CN1397627A - Process and equipment for preparing gasoline and diesel oil from waste plastics and/or heavy oil - Google Patents

Process and equipment for preparing gasoline and diesel oil from waste plastics and/or heavy oil Download PDF

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Publication number
CN1397627A
CN1397627A CN 01120570 CN01120570A CN1397627A CN 1397627 A CN1397627 A CN 1397627A CN 01120570 CN01120570 CN 01120570 CN 01120570 A CN01120570 A CN 01120570A CN 1397627 A CN1397627 A CN 1397627A
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outlet
scission reaction
reaction
reactor
steel pipe
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张远谋
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GUOSHUO SCIENCE TECHNOLOGY DEVELOPMENT CO LTD BEIJING
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GUOSHUO SCIENCE TECHNOLOGY DEVELOPMENT CO LTD BEIJING
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Priority to CN 01120570 priority Critical patent/CN1397627A/en
Priority to PCT/CN2001/001516 priority patent/WO2003010258A1/en
Publication of CN1397627A publication Critical patent/CN1397627A/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste

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

Abstract

A process for preparing gasoline and diesel oil from waste plastics and/or heavy oil features the raw material is thermally cracked and then catalytically cracked at different temp. Its advantages are continuous production, high output rate, and discharging inorgnaic material. Its system is composed of cracking reactor, spiral tube type reactor and hydrocarbon oil collector.

Description

A kind of method and apparatus of producing gasoline, diesel with plastic waste and/or heavy oil
The present invention relates to plastic waste and/or heavy oil is the method and apparatus of raw material production gasoline, diesel, is a kind of method and apparatus of producing gasoline, diesel oil and low boiling hydrocarbon by thermo-cracking and catalytic pyrolysis from plastic waste and/or heavy oil.
About plastic waste, heavy oil and high boiling hydrocarbon is the existing a lot of reports of method and apparatus of raw material production low boiling hydrocarbon, a kind of method and apparatus of producing hydro carbons from plastic waste or waste rubber is disclosed at EP-A-0607862 (the application people is Mazda Motor Corporation), reactor is vertical, does not disclose the discharge method of reaction residues.In ZL94213266.1, a kind of equipment with plastic waste production gasoline, diesel is disclosed, adopt the vertical retort structure, the residue of discharging at the bottom of the still contains a large amount of hydrocarbon ils, causes the yield of product to reduce.In ZL97225728.4, plastic waste and crack crude equipment are disclosed, the Slagoff method that adopts vertical cracking still and spiral to combine with circulation, the residue of discharge contains a large amount of hydrocarbon ils equally.In many similar application in the whole world and disclosed patent documentation such as the USP 5744668 of USP4851601, JP0386790 and the applicant invention, to the oiling reduction of plastic waste and/or high boiling hydrocarbon or the residue discharging in the cracking process, the residue serialization discharging in particularly producing is not all reported.
Now, the main key issue that the oiling reduction technique of plastic waste or heavy oil exists is deslagging difficulty, the easy coking of reactor, causes producing discontinuous instability, can't mass industrialized production.Adopt mostly and be interrupted deslagging, and contain a large amount of hydrocarbon ils in the slag, product yield reduces.
Purpose of the present invention is exactly the weakness that will overcome above-mentioned technology, and a kind of method and apparatus of producing gasoline, diesel with plastic waste and/or heavy oil is provided.Particularly, the invention provides same raw material is carried out thermo-cracking and catalytic pyrolysis under two kinds of differing tempss of two-stage, make its charging and deslagging serialization, the residue of discharge does not contain organism, but belongs to inorganic powder, gasoline, diesel yield height.Method of the present invention comprises:
Described plastic waste through pulverizing or not pulverizing, is ceaselessly pushed in the closed reaction kettle continuously with spiral extruding machine or reciprocating type charger, or with pump heavy oil pumped in the reactor,, carry out first step scission reaction to the reactor heating.The gas phase hydrocarbon that first step scission reaction is generated is discharged reactor; Simultaneously, containing oil residue completely with not being decomposed ceaselessly enters continuously in another airtight tubular reactor that has a spiral stirrer and carries out second stage scission reaction.Heat to tubular reactor, and rotation and the promotion continuously of the screw mixer in the electricity consumption driving tube, contain oil residue or high-carbon hydrocarbon material that first step scission reaction produces are proceeded second stage scission reaction under the hot conditions in tubular reactor, the organism in the residue is thoroughly decomposed.Simultaneously, the inorganic residues that second stage scission reaction is produced ceaselessly stirs carrying device continuously with the screw mixer in the tubular reactor.The gas phase hydrocarbon that second stage scission reaction is generated is discharged reactor.The gas phase hydrocarbon that first and second grade scission reaction is discharged is introduced catalytic fixed bed,, collect by the gas phase hydrocarbon of discharging after the catalyzed reaction with the catalyzer generation catalyzed reaction in the fixed bed.And carry out fractionation, condensation, oily water separation according to a conventional method, obtain gasoline, diesel or lower boiling hydrocarbon ils at last.
