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WO1997046721A1 - Procede de recuperation de metaux lourds a partir du residu d'une installation pour l'oxydation partielle d'huile - Google Patents

Procede de recuperation de metaux lourds a partir du residu d'une installation pour l'oxydation partielle d'huile Download PDF

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Publication number
WO1997046721A1
WO1997046721A1 PCT/EP1997/002473 EP9702473W WO9746721A1 WO 1997046721 A1 WO1997046721 A1 WO 1997046721A1 EP 9702473 W EP9702473 W EP 9702473W WO 9746721 A1 WO9746721 A1 WO 9746721A1
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WO
WIPO (PCT)
Prior art keywords
soot
synthesis gas
oil
heavy metals
gasifier
Prior art date
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/EP1997/002473
Other languages
German (de)
English (en)
Inventor
Adrian Brandl
Wolfgang Klos
Michael Buxel
Heinz Jochen Keller
Karsten Radtke
Christoph LÜTGE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ThyssenKrupp Industrial Solutions AG
Original Assignee
Krupp Uhde GmbH
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 Krupp Uhde GmbH filed Critical Krupp Uhde GmbH
Priority to AU29549/97A priority Critical patent/AU2954997A/en
Publication of WO1997046721A1 publication Critical patent/WO1997046721A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/14—Cements containing slag
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/487—Separation; Recovery
    • 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
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Definitions

