Treatment by hydrofining and dewaxing to up jet engine fuel freezing point
FIELD: engines and pumps.
SUBSTANCE: invention relates to production of fuel for jet engines from kerosene stock. Proposed method comprises hydrofining of kerosene stock with freezing point interval of 163-302°C (325-575°F) over hydrofining catalyst under conditions of hydrofining. This allows getting hydrofined kerosene stock. Besides, it includes dewaxing of, in fact, all hydrofined kerosene stock over catalyst including 1-D molecular sieve with ten rings under conditions of dewaxing to get water-dewaxed kerosene stock. Also, it includes fractionating of water-dewaxed kerosene stock to get fuel for jet engines.
EFFECT: higher yield, better properties.
10 cl, 1 dwg, 2 tbl, 1 ex
The technical field
This invention relates to a method of increasing output and improving the properties of jet fuel derived from raw kerosene fraction. More specifically, the raw material oil fraction is subjected to Hydrotreating, and dewaxing to obtain fuel for jet engines having improved properties.
The level of technology
The jet fuel is obtained from the refining of oil. Getting fuel for jet engines can be a simple get fraction from fractionation column for crude oil. Most jet fuel is passed through various stages of processing to ensure compliance with such technical characteristics as pH, content of aromatic compounds, olefins, naphthalene, maximum height mecoptera flame, sulfur and mercaptans, the freezing temperature and chromaticity. The specific processing depends on the cultivar derived fuel for jet engines. Light fuels, corresponding to the first grade of fuel for jet engines, are typically kerosene straight race, obtained from the distillation of crude oil. Higher grades of jet fuel, such as JP-5 and JP-6, contain various additives, such acanthocinini, corrosion inhibitors, dispersing agents, etc. to meet the specific requirements of the final application. Such requirements can be international in scope, since the fuel for jet engines used in the world market.
While the market kerosene as a whole is undergoing a decline since the 1970's, the market for jet fuel in most developing countries. Thus, the majority of refiners in the U.S. are directly above in order to meet the needs of consumers of fuel, including fuel requirements for jet engines. Currently, (2005-2006) the U.S. consumes a little less than 318 million liters (2 million barrels) per day of jet fuel. Most of this volume is produced domestically and only a small number get through imports. Export is also very small and mostly includes fuel, which is filled planes for international flights.
A significant amount of jet fuel derived from petroleum, used for blending with diesel fuel in cold climates. This application can be reduced, because the jet fuel typically contains more sulfur than is allowed by the new standards, providing diesel fuel with full-time the low sulfur content (CCF was made). However, the implementation of the requirements of the standard CCF was made may increase the need for kerosene inside the refinery as raw material components for diesel fuel because it is easier to remove sulfur from fuel than diesel fuel.
The cost of jet fuel has become a serious problem for operators of overhead lines. In General, the price of jet fuel varies approximately as the price of crude oil. Thus, operators of overhead lines feel a significant increase in fuel prices for jet engines.
There is a need to maximize the yield of high-quality jet fuel derived from kerosene. Factors such as sulfur content, flash point, freezing point and the maximum height mecoptera flame, should be considered in light of the changes to the standards that govern the quality of fuel for jet engines.
Description of the invention
Accordingly, provided is a method of obtaining fuel for jet engines from raw kerosene fractions, including:
the hydrotreatment of the feedstock oil fraction in the presence of a Hydrotreating catalyst at Hydrotreating conditions with obtaining hydrotreated feedstock oil fraction;
the dewaxing hydrocodonehere oil fraction in the presence of a catalyst, includes molecular sieve 1-D desyatiletnimi rings, dewaxing conditions with obtaining hydrodehalogenation raw kerosene fraction and
- fractionation hydrodehalogenation raw oil fraction to obtain fuel for jet engines.
Brief description of drawing
1 schematically shows a reaction system for implementing the method according to one embodiment of the invention.
Detailed description of the invention
In one embodiment, the raw materials for this method is a kerosene. Kerosene, for example kerosene straight race, can be obtained from the fractionation column used for the fractionation of crude oil or acceleration of its factions. In another embodiment suitable raw materials may include conventional fuel derived from crude oil, and paraffin hydrocarbons from other oil sources, such as kerosene from hydrocracking. Other kinds of technological raw materials may include paraffin hydrocarbons, either pure or as a component of raw material from synthetic sources of raw materials, such as hydrocarbons using the Fischer-Tropsch and/or hydrocarbons obtained from biocomponent sources, such as a triglyceride oil or fat, including appropriate connections, such as metrov the e esters of fatty acids (MASK), and from the "oil" of algae. For raw materials, including oxygenated hydrocarbons, it is preferable to pre-process raw materials by hydrogenation to remove oxygen and to convert the unsaturated side chain paraffin hydrocarbons. Conversion of paraffin hydrocarbons in jet fuel by hydroisomerization is one of the distinguishing characteristics of this method are described catalytic system.
Suitable raw materials have a temperature range of boiling points from 149 to 343°C (300 to 650°F), preferably from 163 to 316°C (from 325 to 600°F), when carrying out measurements according to ASTM D86 or ASTM D2887. When compared with conventional kerosene increased the upper limit of the temperature range of the boiling helps to maintain the yield of jet fuel, while increased lower limit helps to raise the temperature of the flash. When increasing the upper limit increases the cloud point and freezing point.
Freezing point (crystallization of paraffins) can be a limiting feature in the production of jet fuel. The primary method of control is to reduce the output of tail fractions (excluding molecules of heavy paraffins) and maximizing the output of the front of the fractions (adding solvent to bring Astor heavy molecules tail fractions). Isomerization of paraffins significantly reduces the impact of molecules of heavy paraffins to the freezing point, which allows you to include more of them, which leads to an increase in output of fuel for jet engines. Other commodities, such as diesel fuel or heating oil, are too heavy to meet the performance requirements of jet fuel in relation to evaporation.
