WO2009082493A1 - Désulfuration par membrane de flux d'alimentation d'hydrocarbures liquides - Google Patents

Désulfuration par membrane de flux d'alimentation d'hydrocarbures liquides Download PDF

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Publication number
WO2009082493A1
WO2009082493A1 PCT/US2008/014075 US2008014075W WO2009082493A1 WO 2009082493 A1 WO2009082493 A1 WO 2009082493A1 US 2008014075 W US2008014075 W US 2008014075W WO 2009082493 A1 WO2009082493 A1 WO 2009082493A1
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Prior art keywords
membrane
sulfur
stream
unrefined
hydrocarbon stream
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Application number
PCT/US2008/014075
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English (en)
Inventor
Esam Zaki Hamad
Ahmad Abdullah Bahamdan
Original Assignee
Saudi Arabian Oil Company
Aramco Services Company
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Filing date
Publication date
Application filed by Saudi Arabian Oil Company, Aramco Services Company filed Critical Saudi Arabian Oil Company
Priority to US12/741,261 priority Critical patent/US20100264065A1/en
Publication of WO2009082493A1 publication Critical patent/WO2009082493A1/fr

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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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/11—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by dialysis
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/13—Use of sweep gas

Definitions

  • the invention relates to processes for desulfurization of a hydrocarbon feed using membrane separation, and more particularly to desulfurization of an unrefined hydrocarbon feed using membrane separation.
  • compositions of natural petroleum or crude oils vary significantly, generally based upon the source. However, virtually all crude oils contain some level of sulfur compounds, including inorganically combined sulfur and organically combined sulfur, i.e., organosulfur compounds.
  • Whole crude oil that contains a substantial concentration of sulfur compounds, such as hydrogen sulfide, sulfur dioxide, and organosulfur compounds such as mercaptans, thiophenes, benzothiophenes, and dibenzothiophenes is referred to as "sour,” whereas whole crude oil that does not contain a substantial concentration of sulfur compounds is referred to as "sweet.”
  • Crude oil is generally converted in refineries by distillation, followed by cracking and/or hydroconversion processes, to produce various fuels, lubricating oil products, chemicals, and chemical feedstocks.
  • Fuels for transportation are generally produced by processing and blending distilled fractions from crude oil to meet the particular product specifications. Conventionally, distilled fractions are subject to various hydrocarbon desulfurization processes to make sulfur-containing
  • sweet crude oil commands a higher price than sour crude oil because it has fewer environmental problems and requires less refining to meet sulfur standards imposed on end product fuels.
  • Hydrocarbon desulfurization processes are required to reduce the sulfur content.
  • most desulfurization processing occurs after varying levels of refining of the crude oil.
  • hydrocarbon desulfurization The most common hydrocarbon desulfurization process is hydrotreating, or hydrodesulfurization.
  • oil and hydrogen are introduced to a fixed bed reactor that is packed with a hydrodesulfurization catalyst, commonly under elevated operating conditions, including temperatures of about 300 to 400°C and pressures of about 30 to 130 atmospheres.
  • the temperatures and pressures in hydrotreating processes must be further elevated to achieve the low and ultra low sulfur content requirements.
  • hydrocarbons are typically converted to less desirable intermediates or products.
  • Typical advances in the industry for minimizing these undesirable effects include development of more robust hydrotreating catalysts and advanced hydrodesulfurization reactor designs.
  • Alternative processes are also being developed to meet the requirements of decreased sulfur levels in fuels and other petrochemical products.
  • membrane separation One alternate desulfurization process that has been proposed for treating various refined fractions of hydrocarbons is membrane separation.
  • membrane separation technology involves selective transport of a material through the membrane, a permeate, leaving behind a retentate on the feed side of the membrane. Permeated components of the mixture are removed by various driving forces. Membrane processes that rely upon pressure driving forces are known as pervaporation processes, and membrane processes that rely upon concentration gradients across the membrane are known as perstraction processes. Membrane separation often relies on the affinity of a specific compound or class of compounds for the membrane. Components in a mixture having affinity for the membrane will permeate the membrane. Membrane separation has been used for desulfurization of refined hydrocarbon fractions.
