WO2015039978A1 - Installation de production de pétrole équipé d'un dispositif de génération de composés organiques liquides provenant du gaz associé au pétrole - Google Patents

Installation de production de pétrole équipé d'un dispositif de génération de composés organiques liquides provenant du gaz associé au pétrole Download PDF

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Publication number
WO2015039978A1
WO2015039978A1 PCT/EP2014/069568 EP2014069568W WO2015039978A1 WO 2015039978 A1 WO2015039978 A1 WO 2015039978A1 EP 2014069568 W EP2014069568 W EP 2014069568W WO 2015039978 A1 WO2015039978 A1 WO 2015039978A1
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plasma
gas
crude oil
boiling point
stream
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PCT/EP2014/069568
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German (de)
English (en)
Inventor
Rene König
Philipp Brüggemann
Michael HÜBNER
Jörg EBRECHT
Eduard KUNKES
Andries WEVER
Wieland Koban
Otto Machhammer
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Basf Se
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Publication of WO2015039978A1 publication Critical patent/WO2015039978A1/fr

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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
    • C10G5/00—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas

Definitions

  • Petroleum extraction plant with apparatus for producing liquid organic compounds from associated petroleum gas
  • the present application relates to a petroleum production plant, which is adapted to collect escaping from a source of crude oil associated gas, to produce one or more organic compounds having a boiling point of 15 ° C or higher from gaseous constituents of the trapped crude oil associated gas and these organic compounds in to feed a crude oil stream withdrawn from the petroleum source so that a modified crude oil stream is formed, which can be transported away from the petroleum production plant by means such as are usually used for the removal of the crude oil and are present in an operating crude oil production plant.
  • Associated Petroleum Gas is understood to mean a mixture of gaseous chemical compounds similar in composition to natural gas, which is released from an oil well during oil production. Depending on the eligible area, up to 800 cubic meters of associated petroleum gas accumulates per tonne of oil produced. Crude gas oil contains methane in a proportion of typically 35 to 90 mol%, based on the total of all gaseous constituents of the associated petroleum gas, as well as, in addition, typically other short-chain hydrocarbons to hexane, which are partly liquid at room temperature. Therefore, associated petroleum gas is also called wet gas. In addition, untreated crude oil associated gas contains water vapor, hydrogen sulfide, carbon dioxide, nitrogen, noble gases, heavy metals and other ingredients. The composition of the associated petroleum gas varies with the geographical location and the type and depth of the oil deposit.
  • the associated petroleum gas is either vented or flared at many production sites. Both approaches are harmful from the point of view of climate and environmental protection. During deflation, methane and other pollutants acting as greenhouse gases reach the atmosphere; especially when burning large amounts of carbon dioxide, in addition to other pollutants such as sulfur oxides, unburned hydrocarbons, carbon monoxide, nitrogen oxides, heavy metals and fine dust. For this reason, legal measures have been taken in some oil-producing states to restrict or stop the discharge and flaring of associated petroleum gas.
  • An alternative to deflagration and flaring is the re-injection of the associated petroleum gas into the reservoir. This method has the advantage that the associated petroleum gas fed back into the deposit causes a pressure build-up which is advantageous for oil production.
  • the process comprises, as a first step, the conversion of methane to acetylene by means of a thermal plasma quenched by contact with the reactor walls or aerodynamically by expansion by means of a supersonic nozzle and, as a second step, the conversion of acetylene into liquid products in a catalytic process ,
  • the method is intended in particular for use at remote natural gas production facilities, eg on the north coast of Alaska, for which the construction of a gas pipeline for the removal of the gas is unprofitable.
  • the publication does not indicate how the electrical energy required for the plasma should be provided.
  • the catalytic process downstream of the catalytic process requires purification of the natural gas, in particular desulfurization, and the formation of soot must be avoided. Tonkovich et al.
  • the catalysts for the Fischer-Tropsch synthesis are particularly susceptible to poisoning by sulfur-containing compounds, so it is essential to remove all sulfur compounds from the gas stream before the Fischer-Tropsch synthesis (see also Steve LeViness et al, "Improved Fischer-Tropsch Economics Enabled by Microchannel Technology ", white paper, Velocys ⁇ 201 1 http://www.velocys.com/ocgf06.php)
  • the desulphurisation is usually carried out at 350 to 400 ° C in a catalytic process
  • Water vapor reforming required temperature level 700 ° C to 1 100 ° C
  • the process thus comprises a total of up to four catalysed process steps, each associated with the risk of deactivation of the catalysts involved Fischer-Tropsch synthesis stage to set an optimal CO: H 2 ratio of 1: 2, it is necessary in a Zwi after the steam reforming step, hydrogen is separated from the process gas.
  • the primary object of the present invention is to set up a petroleum extraction plant to collect escaping petroleum gas from a petroleum source, and to form liquid organic compounds from gaseous constituents of the intercepted petroleum associated gas which can be carried away from the petroleum production plant without any additional effort additional effort "means that the same means of transporting the liquid compounds from the crude oil In pipelines or loading on tankers or tankers) can be used, as they are usually used for the removal of crude oil and are present in an operating oil production plant.
  • the methods and devices should be simple, robust, reliable and low maintenance and allow for the typically accumulating amounts of associated petroleum gas from 10 to 700,000 kt / a profitable operation.
  • a Erdölörderstrom comprising a device for removing a crude oil stream from a petroleum source
  • said apparatus comprising means for generating a quenched gas stream by contacting a plasma-treated gas stream with a quench fluid;
  • an apparatus connected to the apparatus for plasma assisted production of one or more organic compounds having a boiling point of 15 ° C or higher for feeding the produced organic compounds having a boiling point of 15 ° C or higher into the crude oil stream withdrawn from the petroleum source or in a crude oil stream generated therefrom to form a modified crude oil stream;
  • the device comprises a region in which the trapped crude oil accompanying gas is exposed to a plasma, so that a plasma-treated gas stream is formed, whereby it is preferred To expose the associated gas to the plasma together with crude oil extracted from the crude oil stream (see below) .
