Classifications

• • 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
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P3/00—Drugs for disorders of the metabolism
  • A61P3/04—Anorexiants; Antiobesity agents
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P3/00—Drugs for disorders of the metabolism
  • A61P3/08—Drugs for disorders of the metabolism for glucose homeostasis
  • A61P3/10—Drugs for disorders of the metabolism for glucose homeostasis for hyperglycaemia, e.g. antidiabetics
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
  • B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
• • 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
  • C10B1/00—Retorts
  • C10B1/02—Stationary retorts
• • 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
  • C10B47/02—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with stationary charge
  • C10B47/06—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion with stationary charge in retorts
• • 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
  • C10B47/28—Other processes
  • C10B47/32—Other processes in ovens with mechanical conveying means
  • C10B47/44—Other processes in ovens with mechanical conveying means with conveyor-screws
• • 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
  • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
  • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
  • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
  • C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
• • 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
  • C10B7/00—Coke ovens with mechanical conveying means for the raw material inside the oven
  • C10B7/10—Coke ovens with mechanical conveying means for the raw material inside the oven with conveyor-screws
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/001—Purifying combustible gases containing carbon monoxide working-up the condensates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00008—Controlling the process
  • B01J2208/00017—Controlling the temperature
  • B01J2208/00389—Controlling the temperature using electric heating or cooling elements
  • B01J2208/00398—Controlling the temperature using electric heating or cooling elements inside the reactor bed
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00008—Controlling the process
  • B01J2208/00017—Controlling the temperature
  • B01J2208/00389—Controlling the temperature using electric heating or cooling elements
  • B01J2208/00407—Controlling the temperature using electric heating or cooling elements outside the reactor bed
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00008—Controlling the process
  • B01J2208/00017—Controlling the temperature
  • B01J2208/00389—Controlling the temperature using electric heating or cooling elements
  • B01J2208/00415—Controlling the temperature using electric heating or cooling elements electric resistance heaters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00008—Controlling the process
  • B01J2208/00017—Controlling the temperature
  • B01J2208/00504—Controlling the temperature by means of a burner
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00008—Controlling the process
  • B01J2208/00539—Pressure
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00796—Details of the reactor or of the particulate material
  • B01J2208/00823—Mixing elements
  • B01J2208/00858—Moving elements
  • B01J2208/00876—Moving elements outside the bed, e.g. rotary mixer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00002—Chemical plants
  • B01J2219/00004—Scale aspects
  • B01J2219/00006—Large-scale industrial plants
• • 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 inventions relates to the recovery of terpenes and terpenoids from the pyrolysis of polymers and elastomers.
• this invention relates to a component mounting system for vacuum pyrolysis of scrap tires to produce pyrolytic oil containing such compounds as dl-limonene and pulogene which has a high price on the market.
• the technology described here provides a combination of a concept totally new to the concept of extraction of value from oils derived from pyrolysis of scrap while preserving the valuable carbon black solids.
• This combination yields high concentrations of highly valued fragrance and essential oils that are known for their unique solvent properties, their usefulness as precursors for pharmaceuticals, odor masking capabilities and "green” character in ultimate disposal.
• the most obvious example of application of these steps is recovery of terpenes and terpenoids from pyrolysis of scrap tires. It achieves maximum value recovery from the oils, the solids (carbon black and metal) and the gas (light hydrocarbons).
• the technology described here provides a combination of a concept totally new to the concept of extraction of value from oils derived from pyrolysis of scrap while preserving the valuable carbon black solids.
• This combination yields high concentrations of highly valued fragrance and essential oils that are known for their unique solvent properties, their usefulness as precursors for pharmaceuticals, odor masking capabilities and "green” character in ultimate disposal.
• the most obvious example of application of these steps is recovery of terpenes and terpenoids from pyrolysis of scrap tires. It achieves maximum value recovery from the oils, the solids (carbon black and metal) and the gas (light hydrocarbons).
• Scrap rubber or similar materials are heated under vacuum and in the presence of a compound which, upon heating, decomposes into an active species which accelerates the de-vulcanization and decomposition of the polymers and elastomers in the scrap.
• a compound which, upon heating, decomposes into an active species which accelerates the de-vulcanization and decomposition of the polymers and elastomers in the scrap.
• the reactor is designed such that there are exhausts in the immediate region to carry away vapors, but by the point in the reactions, the catalyst has decomposed and the catalytic species is directly in contact with the melting materials. Therefore, the catalyst precursor cannot be carried away by escaping vapors.