In the aforesaid method, scission reaction comprises heat scission reaction and catalytic cracking reaction.Main catalytic cracking reaction be on catalytic fixed bed, carry out solid----catalyst system therefor is a ZBXQ-1 type catalyzer in the solid/liquid/gas reactions, fixed bed; Also can be with commercially available degraded commonly used or pour point depression solid powder th-1 catalyst, follow plastic waste or heavy oil feedstock together, join simultaneously in the scission reaction still, in reactor, consolidate---liquid scission reaction, this degraded or pour point depression solid powder th-1 catalyst can promote that high molecular plastic waste or heavy oil decompose, cracking and pour point depression; Scission reaction can be kept normal pressure or be higher than normal pressure, and first step scission reaction temperature is 350-450 ℃, and second stage scission reaction temperature is 400-800 ℃.
Equipment of the present invention mainly comprises the scission reaction still, has the tubular reactor and the hydrocarbon ils collection device of spiral stirrer.
Described scission reaction still comprises:
Cylindrical steel mass shell body by the steelframe of hull outside, supports cylindrical housings on the ground, skin in cylindrical housings, be equipped with another heat insulating layer, leave enough space between two-layer, i.e. heating chamber for the high-temperature flue gas circulation to reactor heating; Have high-temperature flue gas entry in the heating chamber bottom, its top has the low-temperature flue gas outlet;
Stirrer vertically is assemblied in reactor inside, can along or despining;
Screw feeder or reciprocating type charger, it is disposed on the top or end socket of cylindrical housings, and links with reactor inside;
The gas-phase product outlet that catalytic fixed bed, its import and first step scission reaction are produced communicates, and its outlet links with the import of separation column;
The described tubular reactor that has screw mixer comprises:
One or more round steel pipe all is composed in series by curved shape; And fix on the ground motionless, all be equipped with the screw rod agitator in the every steel pipe, be subjected to electric motor driving and rotate, a gaseous phase outlet is all opened on an end top of every steel pipe, every outlet merges the back and forms a thick gaseous phase outlet, the import of this outlet and the fixed bed connection that links.One end upper opening of first steel pipe is the import of raw material, the bottom deslagging outlet of this import and scission reaction still is connected, the upper inlet of the other end lower part outlet of first steel pipe and second steel pipe one end links, the upper inlet of the lower part outlet of second steel pipe the other end and the 3rd steel pipe one end links, and by the logical many steel pipes of above-mentioned rule connection, the other end outlet of last root steel pipe is the deslagging outlet of tubular reactor, and the upper inlet of this outlet and residue collection cylinder links;
The residue collection cylinder, a kind of metal vessel, vertical, horizontal all can, cylindrical, rectangle all can, the top of cylinder is the import of material, the outlet of last root steel pipe in this import and the tubular reactor connection that links, the bottom of cylinder is equipped with the outlet of remnant;
Heating chamber, steel or refractory materials constitute, and rectangle and case structure are wrapped in above-mentioned one or more steel cylindrical tube that is equipped with spiral stirrer in the heating chamber, and the bottom of heating chamber has high-temperature flue gas import or bottoming hole; Its top has flue gas outlet; Two ends of every steel pipe all are equipped with bearing, seal cartridge and the arbor wheel of spiral stirrer, can not be wrapped in the heating chamber.The gas-phase product outlet that fixed bed, its import and second stage scission reaction are produced communicates, and its outlet links with the import of separation column;
Brief description of drawings
Fig. 1 is a simple and easy schema of producing hydro carbons with the present invention
Fig. 2 is scission reaction still of the present invention and the equipment drawing that has the tubular reactor of spiral stirrer.
