WO2013141688A1 - Procédé de dépolymérisation pour la production de brut hors spécifications et de noir de carbone à partir de pneus de rebut - Google Patents

Procédé de dépolymérisation pour la production de brut hors spécifications et de noir de carbone à partir de pneus de rebut Download PDF

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Publication number
WO2013141688A1
WO2013141688A1 PCT/MY2012/000280 MY2012000280W WO2013141688A1 WO 2013141688 A1 WO2013141688 A1 WO 2013141688A1 MY 2012000280 W MY2012000280 W MY 2012000280W WO 2013141688 A1 WO2013141688 A1 WO 2013141688A1
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WO
WIPO (PCT)
Prior art keywords
spec
crudes
fraction
polymerized
heavy
Prior art date
Application number
PCT/MY2012/000280
Other languages
English (en)
Inventor
Fei Tho CHOO
Original Assignee
Ecopyrotech International Sdn Bhd
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 Ecopyrotech International Sdn Bhd filed Critical Ecopyrotech International Sdn Bhd
Publication of WO2013141688A1 publication Critical patent/WO2013141688A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/482—Preparation from used rubber products, e.g. tyres
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B47/00—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
    • C10B47/18—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with moving charge
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics

Definitions

  • This invention relates to processes for the recovery of off-spec crudes and solid residue "carbon black" from vulcanized rubber chips.
  • Ethanol and biodiesel are crop-based fuels, produced from corn and soya beans respectively.
  • Crop based fuels faces great challenges as a replacement for oil as these are number one source of food calories.
  • Incineration or heat based via direct furnace-burner of the organic portion of the rubber chips does not appear to be the solution.
  • Off gases produced during intense heat incineration contain air pollutants such as sulfur dioxide (SO2), Nitrogen oxide (NO,,), carbon monoxide (CO) and ash.
  • SO2 sulfur dioxide
  • NO,, Nitrogen oxide
  • CO carbon monoxide
  • ash To avoid air pollution, these pollutants must be diminished or trapped in the process. This requires costly devices such as electrostatic precipitators and the like. What is needed is an efficient, economical method for handling rubber chip wastes produced by the society from the millions of discarded waste scrap tires, which can recover off- spec crudes and residue solid "carbon black" from the organic portion while substantially reducing the volume of gaseous discharge effluents, which must be treated to eliminate air pollution during processing.
  • the ash and particulate emission will increased when the pyrolytic oil is burned for consumption.
  • Prior method of gravitational filtration or centrifuging has not been successful in resolving the solid removal issues. Therefore, an improvement in the solids separation while retaining the inherent fluidity of the off-spec crudes is the desire recourse.
  • the desired result is being achieved by utilizing a unique clarification process at 80 degree Celsius with a centrifugation-purification process. Together with a reflux light fraction into condenser No.l, a quality reflux off-spec crudes light fraction can be achieved economically; as the said dual proprietary catalyst heating system (manufactured by Energeia [S] Pte. Ltd) and centrifuging- purifying components (manufactured by Alfa Laval Ltd) ensure a low consumption of within 270 amperes of 80-400 degree Celsius.
  • a process and apparatus related to the de-polymerization of organic vulcanized rubber chips for the production of valued off-spec crudes of heavy and light fractions and subsequent separation of solid residue "carbon black" for recycle back into the economy.
  • Organic fractions of a mixture of vulcanized rubber chips and crumbs of a size of 10-50 millimeter (mm) are subjected to a de-polymerization process.
  • the de-polymerization consists of an operation wherein the dried organic fraction mixture is combined with an endothermic source of heat and a carrier gas which is non-reactive with respect to the product of de- polymerization under regulated turbulent push-throw conditions of the mixture and particulate matter in a de-polymerized zone maintained at a temperature of about 300 degree Celsius to about 450 degree Celsius.
  • Hydrocarbon residue solid "carbon black” and condensable off-specs crudes are formed as the de-polymerization products.
  • the off-spec crudes vapors produced in the de-polymerized process contain solids arises from inorganic particulates formed from the decomposition of vapors.
  • Heavy fraction off-spec crudes are produced by quenching at least a portion of the de-polymerized vapor. Solid particulate becomes entrained in these heavy off-spec crudes.
  • medium heavy fraction off-spec crudes with lesser substantiated particulate matters is produced.
  • the medium heavy fraction is further condensed at the cooler condenser at a temperature of 80 degree Celsius.
  • the medium heavy fraction is generally made up of American Petroleum Institute (API) gravity ⁇ 29°, heavy off- spec crudes which is further clarified, centrifuged and purified to a light fraction.
  • the light fraction produced at a temperature 80 degree Celsius upon clarification- centrifugation-purification contains a substantially reduced amount of particulate matters.
  • the solid residue separated from the distillation of the de-polymerized vapor can be reclaimed as "carbon black".
  • the process comprises the de- polymerization of vulcanized rubber chips by breaking down the number of carbon atoms in molecules to a range of 20-27 at standard atmospheric pressure at an approximate boiling temperature of 350-450 degree Celsius.
  • the de-polymerization process utilizes endothermic heat to decompose the long chain polymers of rubber chip into short petroleum hydrocarbon with a maximum length of 27 carbons.
  • Crude oil consist of 84-87% carbon atoms, 1 1-14% hydrogen atoms, 0%-6% sulfur atoms and less than 1% nitrogen atoms, oxygen atoms, metals and salts.
  • This process consist of endothermic heating of rubber chips via a stationary jacketed reactor; that propels the rubber chips forward by extruders arms welded to a heated-up rotating shaft within the reactor. Heating of the rubber chips in the stationary reactor from an endothermic heat source, generated from a sodium nitrates catalyst heating system.
  • the proprietary heating tanks-clarification system is especially designed- manufactured by Energeia (S) Pte. Ltd. (utilized particularly for this de- polymerization process only) together with a proprietary centrifuging system from Alfa Laval Company forms an integral part of this process system.
  • the rubber chip is de-polymerized into an off-spec crudes hydrocarbon vapor and solid residue.
  • the vaporized off-spec crudes with entrained particulate matter is quenched in condenser no.l; off-loading heavy end off-spec crudes fraction of approximate 35 carbon atoms in molecules into an off-spec crudes heavy oil tank; while the middle distillates off- spec crudes fraction hydrocarbon vapor is substantially free of a heavy fraction containing entrained particulate matter, proceed to condenser no.2 and cooled into off-spec crudes liquid form by a cooler heat exchanger.
