EP2937403B1 - Verfahren zur Verarbeitung von Industrie- und Haushaltsabfällen, insbesondere Kunststoff- und/oder kautschukhaltigen Abfällen, zur Herstellung von Erdölprodukten zur Verwendung als Motorölkomponenten und Chemierohstoffe - Google Patents

Verfahren zur Verarbeitung von Industrie- und Haushaltsabfällen, insbesondere Kunststoff- und/oder kautschukhaltigen Abfällen, zur Herstellung von Erdölprodukten zur Verwendung als Motorölkomponenten und Chemierohstoffe Download PDF

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Publication number
EP2937403B1
EP2937403B1 EP14187755.5A EP14187755A EP2937403B1 EP 2937403 B1 EP2937403 B1 EP 2937403B1 EP 14187755 A EP14187755 A EP 14187755A EP 2937403 B1 EP2937403 B1 EP 2937403B1
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EP
European Patent Office
Prior art keywords
starting material
catalyst
wastes
rubber
metal
Prior art date
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EP14187755.5A
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English (en)
French (fr)
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EP2937403A1 (de
Inventor
Natalia Popova
Konstantin Fridzon
Vladimir Platonov
Nikolay Vorobev
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PLATONOV, VLADIMIR
POPOVA, NATALIA
VOROBEV, NIKOLAY
Original Assignee
Popova Natalia
Vorobev Nikolay
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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
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
    • 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
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/086—Characterised by the catalyst used
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]

Definitions

  • the present invention relates to the chemical processing of a starting material containing industrial and domestic organic wastes, in particular plastic and/or rubber-containing wastes, to produce petroleum products, in particular liquid petroleum products for use as motor oil components or as raw materials in the basic organic, petrochemical and biochemical synthesis industries, the production of anode paste for electrothermal and electrochemical enterprises, water-, heat- and sound-insulating materials, and bituminous concrete for road making.
  • rubber is a product originating from petroleum it would be highly desirable to have a process that allows for ecologically clean comprehensive chemical processing of plastic and/or rubber-containing materials with the object of producing liquid petroleum products for use as boiler fuel, components of high-octane motor fuels, raw materials for the petrochemical, organic and biochemical synthesis industries, production of water-, heat- and sound-insulating materials, bituminous concrete for road making, carbon-graphite materials and anode paste for electrothermal and electrochemical plants.
  • US 2012/310023 discloses a method of producing liquid fuels, such as gasoline, diesel or fuel oil, from solid using a supported metal catalyst.
  • the method involves mixing a solid plastic waste with a metal hydride and a supported metal catalyst followed by gasifying the mixture at a temperature of about 300 to 800 °C and a pressure of about 1 atm to 20 atm in order to produce the desired liquid fuels.
  • the solid plastic waste may also be melted prior to the addition of the metal hydride and/or supported metal catalyst.
  • US 3 332 926 discloses to the thermal degradation of polyolefins in the presence of a metal salt carboxylic acid catalyst to produce relatively low molecular weight hydrocarbon polymers.
  • US 4,175,211 discloses a method for processing plastic and/ or rubber-containing wastes - scrap automobile tires - which comprises grinding the latter to 4-0.75 mm, mixing with petroleum products, and heating the resultant mass in a reactor at 65-370 °C for a time sufficient for the material to dissolve.
  • the method involves catalytic cracking of the resultant solution in a reactor at a temperature of not lower than 450 °C and under elevated pressure, discharging the product from the reactor and subsequently distilling it to produce gaseous products, a gasoline fraction, and light and heavy oils.
  • US 4,175,211 is characterized by its multi-stage nature and the complexity of the process. Said method also requires grinding the scrap tires, which is extremely challenging, particularly when metal cord is present; using a specific catalyst and periodically regenerating this, and employing high temperatures and pressure, which results in the formation of significant amounts of low-molecular gaseous products and also of high-molecular asphaltenic hydrocarbons due to condensation reaction.
