Methods for managing fly ash from the combustion of petroleum products.

Abstract

The present invention deals with a method for the utilization of fly ash derived from the combustion of petroleum-derived products, in particular comprising the step of preparing a filler for thermoplastic polymers or the step of recovering metals, in particular vanadium, from fly ash derived from the combustion of heavy fractions of petroleum-derived products. The present invention also provides filters and composites of thermoplastic polyolefin polymers comprising the filter according to the invention.

Description

[Technical Field]

[0001] The present invention deals with a method for the utilization of fly ash derived from the combustion of petroleum-derived products, in particular comprising the step of preparing a filler for thermoplastic polymers or the step of recovering metals, in particular vanadium, from fly ash derived from the combustion of heavy fractions of petroleum-derived products. The present invention also provides filters and composites of thermoplastic polyolefin polymers comprising the filter according to the invention.

[0002] FIELD OF THE INVENTION The technical field of the present invention is the management of fly ash from the combustion of petroleum products. [Background technology]

[0003] Fly ash is a solid residue from combustion that is captured in electrostatic precipitators. Fly ash from the combustion of solid fuels, especially coal and lignite, is commonly known and used. Unlike coal ash, fly ash from the combustion of heavy oil fractions, including heavy fuel oil (mazut), (heavy oil fly ash, HOFA - heavy oil fly ash) has received less attention and concern. The amount of ash produced is also much less compared to coal combustion. 1m 3 The combustion of fuel oil is about 0.4 kg / dm 3 Fly ash is a very light dust with a density of 10 ...

[0004] The vanadium content can range from 2.5% to 30%, depending on the origin of the oil and the combustion conditions [Manaa ESA Selective Leaching of Vanadium from Boiler Oiled Ash Residue Using Sodium Carbonate-Bicarbonate Binary Solution. Chem Technol Ind J. 2018;13(1):124].

[0005] Due to the specific composition of the fly ash under consideration, the primary method for disposing of fly ash today is to store it in designated landfills. Only a relatively small proportion is used as a raw material for the extraction of valuable metals, primarily vanadium and nickel, or as an additive in the production of building materials [YS Al-Degs et al. Characterization and utilization of fly ash of heavy fuel oil generated in power stations, Fuel Processing Technology 123 (2014) 41-46, doi.org / 10.1016 / j.fuproc.2014.01.040].

[0006] Generally, vanadium compounds are leached from the ash using acid or alkali. The precipitate remaining after the soluble components have been leached in acid or alkali, respectively, is usually considered waste. After filtration, vanadium and other components are extracted from the resulting solution by selective extraction or precipitation using appropriately selected precipitants.

[0007] A method is known from US Patent No. 10,406,983 (B2) (Vanadium Recovery Method) and publications such as S. Vitolo et al., "Recovery of vanadium from a previously burned heavy oil fly ash," Hydrometallurgy 62 (2001), pp. 145-150, which uses fly ash from the combustion of heavy fuel oil as a raw material for obtaining vanadium compounds after combustion of the carbon contained in the ash. This patent discloses a method in which, in a first step, the coal in the ash is combusted, resulting in a significant reduction in the weight of the ash from which vanadium is separated, by up to 90%, and a significant increase in its content in the carbon combustion residue.

[0008] Also known are methods involving direct leaching of metal components under acidic or alkaline conditions without pre-combustion of the carbon contained in the ash, followed by selective extraction of vanadium compounds from the resulting solution using various solvents [A. Aburizaiza, Sequential Leaching of Vanadium from Heavy Fuel Oil Fly Ash Generated from Saudi Arabia Thermal Power Plants, Current Journal of Applied Science and Technology, 32(4), 2019, pp. 1-17, doi:10.9734 / CJAST / 2019 / 46032; R. Navarro et al., Vanadium recovery from oil fly ash by leaching, precipitation, and solvent extraction processes, Waste Management 27(2007) 425-438].

[0009] Methods involving direct leaching and extraction of vanadium compounds using various solvents are also known [A. Aburizaiza, Sequential Leaching of Vanadium from Heavy Fuel Oil Fly Ash Generated from Saudi Arabia Thermal Power Plants, Current Journal of Applied Science and Technology, 32(4), 2019, pp. 1-17, doi:10.9734 / CJAST / 2019 / 46032]. The main limitation of this method involves the problematic utilization of the large amounts of waste liquid and sludge generated after the extraction / leaching process, which are usually considered waste intended to be stored in landfills.