  • the invention relates to a method with which a metallurgical raw material is produced in addition to synthesis gas from an oil containing heavy metals and from residual materials to be disposed of.
  • oils can be contaminated with heavy metals. This applies in principle to all crude oils, the quality of which decreases with decreasing resources, especially for those from Venezuela and Russia, but also for refinery residues, bitumen, waste oils and pyrolysis oils.
  • the heavy metals vanadium and nickel occur particularly frequently as impurities.
  • the heavy metal content leads to problems: on the one hand, when burned or partially oxidized, heavy metal compounds are formed which have extremely corrosive effects and can become molten or pasty at the prevailing working temperatures Tending to cake and consequently lead to malfunctions.
  • these heavy metal compounds may only be emitted in gaseous or liquid form in very small quantities. Landfilling as residues in solid form is expensive and is subject to strict legal regulations. For these reasons, plant operators preferably use oils with low heavy metal contents as raw material, which reduces the value for the heavy is metal-containing oils.
  • Liquid hydrocarbons especially if they are chlorinated, can only be disposed of in complex combustion plants because of the dioxin / furan formation. This happens among other things with used, organic solvents.
  • residues also contain hydrocarbon compounds, which include can also be halogenated.
  • these residues can carry a large number of metals and metal compounds with them.
  • Electronic scrap is an example of this type of waste, e.g. Printed circuit boards and similar assemblies.
  • the residues can also arise with considerable other impurities, e.g. are embedded as fillers in the plastics. All such residues are referred to below as "problematic residues". It is desirable to recover all of their ingredients as possible and to reuse them.
  • the present invention solves the problems described in that heavy metal-containing oil is fed to a partial oxidation in order to add a metallic raw material produce by separating the heavy metal-containing soot formed in the partial oxidation of the oil in a primary oil gasifier from the other, resulting substances and thermally decomposing them together with residues, as a result of which the heavy metals occur in a separate phase.
  • the thermal decomposition of the soot containing heavy metal containing soot can either take place in a molten metal bath or in a soot gasifier.
  • the heavy metal alloy melt forms the own phase and is withdrawn from the metal melt bath.
  • the solidified, heavy metal alloy melt is the reusable material.
  • the soot is thermally decomposed in a soot gasifier by means of partial oxidation, secondary synthesis gas is also produced.
  • the secondary synthesis gas formed in the soot gasifier also has the surprising advantage according to the invention that it can be added to the primary synthesis gas.
  • the heavy metals accumulate in oxidized form as ash containing heavy metals and form the reusable material in its own phase.
  • the heavy metal-containing oil is converted in a plant for partial oxidation, hereinafter referred to as primary oil gasification.
  • primary oil gasification Usually, in an installation for gasifying liquid or solid, carbon-containing fuels, only an incomplete conversion of the carbon compounds takes place. This is because there is a lack of oxygen within the flame in which the reaction mainly takes place. This lack of oxygen has two causes: on the one hand, partial oxidation requires considerably less oxygen than combustion, hence oxygen is added comparatively sparingly. On the other hand, an almost perfect mixing of oxygen with oil mist is very difficult to achieve technically, so that areas with a greater lack of oxygen besides those well supplied with oxygen coexist within the reaction zone. The worse the mixing, the more soot is formed.
  • the three or more current burner solves the task of ensuring particularly good mixing and distribution of fuel and fuel gas.
  • An embodiment of the present invention therefore provides that the primary oil gasifier is equipped with a three- or multi-flow burner which achieves a high carbon conversion to the primary synthesis gas and accordingly produces little soot.
  • a common technique for disposing of the soot is to return it to the gasification reactor. In this recirculation, a large part of the soot returned is converted to synthesis gas.
  • Direct recycling of heavy metal-containing soot from an oil gasification into the gasification reactor would lead to an accumulation of the heavy metals in the gasification reactor and in the following apparatuses and consequently to the operational problems already mentioned. For this reason, the heavy metals have to be separated from the soot in a complex manner before it is technically expedient to recycle the soot. This is usually done in an extraction plant in the Naphtha serves as an extractant. Since such a separation can never be achieved perfectly at a reasonable cost, heavy metal accumulation in the gasification reactor and downstream devices can always be expected.
  • EP-0 542 322-A1 describes the thermal treatment of residues containing vanadium.
  • the resulting carbon black which contains the heavy metals in accumulated chemical compounds, is washed out of the primary synthesis gas formed in an aqueous washing solution, so that soot water is formed.