  • US 3,895,059 discloses a method for the preparation of liquid products from rubber-containing wastes by heating these wastes at a temperature above 200 °C in a hydrocarbon liquid for a time ensuring conversion of the rubber into a viscous oil-like product. Then, the latter is treated with an alkylation catalyst (H 2 SO 4 , S 2 Cl 2 ) after addition of an aliphatic aldehyde or ketone thereto. The resultant resin is added to rubber mixtures in tire production.
  • an alkylation catalyst H 2 SO 4 , S 2 Cl 2
  • the above method is also characterized by a multi-stage nature, the need to use sulfuric acid and sulfur monochloride, which can induce deep condensation reactions, and densification, which complicates the formation of low-molecular liquid products. Furthermore, the fields of application of the resultant product are restricted and specific.
  • SU 1613455 discloses a method for processing rubber-containing wastes by stirring a solution of plastic and/or rubber-containing wastes with a concentration of 10-80 wt.% in a hydrocarbon medium at a temperature of 290-380 °C and distilling off low-boiling fractions.
  • the hydrocarbon medium employed is the product of propane deasphaltation of oil tar containing 2.4-5.9 wt.% of asphaltenes.
  • Low-boiling fractions with a boiling point of 230-310 °C are distilled off continuously during the entire stirring process.
  • Disadvantages of the method of SU 1613455 relate primarily to limitations regarding the content of asphaltenes in the hydrocarbon medium. This condition is difficult to meet, since the crude oils produced in recent years and the products of their refining have usually a high content of asphaltenes and tarry and organosulfur compounds. Consequently, numerous cycles of extraction of the aforesaid compounds are required to reduce their content in the hydrocarbon medium. Furthermore, the yield of light fractions with a boiling point of up to 230 °C is below 40 wt.%.
  • US 3,896,059 discloses a method for processing rubber-containing wastes involving heat-treatment of the wastes in a hydrocarbon solvent at 204-427 °C for 0.1-50 hours, followed by treating the hot dissolution product thus obtained with an alkylation catalyst (a Lewis acid) or a condensation catalyst (0.1-20 wt.% of the product) at 16-149 °C for 0.5-50 hours.
  • an alkylation catalyst a Lewis acid
  • a condensation catalyst 0.1-20 wt.% of the product
  • Drawbacks of the above method are its complexity and multiple stages, and most importantly the limited use of the resultant final product, which is preferably added to rubber mixtures in tire production.
  • SU 1289872 discloses a method for processing scrap tires and various rubber-containing wastes by heat-treating a mixture of a previously prepared rubber powder and a plasticizer (shale oil or anthracene oil), first at 190-220 °C and then at 240-260 °C.
  • a plasticizer shale oil or anthracene oil
  • bitumen polyethylene wax, sulfur, etc.
  • Said process is multi-stage and requires prior grinding of the starting material to particles of less than 1 mm, which is impracticable when recycling tires which contain metal cords and metallic parts.
  • the method of SU 1289872 does not provide for the production of boiler and motor fuel or carbon black as the resultant product is a rubber-bitumen composition containing carbon black and mineral components of the rubber (kaolin, talc, oxides of zinc and titanium, etc.), which restricts the usability of the resultant product.
  • RU 2,153,415 discloses a method for recycling scrap automobile tires and rubber-containing goods.
  • the starting material is heat-treated with petroleum products at 260-290 °C until the rubber is fully dissolved.
  • the resultant rubber-bitumen composition is poured off while the residue of carbon black, mineral components and metal cord remains in a specially perforated basket.
  • the resultant rubber-bitumen composition is used as a material for damp-proofing and roofing work, and for the manufacture of bituminous concrete.
  • RU 2,109,770 discloses a method for processing rubber-containing wastes by processing the wastes at 270-420 °C and a pressure of 1-6 MPa in a hydrocarbon solvent and in the presence of rare-earth metals (REM).
  • REM-based intermetallic compounds or titanium hydride are used in an amount of 0.5-10.0 wt.% of the reaction mixture.
  • the method provides for thermal liquefaction with a 2:1-4:1 weight ratio of hydrocarbon solvent and wastes.
