Fuel processing method

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: invention, in particular, relates to removing at least some trace impurities from liquid hydrocarbon fuels and to a method for clearing gasoline hydrocarbon fuel. Invention especially concerns those impurities selected from inanes, naphthalenes, phenantrenes, pyrene, alkylbenzenes, and mixtures thereof. At least a part of liquid hydrocarbon fuel, which is gasoline, is brought into contact with decolorizing activated carbon according to method disclosed in the present application. Employment of resulting gasoline in spark-ignition engines or at least in one zone in engine intake system is also described.

EFFECT: reduced formation of deposits in engines.

18 cl, 1 dwg, 2 tbl, 2 ex

 

The present invention relates to a method of fuel treatment, in particular to a method of bleaching a gasoline hydrocarbon fuel.

Hydrocarbon fuel, a common source of which is crude oil, used for many purposes, such as transport fuels, to generate electricity, for heating and lighting. The products that are available in the simple distillation of crude oil, as a rule, subjected to further processing with the purpose of obtaining materials of satisfactory quality for delivery to the market. Examples of such methods include (a) cracking and hydrocracking of high-boiling materials to low-boiling products, b) reforming and isomerization to ensure improved Flammability and C) the alkylation/polymerization for the conversion of gases in liquids.

In addition to these standard methods there are several methods for improving product quality by removing or turning impurities, for example g) Hydrotreating to remove serosoderjaschei substances, d) Merox and deodorizing the desulfurization using copper chloride to convert/remove serosoderjaschei substances and e) processing the clay to remove surface-active substances.

Thanks to the application of modern methods of processing and purification receive the products of acceptable quality for delivery to the market. However, the convey these products are obtained from natural source they often remain or are formed due to post-processing trace amounts of colored substances that report finished product yellow/green or another color. Such staining can affect the acceptance of the product on the market as a high quality material or cause difficulties in cases where in order to inform specific colour or to collect the appropriate fees, you must add the dyes.

Known to produce transparent as water, gasoline by distillation to remove high-boiling telling colouring compounds.

Discoloration asfaltobetonnyh solutions described Ken-ichi Yamamoto and others in CA 32:a and CA 32:s. While using a variety of absorbents, including activated carbon. In SA 25:2840 also described decolorizing ability acidic clay. Discoloration of kerosene, gasoline and petroleum distillates using clay described in CA-23:a. In SA 39:36592describes the removal of tetraethyl lead and coloring substances from leaded gasoline with the use of hydrated silicate A1. The use of activated clay was also described in CA 39:4470h. In SA 22:a described bleaching and deodorizing the cracking of gasoline chlorsulfuron aluminum. In JP 6136370 described bleaching light oil introducing them into account is t with activated charcoal.

Developed a new and simple commercial process for the removal of trace quantities of gasoline coloring substances.

In accordance with this invention proposes a method of bleaching liquid hydrocarbon fuel, which is a gas, and this method includes the introduction of at least part of the liquid gasoline into contact with decolorizing charcoal.

It was found that the introduction of gasoline into contact with decolorizing charcoal helps to remove at least some of the trace impurities selected from a range that includes indāni, naphthalenes, phenanthrenes, pyrene, alkyl benzenes and mixtures thereof.

Thus, in accordance with another object of the present invention proposes a method of removal from liquid hydrocarbon fuels, mainly gasoline, at least some of the content of trace quantities of impurities selected from a range that includes indāni, naphthalenes, phenanthrenes, pyrene, alkyl benzenes and mixtures thereof, and this method includes the introduction of at least part of the liquid hydrocarbon fuel, mostly gasoline, in contact with decolorizing charcoal. This fuel may be diesel fuel or preferably gasoline. When the fuel is a diesel fuel, this fuel can be used to power a diesel engine, lubog the type for example, automotive diesel engine or a marine diesel engine. When the fuel is a gas, this fuel can be gasoline or aviation gasoline for use in any engine with spark ignition. Fuel may be kerosene for use in aviation gas-turbine engine as fuel for jet engines or for use in ground-based gas turbine engine. Alternatively kerosene can be used for heating or lighting, and transparent product may include a dye, is introduced to differentiate itself.