The present invention is auspicious to be stated:
The purpose of this invention is to provide a kind of method of producing gasoline, diesel with waste plastics and/or heavy oil And equipment. Comprise: waste plastics is not pulverized or is ground into 2-5 centimetre of specification, by the spiral extrusion molding The promotion of machine or reciprocating type charger, it is airtight with in the reactor of agitator or with heavy oil to pack into Pump in the airtight reactor, available fuel oil, natural gas, lower carbon number hydrocarbons combustible gas or coal are as warm Heat to reactor with the high-temperature flue gas that produces in the source, starts the interior mixer of still and stir, anti-Answer temperature in the kettle to be controlled at 350-450 ℃, pressure is normal pressure or is higher than normal pressure, also can in the reactor Adding normally used degradation catalyst, accelerate and short such as the oxide of aluminium or silicon or compound etc. Advance the cracking of waste plastics or heavy oil, carry out first order cracking reaction, will react the gas phase hydrocarbon that generates Discharge reactor, the remaining reaction remnant in reactor bottom belongs to full-bodied residual oil, and contains A large amount of macromolecules that are not decomposed and big molecule hydrocarbon will react remnant continuously from reactor The outlet of bottom enters in another airtight tubular reactor with spiral agitator, proceeds the The reaction of secondary Pintsch process; Reaction temperature is controlled at 400-800 ℃, and pressure is normal pressure or is higher than normal Press, the gas phase hydrocarbon that reaction generates is discharged in the tubular reactor, and remaining remnant enters residual after the reaction In the slag collection cylinder. Because the residue of discharging has been decomposed thoroughly, does not conform to the organic matter composition, the residue warp Obtain commercial inorganic filler or building materials raw material after pulverizing, magnetic separation, the separation. With first and second grade cracking The gas phase hydrocarbon that reaction is drawn all enters fixed bed, with the catalyst generation Catalytic Cracking Unit of Measure in the fixed bed Should. Hydrocarbon by obtaining after conventional process and the collection catalytic reaction obtains gasoline, diesel oil at last Or low boiling hydrocarbon ils.
In the said method step, described cracking reaction comprises that heat scission reaction and catalytic pyrolysis are anti-Should. If do not put in the catalytic fixed bed and do not put into degraded or the catalysis of coming in catalyst or the reactor Catalytic cracking reaction does not then take place in agent, and heat scission reaction only takes place; Can collect behind the heat scission reaction To low boiling mixing hydrocarbon ils.
The catalytic reaction of carrying out in the described fixed bed belongs to solid-solid/liquid/gas reactions, and the catalytic reaction temperature is 350-450 ℃, pressure is normal pressure or is higher than normal pressure; Be mounted with catalytic cracking reaction institute on the fixed bed Need catalyst, usually select ZBXQ-1 type catalyst, it consists of REY is 30%; The sial mole Than the modenite that is 12: 1 be 20% and ZSM-5 be 50%, each component is fully mixed After can be used for catalytic cracking reaction of the present invention.
Described degraded or pour point depression catalytic reaction belong to solid-liquid reaction, are anti-at reactor and tubular type Answer and carry out respectively in the device; Beginning is carried out in the cracking reaction still, then, follows residual oil one at the bottom of the still With entering in the tubular reactor; Degraded or the catalyst that comes are made of inorganic matter, and it does not decompose, Do not vaporize yet, finally enter in the residue collection cylinder of tubular reactor, and with second level cracking reaction Remaining inorganic remnant or lime-ash be discharger together.
Above-mentioned reaction is normal pressure or is higher than normal pressure. The gas that after first and second grade cracking reaction, obtains The phase product obtains various after catalytic reaction or non-catalytic reaction after according to a conventional method condensation, the separation The hydrocarbon ils of purposes and imflammable gas. With remaining inorganic residues discharge pipe after the cracking reaction of the second level Outside the formula reactor, obtain commercial inorganic filler or building materials through pulverizing, magnetic separation with after separating.
The raw material that available the inventive method is processed comprises: waste plastics, mud, contain the sand ground crude oil, Macromolecule organic waste that can melting after residual oil, heavy oil and other are heated.