  • the method is characterized by a low hydrogen potential utilization coefficient of the components of the solvent, which demands repeated use thereof in the process, continuous separation of the initial material from the liquid products of thermal liquefaction and also maintenance of an elevated pressure in the reaction apparatus.
  • a further disadvantage is the use of (liquid) synthetic rubber production wastes as the hydrocarbon solvent, as these are not always available in the required amount.
  • RF Patent No. 2110535 discloses a method for processing rubber-containing and also organic industrial and domestic wastes into chemical raw materials and motor fuel components, which is performed in a manner similar to that of RU 2109770 described above.
  • one or more alkylbenzenes (toluene, xylenes, ethylbenzenes, diethyl-, dimethyl- and tetramethylbenzenes) are employed as a hydrogen-donor solvent, these being the basis of "crude benzene" - the product of high-temperature coking of hard coals.
  • RF Patent No. 2167168 discloses a method for processing organic wastes involving thermal liquefaction of the wastes at a temperature above 270 °C and at elevated pressure of at least 6 MPa in alkylbenzene. Further steps involve separation of the liquid fraction and distillation thereof. After distillation, the liquid fraction with a boiling point above 210 °C is re-added to the reaction mixture for subsequent thermal cracking to produce kerosene and solar oil fractions.
  • a significant disadvantage of said method is its inefficiency in production of a high-octane gasoline fraction due to the removal of the liquid fraction with a boiling point of less than 200 °C from the reaction mixture. Since the most active chain extension initiators of radical reactions are contained in the up to 200 °C fraction, they are also removed from the reaction mixture, leading to a deceleration of the process as a whole and impeding the production of a high-octane gasoline fraction.
  • RF Patent No. 2272826 discloses a method for processing plastic and/or rubber-containing wastes through thermocatalytic liquefaction of the wastes at elevated temperature and pressure.
  • the process is performed in the presence of a solvent, which is a mixture of hydrogen-donor hydrocarbons comprising alkylbenzenes and tetraline.
  • a solvent which is a mixture of hydrogen-donor hydrocarbons comprising alkylbenzenes and tetraline.
  • the latter has a low induction period value, which allows the process to be performed at 200-320 °C.
  • Metal containing phthalocyanines and dimethylglyoximates are used as the catalyst.
  • the problem solved by the present invention is therefore to provide a process that allows for a safe, simplified, ecologically clean comprehensive chemical processing of a variety of industrial and domestic organic wastes, in particular plastic and/or rubber-containing wastes, in order to obtain high quality liquid petroleum products that can be utilized as motor fuel components and chemical raw materials.
  • thermolysis in particular thermocatalytic liquefaction
  • a starting material containing industrial and domestic organic wastes, in particular plastic and/or rubber-containing wastes.
  • the process of the present invention involves treating the starting material with a catalyst and an initiator comprising at least one metal hydride, optionally in the presence of a hydrogen donor, at elevated temperature and pressure, preferably at a temperature of 200-400 °C and a pressure of 3-7 MPa.
  • the catalyst comprises one or more metal carboxylate salt(s), wherein the carboxylate anion A of each metal carboxylate salt is independently of one another selected from the group consisting of anions of saturated C1-C20 carboxylic acids, and the metallic cation M of each metal carboxylate salt is independently of one another selected from the group consisting of cations of titanium (Ti), aluminum (Al), germanium (Ge), zirconium (Zr), iron (Fe), cobalt (Co), nickel (Ni), chromium (Cr), molybdenum (Mo), manganese (Mn), lanthanum (La), cerium (Ce), neodymium (Nd), samarium (Sm), dysprosium (Dy).
  • the carboxylate anion A of each metal carboxylate salt is independently of one another selected from the group consisting of anions of saturated C1-C20 carboxylic acids
  • the metallic cation M of each metal carboxylate salt is independently of one another selected from the
  • the general formula of the metal carboxylate salt is [(M n+ )(A - ) n ], with the number n being the degree of oxidation.
  • the catalyst comprises a metal carboxylate salt of which the metallic cation M is iron (II), the number of n is 2.