  • the soot water is filtered in a chamber filter press in such a way that the filtrate obtained first is collected and filtered again.
  • the soot which essentially comes from the unreacted coal If there is oil, it is discharged in dust form from the primary oil gasification reactor and contains heavy metal compounds in solid form.
  • the soot is separated from the primary synthesis gas in a subsequent water wash, which can be preceded by waste heat recovery. It is then present as an approximately 1% aqueous suspension, hereinafter referred to as "soot water".
  • the heavy metal compounds are present in the soot water both in dissolved form and in a form firmly bound to the soot particles.
  • the soot which contains heavy metals, is filtered off from the soot water after the soot water has expanded and steam stripping, if necessary, using a filter press.
  • the filter cake has a soot content of 15-25%, the rest is water.
  • the extraction of the heavy metals from the soot must take place at this point, the heavy metals thereby entering a wastewater solution which has to be post-treated in order to be able to dispose of them.
  • Filtering in the chamber filter press also shows that at the beginning of the filtration process a filtrate is obtained which still contains a noticeable heavy metal content, whereas the heavy metal load on the filtrate decreases sharply after formation of a sufficiently thick filter cake and decreases to very low concentrations. Only the Part of the filtrate, which is pressed through a sufficiently thick filter cake layer, meets the requirements for discharge as waste water. Because heavy metals are retained in the filtration process by a minimum thickness of the filter cake, the filter cake is not, as otherwise desired, low in heavy metals. Therefore, according to the prior art, either additional measures for removing heavy metals from the filtrate and / or from the filter cake must be taken.
  • the filtrate is therefore collected in a container from the beginning of the filtration until the heavy metal concentration of the filtrate currently running off is below the legal limit values for waste water.
  • the filtered water containing heavy metals is then gradually filtered out of the container in the same chamber filter press, the filter cake already formed being used as a heavy metal adsorbing layer.
  • the filtrate now draining is no longer fed into the container. It is so low in heavy metals that both the legal provisions for discharging waste water are observed and none significant losses of valuable heavy metals must be tolerated, both of which are advantages of the invention.
  • the filter cake obtained contains the heavy metals almost completely.
  • this filter cake is not freed from its heavy metals and there is also no provision for the soot to be returned to the gasification; rather, the soot present as a filter cake is possibly combined with problematic ones Residues subjected to thermal decomposition according to the invention.
  • soot gasification of the soot containing heavy metals is to be carried out by means of partial oxidation instead of the molten metal bath.
  • the filter cake is filled with oil containing heavy metals mashed and pumped into the soot carburetor. In this case, however, it is possible to mix in liquid problematic residues if the exposure to chlorine containing chemical compounds in the problematic residues is low.
  • melt pool must be provided. If this weld pool is to be built in a particularly compact manner because of the complex equipment, the filter cake is dried and pneumatically added to the melt as dust. By reducing the water content, the calorific value is increased and the amount of gas produced is reduced.
  • the filter cake is mixed with oil containing heavy metals, preferably in a ratio of 1 part of soot to 2 parts of oil, and then pumped into the molten bath.
  • the amount of synthesis gas is greater than when soot dust is added to the weld pool, and thus the required weld pool dimensions also increase.
  • the filter cake must be dried according to the invention after drying to ensure that the water content is ⁇ 10% so that no explosive mixture is formed.
  • the drying It is therefore advisable to use an inert atmosphere. It was found that in gasification plants which are operated with oxygen-enriched air or oxygen, there is sufficient excess nitrogen available from an air separation plant which cannot be used for any other purpose and can therefore advantageously be used as a drying medium. Drying using this nitrogen in a single pass saves time-consuming and expensive cooling and condensing apparatus and circulation devices, as are required for gas recirculation.
  • the drying itself is preferably carried out in systems in which the fine grain spectrum required for the subsequent partial oxidation is produced directly during drying. Suitable for this are e.g. Grinding dryer, current dryer with grinder and sifter or spray dryer, the drying gas, e.g. the above-mentioned nitrogen, which is used to heat the waste heat of the secondary synthesis gas, which is produced during the catalytic soot decomposition.
  • the drying gas e.g. the above-mentioned nitrogen, which is used to heat the waste heat of the secondary synthesis gas, which is produced during the catalytic soot decomposition.
  • the filter cake obtained in the chamber filter press which contains the heavy metals almost completely, is either in a spray dryer, a current dryer with a grinder or a grinding dryer with heated inert gas a residual moisture content of ⁇ 10% dried.
  • the present invention provides for the filter cake to be mixed in an extruder.
