EP2072565A1 - Method for extracting fuel - Google Patents

Abstract

Procedure for production of fuel by degradation of organic material at increased pressure and increased temperature, comprises degrading the organic material, in which at least a part is liquid at reaction temperature, at a temperature of 250-500[deg] C and a pressure of 3-10 MPa, in the presence of a hydrogen donor, a reagent for the transfer of hydrogen and an isomerization catalyst, where the octane number of the degradation product is increased by isomerization.

Description

The present invention relates to a process for recovering fuel from organic material.

Today, the disposal of ever-increasing amounts of organic materials, such as used tires, is increasingly causing significant problems. For example, worldwide used tire volume is estimated at 10 million tons per year; In the medium term, 17 million tonnes per year must be expected (world production of tire rubber in 2002).

Of the approximately 2.3 million tonnes of scrap tires disposed of in Europe in 2002, 42% were incinerated in cement, power and heating plants and 46% stored in landfills. For the remaining 12% or 0.3 million tonnes of used tires, some of which have been exported, the type of disposal is unknown. In the United States, Florida dumped around two million used tires in the 1970s as an "artificial reef". The costly recovery and disposal of these contaminated sites is expected to last until 2030 and cost several million US dollars. Florida is just the tip of the iceberg: even off South Australia, North and South Carolina and Maryland, just to name a few places, used tires were sunk in the sea.

Since 2006, the dumping of used tires in the European Union has been banned. In addition, the emission limits for the combustion of tires have been tightened. The development of alternative methods that enable the ecological utilization of such organic materials is therefore of great importance.

A car tire usually contains various synthetic and natural rubbers, carbon black, textile and steel, as well as additives, such as waxes, oils, pigments or antioxidants. Since tire rubber consists to a large extent of hydrocarbons, it has a high calorific value. These hydrocarbons are present as macromolecules. Rubber compounds to be used, for example, in tire manufacturing are vulcanized with the aid of sulfur compounds and thus made elastic.

In addition to organic constituents and sulfur, the tires typically contain iron and zinc, as well as traces of magnesium, copper, lead, cobalt and other metals. The sulfur and metal compounds result in combustion or pyrolysis to undesirable by-products, which represent a significant environmental impact.

In order to at least partially sensibly utilize used tires, it was attempted to produce fuel therefrom by means of thermal and catalytic processes:

US 4,175,211 discloses a method for treating solid plastic waste. The plastic waste is ground after the removal of insoluble solids, treated with a petroleum derivative and treated at 65-370 ° C. Catalytic cracking at elevated temperature followed by distillation yields gasoline, light and heavy oil.

According to SU 1613455 For example, gum-containing wastes are heated to 290-380 ° C in the presence of 10-80 wt% of a hydrocarbon-containing liquid. The hydrocarbon compound used is a tar derivative not exceeding 2.4-5.9 wt% pyrobitumen. The required low pyrobitumen content can only be achieved by multiply extracting the tar before it is used.

RU 2109770 and RU 2110535 describe a process for producing fuel and chemical raw materials from rubbery wastes. The rubber-containing waste is liquefied at 270-420 ° C and 1-6 MPa in a hydrocarbon solvent and in the presence of a catalyst ("thermofluidizing"). The catalyst used is titanium hydride or a rare earth metal compound. As the hydrocarbon solvent, either alkylbenzenes ( RU 2110535 ) or a waste product from synthetic rubber production ( RU 2109770 ) used.

RU 2167168 describes a process for processing polymeric industrial and household waste for the production of chemical raw materials and fuel. The waste is mixed with alkylbenzene (s) and a metallic catalyst and liquefied at> 270 ° C and a pressure of> 6 MPa. Subsequent distillation delivers the desired products. The volatile substances with a boiling point of ≤ 210 ° C are recycled in a next processing cycle.

RU 2156270 discloses a method for treating gummy industrial and household waste. The gum-containing waste becomes 220-360 ° C and 1-3 MPa of a liquefaction thermocatalytic. in the presence of a hydrogen donor, an initiator and a catalyst. The hydrogen donors are alkylbenzenes, and organic and inorganic iodides as initiators.

RU 2275397 describes a very similar procedure as RU 2156270 in which, in addition to the alkylbenzene, tetralin or gas oil having a boiling point of 230-280 ° C is used as the hydrogen donor.

