Classifications

• • 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
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1088—Olefins
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4006—Temperature
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/80—Additives
  • C10G2300/802—Diluents

Definitions

• the invention relates to a process for the hydrogenation of olefin- and sulfur-containing material streams, such as occur frequently in oil refineries.
• the sulfur compounds present in these streams are completely or partially converted into alkanes by hydrogenation in a reactor in whole or in part in hydrogen sulphide and the olefins contained in these streams by hydrogenation.
• the control of the process and in particular the temperature distribution in the reactor is achieved by controlling the Olefinan- part in the reactor-supplying feed streams.
• the invention also relates to a device with which the method can be carried out and which is suitable for the implementation of said method steps.
• DE 102007059243 A1 describes a process for the hydrogenation of olefin-containing material streams which contain organic sulfur compounds and which are converted into hydrogen sulfide during the hydrogenation.
• the sulfur compounds can be removed from the material stream used by the hydrogen sulfide is removed after the hydrogenation by a gas scrubbing from the product gas as a mixture obtained.
• the feed streams are passed through a reactor which contains a plurality of successive catalyst beds in the gas flow direction in which a successive hydrogenation is carried out.
• the feed streams are typically a gas or a vaporized liquid.
• Behind each catalyst bed is an introduction device for a further feed stream, with which further feed stream can be passed into the gas stream in the reactor. Since the catalyst beds and the gas stream in the reactor reheat after each hydrogenation step, the temperature distribution in the reactor can be controlled by the distribution of the feed stream behind the individual catalyst beds. By adding fresh feed stream behind the respective catalyst bed, the feed stream cools again. In this way it is possible to carry out the hydrogenation always in the optimum temperature range. As a result, the catalyst can be kept at a temperature which corresponds to its optimum area of use.
• the invention solves this problem by the addition of feed streams containing a precisely controlled Olefinanteile. Since the heating of the gas stream and the catalyst bed in the reactor is effected only by the heat of reaction of the hydrogenation reaction of the olefins, the temperature distribution in the reactor can be controlled by the addition of feed streams having different olefin content.
• a feed stream is always to be understood as meaning a gaseous stream.
• the olefin-containing feed stream is divided into the reactor before being fed, so that at least two feed streams are obtained, and
• the first feed stream is passed via suitable devices over the head of the reactor through a catalyst bed in the reactor with a partial amount of hydrodesulphurisation suitable catalyst, and second feedstream laterally behind the first catalyst bed into the reactor and to the one heated by the first hydrogenation Reaction mixture is added, and the resulting gas stream is passed through a second catalyst bed in the reactor, and which is characterized in that • the proportion of olefins in at least one feed stream by separate
• Supply of olefins or diluent gas in the individual feed streams is controllable, wherein The temperature in the reactor is controlled by controlling the proportion of olefins in at least one feed stream.
• the temperature at the top of the reactor is usually about 300 ° C., at which the hydrogenation reaction can be carried out well.
• the proportion of olefins in the first olefin-containing feed stream can advantageously be regulated by adding an oil-sparing or an olefin-free dilution stream or from both dilution streams into the first feed stream. As a result, an olefin-containing feed stream is present.
• the olefinarme and olefin-free feed stream can be added as a mixture, these substances can be added separately in two separately regulated streams or premixed.
• the feed stream can then be further diluted.
• the proportion of olefins in the first feed stream can be increased by separate addition of an olefin-rich stream into the first feed stream. In principle, the first feed stream used already contains olefins.
• an olefin-poor and an olefin-free material stream are added as dilution stream in the first feed stream.
• the hydrogenation can be controlled to provide a well-defined amount of heat.
• the temperature behind the first catalyst bed is thereby adjusted to provide, when mixed with the second feed stream, precisely the temperature required to pass through the second catalyst bed.
• the reactor may also contain more than two catalyst beds.
• the stream obtained in the reaction is passed through a third catalyst bed, whereby this and the gas stream passed through heated. This means that behind the second catalyst bed, a third feed stream is added laterally behind the second catalyst bed into the reactor to the stream heated by the second hydrogenation and the gas stream for hydrogenation flows through a third catalyst bed after passing through the second catalyst bed.
• a third feed stream is added laterally behind the second catalyst bed in the reactor to the stream heated by the second hydrogenation, and the stream for hydrogenation flows after passing through the second catalyst bed by a third catalyst bed. It is possible to pass the material stream obtained after passage through the third subset of the hydrogenating desulfurization catalyst through a further or several further subsets of a hydrogenating desulfurization catalyst and to add a further feedstream laterally behind the catalyst beds into the reactor.
• an olefinarmer and an olefin-free material flow is performed in the supply line for the second feed stream behind the first catalyst bed. Due to the admixture amounts of the individual material flows, the olefin content can also be controlled in this second feed stream. This in turn makes it possible to control the temperature in the third catalyst bed. Again, it may be possible in one embodiment of the invention to additionally direct an olefin-rich material flow into the reactor.
• the olefin-free gas is preferably hydrogen, methane or a mixture of these substances.
• the olefinarmen gas is preferably a gas containing as main component hydrogen or methane or both.
• another gas may be, for example, alkanes or carbon dioxide.
• the olefin-rich, the olefinarm or the olefin-free material stream can be mixed as desired. Also, they advantageously contain no undesirable foreign gases.
• the feed stream is preferably fed via the top of the reactor of the hydrogenation reaction.
• the proportion of gas fed in overhead may in principle be arbitrary, but is preferably from 1 to 99% by mass. Ideally, the mass flow of the overhead gas is 5 to 15 mass percent.
• the feed stream as feed stream for hydrodesulfurization preferably contains light olefins which are gaseous at the operating temperature. These are preferably in the C number range from 2 to 6. However, it is also possible to use higher olefins which are liquid at the starting temperature or heavier hydrocarbons. These can also be in the higher C-number range. In principle, all olefins which can be desulfurized by hydrogenation and purification are suitable as the feed stream.
• the reaction of the hydrogenation is preferably carried out at a temperature of 150 to 500 0 C. Optimal temperature ranges from 250 to 400 0 C.
• the feed stream is therefore preferably at a temperature of 200 to 400 0 C fed into the reactor.
• a particularly suitable reaction is the hardening Ström to the reactor at a temperature of 250 0 C to 350 0 C.
• the respective temperature in the reactor is then given by the appropriate reaction.
• the reaction mixture is cooled.
• the pressure in the reactor can be controlled much better. This is for a favorable type of execution at 0, 1 to 10 MPa.
