EP0534046A2 - Procédé pour le traitement d'hydrocarbures ou composés d'hydrocarbures contaminés liquides, liquéfiables ou solides - Google Patents

Procédé pour le traitement d'hydrocarbures ou composés d'hydrocarbures contaminés liquides, liquéfiables ou solides Download PDF

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Publication number
EP0534046A2
EP0534046A2 EP92102592A EP92102592A EP0534046A2 EP 0534046 A2 EP0534046 A2 EP 0534046A2 EP 92102592 A EP92102592 A EP 92102592A EP 92102592 A EP92102592 A EP 92102592A EP 0534046 A2 EP0534046 A2 EP 0534046A2
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EP
European Patent Office
Prior art keywords
reaction
hydrocarbons
substances
hydrocarbon compounds
hydrogen
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Application number
EP92102592A
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German (de)
English (en)
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EP0534046A3 (en
EP0534046B1 (fr
Inventor
Wolfdieter Klein
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Individual
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Priority to EP92102592A priority Critical patent/EP0534046B1/fr
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Publication of EP0534046A3 publication Critical patent/EP0534046A3/de
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    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only

Definitions

  • the invention relates to a process for the treatment of hydrocarbons and / or hydrocarbon compounds which are contaminated by inorganic and / or organic substances, for the production of raw materials for reuse in refineries and / or in petrochemicals.
  • hydrocarbons or hydrocarbon compounds can be worked up more or less successfully by non-hydrogenating and hydrogenating processes.
  • Thin film evaporation is used as the separation process. This creates a residue with a high load of accompanying substances and lightly contaminated distillates.
  • the hydrating treatment is limited to the distillates, which hardly contain any catalyst poisons.
  • catalyst poisons such.
  • metal, sulfur, nitrogen and chlorine compounds are known, which is why hydrocarbons can not be used with these accompanying substances.
  • coal can be hydrogenated in a tubular reactor according to DE-31 50 991 A1 at a temperature in the range from 465 to 550 ° C. and a pressure of more than 700 bar.
  • the heat of reaction is dissipated to an external cooling medium via the reactor wall.
  • the required hydrogen for reaction is fed at several points along the tube reactor in such quantities that at least 70% by weight is dissolved in the suspension under hydrogenation conditions. This method has also been used experimentally for the hydrogenation of heavy oils.
  • thermoplastics When recycling liquefiable hydrocarbons, so-called thermoplastics, it is known that they can be recovered and processed for inferior products, e.g. B. for the production of packaging materials, building materials and transport containers.
  • thermosets Due to chemical changes, e.g. B. by embrittlement, or color mixing, the number of reprocessing cycles as the use is limited. Ultimately, this leads to either incineration or landfill of these waste materials. Recycling is hardly possible with thermosets. Incineration can mainly be used for disposal. Furthermore, the thermoplastics and thermosets are not dealt with, since their disposal is assumed to be generally known.
  • the object of the invention is to contaminate liquid and / or liquefiable and / or solid hydrocarbons and / or hydrocarbon compounds such as lubricants, greases, waste oils, waste oil sludges, solvents, plastics (thermoplastics such as thermosets), rubber and waste tires, as well as materials containing these substances are called in the further feed and with metal, sulfur, nitrogen, fluorine and especially chlorine compounds, such as. B. furan compounds and / or PCB compounds, etc., hereinafter referred to as an accompanying substance, are contaminated to be freed from these accompanying substances by this method.
  • liquid and / or liquefiable and / or solid hydrocarbons and / or hydrocarbon compounds such as lubricants, greases, waste oils, waste oil sludges, solvents, plastics (thermoplastics such as thermosets), rubber and waste tires, as well as materials containing these substances are called in the further feed and with metal, sulfur, nitrogen, fluorine and especially chlorine compounds, such
  • the task consists in converting the feedstocks with accompanying substances into valuable substances largely free of accompanying substances, to make them economically viable as raw materials for use in refineries and petrochemicals.
  • the reaction takes place in the liquid phase.
  • a disposable catalyst is preferably added to the feedstocks with accompanying substances.
  • the reaction mixture of carrier oil or contaminated liquid and solid is then premixed in a container and pumped to a reaction pressure of 200 to 2000 bar, preferably 400 to 1200 bar, in particular up to about 1000 bar.
  • the starting materials are then catalytically reacted in a reactor in the presence of hydrogen at a reaction temperature between 300 to 550 ° C., preferably 400 to 500 ° C. and in particular at about 430 ° C.
  • the accompanying substances can be bound using suitable additives.
  • the products produced only contain small amounts of halogens, sulfur, nitrogen and oxygen as well as undesirable substances that can be further reduced by known refinery processes, such as refiner or reformer technologies.
  • the process pressure is expediently chosen so that 90 to 100% of the starting material is present as or in the liquid phase under the process conditions.
  • hydrocarbons are understood to mean liquid, liquefiable and solid hydrocarbons of any molecular weight, that is to say both in monomeric and in polymeric form. These can be uniform substances as well as mixtures of different hydrocarbons, which can be contaminated by additives, fillers, degradation products or added foreign substances.
  • hydrocarbon compounds are understood as meaning liquid, liquefiable and solid high or low molecular weight compounds which contain foreign atoms in addition to carbon and hydrogen atoms. Like the hydrocarbons, they can be in monomeric or polymeric form and can be contaminated by other substances.
  • Inorganic and / or organic contaminating substances are understood to mean those substances which are found in the above-mentioned hydrocarbons and hydrocarbon compounds as additives, degradation products, additives or impurities.
  • “Additives” as they can be used according to the invention are understood to mean those substances which can react chemically with foreign atoms contained in the hydrocarbons and / or hydrocarbon compounds after their cleavage and in the reactive compounds containing organic contaminants or their cleavage products.
  • these are compounds which can reactively neutralize acidic or basic cleavage products, salt formation being particularly preferred.
  • Typical compounds for this purpose are alkali and alkaline earth carbonates, in particular sodium carbonate and calcium carbonate, ammonia, ammonium compounds and salts containing hydrogen ions, such as, for example, alkali metal hydrogen carbonates and sulfates.
  • Metal sulfides and oxides can also be used, in particular alkali sulfides and alkaline earth metal or heavy metal oxides.
  • Forming atoms are understood to mean other than carbon and hydrogen atoms in hydrocarbon compounds.
  • metals, oxygen, sulfur, nitrogen, phosphorus and halogens are to be mentioned here, among the latter in particular fluorine, chlorine and bromine.
  • Chlorine-containing impurities are of particular importance and plastics. These foreign atoms are more or less completely split off from their molecular structure by catalytic hydrogenation under the conditions mentioned and converted into ionic or covalent hydrogen-containing products, which in turn may be capable of reacting with the additives mentioned above.
  • Nitrogen is often split off from nitrogen-containing compounds in the form of ammonia, chlorine from chlorine-containing compounds in the form of hydrogen chloride.