  • each metal carboxylate salt preferably contains the same type of carboxylate anion A but a different metallic cation M.
  • the process of the present invention has the advantage that a wide variety of industrial and organic domestic wastes, in particular plastic and/or rubber-containing wastes, can be utilized as starting material.
  • industrial and organic domestic wastes in particular plastic and/or rubber-containing wastes
  • scrap tires industrial rubber goods, polyethylene, polypropylene, polystyrene, polyisobutylene, polyester, (e.g. kapron, lavsan, enant), polyamide (e.g. nylon), polyvinylchloride, phenolformaldehyde (e.g. novolac resins) etc.
  • scrap tires industrial rubber goods, polyethylene, polypropylene, polystyrene, polyisobutylene, polyester, (e.g. kapron, lavsan, enant), polyamide (e.g. nylon), polyvinylchloride, phenolformaldehyde (e.g. novolac resins) etc.
  • polyamide e.g. nylon
  • the latter can subsequently be rectified to give liquid product fractions with boiling points ranges of i) up to 200 °C, ii) 200-320 °C and iii) above 320 °C. These fractions can be used as high-octane components of motor fuel and as chemical starting materials for basic organic, biochemical and petrochemical synthesis.
  • starting material encompasses both, materials containing only one single kind of organic waste as well as material mixtures containing two or more different kinds of organic materials, in particular rubber materials.
  • waste is to be understood as materials that are disposed goods, independent of their origin.
  • waste as used in the present application encompasses not only trash materials but also new materials, which have been overproduced or are defective in any way.
  • An important benefit of the process of the present invention is the use of metal salts of saturated carboxylic acids as catalyst as they are readily soluble in the reaction mixture, forming a homogeneous solution, which provides high availability of the catalyst to the starting material.
  • the process of the present invention has the advantage of a high uniformity of catalyst distribution in the reaction mixture.
  • thermolysis of the catalyst results in the formation of nano-size free metal particles.
  • These metal nano-particles exhibit high activity and selectivity in reactions of hydrogenation, dehydrogenation, hydrodealkylation, isomerization and cyclization in the course of the process of thermal liquefaction of the starting material.
  • atomic hydrogen is readily detached from the starting material and/or the hydrogen donor and the metal hydride and transferred to radical products, which are formed in the course of thermal decomposition of the starting material.
  • carbon monoxide is liberated during the thermolysis of the catalyst used in the process of the present invention in accordance with the principle of the oxosynthesis reaction.
  • Carbon monoxide is an efficient hydrogen carrier of hydrogen from the starting material and/or the hydrogen donor and the metal hydride to the radical products.
  • the process of the present invention allows for enhancement of the hydrogen donor potential of the reactants and, thanks to this more efficient utilization of hydrogen, it is possible to avoid the use of molecular hydrogen (H 2 gas) under high pressure.
  • the initiator comprising at least one metal hydride as used in the process of the present invention acts as a donor of atomic hydrogen and makes it possible to substantially reduce the induction period of the process of thermolysis of the starting material. This is because, during the process of the present invention, the initiator readily undergoes thermolysis, which results in liberation of atomic hydrogen. Thanks to this hydrogen liberation, the process induction effect and consequently the process temperature can be significantly reduced. Also, the liberated atomic hydrogen is available for recombination of radical products formed during thermolysis of the starting material. As such, the productivity of the reaction apparatus is improved and the economic parameters of the process as a whole can be enhanced.
  • the process of the present invention provides a simplified way for thermolysis of a plastic and/or rubber-containing starting material of complex chemical composition, while allowing for an increased process selectivity and productivity with simultaneous improvement in explosion and fire safety and ecological cleanness. Further benefits are elimination of dependence on the nature of the hydrogen donor and the composition of the starting material, as well as an increase in yield of liquid products in relation to their qualitative and quantitative composition.
  • the process of the present invention allows for obtaining liquid petroleum products with a low content of oxygen-, nitrogen- and sulfur-containing unsaturated compounds.