[0010] Direct leaching of vanadium under alkaline conditions and selective precipitation of vanadium from the resulting solution is known, for example, from US Pat. No. 4,640,823 and WO 2019 / 193510 A1.

[0011] A process involving leaching vanadium with acid is known, for example from US Pat. No. 10,301,705 (B2), in which vanadium compounds are recovered in the form of an electrolyte solution for use in redox flow batteries.

[0012] WO 2004 / 090179 discloses a method for recovering vanadium from ash, which involves dissolving vanadium compounds in sulfuric acid at a pH of 1 to 1.5. After filtering off the undissolved precipitate, the resulting solution is treated with Na2SO3 to reduce the vanadium compounds to their tetravalent form. The solution is then brought to a pH of 5.2 to 5.5 with NaOH, precipitating the vanadium as V2O4.

[0013] Fly ash (HOFA) derived from the combustion of heavy fuel oil product fractions has been used as an additive in the production of Portland cement and geopolymers due to its high carbon content [M. Alshaaer et al., Production of Heavy Fuel Oil Fly Ash (HFO)-based Geopolymers for Passive Cooling Systems, International Journal of Applied Engineering Research, vol. 13(1) 2018, pp. 137-143]. It is also known to be used as a pigment for concrete, where metallic impurities in HOFA are fixed in the concrete matrix [Woo-Teck Kwon, Dong-Hyun Kim, and Yung-Phil Kim, Characterization of Heavy Oil Fly Ash Generated from a Power Plant, "Advances in Technology of Materials and Materials Processing," 6[2] (2004) 260-263. DOI: 10.2240 / azojomo0135].

[0014] HOFA is also known to be used as a raw material for the preparation of activated carbon [S. Salehin, et al. Activated carbon from residual oil fly ash for heavy metals removal from aqueous solution, Desalination and Water Treatment 57 (2016) 278-287, doi:10.1080 / 19443994.2015.1006824, MARabah et al. Preparation of valuable products from cleaned carbon of fuel ash, AIMS Materials Science, 4 (5), 2017, 1186-1201, doi:10.3934 / matersci.2017.5.1186].

[0015] The use of fly ash derived from the combustion of heavy fuel oil as an asphalt additive is also known [WO 2012 / 061371 A1, Utilization of heavy oil fly ash to improve asphalt binder and asphalt concrete performance], but for this purpose only ash containing more than 90% carbon and therefore small amounts of water- or acid-soluble components is used.

[0016] WO 2017 / 182043 also discloses composites based on a matrix of thermoplastic polymers such as polyvinyl chloride, polyethylene or polypropylene, and the filler is ash derived from the combustion of oil shale, however this type of ash is more similar in nature to ash derived from coal combustion due to the high content of mineral fractions derived from shale rock.

[0017] The production of thermoplastic polymer composites with inorganic fillers in the form of powder, especially ash, is generally known and currently used on a large scale. The loading of polymeric materials with inorganic fillers improves the properties of the products, primarily by reducing the deleterious effects of thermal, post-reaction, or post-crystallization shrinkage of the products during their manufacture using various processing techniques, and by reducing the cost of the plastic products. The principles of closed-loop economics and economic considerations make fly ash obtained from the combustion of coal and lignite an interesting material. Such ash is characterized by very high contents of silicon, aluminum, iron, and calcium. Furthermore, metals such as Cr, Co, Ni, Cu, Zn, Cd, and Pb are also present in relatively small amounts [K. Galos, A. Uliasz-Bochenczyk, "Zrodla i uzytkowanie popiolow lotnych ze spalania wegli w Polsce" Gospodarka Surowcami Mineralnymi, vol. 21 2005 no. 1, 23-42; T. Ratajczak et al. “Charakterystyka popiolow lotnych ze spalania niektorych wegli kamiennych i brunatnych”, Polskie Towarzystwo Mineralogiczne-Prace Specjalne no. 13, 1999].