  • a further embodiment of the present invention provides that the moist filter cake obtained in the chamber filter press, which contains almost all of the heavy metals as it is obtained, in an extruder with oil, preferably with the heavy metal-containing oil, the is also used for primary oil gasification, mashed in such a way that the soot filter cake is added to the extruder first and then the oil and the resulting suspension can be pumped.
  • melt pool is described, for example, in the patents US Pat. No. 5,491,279, WO 93/25277, US Pat. No. 4,574,714, US Pat. No. 5,298,233, US Pat. No. 5,443,572, US Pat. No. 5,301,620, US Pat. No.
  • the procedure according to the invention is carried out in such a way that only the soot conditioned in the drying process is dusty in a molten bath given that contains a liquid, metallic and a liquid, ceramic phase and is operated under a pressure of up to 10 bar, oxygen, and that the dust-like soot in the melt is catalytically broken down and partially oxidized, being a ceramic slag, secondary Synthesis gas and a molten metal which contains the heavy metals from the heavy metal-containing compounds of the carbon black are formed.
  • the procedure is such that only the suspension mashed in an extruder made of moist soot with oil and possibly liquid, problematic residues in one Melt bath is given, which contains a liquid, metallic and a liquid, ceramic phase and is operated under a pressure of up to 10 bar, further oxygen, and that the suspension in the melt is catalytically broken down and partially oxidized, one ceramic slag, a molten metal which contains the heavy metals from the heavy metal-containing compounds of the suspension, and secondary synthesis gas.
  • the piece of Some problematic residues are added to said molten bath, which contains a liquid, metallic and a liquid, ceramic phase and is operated under a pressure of up to 10 bar, and oxygen, with all residues being catalytically broken down in the melt and partially together with the soot are oxidized, and a ceramic slag, a metal melt which contains the heavy metals from the problematic residues and the soot, and secondary synthesis gas are formed.
  • the slag drawn off from the melt pool is used to produce cement. Furthermore, in another embodiment of the present invention, the molten metal withdrawn from said molten bath is poured into molds where it solidifies and the raw metal obtained in this way is then fed to further metallurgical use.
  • the secondary synthesis gas generated in the melt pool must be compressed again if it is to be added to the primary synthesis gas of the primary oil gasifier. In order to be able to compress it, it must first be cooled. This takes place either in a water quench by adding water or by using heat by means of a heat exchanger or through both.
  • the present invention provides a further embodiment in which the hot secondary synthesis gas drawn off from the melt pool is passed over a heat exchanger in order to obtain at least part of the thermal energy of the secondary synthesis gas as waste heat.
  • the present invention also has an embodiment in which the hot secondary synthesis gas drawn off from the melt pool is cooled and washed in a water quench.
  • the secondary synthesis gas obtained above the melt pool is, according to the invention - after cooling by means of a quench with water or by means of both - recompressed to a pressure which also prevails in the main stream of the primary synthesis gas from the primary oil gasification, and then this main stream of the primary synthesis gas mixes.
  • the present invention also has a configuration in which the hot secondary synthesis gas drawn off via said melt pool after cooling in accordance with the relevant configurations above is compressed in a compressor to a pressure which compresses the mixture - admixture to the primary synthesis gas generated by the primary oil gasifier and that this admixture carries out. If the soot is to be added to the melt as dust, the invention provides for the waste heat to be used to heat the inert gas which is used to dry the soot filter cake.
  • the soot-oil suspension can also be fed into a soot gasifier.
  • the soot-oil suspension is made pumpable by mashing the filter cake in an extruder with oil, preferably with the heavy metal oil which is also used for primary oil gasification.
  • this suspension is mixed with the problematic liquid residues to be disposed of, if necessary.
  • This soot-oil emulsion is then, optionally extended with liquid, problematic residues, if these contain compounds containing little chlorine, liquid in a small soot gasifier, which is preferably equipped with a three-stream burner, partially oxidized together with oxygen.
  • an embodiment of the present invention provides that the suspension is conveyed from the extruder into a soot converter and there partially with oxygen is oxidized under the pressure under which the partial oxidation takes place in the primary oil gasifier.
  • the resulting secondary synthesis gas is therefore immediately cooled and washed in a direct quench, which forms a unit with the small soot gasifier.
  • a corresponding embodiment provides that the secondary synthesis gas is quenched with water and washed immediately after the partial oxidation in the soot gasifier.
  • the quench water When the secondary synthesis gas is quenched, the quench water is loaded with the heavy metal-containing ash, so the quench water can be drawn off from the direct quench and filtered.