Another advantage of this method is that it can expand the output of dual purpose kerosene, i.e. kerosene, which can be used as diesel fuel No. 1 winter mixtures or as fuel for jet engines, depending on market needs.
Raw oil fraction normally contains impurities of sulfur and/or nitrogen, is unacceptable for jet fuel. Accordingly, to obtain a hydrotreated kerosene feedstock kerosene fraction is brought into contact with a Hydrotreating catalyst at conditions effective to remove at least part of the contaminants of sulfur and/or nitrogen. The Hydrotreating catalysts suitable for use in this process are the catalysts containing at least one metal of group 6 (based on the IUPAC Periodic table, group having 1-18) and at least one metal of groups 8-10, including mixtures thereof. Preferred metals include Mi, W, Mo, Co and mixtures thereof. These metals or mixtures of metals are usually present in the form of oxides or sulfides on the native oxide of the refractory metal. This mixture of metals may also be present in the form of a bulk metal catalysts, in which the amount of metal is 30% of the mass. or more, based on the catalyst.
Suitable carrier materials of metal oxides include oxides such as silicon dioxide, aluminum oxide, silicon dioxide-aluminum oxide or titanium dioxide, preferably alumina. The preferred alumina is a porous aluminum oxide, such as gamma - or ETA-alumina. These catalysts typically include metals within the range described above relative to the bulk catalyst, and at least one forming agent. The number of metals to applied catalysts for Hydrotreating, individually or in mixtures, is from 0.5 to 35% of the mass. in the calculation of the catalyst. In the case of the preferred compounds of metals of group 6 or groups 8-10 metals of groups 8-10 present in an amount of from 0.5 to 5% of the mass. in the calculation of the catalyst, and the metals of group 6 are present in an amount of 5 to 30 wt%. The number of metals can be measured using atomic absorption spectroscopy, atomic emission spectrometry with in active coupled plasma or other methods, these ASTM for individual metals. Non-limiting examples of suitable commercially available Hydrotreating catalysts include NEBULA™, KF-840, KF-848, KF-757 and DN-200. Preferred catalysts have low acidity, while catalysts with high metal content include KF-848 and NEBULA™.
Upon contact with a Hydrotreating catalyst in the feedstock oil fraction reduced content of nitrogen and/or sulfur. The nitrogen content in the raw material is usually reduced to 10 mass. parts per million, preferably up to 5 wt. parts per million or less. The sulphur content in the raw material is usually reduced to 500 mass. parts per million, preferably up to 300 mass. parts per million or less.
The Hydrotreating conditions include a temperature of from 240 to 400°C., preferably from 300 to 380°C., at a pressure of from 1480 to 20786 kPa (200 to 3000 psig), preferably from 2859 to 13891 kPa (400 to 2000 psig); hourly space velocity of the liquid is from 0.1 to 10 h-1preferably from 0.1 to 5 h-1and consumption of hydrogen gas for processing from 18 to 890 m3/m3(from 100 to 5000 cubic feet (N.U.)/bbl), preferably from 44 to 178 m3/m3(from 250 to 1000 cubic feet (N.U.)/barrel).
Hydrotreating is typically reduces impurities of nitrogen and sulfur in the raw material oil fraction by transformation of these pollutants into ammonia and hydrogen sulfide to the corresponding the no. These gaseous contaminants can preferably be separated from the hydrotreated kerosene using conventional techniques and equipment, such as a Stripping apparatus, vybavenie drums etc. Alternative, the entire flow of the gas and the liquid emerging from the Hydrotreating can be sent to the next stage. Preferred to enter in existing reactors, which have no separation between stages, is a direct cascade.
The reaction stage Hydrotreating may consist of one or more reactors or reaction zones with a fixed layer, each of which may include one or more layers of catalyst consisting of identical catalyst for Hydrotreating. Although you can use other types of catalytic layers, it is preferable to the fixed layer. Such other types of catalytic layers include fluid layers, layers boiling, suspension layers and active layers. Between reactors or reaction zones, or between the catalyst layers in the same reactor or reaction zone, you can miladina cooling or heating, because the desulfurization reaction is usually exothermic. Part of the heat produced during the hydrotreatment, you can recover. If heat recovery is impossible, you can make a regular on ladenia through the cooling means, such as cooling water or air, or through the use of a stream of hydrogen for rapid cooling. Thus it becomes easier to maintain the optimum reaction temperature.
In an alternative embodiment it is possible to choose the raw material oil fraction, which has a low level contaminants. In this embodiment stage Hydrotreating can be omitted. Examples of the raw material oil fraction, which has a fairly low level contaminants include kerosene derived from hydrocracking, and kerosene from hydrocarbons produced in the Fischer-Tropsch process.
Output stream, preferably the entire thread, most preferably the entire flow, subjected to Stripping, from the Hydrotreating then brought into contact with the catalyst hydroisomerization when dewaxing in the second stage of the reaction in terms of hydroisomerization, obtaining hydrotreated and deparaffinizing raw kerosene fraction. The dewaxing catalyst usually contains a metal hydrogenation component and a molecular sieve 1-D desyatiletnimi rings deposited on the refractory metal oxide. Metal hydrogenating component preferably is a metal of groups 8-10, more preferably a noble metal, most prefer is Ino Pd, Pt or their mixture. The amount of metal component is from 0.1 to 5 wt. -%, in the calculation of the catalyst, preferably from 0.1 to 2% of the mass. The refractory metal oxide may be alumina, silica, silica-alumina, titanium dioxide, zirconium dioxide and the like, preferably aluminum oxide, most preferably gamma-alumina.