[0018] The use of this type of fly ash in composites is known [D. Czarnecka-Komorowska, M. Szostak, N. Kujawa Popioly lotne sa znane jako napelniacze tworzyw sztucznych Inz.Ap.Chem.2010,49,5,31-32, WO 2012083972 (A1) Composite of polymeric material with mineral fillers, Polish Patent Application No. 398503, Sposob otrzymywania masy tworzywa kompozytowego z termoplastycznych tworzyw sztucznych i popiolow lotnych,powstalych w wyniku spalania wegli w jednostkach energetycznych]. Summary of the Invention

[0019] The essence of the present invention is a process for the utilization of fly ash from the combustion of petroleum-derived products, comprising the extraction of water-soluble or acid-soluble components using water and / or acid, characterized in that water is added to fly ash from the combustion of heavy fractions of petroleum in a ratio of 1:3 to 1:5 and at a temperature of 15°C to 80°C, preferably 20°C to 40°C, followed by mixing and optionally adding a solution of sulfuric acid (VI) or sulfuric acid (IV) to produce a strongly acidic solution with a pH below 2, preferably 0.5 to 1.5, followed by separating the resulting solution from undissolved precipitates using known methods, preferably by filtration or centrifugation, followed by the addition of an aqueous solution of a strong oxidizing agent, preferably a 20 to 30% aqueous solution of hydrogen peroxide, and maintaining the mixture at a temperature of 70°C to 90°C, preferably 80°C to 85°C, for 0.5 to 5 hours, preferably 1 to 2 hours, thereby precipitating vanadium compounds from the purified solution. Here, other metals that form insoluble hydroxides, in particular nickel, iron, and aluminum, are precipitated from the solution remaining after the precipitation of vanadium by increasing the pH of the solution to 9.0-11.0, preferably 10.5, using alkaline hydroxides, followed by filtering the precipitate obtained under alkaline conditions and precipitating the sulfate from the filtrate obtained in the form of calcium sulfate using a soluble calcium compound. The precipitate separated from the solution after extraction of the combustion gases considered in the first step is then washed with water until the electrolytic conductivity of the filtrate is below 1 mS, followed by drying the precipitate in solid form.

[0020] In the first step of the process of the present invention, the water-soluble and acid-soluble components are leached / extracted. Valuable components such as vanadium and nickel, as well as sulfate in the form of gypsum, are extracted from the resulting solution in subsequent steps, and the residue after leaching / extraction is used as a pigment and / or filler in composites with thermoplastic polymers such as polyethylene (PE) or polypropylene (PP). The use of fly ash in composites of this type is known, but this mainly concerns ashes derived from the combustion of coal or lignite containing mineral components [D. Czarnecka-Komorowska, M. Szostak, N. Kujawa "Composite of polymeric material with mineral fillers", Inz.Ap.Chem.2010,49,5,31-32, WO 2012083972(A1) Composite of polymeric material with mineral fillers, Polish Patent Application No. 398503, Sposob otrzymywania masy tworzywa kompozytowego z termoplastycznych tworzyw sztucznych i popiolow lotnych,powstalych w wyniku spalania wegli w jednostkach energetycznych].

[0021] In the method of the present invention, fly ash (HOFA) produced after combustion of heavy crude oil fractions, in particular heavy fuel oil, or petroleum-derived products in the form of oil distillation residues, has a carbon content (loss on ignition) ranging from about 40% to more than 90%, mineral components mainly silicon compounds, iron, aluminum, sulfur, and heavy metals, mainly vanadium, nickel, or molybdenum, and water- and acid-soluble components accounting for 20 to 60%, is separated by water leaching into a water- and acid-insoluble fraction and a solution containing dissolved compounds.

[0022] Heavy metals, primarily vanadium and nickel, and sulfate in the form of calcium sulfate are selectively separated from the solution, and the solution remaining after separation of the precipitate is purified using membranes and nanofiltration. The purified water is returned to the process as wash water, thus substantially eliminating the generation of waste liquids.

