WO2014187780A1 - Procédé de purification d'un flux de gaz de pétrole liquéfié - Google Patents

Procédé de purification d'un flux de gaz de pétrole liquéfié Download PDF

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Publication number
WO2014187780A1
WO2014187780A1 PCT/EP2014/060252 EP2014060252W WO2014187780A1 WO 2014187780 A1 WO2014187780 A1 WO 2014187780A1 EP 2014060252 W EP2014060252 W EP 2014060252W WO 2014187780 A1 WO2014187780 A1 WO 2014187780A1
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WO
WIPO (PCT)
Prior art keywords
dme
oxygenate
lpg
contaminated
stream
Prior art date
Application number
PCT/EP2014/060252
Other languages
English (en)
Inventor
Hendrik Adriaan Kooijman
Jeroen Van Westrenen
Gosina Geertruida BURGGRAAF
Sivakumar SADASIVAN VIJAYAKUMARI
Original Assignee
Shell Internationale Research Maatschappij B.V.
Shell Oil Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij B.V., Shell Oil Company filed Critical Shell Internationale Research Maatschappij B.V.
Publication of WO2014187780A1 publication Critical patent/WO2014187780A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/12—Liquefied petroleum gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/46—Compressors or pumps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/543—Distillation, fractionation or rectification for separating fractions, components or impurities during preparation or upgrading of a fuel

