WO1999009116A1 - Procede de production d'huile hydrocarbonee a partir de matieres organiques ou de matieres de rebut de masse moleculaire elevee et appareillage correspondant - Google Patents

Procede de production d'huile hydrocarbonee a partir de matieres organiques ou de matieres de rebut de masse moleculaire elevee et appareillage correspondant Download PDF

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Publication number
WO1999009116A1
WO1999009116A1 PCT/CN1997/000124 CN9700124W WO9909116A1 WO 1999009116 A1 WO1999009116 A1 WO 1999009116A1 CN 9700124 W CN9700124 W CN 9700124W WO 9909116 A1 WO9909116 A1 WO 9909116A1
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Prior art keywords
reaction
reaction kettle
reactor
kettle
waste
Prior art date
Application number
PCT/CN1997/000124
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English (en)
Chinese (zh)
Inventor
Li Xing
Original Assignee
Li Xing
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Li Xing filed Critical Li Xing
Priority to AU49399/97A priority Critical patent/AU4939997A/en
Publication of WO1999009116A1 publication Critical patent/WO1999009116A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production 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

Definitions

  • the present invention relates to a method and apparatus for producing hydrocarbons from waste, and more particularly to a method and apparatus for producing hydrocarbons from organic or polymer waste by thermal cracking and catalytic cracking.
  • BACKGROUND OF THE INVENTION With the rapid development of modern industry, the impact of industrial wastes on the human living environment has become a common concern, and the economic and effective treatment of domestic and industrial waste has become a research topic that is generally concerned around the world. In the prior art, many technical solutions for solving this problem have been disclosed. For example, Chambers in U.S. Patent No. 4,235,676 discloses equipment for producing hydrocarbons from waste tires and industrial and domestic waste.
  • the disclosed apparatus uses a vacuum system to perform a thermal cracking reaction in a reactor equipped with a spiral agitation.
  • the raw materials are added from one end of the reaction kettle, and while being thermally cracked, they are transported to the other end by a spiral stirrer, the cracked gas is discharged from the upper part of the reaction kettle, and the reaction residue is discharged from one end of the reaction kettle. Since the equipment disclosed here is fixed in the reactor, the viscous residue generated during the reaction is very likely to coke on the bottom of the reactor. The removal of coke from the bottom of the reactor is time-consuming and laborious, which affects the continuity of production.
  • EP-A-0607862 (applicant is Mazda Motor Corporation) discloses a method and equipment for preparing hydrocarbon oil from waste plastic or rubber, said method comprising feeding raw materials into a vertical reactor by means of a screw feeder for thermal cracking A catalytic cracking reactor is arranged above the thermal cracking reactor to further crack the cracked product. This application does not specifically disclose a method for discharging thermal cracking slag.
  • the applicant, also Hyundai Motor Corporation White EP-A-0607994 discloses another method for producing hydrocarbon oil from waste plastic or waste rubber, which comprises cooling the thermal cracked product to a liquid state, and then carrying out chemical cracking, a thermal cracking device and Catalytic cracker separation.
  • an object of the present invention is to provide a method and an apparatus for preparing hydrocarbons from organic or polymer waste. More specifically, the present invention provides a method and apparatus for producing hydrocarbons from organic or polymer waste by thermal cracking and catalytic cracking.
  • the method of the present invention includes:
  • the waste is pulverized or not pulverized, it is loaded into a closed horizontal reaction kettle; the reaction kettle is rotated and heated to perform a cracking reaction;
  • the cracking reaction includes a thermal cracking reaction and a catalytic cracking reaction, wherein the catalytic cracking reaction is performed on a catalytic bed placed inside the reaction kettle.
  • the pressure requirements in the reactor are not very strict and can be maintained at or above normal pressure.
  • the temperature of the catalytic reaction is 350 600 ° C.