RU 2272826 discloses a process for treating gum and other organic industrial and household waste for the production of fuels and chemical raw materials. The wastes are subjected to thermocatalytic fluidization at 200-320 ° C and 1-3 MPa in the presence of a hydrogen donor mixture and an organometallic catalyst. The hydrogen donor compound contains alkylbenzenes as well as tetralin or gas oil with a boiling point of 230-280 ° C. The catalyst used are organometallic copper, nickel, cobalt, molybdenum, titanium and / or iron salts.

All of the processes described are economically unsatisfactory because they have a high energy requirement and / or cause high solvent costs. The high energy and solvent requirement is also environmentally undesirable. In addition, it is problematic that sulfur and metal-containing by-products are formed in these processes. And last but not least, the quality of the products is unsatisfactory due to their low octane number.

It is therefore an object of the invention to provide an economically and environmentally more advantageous method of producing fuel from organic materials. In particular, higher quality fuels, a lower Environmental impact and lower production costs can be achieved.

According to the invention, this object is achieved by a method according to claim 1. Further preferred embodiments are claimed in the dependent claims.

In the process of this invention, fuel is recovered by decomposition of organic material at elevated temperature and pressure. In this case, the organic starting material, at least part of which is liquid at the reaction temperature, degraded in the presence of a hydrogen donor, a reagent 'for the transfer of hydrogen and an isomerization catalyst, wherein the octane number of the degradation product is increased by isomerization. The process is carried out at a temperature of 250-500 ° C, preferably at a temperature of 320-420 ° C, and at a pressure of 3-10 MPa, preferably at a pressure of 3-5 MPa.

As the organic starting material in the process according to the invention serve synthetic and natural materials containing or consisting of hydrocarbons. In particular, the method according to the invention serves for the beneficial and energy-saving disposal of such materials. For example, tires of all types, especially scrap tires, tire tubes and other tire components, petroleum distillation products, and materials containing polyethylene, polystyrene, polypropylene, polyisobutylene, neoprene, polyamide, nylon and / or polyester can be used. The Advantages of the method according to the invention basically appear in all of these materials, but will be clarified below in each case on the basis of the utilization of the particularly problematic used tires.

The organic materials used in the fuel recovery process of the present invention must have a low water content. Preferably, the water content of the organic materials 5 5 wt%. If necessary, the organic materials may be dried before use, for example by means of hot air. The heat for heating the air can originate, for example, from the process according to the invention.

It is assumed that in the process according to the invention the molecules of the organic starting material are first degraded in a radical process to shorter, linear alkyl radicals. By transferring hydrogen from a hydrogen donor to the alkyl radicals, the latter are hydrogenated and converted into linear alkanes (n-alkanes). A hydrogen donor is added, preferably even when the organic starting material or a component thereof is a hydrogen donor.

In addition, the process according to the invention is carried out in the presence of a reagent for the transfer of hydrogen. It is believed that the hydrogen is transferred to the alkyl radicals in the form of hydrogen radicals.

For a high quality fuel, a high knock resistance is essential. However, mixtures of linear hydrocarbon compounds have a low Octane number and thus a low knock resistance. In the process according to the invention, the linear alkanes are isomerized in the presence of the isomerization catalyst to branched alkanes (isoalkanes). It is believed that the catalytic isomerization is based on an ionic mechanism. The isomerization significantly increases the octane number of the products. As an example: In the process according to the invention, in the process according to the invention, about 50-60% of isoalkanes (octane number about 80-100) and 40-50% of n-alkanes are formed during the isomerization of pure n-alkanes (octane number 0).

By combining a reagent for transferring hydrogen and an isomerization catalyst, high quality fuels are recovered.

In the process of the invention, a product mixture is recovered in a reactor, which is separated for recovery. The product mixture generally contains various volatile components, for example hydrogen, methane, ethane, ethylene, gasoline, CO ₂ or ammonia, and higher boiling components, for example kerosene or diesel. In addition, depending on the starting materials different solids, for example carbon.

