WO1995009902A1 - Liquifaction de matieres plastiques - Google Patents

Liquifaction de matieres plastiques Download PDF

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Publication number
WO1995009902A1
WO1995009902A1 PCT/US1994/011172 US9411172W WO9509902A1 WO 1995009902 A1 WO1995009902 A1 WO 1995009902A1 US 9411172 W US9411172 W US 9411172W WO 9509902 A1 WO9509902 A1 WO 9509902A1
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WIPO (PCT)
Prior art keywords
gas
range
plastic
solid carbonaceous
partial oxidation
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Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US1994/011172
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English (en)
Inventor
Motasimur Rashid Khan
Christine Cornelia Albert
Stephen Jude Decanio
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Texaco Development Corp
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Texaco Development Corp
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 Texaco Development Corp filed Critical Texaco Development Corp
Priority to AU78475/94A priority Critical patent/AU7847594A/en
Publication of WO1995009902A1 publication Critical patent/WO1995009902A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/466—Entrained flow processes
    • 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
    • C10K1/002—Removal of contaminants
    • 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
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
    • 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
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • 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
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/101—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids with water only
    • 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
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
    • C10K1/121—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors containing NH3 only (possibly in combination with NH4 salts)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1687—Integration of gasification processes with another plant or parts within the plant with steam generation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1846—Partial oxidation, i.e. injection of air or oxygen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1884—Heat exchange between at least two process streams with one stream being synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1892—Heat exchange between at least two process streams with one stream being water/steam

Definitions

  • This invention relates to an environmentally safe method for disposing of scrap plastic materials.
  • Scrap plastics are solid organic polymers and are available in such forms as sheets, extruded shapes, moldings, reinforced plastics, laminates, and foamed
  • plastics 10 plastics. About 60 billion pounds of plastics are sold in the United States each year. For example, automobiles are increasingly being manufactured containing more plastic parts. A large part of these plastic materials wind up as scrap plastics in landfills.
  • This invention relates to an environmentally acceptable process for converting a wide range of solid carbonaceous plastic materials into a high quality transportation fuel and includes the partial oxidation of a fractionator bottoms stream comprising liquid hydrocarbonaceous material and separated inorganic material; wherein synthesis gas, reducing gas, or fuel gas is produced by said process comprising the steps of:
  • a pumpable slurry comprising the following materials in weight percent room temperature and pressure: a. a slurry comprising solubilized plastic, 50 to 95 solubilized solid carbonaceous fuel, and hydrocarbonaceous liquid solvent b. unconverted organic and inorganic material 5 to 50
  • a hydrocarbonaceous distillate comprising a mixture of C 5 to C 30 compounds selected from the group consisting of naphthenes, paraffins, aromatics, olefins, and mixtures thereof, wherein said distillate has an initial atmospheric boiling point in the range of about 130°F to 500"F, a viscosity in the range of about 100 to 1500 centipoise at room temperature, and a specific gravity of about 0.7 to 1.1; b.
  • a bottoms stream comprising aromatic and paraffinic hydrocarbonaceous materials containing C 20 or higher compounds in admixture with inorganic material from said plastic and solid carbonaceous fuel; wherein said bottoms stream has an initial boiling point in the range of about 300°F to 1500°F, a viscosity in the range of about 1500 to 15,000 cP at room temperature, a solids content in the range of about 60 to 90 wt. %, a specific gravity of 0.9- 1.3; and (6) reacting by partial oxidation in a free-flow partial oxidation gasifier with a free-oxygen containing gas in the presence of a temperature moderator said bottoms stream (5) (b) to produce raw synthesis gas, fuel gas or reducing gas, and slag.
  • Scrap plastics are disposed of by the process of the subject invention without polluting the nation's environment. Simultaneously, useful by-product nonpolluting synthesis gas, reducing gas, fuel gas and nonhazardous slag are produced.
