EP1201730A1 - Verfahren zur herstellung von komponenten für verbrennungsmotoren - Google Patents

Verfahren zur herstellung von komponenten für verbrennungsmotoren Download PDF

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Publication number
EP1201730A1
EP1201730A1 EP00925772A EP00925772A EP1201730A1 EP 1201730 A1 EP1201730 A1 EP 1201730A1 EP 00925772 A EP00925772 A EP 00925772A EP 00925772 A EP00925772 A EP 00925772A EP 1201730 A1 EP1201730 A1 EP 1201730A1
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hydrogen
reforming
zone
hydrocarbon gases
products
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French (fr)
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EP1201730A4 (de
Inventor
Alexandr Sergeevich Bely
Valery Kuzmich Duplyakin
Vladimir Alexandrovich Likholobov
Sergei Petrovich Kildyashev
Dmitry Ivanovich Kiriyanov
Mikhail Dmitrievich Smolikov
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Boreskov Institute of Catalysis Siberian Branch of Russian Academy of Sciences
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Boreskov Institute of Catalysis Siberian Branch of Russian Academy of Sciences
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Publication of EP1201730A4 publication Critical patent/EP1201730A4/de
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/007—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 in the presence of hydrogen from a special source or of a special composition or having been purified by a special treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/08—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of reforming naphtha