The highly volatile components are present as gas due to the high temperature in the reactor and are derived. After a first cooling stage gas is separated from the gas. The heat from the first cooling stage is returned to the reactor. The components that are gaseous after the first cooling stage are preferably cleaned. The purified gas, which consists to a large extent of hydrogen, methane, ethane and ethylene, becomes burned for heat. The heat that is recovered during combustion is used in particular for adjusting the elevated temperature in the reactor.

After the volatile components have been removed, higher-boiling components and solids remain in the reactor. The solids are separated from the higher boiling components, for example by sedimentation and / or centrifugation.

From the higher-boiling components is obtained by rectification, preferably with steam, kerosene and / or diesel.

The solid content consists mainly of carbon and is used to produce carbon with technical purity. The technical carbon can be used, for example, as a filler in tire manufacturing. Alternatively, the technical carbon may be cleaned before further utilization, for example with gasoline. The purified technical carbon can be used, for example, for the production of carbon fibers.

As isomerization catalyst in the process according to the invention is preferably an organometallic compound of the general formula

(C _n H _m COO) ^- _k M ^{k +}

where n = 10-25, m = 21-51, k = 2-8, and M is a metal selected from the group of B, Al, La, Ti, Zr, Cr, Mo, W, Fe, Ru , Os, Co, Rh, Ir, Ni, Pd, Pt, and Zn.

The isomerization catalyst is prepared by the standard reaction well known to those skilled in the art according to reaction equation (I):

(a * k) C _n H _m COOH + M _a X _k → (C _n H _m COO) ^- _k ⁺ M ^k + k H _a X (I)

Where n = 10-25, m = 21-51, k = 2-8, a = 1-2, M is a metal selected from the group of B, Al, La, Ti, Zr, Cr, Mo, W , Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, and Zn, and X is an anion selected from the group of F, Cl, Br, I, and SO ₄ . The preparation of the isomerization catalyst is usually carried out under anhydrous conditions to prevent hydrolysis of educts and / or products. The metal salt (M _a X _k ) should be chosen so that it is soluble under the reaction conditions in the preparation of the isomerization catalyst.

In contrast to the catalysts used hitherto, the inventive isomerization catalyst completely dissolves under the process conditions. The method is therefore based on homogeneous catalysis.

In a preferred embodiment, the isomerization catalyst is an organometallic compound of the general formula

(C ₁₇ H ₃₅ COO) ^- 3 M ³⁺

where M is a metal selected from the group consisting of B, Al, La, Ti, Zr, Cr, Mo, W, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, and Zn.

In a preferred embodiment, aluminum stearate is used as the isomerization catalyst.

As the reagent for transferring hydrogen, a metallic or organometallic reagent is preferably used. The metal or metal ions contained therein have p, d and / or f orbitals. For example, iron, cobalt, nickel, copper, zinc, aluminum, molybdenum and / or vanadium-containing reagents can be used. It is believed that under the reaction conditions at least partially the free metal is formed from the organometallic reagent.

Preferably, a metallocene and / or oxalate is used as the reagent for the transfer of hydrogen. Typically, the metallocene is used in an amount of 0.5-2.0 wt% and the oxalate in an amount of 0.5-4.0 wt%.

In a preferred embodiment, ferrocene is used as the metallocene. Preferably, the oxalate used is nickel oxalate.

In a preferred embodiment are used as organic materials Mazut, scrap tires, parts thereof, and / or gas oil having a boiling point of 230-340 ° C, preferably 230-280 ° C.

As Mazut (heavy oil) refers to the distillation residue with a boiling point> 340 ° C, which is obtained in the processing of petroleum. It is therefore a "waste product" of the petroleum industry, which must be further processed, for example by cracking. However, Mazut's cracking provides inferior low octane products. The use of mazut in the process according to the invention contains the high-boiling hydrocarbon compounds present converted into high quality high octane fuel. Mazut can be used alone or in combination with other starting materials.

The starting material Mazut also contains such hydrocarbon compounds which can act as hydrogen donors in the process according to the invention. The ingredients of Mazut are at least partially converted to fuel in the course of the process. The portion of mazut that is not converted can be reused as organic feedstock and thus recycled.

Due to Mazut's high sulfur content - up to 5%, depending on its source - Mazut's processing and recycling is problematic: many catalysts used in similar processes are poisoned by sulfur. The use of the isomerization catalyst according to the invention solves this problem. In addition, the utilization according to the invention of Mazut is also environmentally advantageous, since the sulfur is bound by the isomerization catalyst.