Definitions

  • the current invention concerns liquefied petroleum gas (LPG) . More in particular it concerns a process for converting a LPG stream that is contaminated with
  • oxygenate content More in particular it concerns a process for converting an LPG stream that is contaminated with an oxygenate such as dimethylether (DME) into a purified LPG stream with an oxygenate content that is reduced to 5 percent by weight (wt%) or less, preferably 50 ppmw or less, more preferably 10 ppmw or less.
  • DME dimethylether
  • Liquefied petroleum gas also called LPG, GPL, LP Gas, liquid petroleum gas or autogas
  • LPG Liquefied petroleum gas
  • GPL propane
  • LP Gas liquid petroleum gas or autogas
  • LPG has such a simple chemical structure, it is among the cleanest of any alternative fuels. It is used as a fuel in heating appliances and vehicles.
  • the boiling point of LPG is less than 25 °C, even less than 1 °C. Typically, the boiling point ranges from —42 °C to 0 °C depending on its mixture percentage of C3 and C4. Standard product specifications require LPG to be delivered as a single-phase pressurized liquid product. Both for propane, butane and mixtures thereof,
  • hydrocarbons and other components This includes
  • LPG is typically prepared by refining petroleum or "wet" natural gas, and is almost entirely derived from fossil fuel sources. It is typically manufactured during the refining of petroleum (crude oil) , or extracted from petroleum or natural gas streams as they emerge from the ground.
  • This hydrocarbon fraction is referred to as an LPG stream.
  • this fraction has an upper boiling temperature below 25°C at ambient pressure.
  • the LPG stream is typically brought on-spec using a de-ethanizer and the like. Cryogenics may also be used, in particular for hydrocarbon feeds based on natural gas.
  • Oxygenates are used for Enhanced Oil Recovery
  • a system for producing oil and/or gas from an underground formation including a well above the formation; a mechanism to inject an enhanced oil recovery formulation into the formation, wherein the enhanced oil recovery formulation includes dimethyl ether (DME) .
  • DME dimethyl ether
  • a downside of this EOR and/or EGR use is that the produced hydrocarbons are contaminated with oxygenates, DME in particular.
  • the LPG stream derived therefrom will contain anywhere from 20 to 80 mol%, more typically from 30 to 70 mol%, still more typically from 40 to 60 mol% DME.
  • the total oxygenate specification is therefore greatly exceeded.
  • This DME-contaminated LPG stream can be purified before the final on-spec production step, e.g., by distillation or by washing. However, this additional distillation or washing step adds costs. This adversely affects the economics of the LPG.
  • the DME- contaminated LPG stream can be used as low quality fuel. Either way, DME, which is a valuable product is lost without any benefits. It is therefore desirable to improve the purity of the DME-contaminated LPG stream without increasing costs while at the same time
  • the current invention provides a process for converting a contaminated LPG stream comprising C3 and/or C4 and further comprising from 80 to 20 mol% of DME, into a purified LPG stream with an oxygenate content of 10 ppmw or less, wherein the DME-contaminated LPG stream is fed to an oxygenate-to-olefin (OTO) process at conditions whereby the DME reacts to form olefins, and wherein the purified LPG stream is obtained.
  • OTO oxygenate-to-olefin
  • the invention also relates to a system for producing oil and/or gas from an underground formation, including a well located in the formation; a mechanism to inject an enhanced oil recovery formulation into the formation, and an oxygenate-to-olefin reactor.
  • DME is injected into an underground formation, and oil and/or gas are recovered from the production wells .
  • the recovery of oil and/or gas from the underground formation may be accomplished by any known method.
  • Suitable methods include subsea production, surface production, primary, secondary, or tertiary production. The selection of the method used to recover the oil and/or gas from the underground formation is not
  • the miscible enhanced oil recovery formulation may be injected into a single conduit in a single well, allowing dimethyl ether formulation to soak, and then pumping out at least a portion of the dimethyl ether formulation with gas and/or liquids.
  • Another suitable method is injecting the miscible enhanced oil recovery formulation into a first injection well, and pumping out at least a portion of the miscible enhanced oil recovery formulation with gas and/or liquids through a second production well.
  • the selection of the method used to inject at least a portion of the miscible enhanced oil recovery formulation and/or other liquids and/or gases is not critical.
  • the enhanced oil recovery formulation may comprise further components.
  • Such further components include one or more of hydrogen sulfide, carbon dioxide, octane, pentane, LPG, C2-C6 aliphatic hydrocarbons, nitrogen, diesel, mineral spirits, naphtha solvent, asphalt solvent, kerosene, acetone, xylene, trichloroethane, and mixtures thereof.
  • water in gas or liquid form, air, nitrogen, and mixtures thereof may be used.
  • the crude oil and or gas so produced is refined and separated in various fractions.
  • DME fractional distillation
  • LPG fractional distillation
  • the DME used in the EOR and/or EGR will concentrate in the LPG fraction with a content of from 20 to 80 mol%, typically from 30 to 70 mol%, more typically from 40 to 60 mol%, conveniently about 50 mol%.
  • the oxygenate specification is greatly exceeded and separation of DME on the one hand and the C3/C4 fraction on the other hand is required for use.
  • the DME- contaminated LPG fraction is fed to an OTO reactor.
  • the search for alternative materials for light olefin production has led to the use of oxygenates such as alcohols and, more particularly, to the use of methanol (MeOH) , and or ethanol, or their derivatives such as dimethyl ether (DME), for example.
  • MeOH methanol
  • DME dimethyl ether
  • oxygenate feedstocks are methanol (MeOH) and/or
  • the oxygenate is converted in an oxygenate-to- olefin reactor to ethylene and propylene using a suitable conversion catalyst.
  • Molecular sieves such as microporous crystalline zeolite and non-zeolitic catalysts,
  • SAPO silicoaluminophosphates
  • hydrocarbon mixtures particularly hydrocarbon mixtures composed largely of light olefins.
  • the conversion of alcohols is for instance described in US 3,894,107 . It is generally known that the process can be optimized to produce a major fraction of C2 - C3 olefins.
  • paraffins, aromatics, naphthenes and higher olefins can be formed by a combination of hydrogen transfer, alkylation, cyclisation and
  • such processing typically produces or results in a reaction effluent containing a range of olefin reaction products as well as unreacted oxygenates, oxygenate derivatives, and other trace oxygenates.
  • Typical or common OTO processing schemes include an oxygenate absorber whereby methanol and or water
  • oxygenate-containing circulated water is subsequently stripped in an oxygenate stripper to recover methanol and DME, with such recovered materials ultimately recycled to the oxygenate conversion reactor.
  • conversion product stream resulting from the oxygenate absorber is typically passed to one or more compressors. Moreover, it is treated, for instance between the 4th and 5th stage of compression, in a C02 removal zone wherein the dewatered oxygenate conversion product stream is contacted with caustic solution to remove carbon dioxide.
  • reaction effluent is first
  • reaction effluent first to a quench tower. Here typically most of the water and residual oxygenates may be removed. Subsequently it is common to submit the first effluent stream to one or more compressors or compression stages; to an oxygenate stripper, and/or to a C02 removal zone. Finally, it is common to send the first effluent stream to a drier.
  • an oxygenate stripper and/or C02 removal zone may be part of a "compression train". In this case, after C02 removal the product gas is further compressed.
