CN103555354A - 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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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, relate in particular 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 domesticly also has a large amount of import rubbish, as Zhaoqing Guangdong, plant resources in Wenling, Jinghai, Yingkou, Liaoning, Hong Kong and other places, often the electronic waste of receiving developed country, abandoned car etc. reach tens tons every year, wherein plastic waste enormous amount, is important source of pollution that cause environmental pollution.
Using plastic waste as renewable energy source, recycling is a good thinking, but due to technology imperfection, domestic waste plastic oil-refining technology has only been moved several years after being born the nineties in last century, Jiu Bei State Environmental Protection Administration (existing Chinese Ministry of Environmental Protection) forces and has forbidden, major cause is, oil Refining Technologies at that time can not realize serialization and produce, so in oil refining process, surrounding enviroment has been caused to malignant pollution, 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 are propagated by mode among the people, make waste plastic oil-refining project all the time in illegal operation state, and the environmental problem of bringing is also increasing.
In recent years along with the progress of technology and the rapid increasing of plastic waste output, the technology of country aspect waste plastic oil-refining obtained new breakthrough, therefore from policy aspect, relaxed reclaiming the restriction of the plastic waste energy, 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 serialization production problem and the coking problem of oil refining.
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 problems such as high energy consumption that prior art exists, coking.
The object of the invention is to be achieved through the following technical solutions:
A 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 ℃ of conditions, the plastic waste after pulverizing is carried out to depolymerization reaction, 45 minutes to 1 hour depolymerization reaction time;
3) use the acid product in aqueous sodium hydroxide solution and after depolymerization;
4) further wash, after washing, through oily water separation, deviate from water and the sodium sulfate in liquid, obtain plastics depolymerization chlorobenzene and dissolve liquid;
5) plastics depolymerization chlorobenzene is dissolved to liquid and carry out underpressure distillation, obtain plastics depolymerization liquid, be transported in preheating can;
6) the plastics depolymerization liquid that is preheated to 90-110 ℃ is transported in heating pyrolyze stove and is heated, Heating temperature is not higher than 360 ℃, depolymerization liquid adds catalyst for cracking to carry out cracking after forming steam, make it by macromolecular chain composition, fragment into the small molecules chain composition below 16 carbon, then after condensation, change liquid into, obtain Pyrolysis fuel oil PFO mixture; And
7) Pyrolysis fuel oil PFO is carried out to rectifying catalysis, use respectively copper catalyst and ferronickel catalyzer guiding cut to be transformed into gasoline or diesel oil.
Further, step 2) in, the input of solvent chlorobenzene is 50% of plastic waste weight, and sulphuric acid is solvent adding amount 2%.
Further, in step 4), in solution, add industrial pure water to wash, the add-on of industrial pure water is 10% of solution total amount.
Further, in step 5), collect the chlorobenzene steam after distillation when underpressure distillation obtains plastics depolymerization liquid, chlorobenzene steam is carried out to cryogenic condensation, condensed liquid continues to use as solvent cycle.
Further, described catalyst for cracking for sintering the compound nickel salt chromic salts that particle gap reaches 200-300 nanometer micropores into after pre-treatment, 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 the 300 object powder step of going forward side by side and makes lotion;
2) lotion is twisted into spheroid or the right cylinder particle that diameter is sizes between 0.5mm-4mm, then sinter molding under 800 ℃ of conditions;
3) after catalyst failure, catalyzer is sent in sintering oven, under oxidizing atmosphere, under 800 ℃ of conditions, sintering is 24 hours, recovers catalyst function.
A kind of plastic waste depolymerization liquefaction oil refining apparatus, comprise the plastics depolymerization liquefaction subsystem and the heatable catalytic cracking subsystem that by service engineering subsystem controls, connect, 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, on liquefaction depolymerization reaction tank, be communicated with sour hold-up vessel and solvent storage tank, liquefaction depolymerization reaction tank below is provided with solid-liquid separating machine, during solid-liquid separating machine is connected with and water washing tank and water-and-oil separator, water-and-oil separator connects described underpressure distillation device, water ring vacuum pump and subcooling condenser are installed on underpressure distillation device, subcooling condenser is connected with refrigerator and is connected with described solvent storage tank, described underpressure distillation device below is provided with depolymerization oil tank and connects described heatable catalytic cracking subsystem, described heatable catalytic cracking subsystem comprises pyrolyzer and rectifying tower, described pyrolyzer connects described plastics depolymerization liquefaction subsystem, pyrolyzer below is provided with electric heater and is connected with heavy oil storage tank, pyrolyzer top is provided with catalyst channels and is connected to the low-temp cooling tower of condensation withdrawing can, refrigerator is installed on low-temp cooling tower, described condensation withdrawing can connects fuel oil tank and described rectifying tower, and rectifying tower is connected with respectively gasoline tank and diesel oil tank, described service engineering subsystem comprises pump, valve, pipeline, electrical control system and boiler exhaust gas treatment system.