If old tires are used, preferably whole tires are used. In addition, when using scrap tires or parts thereof, at least one additional organic material that is liquid at the reaction temperature must be used. The use of scrap tires or parts thereof in the inventive method allows an economically and ecologically beneficial and meaningful recycling of scrap tires, and thus the solution of the associated environmental problem: From a problematic waste material is obtained high quality fuel, and the resulting by-products can be used technically, ecologically and economically meaningful.

The sulfur content of scrap tires is estimated to be about 1-1.5 wt%. Many catalysts used in the prior art processes are poisoned by sulfur. Therefore, materials containing sulfur are usually undesirable as starting materials for catalytic processes. By contrast, the isomerization catalyst used in the process according to the invention retains its catalytic activity even in the presence of sulfur. And not only that: By using the isomerization catalyst in a homogeneous catalysis in the inventive process, most of the sulfur does not enter the volatile phase, which prevents release via exhaust gases.

If waste tires or parts thereof are used in combination with Mazut and / or gas oil, the mass ratio of tires or tire parts to Mazut and / or gas oil is preferably 1: 2 to 1: 4. But it is also conceivable that a larger excess of mazut and / or gas oil is used.

Furthermore, gas oil having a boiling point of 230-340 ° C, preferably 230-280 ° C, alone or in combination with other substances can be used as the organic starting material. The gas oil typically contains cyclic (naphthenes) and acyclic (paraffins) hydrocarbons. The exact composition (proportions and molecular mass of the individual components) varies depending on the origin of the petroleum.

The naphthenes contained in the gas oil can at least partially take over the function of the hydrogen donor in the process according to the invention. At elevated temperature, C-H bonds of naphthenes are homolytically cleaved. The resulting hydrogen radicals are then transferred to the alkyl radicals. Since the C-H dissociation energy in naphthenes is lower than in the alkylbenzenes used hitherto, the cleavage of the C-H bonds can be effected even at a lower temperature. Thereby, the initial temperature, the pressure and the duration of the process can be reduced, which leads to a reduction of the costs.

Preferably, the isomerization catalyst is used at least in an amount that allows the quantitative removal of the sulfur from the organic materials used. For this purpose, the total sulfur content of all starting materials is determined and calculated on the basis of which the amount of catalyst. Preferably, the isomerization catalyst is used in excess compared to the sulfur, for example in an excess of 10-30%, optionally in a larger excess.

In a preferred embodiment, at least one polycyclic hydrocarbon compound is used as the hydrogen donor. Preferably, the polycyclic hydrocarbon compound has both an aromatic and an at least partially saturated ring. In particular, the process according to the invention is carried out in the presence of tetralin as a hydrogen donor, preferably in the presence of 2-10% by weight of tetralin. Tetralin gives off even at temperatures from about 200 ° C radical hydrogen.

This produces naphthalene, which contributes to a better product quality due to its high octane number.

The exact process conditions must be adapted to the starting materials and the desired products. The standard preliminary tests are well known to those skilled in the art.

The invention will be further illustrated by the attached figures.

Fig. 1

eine schematische Darstellung des erfindungsgemässen Verfahrens zur Herstellung von Treibstoff; und

Fig. 2

eine schematische Darstellung eines Verfahrens zur Reinigung von technischem Kohlenstoff.

Show it:

Fig. 1

a schematic representation of the inventive method for the production of fuel; and

Fig. 2

a schematic representation of a method for the purification of technical carbon.

FIG. 1 shows a schematic representation of a method according to the invention. In a reactor 2, fuel is recovered from an organic material, for example scrap tires. To this end, in the presence of reaction temperature-temperature organic materials, for example, Mazut, the tires are hydrogen donor, for example, tetralin, a reagent for transferring hydrogen, for example, ferrocene and / or nickel oxalate, and an isomerization catalyst at a temperature of 320-500 ° C and a pressure of 3-10 MPa implemented.

The readily volatile components are passed via a line 4 in a gaseous state into a first heat exchanger 6. In the heat exchanger 6, they are preferably cooled to room temperature and the resulting condensate 10 is collected in a condensation chamber 8. The condensate 10 is depending on the temperature mainly of gasoline.