Definitions

  • the present invention relates to the production of high octane components of motor fuels, aromatic hydrocarbons, and hydrogen from gasoline fractions of petroleum and gas condensate origin and C 1 -C 4 hydrocarbon gases.
  • the present invention may find application in petroleum processing and gas processing industries.
  • a disadvantage of this process is that adding gas to the reforming zone does not influence the selectivity of the process, but only contributes to improving the stability of the catalyst operation.
  • the yield of the target product - a high octane component and aromatic hydrocarbons - as a rule does not exceed 75-85 percent by weight on conversion to the amount of gasoline fractions to be processed.
  • from 15 to 25% of the initial costly feed are converted to less valuable C 1 -C 4 hydrocarbon gases. This lowers the effectiveness of the process and tells negatively on its economic characteristics.
  • Said object is accomplished by the provision of a process of producing high octane components of motor fuels, comprising reforming in the presence of a platinum-containing catalyst, followed by separating liquid high octane products from gaseous products (hydrogen and C 1 -C 4 hydrocarbon gases) and recycling C 1 -C 4 hydrocarbon gases to the reforming zone.
  • the obtained gaseous products of reforming are subjected to separation by binding hydrogen when contacting thereof with aromatic hydrocarbons in a catalytic hydrogenation zone, whereafter the hydrogenation products are separated and C 1 -C 4 hydrocarbon gases are recycled to the reforming zone.
  • C 1 -C 4 hydrocarbon gases continuously recirculate in a closed system from the hydrogenation zone to the reforming zone and back without being removed from the process.
  • the rate of binding hydrogen in the hydrogenation zone is maintained equal to the rate of hydrogen evolution in the reforming zone.
  • the process in the hydrogenation zone is carried out at a pressure of at least 0.3 MPa and a temperature of 50-300°C on a catalyst containing Group VIII metal(s).
  • the hydrogenation products are separated into cyclohexane hydrocarbons and C 1 -C 4 hydrocarbon gases by the method of medium-temperature separation of phases. Bound hydrogen in the form of cyclohexane hydrocarbons are removed from the process.
  • Cyclohexane hydrocarbons are directed to the catalytic dehydrogenation zone with subsequent separation of the dehydrogenation products into aromatic hydrocarbons, which are then recycled to the hydrogenation zone, and hydrogen.
  • the process in the dehydrogenation zone is carried out at a temperature of 300-500°C on a catalyst containing Group VIII metal(s).
  • C 1 -C 4 hydrocarbon gases dissolved in liquid reforming products are separated and recycled to the reforming zone for blending with liquid feedstock.
  • the reforming zone comprises one reaction vessel or a system of several reaction vessels.
  • the feedstock of the process are straight-run gasoline fractions of petroleum or gas condensate origin, boiling out within the temperature range of 62°C to 190°C, with sulfur content not over 0.0001 percent by weight.
  • the feedstock is heated in a heat exchanger 1 by the reaction products, blended with a flow of C 1 -C 4 hydrocarbon gases recycled from the hydrogenation zone, and then heated in a multiple zone furnace 2 to the reforming temperature in a reaction vessel 3 (where n ⁇ 1).
  • a complex of catalytic reforming reactions is carried out on platinum-containing catalysts.
  • the reaction gives aliphatic hydrocarbons (having predominantly an iso-structure), aromatic hydrocarbons, hydrogen, and C 1 -C 4 hydrocarbon gases.
  • reaction products give off their heat in the heat exchanger 1, become cooled in a cooler 6 and come to a separator 7.
  • gaseous reaction products are separated from liquid ones.
  • Liquid products from the separator 7 come to a low-pressure separator 22, wherein additional separation of light hydrocarbon gases, predominantly of C 1 -C 4 , takes place.
  • the liquid high octane product from the separator 22 through a heat exchanger 23 comes to a column 17, wherein final separation of dissolved gases is effected by precise fractionation.
  • the liquid product from the bottom of the column 17 is removed from the process through the heat exchanger 23. Gaseous products from the separator 22 and column 17 are recycled for blending with the reforming feedstock.
  • the liquid hydrocarbons of the cyclohexane series are heated to a temperature of 300-500°C and directed to a reaction vessel 15 containing a heterogeneous catalyst for the selective dehydrogenation of naphthene hydrocarbons.
  • a reaction vessel 15 containing a heterogeneous catalyst for the selective dehydrogenation of naphthene hydrocarbons.
  • the reaction vessel 15 there takes place evolution of bound hydrogen in the reaction of catalytic dehydrogenation of hydrocarbons of the cyclohexane series:
  • reaction runs with a high speed and with selectivity close to 100%, which provides the possibility of obtaining hydrogen with a high degree of purity (> 95 mol.%).