  • This plasma-treated gas stream forms a quenched gas stream in the apparatus by contacting it with a quench fluid
  • the apparatus optionally comprises further regions in which the quenched gas stream is further treated without being exposed to a plasma.
  • Another aspect of the present invention relates to a method of producing a modified crude oil stream within a petroleum production plant comprising the steps
  • “Plasma assisted generation of one or more organic compounds having a boiling point of 15 ° C or higher from constituents of the trapped petrochemical associated gas having a boiling point below 15 ° C” means at least during a process step of producing one or more organic compounds having a boiling point of 15 ° C or higher, the associated petroleum gas is exposed to a plasma to form a plasma-treated gas stream, and it is preferable to expose the associated petroleum gas to the plasma together with crude oil withdrawn from the crude oil stream (see below) ). From the plasma-treated Gas stream is formed by contacting with a quench fluid a quenched gas stream. This step is followed, if appropriate, by further process steps in which the quenched gas stream is further treated without being exposed to a plasma.
  • the apparatus for plasma-assisted generation of one or more organic compounds having a boiling point of 15 ° C or higher preferably comprises
  • the plasma-treated gas stream is contacted with a quench fluid to form a quenched gas stream
  • quenched gas stream optionally further treated.
  • a plasma gas-preferably a gas available or producible on the petroleum-producing plant- is partially ionized by the action of an arc formed between two electrodes.
  • the above-mentioned means for generating a plasma accordingly comprise the electrodes for generating the arc together with the power supply and means for bringing a plasma gas into the arc.
  • the plasma formed (DC plasma) has a temperature in the range of 5000 ° C to 30000 ° C, preferably 7000 ° C to 27000 ° C, more preferably 10000 ° C to 25000 ° C.
  • the plasma reaction space is actively cooled.
  • the plasma contains ions, electrons and atoms in equilibrium. In the recombination of ions and electrons As a result, thermal energy is released. Suitable ways of producing plasma on a petroleum production facility with on-site, available or producible supplies and energy carriers are detailed below.
  • the associated petroleum gas Before entering the plasma reaction space, the associated petroleum gas is heated to a temperature in the range from 100.degree. C. to 1200.degree. C., preferably from 200.degree. C. to 1000.degree. C., more preferably from 400.degree. C. to 700.degree. preheated. If oil associated gas is exposed to the plasma together with crude oil, the crude oil is also preheated accordingly.
  • a prior purification of the petroleum feed gas e.g. by desulfurization and / or separation of water vapor and / or carbon dioxide is not absolutely necessary for the device according to the invention or the method according to the invention, since the device according to the invention or the method according to the invention can be operated without catalysts.
  • Sulfur-containing components of the associated petroleum gas primarily hydrogen sulfide and low molecular weight thiols
  • the solid or liquid reaction products of the sulfur-containing constituents of the associated petroleum gas are fed, together with the other produced organic compounds having a boiling point of 15 ° C.
  • methyl radicals and hydrogen radicals are pyrolyzed and dissociate into free-radical species, for example methyl radicals and hydrogen radicals.
  • the methyl radicals form by dimerization and hydrogen cleavage unsaturated C 2 hydrocarbons (mainly acetylene, next to ethylene, wherein the molar ratio between acetylene and ethylene is influenced by the choice of process parameters pressure, temperature, average residence time and quench rate), from which optionally by oligomerization higher molecular weight organic compounds are formed, which in turn optionally act as a starting material for the formation of carbon black.
  • the composition of the reaction products formed can be influenced by the choice of the process parameters pressure, temperature, average residence time in the plasma and quench rate.
  • the reaction is either controlled so that unsaturated C 2 hydrocarbons formed in the plasma oligomerize to the desired organic compounds having a boiling point of 15 ° C or higher such that the quenched gas stream will have organic compounds with a boiling point of 15 ° Contains C or higher; or alternatively, the reaction is controlled so that no or at least no significant oligomerization of the unsaturated C 2 hydrocarbons formed occurs, so that the quenched gas stream contains predominantly acetylene and / or ethylene and then in a second reaction space to form the desired organic compounds with a Boiling point of 15 ° C or higher is treated. Both embodiments are encompassed by the present invention and are each characterized by specific advantages.
  • the pyrolysis of the higher hydrocarbons present in the crude oil shifts the molar ratio of hydrogen to unsaturated C 2 hydrocarbons in favor of the unsaturated one C 2 hydrocarbons, so that their further reaction for the formation of organic compounds having a boiling point of 15 ° C or higher is favored.
  • the means for contacting the plasma-treated gas stream with a quench fluid are located at the exit of the plasma reaction space or within the plasma reaction space near the exit thereof.
  • the quench fluid is preferably selected from the group consisting of air, associated petroleum gas, water, crude oil and mixtures thereof.
  • Crude oil or crude oil as a quenching fluid cause a shift in the selectivities and yields in favor of organic compounds having a boiling point of 15 ° C or higher.
  • Water as a quench fluid is able to abruptly interrupt the reactions taking place in the plasma reaction space so that high yields of gaseous C 2 species are achieved, optionally with hydrogen and carbon monoxide as by-products.
  • Water as a quench fluid is therefore particularly preferred for a particular variant of the device of the invention wherein a further reaction space is provided in which one or more catalysts for forming one or more organic compounds having a boiling point of 15 ° C or higher are contained in the quenched gas stream Acetylene and / or ethylene are arranged (see below), or the inventive method, wherein from the quenched gas stream contained acetylene and / or ethylene in the presence of one or more catalysts, one or more organic compounds having a boiling point of 15 ° C or be formed higher (see below).