The components which are gaseous at room temperature are conducted via a line 12 into a first scrubber 14. In the first scrubber 14, ammonia is removed from the gaseous components by means of dilute sulfuric acid. The freed of ammonia gas stream is passed via a line 16 in a second scrubber 18. In the second scrubber 18, CO _{2 is} removed from the gas stream with the aid of an aqueous calcium hydroxide solution. In addition, traces of hydrogen sulphide are also removed here. The purified gas, which mainly contains hydrogen, methane, ethane and ethylene, is introduced via a line 20 into a combustion furnace 22 where it is burned. The resulting heat 24 is preferably used to heat the reactor 2 and its contents.

The non-gaseous components are discharged via a line 26 from the reactor 2. After cooling in a second heat exchanger 28, solid and liquid components in a device 30 are separated from each other.

The solids are passed via line 32 to a first centrifuge 34 where solid and liquid components are separated in a second stage. The product is technical carbon 36.

The liquid components are passed via a line 38 into a second centrifuge 40 and freed from solid residues. The purified liquid is rectified in one or more rectification columns 42. The fuels kerosene 44 and diesel 46 are won. As a rectification residue remains Mazut 48 back, which can be recycled and in turn can be used as organic starting material in the reactor 2.

FIG. 2 shows purely schematically a method for the purification of technical carbon, which was obtained, for example, in a method according to the invention. The technical carbon is slurried in a container 50 with gasoline, for example obtained as product 10 in a process according to the invention. The carbon-gasoline mixture is cooled in a third heat exchanger 52 and separated into solid and liquid components in a sedimentation vessel 54. The solid components are freed of liquid residues in a third centrifuge 56. The product obtained is purified technical carbon 58, which can be used, for example, for the production of carbon fibers.

The present invention will be further elaborated on the basis of the following examples:

example 1

In a rotating autoclave with a volume of 2 liters, 900 g of Mazut M40 are heated to 400 ° C. for 80 minutes. After cooling and opening the autoclave, the autoclave contains 833 g (92.5%) of liquid. The observed losses (7.5%) can be attributed mainly to gaseous products.

Three fractions are recovered from the liquid by rectification: 7.55% of a first fraction having a boiling point ≤ 180 ° C, 42.07% of a second fraction having a boiling point of 180-340 ° C and 50.38% of a third fraction having a boiling point ≥ 340 ° C ,

The composition of the first fraction is analyzed by HPLC (High Performance Liquid Chromatography) and is summarized in Table 1. Table 1 Composition of the first fraction n-alkanes 28.35% isoalkanes 24.15% naphthenes 20.87% aromatic hydrocarbons 9:42% olefins 12.07%

The calculated octane number of this fraction is 69.7.

Example 2

In a rotating autoclave with a volume of 2 liters, 100 grams of scrap tire pieces and 400 grams of Mazut M40 are heated to 400 ° C for 80 minutes. After cooling and opening the autoclave, 425 g (85.0%) of liquid are in the autoclave.

From the liquid three fractions are obtained by rectification: 12.5% of a first fraction with a boiling temperature ≤ 180 ° C, 48.70% of a second fraction having a boiling point of 180-340 ° C and 38.8% of a third fraction having a boiling point ≥ 340 ° C.

The composition of the first fraction is analyzed by HPLC and is summarized in Table 2. Table 2 Composition of the first fraction n-alkanes 24.52% isoalkanes 25.83% naphthenes 21.75% aromatic hydrocarbons 10:35% olefins 6.63%

The calculated octane number of this fraction is 71.5.

Example 3

In a rotating autoclave with a volume of 2 liters, 100 g scrap tires, 400 g Mazut M40, 5.0 g (0.5 wt% Ni) nickel oxalate and 65 g (0.5 wt% Al) aluminum stearate are heated to 400 ° C for 80 min , After cooling and opening the autoclave are in the autoclave 460 g (80.6%) of liquid.

Three fractions are recovered from the liquid by rectification: 17.91% of a first fraction having a boiling point ≤ 180 ° C, 63.71% of a second fraction having a boiling point of 180-340 ° C and 18.32% of a third fraction having a boiling point ≥ 340 ° C ,

The composition of the first fraction is analyzed by HPLC and is summarized in Table 3. Table 3 Composition of the first fraction n-alkanes 21:22% isoalkanes 27.83% naphthenes 23:45% aromatic hydrocarbons 11.82%

The calculated octane number of this fraction is 88.9.

