WO1997046721A1 - Process for recovering heavy metals from the residue of a plant for the partial oxidation of oil - Google Patents

Abstract

The aim of the invention is to recover heavy metals from the residue of a plant for the partial oxidation of oils. To this end, the heavy metal-containing soot produced during the partial oxidation of the oil in the primary oil gasifier is separated from the other substances produced, and thermally decomposed together with residues, whereby the heavy metals occur in their own phase either in oxidised or metallic form. According to the invention, the separated heavy metal-containing soot may be thermally decomposed in a metal melting bath or in a soot gasifier.

Description

"Process for the recovery of heavy metals from the residue of a plant for the partial oxidation of oil"

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.

As is well known, 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. In the energetic or material conversion of such oils, 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. On the other hand, 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.

There is also a need for disposal with regard to other residues. 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.

In addition to the organic carbon compounds, other residues also contain hydrocarbon compounds, which include can also be halogenated. In addition, 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.

According to the invention, 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.

If the thermal decomposition of the carbon black containing heavy metals takes place together with the residues in a metal melt bath, this is operated above the melting point of the metals used, depending on the metal at 800 to 1800 ° C. In this bath, the molecular bonds of the residues that are introduced are broken down, with intermediate bonds being formed with metals. The addition of a selected reaction agent and variation of the operating states result in adjustable products which can be recycled. Since the main part of these products is a synthetic gas, it has been shown that, surprisingly, it is an advantage inherent in the present invention if the secondary synthetic gas generated in the molten metal bath is used as a valuable substance in the primary synthetic gas, namely the synthesis generated by partial oxidation ¬ gas, is added. The heavy metals fall into metallic O 97/46721 PC17EP97 / 02473

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shape in the molten metal bath. 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.

If, as an alternative to the thermal decomposition of the soot containing heavy metals in the molten metal bath, 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. 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.

In a method described in DE-43 09 825-A1, a filter cake is treated with acid. EP-0 542 322-A1 describes the thermal treatment of residues containing vanadium.

In one embodiment of the present invention, 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.

In a special embodiment of the present invention, the soot water is filtered in a chamber filter press in such a way that the filtrate obtained first is collected and filtered again.

In the present invention, therefore, the elaborate separation of the heavy metals from the soot is eliminated, which as an advantage brings considerable savings in terms of equipment and an increase in operational reliability. It is desirable to use carbon black with as high a content as possible - 7 -

To get heavy metals. Only devices are provided which do not allow operational problems to be expected. An extractive separation process for soot and heavy metals, for example, can therefore be dispensed with.

Special configurations of the present invention have therefore been created, in which heavy metal-containing oil is fed to the partial oxidation in a primary oil gasifier, which is preferably equipped with a three- or multi-flow burner, which achieves a high carbon conversion to synthesis gas and correspondingly little soot is generated in the primary synthesis gas.

As a result, it is surprisingly possible to extract more useful heat from the synthesis gas, since heavy metals no longer accumulate due to the return of soot, and this makes it possible to use heat exchangers for heat recovery at higher temperatures without exposing them to the risk of caking and corrosion attack. The overall efficiency of a combined gas-steam turbine power plant with integrated gasification for the generation of electrical energy from synthesis gas can thus be improved, for example, by up to 5 percentage points, which is a further advantage of the invention.

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. In the conventional state of the art, 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.

In the present invention, removal of the heavy metals from the filter cake is not desirable since the filter cake is to be further processed for the purpose of recovering the metals. In accordance with the already mentioned laid-open patent application DE-43 09 825, 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.

In deviation from the patent specification DE-43 09 825, 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.

Which type of thermal decomposition is now used according to the invention for further treatment of the filter cake depends on the shape of the residues to be disposed of:

If raw materials are only to be disposed of in liquid form and there is no need to dispose of lumpy, problematic residues, soot gasification of the soot containing heavy metals is to be carried out by means of partial oxidation instead of the molten metal bath. In this case too, 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.

If lumpy, problematic residues are to be disposed of in small quantities in addition to the soot, a 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.

If particularly many lumpy, problematic residues are to be disposed of in large quantities in addition to the soot, 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.

If the soot is to be added as a dusty soot to a molten bath, 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.

Therefore, in a further embodiment of the present invention, 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.

If the soot is to be added as a pumpable soot-oil suspension, irrespective of whether it is in a molten bath or in a soot gasifier, the present invention provides for the filter cake to be mixed in an extruder.

Such a mashing of moist filter cake with a liquid is already described in the documents DE-33 28 289 and DE-34 09 326. These documents describe how to first heat a highly viscous liquid, then add moist carbon black, then the suspension is stirred and homogenized. The moist carbon black is added to the liquid by means of an extruder, followed by stirring and homogenization under pressure. In deviation from this, however, the present invention provides that the soot filter cake is first placed in an extruder and only then is the heavy metal oil added. Furthermore, the oil containing heavy metals according to the present invention is heated only in the extruder used and not before. Liquid, problematic residues are then optionally added at a further addition point. This sequence allows the subsequent stirring and homogenization to be omitted, which is an advantage of is. In addition to mixing and heating, the extruder also transports it to the subsequent soot gasifier or the molten bath.