  • the reaction products are cooled in the heat exchanger 9, then in cooler 13, and fed to a separator 14.
  • pure hydrogen is separated from aromatic hydrocarbons that are formed according to reaction (2). This hydrogen is removed from the process as an end product.
  • Liquid aromatic hydrocarbons are heated in the heat exchanger 9, blended with the hydrogen-containing gas from the separator 12, and recycled to the process (reaction vessel 10) for binding and separating hydrogen from C 1 -C 4 hydrocarbon gases.
  • the process is carried out continuously by effecting as complex of the above-described operations in the reaction vessels 3, 10 and 15.
  • An essential distinctive feature of the proposed method of processing is the separation of gaseous reforming products into C 1 -C 4 hydrocarbon gases and pure hydrogen.
  • the separation is carried out by contacting with aromatic hydrocarbons in the catalytic hydrogenation zone. Hydrogen becomes bound, separated from C 1 -C 4 hydrocarbon gases, and passes into the composition of the forming hydrocarbons of the cyclohexane series.
  • Constancy of hydrogen concentration by maintaining the equality of the rates of hydrogen binding in the hydrogenation zone and of hydrogen evolution in the reforming zone is one of the distinctive features of the proposed method of processing.
  • the rate of removing hydrogen from the reforming zone must be such as to compensate for the increase in the gas volumes in the reforming reaction zone.
  • the amount of forming hydrogen is from 1.5 to 3.0 percent by weight of the amount of processed gasoline. Consequently, the catalyst operation conditions in the hydrogenation reaction vessel must insure binding said amount of hydrogen. This is achieved owing to the conditions of running the reaction (pressure, temperature), type of the catalyst (metals of Group VIII), and rate of feeding aromatic hydrocarbons to the hydrogenation reaction vessel 10.
  • Optimal conditions for carrying out this operation are temperature of 50 to 300°C and pressure in the reaction vessel 10 of at least 0.3 MPa.
  • the best catalysts are applied catalysts from Group VIII metals (platinum, palladium, rhodium, etc).
  • aromatic hydrocarbons which have low volatility of vapors at temperatures of 15-30°C: this insures complete separation of their hydrogenation products from C 1 -C 4 hydrocarbon gases at elevated pressures in the C 2 separator.
  • aromatic hydrocarbons with the number of carbon atoms greater than seven (toluene, xylenes, aromatic hydrocarbons C 9 and higher).
  • the chemical composition of the catalysts and the conditions of carrying out the process are presented in the Table. If the above-stated condition is not insured (see Example 5 in the Table), the pressure in the reforming system grows.
  • the rate of this process is the higher, the greater the difference between the rate of hydrogen evolution in the reforming zone and the rate of hydrogen binding in the hydrogenation reaction vessel ⁇ is.
  • the necessary condition for the trouble-free carrying out of the process is the removal of excess part of hydrogen-containing gas.
  • the main principle of the proposed process which consists in complete recycling of the forming hydrocarbon gases to the reforming zone, with the hydrogen concentration and the pressure in the reforming system maintained constant, is violated. With the given technique, two essential effects are achieved, each of which to a considerable extent depends on the value of partial pressure of C 1 -C 4 hydrocarbon gases in the reforming zone.
  • the hydrogen-containing gas contains 70-80 vol.% of hydrogen and 20-30 vol.% of hydrocarbon gases. Consequently, the partial pressure of hydrocarbon gases in the reaction zone of typical reforming is 20-30% of the overall process pressure, or 0.2-0.3 P o .
  • a real opportunity is provided for increasing the partial pressure of C 1 -C 4 hydrocarbon gases in the reaction zone, equal to 0.3-0.95 P o .
  • the proposed process insures the attainment of the yield of the end product (high octane gasoline and aromatic hydrocarbons) equal to 93-98 percent by weight as calculated for the amount of straight-run low octane gasoline fed for processing.
  • the effectiveness of the proposed process excels the effectiveness of the known analogs by 10-20 percent by weight and approaches the theoretically possible level (100% as calculated for the supplied feedstock).
  • the significance of said effect is such that the resource saving result attained in the present process for the feedstock is equivalent to additionally involving up to 20 percent by weight of petroleum feedstock for processing by the known methods.
  • a distinctive feature of the proposed method of processing is also that C 1 -C 4 hydrocarbon gases formed as a by-product are not removed from the process, but continuously recirculate in the closed system from the hydrogenation zone to the reforming zone and back.
  • this effect is compensated for by supplying to the flow of the recirculating C 1 -C 4 hydrocarbon gas a light hydrocarbon gas from an external source (C 1 -C 4 hydrocarbon gas from natural gas deposits, dry gas from petroleum processing plants, etc.).