It was found that when the present invention receives gasoline product, which in comparison with the untreated gasoline in the intake forms in less engine deposits. Thus, in particular, when the consumption of such gasoline product forms in the combustion chamber unexpectedly significantly reduced the amount of sediment. Finally, in one experiment the amount of sediment was decreased, as was established, to levels that were lower than achieved using well-known detergent additives to gasoline. Moreover, when the use of such gasoline product forms fewer deposits in the intake manifold. The use of these benefits can the t to decrease or even eliminate the need for consumption of detergent additives to gasoline.

Thus, in accordance with another variant of implementation of the present invention features the use of engine with a spark ignition gasoline in accordance with the present invention to reduce the amount of deposits in the engine, it is preferable to reduce the engine the amount of sediment formed on at least one site selected from the group comprising an intake system of the engine, the intake valves of the engine, the combustion engine and the exhaust system of the engine.

In addition, the present invention proposes a method of reducing deposits in the engine that includes a combustion engine with spark ignition gasoline obtained by the method in accordance with the present invention, preferably which reduced the amount of sediment formed on at least one site selected from the group comprising an intake system of the engine, the intake valves of the engine, the combustion engine and the exhaust system of the engine.

It was found that the use of gasoline according to the present invention reduces, in particular, the amount of deposits formed in the combustion chamber of the engine. Thus, in a preferred embodiment, the gasoline according to the present invention can be used in gasoline d is a " direct injection fuel in which it is injected directly into the combustion chamber.

The implementation of the present invention can also reduce the sulphur content in liquid gasoline that can contribute to the achievement of very low sulfur content in the gasoline product.

The present invention also offers a method of obtaining transparent as water, gasoline, without the need for distillation to remove high-boiling telling colouring compounds.

In a preferred embodiment, liquid fuel (gasoline) is passed through the carbon filter bed to remove trace of coloring substances. However, it is also possible introduction of particles decolorizing charcoal fuel (gasoline) and subsequent removal of these particles from the fuel (gasoline) after processing. For the preparation of decolorizing charcoal used in the present invention can be applied to any source of coal. However, the preferred coal obtained from wood, coke or coal. Such coal can be activated, for example, by treatment with an acid, alkali or water vapor. Suitable decolorizing carbons are described in Kirk-Othmer Encyclopedia of Chemical Thechnology, edition 3, volume 4, S. 562 - 569. Preferred decolorizing carbons can be obtained from Norit, General Filtration, CPL Carbon Link and Fengroup.

Fuel (gasoline) can be obtained from crude oil. So, for example, gasoline may be used as disti let crude oil. In a preferred embodiment, the fuel or gasoline is a distillate of crude oil, which is processed by one or more of the following processing stages: (a) cracking and/or, b) reforming and isomerization, and b) alkylation/polymerization. The distillate of crude oil can be processed to improve the quality of the product removal or transformation of contaminants. Such processing stages include d) Hydrotreating to remove serosoderjaschei substances, d) Merox and deodorizing the desulfurization using copper chloride to convert/remove serosoderjaschei substances and e) processing the clay to remove surface-active substances. In addition, the fuel (gasoline) may also include components that are generated by other sources, such as chemical processes for the production of aromatic compounds, ethers or material derivatizing from biomass, such as ethanol and methanol.

In a preferred embodiment, the fuel (gasoline) includes at least one paraffin fraction of crude oil or derivatizing from crude oil. Fuel (gasoline) may include at least 20 vol.%, more preferably at least 40 vol.%, this paraffin fraction. Paraffin fraction, typically includes at least one saturated aliphatic hydrocarbon containing from 4 to 20 operon the x atoms. In a preferred embodiment, the aliphatic hydrocarbon comprises from 4 to 12 carbon atoms. Such aliphatic hydrocarbons can be linear or branched. Acceptable linear hydrocarbons include n-butane, n-pentane, n-hexane, n-heptane, n-octane, n-nonan, n-decane, n-undecane and n-dodecane. Suitable hydrocarbons with branched chains include alkanes containing 4 to 8 carbon atoms each having in its alkyl chain at least one lateral group (for example, 2 or 3 side groups). Examples of acceptable branched alkanes include isobutane, isoheptane, isohexane and isooctane.