• Figure 1 shows a diagram of one embodiment of the present invention related to a continuous reactor process
• Figure 2 shows a system diagram of one embodiment of the present invention related to a batch reactor process
• Figure 3 shows a system diagram of one embodiment of the present invention related to a contactor/separator system
• Figure 4 shows a system diagram for one embodiment of the present invention related to a process that uses ultraviolet light.
• Corresponding reference letters and numerals indicate corresponding steps or parts throughout the several figures of the drawings.
• catalysts to rubber pyrolysis is optional. Some researchers claim no catalyst is necessary or even desirable for rubber pyrolysis; other researchers claim that whole groups of materials can give a catalytic effect. However, it is often the case that observed catalytic effects in laboratory bench-scale batch tests disappear when the technology is scaled-up to commercial size and operations are switched from "batch” to "continuous.”
• the approach here results from the desire to produce the catalytic species in situ, i.e., to convert relatively inert materials to active species just as the temperature and reactant state are optimal to utilize the catalyst.
• the best catalyst to achieve this is a Group 1 element, such as Sodium or Potassium.
• the compounds most able to carry the Group 1 element into the high temperature zone are carbonates or bicarbonates. So, for scrap rubber containing raw materials, Potassium Carbonate is the best material to yield K+ ion directly in the mixture and in intimate contact with the polymeric and elastomeric materials in rubber.
• Full-sized commercial processing units can be "batch” or “continuous.”
• the reactor must be designed so that the additive which is the catalyst precursor must be present as the temperature reaches the point where the rubber melts, the additive decomposes to release the catalytic species and the organic vapors do not carry the precursor additive or valuable carbon black away. This is achieved differently in continuous and batch systems.
• the feed materials e.g., scrap rubber and catalyst/additive are blended together and fed via a screw system.
• the temperature rises as the mass passes through the heated reactor.
• the exhausts for the vapors are located just beyond the point where the rubber melts and the additive decomposes to yield the catalyst.
• the catalyst/additive is placed in a container above the rubber placed inside the reactor. As the temperature rises, the container is dumped and its contents dispersed over the rubber as it reaches the melting temperature.
• the additive In either batch or continuous systems, the additive is in contact with the melting rubber just as the additive decomposes and releases the catalytic Group 1 ion. But, this additive decomposition intimate contact occurs before escaping organic vapors can carry the additive material away.
• Mercaptans of the carbon-chain length found in the organic liquids downstream of rubber pyrolysis can be removed by addition of an oxidant, but the amount of oxidant required is quite high and the particular oxidants necessary are expensive. One cannot introduce significant amounts of new materials without incurring other negative results, such as disposal costs or reduced value of remaining materials. That problem is easily handled here by adding small quantities of a specific oxidant, a Sodium or
• Potassium Percarbonate to the small volume stream containing the terpenes and terpenoids.
• Sodium Percarbonate is the principal ingredient in an existing consumer product sold in large volume.
• one embodiment of the present invention is disclosed that provides a continuous reactor process B.
• Shredded scrap material 1 such as automobile tires after being washed and dried, is fed into a nitrogen-blanketed bin 3. From nitrogen-blanketed bin 3 the shredded scrap material 1 flows through vacuum-lock valves 5 (also called "Double Dump" valves) and the additive/catalyst precursor is added at fill point 23.
• the shredded scrap material 1 and the additive/catalyst enters a tubular reactor 7 which has a helical screw 9 which slowly turns at between about 0.2 to about 2.0 rpm. so that the mixture of the shredded material and the additive/catalyst precursor is conveyed through the tubular reactor which is heated electrically heating bands 1 1 .
• the shredded material 1 reaches its melting point.
• Organic vapors 21 evolving from the melting shredded material 1 are drawn from the first exit port 25 on the tubular reactor 7.
• the temperature continues to increase until the temperature of the shell near the exit is approximately 450 degrees Centigrade.
• the shredded material 1 continues to
• the solids 19 which are generally about 80+% carbon black by weight, proceed to other locations for further finishing and processing for sale.
• the organic vapors 21 enter a Contactor/Separator D where initial condensation occurs of the organic vapors, utilizing in certain embodiments, an oil spray of previous cooled liquid material. From this point in the process, the recovery process is the same for either a continuous system or a batch recovery system.
• Whole tires, especially whole large, off-the-road and heavy equipment tires 27 are loaded into a large vacuum-sealed furnace 29.
• the vacuum sealed furnace 29 is evacuated using a vacuum pump 31 .
• the heating of the sealed furnace 29 is initiated by operating a heating device 33. It is understood that the heating device 33 may be either an electric heater or a suitable gas burner. Once a suitable low pressure of about 0.1 atmosphere is achieved, a pressure valve 35 that is operatively connected to vacuum pump 31 is closed and a pressure gauge 37 is monitored to maintain the suitable low pressure needed for the process.