  • the loss of C 1 -C 4 gases owing to their conversion into liquid components of motor fuels is thus compensated for, and prerequisites are provided for additional formation of the end product.
  • the attained level of the yield of reforming gasoline due to this effect is 95-98 percent by weight, as calculated for low octane gasoline fed for processing. This is equivalent to additionally involving another 5-7 percent by weight of liquid petroleum feedstock for processing by the known methods.
  • maintaining constant pressure in the system by supplying to the recirculating flow the required amount of C 1 -C 4 hydrocarbon gases from an external source is one more distinctive feature of the proposed method of processing.
  • Another distinctive feature of the proposed method of processing is the production of high-purity hydrogen by bringing hydrogen to the bound state, i.e., by incorporating it into the composition of the molecules of cyclohexane hydrocarbons that are formed in the hydrogenation zone and subsequent treating them in the catalytic dehydrogenation zone to release pure hydrogen.
  • the reaction is carried out at high space velocities of feeding liquid hydrocarbons of the cyclohexane series (10-50 hr -1 ) and temperatures within the range of 300-500°C.
  • the use of industrial platinum catalysts, for instance, of a reforming catalyst, for carrying out the reaction, provides for the selectivity of the process, close to 100%. This circumstance constitutes the basis for obtaining high-purity hydrogen (> 99.0 mol.%).
  • the reaction is run in the reaction vessel 15 (Fig. 2).
  • This reaction vessel is supplied with hydrocarbons of the cyclohexane series from the separator 12, said hydrocarbons being preheated in a one zone furnace 16 to the reaction temperature.
  • the reaction products are aromatic hydrocarbons and hydrogen, which are successively cooled in the heat exchanger 9 and cooler 13 and come to the separator 14.
  • high-purity hydrogen is separated from liquid aromatic hydrocarbons. Gaseous hydrogen is removed from the process as the end product.
  • Aromatic hydrocarbons are recycled to the reaction vessel 10 for binding and separating reforming hydrogen from C 1 -C 4 hydrocarbon gases.
  • the feedstock of the process are hydrocarbon fractions containing from 5 to 12 carbon atoms in the molecules of the components and boiling out within the range of temperatures from 65 to 190°C.
  • Natural gas containing 95 vol.% of methane and hydrocarbon gas from a petroleum processing plant, containing 5 vol.% of ethane, 55 vol.% of propane, and 40 vol.% of butanes were used as the hydrocarbon gases.
  • Example 5 is given for comparison.
  • Example 1 illustrates the known method of catalytic reforming of gasoline fractions.
  • the setup is illustrated diagrammatically in Fig. 1.
  • one reaction vessel is used with the 100 cm 3 volume of the reaction zone.
  • the process is carried out under catalytic reforming conditions.
  • the feedstock of a gasoline fraction with a 105-190°C, having a density of 0.743 kg/l is supplied to a reforming reaction vessel 4 with the velocity of 150 ml/hr.
  • a reforming reaction vessel 4 With the velocity of 150 ml/hr.
  • hydrogen, a light hydrocarbon gas, and liquid hydrocarbons (catalyzate) which are cooled first in a heat-exchanger 1, then in a cooler 6, and after that are supplied for separation to a first-step separator 7.
  • the pressure in the reforming system increases to 2.2 MPa.
  • the yield of the reaction products is as follows: high octane component, 79.2; dry hydrocarbon gas from the separator 7, 14.8; liquefied C 3 -C 4 gases, 4.0; hydrogen, 2.0.
  • the motor octane number of the reforming gasoline is 83 M.O.N.
  • the content of aromatic hydrocarbons is 61.1 percent by weight.
  • Example 2 illustrates the proposed method of producing motor fuels and hydrogen.
  • the process is carried out in a reforming setup which is illustrated diagrammatically in Fig. 2.
  • a reaction vessel is used with the 100 cm 3 volume of the reaction zone.
  • the reaction vessel as in Example 1, is charged with a polymetallic reforming catalyst, containing, in percent by weight: platinum, 0.25; rhenium, 0.3; chlorine, 0.1; carrier (aluminum hydroxysulfate), the balance.
  • the reactors 10 and 15 are charged with the same catalyst, in the amount of 25 g each.
  • the catalysts in each reactor are reduced with hydrogen at 500°C, at the pressure of 1.0 MPa, and the hydrogen circulation rate of 10 nl/l cat per hour.
  • the feedstock of a hydrocarbon fraction with a 62-190°C, having a density of 0.743 kg/l is supplied to the reforming reaction vessel 4 with the velocity of 150 ml/hr.
  • the reaction products from the reaction vessel 4 are cooled to a temperature of 15-30°C and fed to the high-pressure separator 7.
  • Hydrogen (80 vol.%) and hydrocarbon gases (20 vol.%) from the separator 7 are fed for blending with a flow of toluene, which is supplied from the separator 14 with the velocity of 62.3 ml/hr.