  • the scrap plastic materials which are processed as described herein include at least one solid carbonaceous thermoplastic and/or thermosetting material that may or may not contain associated inorganic matter e.g. fillers and reinforcement material. Sulfur is also commonly found in scrap plastics. Scrap plastic materials may be derived from obsolete equipment, household containers, packaging, industrial sources and junked automobiles. The mixture of plastics is of varying age and composition. With the presence of varying amounts of incombustible inorganic matter compounded in the plastic as fillers, catalysts, pigments and reinforcing agents, recovery of the plastic material is generally impractical. Further, complete combustion can release toxic-noxious components including volatile metals and hydrogen halides.
  • Associated inorganic matter in the scrap solid carbonaceous plastic may include fillers such as titania, talc, clays, alumina, barium sulfate and carbonates.
  • Catalysts and accelerators for thermosetting plastics include tin compounds for polyurethanes, and cobalt and manganese compounds for polyesters.
  • Dyes and pigments such as compounds of cadmium, chromium, cobalt, and copper; non-ferrous metals such as aluminum and copper in plastic coated wire cuttings; metal films; woven and nonwoven fiber glass, graphite, and boron reinforcing agents; steel, brass, and nickel metal inserts; and lead compounds from plastic automotive batteries.
  • Other heavy metals e.g.
  • the inorganic constituents may be present in the solid carbonaceous plastic-containing material in the amount of about a trace amount to about 60 wt. % of said solid carbonaceous plastic-containing material, such as about 1 to 20 wt. %.
  • the scrap plastic material may be in the form of sheets, extruded shapes, moldings, reinforced plastics, and foamed plastics.
  • Figure 1 gives a breakdown of 1991 sales in the United States of applicable solid carbonaceous plastics.
  • ABS Acrylobutadienestyrene
  • the solid carbonaceous plastic material that may contain associated inorganic matter e. g. filler or reinforcement material, has a higher heating value (HHV) in the range of about 3000 to 19,000 BTU per lb of solid carbonaceous plastic-containing material.
  • the plastic material is granulated by conventional means to a maximum particle dimension of about 1/4", such as about 1/8". Granulating is the preferred method for reducing the size of plastic. Any conventional plastic granulator and mill may be used. For example, a granulator will readily shred/grind solid plastic pieces to a particle size which passes through ASTM E 11 Alterative Sieve Designation 1/4" or less.
  • a mill can take the product from the granulator (i.e., -1/4") and readily convert it to smaller sizes (-1/8" or less) , such as ASTM Ell Alternative Sieve Designation No. 7 or less.
  • a suitable granulator and mill are made by
  • a sludge material having a solids content in the range of about 45 to 95 wt.% and having a minimum higher heating value (HHV) of about 10,000 BTU/lb. of slurry.
  • liquid hydrocarbonaceous solvent as used herein to describe suitable liquid solvents is a liquid hydrocarbonaceous fuel selected from the group consisting of liquefied petroleum gas, petroleum distillates and residues, gasoline, naphtha, kerosine, crude petroleum, asphalt, gas oil, residual oil, tar sand oil and shale oil, coal derived oil, aromatic hydrocarbons (such as benzene, toluene, xylene fractions) , coal tar, cycle gas oil from fluid-catalytic-cracking operations, furfural extract of coker gas oil, and mixtures thereof. Waste hydrocarbon motor oil may also be used as a liquid solvent.
  • Hydrocarbon oils having the following properties are suitable: initial atmospheric boiling point, greater than 500°F; Neutralization No., mg KOH/g 0.70 to 1.0; and Aniline point °F 100 to 110.
  • Other suitable oils comply with ASTM specification D2226, Types 101 and 102.
  • the expression "A and/or B" is used herein in its usual manner and means A or B or A and B.