  • the process of the present invention helps to resolve serious ecological problems caused by the need to recycle industrial and domestic organic wastes, in particular plastic and/or rubber-containing wastes, allows to lower the prime cost of the products obtained, and to improve the economic parameters of the process as a whole.
  • the carboxylate anion A of each metal carboxylate salt is independently of one another selected from the group consisting of anions of saturated C1-C10 carboxylic acids.
  • the catalyst comprises a mixture of at least two metal carboxylate salts different from one another.
  • the catalyst comprises at least two different metal carboxylate salts, which contain the same type of carboxylate anion A but a different metallic cation M.
  • the catalyst comprises at least three different metal carboxylate salts, which preferably contain the same type of carboxylate anion A but metallic cations M1, M2 and M3.
  • the catalyst comprises a first metal carboxylate salt [(M1 n+ )(A - ) n ], a second metal carboxylate salt [(M2 n+ )(A - ) n ] a third metal carboxylate salt [(M3 n+ )(A - ) n ].
  • a specific example would be a catalyst comprising a mixture of iron(II) or iron(III) formate, dysprosium(III) laurate and cerium(III) stearate.
  • the initiator comprises at least one metal hydride comprising a metallic cation selected from cations of the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), francium (Fr), copper (Cu), silver (Ag), gold (Au), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), zinc (Zn), cadmium (Cd), mercury (Hg), titanium (Ti), zirconium (Zr), hafnium (Hf), rutherfordium (Rf), silicon (Si), germanium (Ge), tin (Sn) and lead (Pb).
  • a metallic cation selected from cations of the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), francium (Fr), copper (Cu), silver (Ag
  • the at least one metal hydride comprising a metallic cation selected from cations of the group consisting of Li, Na, K, Cu, Ag, Mg, Ca, Sr, Zn, Ti, Zr, Si, Sn and Pb. It is also preferred to use a cation mixture comprising two or more cations of the metals listed above.
  • the at least one metal hydride comprises a metallic cation selected from cations of the group consisting of Ca, Na, K, Ba and Ti. Thermolysis of these hydrides in the process of the thermolysis reaction of the starting material results in the release of atomic hydrogen, which is then available for recombination with radical products formed during the reaction.
  • the hydroxides which are often formed as recombination products, can act then as neutralizers in the process of the present invention, as will be explained further below.
  • the metallic cation is preferably a cation selected from cations of the group consisting of Zn, Cd, Hg, Ti, Zr, Hf, Si, Ge, Sn and Pb. These hydrides have the advantage that they are not negatively affected by the presence of water, whereby Ti, Zr and Hf are particularly preferred.
  • the hydrogen donor does not necessarily have to be an additional material added to the reaction mixture but the hydrogen donor may also be already present in the starting material.
  • the starting material may comprise polycyclic arenes, which are efficient carriers of hydrogen to the radical products of thermolysis of hydrocarbons. If the nature of the starting material requires it, an additional hydrogen donor is added to the reaction mixture. As such, the process of the present invention avoids dependence on the chemical composition of the starting material.
  • the hydrogen donor also acts as a solvent for the catalytic reaction.
  • the hydrogen donor is derived from crude oil and preferably comprises crude paraffinic-naphthenic oil.
  • Paraffinic-naphthenic oil especially the 230-280 °C fraction thereof, is generally characterized by a high content of isoalkanes, cycloalkanes and low-molecular polycyclic arenes, which are efficient carriers of atomic hydrogen and are available in large quantities.
  • the hydrogen donor essentially consists of crude oil, in particular crude paraffinic-naphthenic oil.
  • the process of the present invention allows for using crude oil as the hydrogen donor.
  • crude oil there is no need for prior deasphaltation and rectification of a crude oil in order to obtain a 230-280 °C fraction thereof. This significantly simplifies the process technology as a whole.
  • the starting material and the hydrogen donor are used in a weight ratio of 1:2-1:5. This weight ratio is particularly effective for the production of liquid petroleum products with a high octane number and minimum sulfur content.
  • the catalyst and the hydrogen donor are preferably used in a weight ratio of 1:50-1:200.
  • metal hydride and the hydrogen donor are used in a weight ratio of 1:50-1:200.