  • the ash containing heavy metals is filtered out of the aqueous solution which is drawn off from the direct quench and can be further processed metallurgically.
  • the filtrate is expediently admixed with the soot water from the primary oil gasification in order to re-separate solved to achieve heavy metal connections in the manner described above.
  • the filtrate is passed into the soot filter press after a pressure release in order to separate remaining heavy metals onto the soot filter cake.
  • the filtrate is mixed with the soot water stream coming from the primary oil gas in order to avoid losses due to dissolved metals.
  • soot gasifier if it is equipped with a three- or multi-flow burner analogously to the primary oil gasifier, can likewise convert the soot particularly effectively into secondary synthesis gas.
  • Another embodiment of the present invention is therefore available, in which the soot gasifier is equipped with a three- or multi-flow burner which achieves a high carbon conversion to synthesis gas and accordingly produces little soot.
  • the heavy metal oil is converted in a primary oil gasification by means of partial oxidation.
  • heavy metal-containing oil 3 is injected into the primary oil gasifier 1 using a three-flow burner and from the two oxygen flows 2 and 4 atomized into a fine oil mist.
  • a partial oxidation takes place under high pressure and at a temperature of approximately 1400 ° C., in which the heavy metal-containing oil 3 is converted to over 99% to synthesis gas and to less than 1% to soot, to which the heavy metal compounds adhere to store.
  • the raw synthesis gas 5 formed is passed into a crude gas cooler with heat recovery 6, which cools it down to approx. 200 ° C.
  • the cooled raw gas 7 is then passed into a water quench 8, where the soot is washed out with water 9 together with other soluble substances.
  • the prepurified synthesis gas 10 is derived for further use.
  • the hot soot water 11 is expanded and cooled to atmospheric pressure in a soot water flash 12.
  • the flash gas 13 escapes, which contains the gases which are less soluble in water at lower pressure and lower temperature.
  • the cold soot water 14 is passed into a filter press 15 and filtered.
  • the filtrate 17 which is first obtained and contains heavy metals is branched off and temporarily stored in an intermediate filtrate container 18.
  • the filter kitchen 20 is placed in the dryer 21 after the end of the filtration process and is dried with hot inert gas 22.
  • the soot particles are also comminuted in the dryer 21. It also contains a soot filter, which prevents the moist inert gas 23 from entraining soot particles 21 when it leaves the dryer.
  • the moist inert gas 23 can be discharged to the atmosphere since it contains hardly any impurities.
  • the dried soot is pneumatically conveyed into the molten bath 25 as soot dust 24.
  • a thermal and catalytic decomposition of the soot takes place in the melt bath 25. For this, oxygen 27 is added.
  • the ability of the molten bath for catalytic decomposition is also used to convert problematic residues 26.
  • the result is hot synthesis gas 30, ceramic slag 28 and liquid metal 29, all of which are drawn off separately.
  • the hot synthesis gas 30 is cooled in the synthesis gas-inert gas heat exchanger 31, the waste heat is used to heat the cold inert gas 35, which is used for drying the soot filter cake.
  • the cooled synthesis gas 32 is post-compressed in the compressor 33.
  • the compressed synthesis gas 34 is mixed with the pre-cleaned synthesis gas 10 and the mixed synthesis gas 36 is released for further use. 2 shows that the filter cake 20 is placed in an extruder 37. There it is mashed with heavy metal oil 38.
  • the soot-oil suspension 39 is conveyed from the extruder into the molten bath 25.
  • a thermal and catalytic decomposition of the soot and the oil takes place in the melt pool 25.
  • oxygen 27 is added.
  • the ability of the melt pool to catalytically decompose is also used to convert problematic residues 26.
  • the result is hot synthesis gas 30, ceramic slag 28 and liquid metal 29, all of which are drawn off separately.
  • the hot synthesis gas 30 is quenched in the water quench 40 by adding the water 41 and thereby cooled, and further cooling by cooling water can also take place.
  • the cooled synthesis gas 32 is post-compressed in the compressor 33.
  • the compressed synthesis gas 34 is mixed with the prepurified synthesis gas 10 and the mixed synthesis gas 36 is released for further use.
  • Fig. 3 it is shown that the filter cake 20 is placed in an extruder 37. There it is mixed with oil 38 containing heavy metals and the problematic residue 26.
  • the soot-oil suspension 39 is conveyed from the extruder into the soot gasifier 44, where it is injected with a three-flow burner together with the oxygen streams 42 and 43 and stored under the same pressure as in the primary oil gasifier 1. partially oxidized.
  • the ash-containing synthesis gas formed in the process is immediately quenched with water 46 in a direct quench 45 and washed.
  • the synthesis gas 47 is mixed with the synthesis gas 10 and the mixed synthesis gas 36 is derived for further use.
  • the ash water drawn off from the direct quench 45 is filtered under pressure in the ash filter 49.
  • the filter cake 50 contains the heavy metals in concentrated form and is further processed metallurgically.
  • the filtrate 51 still contains dissolved heavy metals and gases and is passed into the soot water flash with cooler 12. This measure prevents losses of