  • solid carbonaceous fuels as used herein to describe suitable solid carbonaceous feedstocks, is intended to include various materials and mixtures thereof from the group consisting of coal, coke from coal, char from coal, coal liquefaction residues, petroleum coke, particulate carbon soot, and solids derived from oil shale, tar sands, and pitch. All types of coal may be used including anthracite, bituminous, sub-bituminous, and lignite.
  • the particulate carbon soot may be that which is obtained as a byproduct of the subject partial oxidation process, or that which is obtained by burning fossil fuels.
  • the amount of inorganic matter e.g.
  • ash in solid carbonaceous fuels in weight percent may be in the range of about 0.2 for petroleum coke to 20 for coal.
  • the ash particles in the hot gas stream have not reached the melting temperature of the mineral matter originally contained in the solid fuel. These ash particles are typically less than 74 microns in size.
  • Typical compositions of the ash particles in the gas stream from a coal feed for example in wt. % follow: Si0 2 58.8-62.6; A1 2 0 3 15.8-20.0; Fe 2 0 3 3.3-5.1; Ti0 2 0.8-1.4; CaO 5.3-7.6; MgO 0.5-1.6; Na 2 0
  • the sludge material is introduced into a closed autoclave where the granulated plastic material and solid carbonaceous fuel are directly contacted by said pumpable liquid hydrocarbonaceous solvent and hydrogen gas.
  • About 4 to 50 parts by weight of liquid hydrocarbonaceous solvent and about 0.l to 1.0 parts by weight of hydrogen gas contact each part by weight of plastic material and each part by weight of solid carbonaceous fuel.
  • the hydrogen gas is derived from a portion of the synthesis gas produced subsequently in the process.
  • the temperature in the autoclave is in the range of about 500°F to 1500°F.
  • the pressure in the autoclave is in the range of about 270 psig to 2750 psig.
  • the solubilized plastic and solubilized solid carbonaceous fuel is that portion of the granulated plastic material and the solid carbonaceous fuel that is liquefied by contact with liquid hydrocarbonaceous solvent and hydrogen.
  • the slurry in a. has an initial atmospheric boiling point in the range of about 180 ⁇ F to 600 ⁇ F and a specific gravity in the range of about 0.8 to 1.2. It comprises C 5 to C 35 compounds selected from the group consisting of naphthenes, aromatics, olefinics, and mixtures thereof.
  • the unconverted organic and inorganic material is the material produced by the solvent liquefaction treatment of the granulated plastic material and solid carbonaceous fuel that is not liquefied and may be easily separated from the remainder of the slurry by settling, screening, filtering, or centrifuging.
  • the density of these materials is greater than 1.2.
  • Typical inorganic compounds are selected from the group consisting of silica, alumina, calcium carbonate, and mixtures thereof. Also included are the oxides and/or sulfides of Na, Ca, Mg, Fe, and mixtures thereof.
  • the unconverted organic material represents that portion of the carbon-containing compounds in the feed that is not readily converted during the liquefaction step and is composed of carbonaceous material containing carbon, hydrogen, nitrogen and sulfur.
  • the autoclave is vented and a gas mixture comprising the following is separated from the pumpable slurry: H 2 , CO, C0 2 , C-,-C 6 gases, H 2 0 and H 2 S.
  • the vented gases may be sent to a partial oxidation gasifier (to be further described) as a supplemental fuel, or purified in a conventional gas purification zone prior to discharge.
  • the degassed pumpable slurry comprising solubilized plastic and solid carbonaceous fuel, hydrocarbonaceous liquid solvent, separated inorganic material, and unseparated inorganic material is heated in a conventional distillation zone and fractionated into a distillate having an initial atmospheric boiling point in the range of about 130°F to 500°F, a viscosity in the range of about 100 cP to 1500 cP at room temperature, and a specific gravity in the range of about 0.7 to 1.1.
  • the distillate comprises C 5 to C 25 compounds selected from the group consisting of naphthenes, aromatics, olefinics, and mixtures thereof.
  • the bottoms stream from the fractionator comprises liquid hydrocarbonaceous material and said unconverted organic and inorganic material.