• the general recovery of the valuable terpene material is accomplished by inserting the liquid oil that results form the above described batch or continuous operation processes.
• a Contactor/Separator System D ( Figure 3) is used for recovery and purification of the terpene materials.
• the liquid oil enters a first distillation column 43 where the liquid oil proceeds downward by gravity.
• the preferred internal components for the first distillation column 43 are filter trays 45. In smaller systems having a internal diameter of less than about 20 centimeters to about 30 centimeters, the filter trays 45 would be of Snyder-type, floating ball design.
• the filter trays 45 In larger columns having an internal diameter of about 2 centimeters to about 3 centimeters, the filter trays 45 would be bubble cap or "top hat" design in preference over sieve trays, however, sieve trays may still be used in the upper portion of the larger column. Whichever trays are employed, it is understood that the vapors in the first distillation column 43 rise and liquids fall by the operation of gravity. Heat is supplied to the first distillation column 43 by means of a re-boiler 47 that will normally be steam- heated in larger systems and heated by electricity in smaller systems. In an integrated plant, waste heat from unrelated sources may also be used to provide the necessary heat. Regardless of the heat source, however, the bottom 49 of first distillation tube column 43 will be approximately 200 degrees Centigrade.
• the liquid material from the bottom 49 of the re-boiler 47 approximates the properties of crude oil which is taken for sale and constitutes roughly 55% by volume of the liquid oil fed to the first distillation column 43.
• the residual vapors rising within the first distillation column 43 are the lighter materials (shorter molecular chains or smaller molecular formula weight).
• the temperature near the top of the first distillation column 43 is approximately 1 85 degrees Centigrade at 760 mm Hg or 760 torr.
• the light liquid oil 55 from the separator 57 enters the second distillation column 59 where the light liquid oil 55 partially flashes and the remaining liquid oil 55 proceeds downward through a set of connective piping 61 by gravity.
• components 63 for the second distillation column 59 include sieve trays or structured packing. In smaller systems of between about 1 centimeter and about 2 centimeters, the internal components 63 can be trays and may be of the Snyder-type, floating ball design. Heat can be supplied to the column by means of a second re-boiler 65. In an integrated plant, waste heat may be used to provide the heat to the second distillation column 59 as long as the bottom 67 of the second distillation column will be approximately 100 degrees Centigrade to ensure minimal degradation of terpenes or terpenoids.
• the liquid material from the bottom of the second distillation column 59 approximates the properties of light crude oil. That light crude oil is then combined with the bottom 49 of first distillation column 45 and taken away for sale.
• Auxiliary vacuum pumps 71 and auxiliary liquid pump 73 are used to generally operate or evacuate the system.
• the product mixture from the distillation process ( Figure 4) 73 can be irradiated by a broad spectrum ultraviolet lamp 75 which is triggered by pulses of voltage increase. After exposures of two hours, four hours and seven hours to the uv light, significant changes in the relative concentrations of terpenes and other valuable materials takes place and the appearance of the product material 80 darkens noticeably. Substantial cooling is required to remove excess heat from the irradiation chamber and an additional pump 79 may be required. Coolant 76 from a refrigeration system removes such excess heat which is carried away as a heating fluid 77 to be used elsewhere in the process. Analysis by gas chromatography indicates that the concentration of some terpenes such as isopulegol has more than doubled while other materials such as toluene may decrease by 25% or more. This entire portion of the process may be located within the distillation process.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Diabetes (AREA)
• Combustion & Propulsion (AREA)
• General Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
• Public Health (AREA)
• Obesity (AREA)
• Pharmacology & Pharmacy (AREA)
• Hematology (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Veterinary Medicine (AREA)
• Bioinformatics & Cheminformatics (AREA)
• Wood Science & Technology (AREA)
• Endocrinology (AREA)
• Emergency Medicine (AREA)
• Child & Adolescent Psychology (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

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Citations (3)

• 2013
  • 2013-04-10 WO PCT/US2013/036052 patent/WO2013155238A1/fr not_active Ceased
  • 2013-04-10 JP JP2015505888A patent/JP2015518510A/ja active Pending
  • 2013-04-10 EP EP13719252.2A patent/EP2836571A1/fr not_active Withdrawn
  • 2013-04-10 CA CA2870183A patent/CA2870183A1/fr not_active Abandoned
• 2014
  • 2014-09-29 CL CL2014002605A patent/CL2014002605A1/es unknown

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