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

Definitions

• the method according to the invention relates to the thermal treatment of synthetic, organic wastes with the cleavage of chemical bonds in a selected temperature, pressure and residence time range in which no or only little coke formation occurs.
• EP-B-0 236 701 describes a thermal pretreatment under hydrogen or inert gas in a temperature range of 75-600 ° C., a pressure range of 1-600 bar and a residence time of 1 minute to 6 hours.
• the addition of protic solvents is also disclosed in this patent as well as the addition of grinding oils and catalysts. Tables 6 and 8 of this document summarize test results which were obtained during the thermal pretreatment without the addition of rubbing oils. It was worked at temperatures of 350-470 ° C.
• the thermal treatment can also be favored by adding certain additives with or without mashing oil.
• additives for example, one or more compounds from the group: phenols, sulfur compounds, alcohols, amines and water can be added as additives. These additives are generally added in an amount of 0.1 to 3 parts additive per part waste mixture.
• the presence of the additives may also reduce the temperature during the thermal treatment to 230 to 300 ° C.
• the residence times are from 0.5 to 24 hours, with shorter residence times of, for example, 0.5 to 5 hours being possible when additives and / or mashing oils are added. In general, longer residence times are used at lower temperatures. Even in the presence of the additives and / or mashing oils, coke formation is avoided or largely avoided under the conditions according to the invention.
• the present invention accordingly allows waste for the first time.
• Common high-pressure pumps or other high-pressure conveying devices such as extruders can be used as pumps. It can be particularly advantageous at high throughputs that the heat required for the thermal treatment by an extruder with direct heat input or heat input by friction or by a heatable screw, such as a double-run screw Feed snail at least partially.
• All synthetic, organic waste such as thermoplastics, thermosets, elastomers, waste oils, shredder waste, difficult-to-dispose organic chemicals, rejects, cable waste, textile waste, etc., are suitable as mixtures according to the invention.
• mashing oils can include at least one component from the group: crude oil, crude oil components and products from crude oil, coal including lignite, coal components and products from coal, oil shale, oil shale components and products from oil shale, oil sand, pyrolysis oils, bitumen, asphalt, asphaltenes, their components and whose products are used.
• the particular advantage of the present invention is that pumpable mixtures can also be produced coke-free when using any waste mixtures, hydrocarbons, in particular in the gasoline and medium oil boiling range, can be obtained in the subsequent hydrogenative cleavage, the heteroatoms present in the waste being Hydrogen compounds, such as HCl, H2S, NH3 etc. arise.
• the splitting thermal treatment can be carried out discontinuously and continuously.
• a cascade of stirred tanks can be used for the continuous mode of operation.
• the setting of the gap temperature and residence time can be carried out particularly favorably.
• the viscosity can then be reduced Temperature by approx. 50 ° K, the further splitting can be interrupted or slowed down undesired post-reactions in further processing containers, such as in a receiver upstream of the hydrogenation reactor, can be achieved by adding a radical stopper, such as polyphenol.
• the addition of radical formers with a relatively high decomposition temperature can favor the thermal breakdown, so that the desired thermal breakdown can be achieved at lower temperatures and a shorter residence time, similar to the addition of the additives and mashing oils mentioned
• the cleavage can also be promoted by adding catalysts.
• Suitable catalysts are, for example, aluminum oxide and / or bleaching earth with or without pretreatment, such as by means of acids, iron compounds such as ferrocene and / or iron pentacarbonyl and others, the iron compounds preferably only towards the end of the thermal cleavage
• the catalysts mentioned can also prove to be advantageous in the later hydrogenative cleavage. Solid unwanted fractions in the waste mixture or those that are only formed during the thermal treatment can be separated off before or after the same by filtration, centrifuging and other separation processes. It is also possible to grind such solid fractions so that a separation is not necessary.
• a mixture of 45% by weight of polyethylene, 30% by weight Polypropylene and 25% by weight of polystyrene were subjected to a thermal treatment at 300 ° C for 5 hours.
• the viscosity of the starting mixture was not measurable at 200 ° C, but was 1200 mPas after the thermal treatment.
• the mixture was conveyable using a conventional pump Coke formation was not detectable.
• a mixture of 50% by weight of polyethylene, 30% by weight of polypropylene, 10% by weight of polystyrene and 10% by weight of polyurethane was subjected to a thermal treatment at 300 ° C. for 5 hours.
• the mixture liquefied, only that The polyurethane content was largely retained as a highly viscous second phase.
• the same mixture was thermally treated with the addition of 0.5% by weight of tert-butyl hydroperoxide for 2 hours at 360 ° C. This resulted in a homogeneous liquid without a separate polyurethane phase with a viscosity of 1000 mPas at 200 ° C, which could be pumped without problems was. Due to the high temperature during the second treatment, coke formation was noticeable.
• the second treatment was repeated at 280 ° C and a residence time of 5 hours. A homogeneous liquid was obtained with a viscosity of 1200 mPas at 200 ° C. There was no coke formation.
• a mixture of 40 wt .-% polyethylene, 30 wt .-% polypropylene, 10 wt .-% polystyrene, 10 wt .-% polyurethane and 10 wt .-% polyvinyl chloride was at 260 ° C during Thermally treated for 8 hours. After the treatment, the viscosity was 1300 mPas at 200 ° C. A small amount of coke particles was found in the mixture. The grain size of the coke could be reduced to less than 10 ⁇ by stirring during the thermal treatment. The thermal treatment was carried out at normal pressure. Chlorine was released as HCl during the thermal treatment. The residual chlorine content after treatment was 300 ppm.
• Example 3 was repeated, but nitrogen was passed through the mixture at the same time with stirring at 50 mbar.
• the residual chlorine content was 2 ppm after the treatment.
• the coke formed remained in suspension owing to its small particle size of less than 10 ⁇ .
• the pumpability of the mixture was not significantly affected by the coke content. Due to its low residual HCl content, the mixture obtained can be processed in conventional high-pressure equipment, so that chlorine-resistant, expensive steels do not have to be used.
• a plastic mixture of domestic waste was treated for 7 hours at 270 ° C. During the treatment, nitrogen was passed through the mixture at normal pressure. The treated product had a viscosity of 1400 mPas at 200 ° C and a residual chlorine content of 30 ppm. The mixture contained coke particles. The experiment was repeated, but 15% by weight of crude oil residue and 0.5% by weight of stearylamine were added. The amount of coke formed was significantly less.

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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)
• Processing Of Solid Wastes (AREA)
• Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

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Cited By (7)

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• 1991
  • 1991-05-03 DE DE19914114434 patent/DE4114434C2/de not_active Expired - Lifetime
• 1992
  • 1992-05-05 EP EP19920107587 patent/EP0512482A3/de not_active Withdrawn

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