  • the bottoms stream has an initial boiling point in the range of about 300°F to 1500°F, a viscosity in the range of about 1500 cP to 15,000 cP at room temperature, a specific gravity in the range of about 0.9 to 1.3, a solids content in the range of about 60 to 90 wt. %, and comprises compounds having greater than C 30 carbon atoms.
  • the distillate material was found to be a high quality transportation fuel.
  • a temperature moderator e.g. H 2 0, C0 2 e.g. H 2 0, C0 2
  • a stream of free-oxygen containing gas are introduced into the reaction zone of a free-flow unobstructed downflowing vertical refractory lined steel wall pressure vessel where the partial oxidation reaction takes place for the production of synthesis gas, reducing gas, or fuel gas.
  • a typical gas generator is shown and described in coassigned U.S. Pat. No. 3,544,291, which is incorporated herein by reference.
  • 3847,564, and 4,525,175, which are incorporated herein by reference, may be used to introduce the feedstreams into the partial oxidation gas generator.
  • free-oxygen containing gas for example in admixture with steam, may be simultaneously passed through the central conduit 18 and outer annular passage 14 of said burner.
  • the free-oxygen containing gas is selected from the group consisting of substantially pure oxygen i.e. greater than 95 mole % 0 2 , oxygen-riched air i.e. greater than 21 mole % 0 2 , and air.
  • the free-oxygen containing gas is supplied at a temperature in the range of about 100"F. to 1000°F.
  • the aforesaid bottoms stream (b) is passed into the reaction zone of the partial oxidation gas generator by way of the intermediate annular passage 16 at a temperature in the range of about ambient to 650°F.
  • the aforesaid stream of vent gas may be simultaneously introduced into the free-flow gas generator by way of a separate passage in the burner and reacted by partial oxidation simultaneously with the partial oxidation reaction of said bottoms stream.
  • the burner assembly is inserted downward through a top inlet port of the noncatalytic synthesis gas generator. The burner extends along the central longitudinal axis of the gas generator with the downstream end discharging a multiphase mixture of fuel, free-oxygen containing gas, and temperature moderator such as water, steam, or C0 2 directly into the reaction zone.
  • the relative proportions of fuels, free-oxygen containing gas and temperature moderator in the feedstreams to the gas generator are carefully regulated to convert a substantial portion of the carbon in the fuel feedstream, e.g. , up to about 90% or more by weight, to carbon oxides; and to maintain an autogenous reaction zone temperature in the range of about 1800°F. to 3500°F.
  • the temperature in the gasifier is in the range of about 2400°F. to 2800°F., so that molten slag is produced.
  • the pressure in the partial oxidation reaction zone is in the range of about 1 to 30 atmospheres.
  • the weight ratio of H 2 0 to carbon in the feed is in the range of about 0.2 - 3.0 to 1.0, such as about 0.5 - 2.0 to 1.0.
  • the atomic ratio of free-oxygen to carbon in the feed is in the range of about 0.8 - 1.5 to 1.0, such as about 0.9 -1.2 to 1.0.
  • the dwell time in the partial oxidation reaction zone is in the range of about 1 to 15 seconds, and preferably in the range of about 2 to 8 seconds.
  • the composition of the effluent gas from the gas generator in mole % dry basis may be as follows: H 2 10 to 60, CO 20 to 60, C0 2 5 to 60, CH 4 nil to 5, H 2 S+C0S nil to
  • the composition of the generator effluent gas in mole % dry basis may be about as follows: H 2 2 to 20, CO 5 to 35, C0 2 5 to 25, CH A nil to 2, H 2 S+COS nil to 3, N 2 45 to 80, and Ar 0.5 to 1.5.
  • Unconverted carbon, ash, or molten slag are contained in the effluent gas stream.
  • the effluent gas stream is called synthesis gas, reducing gas, or fuel gas.