The amount of molecular sieve dewaxing catalyst is from 10 to 100 wt. -%, preferably from 40 to 80 wt. -%, in the calculation of the catalyst. The rest of the dewaxing catalyst comprises a refractory carrier and metal hydrogenating component. These catalysts can be obtained by methods such as drying by spraying, extrusion, etc. the dewaxing Catalyst can be used in solifidians or nesulfatirovannah form, preferably in solifidians form.
Molecular sieve 1-D desyatiletnimi rings can be a ZSM-23, ZSM-35, ZSM-48, or other suitable molecular sieves. Preferably the molecular sieve is a ZSM-48, with a ratio of silica to alumina ZSM-48 is less than approximately 110:1.
At least one hydrogenating metal is included, that is deposited on the catalyst before or after, preferably after, as a binder and/or wear the spruce, for example, the carrier oxide refractory metal, is connected with the molecular sieve. At least one hydrogenating metal may be deposited by any means known that they are effective for this deposition. Non-limiting examples of a suitable method of administration include impregnation method on capacity, ion exchange, mechanical mixing of the precursor(s) of metal oxide with a molecular sieve and a binder, or a combination thereof; the preferred method is a method of impregnation on capacity.
In one of the embodiments of the present invention the flow of raw material oil fraction is brought into contact with the above-described hydrodewaxing catalyst in the reaction stage under conditions effective to hold the unit. The reaction stage, including the hydrodewaxing catalyst used in this invention may consist of one or more reactors or reaction zones with a fixed catalyst bed, each of which may include one or more layers of the same or different catalysts. Although you can use other types of layers of catalyst are preferred fixed layers. Such other types of catalyst include fluid layers, layers boiling, suspension layers and active layers. Between the reaction is-ora, the reaction zones, or between the layers of the catalyst can be performed miladina cooling or heating. You can also recover any amount of heat. If heat recovery is not possible, you can carry out conventional cooling with a cooling means such as cooling water or air, or using a flow of hydrogen for rapid cooling. Thus it becomes easier to maintain the optimum reaction temperature. It should be noted that the reaction stage containing a dewaxing catalyst, sometimes called the second reaction stage.
Effective hydrodewaxing conditions include a temperature of from 240 to 400°C., preferably from 300 to 380°C., at a pressure of from 1480 to 20786 kPa (200 to 3000 psig), preferably from 2859 to 13891 kPa (400 to 2000 psig); hourly space velocity of the liquid is from 0.1 to 10 h-1preferably from 0.1 to 5 h-1and consumption of hydrogen gas for processing from 18 to 890 m3/m3(from 100 to 5000 cubic feet (N.U.)/bbl), preferably from 44 to 178 m3/m3(from 250 to 1000 cubic feet (N.U.)/barrel).
The use of a catalyst containing molecular sieve 1-D desyatiletnimi rings, improves low temperature properties, at the same time minimizing the amount of kerosene to be converted nisaki Asia faction, such as naphtha. Thus, some ISO or can be subjected to hydrocracking, or, preferably, subjected to isomerization to a more branched molecules. These more highly branched ISO protected from further reaction, for example, from cracking. In particular, ZSM-48 is an excellent catalyst for hydroisomerization straight chain and once branched isoparaffins, without appreciable leakage cracking. This increases the yield of jet fuel. Furthermore, the method provides an overall improvement to acceptable values for the maximum height mecoptera flame by saturating aromatic compounds, and also provides a cost-effective way of reducing the number of contaminants containing sulfur and nitrogen, to acceptable values.
In one of the embodiments of the catalyst in the Hydrotreating and dewaxing catalyst are placed in various fixed layers of the same reactor. Preferably, first and provide contact with the raw material oil fraction Hydrotreating catalyst, i.e. it is placed above the course of the process relative to the dewaxing catalyst. In the embodiment where the molecular sieve is selected ZSM-48, preferably the number of N2S/NH3obtained by Hydrotreating, not the C is too large; the entire stream coming from the stage Hydrotreating can be sent to stage dewaxing, as ZSM-48 better carries these pollutants than other isomerization catalysts during dewaxing. However, if the number of N2S/NH3produced during the hydrotreatment is too large, the flow coming from the stage Hydrotreating, can be subjected to Stripping to remove these impurities. The flow of feedstock through the reactor can be co-current or countercurrent, preferably countercurrent. Hydrogen can be added to the flow of raw materials before entering into the reactor.
In another embodiment, the Hydrotreating catalyst is in a separate first reactor. The stream exiting the first reactor, with direct Stripping for removal of gases such as light hydrocarbons and N2S/NH3or without it, in the second reactor containing the catalyst dewaxing. And again, the decision to support the Stripping columns between stages depends on the nature of the molecular sieve and the degree of contamination of the stream exiting the first reactor. Alternatively, between the stages of the Hydrotreating and dewaxing you can use another type of separator.
In any embodiment of the flow coming from the stage dewaxing, can be directed into the separator, preferably in a high pressure separator, and the flow is hidcote from the separator is directed in a fractionation column to obtain the desired jet fuel with increased output and improved properties.
The reaction system suitable for the above-described method, is shown schematically in figure 1. Figure 1 is a raw material 108 oil fraction is introduced into the first reactor 110 Hydrotreating. Stream 115 of hydrogen gas for processing is introduced into reactor 110 Hydrotreating. In the first reactor 110 Hydrotreating feedstock kerosene fraction is in the Hydrotreating conditions in the presence of one or more catalytic layers, which contain Hydrotreating catalyst. If necessary, the processed raw material is passed into the separator 122, where the gaseous products are separated from the liquid. If necessary, the portion of gaseous products separated in the separator 122 may be directed by gravity back into the first reactor as a recycled stream of hydrogen gas for processing (not shown). After passing through the first reactor 110 Hydrotreating and possibly separator 122 processed raw materials into the reactor 140 dewaxing, together with the second flow 125 of hydrogen gas for processing. Then the processed raw materials can pass through the separator 142 to separate the fuel, suitable for use as fuel for jet engines. In an alternate embodiment of stage Hydrotreating and dewaxing can be carried out in one reactor.