Fuel (gasoline) may also include at least one olefin. However, in the preferred embodiment, the olefin content of the fuel (gasoline) is less than 20 vol.%, more preferably less than 10 vol.%. When the fuel (gasoline) is the olefin, the olefin may be alkene containing from 5 to 10, for example from 6 to 8, carbon atoms. Such alkenes can be linear or branched. Suitable examples include penten, isopentene, hexene, isohexane, hapten, 2-methylpentan and their mixture. Such alkenes can be obtained by any acceptable method known in the art, such as catalytic or thermal cracking residue from the refining of crude oil.

Fuel petrol) may also include aromatic substances. However, in the preferred embodiment, the aromatic component content in the fuel (gasoline) is less than 50 vol.%, more preferably less than 35 vol.%, even more preferably less than 25 vol.%, and most preferably less than 10 vol.%. Acceptable aromatic compounds that may be contained in the fuel, include toluene, o-, m-, p-xylenes and trimethylbenzene. Can also contain a mixture of aromatic compounds. Such mixtures can be derivationally obtained from catalytic reforming or cracking of gasoline, which is prepared, for example, from heavy naphtha. The preferred fuel (gasoline) is almost free from benzene, the content of which is, for example, less than 1%vol.

Fuel (gasoline) may also include at least one oxidation product. Acceptable oxidation products include alcohols and ethers, such as ethanol and dialkyl ethers. In a preferred embodiment, use of asymmetric simple ether. Examples include tert-butyl ether (MTBE), estiltrat-butyl ether and tert-amyl ether. The preferred amount of the oxidation product in the fuel (gasoline) is less than 15%vol.

The preferred final boiling point of the fuel (gasoline) is less than 200°S, more preferably less than 180°With, for example, is within 155 and 15° C.

Preferred sulfur content in the fuel (gasoline) is less than 10 ppm million, more preferably less than 5 ppm million, even more preferably less than 1 part./million, and most preferably less than 0.5 ppm million

Fuel (gasoline) according to the present invention can be characterized octane number determined by the motor method (OCM)at least 82 and road octane number (DAUGHTER), at least 92. The preferred fuel (gasoline) has OCM from 85 to 90 and DAUGHTER from 95 to 100.

Fuel (gasoline) according to the present invention can be characterized by Reid vapor pressure (SIMP) from 30 to 110 kPa, preferably from 30 to 60 kPa.

The density of the fuel (gasoline), may constitute more of 0.60 g/cm3preferably more 0,70 g/cm3more preferably more 0,72 g/cm3. The preferred density of the fuel (gasoline) does not exceed 0,775 g/cm3.

Fuel (gasoline) may be prepared by any suitable method, such as mixing between the respective components. In one embodiment, the fuel (gasoline) is prepared by mixing isoparaffin (alkylate), the product of the hydrocracking and isomerization product. Isoparaffin can be used in such quantity that he is from 20 to 80 vol.%, preferably from 50 to 70 vol.%, for example 60%, ready fuel (gasoline) the composition is. The product of the hydrocracking can be used in such quantity that he is from 5 to 35 vol.%, preferably from 10 to 30 vol.%, for example, 20 vol.%, ready fuel (gasoline) compositions. The isomerization product may be used in such quantity that he is from 10 to 50 vol.%, preferably from 20 to 40 vol.%, for example 30%, ready fuel (gasoline) compositions. This may also require inclusion in the fuel (gasoline) composition of the product of the reforming process and/or large fractions of catalytic cracking gasoline (SFBC). The first can be used in amounts of from 0 to 40 vol.%, for example, 20 vol.%, and the last number from 0 to 30 vol.%, for example, 15%vol.

Part of the fuel (gasoline) may be processed in accordance with the present invention separate or combined with the introduction of one or more components that make up the fuel (gasoline), in contact with the coal prior to their combination with obtaining the fuel (gasoline). Alternatively, the fuel (gasoline), including one or more components that can be processed entirely.

Such fuel (gasoline) may be a gasoline or aviation gasoline for use in any engine with spark ignition.