  • synthesis gas comprises mixtures of H 2 + CO that can be used for chemical synthesis; reducing gas is rich in H 2 + CO and is used in reducing reactions; and fuel gas comprises mixtures of H 2 + CO, and may also includes CH 4 .
  • the toxic elements in any inorganic matter from the solid carbonaceous plastic and fuel materials are captured by the noncombustible constituents present and converted into nontoxic nonleachable slag. This permits the nontoxic slag to be sold as a useful by-product.
  • the cooled slag may be ground or crushed to a small particle size e.g. less than 1/8" and used in road beds or building blocks.
  • the hot gaseous effluent stream from the reaction zone of the synthesis gas generator is quickly cooled below the reaction temperature to a temperature in the range of about 250°F. to 700°F. by direct quenching in water, or by indirect heat exchange for example with water to produce steam in a gas cooler.
  • the cooled gas stream may be cleaned and purified by conventional methods.
  • gasifying plastics that contain halides such as polyvinylchloride, polytetrafluoroethylene, by partial oxidation, the halide is released as hydrogen halide (i.e.
  • the plastic-containing sludge is liquefied in a closed autoclave while in contact with hydrogen gas at a temperature of about 800"F and a pressure of about 1000 psig. About 1.0 parts by wt. of hydrogen gas is in contact with each part by wt. of plastic-containing sludge.
  • the reaction is continued for 0.5 hrs. to produce a pumpable slurry comprising the following ingredients in wt. % when measured at room temperature and pressure: a. solubilized plastic, solubilized solid carbonaceous fuel, and hydrocarbonaceous liquid solvent 68, and b. unconverted organic and inorganic material 32. Gases from the autoclave are sent to a conventional gas purification zone.
  • the degassed pumpable slurry at the temperature in the autoclave is heated and fractionated to produce a hydrocarbonaceous distillate having an initial atmospheric boiling point of 200 ⁇ F, and a viscosity of 200 cP, when measured at room temperature.
  • the bottoms stream from the fractionation zone comprising a pumpable slurry of liquid hydrocarbonaceous material and said unconverted organic and inorganic material is reacted by partial oxidation in a conventional free flow noncatalytic gas generator at a temperature of about 2400°F and a pressure of about 500 psig with about 6 tons per day of a free-oxygen containing gas in the presence of a temperature moderator e.g.
  • H 2 0 to produce raw synthesis gas, fuel gas, or reducing gas, and slag.
  • Objectionable gases e.g. H 2 S, COS, C0 2 may be removed from the aforesaid raw gas streams in a conventional gas purification zone.
  • Synthesis gas comprising H 2 + CO is produced along with about 0.05 tons of slag.
  • the slag is a coarse, glassy nonleachable material. If however, the same mixture of plastics were fully combusted in air, the slag may contain toxic elements, e.g. chromium in a leachable form.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

L'invention concerne un procédé de transformation de déchets de matière plastique en carburant de transport de qualité supérieure. On granule la matière plastique et on la mélange avec un combustible carboné solide granulé tel que du charbon et un solvant hydrocarboné liquide tel que de l'huile de moteur usée de manière à produire une boue contenant du plastique. On liquéfie ensuite ladite boue contenant du plastique en contact avec de l'hydrogène gazeux. On chauffe la boue pompée dans l'autoclave et on la fractionne dans une zone de fractionnement de manière à produire un distillat hydrocarboné pouvant être utilisé pour un carburant de transport. On fait réagir par oxydation partielle un courant de fond contenant une substance hydrocarbonée et une substance inorganique en provenance de la zone de fractionnement de manière à produire des scories non toxiques et un gaz de synthèse brut, un gaz combustible ou un gaz réducteur pouvant être purifié dans une zone de purification de gaz.