  • the catalyst used is SR-1 type catalyst. Its composition (weight) includes: CHO (trade name, produced by Qilu Petrochemical Catalyst Plant) 15%, REY 20%, mordenite 30% and ZSM -5 catalyst 45%.
  • the equipment of the present invention mainly includes a horizontal rotary reactor and a hydrocarbon oil collecting device.
  • the horizontal rotary reactor includes: a cylindrical shell supported on the ground by bearing seats and brackets placed at both ends thereof, wherein the bearing seats Placed on the bracket; a rotating shaft, which is connected to both ends of the reaction housing to be integrated with the reaction housing, and coincides with the bearing housing, and drives the operation of the reaction kettle by rotating in the bearing housing; a central hollow tube shaft It includes a liquid feed hollow tube shaft and a discharge hollow tube shaft, which enter the reaction kettle shell through the rotating shaft and the two ends of the middle part of the shell and are connected and fixed to the bearing seat.
  • FIG. 1 is a simplified flow chart for the production of hydrocarbons using the apparatus of the present invention.
  • One of the objectives of the present invention is to provide a method for producing hydrocarbons from organic or polymer waste, comprising: pulverizing the waste or not pulverizing the waste into a closed horizontal reactor; rotating And heating the reaction kettle to carry out the cracking reaction; discharging the hydrocarbons generated by the reaction out of the reaction kettle, if necessary, simultaneously discharging the reaction residues; and collecting the hydrocarbons drawn from the reaction kettle.
  • the cracking reaction includes a thermal cracking reaction and a catalytic cracking reaction according to different raw materials to be processed.
  • the cracking reaction is not necessary, that is, the thermal cracking reaction is only required to process the above raw materials.
  • the raw material is high-molecular waste such as waste plastic or waste rubber, it can be completed through thermal cracking and catalytic cracking reactions.
  • the catalytic cracking reaction is performed on a fixed bed arranged in a reaction kettle. The fixed bed is loaded with the catalyst required for the catalytic cracking reaction.
  • the catalyst is selected according to the different raw materials to be processed, but usually the SR-1 type catalyst is used. Its composition is: CH015%, REY20%, mordenite (silicon-aluminum molar ratio is 12: 1) 30%, and 45% ZSM-5 catalyst.
  • the temperature for carrying out the catalytic cracking reaction of the present invention is generally 350 ° -600 ° C.
  • the heat in the reaction kettle is sufficient to maintain the catalytic cracking reaction at this temperature, and the reaction pressure is normal pressure or higher than normal pressure.
  • the products cracked in the reaction kettle are separated and condensed by conventional methods to obtain hydrocarbon oil and combustible gas for various purposes.
  • After the thermal cracking if there is a residue in the reaction kettle, when the amount reaches a certain level, it can be discharged out of the kettle through a slag discharge port through a spiral stirrer.
  • Organic or high-molecular waste materials that can be treated by the method of the present invention include waste plastic waste, waste tires, domestic waste, sludge, wood chips, ground-laid sandy crude oil produced during oil extraction, and residues and heavy oil discharged from refineries.
  • the method of the present invention includes steps:
  • the fixed bed is installed in a rotating cylindrical thermal cracking reactor.
  • the gas phase hydrocarbons generated by the thermal cracking reaction flow through the fixed bed, they come into contact with the catalyst in the fixed bed to perform the catalytic cracking reaction to generate gas phase hydrocarbons.
  • Heat is supplied from a thermal cracking reactor;
  • Another object of the present invention is to provide equipment for realizing the above method, which mainly includes a horizontal rotary reactor and a hydrocarbon oil collection device.
  • the horizontal rotary reactor includes: a cylindrical shell, and bearing housings placed at both ends thereof; And the bracket is supported on the ground, which The middle bearing seat is placed on the support; the rotating shaft is connected to the two ends of the reaction vessel shell and coincides with the 7 seat of the shaft, and the rotation of the reaction vessel is driven by its rotation in the bearing seat; the central hollow tube shaft includes The liquid feeding hollow tube shaft and the discharging hollow tube shaft enter the reaction kettle shell through the rotating shaft and the two ends of the middle part of the reaction kettle and are connected and fixed with the bearing seat.