Example 4

In a rotating autoclave with a volume of 2 liters, 100 g scrap tires, 400 g Mazut M40, 10.0 g (1.0 wt% Ni) nickel oxalate and 130 g (1.0 wt% Al) aluminum stearate are heated to 400 ° C for 80 min , After cooling and opening the autoclave, there are 542 g (84.7%) of liquid in the autoclave.

Three fractions are obtained from the liquid by rectification: 22.5% of a first fraction having a boiling point ≤ 180 ° C, 60.8% of a second fraction having a boiling point of 180-340 ° C and 16.7% of a third fraction having a boiling point ≥ 340 ° C ,

The composition of the first fraction is analyzed by HPLC and is summarized in Table 4.

The calculated octane number of this fraction is 92.1. Table 4 Composition of the first fraction n-alkanes 19:55% isoalkanes 25.60% naphthenes 25.32% aromatic hydrocarbons 13.95% olefins 04.15%

Example 5

In a rotating autoclave with a volume of 2 liters, 100 g of scrap tires, 400 g of Mazut M40 and 13.3 g (1.0 wt% Fe) of ferrocene are heated to 400 ° C for 80 minutes. After cooling and opening the autoclave are in the autoclave 413.2 g (80.5%) liquid.

Three fractions are recovered from the liquid by rectification: 14.2% of a first fraction having a boiling point ≤ 180 ° C, 59.7% of a second fraction having a boiling point of 180-340 ° C and 26.1% of a third fraction having a boiling point ≥ 340 ° C ,

The composition of the first fraction is analyzed by HPLC and is summarized in Table 5. Table 5 Composition of the first fraction n-alkanes 25.83% isoalkanes 21:22% naphthenes 19.80% aromatic hydrocarbons 8:35% olefins 7.73%

The calculated octane number of this fraction is 82.3.

Example 6

In a rotating autoclave with a volume of 2 liters, 100 g of scrap tires, 400 g of Mazut M40, 10.0 g of nickel oxalate and 130 g of aluminum stearate are heated at 400 ° C. for 120 minutes. After cooling and opening the autoclave there are 503 g (78.6%) of liquid in the autoclave.

Three fractions are recovered from the liquid by rectification: 17.55% of a first fraction having a boiling point ≤ 180 ° C, 56.65% of a second fraction having a boiling point of 180-340 ° C and 25.80% of a third fraction having a boiling point ≥ 340 ° C ,

The composition of the first fraction is analyzed by HPLC and is summarized in Table 6. Table 6 Composition of the first fraction n-alkanes 20.93% isoalkanes 24.25% naphthenes 23.91% aromatic hydrocarbons 15:25% olefins 4.83%

The calculated octane number of this fraction is 84.6.

Example 7

In a rotating autoclave with a volume of 2 l, 100 g of scrap tire pieces, 400 g Mazut M40, 10.0 g Nickel oxalate and 130 g of aluminum stearate heated to 380 ° C for 80 min. After cooling and opening the autoclave, there are 544.6 g (85.1%) of liquid in the autoclave.

Three fractions are obtained from the liquid by rectification: 18.75% of a first fraction having a boiling point ≤ 180 ° C, 61.42% of a second fraction having a boiling point of 180-340 ° C and 19.83% of a third fraction having a boiling point ≥ 340 ° C ,

The composition of the first fraction is analyzed by HPLC and is summarized in Table 7. Table 7 Composition of the first fraction n-alkanes 20.93% isoalkanes 23.75% naphthenes 23.90% aromatic hydrocarbons 11.87% olefins 4.75%

The calculated octane number of this fraction is 84.7.

Example 8

In a rotating autoclave having a volume of 2 liters, 100 g of scrap tires, 400 g of gas oil (230-340 ° C fraction), 5.0 g of nickel oxalate and 65.0 g of aluminum stearate are heated to 380 ° C for 80 minutes. After cooling and opening the autoclave are 466.8 g (81.9%) liquid in the autoclave.