In the above description described prepost is more embodiments of the present invention. Expert it is clear that it is possible to develop other equally effective embodiments for implementing the essence of the invention.
The next example illustrates the increased efficiency of the present invention, but it in no way limits the invention.
The Hydrotreating and dewaxing raw kerosene fractions was performed on a system with two reactors, without miladinova steaming between reactors 1 and 2. In the reactor 1 was downloaded commercially available (Criterion) CoMo Hydrotreating catalyst. In the reactor 2 was downloaded the dewaxing catalyst Pt/ZSM-48.
Raw kerosene fraction obtained mainly from Arab light crude oil to further fractionate the crude oil with more heavy kerosene. While ordinary commercial jet fuel is a normal temperature range of the boiling point of from 149 to 288°C (300 to 550°F), a kerosene fraction had an interval of boiling points from 163 to 302°C (from 325 to 575°F). Higher initial boiling point used to raise the temperature of the flash, and a higher temperature at the upper limit of the range used to maintain the same total output in the calculation of crude oil. Feed stream (raw material No. 2) and its properties are presented in table 1. The results of the experiment are presented in table 2.
Table 1 Density (in degrees American petroleum Institute) 43,8 Nitrogen, parts per million a 4.9 Sulfur, parts per million 4204 Hydrogen, wt. -% 13,81 Flash point, °C [D93] 63 Freezing point, °C [D5972] -31,2 Maximum height mecoptera flame, mm 22,2 The aromatic content, % mass. [D5186] 25,7 Flash point, °F [D56] 154 Viscosity, KV at -20°F 8,855 Viscosity, KV at 0°F Naphthalene, % of the mass. [D1840] 3,4 The aromatic content, % vol. [D1319-1] 22,12 Distillation [D2887] Initial boiling point, °C (°F) 149 (300) 5 167 (333) 10 176 (349) 20 to 190.5 (375) 30 203 (397) 40 215,5 (420) 50 229 (445) 60 242 (468) 70 258 (496) 80 273 (524) 90 288 (550) 95 297 (567) The final temperature 314 (597)
|Summary properties of jet fuel|
|Feed stream||Raw material No. 2|
|Pressure, MPa (psig)||was 2.76 (400)||was 2.76 (400)||was 2.76 (400)|
|The temperature of the Hydrotreating (Rxr.)||600||650||650|
|The temperature of the dewaxing (Rxr.)||300||650||675|
|H2m3/m3(cu.ft (N.U.)/barrel||360 (2000)||360 (2000)||360 (2000)|
|Outputs, % of the mass.|
|Consumed H2m3/m3(cu.ft (N.U.)/barrel)||13,5 (75)||17,1 (95)||27 (150)|
|Jet-A||Pilot plant||Hydrotreating||Hydrotreating/ Dewaxing|
|Properties||Technical requirements||Raw material No. 2||Rated VAT residue C (350F)+|
|Density (degrees API)||37-51||43,8||44,2||44,0||43,4|
|Freezing point, °C||< -40 ° C||-31,2||-30||-40,6||-52|
|Flash point, °C (°F)||>37,8 (>100)||62,8 (145)||71,1(160)||68(154)||57,2 (135)|
|Naphthalene compounds, % mass.||<3%||3,4||-||1,2||1,8|
|Aromatics, % vol.||<25||22,1||20,9||20,1||21,8|
|Maximum height mecoptera flame, mm||>18 mm||22,2||23,0||22,5||of 21.2|
|Viscosity, KV at -18°C||8 at-20C||5,8||7,0||6,8||6,8|
|Hydrogen, wt. -%||13,81||13,95||13,87||13,81|
|Sulfur, parts per million||4200||70||15||12|
|Nitrogen, parts per million||5||<0,5||0,5||<0,5|
In the first experiment, denoted MB 330, the catalyst Pt/ZSM-48 was "disabled" by working at low temperature. The results show that one Hydrotreating is ineffective to reduce the freezing temperature to the required specification values. In the second experiment (329 MB) catalyst Pt/ZSM-48 is injected at 343°C (650°F), which leads to 90.2 per cent of the mass. the output of jet fuel with a high flash point and very low sulfur content. The last experiment (334 MB) demonstrates that the catalyst Pt/ZSM-48 can be applied more stringent conditions (357°C, 675°F)to get fuel for jet engines with very low temperature Tamerza the Oia and a high flash point and excellent output (83,0% mass.). In all cases, improved parameters such as maximum height mecoptera flame and the aromatic content.
1. The method of producing jet fuel from a raw material oil fraction, comprising:
the hydrotreatment of the feedstock oil fraction with an interval of boiling points from 163 to 302°C (325°F to 575°F) in the presence of a Hydrotreating catalyst at Hydrotreating conditions with obtaining hydrotreated feedstock oil fraction;
the dewaxing essentially just hydrotreated feedstock oil fraction in the presence of a catalyst comprising the molecular sieve of 1-D desyatiletnimi rings, dewaxing conditions with obtaining hydrodehalogenation raw kerosene fraction and
- fractionation hydrodehalogenation raw oil fraction to obtain fuel for jet engines,
where Hydrotreating conditions include a temperature of from 280 to 400°C, a pressure of from 1480 to 20786 kPa (200 to 3000 psig), hourly volumetric rate of fluid from 0.1 to 10 h-1and the flow rate of the hydrogen gas to the processing of from 89 to 1780 m3/m3(from 500 to 10000 Kubratovo (N.U.)/bbl),
where dewaxing conditions include a temperature of from 300 to 380°C (572°F to 716°F), a pressure of from 791 to 20786 kPa (100 to 3000 psig), hourly volumetric rate of fluid from 0.1 to 10 h1 and consumption of hydrogen gas for processing from 45 to 1780 m3/m3(250 to 10000 Kubratovo (N.U.)/bbl),
where the density of jet fuel in degrees ANI is 37-51, the freezing temperature is less than -52°C (-61,6°F)flash point is more than 37.8°C (100°F), maximum height mecoptera flame is more than 18 mm
2. The method according to claim 1, wherein the Hydrotreating catalysts contain at least one metal of group 6 and at least one metal of groups 8-10, or a mixture thereof.