[0023] The subject of the present invention is also a method for utilizing fly ash from the combustion of heavy fractions of crude oil, comprising the step of preparing a carbon-containing filler, in particular for thermoplastics, by adding water to fly ash from the combustion of heavy fractions of crude oil in a ratio of 1:3 to 1:5 and at a temperature of 15°C to 80°C, preferably 20°C to 40°C, mixing it until it becomes a strongly acidic solution with a pH of less than 2, preferably 0.5 to 1.5, optionally adding a solution of sulfuric acid (VI) or sulfuric acid (IV), and then separating the resulting solution from the undissolved precipitate using known methods, preferably by filtration or centrifugation. The resulting precipitate is washed with water until the electrolytic conductivity of the filtrate is below 1 mS, and then the precipitate is dried to a solid form.

[0024] The essence of the present invention is a powder having a particle size of 10-120 μm, mainly 30-80 μm, containing 50-80%, mostly 70-75%, of carbon, with other components being mainly silicon, iron, aluminum, and sulfur compounds, and having a particle size of 6-15 μm. 2 The present invention relates to a carbon-containing filler, particularly for thermoplastic materials, in the form of a black powder, which comprises spherical porous particles having a specific surface area of more than 1000 nm / g and is derived from fly ash from the combustion of heavy oil fractions after separation of acid-soluble metals and sulfur compounds.

[0025] The thermoplastic polyolefin polymer composite contains a filler used in an amount of 0.5 to 50% by weight based on the polymer matrix.

[0026] A method for utilizing fly ash derived from the combustion of petroleum-derived products, comprising recovering metals, particularly vanadium, from fly ash derived from the combustion of a heavy fraction of petroleum-derived products, comprising adding water to fly ash derived from the combustion of a heavy fraction of crude oil in a ratio of 1:3 to 1:5 at a temperature of 15°C to 80°C, preferably 20°C to 40°C, mixing the mixture to form a strongly acidic solution having a pH of less than 2, preferably 0.5 to 1.5, optionally adding a solution of sulfuric acid (VI) or sulfuric acid (IV), followed by separating the resulting solution from undissolved precipitates using known methods, preferably by filtration or centrifugation. Vanadium compounds are then precipitated from the purified solution by adding an aqueous solution of a strong oxidizing agent, preferably a 20-30% aqueous solution of hydrogen peroxide, and maintaining the mixture at a temperature of 70°C to 90°C, preferably 80°C to 85°C, for 0.5 to 5 hours, preferably 1 to 2 hours.

[0027] Other metals that form insoluble hydroxides, particularly nickel, iron, and aluminum, are precipitated from the solution remaining after removal of the vanadium compounds by using alkaline hydroxides to increase the pH of the solution to 9.0-11.0, preferably 10.5. The precipitate obtained under alkaline conditions is filtered off, and sulfate in the form of calcium sulfate is precipitated from the resulting filtrate using a soluble calcium compound.

[0028] Preferably, once the calcium sulfate precipitate has been removed, the filtrate is purified using membrane and nanofiltration techniques to obtain a concentrate in the form of pure water and brine that is returned to the process. [Problem to be solved by the invention]

[0029] The main limitations of this method include the problematic utilization of large amounts of waste liquid and sludge generated after the extraction / leaching process, and the need to use large amounts of chemicals to selectively precipitate solution components. [Means for solving the problem]

[0030] Surprisingly, it has been found that fly ash derived from the combustion of heavy crude oil fractions, particularly heavy fuel oil and oil distillation residues, can be substantially completely recycled in several processing steps. Furthermore, it has been found that under suitable conditions it is possible to recover substantially all of the vanadium dissolved in water and selectively other ash components with little additional chemical use and reduced waste production.

[0031] Surprisingly, it has been found that fly ash produced after the combustion of heavy crude oil fractions, in particular heavy fuel oil, or petroleum-derived products in the form of oil distillation residues, and having a loss on ignition ranging from about 40% to more than 90%, and whose mineral components are mainly silicon compounds, iron, aluminum, sulfur, and heavy metals, mainly vanadium, nickel, molybdenum, or zinc, can be used as a filler and pigment for composites based on thermoplastic polyolefins, such as polyethylene, polypropylene, and recycled versions thereof, after leaching of the acid-soluble heavy metal compounds.