Three fractions are recovered from the liquid by rectification: 15.91% of a first fraction having a boiling point ≤ 180 ° C, 68.49% of a second fraction having a boiling point of 180-340 ° C and 15.60% of a third fraction having a boiling point ≥ 340 ° C .

The composition of the first fraction is analyzed by HPLC and is summarized in Table 8. Table 8 Composition of the first fraction n-alkanes 24.30% isoalkanes 24.85% naphthenes 16:53% aromatic hydrocarbons 4.96% olefins 7.35%

The calculated octane number of this fraction is 75.6.

Example 9

In a rotating autoclave having a volume of 2 liters, 100 g of scrap tires, 400 g of gas oil (230-340 ° C fraction) and 5.0 g of nickel oxalate are heated to 400 ° C for 80 minutes. After cooling and opening the autoclave there are 426.7 g (84.5%) of liquid in the autoclave.

From the liquid three fractions are obtained by rectification: 13.42% of a first fraction having a boiling point ≤ 180 ° C, 69.75% of a second fraction having a boiling point of 180-340 ° C and 16.83% of a third fraction with a boiling point ≥ 340 ° C.

The composition of the first fraction is analyzed by HPLC and is summarized in Table 9. Table 9 Composition of the first fraction n-alkanes 25.97% isoalkanes 25.79% naphthenes 18:36% aromatic hydrocarbons 6:35% olefins 7.68%

The calculated octane number of this fraction is 74.1.

Example 10

In a rotating autoclave with a volume of 2 liters 900 g of gas oil (230-340 ° C fraction) are heated to 400 ° C for 80 min. After cooling and opening the autoclave are in the autoclave 812 g (90.2%) of liquid.

From the liquid, three fractions are obtained by rectification: 25.5% of a first fraction having a boiling point ≤ 180 ° C and 64.5% of a second fraction having a boiling point of 180-340 ° C.

The composition of the first fraction is analyzed by HPLC and is summarized in Table 10. Table 10 Composition of the first fraction n-alkanes 14:35% isoalkanes 26.73% naphthenes 18:15% aromatic hydrocarbons 28.35% olefins 17.03%

The calculated octane number of this fraction is 91.6.

Claims (11)

Process for the production of fuel by decomposition of organic material at elevated pressure and elevated temperature, characterized in that the organic material of which at least a part is liquid at reaction temperature, at a temperature of 250-500 ° C and a pressure of 3 to 3 10 MPa is degraded in the presence of a hydrogen donor, a reagent 'for the transfer of hydrogen and an isomerization catalyst, wherein the octane number of the degradation product is increased by isomerization. A method according to claim 1, characterized in that the isomerization catalyst is an organometallic compound of the formula

(C _n H _m COO) ^- _k M ^{k +} ,

where n = 10-25, m = 21-51, k = 2-8 and M is a metal selected from the group of B, Al, La, Ti, Zr, Cr, Mo, W, Fe, Ru, Os , Co, Rh, Ir, Ni, Pd, Pt, and Zn. A method according to claim 2, characterized in that the isomerization catalyst is an organometallic compound of the formula

(C ₁₇ H ₃₅ COO) ^- ₃ M ³⁺ ,

wherein M is a metal selected from the group consisting of B, Al, La, Ti, Zr, Cr, Mo, W, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, and Zn , A method according to claim 3, characterized in that is used as the isomerization catalyst aluminum stearate. Method according to one of the preceding claims, characterized in that a metallic or organometallic reagent for the transfer of hydrogen is used. Method according to one of the preceding claims, characterized in that a metallocene and / or an oxalate is used as the reagent for the transfer of hydrogen. A method according to claim 6, characterized in that is used as the metallocene ferrocene. A method according to claim 6 or 7, characterized in that is used as the oxalate nickel oxalate. Method according to one of the preceding claims, characterized in that as an organic material Mazut, used tires, parts thereof and / or gas oil having a boiling temperature of 230-280 ° C is used. Method according to one of the preceding claims, characterized in that the isomerization catalyst is used at least in an amount which allows the quantitative removal of the sulfur from the materials used. Method according to one of the preceding claims, characterized in that as a hydrogen donor at least one polycyclic hydrocarbon compound having both an aromatic and an at least partially saturated ring, in particular tetralin, is used.

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