PCT/US1994/011172 1993-10-04 1994-09-30 Liquifaction de matieres plastiques Ceased WO1995009902A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU78475/94A AU7847594A (en) 1993-10-04 1994-09-30 Liquefaction of plastic materials

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13192293A 1993-10-04 1993-10-04
US08/130,922 1993-10-04

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WO1995009902A1 true WO1995009902A1 (fr) 1995-04-13

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FR2846334A1 (fr) * 2002-10-23 2004-04-30 Jean Dispons Procede de traitement de dechets en polyethylene ou autres polyolefines prealablement a leur craquage thermique
CN102344823A (zh) * 2011-09-06 2012-02-08 六盘水师范学院 一种温和条件下使煤与废塑料共液化的方法
US10472486B2 (en) 2015-07-14 2019-11-12 Solvay Sa Process for the treatment of a composition comprising thermoplastics
CN113396204A (zh) * 2019-02-04 2021-09-14 伊士曼化工公司 塑料和固体化石燃料的气化
CN115052732A (zh) * 2020-02-10 2022-09-13 伊士曼化工公司 溶剂分解二醇塔底副产物流的化学回收
WO2023049029A1 (fr) * 2021-09-21 2023-03-30 Eastman Chemical Company Récupération de co2 à contenu recyclé à partir d'un gaz de pyrolyse
CN116355643A (zh) * 2021-12-29 2023-06-30 深圳世纪星源股份有限公司 水热处理聚烯烃塑料的方法
WO2023178155A1 (fr) * 2022-03-17 2023-09-21 Eastman Chemical Company Récupération de chaleur à partir de courants de déchets à basse pression
US12528995B2 (en) 2019-10-31 2026-01-20 ExxonMobil Product Solutions Company Pyrolysis method and system for recycled waste
US12590253B2 (en) 2021-09-21 2026-03-31 ExxonMobil Product Solutions Company Low carbon footprint integrated process for recycle content olefin producers
US12590257B2 (en) 2020-02-10 2026-03-31 ExxonMobil Product Solutions Company Treatment of heavy pyrolysis products by partial oxidation gasification

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US3856658A (en) * 1971-10-20 1974-12-24 Hydrocarbon Research Inc Slurried solids handling for coal hydrogenation
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2846334A1 (fr) * 2002-10-23 2004-04-30 Jean Dispons Procede de traitement de dechets en polyethylene ou autres polyolefines prealablement a leur craquage thermique
CN102344823A (zh) * 2011-09-06 2012-02-08 六盘水师范学院 一种温和条件下使煤与废塑料共液化的方法
CN102344823B (zh) * 2011-09-06 2014-01-01 六盘水师范学院 一种温和条件下使煤与废塑料共液化的方法
US10472486B2 (en) 2015-07-14 2019-11-12 Solvay Sa Process for the treatment of a composition comprising thermoplastics
CN113396204A (zh) * 2019-02-04 2021-09-14 伊士曼化工公司 塑料和固体化石燃料的气化
US12528995B2 (en) 2019-10-31 2026-01-20 ExxonMobil Product Solutions Company Pyrolysis method and system for recycled waste
CN115052732A (zh) * 2020-02-10 2022-09-13 伊士曼化工公司 溶剂分解二醇塔底副产物流的化学回收
US12590257B2 (en) 2020-02-10 2026-03-31 ExxonMobil Product Solutions Company Treatment of heavy pyrolysis products by partial oxidation gasification
WO2023049029A1 (fr) * 2021-09-21 2023-03-30 Eastman Chemical Company Récupération de co2 à contenu recyclé à partir d'un gaz de pyrolyse
US12590253B2 (en) 2021-09-21 2026-03-31 ExxonMobil Product Solutions Company Low carbon footprint integrated process for recycle content olefin producers
CN116355643A (zh) * 2021-12-29 2023-06-30 深圳世纪星源股份有限公司 水热处理聚烯烃塑料的方法
WO2023178155A1 (fr) * 2022-03-17 2023-09-21 Eastman Chemical Company Récupération de chaleur à partir de courants de déchets à basse pression

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