  • the mixture is heated to 250°C and fed to hydrogenation reaction vessel 10, wherein hydrogen is bound in the course of toluene hydrogenation, giving methylcyclohexane.
  • the reaction is endothermic, so that the temperature over the bed increases by 25-35°C.
  • the reaction products are cooled down to 15-30°C and fed to the separator 12.
  • This separator owing to a great difference in the boiling points of methylcyclohexane and C 1 -C 4 hydrocarbon gases their separation takes place.
  • the hydrocarbon gases and a part of unreacted hydrogen are extracted by the compressor 18 and recycled to the reforming reaction zone.
  • the conditions in the reaction vessel 5 are maintained such that the rate of binding and stripping hydrogen from the hydrogen-containing gas should be somewhat (1.1 to 1.3 times) higher in the beginning of the process and then equal to the rate of hydrogen formation in the reforming zone.
  • the optimal concentration range of the hydrogen-containing gas fed from the separator 12 to the reforming zone is from 20 to 50 vol.%. This insures an increase in the partial pressure of the hydrocarbon gas at the inlet of the reforming reaction vessel to 0.5-0.8 P o , where P o is the total pressure in the system. This condition is decisive for attaining the necessary effectiveness of the process. Under the effect of high concentration in the reaction zone, the hydrocarbon gases are adsorbed on the active sites of the catalyst, this providing for realization of two fundamentally important effects.
  • the hydrocarbon gas circulates in the closed system via the reforming zone and, suppressing the hydrocracking of the feedstock components, becomes incorporated into the composition of liquid high octane hydrocarbons.
  • the yield of stable catalyzate increases from 79.2 to 92.5%, compared to the known methods of reforming, while the yield of gases decreases: the yield of dry gas, from 14.8 to 3.2%; and the yield of liquid hydrocarbon gas, from 4.0 to 1.5%.
  • the factor responsible for the appearance of these gases as products of the process is their dissolution in the liquid product in the separator 7. In addition to these effects, an increase is observed in the selectivity of the target reactions.
  • the content of aromatic hydrocarbons in the catalyzate increases from 62 to 69.3 percent by weight; the motor octane number increases from 83 to 89 M.O.N.; the yield of hydrogen increases from 2.0 to 2.8 percent by weight (see the Table).
  • Methylcyclohexane containing bound hydrogen in its composition is heated to the temperature of 500°C in the furnace 16 and fed to the dehydrogenation reaction vessel 15.
  • methylcyclohexane is dehydrogenated to toluene and hydrogen that are formed in the mole ratio of 1:3.
  • the reaction products are cooled down to 15-30°C and fed to the separator 14, wherein toluene is condensed and hydrogen is stripped therefrom.
  • the purity of hydrogen is 97 mol.%.
  • Liquid toluene is recycled for blending with the hydrogen-containing gas and further to the hydrogenation reaction vessel 10 for binding hydrogen from the reforming reaction zone.
  • Example 3 illustrates the proposed method of carrying out the process.
  • the process is carried out as described in Example 2. The difference is as follows.
  • the reforming reaction vessel 4 is charged with a polymetallic catalyst, comprising the following components, in percent by weight: platinum, 0.35; tin, 0.25; chlorine, 1.5; alumina, the balance.
  • the hydrogenation reactor vessel 10 and the dehydrogenation reaction vessels are charged with a catalyst having the following chemical composition, in percent by weight: platinum, 0.1; palladium, 0.5; alumina, the balance.
  • the temperature in the reaction vessel 4 is 490°C; in the reaction vessel 10, 150°C; in the reaction vessel 15, 400°C.
  • the process pressure is 2.5 MPa.
  • the rate of feeding toluene to the hydrogenation reaction vessel 10 is 67.3 ml/h.
  • straight-run gasoline and a propane-butane fraction are fed to the reforming system in the amount of 5 percent by weight as calculated for the fed gasoline.
  • the main characteristics of the process are presented in the Table.
  • the yield of high octane liquid catalyzate is 98.4 percent by weight as calculated for the feedstock.
  • the yield of dry and liquid gas is 1.8 and 0.4%, respectively.
  • the content of aromatic hydrocarbons in the catalyzate is 70 percent by weight; the octane number is 90 M.O.N.
  • the yield of hydrogen having purity of 98.5 vol.% is 2.9 percent by weight. So, carrying out the proposed process under the above-described conditions has insured an increase in the yield of liquid catalyzate from 79.2 to 98.4%, i.e., by 19.2%. This is equivalent to involving into processing by the known methods an additional amount of gasoline exceeding 20-23 percent by weight for producing the same amount of the end product.
  • Example 4 The process is carried out as described in Example 2, the difference being in that the reforming reaction vessel 4 is charged with 70 g of a catalyst having the following chemical composition in percent by weight: platinum, 0.35; iridium, 0.35; chlorine, 1.3; alumina, the balance.
