DE19622150A1 - Process for the recovery of 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

The invention relates to a method by which Oil containing heavy metals and from the rest to be disposed of In addition to synthesis gas, a metallurgical raw material is produced becomes.

description

As is well known, oils can be contaminated with heavy metals. This basically applies to all petroleum, the quality of which also depends resources is getting worse, especially for those from Venezuela and Russia, but also for refinery returns levels, bitumen, waste oils and pyrolysis oils. Most often tre the heavy metals vanadium and nickel on. In the energetic or material implementation of such The heavy metal content of oils leads to problems: stand in case of combustion or partial oxidation Heavy metal compounds that have extremely corrosive effects fold and melt at the prevailing working temperatures can become liquid or dough, so they tend to stick and subsequently lead to malfunctions. On the other hand these heavy metal compounds only in very small quantities be emitted in gaseous or liquid form. A landfill as Solid residues are expensive and subject to strict ge statutory provisions. For these reasons, Anlagenbe preferred oils with low heavy metal contents than A raw material, which reduces the value of the heavy metal oils is.

There is also Ent with respect to other residues care needs. Liquid hydrocarbons, especially if they are chlorinated because of the dioxin / furan formation  Dispose of only in elaborately designed incineration plants. This happens u. a. with used, organic solvents. In addition to organic carbon, other residues contain compounds also hydrocarbon compounds that u. a. also can still be halogenated. In addition, these residues carry a large number of metals and metal compounds Ren is an example of this type of waste nicotine, e.g. B. PCBs and similar assemblies. The Residues can also contain significant other contaminants accruing if these z. B. as fillers in plastics are embedded. All such residues are listed below referred to as "problematic residues". It is desirable if possible recover all of their ingredients and one To be reused.

The present invention solves the problems described through that heavy metal oil of partial oxidation is supplied to produce a metallic raw material that of the partial oxidation of the oil in a primary oil carburized soot containing heavy metals from the others, resulting substances separated and together with residues is thermally decomposed, whereby the heavy metals in an egg phase.

The thermal decomposition of the separated, heavy metal According to the invention, soot can either be in a molten metal bad or done in a soot carburetor.

Finds the thermal decomposition of the soot containing heavy metals together with the residues in a molten metal bath, so this is above the melting point of the Me talle operated, depending on the metal at 800 to 1800 ° C. In this The molecular bonds of the entered residues become bath split, forming intermediate bonds with metals. By adding a selected reagent and variation The operating states result in adjustable products that one  Recovery can be supplied. Because the bulk of this Products is a synthesis gas, it has been shown to be about surprisingly, one inherent in the present invention Is an advantage if the se generated in the molten metal bath customary synthesis gas as a valuable material for the primarily generated synthesis segas, namely the syn generated by partial oxidation thesegas, is added. The heavy metals fall into metal form in the molten metal bath. The own phase forms the heavy metal alloy melt from the metal melt bad is deducted. The solidified, heavy metal alloy Melt is the recyclable material.

Is used as an alternative to the thermal decomposition of the heavy metal term soot in the molten metal bath, the soot in a soot gasifier thermally decomposed by partial oxidation also secondary synthesis gas. Also in the soot carburetor formed secondary synthesis gas has the surprising and he preference according to the invention that it is the primary synthesis gas can be added. The heavy metals fall in oxidized Form as ash containing heavy metals and form in its own Phase of the recyclable material.

The heavy metal oil is converted in one step was for partial oxidation, hereinafter referred to as primary oil consumption solution. Usually takes place in a plant for ver Gassing liquid or solid, carbonaceous fuel only incomplete implementation of carbon bonds instead. This is because within the flame, in which the reaction takes place mainly, lack of oxygen prevails. This lack of oxygen has two causes: Firstly the partial oxidation requires significantly less oxygen as a combustion, therefore oxygen becomes comparative admitted sparingly. On the other hand, an almost perfect ver Mixing oxygen with oil mist very difficult technically realize so that within the reaction zone with greater lack of oxygen in addition to well oxygenated  coexist. The worse the mixing, the more soot forms. The three or multiple flow burner solves the task particularly good mixing and distribution of fuel and ensure fuel gas. Therefore, an execution of the present invention that the primary oil gasifier with a Three or multi-current burner is equipped, which has a ho hen carbon conversion to primary synthesis gas reached and ent producing little soot.