  • organic compounds having a boiling point of 15 ° C or higher are compounds selected from the group consisting of benzene, alkyl-substituted benzenes (eg methylbenzene (toluene), dimethylbenzenes (xylenes), vinylbenzene (styrene), isopropylbenzene ( Cumene), methylethylbenzene, butylbenzene), further substituted aromatic compounds (eg cresol, biphenyl, indanone), polycyclic aromatic hydrocarbons (PAH, eg indane (cyclopentenobenzene), naphthalene, acenaphthene, phenyltoluene, anthracene, fluoranthene, pyrene and higher polycyclic aromatic Hydrocarbons) and saturated aliphatic hydrocarbons having more than 5 carbon atoms in the molecule (eg decalin).
  • alkyl-substituted benzenes
  • organic compounds produced according to the invention having a boiling point of 15 ° C. or higher are fed into the crude oil stream as withdrawn from the crude oil source.
  • the crude oil stream taken from the petroleum source prior to feeding the inventively produced organic compounds having a boiling point of 15 ° C or higher, is subjected to treatment and / or processing steps (eg, separation of water), and the organics produced according to the invention Compounds with a boiling point of 15 ° C or higher are fed into a crude oil stream which has been produced from the crude oil stream taken from the crude oil source.
  • a modified crude oil stream is formed which contains both components derived from the crude oil and those from constituents of the associated petroleum gas with a boiling point below 15 ° C according to the invention produced organic compounds having a boiling point of 15 ° C or higher.
  • Such a modified crude oil stream produced in accordance with the present invention can be carried away from the petroleum production plant by such means as are commonly employed for the removal of the crude oil and present in an operating petroleum production facility, e.g. by connecting the petroleum extraction plant to a pipeline or by loading onto tankers or vessels.
  • the means for generating a plasma, the plasma reaction space and the means for generating a quenched gas stream adapted to form a quenched gas stream containing one or more hydrocarbons having a boiling point of 15 ° C or higher.
  • crude oil accompanying gas or crude oil is preferably used as the quench fluid.
  • a plasma is generated in such a manner, the crude gas associated possibly exposed together with crude oil to the plasma generated and brought the generated plasma-treated gas stream with a quench fluid in contact that a quenched gas stream containing one or several hydrocarbons having a boiling point of 15 ° C or higher is formed.
  • the device for plasma-assisted production of one or more organic compounds having a boiling point of 15 ° C. or higher is preferably designed such that the average residence time in the plasma reaction space is 0.1 ms to 20 ms. preferably 0, 1 ms to 10 ms, more preferably 0, 1 ms to 5 ms is at a volume flow of associated gas from 1 standard m 3 / h to 10000 standard m 3 / h, preferably from 1 standard m 3 / h to 4000 standard m 3 / h, and an energy input per kg of associated petroleum gas from 1 kWh to 40 kWh, preferably from 1 kWh to 20 kWh and more preferably from 6 to 14 kWh.
  • the quench rate in the first preferred embodiment of the invention is 10 2 K / s to 10 7 K / s, preferably 10 3 K / s to 10 6 K / s, more preferably 10 5 K / s to 10 6 K / s.
  • the pressure in the device is 50 kPa to 5000 kPa, preferably 80 kPa to 1500 kPa, more preferably 100 kPa to 500 kPa.
  • the apparatus for plasma enhanced production of one or more organic compounds having a boiling point of 15 ° C or higher preferably comprises means for circulating the quenched gas stream over a defined average residence time to keep in a certain temperature range.
  • a discharge line following the plasma reaction space is provided in the device.
  • the quenched gas stream is preferably maintained in the outlet section over a mean residence time of 100 ms to 1000 ms, more preferably of 300 ms to 500 ms, at a temperature in the range of 400 ° C to 1000 ° C.
  • Means are preferably arranged at one or more positions in the outlet section in order to bring the gas stream flowing through the outlet section, which has already been brought into contact with a quench fluid in the vicinity of the exit of the plasma reaction space, into contact again with a quench fluid to control the processes taking place in the outlet section and thus the composition of the gas flow.
  • Our own investigations have shown that the average residence time in the first third of the outlet section has a decisive influence on the composition of the quenched gas stream.
  • the average residence time in the first third of the outlet section is preferably 5 ms to 100 ms, preferably 10 ms to 80 ms set to 25 ms to 60 ms.
  • the mean residence time in the first third of the outlet section can be set by appropriate selection of the volume flows of the plasma gas, the associated petroleum gas and the quench fluids.
  • Means are preferably arranged in the first third of the outlet section in order to bring the gas stream, which has already been brought into contact with a quench fluid in the vicinity of the outlet of the plasma reaction space, into contact again with a quench fluid.
  • a conversion based on the methane present in the associated petroleum gas of 5% or higher, preferably 50% or higher and particularly preferably 70% or higher is preferably achieved and a carbon yield of organic compounds having a boiling point of 15 ° C or higher of 2% to 20%, preferably 2% to 30%, more preferably 2% to 70%.
  • the first preferred embodiment of the invention is characterized in that the quenched gas stream leaving the plasma reaction space already contains the desired organic compounds having a boiling point of 15 ° C. or higher.
  • the reactor can be made relatively compact and simple, and a catalyst is not required.
  • the means for generating a plasma, the plasma reaction space and the means for generating of a quenched gas stream adapted to form a quenched gas stream containing one or more hydrocarbons having a boiling point of 15 ° C or higher and carbon black.
  • a plasma is generated in such a manner, the associated gas exposed to the plasma generated plasma and brought the plasma-treated gas stream with a quench fluid in contact that a quenched gas stream containing one or more hydrocarbons with a boiling point of 15 ° C or higher and soot is formed.