3. The method according to claim 2, in which the Hydrotreating catalyst can be applied or not applied to the media.
4. The method according to claim 1, wherein the molecular sieve 1-D desyatiletnimi rings is a ZSM-48.
5. The method according to claim 1, wherein the dewaxing catalyst contains at least one metal hydrogenating component.
6. The method according to claim 5, in which the metal hydrogenating component is a Pt, Pd or mixtures thereof.
7. The method according to claim 1, wherein a catalyst for Hydrotreating and dewaxing catalyst are placed in separate layers in the reactor.
8. The method according to claim 1, wherein a catalyst for Hydrotreating and dewaxing catalyst are placed in separate reactors.
9. The method according to claim 1, further comprising the separation of the hydrotreated feedstock oil fraction before depar what Penisula.
10. The method according to claim 9, in which the division includes steaming hydrotreated feedstock kerosene fraction.
SUBSTANCE: invention relates to method of obtaining basic lubricating oil, including bringing hydropurified raw material and hydrogen-containing gas in contact with catalyst of deparaffinisation under conditions efficient for catalytic deparaffinisation, where combined total content of sulphur in liquid and gaseous formed, supplied to the stage of bringing into contact, constitutes more than 1000 wt ppm with respect to hydropurified raw material. Catalyst of deparaffinisation includes, at least, one zeolite with monosized pores, formed by ten-member rings, at least, one metal of group VIII and, at least, one fire-proof binding agent based on metal oxide with low surface area, and in which catalyst of deparaffinisation has ratio of area of surface of micropores to total surface area equal to 25% or more, where total surface area equals external area of zeolite surface plus area of surface of fire-proof binding agent based on metal oxide.
EFFECT: increased output of deparaffinised lubricating oil.
17 cl, 14 dwg, 7 tbl, 20 ex
SUBSTANCE: invention relates to a method of producing olefin monomers for producing a polymer. The method is characterised by that it includes the following steps: feeding into a catalyst bed (7) biological oil containing more than 50% tall oil fatty acids and up to 25% tall oil resin acids, as well as hydrogen gas; and catalytic deoxygenation of the oil with hydrogen in the catalyst bed (7); cooling the stream coming out of the catalyst bed (7) and separation thereof into liquid phase (10) containing hydrocarbons and a gaseous phase; and steam cracking (4) of the liquid (13) containing hydrocarbons to form a product containing polymerised olefins.
EFFECT: method provides an industrially applied process, which can be used to convert wood-based raw material to olefin monomers used to produce biological raw material-based polymers.
15 cl, 1 tbl, 6 ex, 1 dwg
FIELD: oil and gas industry.
SUBSTANCE: method used for obtaining middle distillates based on the mixture of paraffin hydrocarbons obtained by Fischer-Tropsch synthesis involves the following subsequent stages: a) separation at least of light gas fraction C4-, which has final boiling temperature of less than 20°C, from the flow leaving the Fischer-Tropsch synthesis plant in order to obtain only heavy liquid fraction C5+, which has initial boiling temperature of 20 to 40°C; b) hydrogenation of non-saturated compounds of olefinic type at least of some part of heavy fraction C5+ in presence of hydrogen and hydrogenation catalyst at the temperature of 100 to 180°C, at total pressure of 0.5 to 6 MPa with volumetric hourly velocity of 1 to 10 h-1 and at supply of hydrogen, which corresponds to volumetric "hydrogen/hydrocarbons" ratio of 5 to 80 nl/l/h; c) hydroisomerisation/hydrocracking of the whole hydrogenated liquid fuel of stage b), without implementation of the pre-separation stage in presence of hydrogen and catalyst of hydroisomerisation/hydrocracking; d) distillation of the flow subject to hydrocracking/hydroisomerisation, which has been obtained at stage (c) in order to obtain at least fractions of kerosene and gas oil, and residual fraction. Obtained gas oil has the flow point below 0°C, cetane number exceeds 60, kerosene has setting point of not more than -35°C, and height of smokeless flame exceeds 25 mm.
EFFECT: improvement of gas oil properties.
14 cl, 3 dwg
SUBSTANCE: invention relates to a catalyst for realising a method of hydrogenating olefins and oxygen-containing compounds in synthetic liquid hydrocarbons obtained via a Fischer-Tropsch method, containing a porous support made from γ-aluminium oxide on which a catalytically active palladium component is deposited, characterised by that pores in the support have effective radius of 4.0-10.0 nm, wherein content of foreign-metal impurities in the support is not more than 1500 ppm, and content of palladium in the catalyst is equal to 0.2-2.5 wt %. The invention also relates to a hydrogenation method using said catalyst.
EFFECT: invention enables to obtain saturated hydrocarbons from liquid Fischer-Tropsch synthesis products, which are a complex mixture of paraffin hydrocarbons with 5-32 carbon atoms, with ratio of normal paraffin hydrocarbons to isoparaffin hydrocarbons ranging from 1:1 to 7:1, containing up to 50% olefins and up to 5% oxygen-containing compounds.