A common technique for disposing of the soot is to remove it attributed to the gasification reactor. With this repatriation a large part of the returned soot is converted to synthesis gas set. A direct return of soot containing heavy metals from an oil gasification in the gasification reactor would in the Verga solution reactor and in the following apparatus to an enrichment lead to heavy metals and subsequently to those already operational problems mentioned. That's why the heavy metals are separated from the soot in a complex manner before a return of the soot to the gasification reactor technically makes sense. This is usually done in an extract onsanlage, in which naphtha serves as an extractant. There one such a separation at reasonable cost is never perfect with a heavy metal enrichment in the gasification reactor and downstream facilities always to be expected.

In another method, described in the disclosure DE 43 09 825, the filter cake is treated with acid delt. The acid removes the heavy metals from the soot.

In an embodiment of the present invention, the ent standing soot, which accumulates the heavy metals in chemical Contains compounds in an aqueous washing solution from the resulting primary synthesis gas washed out, soot soot it arises.  

Here, in a special embodiment of the present Er find the soot water in a chamber filter press in such a way filtered to collect the filtrate obtained first and is filtered again.

In the present invention, therefore, the elaborate one is eliminated Separation of heavy metals from soot, which is a significant advantage Savings in equipment costs and an increase in brings operational reliability. It is desirable Carbon black with as high a content of heavy metals as possible hold. Only devices that are operable are provided Don't expect problems. For example, an ex tractive separation process for soot and heavy metals can be waived here.

Therefore, special configurations of the present invention created, in which heavy metal oil the par tial oxidation is supplied in a primary oil gasifier, the preferably equipped with a three or multiple flow burner which is a high carbon conversion to synthesis gas enough and accordingly little soot in the primary synthesis gas he testifies.

This makes it surprisingly possible to use the synthesis gas more effectively to withdraw heat as there is no longer any accumulation of heavy metal len occurs by recycling soot, making it possible is, heat exchanger for heat recovery at higher Use temperature without the risk of caking and expose to corrosion attack. The overall efficiency of a combined gas-steam turbine power plant with integrated ver Gassing for the production of electrical energy from synthesis gas can, for example, be improved by up to 5 percentage points what is another advantage of the invention.

The soot, which is essentially from the unreacted coal material, becomes dusty from the primary oil gasification craze  discharged and contains heavy metal compounds in solid Shape. In a subsequent water wash, which is a waste heat recovery may be preceded by soot from the primary Separated synthesis gas. It is then about 1% aqueous Suspension before, hereinafter referred to as "soot water". The Heavy metal compounds are both dissolved in the soot water as well as in a form firmly bound to the soot particles.

The heavy metal-containing soot is after a relaxation of the Soot water and possibly steam stripping from the soot filtered water with a filter press. The filter cake be sits a soot content of 15-25%, the rest is water. At the Conventional state of the art, the Ex Traction of the heavy metals from the soot take place, the heavy ones talle get into a wastewater solution, which is expensive must be 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 still present contains a noticeable heavy metal content, whereas the Heavy metal contamination of the filtrate after formation of a ge sufficiently thick filter cake decreases sharply and to very small Concentrations decrease. Only the part of the filtrate that is pressed through a sufficiently thick filter cake layer, meets the requirements for discharge as waste water. Thereby, that in the filtration process by a minimum thickness of the filter cake heavy metals are retained in it, too Filter cake is not, as otherwise desired, low in heavy metals. Therefore according to the state of the art either have additional measures Heavy metal removal from the filtrate and / or from the Filter cakes are taken.

In the present invention is removal of the heavy talle from the filter cake is not desirable because of the filter cake for the purpose of recovering the metals. In line with the aforementioned disclosure  DE 43 09 825 therefore becomes the filtrate from the start of the filtration caught in a container until the heavy metal concentration of the currently running filtrate below the legal limits for waste water. From the container the filtered water containing heavy metals is then again gradually filtered in the same chamber filter press, where at the filter cake already formed as a heavy metal load sorbent layer is used. The filtrate now draining is no longer fed into the container. It is so heavy tallarm that both the legal provisions for the Ab drainage are observed as well as no mention losses of valuable heavy metals are tolerated need, both of which are advantages of the invention. The received one Filter cake contains almost all of the heavy metals.