  • the depolymerized off-spec crudes hydrocarbon vapor is condensed and cooled into off-spec crude of 20-27 atoms in molecules, which is further centrifuged and purified producing a light fraction containing entrained particulate matter and pumped into an off-spec crude light oil tank, the solid residue "carbon black” is propel forward and exit via a vibrator-chute via an air lock into a series of conveyors with cutting blades that disintegrate the carbon black into powdery form into a retaining silo with vibrator and an on-off valve for dislodging into packing bags.
  • the process herein is a distillation process for solid organic waste as in vulcanized rubber chips or carboneous organic waste matters which are produced by the air-land transportation and the motoring communities globally.
  • the solid organic waste is treated and distillate to produce and recover valuable products as in heavy and light fractions of hydrocarbon off-specs oil and solid residue "char” "carbon black”.
  • This process hereby said "de-polymerization” is for conversion and/or volatilization of the organic material in the rubber chips to useful organic fuel values such as hydrocarbon off-specs oil and carbon black.
  • the degree of segregation of organic matters from the solid wastes as in rubber chips and/or crumbs can impose uneconomical cost factors on the overall process.
  • Solid wastes can be segregated by shredding by using conventional equipment and processes.
  • the size of the organic solid matter has a maximum dimension of 50 millimeter (mm) x 50 millimeter (mm) and smaller as in 10 millimeter (mm) size of rubber crumbs.
  • maximum dimension is meant the largest dimension, either in width or length.
  • the individual size and shape of the organic particles, as well as the density, can affect the heat transfer to the particles. Any changes in size can therefore, necessitate adjustment of residence times within the de- polymerized zone to ensure that the particles of organic matters within the rubber chip are heated to the desired reaction temperature.
  • de-polymerization is conducted by endothermic heating the organic solid waste aka rubber chips to a temperature between 300 degrees Celsius to about 450 degrees Celsius.
  • a preferred heating rate is from 10 degree Celsius/minute to about 20 degree Celsius/minute until the reactor de-polymerization zone reaches a holding temperature of 400 degree Celsius.
  • the rubber chips are entrained in a turbulent gaseous stream composed of inert gas, waste solids and hot particulate carbon black.
  • the residence time is 60 minutes per cycle at a temperature of about 400 degree Celsius.
  • the rubber chips are composed of natural and synthetic rubber with carbon black, synthetic fibers and short length of binding steel wires.
  • the relationship between temperature, pressure and residence time can be varied to optimize yields of de-polymerized vapor and residue solid. If the temperature and/or residence times are too low, the vaporization and de-polymerized of solid waste is incomplete. When the temperature and/or residence time is too high, the de- polymerized products are degraded producing low yields of products and related fuel values.
  • turbulent stream is meant a stream of gas flowing through a de- polymerized zone.
  • the inert gas, hot carbon black, solid waste and heavy hydrocarbon off-specs oil are introduced into one end of the de-polymerized reactor and rapidly intermixed, physically in contact with each other and propel through the vessel radially to permit the requisite heat transfer to occur.
  • the heat required to de-polymerize the organic matter is provided endothermic through the jacketed reactor by the Energeia heat catalyst system; that is contractually assigned and designed only for the utilization of heat transfer in this particular de- polymerization system. After initial heating up of the mixture, additional heat to remove the volatile chemical value in the rubber chip can be provided in part from the sensible heat in the carbon black and heavy fraction of the off-specs oil.
  • the system of this invention is based on a closed loop system; thereby the effluent from the de-polymerized zone of carbon black, volatized organic fuel and chemical values, water (as steam); inert gas and product gas can be substantially separated from the de-polymerized vapor by a unique clarification-centrifugation- purification for off-specs hydrocarbon oil, carbon black and steel wire. All effluent is reflux into the de-polymerized cycle as part of the end products.
  • Rubber chip (organic matter) is conveyed via a scraper conveyor (1) into a volumetric conveyor (2) thru a rotary airlock and into a cylindrical reactor (3) with propelling arms attached to the center shaft.
  • the stationary reactor has a jacket that permit endothermic heating of the organic solid within the reactor.
  • the de- polymerized vapor exit from the two opening at the top surface of the reactor and travel along the pipework into the condenser-quencher (4). Quenching, in effect condensed at least a portion of the de-polymerized vapor into a heavy fraction off-specs liquid containing entrained particulate matter.
  • the medium heavy fraction off specs oil is condensed at 80 degree C and further condensed-cooled at condenser (6) and is transfer to clarification tank (7), mixed and clarified with effluent water to be discharge via pipeline into a centrifuging-purifying system (8); where at a temperature of about 60 degree C, the medium heavy fraction liquid is converted into a light fraction off-specs hydrocarbon oil and stored at a light fraction off-specs tank (9).
  • the light fraction off-specs oil is reflux via a piping system and into quencher- condenser (4) where the light fraction liquid is used in scrubbing at least a portion of de-polymerized hot vapor from reactor (3).
  • The, at least a portion of heavy fraction hydrocarbon off-spec oil is discharge from the quencher-condenser (4) into a heavy fraction tank (10); where the heavy fraction liquid containing entrained particulate matter is refluxed into the reactor; and mixed with the carbon black, organic solids and hot gaseous inert and resident gases; to repeat the de-polymerized cycle.
  • the residue solid "carbon black” is propel toward the end of reactor (3) and exit via a vibrator chute; conveyed by a propelling paddle enclosed conveyor (11) via an airlock and drop into a conveyor (12) with propelling paddle; into a magnetic drum (13) where the carbon black is magnetically separated from remnant of steel wire; into uplifting conveyor (14) and finally into a carbon storage silo (15).
  • the steel wire is separated by the magnetic drum and deposited via a belt conveyor into a transfer bin.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention porte sur un procédé économique pour la production de bruts hors spécifications et de noir de carbone à partir de copeaux de caoutchouc vulcanisé, issus de pneus de rebut. Le procédé comprend la dépolymérisation des copeaux de caoutchouc par abaissement du nombre d'atomes de carbone dans les molécules par décomposition. Le procédé de dépolymérisation utilise la chaleur endothermique pour décomposer les polymères à longue chaîne de copeaux de caoutchouc en hydrocarbures de pétrole courts. Les copeaux de caoutchouc vulcanisé sont dépolymérisés en une vapeur d'hydrocarbures brute hors spécifications et en un résidu solide.
PCT/MY2012/000280 2012-03-23 2012-11-22 Procédé de dépolymérisation pour la production de brut hors spécifications et de noir de carbone à partir de pneus de rebut WO2013141688A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MYPI2012001343 2012-03-23
MYPI2012001343 2012-03-23