  • the starting material is further treated with a neutralizer comprising at least one metal oxide or hydroxide, wherein the metallic cation is selected form the group consisting of cations of lithium (Li), sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba).
  • a neutralizer comprising at least one metal oxide or hydroxide
  • the metallic cation is selected form the group consisting of cations of lithium (Li), sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba).
  • These oxides or hydroxides may also be formed as an intermediate product during thermolysis of the metal hydride used as an initiator.
  • the neutralizer may be added to the starting material or it may also be formed in situ during the reaction process, in particular during thermolysis of the metal hydride. If a neutralizer is added, it is preferred that the neutralizer and the starting material are used in a weight ratio of 1:10-1:40.
  • a neutralizer comprising at least one metal oxide or hydroxide as indicated above allows for neutralizing hydrogen sulfide and sulfur (IV) oxides that may be present in the starting material.
  • the presence of the neutralizer further reduces limitations with respect to the chemical composition of the starting material being processed. Consequently, the process of the present invention is more generally applicable and not dependent on the chemical composition of the wastes.
  • the process of the present invention permits simultaneous processing of starting materials differing in composition, particularly waste materials comprising a mixture of rubber and plastics (such as polyethylene, polypropylene, polystyrene, polyisobutylene, polyamide, polyester, polyvinylchloride, etc.), into liquid petroleum products.
  • the neutralizer makes it further possible to significantly reduce the corrosion loading on the metal of the reaction apparatus, which helps to increase the service life of the process equipment.
  • the neutralizer is further used for binding gaseous compounds, which are liberated during thermolysis of the starting material (e.g. hydrogen sulfide, carbon disulfide, hydrogen cyanide and hydrogen chloride) into solid products.
  • the binding of these gaseous compounds allows for reducing the pressure in the reaction apparatus and to produce a pyrolysis gas which is virtually free of these gaseous substances.
  • the process of the present invention can avoid ecological problems associated with the need to purify the pyrolysis gas and makes it possible to improve the economic parameters of the process as a whole.
  • the solid products that result from the binding of gaseous compounds to the neutralizer can subsequently easily be separated from the desired liquid petroleum products, e.g. by magnetic separation, filtration, etc.
  • the solid products are determined by the nature of the starting material and often contain metal cord, carbon black and other solid inclusions.
  • the carbon black can be used as a filler for industrial rubber goods, and - after particular treatment - for the production of anode paste used in electrothermal and electrochemical plants.
  • the liquid products separated from the above-mentioned solid products can be rectified to give the target product fractions with boiling points ranges of i) up to 200 °C, ii) 200-320 °C and iii) above 320 °C. These fractions can be used as high-octane components of motor fuel and as chemical starting materials for basic organic, biochemical and petrochemical synthesis plants.
  • a starting material containing a mixture of industrial and domestic organic wastes in particular plastic and/or rubber-containing wastes (e.g. scrap tires, industrial rubber goods, polyethylene, polystyrene, polypropylene, polyisobutylene, synthetic rubber, polyvinylchloride, polyamide (e.g. nylon), kapron, enant, lavsan, etc.) is charged into a rotary autoclave (2-liter).
  • plastic and/or rubber-containing wastes e.g. scrap tires, industrial rubber goods, polyethylene, polystyrene, polypropylene, polyisobutylene, synthetic rubber, polyvinylchloride, polyamide (e.g. nylon), kapron, enant, lavsan, etc.
  • thermolysis in particular thermocatalytic liquefaction, of the starting material is performed at a temperature of 200-320 °C and a pressure of 3-7 MPa (these values being determined by the nature of the starting material).
  • the catalyst comprises - and preferably consists of - at least one metal carboxylate salt.
  • the general formula of the metal carboxylate salt is [(M n+ )(A - ) n ], whereby the number n is the degree of oxidation. For instance, if the catalyst comprises a metal carboxylate salt of which the metallic cation M is Ce (III) and the carboxylate anion A is laurate [C 12 H 23 O 2 ] - , then the number of n is 3.