Therefore, 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.

If lumpy, problematic residues are also to be disposed of, either the mashed soot-oil suspension is pumped into a melt pool or dust-like soot is pneumatically conveyed into a melt pool. In addition, oxygen is injected and the lumpy problematic residues are added using a suitable device. Such a 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. 5,358,549 and in the publication "Molten metal works waste wonders , by Peter Taffe, European Chemical News October 16-22, 1995, pp. 32-33 ". In the molten metal bath, carbonaceous or substances containing hydrocarbons catalytically broken down and partially oxidized. Heavy metal compounds are reduced; the heavy and precious metals form a metallic phase, which is drawn off continuously or in molten batches and collected in suitable vessels, solidifies and can be further processed metallurgically as a raw metal. This raw metal contains the heavy metals, especially vanadium and nickel from the oil containing heavy metals, which get into the weld pool with the soot and the metals from the problematic residues. The alkali metal compounds form a ceramic slag which also contains a lot of chemically bound chlorine and sulfur. This slag can be used as a cement base material.

If for some reason the supply of lumpy, problematic residues is interrupted in a molten metal bath charged with dusty soot, 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 same applies to the molten metal bath, in which the soot is charged with soot by means of a mashed suspension. In this molten metal bath too, the supply of lumpy, problematic residues can be interrupted, in which case in a particular embodiment of the process according to the invention 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.

If, on the other hand, an uninterrupted supply of lumpy, problematic residues to the molten metal bath is provided, then in another embodiment of the present invention, in addition to the soot or to the soot mashed with liquid problematic residues, 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.

In one embodiment of the present invention, 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.

Since it can be expedient to operate the melt pool at a lower pressure than the primary oil gasifier, 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.

Accordingly, 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.

Therefore, 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.

If no lumpy, problematic residues are to be disposed of, 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.

In one embodiment of the present invention, 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.

To this end, 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.

Since the ash containing heavy metals, which is formed in this soot gasification, can lead to caking and corrosion, the synthesis gas formed is directly quenched, and waste heat cannot be used.

The resulting secondary synthesis gas is therefore immediately cooled and washed in a direct quench, which forms a unit with the small soot gasifier. In the present invention, a corresponding embodiment provides that the secondary synthesis gas is quenched with water and washed immediately after the partial oxidation in the soot gasifier.

In contrast to the molten bath, it is not necessary to recompress the synthesis gas because the primary oil gasifier and soot gasifier can be operated at the same pressure level and the synthesis gases formed in both gasifications can be combined in a simple manner.

For this purpose, a separate embodiment of the present invention has been made, in which the secondary synthesis gas after the partial oxidation in the soot gasifier and the immediately following quenching with water without further measures admixed primary synthesis gas generated by the primary oil gasifier.

During soot gasification, the heavy metals accumulate in the ashes that are discharged from the soot gasifier by the secondary synthesis gas. This ash, which contains heavy metals, is to be obtained as a valuable material.

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.

In the present invention, therefore, a further embodiment is created in which the quench water is drawn off and filtered from the quench and in which the filter cake formed, which contains the heavy metals from the soot and possibly from the problematic residues, is further processed metallurgically becomes.

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.

For this purpose, 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.

In one embodiment of the present invention, it is accordingly provided that the filtrate is mixed with the soot water stream coming from the primary oil gas in order to avoid losses due to dissolved metals.

It has been shown that the 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.

1, 2 and 3 show three process flow diagrams in which the process according to the invention is described by way of example in three different configurations. In the method shown in FIG. 1, lumpy, problematic residues are to be disposed of in small quantities in addition to the soot.

In the process shown in FIG. 2, a particularly large number of lumpy, problematic residues must be disposed of in large quantities in addition to the soot.

In the method shown in FIG. 3, residual substances present only in liquid form are to be disposed of in addition to the soot.

In these three flow diagrams it is shown that - starting with the soot formation during the partial oxidation of the heavy metal-containing oil and ending with the removal and separation of the soot as a filter cake - these first process steps are provided identically for each embodiment according to the invention. Accordingly, all three exemplary embodiments are given their own first method steps in the same way, only once in the first place here afterwards.

The heavy metal oil is converted in a primary oil gasification by means of partial oxidation. For this purpose, 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. After admixing compressed synthesis gas 34 or synthesis gas 47, 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. As soon as the heavy metal concentration of the filtrate flow from the filter press 15 has dropped below a value which permits disposal as waste water, the clean filtrate 16 is drained off. The intermediate filtrate 19 is gradually returned to the filter press 15 and filtered again. The heavy metals from that already formed filter cake added.

1 that 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. For this, 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.

In 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 heavy metals.