In deviation from the patent specification DE 43 09 825, this is Filter cake but not freed of its heavy metals and it is also not intended to return the soot to the gasification supply, rather the soot present as a filter cake possibly together with problematic residues of the subjected to thermal decomposition according to the invention.

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

• - Are only raw materials available in liquid form to dispose of and can be arranged for co-disposal of lumpy, problematic residues are avoided instead a soot gasification of the heavy metal make soot by means of partial oxidation, too in this case the filter cake will contain heavy metals Mashed oil and pumped into the soot carburetor. In this case but it is possible to use liquid problematic residues mash up when the exposure to chlorine, chemi  low connections in the problematic residues is.
• - Should be lumpy, problematic residues in smaller sizes Amounts to be disposed of in addition to soot is one Melting bath to be provided. If this melt pool because of the on maneuverable equipment is to be built in a particularly compact manner, the filter cake is dried and pneumatically in as dust entered the melt. By reducing the amount of water the calorific value is increased and the resulting gas quantity is reduced.
• - Should a particularly large number of lumpy, problematic residues in large quantities are also disposed of in addition to the soot Filter cake mashed with oil containing heavy metals, before preferably in a ratio of 1 part carbon black to 2 parts oil, and then pumped into the weld pool. The amount of synthesis gas is larger than when adding soot dust into the weld pool and thus the required weld pool dimensions also increase.

If the soot addition is presented as a dusty soot in a weld pool to be taken, the filter must closing drying of the filter cake according to the invention with a water content of <10%, note that does not form an explosive mixture. The drying he therefore suitably follows under an inert atmosphere. It showed that in gasification plants that are enriched with oxygen air or oxygen are operated sufficiently above surplus nitrogen from an air separation plant for ver stands, which is not otherwise usable, and therefore can advantageously be used as a drying medium. The Drying using this nitrogen in one time Throughput saves complex and expensive cooling and condensing tion apparatus and circulation devices, such as those used for gas recirculations are required.  

The drying itself is preferably done in systems where de necessary for the subsequent partial oxidation fine grain spectrum is generated immediately during drying. Suitable are z. B. grinding dryer, current dryer with grinding plant and classifier or spray dryer where the drying gas, e.g. B. the above nitrogen, with the waste heat of the secondary Ren synthesis gas is heated, which in the catalytic Soot decomposition occurs.

Therefore, in a further embodiment of the present Er finding the filter cake accumulating in the chamber filter press, which contains almost all of the heavy metals, either in a spray dryer, a current dryer with grinder or egg to a residual moisture with a heated inert gas dried from <10%.

If the soot is added as a pumpable soot-oil suspension should be, it does not matter whether in a weld pool or in a soot carburetor, the present invention sees one Mash the filter cake in an extruder.

Such a mashing of moist filter cake with a Liquid is already in the documents DE 33 28 289 and DE 34 09 326 described. These writings describe how to heat a highly viscous liquid first, then add damp soot, then the suspension is stirred and homogenized. The addition of the wet soot to the rivers liquid takes place by means of an extruder, followed by eats stirring and homogenizing under pressure. Dev However, the present invention provides that the Soot filter cake first placed in an extruder and only then finally the heavy metal oil is added. Of the oil containing heavy metals is also heated according to the present invention only in the extruder used and not before. Then at another addition point  optional the addition of liquid, problematic residues. This order allows the subsequent stirring and Ho Mogenize is eliminated, which is an advantage of the invention. Of the In addition to mixing and heating, the extruder also takes care of that Delivery in the subsequent soot gasifier or the melt pool.

Therefore sees a further embodiment of the present Er finding that one in the chamber filter press moist filter cake, the heavy metals almost completely contains, as it is obtained, in an extruder with oil, preferably with the heavy metal oil, which is also suitable for Primary oil gasification is used, so that the first Soot filter cake is added to the extruder and then the oil, and that the resulting suspension is pumpable.