• the heating of the feed stream to the temperature necessary for the reaction can be done arbitrarily. This can be done for example via burners or steam heaters. The heating of the feed stream but is preferably done via heat exchangers. This can be done anywhere. As a heating medium can serve for this purpose the heated material flow in the reactor. The heating by the heat exchanger can be done anywhere. This can be done, for example, at the individual feed streams. But this can also be done on the streams that are added to the feed streams. This can also be done on the feed stream, which is fed into the reactor head.
• the process for hydrogenating desulfurization is followed by gas scrubbing or separation for hydrogen sulfide. This can be of any kind and can be executed at any point in the process.
• the process for hydrogenating desulphurization is followed by an adsorption process with a chemical adsorption.
• the invention also claims a device with which the inventive method can be performed. Claimed is in particular a device, and which is characterized in that
• the header line leading the first feed stream leads from the top side into a reactor equipped with a plurality of horizontally arranged catalyst beds, wherein the reactor contains at least two horizontally arranged catalyst beds, and On the reactor between the first and the second catalyst bed, a second pipe leading laterally into the reactor is installed, which introduces the second feed stream into the downwardly flowing stream, so that the resulting stream flows through the second catalyst bed, and • the pipes for at least contain a feed stream supply lines for material flows, which can be used to regulate the proportion of olefin in the feed stream.
• This may be a feed line with which an olefin-rich material stream is added to the feed stream.
• the olefin content in the feed stream increases and the temperature in the subsequent catalyst bed increases accordingly.
• these can also be feed lines for a polyolefin-free or olefin-free material stream, in order to correspondingly reduce the olefin content of the feed streams.
• the feed streams for streams may be located anywhere on the reactor or in the feed lines for the feed streams. These can also be present in any combination.
• the olefin content in the feed streams can be accurately metered.
• This also allows the temperature in the reactor to be precisely controlled.
• a device for dividing the feed stream For dividing the gas stream is located directly on the supply line for the fresh feed stream, a device for dividing the feed stream.
• the device according to the invention also includes valves with which the supply of the gas to the individual injection or injection devices in the reactor can be precisely controlled. Depending on the heating of the gas in the individual catalyst beds, the supplied amount of substance is then metered. Thus, the temperature in the reactor can be maintained within the prescribed temperature limits.
• the reactor contains more catalyst beds. This also includes the corresponding further introduction devices for the feedstock and material flows. In this case, a device is claimed, wherein
• • are installed in the reactor in three or more further horizontally installed catalyst beds, wherein • three or more further pipelines leading laterally into the reactor are installed in the reactor, which can introduce feed streams into the downstream stream, so that the stream obtained can flow through the further catalyst beds, and
• the pipelines for the additional feed streams contain feed lines for olefin-containing material streams, with which the proportion of olefin in the feed stream can be regulated.
• the feed rate and the composition of the feed stream into the reactor are preferably controlled via the temperature as a parameter. Therefore, temperature sensors or thermometers can be located anywhere in the reactor. Also, heaters or cooling devices can be located at any point in the device according to the invention, with which the temperature can be additionally controlled. Of course, the device according to the invention also include the control devices necessary for the control, it does not matter if they are electrical, electronic or mechanical nature. The regulation of the amount and composition of the supplied material flow is also possible via other signals, for example via the sulfur or olefin content of the gas or a combination of these measured values. For this purpose, measuring sensors can be located at any point in the supply lines or in the reactor.
• the device according to the invention is already shown in principle in the patent DE 102008059243 A1. This differs from the present device in particular by the additional pipes for olefin Vietnamese feed streams.
• the device according to the invention may further comprise at any point devices that are necessary to maintain optimal operation. These may be, for example, valves, pumps, gas distributors or gas conveyors. But these can also be sensors, thermometers, flow meters or analytical devices. These can be located anywhere in the device according to the invention.
• the inventive method and apparatus of the invention allow the hydrogenating desulfurization of olefin-containing gases with little equipment and without expensive cooling or heating.
• the desulphurisation system is effective, so that the sulfur content of the feed stream in the subsequent gas scrubbing down to the ppb range: can be reduced (ppb parts per trillion, 10 "7 mole percent)
• the method allows reliable and safe temperature control and handling of the process by..
• the process according to the invention comprises a product gas which essentially contains only hydrogen sulfide as sulfur compound.
• FIG. 1 shows a reactor according to the invention by way of example with three catalyst beds for carrying out a hydrodesulfurization.
• the feed stream (1) is divided by a gas distributor (2) into three feed streams (3,4,5).
• the feed stream usually already contains the necessary amount of olefins.
• three valves (3a, 4a, 5a) for regulating the feed stream are installed.
• the first feed stream (3) is preheated by means of a heating device (6) or a heat exchanger (with heat flow, 6a) and introduced into the reactor (7) via the reactor head (3b) (8a). Ideally, the temperature when introducing the first stream 300 0 C.
• the first feed stream meets there on the first catalyst bed (8) and heats up there.
• the catalyst bed (8) contains the catalyst (8b) on suitable carrier particles and a grid (8c) or another suitable holding device.
• the temperature at the outlet at the bottom grid floor for the first catalyst bed (8) can be up to 390 0 C, but is typically 370 0 C.
• the temperature in this first catalyst bed is controlled via the olefinsulfonates financed part of the first feed stream (3b).
• the first catalyst bed (8) heats up more.
• the olefin content can in turn be regulated by means of different material streams (9a, b, c), which are passed here by way of example as dilution gas stream into the first feed stream (3).
• a further dilution stream (4) is introduced here behind the first catalyst bed (8) without further control in a second feed stream (10a). There- the stream cools again, ideally to 300 ° C. Thus, this stream impinges on the second catalyst bed (10) with catalyst (10b) on a holding device (10c). There the material stream heats up again by the hydrogenation reaction. To set the correct reaction temperature, a further feed stream (11a) is then introduced behind the catalyst bed. The resulting stream then again meets a third catalyst bed (12) with catalyst (11b). The catalyst is held in the reactor by gratings (8c, 10c, 11c) or other holding devices.
• a product gas (12) is obtained, which essentially contains only hydrogen sulfide as sulfur compound.
• the product gas is carried out at the end of the reactor (13).
• the first feed stream (3b) is preheated by way of example via a heat exchanger (6).
• the heat energy of the feed stream (13) is also used (14a), for example, to preheat the olefin-poor stream (9b) via a heat exchanger (14), which is placed in the first feed stream (3).
• the feed stream (3) can be further heated via a further heat exchanger (14b) for adjusting the temperature.
• the individual material flows (9a, b, c) can be regulated via valves (15a, b, c). On the side typical reactor temperatures are given.