2 cl, 1 tbl, 7 ex
SUBSTANCE: invention relates to a method of producing middle distillates from paraffin material obtained via Fischer-Tropsch synthesis, involving, before the hydrocracking/hydroisomerisation step, a step for hydrofining and purifying and/or removing impurities by passing through at least one multifunctional protective layer, where the protective layer contains at least one catalyst saturated with an active hydrogenating-dehydrogenating phase and having the following characteristics: volume of macropores with average diametre of 50 nm determined from mercury is higher than 0.1 cm3/g, the complete volume is greater than 0.6 cm3/g. The method also relates to apparatus for realising the disclosed method.
EFFECT: efficient method of obtaining middle distillates from paraffin material.
16 cl, 5 ex, 2 tbl, 5 dwg
SUBSTANCE: invention relates to a method for desulphuration of two streams containing hydrocarbon material involving the following steps: (a) reaction of a first hydrocarbon material-containing stream (1), containing hydrocarbon components which boil above 343°C, and hydrogen (28), with a desulphuration catalyst in a desulphuration zone (3) used in desulphuration conditions to produce an outgoing stream (4) from the desulphuration zone; (b) feeding the outgoing stream from the desulphuration zone into vapour-liquid separator (5) which provides a vaporous stream (17) and a first liquid hydrocarbon-containing stream (6); (c) feeding the vaporous stream (17) and a second hydrocarbon-containing stream (18) into a hydrocracking zone (21) to produce an outgoing stream from the hydrocracking zone. (d) feeding the outgoing stream from the hydrocracking zone and the hydrocarbon-containing stream (16) of a repeated cycle into a hydrogenation zone (22) to produce an outgoing stream (23) from the hydrogenation zone; (e) fractionation of the outgoing stream (23) from the hydrogenation zone to produce an ultralow-sulphur hydrocarbon-containing stream (38); and (f) fractionation of the first liquid hydrocarbon-containing stream (6) extracted from step (b) to obtain a hydrocarbon-containing stream (16) of the repeated cycle, and a second liquid hydrocarbon-containing stream (17) containing hydrocarbon components and having low sulphur concentration.
EFFECT: obtaining ultralow-sulphur hydrocarbon products.
7 cl, 1 ex, 3 tbl, 1 dwg
SUBSTANCE: invention relates to converting and/or processing distillation residues. Invention relates to a method of processing hydrocarbon material, involving a sequence of a first hydroconversion process which is realised upstream in at least one reactor, involving a reaction or reactions inside the said reactors and which activate at least one solid phase, at least one liquid phase and at least one gaseous phase, and a second reforming process realised downstream, conversion with water vapour, which includes at least one reactor, where the said process which is carried up stream is carried out in suspension and/or boiling bed and the said process which is realised upstream involves a first step for at least partial conversion of gaseous phase hydrocarbons, which are heavier than methane, to methane, where the step is called a pre-reforming step, and the reforming reaction(s) inside the said reactors downstream enable to obtain a hydrogen reagent required for chemical reactions in the first process.
EFFECT: self-sustenance of the hydroconversion process with hydrogen, high conversion of hydrocarbons.
3 ex, 1 dwg
SUBSTANCE: invention relates to a benzene hydrogenation and ring opening method and isomerisation of C5-C6 paraffins of starting paraffin material, which contains normal paraffins C5-C6 and at least 1 wt % benzene, involving: (a) feeding starting material, without tapping or condensing hydrogen, into a drier for removing water and obtaining dried starting material containing not less than 0.5 wt % water; (b) combination of dried starting material with a hydrogen-rich gas stream with formation of a mixed load; (c) feeding the mixed load at temperature ranging from 38 to 232°C into the hydrogenation zone, and bringing the said mixed load into contact with a hydrogenation catalyst under hydrogenation conditions in order to saturate benzene and form a stream of products, removed from the hydrogenation zone, with temperature ranging from 149 to 288°C and containing less than 1.5 wt % benzene; hydrogenation conditions include excess pressure from 1400 kPa to 4800 kPa, hourly space velocity for feeding the load from 1 to 40 h-1 and ratio of contained hydrogen to hydrocarbons ranging from 0.1 to 2; (d) regulation of temperature of the stream of product removed from the hydrogenation zone in the interval from 104 to 204°C through at least heat exchange of the product removed from the hydrogenation zone with the mixed load; (e) feeding at least part of the product removed from the hydrogenation zone into the isomerisation zone and bringing the stream of the said load into contact with an isomerisation catalyst under isomerisation and ring opening conditions at excess pressure ranging from 1380 to 4830 kPa; and (f) extraction of the isomerisation product obtained in the isomerisation zone. The invention also relates to a device for realising the proposed method.
EFFECT: use of the proposed invention provides for economisation by reducing the number of units of the equipment used and equipment expenses, and also reduces amount of hydrogen required for carrying the process.
9 cl, 1 tbl, 1 dwg
FIELD: fuels, chemical technology.
SUBSTANCE: invention relates to the content of benzene in commercial gasoline. Invention claims a method for decreasing the content of benzene in gasoline fractions by hydrogenation and isomerization in the presence of catalysts at increased temperatures and pressure of raw consisting of HK-85C fraction of the stable reforming fraction containing paraffins, naphthtenes and aromatic hydrocarbons with a directly distilled fraction wherein a directly distilled fraction represents HK-70C fraction and with recycle of flow isolated from products of isomerization of a hydrogenated fraction, regulation of temperature in the isomerization block of hydrogenation by measurement of amount of recycle taken in the amount 10-30% as measured for the parent raw.
EFFECT: improved decreasing method.
6 cl, 7 tbl, 11 ex
SUBSTANCE: initial hydrocarbon raw material is initially separated and first part of initial raw material is introduced into first zone of dehydration reaction, which functions without oxidation re-heating, and obtained as a result output flow is introduced into second zone of dehydration reaction, which functions without oxidation re-heating. Obtained as a result output flow from second zone of dehydration reaction, together with second part of initial raw material is introduced into third zone of dehydration reaction, which functions with oxidation re-heating.