  • the equipment of the present invention includes a horizontal rotating cylinder reactor (1), a forward or reverse speed regulating motor (29), a combustion furnace (17), a heating chamber (19), a hydrocarbon oil collection tank (32), and water. Sealing (24) and other devices (see Figure 1). Referring to Figs.
  • the horizontal rotary cylindrical reactor (1) is supported on the ground by the rotating shaft (12) bearing housing (15) and the bracket (6) at both ends of the reactor, and can rotate freely.
  • a large gear disc (18) is installed at one end of the reaction kettle (1).
  • the speed-regulating motor (29) is connected to the gearbox 28 in a forward or reverse direction.
  • the small gear (33) on the gearbox (28) is aligned with the large gear plate (18) on the reactor (1).
  • Start the forward and reverse rotation speed-regulating motor (29), and the horizontal rotary cylinder reactor (1) can freely forward or reverse.
  • the central axes (8) and (9) on the heads (5) at the ends of the reactor (1) are hollow tubes.
  • the reaction kettle (1) is provided with a fixed bed (14), the fixed bed (14) is vertically upward, and communicates with the central hollow shaft tube (9) on the right end head (5) of the reaction kettle (1).
  • the central hollow tube shaft (8) at the other end of the reaction kettle (1) is a channel for liquid raw materials to enter the reaction kettle, and the liquid raw materials enter the reaction kettle (1) through the hollow central tube shaft (8) under the action of the pump (26).
  • the solid raw material can be charged into the reaction kettle (1) through the feeding hole (7) on the end cap (5) of the reaction kettle (1).
  • the loading of liquid or solid raw materials should not exceed 2/3 of the horizontal level of the reactor.
  • Coal, heavy oil, and combustible gases are burned in a combustion furnace (17) to generate high-temperature flue gas (31) to heat the reaction kettle (1).
  • the reaction kettle (1) is equipped with an electrically driven helical stirrer (16), which can be reversed or reversed for stirring raw materials and slag discharge.
  • a variable-speed motor (47) driving the rotation of the auger stirrer (16) is installed and fixed on the head (5) at one end of the reactor (1), and when the reactor (1) rotates, it also follows the rotation at the same time.
  • the solid residues remaining in the thermal cracking reaction are discharged out of the kettle through the screw stirrer (16) in the reactor (1).
  • the reaction kettle (1) stops when the slag discharge hole (2) is turned down (see Figure 2), and the slag discharge hole is opened
  • the central hollow shaft (8) of the reactor is equipped with a water vapor inlet pipe valve (4) at the end. Water vapor can enter the reactor from the hollow central shaft tube (8) of the reactor through the port (25), and the central hollow shaft from the other end.
  • the nozzle (3) of (9) is discharged from the reactor (1).
  • thermometer (22), a pressure gauge (23) and an overpressure safety valve (11) are installed on the head (5) at the end of the reactor to monitor the temperature and pressure during the reaction and release the pressure.
  • the method of the present invention is further described with reference to FIG. 1.
  • the pump (26) is used to drive the liquid raw material from the left central hollow shaft (8) of the reaction kettle (1) through the orifice (25) into the reaction kettle (1) or the solid raw material is charged into the reaction kettle (7) from the feeding hole (7) ), Close the feed hole (7) and the liquid feed valve (27).
  • High temperature flue gas (31) generated by combustion of coal, heavy oil or combustible gas in the combustion furnace (17) flows through the heating chamber (19) to heat the reaction kettle (1).
  • the water vapor valve (4) and the exhaust valve (30) are opened, and the reaction is performed by water vapor.
  • the air in the kettle (1) is driven out of the reactor (1).
  • the variable speed motor (29) is driven by electricity to make the reaction kettle (1) reverse or reverse.