Further, described solid-liquid separating machine below is provided with solid residue tank, and described water-and-oil separator below is provided with Sewage treatment systems.
Further, described low-temp cooling tower is all connected described gas fired-boiler by combustion gas withdrawing can with rectifying tower.
Beneficial effect of the present invention is: on the basis of the plastics liquefaction technology such as the urethane using in chemical fibre industry, polyester, use solvent+acid catalysis technology, realized the depolymerization liquefaction of plastics; In heating pyrolyze, adopted strict temperature limitation, cracking temperature is controlled in 360 ℃, made not produce coking phenomenon in heating pyrolyze, remaining composition is liquid double distilled composition, can be used as industrial heavy oil and uses; Use porous nickel salt chromic salts load catalyzer, utilize ceramic post sintering means to make catalyzer, guaranteed 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, liquefaction depolymerization reaction tank; 3, solid-liquid separating machine; 4, in and water 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 ℃ of conditions, carries out depolymerization reaction, and the depolymerization reaction time is about 45 minutes to 1 hour.
2) product after depolymerization is acid, use aqueous sodium hydroxide solution to neutralize, then wash, after washing, through oily water separation, deviate from water and the sodium sulfate in liquid, obtain plastics depolymerization chlorobenzene and dissolve liquid, plastics depolymerization chlorobenzene is dissolved to liquid and carry 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 of hot (90-110 ℃) is transported in heating pyrolyze stove and is heated, Heating temperature is not higher than 360 ℃, since 200 ℃, produce depolymerization liquid vapour, steam is by cleaved after catalyst for cracking passage, by macromolecular chain composition, fragment into the small molecules chain composition below 16 carbon, then after condensation, change liquid into.
5) Pyrolysis fuel oil PFO is carried out to rectifying catalysis, use respectively copper catalyst and ferronickel catalyzer guiding cut to be transformed into gasoline or diesel oil.
In cracking process, mainly there are two class reactions, the one, scission reaction, generates small molecules hydro carbons and gets final product the materials such as combustion gas body, gasoline hydro carbons, diesel oil hydro carbons, is mainly the small molecules hydro carbons material below 16 carbon; Another kind of is that condensation reaction is that aromatic hydrocarbons in raw material and intermediate product, alkene etc. are condensed into larger molecular product, with Residual oil form, exists.Thermo-cracking is according to radical reaction mechanism, and C-C key place fracture that first bond energy is lower in molecule, generates two free radicals:
（R—R）n?——→?nR+nR
The small molecules free radical generating is captured hydrogen from raw material, itself becomes alkane or alkene, and raw material is become to free radical, and when two combined with radical, chain reaction stops.Catalytic cracking reaction is under certain temperature condition, the cracking occurring while having catalyzer to exist, hydrogen transference, lock and etc. characteristic reaction, and catalyzer requires to 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 cracking chain reaction and condensation chain reaction to carry out continuously, and to scission reaction, provide a large amount of hydrogen by condensation reaction.Owing to following coking reaction in reaction, after working long hours, can produce carbon distribution at catalyst surface, make catalyst deactivation, now catalyzer is burnt and processes Regenrable catalyzed dose.
Scission reaction resultant enters condensate recycling device condensation with steam form through after catalyst channels, and condensation reaction resultant flows backwards back in scission reaction still.
After scission reaction, plastics depolymerization liquid rotating becomes three kinds of compositions, and a kind of is uncondensable gas, and main component is the hydro carbons 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 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, with raffinate form, stays in scission reaction still, can be used as industrial heavy oil product, has certain recovery value.