  • the formation of carbon black can be achieved by appropriate adjustment of the o.g. Process parameters, e.g. Choice of a relatively high energy input per kg of associated petroleum gas and a relatively long residence time in the outlet section, wherein the higher the residence time, the smaller the temperature in the outlet section. It is suitable, e.g. an energy input of 14 kWh / kg associated petroleum gas or more in the plasma reaction chamber in combination with a mean residence time of 400 ms or more at an average temperature of the outlet line of 500 ° C or more, and an energy input of 20 kWh / kg of associated petroleum gas or more in the plasma reaction room in combination with an average residence time of 300 ms or more with a mean outlet temperature of 200 ° C or more.
  • Process parameters e.g. Choice of a relatively high energy input per kg of associated petroleum gas and a relatively long residence time in the outlet section, wherein the higher the residence time, the smaller the temperature in the outlet section. It is suitable, e.g. an energy input of 14 kWh / kg associated petroleum gas or
  • the hydrocarbons formed having a boiling point of 15 ° C or higher are partially adsorbed by the resulting carbon black.
  • the proportion of hydrocarbons having a boiling point of 15 ° C or higher adsorbed by carbon black is 10 to 30 mol% based on the total amount of hydrocarbons having a boiling point of 15 ° C or higher.
  • the carbon black adsorbed compounds are predominantly aromatic hydrocarbons (including polycyclic aromatic hydrocarbons).
  • the content of carbon black adsorbed on aromatic hydrocarbons is preferably up to 25 wt .-%, preferably up to 30 wt .-%, particularly preferably up to 50 wt .-%.
  • This carbon black is preferably fed together with the produced organic compounds having a boiling point of 15 ° C or higher into the crude oil stream withdrawn from the petroleum source or a crude oil stream produced therefrom, so that a modified crude oil stream is formed.
  • the carbon black content of the modified crude oil stream is at most 10% by weight, based on the total mass of crude oil and carbon black, preferably less than 10% by weight, based on the total mass of crude oil and carbon black.
  • the means for generating a plasma, the plasma reaction space and the means for generating a quenched gas stream are adapted to form a quenched gas stream containing acetylene and / or ethylene, and is another reaction space for forming one or more organic compounds with one Boiling point of 15 ° C or higher from provided in the quenched gas stream contained acetylene and / or ethylene.
  • a plasma is generated in such a way, the crude gas associated possibly exposed together with crude oil to the plasma generated and the plasma-treated gas stream with a quench fluid in contact, that a quenched gas stream containing acetylene and / or ethylene is formed, - and are in one further step of acetylene and / or ethylene contained in the quenched gas stream one or more organic compounds having a boiling point of 15 ° C or higher formed.
  • the device to be used according to the invention comprises two successive reaction spaces (a plasma reaction space and a further reaction space), in which the gas flow is in each case for a defined average residence time is exposed to certain conditions, so that run in each of the two reaction spaces, the desired reactions.
  • the device for plasma-assisted production of one or more organic compounds having a boiling point of 15 ° C. or higher is preferably designed such that the average residence time in the plasma reaction space is 0.1 ms to 20 ms. preferably 0, 1 ms to 10 ms, more preferably 0, 1 ms to 5 ms is at a volume flow of associated gas from 1 standard m 3 / h to 10000 standard m 3 / h, preferably from 1 standard m 3 / h to 4000 standard m 3 / h and an energy input per kg of associated petroleum gas from 1 kWh to 40 kWh, preferably from 3 kWh to 20 kWh and more preferably from 8 to 13 kWh.
  • the quench rate in the second preferred embodiment of the invention is 10 2 K / s to 10 7 K / s, preferably 10 3 K / s to 10 6 K / s, particularly preferably 10 5 K / s to 10 6 K / s.
  • the pressure in the device is 50 kPa to 6000 kPa, preferably 80 kPa to 1500 kPa.
  • the level of pressure influences the selectivity with regard to the formation of acetylene or ethylene. If a high proportion of acetylene is desired, the pressure is preferably selected in the range 100 kPa to 1000 kPa, for a high proportion of ethylene, however, in the range of 1000 kPa to 6000 kPa.
  • no catalysts are provided in the second reaction space.
  • the associated petroleum gas is exposed to the plasma together with crude oil.
  • this is preferably designed such that the mean residence time is 0.1 s to 120 s, preferably 1 s to 60 s, more preferably 2 s to 30 s is at a temperature in the range of 100 ° C to 1500 ° C, preferably from 100 ° C to 1300 ° C, more preferably from 200 ° C to 800 ° C, wherein in the second Reaction space no catalysts are provided.
  • Means are preferably arranged at one or more positions in the second reaction space in order to bring the gas stream flowing through, which has already been brought into contact with a quench fluid in the vicinity of the exit of the plasma reaction space, into contact again with a quench fluid in order to achieve the effect as described in US Pat second Reaction space running processes and thus to control the composition of the gas stream.
  • the mean residence time in the first third of the second reaction space is preferably 1 ms to 80 ms, preferably set to 2 ms to 50 ms, more preferably set to 5 ms to 30 ms.
  • the mean residence time in the first third of the second reaction space is adjustable by appropriate selection of the volume flows of the plasma gas, the associated gas and the quench fluids.
  • Means are preferably arranged in the first third of the second reaction space in order to bring the gas stream, which has already been brought into contact with a quench fluid in the vicinity of the outlet of the plasma reaction space, into contact again with a quench fluid.
  • a constant temperature selected from the region defined above, preferably from the area designated as preferred, is impressed on the second reaction space by cooling or heating.
  • the second reaction space is subdivided into individual successive reaction modules each with individually adjustable temperature and with means for bringing the gas flow into contact with a quench fluid, the quench rate being individually adjustable for each module.
  • the temperatures are adjusted so that the temperature decreases from module to module in the direction of flow.
  • the temperatures of the individual modules being selected from the range defined above, preferably from the area designated as preferred.
  • Particularly preferred is a temperature profile which extends from a maximum value of 1000 ° C at the entrance of the second reaction space to a minimum value of 100 ° C at the outlet of the second reaction space. Size and number of consecutive modules are thereby designed so that the desired average residence time, based on the second reaction space as a whole, is achieved.