Particularly, method of the present invention comprises step:
1, waste plastics is not pulverized or is ground into 2-5 centimetre of specification, by spiral extruding machine or past The promotion of compound charger, airtight anti-with agitator of ceaselessly or once packing into continuously Answer in the still or with heavy oil and pump in the airtight reactor;
2. can be normally used pressed powder degraded or pour point depression catalyst, such as aluminium or element silicon Oxide, compound or the catalyst for cracking take aluminium or element silicon as main component etc., with Waste plastics is together sent in the airtight reactor with spiral extruding machine or reciprocating type charger, promotes former The degraded of material, come and decompose; Also can not add degraded or pour point depression catalyst in reactor;
3, use fuel oil, natural gas, lower carbon number hydrocarbons imflammable gas or coal as thermal source, in burning Burning produces high-temperature flue gas in the stove, heats to reactor with high-temperature flue gas; Start agitator in the still, Make reactor temperature be controlled at 350-450 ℃, pressure is normal pressure or is higher than normal pressure, carries out first The level cracking reaction; The gas phase hydrocarbon that cracking reaction produces is discharged outside the still, and enters catalytic fixed bed and carry out Catalytic cracking reaction;
4, will do not discharged from the bottom of reactor by the residual oil of fully cracking, and directly fall into another In the tubular reactor with spiral agitator, carry out the cracking reaction under the hot conditions of the second level;
5, give the tubular reactor heat supply with high-temperature flue gas, electricity consumption drives the spiral shell in the tubular reactor Revolve agitator rotation and stirring, material in the pipe is ceaselessly pushed continuously to the direction of residue collection cylinder; Temperature is controlled at 400-800 ℃ in the pipe, and pressure is normal pressure or is higher than normal pressure; First order cracking reaction The higher hydrocabon that is not decomposed is completely proceeded second level Pintsch process in this tubular reactor Reaction; Because the continuously ceaselessly Stirring and forward promotion work of agitator in the tubular reactor With, the inorganic remnant that second level cracking reaction produces ceaselessly enters the residue collection cylinder continuously In, through spiral slag-discharging device discharger; The gas phase hydrocarbon discharge tubular type that the Pintsch process reaction produces is anti-Answer outside the device, and enter catalytic fixed bed and carry out catalytic cracking reaction;
The gas phase hydrocarbon that heat scission reaction and catalytic cracking reaction produce is collected by traditional method, promptly carried out fractionation, condensation, refining, obtain gasoline, diesel oil, various lower boiling hydrocarbon ils (as, oil fuel) and inflammable gas at last.The final residue of scission reaction is an inorganics, obtains mineral filler or building materials raw material after pulverizing, magnetic separation, separation.
Another object of the present invention provides the equipment of realizing aforesaid method, mainly comprises the scission reaction still, has the tubular reactor and the hydrocarbon ils collection device of spiral stirrer.
Described scission reaction still comprises: cylindrical steel mass shell body, steelframe by hull outside, cylindrical housings is supported and fixes on the ground, skin in cylindrical housings, be set with another cylindrical heat insulating layer to the reactor heat supply, leave the space of enough circulating between two-layer, i.e. heating chamber for high-temperature flue gas; Wherein, advance,, discharge from the other end through heating chamber to the high-temperature flue gas of reactor heating a end from heating chamber; Stirrer, its central shaft vertically is assemblied in the center of reactor inside, spiral is installed on the central shaft stirs leaf and/or stir frame, axle can along or despining; Spiral extruding machine or reciprocating type charger, it is disposed on the top or end socket of cylindrical housings, and links with reactor inside; Fixed bed communicates the gas-phase product outlet that scission reaction produced with the import of fixed bed, the outlet of fixed bed and the import of separation column link;
The described tubular reactor that has screw mixer comprises: one or more steel cylindrical tube, and all connecting end to end by curved shape is connected and configuration hermetically; And be fixed on the ground of scission reaction still bottom; All be equipped with the screw rod agitator in the every steel pipe, be subjected to electric motor driving and rotate, drive the arbor wheel of screw rod agitator rotation or the end that gear is installed in every pipe; And a gaseous phase outlet is all opened on the top of the other end of every steel pipe, and its outlet merges the back and forms a thick gaseous phase outlet, the import of this outlet and the fixed bed connection that links; One end upper opening of first steel pipe is the import of raw material, between the bottom deslagging outlet of this material inlet and scission reaction still with the connection that links of a valve; The upper inlet of the other end lower part outlet of first steel pipe and second steel pipe one end links, and the upper inlet of the lower part outlet of second steel pipe the other end and the 3rd steel pipe one end links, and can connect logical many steel pipes by above-mentioned rule; The other end outlet of last root steel pipe is the deslagging outlet of tubular reactor, and the upper inlet of this outlet and residue collection cylinder links; The