  • fractionate the reaction effluent stream into a first product fraction comprising C2 and C3 hydrocarbons and a second fraction comprising the C4+ olefins.
  • a series of distillation columns may be used.
  • the reaction effluent stream, or the first fraction if a split has already been made may be sent to a de-ethanizer, typically operating at 22- 26 bar a, wherein C2 hydrocarbons are isolated from the top.
  • the CI- component therein may be compressed and further purified, if needed.
  • the bottom stream after the de-ethanizer may then be sent to a de-propanizer, typically operating at 12-21 bars, wherein C3
  • hydrocarbons are isolated from the top.
  • the overhead of the de-ethanizer and of the de-propanizer may be sent to a C2 splitter, where the ethylene and the ethane are split, respectively to a C3- splitter, where the
  • propylene and the propane are split.
  • the C4 saturates (butanes) may be removed from the bottom stream of the de-propanizer. This process may include recycle streams, for instance with respect to the product of the oxygenate stripper and/or part of the bottom stream of the de- propanizer .
  • the saturated components (primarily C3 and C4) of a DME-contaminated LPG fraction are substantially inert when fed into the OTO reactor. Subsequently, the C3 and C4 saturates may be separated from the C3 and C4 olefins contained in the DME-contaminated LPG fraction, if any, and/or produced in the OTO reactor. The olefinically unsaturated components of the LPG fraction, if any, may be removed from the OTO product together with the formed olefins. This process thus may result in LPG that satisfies the oxygenates specification and the olefins specification at the same time.
  • the DME- contaminated LPG fraction can be a valuable stream of light olefins which may be used as building blocks in modern petrochemical and chemical industries. Remaining olefins in the LPG fraction after treatment in the OTO reactor, if any, may be hydrogenated to meet the olefin specification .
  • the LPG fraction that is contaminated with DME may be used as single feed in an OTO reaction, or mixed with another oxygenate feed. For instance, it may be used as supplement feed in an existing OTO process that runs on methanol or a methanol/olefin feed. If used as supplement feed, then the ratio is selected such as to achieve the highest efficiency in the OTO reaction.
  • reaction diluent typically used as reaction diluent.
  • a reaction diluent is typically used in a molar ratio, diluent/oxygenate, of about 1 or greater, wherein ethers such as DME are considered to represent 2 oxygenate molecules.
  • ethers such as DME are considered to represent 2 oxygenate molecules.
  • the diluent/oxygenate ratio is no more than 10,
  • the OTO process is described in more detail herein below.
  • an oxygenate feed is provided to a first reaction zone.
  • the oxygenate feed in the current invention comprises DME that is part of the contaminated LPG fraction as main or supplementary feed.
  • Reference herein to the oxygenate feed is to a single feed
  • the oxygenate feed is contacted with a suitable catalyst. This may, for example, for
  • Catalysts suitable for converting the oxygenate feed comprise one or more molecular sieves.
  • Such molecular sieve- comprising catalysts typically also include binder materials, matrix material and optionally fillers.
  • Suitable matrix materials include clays, such as kaolin.
  • Suitable binder materials include silica, alumina, silica-alumina, titania and zirconia, wherein silica is preferred due to its low acidity.
  • Molecular sieves preferably have a molecular
  • [A104] and/or [P04] tetrahedral units These silicon, aluminum and/or phosphorus based molecular sieves and metal containing silicon, aluminum and/or phosphorus based molecular sieves have been described in detail in numerous publications including for example, US
  • the molecular sieves have 8-, 10- or 12-ring structures and an average pore size in the range of from about 3 A to 15 A.
  • Suitable molecular sieves are silicoaluminophosphates
  • SAPO SAPO-17, -18, 34, -35, -44, but also SAPO-5, -8, -11, -20, -31, -36, 37, -40, -41, -42, -47 and -56; aluminophosphates (A1PO) and metal substituted
  • MeAlPO (silico) aluminophosphates
  • MeAlPO aluminophosphates
  • the Me in MeAlPO refers to a substituted metal atom, including metal selected from one of Group IA, IIA, IB, IIIB, IVB, VB, VIB, VIIB, VIIIB and Lanthanides of the Periodic Table of Elements.
  • Me is selected from one of the group consisting of Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn and Zr.
  • the conversion of the oxygenate feed may be accomplished by the use of an aluminosilicate- comprising catalyst, in particular a zeolite-comprising catalyst.
  • Suitable catalysts include those containing a zeolite of the ZSM group, in particular of the MFI type, such as ZSM-5, the MTT type, such as ZSM-23, the TON type, such as ZSM-22, the MEL type, such as ZSM-11, and the FER type.
  • Other suitable zeolites are for example zeolites of the STF-type, such as SSZ-35, the SFF type, such as SSZ-44 and the EU-2 type, such as ZSM-48.
  • Aluminosilicate-comprising catalyst and in
  • zeolite-comprising catalyst are preferred when an olefinic co-feed is fed to the oxygenate conversion zone together with oxygenate, for increased production of ethylene and propylene.
  • Preferred catalysts for OTO processes comprise SAPO, MEL and/or MFI type molecular sieves, whereby the latter two are zeolite molecular sieves. More preferred catalyst comprise SAPO-34, ZSM-11 and/or ZSM-5 type molecular sieves.
  • a preferred MFI-type zeolite for the OTO catalyst has a silica-to-alumina ratio, SAR, of at least 60, preferably at least 80. More preferred MFI-type zeolite has a silica-to-alumina ratio, SAR, in the range of 60 to 150, preferably in the range of 80 to 100.
  • the catalyst may further comprise phosphorus as such or in a compound, i.e. phosphorus other than any
  • phosphorus included in the framework of the molecular sieve is preferred that a MEL or MFI-type zeolite comprising catalyst additionally comprises phosphorus.
  • the oxygenate feed is contacted with the catalyst at a temperature in the range of from 350 to 1000 °C, preferably of from 450 to 650°C, more preferably of from 530 to 620°C, even more preferably of from 580 to 610°C; and a pressure in the range of from 0.1 kPa (1 mbar) to 5 MPa (50 bar), preferably of from 100 kPa (1 bar) to 1.5 MPa (15 bar), more preferably of from 100 kPa (1 bar) to 300 kPa (3 bar) .
  • Reference herein to pressures is to absolute pressures.
  • the current invention also relates to a system for producing oil and/or gas from an underground formation, including a well above the formation; a mechanism to inject an enhanced oil recovery formulation into the formation, and an oxygenate-to-olefin reactor.
  • this is a system primarily for enhanced oil recovery, given the beneficial use of DME for EOR.
  • the system further includes a refinery wherein produced hydrocarbon from the system is
  • a system for producing oil and/or gas from an underground formation may be used, which system includes a well above the formation; a mechanism to inject an enhanced oil recovery formulation into the formation, and a production well.
  • the LPG fraction containing DME is introduced as such into the OTO reactor.
  • the feed is reacted in a fluidized bed reactor at a weight hourly space velocity (WHSV) of 5-40 h-1 at 600°C in the presence of ZSM-5 as catalyst.
  • WHSV weight hourly space velocity
  • the reaction effluent is quenched and condensed. Any residual oxygenate is stripped and recycled.
  • the paraffin fraction is now an upgraded LPG fraction with an
  • the LPG fraction containing DME is mixed 1:1 volume ratio with a MeOH feed. In other words, it is integrated in an existing OTO plant. However, no steam is used as would have been the case in a conventional process.
  • the feed is fed to an OTO reactor where the feed is reacted in the same manner as described in embodiment 1.
  • the amount of olefins produced will be higher, due to the higher content of oxygenates in the feed.
  • the LPG so produced meets the specification
  • this embodiment has the additional advantage of a significantly reduced steam consumption.