  • a disposable catalyst is preferably used in the process according to the invention.
  • a disposable catalyst can be present, for example, in the form of iron oxide compounds, for example hematite in the form of turf iron ore, or of substances containing iron oxide, for example red mud or lux mass.
  • Coal coke made from hard coal and / or lignite can also be used as a catalyst due to the foreign substance content.
  • Other catalytically active substances that can be used both as one-way and as reusable catalysts are CoO / MoO catalyst dusts.
  • Substances which are reactive towards the products of the cleavage reactions and / or towards contaminating accompanying substances and which convert them into harmless, separable substances, preferably into salts, by chemical bonding are preferably added as reactive additives.
  • These additives can be added to the feedstock at the beginning of the process, for example together with the catalyst, but they can also be added to the reaction at a later stage in the process or after the hydrogenation process.
  • the additives are preferably mixed into the feedstock together with the catalyst at the start of the process. It is understood that a catalyst with a chemical binding effect against the cleavage products can simultaneously act as an additive and an additive with simultaneous catalytic effect can take over the function of the catalyst.
  • Particularly preferred additives are acids, bases and / or sulfur-binding substances, in particular inorganic salts, which are added to the process in finely divided form.
  • reaction temperature is therefore kept constant by feeding cold, hydrogen-containing gas into the reactor in order to avoid coke formation and methanation.
  • the reaction is endothermic to exothermic, depending on the starting material.
  • the reaction temperature cannot always be regulated using measures customary in conventional processes. It is therefore advantageous if the heat required to set the desired reaction temperature can be both supplied and removed.
  • the proportion of hydrogen is advantageously operated with an excess of 0.5 to 5% by weight, based on the hydrogen consumption of the hydrogenation reaction, preferably with an excess of 1% by weight.
  • the hydrogen required to saturate the cleavage reaction is mixed in depending on consumption so that it is predominantly in solution in the liquid phase.
  • the reaction is preferably carried out in a heat-tight or externally temperature-controlled tubular reactor.
  • the temperature can be controlled using a liquid metal bed, molten salt or organic heat transfer oils. It is also possible to heat the tube reactor via a double-walled tube using steam.
  • a canned furnace which is designed as a circulating furnace is also suitable as a reactor.
  • Other conventional reactors which are suitable for carrying out a hydrogenation reaction, in particular in a liquid phase containing solid fractions, can also be used.
  • a particularly advantageous variant of the process according to the invention is based on the fact that solid hydrocarbons and / or hydrocarbon compounds are mixed with liquid hydrocarbons and / or hydrocarbon compounds and in this form, mixed with catalyst and optionally additives, are fed into the reactor. Contaminated and / or oxidized non-process hydrocarbons can also be used for mashing, as can process-derived liquids.
  • the method according to the invention is particularly suitable for the treatment of solid hydrocarbons and / or hydrocarbon compounds, for example in the form of plastics and plastic products.
  • the solid starting materials and also the added catalyst and additives are expediently comminuted to a particle size of ⁇ 1 mm, in particular ⁇ 100 ⁇ m.
  • the solids content consisting of catalyst, additives and solid hydrocarbons and hydrocarbon compounds, is expediently adjusted so that the mash is still pumpable. It is therefore up to 60% by weight, preferably up to 45% by weight.
  • the catalyst is mixed in an amount of 1 to 5% by weight, based on the starting material and, depending on the starting material, preferably about 2.5% by weight, advantageously in finely divided form.
  • the gases formed are separated from the resulting products in a separation tank, the gases are discharged overhead and the liquid with all solids is released into a downstream second separation tank.
  • the product is drawn off in the top of the separation container.
  • the remaining residues (single-use catalyst, salts formed, solids, etc.) are discharged from the bottom of the separation container at a solids concentration of approx. 50%.
  • the solids concentration is adjusted by an upstream cooler, in which heat is removed from the product.
  • the vaporous top products of the second separation container are condensed by cooling, separated from residual hydrogen and gases formed in a separation container and expanded to normal pressure.
  • the boiling range is determined by the feed materials to be processed or by the composition of the liquids, and the temperature is determined by the required reaction temperature, it is possible to influence the evaporation equilibrium via the pressure and to adjust the gas / vapor content.
  • the process according to the invention is to take place in the liquid phase, it is necessary to adjust the pressure so that 70 to 100% by weight, preferably about 100% by weight, of the starting material in the liquid or liquid-suspending solid phase when entering the reaction space are available.
  • the pressure is increased or decreased, thereby always providing the most technically and economically advantageous reaction space.
  • the residence time can thus be influenced by changing the equilibrium conditions by setting a more or less large proportion of the gas / vapor mixture. This gas / vapor component changes the speed in the tubular reactor and thus the dwell time with the reactor dimensions remaining the same.
  • the proportion of hydrogen in the tubular reactor or in the canned furnace is limited to a maximum of the proportion which goes into solution under the process condition. However, it should be at least 20% above the chemical requirements of the input materials.
  • the gas / vapor content is therefore dependent on the temperature, the fresh hydrogen added, the variably adjustable pressure (all in solution) and the chemical consumption of the feed materials.
  • the equipment technology required for this is known.
  • the entire apparatus technology of the hydro-cracking process and the hydrogenation of coal or oil can be used to heat the feed materials.
  • the method is shown schematically in FIG. 1.
  • the feed 2 is mixed with catalyst 3 and additives 4 and the mixture is fed via line 5 to the pump 6. This presses the mixture to reaction pressure.
  • the mixture is mixed with hydrogen via line 7, and there is a common heating to reaction temperature.
  • the heating can e.g. B. by indirect Heat exchange of the product can be carried out with a heat transfer system 8.
  • the thermal-catalytic breakdown of the starting materials and the breakdown of the accompanying substances takes place. This is promoted by the presence of the catalyst.
  • the hydrocarbons split off are saturated with hydrogen, the accompanying substances split off are bound by the additives and / or the hydrogen.
  • the product produced is fed to a separation container 11 by means of line 10. In this the gases are separated from the liquid with solids. The gases are discharged via line 12 under pressure control.
  • the product with solids drawn off in the sump of the separating container 11 is fed to the further processing in a controlled manner via the line 13.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Physical Water Treatments (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Processing Of Solid Wastes (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
EP92102592A 1991-09-19 1992-02-15 Procédé pour la désintégration de matières plastiques contaminées Expired - Lifetime EP0534046B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP92102592A EP0534046B1 (fr) 1991-09-19 1992-02-15 Procédé pour la désintégration de matières plastiques contaminées