EFFECT: increased method productivity.
10 cl, 1 dwg
FIELD: oil and gas industry.
SUBSTANCE: invention is referred to method of production of high-octane petrol and includes fractionation of hydrotreated naphtha into light and heave fractions; light naphtha isomerisation and heavy naphtha reforming in presence of platinum-containing catalyst with delivery of excessive hydrogen from reforming to isomerisation. Isomerisation is carried out with sulfate-zirconia catalyst with subsequent separation of isomerisate into three fractions: low-boiling fraction, medium fraction containing n-hexane and methylpenthanes and high-boiling fraction; medium fraction is recirculated to isomerisation raw material. By rectification from reformate light and heavy reforming fractions are obtained; heavy fraction is mixed with low- and high-boiling fractions of isomerisate with production of the target product while light fraction of reforming boiling away up to 85-95°C is subjected to hydroisomerisation at 250-300°C in presence of platinum-containing catalyst and obtained hydroisomerisate is delivered to be mixed with isomerisate.
EFFECT: reduction of benzole and aromatic hydrocarbons content in compliance with requirements to modern types of petrol with preservation of integration for reforming and isomerisation processes.
2 cl, 1 tbl, 7 ex
SUBSTANCE: invention relates to a method for hydrocracking a hydrocarbon stream involving the following operations: providing hydrocarbon starting material (12); feeding the hydrocarbon starting material (12) into a hydrofining zone (14) to obtain an output stream (30) of the hydrofining zone; feeding the output stream (30) of the hydrofining zone into a separation zone (16) in order to separate one or more streams of hydrocarbons with a lower boiling point (34, 58, 62, 66) from a stream of liquid hydrocarbons with a higher boiling point (68); inlet of at least a portion of the stream of liquid hydrocarbons with a higher boiling point as material (68) for hydrotreatment without using a considerable amount of hydrocarbons coming from the hydrotreatment zone with an essentially continuous liquid phase; adding hydrogen (70) to the material (68) for hydrotreatment in an amount which is sufficient to maintain essentially liquid-phase conditions; feeding the material (68), mixed with hydrogen, for hydrotreatment into the hydrocracking zone (24) with an essentially continuous liquid phase; and carrying out a reaction for hydrocracking the material (68) for hydrotreatment in the hydrocracking zone (24) with an essentially continuous liquid phase with a hyrocracking catalyst in hydrocracking conditions to obtain an output stream (72) of the hydrocracking zone having a lower boiling point compared to the stream (68) of liquid hydrocarbons with a higher boiling point. The invention also relates to another method for hydrocracking a hydrocarbon stream.
EFFECT: improved characteristics of products, higher conversion.
16 cl, 5 dwg, 4 tbl, 1 ex
FIELD: power engineering.
SUBSTANCE: method is described to produce hydrocarbon fractions, which may be used as diesel fuel or as components of diesel fuel, based on a mixture of biological origin, containing ethers of fatty acids, possibly, with a certain amount of free fatty acids, which includes the following stages: 1) hydrodesoxygenation of a mixture of organic origin; 2) hydroisomerisation of a mixture produced at the stage (1), after possible treatment for cleaning; besides, the specified stage of hydroisomerisation is carried out in presence of a catalytic system, which contains the following: a) a carrier of acid nature, including a fully amorphous micro-mesoporous silicon-aluminium oxide, having a mole ratio SiO2/Al2O3 in the range from 30 to 500, the surface area of more than 500 m2/g, volume of pores in the range from 0.3 to 1.3 ml/g, the average diameter of pores below 40 Ǻ, b) a metal component containing one or more metals of group VIII, possibly mixed with one or more metals of the group VIII.
EFFECT: production of a hydrocarbon fraction, which may be applied as diesel fuel or as a component of diesel fuel.
55 cl, 4 tbl, 3 dwg, 2 ex
SUBSTANCE: invention relates to a method of producing jet fuel for supersonic aircraft via hydrogenation and subsequent hydrodewaxing of secondary petroleum material in the presence of a hydrogen-containing gas and catalysts, at high temperature and pressure in two hydrogenation reactors and in a hydrodewaxing reactor. The secondary material used is a mixture of gas oils from catalytic cracking and delayed coking in ratio from 90%-10% to 70%-30% and straight-run gas oil is further added in amount of not more than 30 wt % based on the total load of the material, wherein the straight-run gas oil is fed into the top part of the first or second hydrogenation reactor or in different fractions into the top part of the first and second hydrogenation reactors, wherein the hydrogenation reactors are loaded with nickel sulphide - tungsten catalyst, and the hydrodewaxing reactor is 70% loaded with a molybdenum catalyst on a zeolite support, and 30% by a nickel sulphide - tungsten catalyst.
EFFECT: wider range of raw material resources for producing scarce jet fuel for supersonic aircraft, improved technological effectiveness of the process owing to a simple temperature control scheme in the reaction zone and high output of the end jet fuel.
3 cl, 3 ex
SUBSTANCE: invention relates to a method for synthesis of branched olefins, said method involving dehydrogenation of an isoparaffin composition containing 0.5% or less quaternary aliphatic carbon atoms on a suitable catalyst. Said isoparaffin composition is obtained via hydroisomerisation a paraffin composition and contains paraffin containing 7-18 carbon atoms. Said paraffins, at least some of their molecules, are branched, where content of branched paraffins in the isoparaffin composition is equal to at least 50% of the weight of the isoparaffin composition. The average number of branches per paraffin molecule is between 0.5 and 2.5 and the branches include methyl and optional ethyl branches. Said branched olefins contain 0.5% or less quaternary aliphatic carbon atoms. Said paraffin composition is obtained using Fischer-Tropsch method. The invention also relates to methods of producing a branched alkyl aromatic hydrocarbon and branched alkylaryl sulphonates including the method described above.
