rectifying tower (20), described pyrolyzer (16) connects described plastics depolymerization liquefaction subsystem (28), pyrolyzer (16) below is provided with electric heater (26) and is connected with heavy oil storage tank (25), pyrolyzer (16) top is provided with catalyst channels (17) and is connected to the low-temp cooling tower (18) of condensation withdrawing can (19), low-temp cooling tower (18) is provided with refrigerator two (27), described condensation withdrawing can (19) is connected with fuel oil tank (24) and described rectifying tower (20), rectifying tower (20) is connected to gasoline tank (22) and diesel oil tank (23), described service engineering subsystem (30) comprises pump, valve, pipeline, electrical control system and boiler exhaust gas treatment system.
8., according to the plastic waste depolymerization liquefaction oil refining apparatus described in claim 7, it is characterized in that: described solid-liquid separating machine (3) below is provided with solid residue tank (13), described water-and-oil separator (9) below is provided with Sewage treatment systems (15).
9. plastic waste depolymerization liquefaction oil refining apparatus described according to Claim 8, is characterized in that: described low-temp cooling tower (18) is all connected described gas fired-boiler (10) by combustion gas withdrawing can (21) with rectifying tower (20).
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| CN104449885B (en) * | 2014-11-14 | 2016-12-07 | 西藏拜尔环保科技有限公司 | A kind of method utilizing waste plastics to prepare light Fuel |
| MY186393A (en) | 2014-12-17 | 2021-07-22 | Pilkington Group Ltd | Furnace |
| CN107922848A (en) * | 2015-12-18 | 2018-04-17 | 索尔维公司 | Method for producing wax and liquid fuel from waste plastics |
| CN106085488B (en) * | 2016-07-23 | 2017-12-01 | 侯平福 | A kind of preparation method of recycle oil and its pickling nertralizer in preparation process |
| CN113980700B (en) * | 2021-12-14 | 2023-12-22 | 青海天创新能源科技有限公司 | Production line and method for depolymerizing and converting waste plastics into fuel oil |
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| CN1562947A (en) * | 2004-04-08 | 2005-01-12 | 浙江大学 | Method for producing benzoic acid by degrading waste plastic of polystyrene through catalysis in liquid phase |
| CN101161781A (en) * | 2006-10-14 | 2008-04-16 | 张军 | Method for preparing liquefied petroleum gas by employing waste and old plastics |
| CN101235298A (en) * | 2008-01-16 | 2008-08-06 | 任春山 | Technique for preparing substitutive diesel oil from coal tar |
| CN203530234U (en) * | 2013-10-22 | 2014-04-09 | 惠州市神州创宇低碳技术发展有限公司 | Waste plastic depolymerizing liquefying oil-refining device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562947A (en) * | 2004-04-08 | 2005-01-12 | 浙江大学 | Method for producing benzoic acid by degrading waste plastic of polystyrene through catalysis in liquid phase |
| CN101161781A (en) * | 2006-10-14 | 2008-04-16 | 张军 | Method for preparing liquefied petroleum gas by employing waste and old plastics |
| CN101235298A (en) * | 2008-01-16 | 2008-08-06 | 任春山 | Technique for preparing substitutive diesel oil from coal tar |
| CN203530234U (en) * | 2013-10-22 | 2014-04-09 | 惠州市神州创宇低碳技术发展有限公司 | Waste plastic depolymerizing liquefying oil-refining device |
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