  • thermolysis reaction of the catalyst is as follows: (HCOO) 2 Fe ⁇ Fe (nano particles) + CO + H 2 O + CO 2
  • atomic hydrogen is readily detached from polycyclic arenes (e.g. naphthenes and hydroaromatic components) of the starting material and/or the hydrogen donor - and transferred to radical products. Further atomic hydrogen is supplied by the metal hydride type initiator and hydrogen transfer to radical products is intensified by hydrogen carriers of the polycyclic arenes and carbon monoxide.
  • polycyclic arenes e.g. naphthenes and hydroaromatic components
  • the present invention therefore provides a process that allows for deep thermolysis of industrial and domestic organic wastes, in particular plastic and/or rubber-containing wastes, to obtain liquid petroleum products with a low content of oxygen-, nitrogen- and sulfur-containing and also unsaturated compounds in high yield.
  • the yield of the up to 200 °C fraction of the liquid products can be particularly increased by the process of the present invention.
  • said up to 200 °C fraction can be obtained with a low content of sulfur, preferably below 0.040 wt.% and a high octane number, preferably above 80.
  • 300 g of industrial rubber goods, 900 g of paraffinic-naphthenic oil, 4.5 g of calcium hydride, 4.5 g of cerium(III) formate, and 15 g of a neutralizer comprising calcium dihydroxide or sodium hydroxide, are charged into a rotary autoclave (2 liter). The process is performed at 360 °C and a pressure of 5 MPa for 60 min.
  • the yield of liquid products is 96 wt.% of the organic substance of the wastes; the content of the up to 200 °C fraction is 86 wt.% of the liquid products; and that of the 200 to 320 °C fraction is 9 wt.%, while the content of sulfur in the up to 200 °C fraction is 0.015 wt.%.

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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)

Claims (14)

  1. Ein Verfahren zur Thermolyse von organischen Industrie- und Haushaltsabfällen, insbesondere Plastik- und/oder Gummi-enthaltenden Abfällen, die als Ausgangsmaterial verwendet werden,
    bei welchem das Ausgangsmaterial mit einem Katalysator und einem Initiator, gegebenenfalls in Anwesenheit eines Wasserstoff-Donors, bei erhöhter Temperatur und erhöhtem Druck behandelt wird,
    wobei der Katalysator eines oder mehrere Metallcarboxylat-Salz(e) umfasst
    dadurch gekennzeichnet, dass das Carboxylat-Anion A jedes Metallcarboxylat-Salzes unabhängig voneinander aus der Gruppe bestehend aus Anionen von gesättigten C1-C20 Carboxylsäuren ausgewählt ist,
    und das Metallkation M jedes Metallcarboxylat-Salzes unabhängig voneinander aus der Gruppe bestehend aus Kationen von Aluminium, Germanium, Zinn, Titan, Chrom, Molybdän, Mangan, Eisen, Nickel, Kobalt, Lanthan, Cer, Neodym, Samarium und Dysprosium ausgewählt ist,
    und der Initiator mindestens ein Metallhydrid umfasst,
    wobei die Thermolyse bei einer Temperatur von 200-400°C und einem Druck von 3-7 MPa durchgeführt wird.
  2. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass die Thermolyse bei einer Temperatur von 280-380°C durchgeführt wird.
  3. Verfahren gemäss Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Katalysator eine Mischung von mindestens zwei unterschiedlichen Metallcarboxylat-Salzen umfasst.
  4. Verfahren gemäss einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass der Katalysator eine Mischung von mindestens drei unterschiedlichen Metallcarboxylat-Salzen umfasst.
  5. Verfahren gemäss einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass das mindestens ein Metallhydrid ein Metallkation aus der Gruppe bestehend aus Kationen von Lithium, Natrium, Kalium, Kupfer, Silber, Magnesium, Kalzium, Barium, Zink, Titan, Zirkon, Silizium, Zinn und Blei umfasst.
  6. Verfahren gemäss Anspruch 5, dadurch gekennzeichnet, dass das mindestens eine Metallhydrid ein Metallkation aus der Gruppe bestehend aus Kationen von Natrium, Kalium, Kalzium, Barium und Titan umfasst.