[0032] The residue remaining after leaching of the water and acid soluble compounds in the form of a free-flowing black powder has a particle size of about 10-120 μm, mainly 30-80 μm, and a minimum of 6-15 μm. 2 / g, and contains spherical porous particles mainly containing more than 70-75% carbon, as well as components such as silicon, iron, and aluminum, whose standard water extract has an electrolytic conductivity (S:L ratio = 1:10) of less than 1.0 mS, and can be used as a filler for composites based on thermoplastic polyolefins such as polyethylene, polypropylene, or recycled products thereof.

[0033] According to the present invention, it has been found that composites with very good mechanical and processing properties can be obtained using fillers derived from fly ash (HOFA) generated by the combustion of heavy petroleum-derived fractions, particularly petroleum-derived products in the form of heavy fuel oil or crude oil distillation residues, which have a loss on ignition ranging from about 40% to more than 90%, contain 50-80% carbon, and whose mineral components are mainly compounds of silicon, iron, aluminum, sulfur, and heavy metals, mainly vanadium, nickel, molybdenum, or zinc, after leaching of the soluble compounds in a highly acidic environment.

[0034] Advantageous Effects of the Invention The present invention allows the recovery and further use of all fly ash components generated in power plants during the combustion of heavy fractions of petroleum-derived products, in particular heavy fuel oils or oil distillation residues.

[0035] Heavy metals from HOFA are leached primarily using water, which forms a strongly acidic solution (having a pH less than 1) with sulfur compounds, particularly SO2. Under these conditions, through repeated leaching, all acid-soluble components are removed. Elemental analysis shows that the post-leaching residue, which is the filler of the present invention, contains primarily carbon: greater than 70% to 75%, while XRF analysis also reveals the presence of silicon, iron, and aluminum. The resulting precipitate is hydrophilic, unlike carbon black-type fillers.

[0036] Studies have shown that the resulting material has very good properties as an active-enhancing filler in polyolefin composites. It also has very good coloring properties as a black pigment. Even at a content of 1% in the composite, the intensity of the black color is comparable to that of composites containing 30% filler, regardless of whether pure polymer or colored reclaim is used.

[0037] The preparation of polyolefin and filler composites according to the present invention involves mixing the filler in an amount of 0.5 to 50% by weight relative to the polymer matrix with the polyolefin in a suitable ratio, and processing into the final product using known methods.

[0038] The resulting composites, regardless of matrix type, showed an increase in Young's modulus values with increasing filler content, and for polyethylene matrices and PE reclaim, an increase in tensile strength was also found. The composites of the present invention, even those with significant filler percentages of up to 50%, are characterized by parameters at least similar to those of the polymer matrix, while Young's modulus and tensile strength increase by more than 50% compared to unfilled polymers, regardless of the polyolefin matrix used. A reduction in elongation at break was found for all composites tested, while an almost 30% increase in impact strength of notched specimens was found for 20% filled isotactic polypropylene. [Example]

[0039] The invention is illustrated by the following examples.

[0040] Example I 100 g of fresh fly ash, derived from the combustion of a heavy crude oil fraction with a bulk density of approximately 0.36 kg / dcm3 and exhibiting a loss on ignition of over 60% and a content of 5% vanadium, 4% nickel, and 12% iron, was added to 350 mL of demineralized water and vigorously stirred at room temperature for 3 hours. A significant proportion of the ash (over 40%) dissolved, and the pH of the resulting mixture stabilized at 0.8. The mixture was then filtered, and the remaining precipitate was washed. The solutions from the initial filtration and the precipitate washing were collected separately. After washing, the precipitate can be used as a filler in composites with thermoplastic polyolefin materials. The solution from the initial filtration (without washing the precipitate with water) was used to separate acid-soluble compounds in a subsequent step, while the filtrate from the precipitate washing was used instead of demineralized water to process the next batch of raw ash.

[0041] Example II Approximately 0.45 kg / dcm containing approximately 10% vanadium, 4% nickel, 6% iron, 13% sulfur, and small amounts of aluminum, magnesium, and zinc. 3To 100 g of fly ash derived from the combustion of a heavy crude oil fraction having a bulk density of 1000 kJ / L, 350 mL of demineralized water was added and vigorously stirred for 1 hour at a temperature of about 60° C. A significant proportion of the ash (about 60%) dissolved, and the pH of the resulting mixture stabilized at a pH of about 3.5 and was then lowered to pH 1.5 by adding a solution of sulfuric acid (VI) or sulfuric acid (IV). The further procedure was the same as in Example I.