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 molten bath is e.g. B. in the patents US 5,491,279, WO 93/25277, US 4,574,714, US 5,298,233, US 5,443,572, US 5,301,620, US 5,358,549 and in the publication "Molten metal works waste wonders, by Peter Taffe, European Chemical News 16-22 October 1995 , pp. 32-33 ". In the molten metal bath, carbon-containing or hydrocarbon-containing substances are broken down and partially oxidized. Connections containing heavy metals are reduced; the heavy and precious metals form a metallic phase, which is melted off continuously or in a single batch in a molten state 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 that also contains a lot of chemically bound chlorine and sulfur. This slag can be used as a cement base.

Will be for some reason with a dusty soot metal molten bath sent the supply of lumpy, problema table residues is interrupted, so in its own out design of the method according to the invention in this way gene that only the soot conditioned in the drying is put into a molten bath in dust form, which contains a liquid, contains metallic and a liquid, ceramic phase and un is operated under a pressure of up to 10 bar, still acid substance, and that the dusty soot in the melt catalyzes table is disassembled and partially oxidized, with a ceramic Slag, secondary synthesis gas and a molten metal, the the heavy metals from the heavy metal compounds of the Contains soot, arise.

The same applies to the molten metal bath, in which the coating Kung happens with soot using a mashed suspension. Also in this molten metal bath, the supply of lumpy, pro Blematic residues are interrupted, then in egg ner special embodiment of the method according to the invention the procedure is such that only those in an extruder from damp soot with oil and possibly liquid, problema mastic suspension in a molten bath is given that a liquid, metallic and a liquid, contains ceramic phase and under a pressure up to 10 bar operated, continues to oxygen, and that the suspension in the melt pool is catalytically broken down and partially oxidized, being a ceramic slag, a molten metal that the Heavy metals from the compounds containing heavy metals Contains suspension, and secondary synthesis gas arise.

On the other hand, is an uninterrupted supply of lumpy, problematic residues provided for the molten metal bath, so  are in another embodiment of the present inven dung in addition to soot or liquid problemat soiled mastic soot the lumpy problematic residual substances in said melt pool, which flows contains metallic, and a liquid, ceramic phase and is operated under a pressure of up to 10 bar Oxygen, with all residues in the melt pool catalytically disassembled and partially oxidized together with the soot, and being a ceramic slag, a molten metal that the Heavy metals from the problematic residues and the soot contains, and secondary synthesis gas arise.

In one embodiment of the present invention, the said melt removed slag for the production of ze ment used. Another configuration of the present invention withdrawn from said melt pool poured molten metal into molds where it solidifies, and the raw metal thus obtained then becomes a metallurgical one Fed further use.

As it may be convenient to use the weld pool at a low To operate their pressure as the primary oil gasifier, this must be done in Melt pool generated secondary synthesis gas who compresses if it is the primary synthesis gas of the primary oil gasifier should be added. To be able to condense it, it has to before being cooled. This happens either in a water quench by adding water or by using heat means of a heat exchanger or both.

Accordingly, the present invention provides another Design provided, in which the said enamel Bad secondary synthetic gas drawn off over a heat exchanger is passed to at least part of the heat gie of the secondary synthesis gas as waste heat. Also the present invention also has a configuration in  which is the hot secondary withdrawn from said melt pool Synthesis gas is cooled in a water quench and washed.

The secondary synthesis gas generated above the melt pool is according to the invention, - after cooling by means of a quench Water or both - compressed to a pressure, which is also in the main stream of the primary synthesis gas from the Pri prevailing petroleum gasification, and then this main stream of primary synthesis gas admixed.

The present invention therefore also has a configuration tion in which the hot bath withdrawn above said melt pool ß secondary synthesis gas after cooling according to the before upcoming relevant configurations in a compressor is compressed to a pressure that the admixture to the pri allowed synthesis gas from the primary oil gasifier he is produced, and that one carries out this admixture. If the Soot should be added to the melt as dust, it is he provided according to the invention, the waste heat for heating the inert gases to use, which is used to dry the soot filter cake is used.