Itself can be directly used in industrial circle the Pyrolysis fuel oil PFO that scission reaction obtains, as purposes such as oil engine such as boats and ships, boilers, if need to obtain gasoline, diesel oil, need Pyrolysis fuel oil PFO to carry out rectifying catalysis, use respectively copper catalyst conventional in petrochemical industry and ferronickel catalyzer guiding cut to be transformed into gasoline or diesel oil, for automobile-used market.
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 mainly compound nickel salt chromic salts, main component is single nickel salt, chromium sulphate, nickelous carbonate, chromium carbonate, chromic oxide and nickel oxide, on this nickel salt surface, there is cracking reaction and condensation reaction in plastic cracking oil vapour, the hydrogen ion that condensation reaction is deviate from adds in cracking reaction, completes the internal recycle of goods and materials.
In order to guarantee that the product after cracking can pass through catalyst channels completely, and condensation reaction resultant is tackled in heating pyrolyze tank, nickel salt catalyzer need 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 (300 order left and right) of 50 microns of left and right, nickel salt powder is modulated into lotion, be twisted into again spheroid or right cylinder particle that diameter is sizes between 0.5mm-4mm, then sinter molding under 800 ℃ of conditions, make granules of catalyst, the minimum hole of catalyzer granulation is about 200-300 nanometers.
In use, after catalyst pores is reached 60% by area carbon covering, catalyst failure.After catalyst failure, catalyzer is sent in sintering oven, under oxidizing atmosphere, under 800 ℃ of conditions, sintering is 24 hours, and 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 is worked first; use protective gas to be full of system space as argon gas, nitrogen etc.; avoid air residual; the stopping property that needs keeping system in subsequent production, is full of system space with oil gas, prevents that 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 plastics depolymerization liquefaction subsystem 28 and heatable catalytic cracking subsystem 29 by service engineering subsystem 30 control linkages.
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 ends are connected with plastic crusher 1, on liquefaction depolymerization reaction tank 2, be communicated with sour hold-up vessel 12 and solvent storage tank 11, liquefaction depolymerization reaction tank 2 belows are provided with solid-liquid separating machine 3, during solid-liquid separating machine 3 is connected with and water washing tank 4 and water-and-oil separator 9, water-and-oil separator 9 connects described underpressure distillation device 5, water ring vacuum pump 6 and subcooling condenser 7 are installed on underpressure distillation device 5, subcooling condenser 7 is connected with refrigerator 1 and is connected with described solvent storage tank 11, described underpressure distillation device 5 belows are provided with depolymerization oil tank 14 and connect described heatable catalytic cracking subsystem 29, described solid-liquid separating machine 3 belows are provided with solid residue tank 13, described water-and-oil separator 9 belows are provided with Sewage treatment systems 15.
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 belows are provided with electric heater 26 and are connected with heavy oil storage tank 25, pyrolyzer 16 tops are provided with catalyst channels 17 and are connected to the low-temp cooling tower 18 of condensation withdrawing can 19, refrigerator 2 27 is installed on low-temp cooling tower 18, described condensation withdrawing can 19 is connected with fuel oil tank 24 and described rectifying tower 20, and rectifying tower 20 is connected with respectively 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 is all connected described gas fired-boiler 10 by combustion gas withdrawing can 21 with rectifying tower 20.
During concrete use, plastic waste is directly pulverized in plastic crusher 1, plastic waste after pulverizing is rendered in liquefaction depolymerization reaction tank 2, by solvent storage tank 11, in depolymerization reaction tank 2, input solvent chlorobenzene, input is 50% of plastic waste weight, so by gas-steam boiler 10 feedings, dissolve the saturated 140 ℃ of steam heating of poly-retort 2 supply, at plastics, all after liquefaction, start the whipping appts in liquefaction depolymerization reaction tank 2, by sour hold-up vessel 12, to splashing into concentration in liquefaction depolymerization reaction tank 2, be simultaneously 1% sulfuric acid, add-on is 2% of quantity of solvent, when in liquefaction depolymerization reaction tank 2, fluid temperature reaches 110-130 ℃, keep temperature approximately 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, during liquid after filtration directly enters and in water washing tank 4, in startup and the whipping appts of water washing tank 4, use sodium hydroxide saturated aqueous solution to be titrated in depolymerization solution, in and depolymerization solution in acid, after pH value reaches 7, to the industrial pure water that adds solution total amount 10% in solution, all sodium sulfate composition in eluting liquid, then stop whipping appts, after standing 30 minutes of liquid, liquid is entered in water-and-oil separator 9, separated moisture is sent in Sewage treatment systems 15 and is processed, oil component enters in underpressure distillation device 5, use 6 pairs of underpressure distillation devices 5 of water ring vacuum pump to vacuumize decompression, use gas fired-boiler 10 to the saturated 140 ℃ of steam heating of underpressure distillation tank 5 supply simultaneously, the target of distillation is chlorobenzene solvent, chlorobenzene steam after distillation is condensed into liquid after subcooling condenser 7 condensations, be transported in solvent storage tank 11 and recycle, subcooling condenser 7 is by refrigerator one 8 supply water at low temperature (2-5 ℃), to guarantee the reliable recovery of chlorobenzene solvent.