[0042] Example III To the solution from the first filtration of the mixture of Example I, containing about 44 g / L of dissolved vanadium, 60 mL of 20% aqueous hydrogen peroxide was added, then heated to a temperature of about 70° C. and maintained at this temperature for 2 hours. A brownish-black precipitate containing vanadium in the form of oxide, mainly iron compounds, with a small impurity content of less than 2% was precipitated. The precipitate, which was the raw material used to obtain the pure vanadium compound, was separated from the solution by filtration.

[0043] Example IV The procedure for the solution from Example II was the same as in Example III, with the addition of 35 mL of 30% hydrogen peroxide solution and heating for 1 hour at a temperature of about 85° C. As in Example III, a brownish-black precipitate was precipitated containing vanadium in the form of an oxide with small amounts of impurities.

[0044] Example V Following separation of the vanadium compounds, caustic soda solution was added to the filtrate of Example III to obtain a pH of about 10.5 to precipitate the remaining alkali-insoluble metals, primarily nickel, iron, and aluminum, and the resulting mixture was filtered. The filtered precipitate, containing a large amount of nickel, is the raw material used to obtain nickel compounds, while the filtered solution, containing a large amount of sulfates, is the raw material used to obtain calcium sulfate (gypsum plaster).

[0045] Example VI A solution of calcium chloride was added to the filtered solution of Example IV in an amount sufficient to completely precipitate the sulfate in the form of calcium sulfate. After filtration, the resulting precipitate is the raw material used to obtain gypsum plaster. The resulting filtrate was purified using membrane and nanofiltration methods to obtain clean water and brine concentrate that was returned to the process, thus substantially eliminating the generation of waste liquid.

[0046] Example VII The washed precipitate from Example I is dried to a solid mass. The resulting free-flowing black powder has a particle size of about 10-120 μm, mainly 30-80 μm, and a mass of 6-15 μm. 2 The powder contained spherical porous particles with a specific surface area of 1.0 mS / g and was subjected to physicochemical analysis. The electrolytic conductivity of the standard aqueous extract (S:L ratio = 1:10) was below 1.0 mS. Elemental analysis showed that the powder mainly contained >70-75% carbon, while XRF analysis also revealed the presence of silicon, iron, and aluminum. The resulting precipitate exhibited hydrophilic properties.

[0047] Example VIII For the precipitate of Example II, the procedure was the same as in Example VII. The resulting product had similar properties to the product of Example VII.

[0048] Example IX The precipitate from Example I was dried at a temperature of 80° C. for 12 hours and subsequently mixed in various proportions with pellets of polyolefin thermoplastic polymers: Tatren HT3 06 polypropylene from Slovnaft, Malen E FABS 23-D022 polyethylene from Basell Orlen Polyolefins, and recycled polyethylene. The names and characteristics of the resulting composites are summarized in Table 1.

[0049] [Table 1]

[0050] Example X The mixture obtained in Example IX was placed in the hopper of an ENGELES 80 / 20HLS injection molding machine and subjected to the injection process under the following conditions: injection speed: 30 mm / s, cooling time: 35 seconds, packing pressure: 30 MPa, packing time: 7 seconds, nozzle temperature: 220 ° C, mold temperature: 35 ° C. The pellets were used to form dumbbell-shaped molded parts according to the PN-68 / C-89034 standard, which were subjected to mechanical tests: static tensile test (according to the PN-EN ISO527:2012 standard) and Charpy impact test of notched specimens (according to the PN-EN ISO179-1:2010 standard). The results obtained are summarized in Table 2.

[0051] [Table 2]

[0052] The water absorption of the resulting composite was also tested. Despite the hydrophilic nature of the filler, the increase in water absorption of the resulting composite was small, less than 0.5% after 90 days, and therefore not substantially greater than that of the pure polymer.

[0053] The black intensity of the resulting composites was compared, and even though the filler content of Example III in the composite was 1%, the black intensity was comparable to that of the composite containing 30% filler, regardless of whether pure polymer or colored reclaim was used.