residue collection cylinder, a kind of metal vessel, vertical, horizontal all can, cylindrical, rectangle all can, the top of cylinder is the import of material, with the outlet of last root steel pipe in the tubular reactor connection that links, the bottom of cylinder is the outlet of remnant; Heating chamber, be made of steel or refractory materials, the rectangle case structure is wrapped in above-mentioned one or more steel cylindrical tube that is equipped with spiral stirrer in the heating chamber with it, two ends of every steel pipe all are equipped with bearing, seal cartridge and the arbor wheel of spiral stirrer, can not be wrapped in the heating chamber.The bottom of heating chamber has high-temperature flue gas import or bottoming hole; Its top has flue gas outlet; The gas-phase product outlet that catalytic fixed bed, its import and second stage scission reaction are produced communicates, and its outlet links with the import of separation column;
Particularly, equipment of the present invention comprises: scission reaction still (1), the tubular reactor (2) of band spiral stirrer, roasting kiln (5), catalytic fixed bed (20), separation column (21), condenser (23,24), hydrocarbon ils holding tank (27,28), water-and-oil separator (25,26), stripping jar (22), water-sealed tank devices such as (29) are formed (see figure 1).
Referring to Fig. 1 and Fig. 2, scission reaction still (1), comprise cylindrical steel mass shell body (6), by the outside support (33) of housing (6), cylindrical housings (6) is supported and fixes on the ground, skin in cylindrical housings (6), be set with another cylindrical heat insulating layer (16), leave enough space between two-layer, i.e. heating chamber (17) for the high-temperature flue gas circulation to the reactor heat supply; Fuel (32) burnt in roasting kiln (5) to be produced high-temperature flue gas and gives reactor (1) heat supply, and wherein, the high-temperature flue gas of giving reactor (1) heating advances from an end (19) of heating chamber (17), through heating chamber (17), discharges from the other end (18); Stirrer (3), its central shaft vertically are assemblied in the inner center of reactor (1), spiral is installed on the central shaft stirs leaf and/or stir frame (15), axle can along or despining; Spiral extruding machine or reciprocating type charger (4), it is disposed on the top or end socket of cylindrical housings (6), and links with reactor (1) inside; The hole (39) that heavy oil enters reactor (1) is configured on the end socket of reactor (1); Fixed bed (20) communicates the gas-phase product outlet (37) that scission reaction produced with the import (35) of fixed bed, the outlet of fixed bed and the import of separation column (34) link;
The described tubular reactor (2) that has screw mixer comprising: one or more steel cylindrical tube (12), and all connecting end to end by curved shape is connected and configuration hermetically; And be fixed on the ground of scission reaction still (1) bottom; All be equipped with screw rod agitator (10) in the every steel pipe (12), be subjected to motor (8) driving and rotate the end that the arbor wheel of driving screw rod agitator (10) rotation or gear (11) are installed in every pipe (12); And a gaseous phase outlet (36) is all opened on the top of the other end of every steel pipe (12), and its outlet merges the back and forms a thick gaseous phase outlet, the import (35) of this outlet and fixed bed (20) connection that links; One end upper opening of first steel pipe is the import of raw material, between the bottom deslagging outlet of this material inlet and scission reaction still with a valve (7) connection that links; The upper inlet of the other end lower part outlet of first steel pipe and second steel pipe one end links, and the upper inlet of the lower part outlet of second steel pipe the other end and the 3rd steel pipe one end links, and can connect logical many steel pipes by above-mentioned rule; The other end outlet (30) of last root steel pipe is the deslagging outlet of tubular reactor (2), and the upper inlet of this outlet and residue collection cylinder (9) links; Residue collection cylinder (9), a kind of metal vessel vertical, horizontally all can, cylindrical, rectangle all can, the top of cylinder is the import (30) of material, and with the outlet of last root steel pipe in the tubular reactor (2) connection that links, the bottom of cylinder (9) is the outlet (31) of remnant; Heating chamber (38), constitute by steel or refractory materials, the rectangle case structure, with it one or more steel cylindrical tube (12) that is equipped with spiral stirrer (10) is wrapped in the heating chamber (38), the top of heating chamber (38) has an exhanst gas outlet (14), and its underpart has a high-temperature flue gas import or bottoming hole (13) in addition; The gas-phase product outlet (37) that fixed bed (20), its import (35) and second stage scission reaction are produced communicates, and the outlet of fixed bed links with the import (34) of separation column (21); The gas phase hydrocarbon is after separation column (21) fractionation, gasoline is through condenser (23), flow into gasoline water-and-oil separator (21), finally lay in gasoline tank (27), can not be entered the water-sealed tank (29) by the top of agglomerative inflammable gas from gasoline water-and-oil separator (21), discharge from water-sealed tank (29) top, and turn back to reignition recovery heat in the roasting kiln (5); Diesel oil flows into diesel oil condenser (24) behind stripping jar (22), through diesel oil water-and-oil separator (26) finally enters diesel oil tank (28); The heavy oil of separation column (21) bottom can turn back in the scission reaction still (1) cracking again or sell as merchantable fuels oil.