  • a conversion is preferably achieved based on the methane contained in the associated petroleum gas of 5% or higher, preferably 50% or higher and particularly preferably 70% or higher, and a carbon yield of organic compounds having a boiling point of 15 ° C or higher of 5% to 50%, preferably 10% to 60%, particularly preferably 20% to 80%.
  • the second preferred embodiment of the invention is characterized in that acetylene and / or ethylene is first formed with high selectivity and high carbon yield from the associated petroleum gas, and then the acetylene and / or ethylene formed in a controlled thermal oligomerization (ie with higher selectivity and typically higher carbon yield compared to the plasma process in the first embodiment of the invention described above) to compounds with a boiling point of 15 ° C or higher, for example is converted from the group consisting of benzene, naphthalene and anthracene without the need for a catalyst.
  • a controlled thermal oligomerization ie with higher selectivity and typically higher carbon yield compared to the plasma process in the first embodiment of the invention described above
  • the means for generating a plasma, the plasma reaction space and the means for generating a quenched gas stream are arranged so that a quenched gas stream comprising acetylene and / or ethylene is formed, and is another reaction space for forming one or more organic compounds a boiling point of 15 ° C or higher and optionally carbon black from contained in the quenched gas stream acetylene and / or ethylene provided.
  • a plasma is generated in such a way, the associated gas associated with the generated plasma plasma and the plasma-treated gas stream with a Quenchfluid brought into contact, that a quenched gas stream containing acetylene and / or ethylene is formed,
  • one or more organic compounds having a boiling point of 15 ° C or higher and carbon black are formed from acetylene and / or ethylene contained in the quenched gas stream.
  • the formation of carbon black can be achieved by appropriate adjustment of the o.g. Process parameters, e.g. Choice of a relatively high energy input per kg of associated petroleum gas and a relatively long residence time or high temperature in the second reaction space, wherein the higher the residence time, the smaller the temperature in the second reaction is.
  • Process parameters e.g. Choice of a relatively high energy input per kg of associated petroleum gas and a relatively long residence time or high temperature in the second reaction space, wherein the higher the residence time, the smaller the temperature in the second reaction is.
  • soot formation is achieved with mean residence times of more than 20 s at a temperature in the second reaction space of at least 1000 ° C., mean residence times of more than 10 s at a temperature in the second reaction space of at least 1300 ° C., and average residence times greater than 1 s at a temperature in the second reaction space at least 1600 ° C, wherein no catalysts are provided in the second reaction space.
  • an energy input of 14 kWh / kg of associated petroleum gas or more in the plasma reaction space is in combination with an average residence time of 400 ms or more at an average temperature in the second reaction chamber of 500 ° C or more, and an energy input of 20 kWh / kg associated petroleum gas or more in the plasma reaction chamber in combination with a mean residence time of 1 s or more at an average temperature in the second reaction chamber of 300 ° C suitable for soot formation.
  • the hydrocarbons formed having a boiling point of 15 ° C or higher are partially adsorbed by the resulting carbon black.
  • the proportion of hydrocarbons having a boiling point of 15 ° C or higher adsorbed by carbon black is 10 to 30 mol% based on the total amount of hydrocarbons having a boiling point of 15 ° C or higher.
  • the compounds adsorbed by carbon black are predominantly aromatic hydrocarbons (including polycyclic hydrocarbons). aromatic hydrocarbons).
  • the content of carbon black adsorbed on aromatic hydrocarbons is preferably up to 25 wt .-%, preferably up to 30 wt .-%, particularly preferably up to 50 wt .-%.
  • This carbon black is preferably fed together with the produced organic compounds having a boiling point of 15 ° C or higher into the crude oil stream withdrawn from the petroleum source or a crude oil stream produced therefrom, so that a modified crude oil stream is formed.
  • the carbon black content of the modified crude oil stream is at most 10% by weight, based on the total mass of crude oil and carbon black, preferably less than 10% by weight, based on the total mass of crude oil and carbon black.
  • one or more catalysts for forming one or more organic compounds having a boiling point of 15 ° C. or higher from acetylene and / or ethylene contained in the quenched gas stream are arranged in the further reaction space .
  • water is preferably used as the quenching fluid.
  • one or more organic compounds having a boiling point of 15 ° C or higher are formed from acetylene and / or ethylene contained in the quenched gas stream in the presence of one or more catalysts.
  • the second reaction space for forming one or more organic compounds having a boiling point of 15 ° C or higher, in which one or more catalysts are arranged, is preferably designed so that the average residence time 10 ms to 1000 ms, preferably 100 ms to 1000 ms , more preferably 300 ms to 1000 ms at a temperature in the range of 100 ° C to 1500 ° C, preferably from 20 ° C to 600 ° C, more preferably 20 ° C to 300 ° C. Average residence time and temperature are chosen so that the formation of soot, which could deposit on the catalyst and block it, is avoided.
  • a conversion is preferably achieved based on the methane present in the associated petroleum gas of 5% or higher, preferably 20% or higher and particularly preferably 60% or higher.
  • a conversion of 5% or higher, preferably 50% or higher and particularly preferably 70% or higher is achieved and a carbon yield of ethylene of 20% or higher, preferably 40% or higher, and up to 80%, preferably achieved up to 90% and more preferably achieved up to 100% or a carbon yield of acetylene of 10% or higher and up to 50%.
  • the C yields of acetylene and ethylene are additive and taken together are a maximum of 100%.
  • either a gas stream rich in acetylene or in ethylene is advantageous.
  • all catalysts are suitable which have Lewis acidic and / or Brönsted acidic catalytically active centers.
  • catalysts (optionally in combination with promoters) based on elements from the 3rd to 14th group of the periodic table (except carbon) on a suitable support material, preferably a support material having Lewis acid and / or Brönsted acid centers.