[0054] Despite the hydrophilic nature of the filler, the increase in water absorption of the resulting composite was small, less than 0.5% after 90 days. [Industrial Applicability]

[0055] The precipitated vanadium oxide can be the final product or can be used, for example in the form of the ammonium salt, as a raw material to obtain pure vanadium compounds.

[0056] The undissolved precipitate obtained after the first filtration can be used as a filler or pigment in composites with polyolefin thermoplastic polymers (PE, PP).

[0057] The composites obtained are characterized by a deep black color already at a filler content of 1% in the composite, regardless of whether pure polymer or colored regenerant was used.

[0058] Furthermore, DSC studies showed that composites in which fillers obtained from fly ash derived from the combustion of petroleum-derived products were used increased the crystallization temperature of the composites by several degrees, which increased the range of processing parameters.

Claims

1. 1. A method for the utilization of fly ash derived from the combustion of petroleum-derived products, comprising the step of preparing a carbon-containing filler, in particular for thermoplastics, characterized in that water is added to fly ash derived from the combustion of a heavy fraction of crude oil in a ratio of 1:3 to 1:5 and at a temperature of 15°C to 80°C, preferably 20°C to 40°C, mixing it until it becomes a strongly acidic solution having a pH of less than 2, preferably 0.5 to 1.5, optionally adding a solution of sulfuric acid (VI) or sulfuric acid (IV), subsequently separating the solution obtained from undissolved precipitate using known methods, preferably by filtration or centrifugation, subsequently washing the precipitate obtained with water until the electrolytic conductivity of the filtrate is below 1 mS, and subsequently drying the precipitate in solid form.

2. A carbon-containing filler, particularly for thermoplastics, having a particle size of 10 to 120 μm, mainly 30 to 80 μm, containing 50 to 80%, mostly 70 to 75%, of carbon, with other components being mainly compounds of silicon, iron, aluminum, and sulfur, and having a particle size of 6 to 15 μm. ２ 1. A carbon-containing filler, particularly for thermoplastics, characterized in that it is a black powder comprising porous particles having a specific surface area of more than 1000 nm / g and derived from fly ash from the combustion of heavy oil fractions after separation of acid-soluble metals and sulfur compounds.

3. A thermoplastic polyolefin polymer composite with a filler derived from fly ash, characterized in that the filler according to claim 2 is used in an amount of 0.5 to 50% by weight based on the polymer matrix.

4. 1. A method for the utilization of fly ash derived from the combustion of petroleum-derived products, comprising the recovery of metals, in particular vanadium, from fly ash derived from the combustion of a heavy fraction of petroleum-derived products, comprising leaching the metals in an acidic environment and selectively precipitating the metals from the resulting solution, by adding water to said fly ash derived from the combustion of a heavy fraction of petroleum in a ratio of 1:3 to 1:5 and at a temperature of 15°C to 80°C, preferably 20°C to 40°C, mixing this and optionally adding a solution of sulfuric acid (VI) or sulfuric acid (IV) to produce a strongly acidic solution with a pH below 2, preferably 0.5 to 1.5, followed by separating the solution obtained from the undissolved precipitate using known methods, preferably by filtration or centrifugation, followed by leaching the metals in an acidic environment and selectively precipitating the metals from the resulting solution.

1. A method for utilizing fly ash resulting from the combustion of petroleum-derived products, characterized in that vanadium compounds are precipitated from the purified solution by adding a 20-30% aqueous solution of hydrogen peroxide and maintaining the mixture at a temperature of 70°C to 90°C, preferably 80°C to 85°C, for 0.5 to 5 hours, preferably 1 to 2 hours, while, optionally, other metals which form insoluble hydroxides, in particular nickel, iron and aluminum, are precipitated from the solution remaining after the precipitation of vanadium by using an alkaline hydroxide to increase the pH of the solution to 9.0 to 11.0, preferably 10.5, followed by filtering the precipitate obtained under alkaline conditions and precipitating sulfates from the filtrate obtained in the form of calcium sulfate using a soluble calcium compound.

5. 5. The method according to claim 4, characterized in that the filtrate after the calcium sulfate precipitate has been removed is purified using membrane and nanofiltration methods to obtain concentrates in the form of pure water and brine which are returned to the process.

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