If no lumpy, problematic residues are disposed of the soot-oil suspension can also be used in a soot be directed. This makes the soot-oil suspension pumpable made that the filter cake in an extruder with oil, preferably with the heavy metal oil, which is also suitable for Primary oil gasification is used, mashed.

In one embodiment of the present invention, this Suspension, if necessary, the liquid to be disposed of problematic residues mixed.

This soot-oil emulsion is then optionally extended with liquid, problematic residues if they contain little chlorine containing compounds, liquid in a small soot  carburettor, which is preferably equipped with a three-stream burner is partially oxidized together with oxygen.

To this end, an embodiment of the present invention provides that the suspension from the extruder into a soot carburetor changed and partially oxidized there together with oxygen under the pressure under which the partial oxidation in the Pri petroleum gasifier runs out.

Because the heavy metal ash that is used in this soot gasification arises which can lead to caking and corrosion Direct quenching of the synthesis gas formed, ei Heat recovery is not possible.

Therefore, the resulting secondary synthesis gas is immediately in egg nem direct quench, the one with the small soot carburetor forms, cooled and washed. In the present invention A corresponding design therefore provides that the secondary synthesis gas immediately after partial oxidation quenched with water in the soot gasifier and washed.

In contrast to the weld pool, it is not necessary to use the syn Thesegas to compress because primary oil gasifier and soot gas water can be operated at the same pressure level and one Merging the synthesis formed in both gassings gases is possible in a simple manner.

For this purpose, a separate version of the present Er find happen in which the secondary synthesis gas after the partial oxidation in the soot carburetor and follow immediately the quenching with water without any further measures Primary oil gasifier mixed primary synthesis gas.

During soot gasification, the heavy metals collect in the ent standing ash from the secondary synthesis gas from the soot  gas is discharged. This heavy metal ash is said to can be obtained as a resource.

When quenching the secondary synthesis gas, the quench is loaded with the heavy metal ash, so that can Quench water is withdrawn from the direct quench and filtered the.

The ash containing heavy metals is removed from the aqueous solution is withdrawn from the direct quench, filtered and can me be further processed in the valley.

In the present invention, therefore, is another feature design created in which the quench water from the quench is subtracted and filtered, and in which the resulting fil Cake that removes the heavy metals from the soot and, if necessary contains from the problematic residues, metallurgically white is processed.

The filtrate is advantageously the soot water of the primary oil gasification admixed to a post-separation of dissolved Heavy metal compounds in the manner described above to reach.

For this purpose, the filtrate is released into the Soot filter press passed to residual heavy metals on the soot separate filter cake.

Accordingly, in one embodiment of the present invention provided that the filtrate coming from the primary oil gasification sooty water stream is mixed in to solve losses caused by avoiding the most metals.

It has been shown that the soot carburetor, if it is analogous to Primary oil gasifier with a three or multiple flow burner is also equipped to be particularly effective in soot  can implement synthetic syngas. So that's another Embodiment of the present invention in which the Soot carburettor equipped with a three or multiple flow burner which is a high carbon conversion to synthesis gas is sufficient and accordingly produces little soot.

Fig. 1, Fig. 2 and Fig. 3 show three process flow images in which the method according to the invention in three different Ws embodiments will be described by way of example.

In the method shown in Fig. 1 lumpy, per blematic residues in minor amounts are to be disposed of 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 must be disposed of in addition to the soot.

These three flow charts show that, - starting with the formation of soot during the partial oxidation of the heavy metal containing oil and ending with the discharge and separation of soot as a filter cake -, these first process steps provided identically for each configuration according to the invention are. Accordingly, these are all three exemplary examples events in the same way own first procedural steps only specified once in the first place here.