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP91115911 1991-09-19
EP91115911 1991-09-19
EP92102592A EP0534046B1 (fr) 1991-09-19 1992-02-15 Procédé pour la désintégration de matières plastiques contaminées

Publications (3)

Publication Number Publication Date
EP0534046A2 true EP0534046A2 (fr) 1993-03-31
EP0534046A3 EP0534046A3 (en) 1993-04-14
EP0534046B1 EP0534046B1 (fr) 1997-09-10

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EP92102592A Expired - Lifetime EP0534046B1 (fr) 1991-09-19 1992-02-15 Procédé pour la désintégration de matières plastiques contaminées

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EP (1) EP0534046B1 (fr)
AT (1) ATE158013T1 (fr)
DE (1) DE59208886D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0626441A1 (fr) * 1993-05-25 1994-11-30 Wolfdieter Klein Réacteur pour éxécuter des réactions endothermiques ou faiblement exothermiques

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1313057A (fr) * 1958-10-16 1962-12-28 Inst Francais Du Petrole Procédé continu d'hydrotraitement sélectif des pétroles bruts en phase liquide
DE3806365C1 (fr) * 1988-02-27 1989-07-20 Veba Oel Entwicklungs-Gesellschaft Mbh, 4650 Gelsenkirchen, De
US4976848A (en) * 1988-10-04 1990-12-11 Chevron Research Company Hydrodemetalation and hydrodesulfurization using a catalyst of specified macroporosity

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0626441A1 (fr) * 1993-05-25 1994-11-30 Wolfdieter Klein Réacteur pour éxécuter des réactions endothermiques ou faiblement exothermiques

Also Published As

Publication number Publication date
EP0534046A3 (en) 1993-04-14
ATE158013T1 (de) 1997-09-15
DE59208886D1 (de) 1997-10-16
EP0534046B1 (fr) 1997-09-10

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