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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)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 2009
  • 2009-07-10 DE DE102009032802A patent/DE102009032802A1/de not_active Withdrawn
• 2010
  • 2010-07-07 IN IN1106DEN2012 patent/IN2012DN01106A/en unknown
  • 2010-07-07 MY MYPI2012000075A patent/MY172046A/en unknown
  • 2010-07-07 EP EP10739852.1A patent/EP2451903B1/de active Active
  • 2010-07-07 CA CA2767397A patent/CA2767397A1/en not_active Abandoned
  • 2010-07-07 MX MX2012000429A patent/MX2012000429A/es unknown
  • 2010-07-07 EA EA201290030A patent/EA028944B1/ru not_active IP Right Cessation
  • 2010-07-07 DK DK10739852.1T patent/DK2451903T3/da active
  • 2010-07-07 PL PL10739852T patent/PL2451903T3/pl unknown
  • 2010-07-07 WO PCT/EP2010/004092 patent/WO2011003585A2/de not_active Ceased
  • 2010-07-07 US US13/382,822 patent/US20130030235A1/en not_active Abandoned
  • 2010-07-07 CN CN201080031139.2A patent/CN102471703B/zh not_active Expired - Fee Related
• 2012
  • 2012-02-07 CO CO12021311A patent/CO6612178A2/es active IP Right Grant
  • 2012-02-10 ZA ZA2012/00993A patent/ZA201200993B/en unknown

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