After underpressure distillation completes, in underpressure distillation device 5, residuum is plastics depolymerization liquefaction oil, this part plastics depolymerization liquefaction oil is input in depolymerization oil tank 14 and is stored, for cracking.Depolymerization oil tank 14 must keep 60-80 ℃ of temperature, to keep the mobility of depolymerization liquefaction oil, guarantees that follow-up use conveying is smooth, by gas fired-boiler 10 heat supplies.Plastics depolymerization liquefaction ratio is not less than 90%.
Depolymerization liquefaction oil, from 14 outputs of depolymerization oil tank, enters in pyrolyzer 16, and pyrolyzer 16 is by electric heater 26 heat supplies, and oil temperature is controlled in 360 ℃; Liquefaction oil is heated the rear oil vapour orientation producing of boiling by catalyst channels 17, under the effect of catalyzer, there is the scission reaction of polymer long chain hydrocarbon, produce condensation reaction simultaneously, the small molecules chain hydrocarbon steam that cracking produces enters low-temp cooling tower 18 after by catalyst channels 17, the macromole long chain hydrocarbon that condensation reaction generates condenses into liquid and falls back in pyrolyzer 16 and become raffinate, can be used as industrial heavy oil and is recovered in heavy oil storage tank 25 and sells; After entering the oil vapour condensation of low-temp cooling tower 18, fall into condensation withdrawing can 19, low-temp cooling tower 18 is by refrigerator 2 27 supply water at low temperature; 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 obtaining after refining, diesel oil enter respectively direct marketing in gasoline tank 22 and diesel oil tank 23; In the condensation of catalytic pyrolysis gas and refining, in low-temp cooling tower 18 and rectifying tower 20, produce respectively a certain amount of uncondensable combustion gas, combustion gas unification is recovered in combustion gas withdrawing can 21, then is transported in gas fired-boiler 10 burning, required steam in production technique.
In this process, the service engineering subsystem consisting of pump, valve, pipeline, electrical control system, boiler exhaust gas treatment system etc. mainly requires to carry out fixing action according to technical process again.
The light-weight fuel oil of changing cracking generation is not less than 70%, and combustion gas output is about 7-9%, and being born in composition is raffinate industry heavy oil.In partly plastic, contain a small amount of chlorine, sulphur composition, in oil refining process, merge in heavy oil composition, so the lightweight oil obtaining 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 do any variation in its shape or structure; every have identical with a application or akin technical scheme, within all dropping on protection scope of the present invention.
Claims (9)
1. a plastic waste depolymerization liquefaction oil refining method, is characterized in that, comprises 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 ℃ of condition, the plastic waste after pulverizing is carried out to depolymerization reaction, 45 minutes to 1 hour depolymerization reaction time;
3) use the acid product in aqueous sodium hydroxide solution and after depolymerization;
4) further wash, after washing, through oily water separation, deviate from water and the sodium sulfate in liquid, obtain plastics depolymerization chlorobenzene and dissolve liquid;
5) plastics depolymerization chlorobenzene is dissolved to liquid and carry out underpressure distillation, obtain plastics depolymerization liquid, be transported in preheating can;
6) the plastics depolymerization liquid that is preheated to 90-110 ℃ is transported in heating pyrolyze stove and is heated, Heating temperature is not higher than 360 ℃, depolymerization liquid adds catalyst for cracking to carry out cracking after forming steam, make it by macromolecular chain composition, fragment into the small molecules chain composition below 16 carbon, then after condensation, change liquid into, obtain Pyrolysis fuel oil PFO mixture; And
7) Pyrolysis fuel oil PFO is carried out to rectifying catalysis, use respectively copper catalyst and ferronickel catalyzer guiding cut to be transformed into gasoline or diesel oil.