1 and 2 pair of method of the present invention is further detailed in conjunction with the accompanying drawings.
Plastic waste is not pulverized or is ground into 2-5 centimetre of specification, by the promotion of spiral extrusion molding charger (4), pump in the closed reaction kettle (1) through hole (39) in the reactor that has agitator (3) (1) of ceaselessly or once packing into airtight continuously or with heavy oil; Can be normally used pressed powder degraded or pour point depression catalyzer, it as the oxide compound of aluminium or element silicon, compound or with aluminium or element silicon catalyst for cracking of main component etc., together use spiral extruding machine (4) to send in the closed reaction kettle (1) with plastic waste, promote raw material degraded, come and decompose; Also can not add degraded or pour point depression catalyzer in reactor (1); With oil fuel, Sweet natural gas, lower carbon number hydrocarbons is flammable promoting the circulation of qi body or coal as thermal source (32), burning produces high-temperature flue gas in roasting kiln (5), give reactor (1) heating with high-temperature flue gas, start the interior agitator of still (1) (3), make the interior temperature of reactor (1) be controlled at 350-450 ℃, pressure is normal pressure or is higher than normal pressure, carries out first step scission reaction; The gas phase hydrocarbon that scission reaction produces is discharged outside the still (1), and enters catalytic fixed bed (20) and carry out catalytic cracking reaction; To do not discharged from the bottom of reactor (1) in the reactor (1), and directly fall into another tubular reactor that has spiral stirrer (10) (2), carry out the scission reaction under the hot conditions of the second stage by complete cracked residual oil; Give tubular reactor (2) heat supply with high-temperature flue gas, electricity consumption drives spiral stirrer (10) rotation in the tubular reactor (2) and stirs, and will manage the direction that (2) interior material is ceaselessly pushed residue collection cylinder (9) continuously to; Pipe (2) interior temperature is controlled at 400-800 ℃, and pressure is normal pressure or is higher than normal pressure; First step scission reaction is not decomposed, and material and higher hydrocabon are proceeded second stage Pintsch process reaction in tubular reactor (2) completely; Because ceaselessly the rotation stirring and pushing effect forward continuously of the interior agitator of tubular reactor (2) (10), the inorganic remnant that second stage scission reaction is produced ceaselessly enters in the residue collection cylinder (9) continuously, through mud hole (31) discharger; The gas phase hydrocarbon that Pintsch process reaction produces is discharged outside the tubular reactor (2), and enter catalytic fixed bed (20) and carry out catalytic cracking reaction; The gas phase hydrocarbon of heat scission reaction and catalytic cracking reaction generation is collected by traditional method, promptly use separation column (21) carry out fractionation, after condenser (23,24) condensation, water-and-oil separator (25,24) are handled, obtain gasoline, diesel oil, various lower boiling hydrocarbon ils (as, oil fuel) and inflammable gas at last.Gasoline is stored in the storage tank (27), and diesel oil stores in the storage tank (28); Incoagulable inflammable gas turns back to reignition recovery heat in the roasting kiln (5) behind syphon trap (29); The final residue of scission reaction is an inorganics, obtains mineral filler or building materials raw material after pulverizing, magnetic separation, separation.