  • the dehydrogenation reaction vessel 15 is charged with a catalyst having the following chemical composition in percent by weight: palladium, 1.5; alumina, the balance.
  • the temperature in the reaction vessel 10 is 50°C; in the reaction vessel 15, 300°C.
  • the process pressure is 0.3 MPa.
  • the rate of feeding toluene to the reaction vessel 10 is 61 ml/h.
  • Constancy of pressure in the reforming zone is compensated for by pumping into the liquid feedstock a hydrocarbon gas from a petroleum processing plant, containing in percent by weight: ethane, 5; propane, 55; butanes, 40.
  • the main characteristics of the process are presented in the Table.
  • the yield of high octane liquid catalyzate is 98.5 percent by weight as calculated for the supplied feedstock.
  • the yield of hydrogen is 3.1 percent by weight; the purity of hydrogen is 99.0 vol.%.
  • the octane number of the catalyzate is 87 M.O.N.
  • the content of aromatic hydrocarbons is 67.8%.
  • the process is carried out as described in Example 4. The difference is as follows.
  • the temperature in the reaction vessel 10 is maintained equal to 40°C; in the reaction vessel 15 the temperature is maintained equal to 250°C.
  • the initial pressure in the system is ⁇ 0.2 MPa. These conditions do not insure complete binding of hydrogen evolving in the reforming zone. For these reasons there was a constant increase in the process pressure from 0.2 to 3.0 MPa. To prevent pressure growth, it was necessary to remove part of hydrogen and of C 1 -C 4 hydrocarbon gases from the process.
  • the yield of liquid catalyzate is 84.2 percent by weight.
  • the yield of hydrogen is 1.5 percent by weight.
  • Example 6 illustrates the known method of producing high octane motor fuel by the reforming of petroleum fractions (for comparison).
  • the process is carried out as described in Example 1, the difference being in that the reforming system comprises three series-connected reaction vessels.
  • the first reaction vessel is charged with 10 g of a platinum-rhenium catalyst
  • the second reaction vessel is charged with 20 g
  • the third reaction vessel is charged with 40 g of the same catalyst.
  • the total catalyst charge in the reforming zone is, as in Example 1, 70 g of the catalyst.
  • the pressure in the system is 1.5 MPa.
  • the feedstock for the process is a hydrocarbon fraction of gasoline boiling in the temperature range of 65-105°C; the feedstock density is 0.695 kg/l.
  • the yield of liquid catalyzate is 81.6 percent by weight.
  • the octane number is 73 M.O.N.; the content of aromatic hydrocarbons is 42%.
  • Example 7 illustrates the proposed method of carrying out the process.
  • the reforming unit comprises three reaction vessels, as in Example 6, with a similar charge of the same catalyst.
  • the hydrogenation reaction vessel 10 is charged with a catalyst containing the following components in percent by weight: platinum, 0.2; rhodium, 0.25; carrier (alumina), the balance.
  • the dehydrogenation reaction vessel 15 is charged with a catalyst having the following chemical composition in percent by weight: platinum, 0.35; alumina, the balance.
  • the temperature in the reaction vessel 10 is maintained equal to 200°C; the temperature in the dehydrogenation reaction vessel 15 is maintained equal to 450°C.
  • the process pressure is 1.5 MPa.
  • the hydrogenation reaction vessel is fed with orthoxylene with the rate of 55.6 g/h. Dissolved C 3 -C 5 hydrocarbon gases are separated from the high octane product of reforming (from the reforming zone) and from cyclohexane hydrocarbons (from the separator 12) in stabilization columns and directed to blending with the liquid reforming feedstock.
  • the yield of liquid high octane catalyzate is 97.4 percent by weight.
  • the yield of hydrogen is 3 percent by weight.
  • the octane number is 78 M.O.N., the content of aromatic hydrocarbons is 53 percent by weight.
  • Example 8 illustrates the proposed method.
  • the hydrogenation reaction vessel 10 is charged with a catalyst containing the following components in percent by weight: palladium, 3.0; porous silica, the balance.
  • the dehydrogenation reaction vessel 15 is charged with a catalyst containing the following components in percent by weight: platinum, 0.5; silica, the balance.
  • the temperature in the reaction vessel 10 is 300°C; the temperature in the reaction vessel 15 is 500°C.
  • the process pressure is 2.5 MPa.
  • the rate of feeding para-xylene to the reaction vessel 10 is 51.1 g/h.
  • the conditions and characteristics of the process are presented in the Table.
  • the yield of liquid catalyzate is 97.2 percent by weight.
  • the octane number is 76 M.O.N., the content of aromatic hydrocarbons is 50.9 percent by weight.
  • the proposed method of producing high octane gasolines insures a substantial increase in the yield of the target ;product and high-purity hydrogen, compared with the known methods.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
EP00925772A 1999-06-01 2000-04-24 Verfahren zur herstellung von komponenten für verbrennungsmotoren Withdrawn EP1201730A4 (de)