  • Preferred elements from the 3rd to 14th group of the periodic table are molybdenum, manganese, iron, cobalt, nickel, aluminum, boron and silicon.
  • catalysts according to the invention are, for example, zeolite H-ZSM5 (a form of the zeolite ZSM 5 in which the metal cations are exchanged by protons), nickel-doped zeolite ZSM 5 and a catalyst comprising molybdenum on a zeolite, in particular zeolite ZSM 5.
  • the special variant of the second preferred embodiment of the invention described above, in which one or more catalysts are arranged in the second reaction space to form one or more organic compounds having a boiling point of 15 ° C. or higher from acetylene and / or ethylene, is characterized-in particular in the variants characterized as preferred - characterized in that the formation of one or more organic compounds having a boiling point of 15 ° C or higher of acetylene and / or ethylene in the presence of one or more catalysts can be carried out at lower temperatures than in the absence of catalysts because the catalysts lower the activation energies of the reactions in question.
  • Another advantage of this particular variant of the second preferred embodiment of the invention described above is that by appropriate selection of the catalysts, the selectivity of the process and the bandwidth of the spectrum of available reaction products can be influenced. Thus, e.g. by selecting suitable catalysts, the proportion of certain compounds, e.g. Benzen and / or naphthalene can be increased in the formed reaction products.
  • the stream leaving the device for the plasma-assisted production of one or more organic compounds having a boiling point of 15 ° C. or higher contains, in addition to the desired plasma-assisted organic compounds having a boiling point of 15 ° C. or higher and optionally carbon black also constituents with a boiling point below 15 ° C. These ingredients with one In particular, the boiling point below 15 ° C.
  • these components with a boiling point below 15 ° C if possible as supplies and / or energy sources to provide the device provided in the Erdölörderstrom invention for plasma-assisted production of one or more organic compounds having a boiling point of 15 ° C or higher from components of the trapped crude oil associated gas having a boiling point below 15 ° C or for the inventive method ,
  • the process according to the invention additionally comprises the step of separating a hydrogen-comprising gas stream from the stream leaving the device for the plasma-assisted generation of one or more organic compounds having a boiling point of 15 ° C. or higher, or from a stream produced therefrom, in particular from the modified crude oil stream.
  • the separation of a gas flow comprising hydrogen from the stream of material which leaves the device for plasma-assisted production of one or more organic compounds having a boiling point of 15 ° C or higher, ie from the stream, the one or more plasma Supports produced organic compounds having a boiling point of 15 ° C or higher and optionally Carbon black, prior to feeding the produced organic compounds having a boiling point of 15 ° C or higher into the crude oil stream withdrawn from the petroleum source or a crude oil stream derived therefrom.
  • the separation of a gas stream comprising hydrogen from a stream of material which has been generated from the stream leaving the device for the plasma-assisted production of one or more organic compounds having a boiling point of 15 ° C or higher is preferred.
  • the stream leaving the apparatus for plasma assisted production of one or more organic compounds having a boiling point of 15 ° C or higher i. the stream containing one or more plasma assisted organic compounds having a boiling point of 15 ° C or higher and optionally carbon black, without prior separation of gaseous constituents into the crude oil stream withdrawn from the petroleum source or a crude oil stream derived therefrom, such that a modified Crude oil is formed from which then a hydrogen-comprising gas stream is separated.
  • separated gas stream offers within the present invention use as an energy source (in particular for providing the necessary for the generation of the plasma electrical energy) and / or as a plasma gas.
  • the petroleum extraction plant according to the invention additionally contains
  • a device for generating electrical energy which is connected to the means for separating a gas stream comprising hydrogen from the stream, which leaves the device for plasma-assisted production of one or more organic compounds having a boiling point of 15 ° C or higher, or from a stream produced therefrom, in particular from the modified crude oil stream, and
  • Means for transferring the generated electrical energy to the means for generating a plasma additionally comprises the steps
  • the means for generating electrical energy are preferably a gas turbine or a gas and steam (CCGT) turbine.
  • CCGT gas and steam
  • the plasma is a noble gas-free plasma
  • the means for generating a plasma are means for producing a noble gas-free plasma.
  • the use of a noble gas-free plasma takes into account the fact that on a petroleum extraction plant operating materials such as noble gases, which must be brought specifically from outside, are usually available only to a very limited extent or not at all.
  • the plasma gas contains traces of noble gases, since these are optionally part of the associated petroleum gas.
  • the plasma gas not contain noble gas derived from sources other than the trapped crude oil gas leaving the petroleum source; and the means for generating the plasma no noble gas is supplied, which originates from sources other than the trapped from the petroleum source escaping crude oil associated gas.
  • Means for feeding a gas stream comprising hydrogen as a plasma gas in the plasma reaction space comprise means for feeding a gas flow comprising methane from the associated gas or from a gas flow generated therefrom.
  • the means for feeding a hydrogen-comprising gas stream as a plasma gas preferably comprises means for feeding a hydrogen-comprising gas stream separated from the stream leaving the apparatus for plasma-assisted production of one or more organic compounds having a boiling point of 15 ° C or higher , or from a stream produced therefrom, in particular from the modified crude oil stream.
  • a gas stream comprising methane and / or gas stream comprising hydrogen as the plasma gas is preferably used to generate the plasma.
  • the gas stream to be used as the plasma gas to be used is preferably a gas stream comprising the methane separated from the crude oil accompanying gas or from a gas stream produced therefrom.
  • the gas stream comprising hydrogen to be used as plasma gas is preferably one from the stream leaving the apparatus for the plasma-assisted production of one or more organic compounds having a boiling point of 15 ° C.
  • the apparatus for feeding the produced organic compounds having a boiling point of 15 ° C or higher into the crude oil stream taken from the petroleum source or a crude oil stream produced therefrom is preferably a Venturi scrubber.