  7. Verfahren gemäss einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass der Wasserstoff-Donor aus Rohöl stammt und bevorzugt Paraffin-Naphthen-Öl umfasst.
  8. Verfahren gemäss einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass der Wasserstoff-Donor und das Ausgangsmaterial in einem Gewichtsverhältnis von 1:2-1:5, bevorzugt von 1:3-1:5, eingesetzt werden.
  9. Verfahren gemäss einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass der Katalysator und der Wasserstoff-Donor in einem Gewichtsverhältnis von 1:50-1:200 eingesetzt werden.
  10. Verfahren gemäss einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass der Initiator und der Wasserstoff-Donor in einem Gewichtsverhältnis von 1:50-1:200 eingesetzt werden.
  11. Verfahren gemäss einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass das Ausgangsmaterial zusätzlich mit einem Neutralisator enthaltend ein Metalloxid oder Metallhydroxid behandelt wird, wobei das Metallkation aus der Gruppe bestehend aus Kationen von Lithium, Natrium, Kalium, Magnesium, Kalzium, Strontium und Barium ausgewählt ist.
  12. Verfahren gemäss Anspruch 11, dadurch gekennzeichnet, dass der Neutralisator und das Ausgangsmaterial in einem Gewichtsverhältnis von 1:10-1:40, bevorzugt von 1:10-20, eingesetzt werden.
  13. Verfahren gemäss einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass die Oktannummer erhöht wird, vorzugsweise über 80.
  14. Verfahren gemäss einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, dass die Thermolyse in Abwesenheit von Wasserstoffgas durchgeführt wird.
EP14187755.5A 2014-04-23 2014-10-06 Verfahren zur Verarbeitung von Industrie- und Haushaltsabfällen, insbesondere Kunststoff- und/oder kautschukhaltigen Abfällen, zur Herstellung von Erdölprodukten zur Verwendung als Motorölkomponenten und Chemierohstoffe Not-in-force EP2937403B1 (de)

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US3345352A (en) * 1964-02-21 1967-10-03 Allied Chem Catalytic process for the thermal degradation of polyolefins
US3895059A (en) 1972-07-27 1975-07-15 Charles T Link Tape dispenser
US3896059A (en) 1974-02-05 1975-07-22 Firestone Tire & Rubber Co Production of resins from solubilized scrap rubber, the resins thus produced and rubber compounds and products incorporating the resins
US4175211A (en) 1977-03-14 1979-11-20 Mobil Oil Corporation Method for treatment of rubber and plastic wastes
SU1289872A1 (ru) 1985-05-30 1987-02-15 Научно-производственное объединение "Дорстройтехника" Способ приготовлени резинобитумного в жущего
SU1613455A1 (ru) 1988-07-18 1990-12-15 Ставропольский политехнический институт Способ переработки резиносодержащих отходов
RU2109770C1 (ru) 1993-11-02 1998-04-27 Владимир Владимирович Платонов Способ переработки резиносодержащих отходов
RU2110535C1 (ru) 1997-10-29 1998-05-10 Общество с ограниченной ответственностью "ЭКОДЕСТ" Способ переработки органических промышленных и бытовых полимерных отходов
RU2153415C2 (ru) 1998-10-21 2000-07-27 Апостолов Сергей Александрович Способ утилизации отработанных шин и отходов резинотехнических изделий и устройство для его реализации
RU2167168C1 (ru) 2000-08-17 2001-05-20 Летечин Владимир Михайлович Способ переработки органических полимерных отходов
RU2272826C1 (ru) 2005-03-09 2006-03-27 Общество с ограниченной ответственностью "НПК "Технохим" Способ переработки резиносодержащих и других промышленных и бытовых органических отходов в химическое сырье и компоненты моторного топлива
US9200207B2 (en) * 2011-05-31 2015-12-01 University Of Central Florida Research Foundation, Inc. Methods of producing liquid hydrocarbon fuels from solid plastic wastes

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