Fuel (gasoline) may include conventional additives, such as detergents Pris the DKI fuel. An example of a detergent additive is PIB-amine washing additive. In a preferred embodiment, at least some of the additive remains in the fuel (gasoline) or it is added to gasoline after treatment according to the present invention. In a preferred embodiment, the gasoline, prepared according to the present invention practically does not contain detergent additives to gasoline.

Before treatment according to the method according to the present invention, the gasoline may have a nominal value of the color evaluation (yellow/blue) IP (Institute of Petroleum) 17 more than 5 - yellow/more - 5 blue, for example more than 7 - yellow/more than 7 blue. In one embodiment, the gas is characterized by a nominal value of IP 17 9 - yellow 10, blue. After processing according to the present invention, the gasoline may have a nominal value of the color evaluation (yellow/blue) IP 17 less than 5 - yellow/less than 5 blue, for example less than 3 yellow/less 3 blue, less than 1 yellow/less than 1 blue. In one embodiment, after the processing gas is characterized by a nominal value of IP 17 0,7 yellow/less than 0.5 blue. In another embodiment, after the processing gas is characterized by a nominal value of IP 17 0,1 blue. In a preferred embodiment, after processing according to the present invention, the gas becomes transparent, like water (note: 17 IP is the standard the m test Petroleum Institute on the color definition).

In accordance with the method of the present invention evaluation coloring gasoline on Sabato before coming into contact with the coal may be less than 10, and after entering in contact with the coal, it may exceed 20.

These and other objects of the invention hereinafter described with reference to the drawing, which shows a schematic diagram of the installation is acceptable to the exercise of options for performing the present invention.

Figure 1 shows an installation that includes a reservoir 10 for gasoline, the filter unit 12 and control unit 14. The tank 10 for gasoline contains 2500 liters of gasoline. The filter unit 12 consists of 205 litre cylinder, which serves as the casing for the filter layer of granules of activated acid coal (180 kg). The control unit 14 includes an additional filter, which is suitable for removing traces of coal and water.

During the process for pumping gasoline from the tank 10 into the filter unit 12 is applied to the pump 16. The gasoline flows through the filter unit with a flow rate of 1.1 m /h On the way through the layer create and maintain a pressure drop of less than 15 cm of the water column, which is measured using a pressure gauge 18.

When you start the installation using a thermocouple 20 monitor the temperature of the filter unit 12. To ensure the absence of boiling more readily boiling components of gasoline pace is the atur filter unit 12 to be maintained at a level below the threshold, 30°C. However, in case of exceeding this threshold temperature may open the relief valve 24 and safely release all of the excess pressure. After the final filling petrol filter unit 12 is installed in a stationary mode and no further temperature increase does not occur.

After filtration of gasoline is supplied to the control unit 14, which removes all traces captured granulated coal or water. On the way through the control unit 14 creates and maintains the pressure drop is less than 15 cm of the water column, which is measured by the pressure gauge 22.

Next discolored product away from the control unit 14 and is directed into the tank or barrel for storage.

Example 1

In this example, 500 ml of a standard gasoline (with typical green color) was tested in accordance with standard test method 17 Petroleum Institute to define the color (IP 17). During this test a sample map with a number of red, yellow and blue comparative colors. The higher the number, the greater the dyed sample.

Further gas was passed through the filter column length of approximately 20 cm and a diameter of 2 cm with a sintered glass for a delay of the coal. Then, in accordance with IP 17 determines the color of the filtered gasoline. R. the results are presented in the table below.

TestThe base fuel, gasolineBasic fuel after granulated coal
The colouring on IP 179,0 - yellow/10,0 - blue0,7 - yellow/0,5 blue
Detergents, mg/100 ml6843

The test results showed that after the carbon filter, the green color of the sample was almost completely eliminated. Besides, that was unexpected, activated carbon filter was not removed all detergent additive (PIB-amine type), showing a particular affinity for pigmented substances, derivateservlet of fuel.

Example 2

The experiment of example 1 was repeated using acid washed activated carbon.

TestThe base fuel, gasolineBasic fuel after activated carbon
The colouring on IP 179,0 - yellow/10,0 - blue0,1 - blue
Detergents, mg/100 ml6832

Remained only traces of blue paint and re-PIB detergent additive was not completely removed.