  • a further aspect of the present invention relates to the use of a device for plasma-assisted production of one or more organic compounds having a boiling point of 15 ° C or higher from constituents of the trapped crude oil associated gas having a boiling point below 15 ° C, said device Means for generating a quenched gas stream by contacting a plasma-treated gas stream with a quench fluid within a petroleum production plant to produce one or more organic compounds having a boiling point of 15 ° C or higher from constituents of the oil source and exit Petroleum extraction plant Collected associated petroleum gas with a boiling point below 15 ° C.
  • the crude oil production plant according to the invention is preferably an off-shore plant or onshore plant with a supply of associated petroleum gas of 700,000 kt / a or less.
  • one or more of the devices to be used according to the invention are provided on the petroleum-producing plant.
  • a single device to be used according to the invention is suitable for processing gas quantities of up to 20,000 kt / a, and thus sufficient for some petroleum deposits.
  • the apparatus to be used according to the invention and the method according to the invention permit a profitable operation with the typically occurring gas quantities of 10 to 700,000 kt / a, since the apparatus and method have a very small space requirement.
  • the apparatus and the method according to the invention by means of a thermal plasma, which is very localized, the energy required for the conversion of associated petroleum gas into organic compounds with a boiling point of 15 ° C. or higher can be introduced into the process in a targeted and highly efficient manner, i. a high proportion of the energy input is actually available for the desired reactions. Thanks to this high energy efficiency, combined with the relatively small space requirement, the apparatus and the method according to the invention to be used characterized by a particularly high productivity based on the available reaction space and are particularly suitable to under the conditions of limited space to be used on a petroleum extraction plant.
  • Figure 1 is a schematic representation of a Erdölörderstrom invention
  • Figure 2 is a partial schematic representation of a first preferred embodiment of the invention
  • Figure 3 is a partial schematic representation of a variant of the second preferred embodiment of the invention
  • FIG. 4 is a partial schematic representation of another variant of the second preferred embodiment of the invention.
  • FIG. 5 is a partial schematic representation of another variant of the second preferred embodiment of the invention.
  • FIG. 6 shows a flow chart of a method according to the invention.
  • An inventive Erdölörderstrom according to Figure 1 comprises
  • an apparatus 4 connected to the apparatus 3 for collecting associated petroleum gas as described above for producing one or more organic compounds 4a having a boiling point of 15 ° C or higher from gaseous constituents of the trapped crude oil associated gas having a boiling point below 15 ° C.
  • an apparatus 5 connected to the apparatus 4 for producing one or more organic compounds 4a having a boiling point of 15 ° C or higher for feeding the produced organic compounds having a boiling point of 15 ° C or higher into the crude oil stream 2a taken out of the petroleum source 1 or a crude oil stream generated therefrom to form a modified crude oil stream 5a, and
  • a device 6 e.g. in the form of a connection of the petroleum extraction plant to a pipeline or a loading station to effect the removal of the modified crude oil stream.
  • FIG. 2 shows a schematic partial representation of the first preferred embodiment of the invention, in which the device 4 for producing one or more organic compounds having a boiling point of 15 ° C. or higher comprises:
  • a plasma reaction space 41 into which a plasma gas P and oil-accompanying gas APG (and optionally crude oil) are fed;
  • a further reaction space 43 in the form of a discharge path to keep the quenched gas stream containing one or more hydrocarbons having a boiling point of 15 ° C or higher and optionally carbon black over a defined average residence time in a certain temperature range.
  • quench fluid Q2 or Q3 bring into contact, wherein the quench fluid is selected from the group consisting of crude oil, associated gas, air and water.
  • FIG. 3 shows a schematic partial representation of a variant of the second preferred embodiment of the invention, in which the device 4 'comprises one or more organic compounds having a boiling point of 15 ° C. or higher:
  • a plasma reaction space 41a into which a plasma gas P and a companion gas APG (and possibly crude oil) are fed;
  • reaction space 43a for forming one or more organic compounds having a boiling point of 15 ° C or higher from contained in the quenched gas stream of acetylene and / or ethylene
  • the reaction space 43a is designed so that the desired mean residence time of the gas stream is adjusted, and A constant temperature is impressed on the gas stream by cooling or heating via the reaction space 43a, wherein means are optionally provided in the reaction space 43a for bringing the gas stream into contact again with a quench fluid, analogously to the first preferred embodiment of the invention shown in FIG ,
  • FIG. 4 shows a schematic partial representation of a further variant of the second preferred embodiment of the invention, in which the device 4 "comprises one or more organic compounds having a boiling point of 15 ° C. or higher:
  • a plasma reaction space 41 b into which a plasma gas P and associated gas APG (and possibly crude oil) are fed;
  • reaction space 43b for forming one or more organic compounds having a boiling point of 15 ° C or higher from acetylene and / or ethylene contained in the quenched gas stream, wherein the reaction space 43b is divided into individual successive reaction modules, each with individually adjustable temperature and including means for again contacting the quenched gas stream with a quench fluid. Crude oil is used as the quench fluid, with part of the quench fluid being pyrolyzed due to the high temperatures. The quench rate is individually adjustable for each module.
  • the reaction space 43b is designed so that the desired average residence time of the gas flow in the reaction space 43b is set, so that from the acetylene and / or ethylene one or more organic compounds having a boiling point of 15 ° C or higher are formed
  • the second reaction space 43b for example, from 8 to 10 modules with an extent of 10 to 15 cm.
  • a heat transfer medium or cooling water is used to set the temperature of the individual modules of the reaction space 43b.
  • cooling water When operating with cooling water, a relatively strong cooling of the gas flow takes place in the upper (upstream) region of the reaction space 43b, while in the lower (downstream) region of the reaction space 43b the gas flow does not continue to cool significantly.