Publications (1)

Publication Number Publication Date
WO2013141688A1 true WO2013141688A1 (fr) 2013-09-26

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2400284A1 (de) * 1973-01-05 1974-07-18 Agency Ind Science Techn Verfahren zum trockendestillieren von gummi
US20070102279A1 (en) * 2006-02-02 2007-05-10 Novak John F Method and Apparatus for Microwave Reduction of Organic Compounds
US20080179257A1 (en) * 2007-01-25 2008-07-31 Stephen Clarke Process for the Thermal Treatment of Pharmaceutical Waste Material
US20100249353A1 (en) * 2009-03-24 2010-09-30 Recycling International Petroleum Products Inc. Method of Reclaiming Carbonaceous Materials From Scrap Tires and Products Derived Therefrom

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2400284A1 (de) * 1973-01-05 1974-07-18 Agency Ind Science Techn Verfahren zum trockendestillieren von gummi
US20070102279A1 (en) * 2006-02-02 2007-05-10 Novak John F Method and Apparatus for Microwave Reduction of Organic Compounds
US20080179257A1 (en) * 2007-01-25 2008-07-31 Stephen Clarke Process for the Thermal Treatment of Pharmaceutical Waste Material
US20100249353A1 (en) * 2009-03-24 2010-09-30 Recycling International Petroleum Products Inc. Method of Reclaiming Carbonaceous Materials From Scrap Tires and Products Derived Therefrom

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