EFFECT: high versatility and cost effectiveness of the method.
7 cl, 19 ex
FIELD: oil and gas production.
SUBSTANCE: procedure consists in following stages: (a) there is performed hydrocarbon raw stock hydraulic processing by means of gas enriched with hydrogen for production of hydraulically treated output flow containing mixture of fluid and vapour; mixture of fluid and vapour is separated into liquid phase and vapour phase; (b) liquid phase is separated to controlled liquid part and excessive liquid part; (c) vapour phase is connected with excessive liquid part for production of vapour-liquid part; (d) there is extracted fraction containing raw stock for FCC from controlled liquid part and simultaneously there is performed hydro-cracking of vapour-liquid part for production of diesel-containing fraction or there is performed hydro-cracking of controlled liquid part for production of diesel containing fraction and simultaneously there is extracted fraction containing raw stock for FCC from vapour-liquid part. The invention also refers to the device for implementation of the procedure of hydraulic cracking with partial conversion.
EFFECT: production of diesel fuel with ultra-low content of sulphur and substantially better combustibility.
9 cl, 3 ex, 4 tbl, 4 dwg
SUBSTANCE: invention relates to a method for isomerisation of light gasoline fractions containing C7-C8 paraffin hydrocarbons by extracting the C7-C8 fraction from wide gasoline fractions and bringing said C7-C8 fraction into contact with a catalyst containing a hydrogenating-dehydrogenating component on an oxide support in a hydrogen medium at high temperature and pressure in two reactors, fractionation to obtain a product fraction and a fraction of n-paraffins, monomethyl-substituted paraffins and methylcyclohexane which is recirculated into the gas-raw material mixture. The C7-C8 fraction (raw material) is extracted such that its content of C5-C6 hydrocarbons is equal to 0.1-15 wt %, while that of C8 hydrocarbons is equal to 0.1-20 wt %, by mixing the extracted C7-C8 fraction with hydrogen in molar ratio hydrogen: raw material equal to 0.5-4, with formation of a gas-raw material mixture and feeding said mixture into the first of two series-connected isomerisation reactors at temperature 160-250°C, pressure 1.0-4.0 MPa, and bulk speed for feeding material equal to 1-5 h-1. Quenched hydrogen at 40-60°C is fed into the second reactor, with molar ratio hydrogen: raw material equal to (0.1-1.0):1, and the oxide support is a composition of metal oxides: aAI2O3·bZrO2·cWO3·dTiO2·eMnO2, where weight ratios of the oxides are as follows: a=0.04-0.30; b=0.60-0.90; c=0.05-0.15; d=0.001-0.10; e=0.001-0.01.
EFFECT: obtaining isomerisate with high octane number.
2 cl, 3 tbl, 17 ex
SUBSTANCE: invention relates to a fixed layer hydrogen treatment system, as well as methods of improving the existing fixed layer hydrogen treatment systems, involving preconcentration of heavy oil material in one or more suspension-phase reactors using a colloidal or molecular catalyst and further hydrogen treatment of the concentrated material in one or more fixed layer reactors using a supported porous catalyst. The colloidal or molecular catalyst is formed in situ by directly mixing a catalyst precursor composition with heavy oil material and raising temperature of the material to temperature above decomposition point of the catalyst precursor composition. Asphaltene and other hydrocarbon molecules which are in any case are too large for diffusion into pores of the fixed bed catalyst may be impregnated by the colloidal or molecular catalyst. One or more suspension-phase reactors may be made and placed upstream from one or more fixed layer reactors of the existing fixed layer hydrogen treatment system and/or converted from one or more existing fixed layer reactors.
EFFECT: higher conversion level, higher catalyst activity.
78 cl, 6 ex, 5 tbl, 29 dwg
FIELD: oil and gas industry.
SUBSTANCE: invention refers to oil refining industry, namely to method of obtaining high-octane motor petrol. Invention deals with method for obtaining motor petrol, which involves separation of petrol distillate of catalytic cracking into light and heavy fractions, hydroforming of heavy fraction mixed with straight-run diesel fraction, further additional hydroforming of extracted hydrotreated petrol fraction mixed with straight-run petrol fraction. Extracted hydrotreated petrol fraction is separated into two parts, one of which is subject to additional hydroforming mixed with straight-run petrol fraction; after that, it is directed to catalytic reforming, and the other part is mixed with light fraction of petrol distillate of catalytic cracking and catalysate of catalytic reforming in the following ratio, % wt: 20:40:40-10:30:60 respectively so that commercial motor petrol is obtained.
EFFECT: compliance of base components of high-octane motor petrols as to quality with European standards.
4 cl, 3 ex
SUBSTANCE: invention relates to methods of obtaining synthetic analogues of valuable natural minerals, in particular paulingite. Method of obtaining synthetic analogue of paulingite zeolite includes preparation of reaction mixture, mixing reaction mixture and keeping under conditions of autogenic pressure with heating for the time, sufficient for formation and reconstruction of paulingite crystals. As reaction mixture used are sodium hydroxide, potassium hydroxide, water, aluminium hydroxide, aluminium sulfate eighteen-aqueous, silicon sol and tetraethylammonium hydroxide. First, sodium hydroxide, potassium hydroxide, water and aluminium hydroxide NaOH+KOH+H2O+Al(OH)3 are mixed, obtained mixture is heated to 80-100°C to complete dissolution, aluminium sulfate eighteen-aqueous is dissolved in water, after which obtained solutions are mixed, and SiO2 and tetraethylammonium hydroxide TEAOH are added with mixing until gel of homogeneous consistency is formed. After that, obtained gel without aging is placed into autoclave at T=100-180°C and autogenic pressure 5-35 bar and mixed for 12 hours.
EFFECT: zeolite with paulingite structure without admixtures is obtained within 12 hours in reactor under conditions of thermostating.