Additional experiments

Conducted the following additional experimental the options on the discoloration using a 500-ml flask, equipped with a fridge, mixer and indicating the temperature of the device. Originally used 150 grams of gasoline together with the portion of different activated carbons from different sources. Cooking in this scale was possible to visually monitor the removal of paint, which had to be carried out before processing the larger quantitative sample. The results are presented in the following table 1.

The color of the original material on Sabato was estimated as +2.

In table 1 the results show that before using the Aldrich coal must be dried at 140°C for 7 hours When the experiment was repeated, after a residence time of only 1 h reached painting, which was assessed by Sabato as +23. The most effective to improve the color of the coal sample is, obviously, Norit SA. When the content of only 0.5% (weight/volume) in gasoline after only 1 h reached the evaluation Saybolt +24. The handling of coal in this class can be somewhat problematic due to the presence of small things.

The next most successful result was to evaluate color +20, which was achieved by using a sample obtained from the company Sutcliffe Speakman, for about the same duration period, but at a lower content of 0.35%(weight/volume) in gasoline. A sample of granulated coal CPL supplied by the company BP Oil, allowed to achieve assessment colouring on Sabato +19 after the duration of the stay 14 h at a flow rate of 0.17% (weight/volume). When I added more coal, no improvement colouring was not achieved. On this basis I believe that already the initial amount of coal was excessive.

You can use a mixture of coal, for example a mixture of samples of coal Sutcliffe Speakman and Norit.

Motor tests

2000 liters of gasoline were divided into two batches of 1000 litres capacity each. 1000 l was introduced into contact with activated carbon to obtain discolored product. 1000 l was not treated and used as the base fuel. This two fuels were compared by the tendency to the formation of deposits in the engine by holding the industry standard test for determining the characteristics of the engine of Mercedes (test ME) using 300 l fuel. The results are presented in table 2.

Recorded data visual assessment of the resulting deposits in the intake system (manifold, inlet, inlet port and the cylinder inlet valve). Fixed a lot of deposits on the intake valve deposits on the cylinder head inlet valve, soluble deposits on the cylinder head intake valve deposits on the working surface and the wear on the valves and in the combustion chamber (cylinder, piston head and the cylinder). In the combustion chamber (piston head and cylinder head) measured the thickness of the deposits.

In table 2 the results show that in the case of discolored gasoline fuel is more clean engine than the base fuel. Thanks to the implementation of the method according to the present invention is not only discoloration fuel, and selective removal of substances which form engine deposits.

Discolored gasoline fuel has the same performance characteristics as the base fuel plus well-known washing additive to gasoline (330 ml/m3conventional additives, such as BASF Keropur 3540 K5), with the additional advantage consisting in reducing the number of deposits (which is very unusual) in the combustion chamber (piston head and cylinder head). Washing additive to gasoline gave a slight additional advantage of already clean, discolored fuel, and in some cases caused the deterioration of sediments (additive that causes the formation of soot in the combustion chamber). Thus, when implementing the method according to the present invention receives gasoline fuel, which inherently forms a little fat, and no longer requires mandatory inclusion detergent additive to gasoline. sushestvennee the method according to the present invention provides such a decrease in the number formed in the combustion chamber deposits, which using conventional detergents it is unattainable.

The results of the thorough determination of sulfur in both fuels showed that the base contained 49 frequent./million of sulfur, whereas gasoline product included 47 frequent./million of sulfur. Thus, the implementation of the method according to the present invention provides for an efficient purification step, which removes sulfur-containing substances. This can be important in meeting the technical requirements of very low sulfur content, when the maximum sulfur content is 10 ppm million, as it provides additional potential 20%reduction in sulfur content.

The spent carbon from the reactor for discoloration was removed and analyzed desorption mass spectroscopy. The results showed that coal was included adsorbed substances such as indāni, naphthalenes, phenanthrenes, pyrene and alkyl benzenes. In the gasoline contained, apparently, only trace amounts of these materials, and the use of coal for their selective removal created the advantages of reduced formation of deposits in the engine.

1. The method of removal from liquid hydrocarbon fuels at least some of the content of trace quantities of impurities selected from a range that includes indāni, naphthalenes, phenanthrenes, pyrene, alkyl Soli and mixtures thereof, where the fuel is gasoline, comprising the introduction of at least part of the liquid hydrocarbon fuel in contact with decolorizing activated carbon.