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Abstract

Le procédé de l'invention vise à récupérer des métaux lourds à partir du résidu d'une installation pour l'oxydation partielle d'huiles. A cet effet, la suie contenant des métaux lourds, formée lors de l'oxydation partielle de l'huile dans un gazéificateur d'huile primaire, est séparée des autres matières obtenues, puis décomposée thermiquement avec les résidus, ce qui provoque la production de métaux lourds dans une phase qui leur est propre, sous forme oxydée ou métallique. La décomposition thermique de la suie séparée, contenant les métaux lourds, peut s'effectuer dans un bain de fusion de métal ou dans un gazéificateur de suie.
PCT/EP1997/002473 1996-06-01 1997-05-15 Procede de recuperation de metaux lourds a partir du residu d'une installation pour l'oxydation partielle d'huile Ceased WO1997046721A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU29549/97A AU2954997A (en) 1996-06-01 1997-05-15 Process for recovering heavy metals from the residue of a plant for the partial oxidation of oil

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19622150.1 1996-06-01
DE1996122150 DE19622150A1 (de) 1996-06-01 1996-06-01 Verfahren zur Rückgewinnung von Schwermetallen aus dem Rückstand einer Anlage zur partiellen Oxidation von Öl

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FR2780070B1 (fr) * 1998-06-22 2001-06-08 Elf Antar France Procede de moussage d'un laitier recouvrant un bain d'acier en fusion
DE102009034494A1 (de) * 2009-07-22 2011-03-10 Uhde Gmbh Kontinuierliche Rußwasserbehandlung
DE102011014221A1 (de) * 2011-03-17 2012-09-20 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren zur Gewinnung von Schwermetallen aus Rußwasser
EP4008798A1 (fr) * 2020-12-04 2022-06-08 HBI Srl Procédé d'extraction de métaux à partir d'une masse humide de déchets

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GB2026458A (en) * 1978-07-27 1980-02-06 Inst Francais Du Petrole Process for recovering metal elements from carbonaceous products
DE3328289A1 (de) * 1983-08-05 1985-02-21 AMH-Chemie GmbH, 2211 Büttel Verfahren zum kontinuierlichen vermischen einer russmasse mit einer hochviskosen fluessigkeit
EP0539352A1 (fr) * 1991-10-24 1993-04-28 VOEST-ALPINE Industrieanlagenbau GmbH Procédé pour enlever des matières organiques et minérales
EP0542322A1 (fr) * 1991-11-13 1993-05-19 METALLGESELLSCHAFT Aktiengesellschaft Procédé pour le traitement d'un résidu contenant du vanadium
EP0581090A2 (fr) * 1992-07-29 1994-02-02 Dipl.-Ing. SF-Ing. MANFRED BAHNEMANN RECYCLING-SYSTEME GmbH Procédé pour le traitement de boues contenant des métaux
DE4309825A1 (de) * 1993-03-26 1994-09-29 Hoechst Ag Verfahren zur Herstellung von Synthesegas
EP0686598A2 (fr) * 1994-05-11 1995-12-13 Norsk Hydro A/S Procédé pour l'oxydation partielle d'une charge d'hydrocarbures
JPH0857440A (ja) * 1994-08-15 1996-03-05 Ishikawajima Harima Heavy Ind Co Ltd 飛灰の溶融処理設備

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Publication number Priority date Publication date Assignee Title
GB2026458A (en) * 1978-07-27 1980-02-06 Inst Francais Du Petrole Process for recovering metal elements from carbonaceous products
DE3328289A1 (de) * 1983-08-05 1985-02-21 AMH-Chemie GmbH, 2211 Büttel Verfahren zum kontinuierlichen vermischen einer russmasse mit einer hochviskosen fluessigkeit
EP0539352A1 (fr) * 1991-10-24 1993-04-28 VOEST-ALPINE Industrieanlagenbau GmbH Procédé pour enlever des matières organiques et minérales
EP0542322A1 (fr) * 1991-11-13 1993-05-19 METALLGESELLSCHAFT Aktiengesellschaft Procédé pour le traitement d'un résidu contenant du vanadium
EP0581090A2 (fr) * 1992-07-29 1994-02-02 Dipl.-Ing. SF-Ing. MANFRED BAHNEMANN RECYCLING-SYSTEME GmbH Procédé pour le traitement de boues contenant des métaux
DE4309825A1 (de) * 1993-03-26 1994-09-29 Hoechst Ag Verfahren zur Herstellung von Synthesegas
EP0686598A2 (fr) * 1994-05-11 1995-12-13 Norsk Hydro A/S Procédé pour l'oxydation partielle d'une charge d'hydrocarbures
JPH0857440A (ja) * 1994-08-15 1996-03-05 Ishikawajima Harima Heavy Ind Co Ltd 飛灰の溶融処理設備

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Title
PATENT ABSTRACTS OF JAPAN vol. 096, no. 007 31 July 1996 (1996-07-31) *

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DE19622150A1 (de) 1997-12-04
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