The heavy metal oil is reacted in a primary oil gasification with partial oxidation. For this purpose, heavy metal oil ( 3 ) is injected into the primary oil gasifier ( 1 ) using a three-flow burner and atomized by the two oxygen flows ( 2 ) and ( 4 ) to form a fine oil mist. A partial oxidation takes place under high pressure and at a temperature of approx. 1400 ° C, in which more than 99% of the heavy metal oil ( 3 ) is converted to synthesis gas and less than 1% to soot, to which the heavy metal compounds attach. The raw synthesis gas ( 5 ) formed is passed into a raw 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 water ( 9 ) is used to wash out the soot together with other soluble substances. The pre-cleaned synthesis gas ( 10 ) is derived for further use after admixing compressed synthesis gas ( 34 ) or synthesis gas ( 47 ). The hot soot water ( 11 ) is relaxed and cooled in a soot water flash ( 12 ) to atmospheric pressure. The flash gas ( 13 ) escapes, which contains the gases which are less soluble in water at lower pressure and temperature. The cold soot water ( 14 ) is passed into a filter press ( 15 ) and filtered. The first obtained heavy metal-containing fil ( 17 ) 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 that 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 are absorbed by the filter cake that has already formed.

In Fig. 1 it is shown in the following that the filter cake ( 20 ) after the end of the filtration process is placed in the dryer ( 21 ) and dried with hot inert gas ( 22 ). In the dryer ( 21 ) there is also a comminution of the soot particles. It also contains a soot filter, which prevents the moist inert gas ( 23 ) from entraining soot particles when it leaves the dryer ( 21 ). 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 weld pool ( 25 ) as soot dust ( 24 ). In the melt pool ( 25 ) there is thermal and catalytic decomposition of the soot. For this, oxygen ( 27 ) is added. The ability of the melt pool 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.

In Fig. 2 it is shown 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 weld pool ( 25 ). For this, oxygen ( 27 ) is added. The ability of the melt pool 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 quenched in the water quench ( 40 ) by adding the water ( 41 ) and thereby cooled, 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 pre-cleaned 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 mashed with heavy metal oil ( 38 ) and the problematic residue ( 26 ).

The soot-oil suspension ( 39 ) is conveyed by the extruder into the soot gasifier ( 44 ), injected there with a three-flow burner together with the oxygen flows ( 42 ) and ( 43 ) and partially oxidized under the same pressure as in the primary oil gasifier ( 1 ). The ash-containing synthesis gas thus formed is immediately quenched and washed in a direct quench ( 45 ) with the water ( 46 ). The synthesis gas ( 47 ) is added to the synthesis gas ( 10 ) and the mixed synthesis gas ( 36 ) is derived for further use. The ash water withdrawn 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 a cooler ( 12 ). This measure prevents losses of heavy metals.

Reference list

1 primary oil gasifier
2 oxygen
3 oil containing heavy metals
4 oxygen
5 Raw synthesis gas
6 raw gas coolers with waste heat utilization
7 cooled raw gas
8 water quench
9 water
10 pre-cleaned synthesis gas
11 hot soot water
12 soot water flash with cooler
13 flash gas
14 cold soot water
15 filter press
16 clean filtrate
17 filtrate containing heavy metals
18 intermediate filtrate container
19 intermediate filtrate
20 filter cakes
21 dryer
22 hot inert gas
23 moist inert gas
24 soot dust
25 melt pool
26 residues
27 oxygen
28 ceramic slag
29 metallic melt
30 hot syngas
31 Syngas-inert gas heat exchanger
32 cooled synthesis gas
33 compressors
34 compressed synthesis gas
35 cold inert gas
36 mixed synthesis gas
37 extruders
38 heavy metal oil
39 Soot oil suspension
40 water quench
41 water
42 oxygen
43 oxygen
44 soot carburetor
45 direct quench
46 water
47 synthesis gas
48 ash water
49 ash filter
50 ash filter cakes
51 residual water.

Claims (21)