Below to illustrate in greater detail this law by specific embodiment bright, but the present invention is not limited.
Embodiment
(PE300KG, PP400KG, PS300KG) is ground into 2-5 centimetre of specification with the 1000KG plastic waste, by the promotion of spiral extruding machine (4), in the reactor that has agitator (3) (1) of ceaselessly packing into airtight continuously; With the inflammable gas of oil fuel and recovery as thermal source (32), burning produces high-temperature flue gas in roasting kiln (5), give reactor (1) heating with high-temperature flue gas, start the interior agitator of still (1) (3), make the interior temperature of reactor (1) be controlled at 350-400 ℃, pressure is 0.02-0.08MPa, carries out first step scission reaction; The gas phase hydrocarbon that scission reaction produces is discharged outside the still (1), and enters catalytic fixed bed (20), with the ZBXQ-1 type catalyzer generation catalytic cracking reaction in the catalytic fixed bed (20); To do not discharged from the bottom of reactor (1) continuously in the reactor (1), and directly fall into another tubular reactor that has spiral stirrer (10) (2), carry out the scission reaction under the hot conditions of the second stage by complete cracked residual oil or high-carbon hydrocarbon material; Give tubular reactor (2) heat supply with high-temperature flue gas, electricity consumption drives spiral stirrer (10) rotation in the tubular reactor (2) and stirs, and will manage the direction that (2) interior material is ceaselessly pushed residue collection cylinder (9) continuously to; Pipe (2) interior temperature is 400-600 ℃, and pressure is 0.02-0.08MPa; Be not decomposed completely residual oil or high-carbon hydrocarbon material of first step scission reaction proceeded second stage Pintsch process reaction in tubular reactor (2); Because ceaselessly the rotation stirring and pushing effect forward continuously of the interior agitator of tubular reactor (2) (10), the inorganic remnant that second stage scission reaction is produced ceaselessly enters in the residue collection cylinder (9) continuously, through mud hole (31) discharger; The gas phase hydrocarbon that Pintsch process reaction produces is discharged outside the tubular reactor (2), and enter catalytic fixed bed (20) and carry out catalytic cracking reaction; The gas phase hydrocarbon of heat scission reaction and catalytic cracking reaction generation is collected by traditional method, promptly use separation column (21) carry out fractionation, after condenser (23,24) condensation, water-and-oil separator (25,24) are handled, obtain gasoline 350KG (research octane number (RON) is 93.5), diesel oil 370KG (cetane value is 48), inflammable gas 120GK and inorganic residues 160GK at last.Gasoline is stored in the storage tank (27), and diesel oil stores in the storage tank (28); Incoagulable inflammable gas turns back to reignition recovery heat in the roasting kiln (5) behind syphon trap (29); The final residue of scission reaction is an inorganics, obtains the building materials raw material of brickmaking after pulverizing, magnetic separation, separation.

Claims (9)

1. a method of producing gasoline, diesel with plastic waste and/or heavy oil comprises: with described raw material such as plastic waste through pulverizing or not pulverizing, ceaselessly push continuously in the airtight scission reaction still with spiral extruding machine or reciprocating type charger, or heavy oil is pumped in the scission reaction still with pump, to the reactor heating, carry out first step scission reaction.The gas phase hydrocarbon that first step scission reaction is generated is discharged the scission reaction still; Simultaneously, contain oil residue or the high-carbon hydrocarbon that are not decomposed are fully ceaselessly entered continuously another airtight tubular reactor that has a spiral stirrer from scission reaction still bottom and carry out second stage scission reaction, heat to tubular reactor, and the screw mixer that electricity consumption drives in the tubular reactor rotates continuously, contain oil residue or high-carbon hydrocarbon that first step scission reaction produces are proceeded second stage scission reaction under the hot conditions in tubular reactor, make thorough cracking of organism and decomposition in the residue, simultaneously, scission reaction remaining inorganic residues in the second stage is ceaselessly stirred ejecting device down continuously with the screw mixer in the pipe.The gas phase hydrocarbon that second stage scission reaction is generated is discharged reactor.The gas phase hydrocarbon that first and second grade scission reaction is discharged is introduced catalytic fixed bed,, collect by the gas phase hydrocarbon of discharging after the catalyzed reaction with the catalyzer generation catalyzed reaction in the fixed bed.And carry out fractionation, condensation, oily water separation according to a conventional method, obtain gasoline, diesel or lower boiling hydrocarbon ils at last;
2. the process of claim 1 wherein that described scission reaction comprises heat scission reaction and catalytic cracking reaction;
3. the method for claim 2, wherein said catalytic cracking reaction carries out in fixed bed, if do not put catalyzer in the fixed bed, catalytic cracking reaction does not take place then;
4. claim 1 or 2 method, the temperature of wherein said first step scission reaction is 350-450 ℃, and second stage scission reaction temperature is 400-800 ℃, and pressure is normal pressure or is higher than normal pressure;
5. the method for claim 2, the used ZBXQ-1 type catalyzer of wherein said catalytic cracking reaction comprises that (weight): REY is 30%; Silica alumina ratio be 12: 1 mordenite be 20% and ZSM-5 be 50%; The each component thorough mixing;
6. the method for claim 1 further comprises the step of collecting the hydrocarbon ils behind the separation column;
7. the method for claim 1, described raw material comprises: plastic waste, mud, can fused polymer organic waste after containing sand ground crude oil, residual oil, heavy oil and other and being heated.