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RU99111847 1999-06-01
RU99111847A RU2144056C1 (ru) 1999-06-01 1999-06-01 Способ получения компонентов моторных топлив (биформинг-1)
PCT/RU2000/000145 WO2000073401A1 (fr) 1999-06-01 2000-04-24 Procede de production de composants pour carburants pour moteurs

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EP1201730A4 EP1201730A4 (de) 2003-06-25

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AU (1) AU4441100A (de)
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US8598395B2 (en) 2010-01-19 2013-12-03 Uop Llc Process for increasing a mole ratio of methyl to phenyl
US8609917B2 (en) 2010-01-19 2013-12-17 Uop Llc Process for increasing methyl to phenyl mole ratios and reducing benzene content in a motor fuel product
US8702971B2 (en) 2010-03-31 2014-04-22 Uop Llc Process and apparatus for alkylating and hydrogenating a light cycle oil
US8753503B2 (en) 2008-07-24 2014-06-17 Uop Llc Process and apparatus for producing a reformate by introducing isopentane
US8889937B2 (en) 2011-06-09 2014-11-18 Uop Llc Process for producing one or more alkylated aromatics

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WO2007091912A1 (fr) * 2006-02-09 2007-08-16 Institut Problem Pererabotki Uglevodorodov Sibirskogo Otdeleniya Rossiiskoi Akademii Nauk Procédé pour produire des carburants de moteur
WO2008024012A1 (fr) * 2006-08-23 2008-02-28 Institut Problem Pererabotki Uglevodorodov Sibirskogo Otdeleniya Rossiiskoi Akademii Nauk Procédé de fabrication de composants de carburants pour moteurs

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3806447A (en) * 1972-08-03 1974-04-23 Universal Oil Prod Co Continuous low pressure catalytic reforming process
US5013423A (en) * 1987-11-17 1991-05-07 Mobil Oil Corporation Reforming and dehydrocyclization
US5370786A (en) * 1993-03-23 1994-12-06 Uop Method for operating a continuous conversion process employing solid catalyst particles

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4615793A (en) * 1984-02-13 1986-10-07 Chevron Research Company High density recycle gas for reforming process
RU2124553C1 (ru) * 1997-01-31 1999-01-10 Фалькевич Генрих Семенович Способ получения высокооктанового бензина или высокооктанового бензина и ароматических углеводородов

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3806447A (en) * 1972-08-03 1974-04-23 Universal Oil Prod Co Continuous low pressure catalytic reforming process
US5013423A (en) * 1987-11-17 1991-05-07 Mobil Oil Corporation Reforming and dehydrocyclization
US5370786A (en) * 1993-03-23 1994-12-06 Uop Method for operating a continuous conversion process employing solid catalyst particles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO0073401A1 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8753503B2 (en) 2008-07-24 2014-06-17 Uop Llc Process and apparatus for producing a reformate by introducing isopentane
US8563795B2 (en) 2010-01-19 2013-10-22 Uop Llc Aromatic aklylating agent and an aromatic production apparatus
US8598395B2 (en) 2010-01-19 2013-12-03 Uop Llc Process for increasing a mole ratio of methyl to phenyl
US8609917B2 (en) 2010-01-19 2013-12-17 Uop Llc Process for increasing methyl to phenyl mole ratios and reducing benzene content in a motor fuel product
US8702971B2 (en) 2010-03-31 2014-04-22 Uop Llc Process and apparatus for alkylating and hydrogenating a light cycle oil
US8889937B2 (en) 2011-06-09 2014-11-18 Uop Llc Process for producing one or more alkylated aromatics

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RU2144056C1 (ru) 2000-01-10
EA200101118A1 (ru) 2002-04-25
WO2000073401A1 (fr) 2000-12-07
AU4441100A (en) 2000-12-18
EP1201730A4 (de) 2003-06-25
EA002641B1 (ru) 2002-08-29

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