1. A process for producing a metallic raw material from heavy metal-containing oil, which is led to a partial oxidation, characterized in that the heavy metal-containing soot formed in the partial oxidation of the oil in the primary oil gasifier is separated from the other, resulting substances and together with residues is thermally decomposed, which results in the heavy metals in their own phase either in oxidized or in metallic form. 2. The method according to claim 1, characterized in that the soot produced during the partial oxidation, which Heavy metals in attached chemical compounds holds, by means of an aqueous washing solution from the resulting NEN primary synthesis gas is washed out, so that soot water arises. 3. The method according to claim 2, characterized in that the Soot water is filtered in a chamber filter press is that the first filtrate obtained and still is filtered. 4. The method according to claim 3, characterized in that the filter cake thus obtained, the heavy metals almost completely contains, either in a spray dryer, one Current dryer with grinder or a grinding dryer with it 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, the heavy metals almost completely contains, in an extruder with oil, preferably the heavy metal oil that is also used for primary oil solution is mashed so that 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 mixed will. 7. The method according to claim 4, characterized in that the soot conditioned in the form of a dust in the drying process Melting bath is given, which is a liquid, metallic and contains a liquid, ceramic phase and under one Pressure is operated up to 10 bar, still oxygen, and that the dusty soot in the melt pool is catalytic is disassembled and partially oxidized, with a ceramic Slag, secondary synthesis gas and a molten metal, which the heavy metals from the heavy metal-containing compound contains soot. 8. The method according to claims 5 or 6, characterized records that in an extruder from wet soot with oil and optionally liquid, problematic residues mashed suspension is placed in a melt pool, the a liquid, metallic and a liquid, ceramic Phase contains and operated under a pressure up to 10 bar will continue to oxygen, and that the suspension in the Melt pool is catalytically disassembled and partially oxidized, being a ceramic slag, a molten metal that the Heavy metals from the compounds containing heavy metals Contains suspension, and secondary synthesis gas arise. 9. The method according to claim 7 or 8, characterized in that in addition to the soot or that with liquid problemati soiled mash soiled further lumpy proble matical residues are added to said melt pool, the one liquid, metallic and one liquid, ceramic  Phase contains and operated under a pressure up to 10 bar will continue to be oxygen, with all in the melt pool Catalytically decomposed residues and par together with the soot partially oxidized, and with a ceramic slag, a molten metal that separates the heavy metals from the problema table residues and from the soot contains, and secondary Syngas arise. 10. The method according to any one of the preceding claims 7, 8 or 9, characterized in that the said Melt bath removed slag for the production of cement is used. 11. The method according to any one of the preceding claims 7, 8, 9 or 10, characterized in that the said Melt bath removed metal melt poured into molds is where it solidifies, and that the raw metal thus obtained is used for further metallurgical use. 12. The method according to any one of the preceding claims 7, 8, 9, 10 or 11, characterized in that the above said Hot secondary synthesis gas drawn off via an egg NEN heat exchanger is passed to at least a part the heat energy of the secondary synthesis gas as waste heat win. 13. The method according to any one of the preceding claims 7, 8, 9, 10 or 11, characterized in that the said Hot synthesis gas withdrawn from the melt pool in a water cooled and washed quench. 14. The method according to any one of the preceding claims 12 or 13, characterized in that over said melt pool stripped, hot secondary synthesis gas after cooling according to claims 12 or 13 in a compressor on one  Pressure is compressed, which is the admixture to the primary Syngas allowed by the primary oil gasifier according to An saying 1 is generated, and that you can this admixture by leads. 15. The method according to claims 5 or 6, characterized records that the suspension from the extruder into a soot carburetor promoted and there partially with oxygen is oxidized under the pressure under which the partial Oxidation takes place according to claim 1. 16. The method according to claim 15, characterized in that the secondary synthesis gas immediately after the partial oxide tion in the soot gasifier quenched with water and washed becomes. 17. The method according to claim 16, characterized in that the secondary synthesis gas after partial oxidation in soot carburetor and the immediately following quenching with water without further measures that from the primary oil gasifier to Proverb 1 generated primary synthesis gas admixed. 18. The method according to claims 15, 16 or 17, characterized ge indicates that the quench water is withdrawn from the quench and is filtered, and that the filter cake that the Heavy metals from the soot and possibly from problema contains table residues, further processed metallurgically becomes. 19. The method according to claim 18, characterized in that the Filtrate the soot from the primary oil gasification serstrom is added according to claim 3 to losses to be avoided by 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, wel high carbon conversion to secondary synthesis gas reached and correspondingly little soot produced. 21. The method according to any one of the preceding claims, characterized characterized in that the primary oil gasifier with a three or Multi-flow burner is equipped, which a high Carbon conversion to primary synthesis gas reached and ent producing little soot.