Claims

Claims: 1. A process for producing a metallic raw material from heavy metal-containing oil, which is fed to a partial oxidation, characterized in that the heavy metal-containing soot formed in the partial oxidation of the oil in the primary oil carburetor is separated from the other, resulting substances and is thermally decomposed together with residues, as a result of which the heavy metals occur in a separate phase either in oxidized or in metallic form. 2. The method according to claim 1, characterized in that the soot formed in the partial oxidation, which contains the heavy metals in attached chemical compounds, is washed out of the resulting primary synthesis gas by means of an aqueous washing solution, so that soot water is formed. 3. The method according to claim 2, characterized in that the ^' soot water is filtered in a chamber filter press in such a way that the filtrate obtained first is collected and filtered again. 4. The method according to claim 3, characterized in that the filter cake thus obtained, which contains the heavy metals almost completely, either in a Sprührock¬ ner, a current dryer with grinder or a Mahltrock¬ ner with heated inert gas to a residual moisture content of <10% becomes. 5. The method according to claim 3, characterized in that the filter cake thus obtained, which contains the heavy metals almost completely, in an extruder with oil, preferably the heavy metal oil, which is also used for primary oil gasification, mashed so that zu¬ only the soot filter cake is added to the extruder and then the oil, and that the resulting suspension is pumpable. 6. The method according to claim 5, characterized in that the suspension liquid, problematic residues are admixed. 7. The method according to claim 4, characterized in that that the carbon black conditioned in the drying process is put in dust form in a 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, and that the dust-like carbon black is catalytically broken down in the molten bath and is partially oxidized, producing a ceramic slag, secondary synthesis gas and a metal melt which contains the heavy metals from the heavy metal-containing compounds of the carbon black. 8. The method according to claims 5 or 6, characterized in that the mashed in an extruder from wet carbon black with oil and possibly liquid, problematic residues Suspen¬ sion is placed in a molten bath, which is a liquid, metallic and a liquid , contains ceramic phase and is operated under a pressure of up to 10 bar, oxygen, and that the suspension in the molten bath is catalytically broken down and partially oxidized, a ceramic slag, a metal melt, which separates the heavy metals contains the heavy metal-containing compounds of the suspension, and secondary synthesis gas are formed. 9. The method according to claim 7 or 8, characterized in that in addition to the soot or to the problematic with liquid Oxygenated soot, further lumpy 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, oxygen, in the melt ¬ Bad all residues are catalytically broken down and partially oxidized together with the soot, and a ceramic slag, a metal melt, which contains the heavy metals from the problematic residues and from the soot, and secondary synthesis gas. 10. The method according to any one of the preceding claims 7, 8 or 9, characterized in that the slag withdrawn from said melt pool for Manufacture of cement is used. 11. The method according to any one of the preceding claims 7, 8, 9 or 10, characterized in that the molten metal withdrawn from said molten bath is poured into molds where it solidifies, and that the raw metal thus obtained is fed to a further metallurgical use. 12. The method according to any one of the preceding claims 7, 8, 9, 10 or 11, characterized in that the hot secondary synthesis gas drawn off via said 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. 13. The method according to any one of the preceding claims 7, 8, 9, 10 or 11, characterized in that the hot synthesis gas withdrawn from said melt pool is cooled and washed in a water quench. 14. The method according to any one of the preceding claims 12 or 13, characterized in that the hot secondary synthesis gas drawn off via said melt pool is compressed in a compressor to a pressure which cools the admixture to the mixture after cooling according to claims 12 or 13 primary synthesis gas ge, which is generated by the primary oil gasifier according to claim 1, and that one carries out this admixture. 15. The method according to claims 5 or 6, characterized in that the suspension from the extruder in a soot gasifier - 33 - is promoted and partially oxidized there together with oxygen under the pressure under which the partial oxidation according to claim 1 also takes place. 16. The method according to claim 15, characterized in that the secondary synthesis gas is quenched with water and washed immediately after the partial oxidation in the carbon black gasifier. 17. The method according to claim 16, characterized in that the secondary synthesis gas after the partial oxidation in the soot gasifier and the immediately following quenching with water without further measures admixes the primary synthesis gas generated by the primary oil gasifier according to claim 1. 18. The method according to claims 15, 16 or 17, characterized in that the quench water is withdrawn from the quench and filtered and that the filter cake, which contains the heavy metals from the soot and possibly from problematic residues, is further processed metallurgically. 19. The method according to claim 18, characterized in that the filtrate is mixed with the soot water stream coming from the primary oil gasification according to claim 3 in order to avoid losses due to dissolved metals. 20. The method according to any one of the preceding claims 15, 16, 17, 18 or 19, characterized in that the soot gasifier is equipped with a three- or multi-flow burner, which achieves a high carbon conversion to secondary synthesis gas and correspondingly produces little soot. 21. The method according to any one of the preceding claims, characterized in that the primary oil gasifier is equipped with a three or Mehrstrom¬ burner, which achieves a high carbon conversion to primary synthesis gas and correspondingly produces little soot.