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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)

Abstract

L'invention concerne un procédé de conversion, en un flux purifié, d'un flux de gaz de pétrole liquéfié (GPL) contaminé comprenant des hydrocarbures en C3 et/ou C4 et comprenant également de 20 à 80 % en moles d'éther diméthylique (DME), le flux de GPL contaminé par le DME étant introduit dans un procédé de conversion de composés oxygénés en oléfines (OTO), dans des conditions auxquelles le DME réagit pour former des oléfines, permettant ainsi l'obtention d'un flux de GPL purifié. L'invention concerne en outre un système de production de pétrole et/ou de gaz à partir d'une formation souterraine comprenant un puits au-dessus de la formation ; un mécanisme d'injection d'une formulation améliorée de récupération de pétrole dans la formation, ainsi qu'un réacteur de conversion OTO.
PCT/EP2014/060252 2013-05-23 2014-05-19 Procédé de purification d'un flux de gaz de pétrole liquéfié WO2014187780A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP13168865 2013-05-23
EP13168865.7 2013-05-23

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WO2014187780A1 true WO2014187780A1 (fr) 2014-11-27

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080242908A1 (en) * 2007-03-28 2008-10-02 Exxonmobil Chemical Company Law Technology Recycle Of DME In An Oxygenate-To-Olefin Reaction System
US20090326298A1 (en) * 2008-06-30 2009-12-31 Bozzano Andrea G Integration of oto process with direct dme synthesis
US20120037363A1 (en) * 2007-05-10 2012-02-16 Shell Oil Company Systems and methods for producing oil and/or gas

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080242908A1 (en) * 2007-03-28 2008-10-02 Exxonmobil Chemical Company Law Technology Recycle Of DME In An Oxygenate-To-Olefin Reaction System
US20120037363A1 (en) * 2007-05-10 2012-02-16 Shell Oil Company Systems and methods for producing oil and/or gas
US20090326298A1 (en) * 2008-06-30 2009-12-31 Bozzano Andrea G Integration of oto process with direct dme synthesis

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