  • the organic or polymer waste in the reaction kettle (1) undergoes thermal cracking reaction after being heated, and the gas phase hydrocarbons produced by the reaction enter the fixed bed (14). ), A catalytic cracking reaction occurs with the catalyst in the fixed bed (14) (if there is no catalyst in the fixed bed, the catalytic cracking reaction does not occur).
  • the gas phase hydrocarbons produced by the reaction are discharged out of the reaction kettle (1) through the nozzle (3) of the central hollow tube shaft (9) on the head of the kettle (1), and flow into the hydrocarbon with a jacketed water condensation device
  • the oil collecting tank (32) the liquid hydrocarbon oil which has become a low boiling point liquid is stored.
  • Hydrocarbon oil can be further fractionated and purified into gasoline, diesel oil and heavy oil according to the traditional refining method.
  • the heavy oil can be returned to the reactor (1) for cracking or sold as a commercial fuel oil.
  • the non-condensable flammable gas flows into the water-sealed tank (24), is discharged from the top of the tank (24), and is returned to the combustion furnace (17) for combustion and reuse.
  • the gaseous hydrocarbon discharge flow in the reactor (1) decreases, and the values of the thermometers (22) and (10) (which are placed near the discharge port (3)) The sharp drop and the lowest reaction temperature signaled the termination of the reaction process.
  • the solid residue remaining after the reaction is discharged from the kettle (1) using a spiral agitator (16) in the reactor (1).
  • open the water vapor valve (4) and the exhaust valve (3) to pass a certain pressure of high temperature water vapor into the reaction kettle (1), and discharge the remaining gas phase hydrocarbons to the kettle (1) to prevent air An explosion occurred in the reactor (1).
  • Example 1 Waste tire After removing 1,000 kg of waste tires from the surface, the crushed tire is charged into a horizontal rotary cylinder reactor (1), and a fixed amount of SR is charged into a fixed bed (14) in the reactor (1).
  • the -1 type catalyst uses the high-temperature flue gas generated in the combustion furnace to supply heat to the reaction kettle in the heating chamber (19), and the thermal cracking reaction and catalytic cracking reaction of the waste tire occur when the reaction kettle (1) rotates.
  • the spiral agitator in the kettle was stirred intermittently or continuously during the reaction.
  • the reaction was performed at 0.02-0.2MPa and 400-600 ° C.
  • the gas-phase hydrocarbons generated during the reaction flowed into the hydrocarbon oil collection.
  • the tank (32) In the tank (32), it is condensed into a liquid low-boiling hydrocarbon oil.
  • the non-condensable flammable gases H 2 and C r C 4 hydrocarbons are returned to the combustion furnace (17) through the top of the water-sealed tank (24) for combustion and recycling.
  • the reaction temperature decreases, it indicates that the cleavage reaction will be terminated.
  • the gas phase hydrocarbons remaining in the reaction vessel (1) are discharged out of the vessel (1). Then, the slag discharge hole was opened, and the carbon black was discharged out of the kettle with a screw stirrer.
  • the hydrocarbon oil in the hydrocarbon oil collection tank (32) is fractionated by conventional refining methods and equipment, Condensation or purification.
  • the heavy oil produced during fractionation is returned to the reactor (1) and cracked.
  • 138 kg of gasoline, 432 kg of diesel oil, 320 kg of carbon black, and 110 kg of combustible gas were finally obtained.
  • the octane number (RON) of gasoline is 93.5
  • dry point ⁇ 200 ° C induction period is 625 (min)
  • 10% distillation range is 62 ° C
  • 50% distillation range is 102 ° C
  • 90% The distillation range is 180 ° C and the saturated vapor pressure (kPa) is 52.
  • Diesel cetane number is 59, 10% distillation range is 185 ° C, 50% distillation range is ⁇ 290 ° C, 95% distillation range is ⁇ 360 ° C, and freezing point is ⁇ -20 ° C. That is: 57% for oil, 32% for carbon black, and 11% for flammable gas (H2 ⁇ C1-C5). Among them, the content of organic matter in carbon black is less than 1.8%, ash content is less than 0.5%, heating loss is less than 2,5%, iodine absorption value (mg / g) is 112-130, breaking strength (MPa) is more than 30, extension Length rate> 580.
  • Example 2 Waste plastic reaction raw materials: polyethylene (PE) 400 kg, polyethylene (PS) and polypropylene (PP) 200 kg mixture, etc. 1000 kg.
  • Waste composition volatiles 76%, fixed carbon 12%, ash 12% elemental analysis: H5.6%, 021.8%, C53.1%, S0.6%,
  • Flammable gas H 2 , d-Cs 110kg