8. the equipment with plastic waste and/or heavy oil production gasoline, diesel comprises: scission reaction still, the tubular reactor that has spiral stirrer and hydrocarbon ils collection device;
Described scission reaction still comprises:
Cylindrical steel mass shell body by the steelframe of hull outside, supports cylindrical housings on the ground, skin in cylindrical housings, be equipped with another heat insulating layer, leave enough space between two-layer, i.e. heating chamber for the high-temperature flue gas circulation to reactor heating; Have high-temperature flue gas entry in the heating chamber bottom, its top has the low-temperature flue gas outlet;
Stirrer vertically is assemblied in reactor inside, can along or despining;
Screw feeder or reciprocating type charger, it is disposed on the top or end socket of cylindrical housings, and links with reactor inside;
The gas-phase product outlet that catalytic fixed bed, its import and first step scission reaction are produced communicates, and its outlet links with the import of separation column;
The described tubular reactor that has screw mixer comprises:
One or more steel pipe all is composed in series by curved shape; And fix on the ground motionless, all be equipped with the screw rod agitator in the every steel pipe, be subjected to electric motor driving and rotate, a gaseous phase outlet is all opened on an end top of every steel pipe, every outlet merges the back and forms a thick gaseous phase outlet, the import of this outlet and the fixed bed connection that links.One end upper opening of first steel pipe is the import of raw material, the bottom deslagging outlet of this import and scission reaction still is connected, the upper inlet of the other end lower part outlet of first steel pipe and second steel pipe one end links, the upper inlet of the lower part outlet of second steel pipe the other end and the 3rd steel pipe one end links, and by the logical many steel pipes of above-mentioned rule connection, the other end outlet of last root steel pipe is the deslagging outlet of tubular reactor, and the upper inlet of this outlet and residue collection cylinder links;
The residue collection cylinder, a kind of metal vessel, vertical, horizontal all can, cylindrical, rectangle all can, the top of cylinder is the import of material, the outlet of last root steel pipe in this import and the tubular reactor connection that links, the bottom of cylinder is the outlet of inorganic residues;
Heating chamber, steel or refractory materials constitute, and rectangle and case structure are wrapped in above-mentioned one or more steel pipe that is equipped with spiral stirrer in the heating chamber, and the bottom of heating chamber has high-temperature flue gas import or bottoming hole; Its top has flue gas outlet; The gas-phase product outlet that fixed bed, its import and second stage scission reaction are produced communicates, and its outlet links with the import of separation column;
9. the equipment of claim 7 further comprises the hydrocarbon ils collection device, and it belongs to the conventional gasoline, diesel tripping device that uses in this area, comprising: separation column, condenser, water-and-oil separator and water-sealed tank etc.;
CN 01120570 2001-07-23 2001-07-23 Process and equipment for preparing gasoline and diesel oil from waste plastics and/or heavy oil Pending CN1397627A (en)

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PCT/CN2001/001516 WO2003010258A1 (en) 2001-07-23 2001-10-30 A process and an apparatus for producing gasoline and diesel oil from plastic waste and/or heavy oil

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