2. Method of bleaching liquid hydrocarbon fuel, which is a gas, comprising introducing at least part of the liquid gasoline into contact with decolorizing activated carbon.

3. The method according to claim 1 or 2, in which the fuel to reduce sulfur content.

4. The method according to any of the preceding paragraphs, in which the fuel is passed through the carbon filter bed to remove trace of coloring substances.

5. The method according to any of the preceding paragraphs, in which decolourising charcoal is produced from wood, coconut or coal.

6. The method according to any one of claims 1 to 5, in which the gasoline is a gasoline.

7. The method according to any one of claims 1 to 5, in which the gasoline is an aviation gasoline.

8. The method according to any one of claims 1 to 7, in which the density of gasoline does not exceed 0,775 g/m

9. The method according to any one of claims 1 to 8, in which the nominal value of the color evaluation of gasoline standard test Petroleum Institute 17 IP before it is put into contact with the coal is more than 5 yellow/more than 5 blue, and after entering in contact with the coal is less than 5 yellow/less than 5 blue.

10. The method according to any one of claims 1 to 9, in which the assessment of the colour of gasoline on Sabato before coming into contact with the coal is less than 10, and after entering in contact with the coal exceeds 20.

11. Gasoline, prepared according to any one of claims 1 to 10.

12. Gasoline according to claim 11, containing no detergent additive to gasoline.

13. A method of reducing deposits in the engine that includes a combustion engine with spark ignition gasoline, prepared according to the method according to any one of claims 1 to 10.

14. The method according to item 13, in which the gasoline does not contain detergent additives to gasoline.

15. The method according to item 13 or 14, which reduced the amount of sediment produced by an engine and at least one site selected from the group comprising an intake system of the engine, the intake valves of the engine, the combustion engine and the exhaust system of the engine.

16. Application engine with spark ignition gasoline, prepared according to the method according to any one of claims 1 to 10, to reduce deposits in the engine.

17. The application of article 16, where the gasoline does not contain detergent additives to gasoline.

18. The application of article 16, or 17 in the engine for at least one site selected from the group comprising an intake system of the engine, the intake valves of the engine, the combustion engine and the exhaust system of the engine.



 

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3 cl, 2 dwg, 3 ex

FIELD: chemical technology.

SUBSTANCE: method involves filtration of depleted mineral oils through a mixture of Fe3+ oxide and sand taken in the weight ratio sand : Fe3+ oxide = 1:(0.5-1.0). Method provides enhancing degree of purification of depleted mineral oils.

EFFECT: improved method of treatment.

1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention is aimed at solution of environmental problems, namely, at returning waste mineral oils into production and materials recovery. Waste oil is filtered through sulfocationite based on polypropylenepolysterol fibre, then through adsorbent, containing mixture of ash spheres from wastes of coal electric power stations (ash) and wastes of water de-ironing at water intake places, with rate, ensuring time of water staying in zone of contact with adsorbent not less than 1 hour. Mixture of ash spheres from wastes of coal electric power stations (ash) and wastes of water de-ironing at water intake places with ratio of components wt fraction 1:1-2 is subjected to thermal processing within temperature range 180-250°C during 2-6 hours.

EFFECT: increase of degree of waste oil purification and materials recovery.

2 cl, 1 tbl, 11 ex

FIELD: chemistry, technological processes.

SUBSTANCE: composition for hydrocarbon raw material desulfurisation contains metal oxide and activator, in which part of activator is present in form of activator with reduced valency. Method of obtaining composition includes mixing of liquid, zinc-containing compound, material containing silicon oxide, aluminium oxide, drying, burning of dried mixture, introduction of activator, bringing activated mixture into contact with acid, selected from group, including citric acid, tartaric acid and their combinations, with obtaining mixture that has contacted, drying and burning, reduction of burned mixture by means of reducing agent with obtaining of composition, which contains activator with reduced valency, and isolation of said composition.

EFFECT: composition is efficient for application in desulfurisation zone for removal of sulfur from hydrocarbon flow, obtaining desulfurised cracking-benzene or Diesel fuel.

36 cl, 1 dwg, 11 ex

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