  • the temperature profile of the reaction space 43b is not constant, but changes in a reaction space 43b of 90 cm length locally significantly from very hot upstream to downstream very cold as follows:
  • FIG. 5 shows a schematic partial representation of a further variant of the second preferred embodiment of the invention, in which the device 4 '"for producing one or more organic compounds having a boiling point of 15 ° C. or higher comprises:
  • Means for generating a plasma (not shown in Figure 5); a plasma reaction space 41 c is fed into the a plasma gas P and associated petroleum gas APG;
  • a quenching fluid here - in addition to crude oil or petroleum accompanying gas - and water is suitable, which reacts in a heterogeneously catalyzed sequential reaction by addition of acetylene to acetaldehyde, which can be added to the crude oil.
  • the quenched gas stream contains acetylene and / or ethylene;
  • reaction space 43c to form one or more organic compounds having a boiling point of 15 ° C or higher of acetylene and / or ethylene, in which one or more catalysts are arranged in the form of a heated or unheated fixed bed, the reaction space 43c is designed so in that the desired average residence time of the gas stream is set.
  • the apparatus 5 for feeding the produced organic compounds having a boiling point of 15 ° C or higher into the crude oil stream 2a taken from the petroleum source or a crude oil stream produced therefrom so that a modified crude oil stream 5a is formed is in the embodiments of FIGS. 3 to 5 designed as Venturi scrubber.
  • gaseous components mainly hydrogen and methane
  • Hydrogen or methane can be used as plasma gas and / or for energy supply, in particular for the generation of the plasma.
  • a modified crude oil stream 5b is present.
  • FIG. 6 shows a flow diagram of a method according to the invention.
  • Crude oil 3a exiting a petroleum source is expanded in apparatus 3b and at a temperature in the range of 100 ° C to 1200 ° C, preferably 200 ° C to 1000 ° C, more preferably 400 ° C to 700 ° C, preheated.
  • the relaxed and preheated gas stream (and optionally preheated crude oil 2c) is then placed in a device 4 to be used in the invention to produce one or more organic compounds having a boiling point of 15 ° C or higher from constituents of the trapped crude oil associated gas having a boiling point below 15 ° C (as described above) initiated. It is preferable This device is one of the preferred embodiments described above.
  • the effluent leaving this apparatus comprises gaseous components (e.g., hydrogen and unreacted methane), organic compounds 4a having a boiling point of 15 ° C or higher (e.g., benzene), and optionally carbon black.
  • This stream is fed by means of a device 5 into the crude oil stream 2a withdrawn from a petroleum source (not shown), so that a modified crude oil stream 5a is formed, from which in the next step by means 7 a hydrogen-comprising gas stream 7a is separated.
  • the gas stream 7a separated here, after compression and enrichment with further crude oil accompanying gas, is supplied as fuel in a device 8 of a gas turbine 9, which supplies the energy required for the generation of the plasma.
  • the oxidant for the hydrogen gas stream comprising the gas turbine 9 air is supplied.
  • the removal of the modified crude oil stream is effected by a device 6, e.g. in the form of a connection of the petroleum extraction plant to a pipeline or a loading station causes.

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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)

Abstract

L'invention concerne une installation de production de pétrole qui est adaptée pour capter le gaz associé au pétrole sortant d'une source de pétrole, pour générer un ou plusieurs composés organiques ayant un point d'ébullition de 15°C ou plus à partir des constituants gazeux du gaz associé au pétrole et pour injecter ces composés organiques dans un flux de pétrole brut provenant de la source de pétrole de façon à former un flux de pétrole brut modifié qui est transporté de l'installation de production de pétrole avec des moyens qui sont couramment utilisés pour le transport du pétrole brut et qui sont disponibles dans une installation de production de pétrole en fonctionnement.
PCT/EP2014/069568 2013-09-23 2014-09-12 Installation de production de pétrole équipé d'un dispositif de génération de composés organiques liquides provenant du gaz associé au pétrole WO2015039978A1 (fr)

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EP13185528.0 2013-09-23

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0289391A1 (fr) * 1987-04-28 1988-11-02 Institut Français du Pétrole Procédé de conversion/thermique du méthane en hydrocarbures de poids moléculaires plus élevés, réacteur pour la mise en oeuvre du procédé et procédé de réalisation du réacteur
US20030136661A1 (en) * 2002-01-23 2003-07-24 Bechtel Bwxt Idaho, Llc Apparatus and methods for direct conversion of gaseous hydrocarbons to liquids
US20110054231A1 (en) * 2009-08-27 2011-03-03 Synfuels International, Inc. Process for the conversion of natural gas to acetylene and liquid fuels with externally derived hydrogen
WO2012135515A2 (fr) * 2011-03-29 2012-10-04 Fuelina, Inc. Combustible hydride et son procédé de fabrication
WO2012175279A1 (fr) * 2011-06-20 2012-12-27 Evonik Degussa Gmbh Procédé de modification d'un flux gazeux contenant du méthane

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0289391A1 (fr) * 1987-04-28 1988-11-02 Institut Français du Pétrole Procédé de conversion/thermique du méthane en hydrocarbures de poids moléculaires plus élevés, réacteur pour la mise en oeuvre du procédé et procédé de réalisation du réacteur
US20030136661A1 (en) * 2002-01-23 2003-07-24 Bechtel Bwxt Idaho, Llc Apparatus and methods for direct conversion of gaseous hydrocarbons to liquids
US20110054231A1 (en) * 2009-08-27 2011-03-03 Synfuels International, Inc. Process for the conversion of natural gas to acetylene and liquid fuels with externally derived hydrogen
WO2012135515A2 (fr) * 2011-03-29 2012-10-04 Fuelina, Inc. Combustible hydride et son procédé de fabrication
WO2012175279A1 (fr) * 2011-06-20 2012-12-27 Evonik Degussa Gmbh Procédé de modification d'un flux gazeux contenant du méthane

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