2. plastic waste depolymerization according to claim 1 liquefaction oil refining method, is characterized in that: step 2) in, the input of solvent chlorobenzene is 50% of plastic waste quality, sulphuric acid be solvent add quality 2%.
3. plastic waste depolymerization liquefaction oil refining method according to claim 1, is characterized in that: in step 4), in solution, add industrial pure water to wash, the add-on of industrial pure water is 10% of solution total amount.
4. plastic waste depolymerization according to claim 1 liquefaction oil refining method, it is characterized in that: in step 5), when underpressure distillation obtains plastics depolymerization liquid, collect the chlorobenzene steam after distillation, chlorobenzene steam is carried out to cryogenic condensation, 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 for to sinter the compound nickel salt chromic salts that particle gap reaches 200-300 nanometer micropore into after pre-treatment, and main component is single nickel salt, chromium sulphate, nickelous carbonate, chromium carbonate, chromic oxide and nickel oxide.
6. plastic waste depolymerization according to claim 5 liquefaction oil refining method, 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 the 300 object powder step of going forward side by side and makes lotion;
2) lotion is twisted into spheroid or the right cylinder particle that diameter is sizes between 0.5mm-4mm, then sinter molding under 800 ℃ of conditions;
3) after catalyst failure, catalyzer is sent in sintering oven, under oxidizing atmosphere, under 800 ℃ of conditions, sintering is 24 hours, recovers catalyst function.
7. plastic waste depolymerization liquefaction oil refining apparatus, comprise plastics depolymerization liquefaction subsystem (28) and heatable catalytic cracking subsystem (29) by service engineering subsystem (30) control linkage, 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), on liquefaction depolymerization reaction tank (2), be 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), during solid-liquid separating machine (3) is connected with and water washing tank (4) and water-and-oil separator (9), water-and-oil separator (9) connects described underpressure distillation device (5), water ring vacuum pump (6) and subcooling condenser (7) are installed on underpressure distillation device (5), 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), refrigerator two (27) is installed on low-temp cooling tower (18), described condensation withdrawing can (19) is connected with fuel oil tank (24) and described rectifying tower (20), rectifying tower (20) is connected with respectively 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. described plastic waste depolymerization liquefaction oil refining apparatus 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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| CN104449885A (en) * | 2014-11-14 | 2015-03-25 | 西藏拜尔环保科技有限公司 | Method for preparing light-weight fuel from waste plastic |
| CN106085488A (en) * | 2016-07-23 | 2016-11-09 | 侯平福 | The preparation method of a kind of recycle oil and the pickling nertralizer in preparation process thereof |
| CN107922848A (en) * | 2015-12-18 | 2018-04-17 | 索尔维公司 | Method for producing wax and liquid fuel from waste plastics |
| US10551059B2 (en) | 2014-12-17 | 2020-02-04 | Pilkington Group Limited | Furnace |
| CN113980700A (en) * | 2021-12-14 | 2022-01-28 | 青海天创新能源科技有限公司 | Production line and method for depolymerizing waste plastics and converting waste plastics into fuel oil |
Citations (4)
| 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 |
-
2013
- 2013-10-22 CN CN201310502769.9A patent/CN103555354B/en not_active Expired - Fee Related
Patent Citations (4)
| 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 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449885A (en) * | 2014-11-14 | 2015-03-25 | 西藏拜尔环保科技有限公司 | Method for preparing light-weight fuel from waste plastic |
| US10551059B2 (en) | 2014-12-17 | 2020-02-04 | Pilkington Group Limited | Furnace |
| CN107922848A (en) * | 2015-12-18 | 2018-04-17 | 索尔维公司 | Method for producing wax and liquid fuel from waste plastics |
| CN106085488A (en) * | 2016-07-23 | 2016-11-09 | 侯平福 | The preparation method of a kind of recycle oil and the pickling nertralizer in preparation process thereof |
| CN113980700A (en) * | 2021-12-14 | 2022-01-28 | 青海天创新能源科技有限公司 | Production line and method for depolymerizing waste plastics and converting waste plastics into fuel oil |
| 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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