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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

Cette invention, qui a trait à un procédé de production d'huile hydrocarbonée à partir de matières organiques ou de matières de rebut de masse moléculaire élevée, concerne également l'appareillage permettant de mettre en oeuvre ce procédé.
PCT/CN1997/000124 1997-08-13 1997-11-13 Procede de production d'huile hydrocarbonee a partir de matieres organiques ou de matieres de rebut de masse moleculaire elevee et appareillage correspondant WO1999009116A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU49399/97A AU4939997A (en) 1997-08-13 1997-11-13 Process and apparatus for producing hydrocarbon oil from organic or high molecular waste material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN97116740.0 1997-08-13
CN97116740 1997-08-13

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WO1999009116A1 true WO1999009116A1 (fr) 1999-02-25

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8084655B2 (en) 2007-06-15 2011-12-27 E. I. Du Pont De Nemours And Company Catalytic process for converting renewable resources into paraffins for use as diesel blending stocks
CN108977215A (zh) * 2017-05-31 2018-12-11 黄国城 轮胎热裂解系统及裂解方法
EP4306618A1 (fr) * 2022-07-11 2024-01-17 Neste Oyj Système et procédé de traitement des déchets de polymère
WO2024013427A1 (fr) * 2022-07-11 2024-01-18 Neste Oyj Système et procédé de traitement de déchets polymères

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4851601A (en) * 1988-01-19 1989-07-25 Mobil Oil Corporation Processing for producing hydrocarbon oils from plastic waste
JPH05345894A (ja) * 1992-06-16 1993-12-27 Toyo Seikan Kaisha Ltd プラスチックの化学的再利用方法
CN1080312A (zh) * 1992-06-20 1994-01-05 彭培安 用废塑料生产燃料的方法及其装置
EP0607862A1 (fr) * 1993-01-22 1994-07-27 Mazda Motor Corporation Méthode d'obtention d'une huile d'hydrocarbures à partir de déchets de plastiques ou du caoutchouc et appareil utilisé pour effectuer cette méthode
JPH06220460A (ja) * 1993-01-22 1994-08-09 Mazda Motor Corp 廃プラスチック又はゴム材から炭化水素油を得る方法及びその実施に使用される装置
US5368723A (en) * 1992-02-10 1994-11-29 Mazda Motor Corporation Method of and apparatus of producing low boiling point hydrocarbon oil from waste plastics or waste rubbers
CN1144229A (zh) * 1995-08-31 1997-03-05 张庆祥 利用废弃塑料生产汽、煤、柴油的方法和装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4851601A (en) * 1988-01-19 1989-07-25 Mobil Oil Corporation Processing for producing hydrocarbon oils from plastic waste
US5368723A (en) * 1992-02-10 1994-11-29 Mazda Motor Corporation Method of and apparatus of producing low boiling point hydrocarbon oil from waste plastics or waste rubbers
JPH05345894A (ja) * 1992-06-16 1993-12-27 Toyo Seikan Kaisha Ltd プラスチックの化学的再利用方法
CN1080312A (zh) * 1992-06-20 1994-01-05 彭培安 用废塑料生产燃料的方法及其装置
EP0607862A1 (fr) * 1993-01-22 1994-07-27 Mazda Motor Corporation Méthode d'obtention d'une huile d'hydrocarbures à partir de déchets de plastiques ou du caoutchouc et appareil utilisé pour effectuer cette méthode
JPH06220460A (ja) * 1993-01-22 1994-08-09 Mazda Motor Corp 廃プラスチック又はゴム材から炭化水素油を得る方法及びその実施に使用される装置
CN1144229A (zh) * 1995-08-31 1997-03-05 张庆祥 利用废弃塑料生产汽、煤、柴油的方法和装置

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8084655B2 (en) 2007-06-15 2011-12-27 E. I. Du Pont De Nemours And Company Catalytic process for converting renewable resources into paraffins for use as diesel blending stocks
US8119847B2 (en) 2007-06-15 2012-02-21 E. I. Du Pont De Nemours And Company Catalytic process for converting renewable resources into paraffins for use as diesel blending stocks
CN108977215A (zh) * 2017-05-31 2018-12-11 黄国城 轮胎热裂解系统及裂解方法
EP4306618A1 (fr) * 2022-07-11 2024-01-17 Neste Oyj Système et procédé de traitement des déchets de polymère
WO2024013427A1 (fr) * 2022-07-11 2024-01-18 Neste Oyj Système et procédé de traitement de déchets polymères

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