  • Balko United States Patent Number 7,267,761 also assigned to W.R. Grace & Co., describes another process for treating naphtha streams from an FCC unit, where the feedstream is treated in a fractionation zone to produce a low boiling point fraction and a second fraction, both containing sulfur.
  • the low boiling point fraction is treated in a membrane separation zone, where the sulfur-enriched permeate is combined with the second fraction for treatment in a hydrodesulfurization zone.
  • the feed is described as a refinery hydrocarbon product such as naphtha or diesel.
  • hydrocarbon feed streams in all of the above-mentioned references are products of upstream distillation and cracking processes and/or other refining operations.
  • unrefined petroleum products e.g., crude oil
  • a still further object of the invention is to utilize membrane separation to desulfurize an unrefined hydrocarbon stream, and to desulfurize the sulfur-rich retentate using conventional desulfurization processes such as hydrotreating, while minimizing the required capacity of the hydrotreating process.
  • Yet another object of the invention is to separate heteroatom compounds such as sulfur compounds from a liquid unrefined hydrocarbon into a liquid permeate and a liquid retentate.
  • unrefined hydrocarbon is to be understood to mean a distillate product of crude oil (including impurities such as sulfur) that has not been subjected to hydroprocessing, hydrodesulfurization, hydrodenitrogenation, catalytic processing, or cracking, and includes crude oil, unrefined diesel, unrefined naphtha, unrefined gas oil, or unrefined vacuum gas oil.
  • crude oil is to be understood to include a mixture of petroleum liquids and gases (including impurities such as sulfur) as distinguished from refined fractions of hydrocarbons.
  • the process of the present invention is directed to desulfurization of a sulfur-containing unrefined hydrocarbon stream with a membrane separation apparatus, where sulfur compounds are concentrated in a sulfur-rich stream on a permeate side of the membrane, and a sulfur-lean stream is recovered as a retentate.
  • the sulfur-rich stream which has a small volume relative to the original unrefined hydrocarbon stream, is subsequently conveyed to a desulfurization apparatus or system, such as a hydrotreating system, to recover the hydrocarbons associated with the organosulfur compounds.
  • the stream desulfurized by conventional processes, such as hydrotreating, and the hydrocarbon stream desulfurized by the membrane separation apparatus can be combined to provide a low sulfur hydrocarbon effluent with minimal or no significant loss of the original volume.
  • FIG. 1 is a schematic diagram of a combined membrane separation and alternate desulfurization process according to embodiments of the invention.
  • FIG. 2 is a schematic diagram of a membrane separation system used in the experimental analysis described herein.
  • An unrefined hydrocarbon feedstream 12 containing organosulfur compounds is introduced into a membrane separation unit 14 where the feedstream 12 is separated into streams 16, 18.
  • Sulfur-containing hydrocarbon compounds permeate a membrane of the membrane separation system 14 and are concentrated into an unrefined sulfur-rich hydrocarbon stream 16.
  • the portion of the feedstream remaining on the feed side of the membrane, the retentate, is conveyed as an unrefined sulfur-lean hydrocarbon stream 18.
  • the unrefined sulfur-lean hydrocarbon stream 18 has a substantially reduced concentration of sulfur-containing compounds as compared to the feedstream 12.
  • the unrefined sulfur rich stream 16 is transferred to a second stage desulfurization system 20, such as a hydrotreating unit, to recover useful hydrocarbons associated with the organosulfur compounds.
  • a second stage desulfurization system 20 such as a hydrotreating unit
  • Effluent from the second stage desulfurization system 20, a second stage unrefined sulfur-lean stream 22, and the membrane desulfurized unrefined hydrocarbon stream 18, can be combined to provide a low sulfur unrefined hydrocarbon stream 24 with minimal or no loss in volume.
  • the second stage unrefined sulfur-lean stream 22 that may be rich in aromatics is transferred to one or more subsequent processing steps.
  • the combined membrane separation process 10 described herein advantageously is conducted as a liquid separation process.
  • the unrefined hydrocarbon feedstream 12, the unrefined sulfur-rich hydrocarbon stream 16 and the unrefined sulfur-lean hydrocarbon stream 18 are all maintained in the liquid phase.
  • the feedstream 12, which can be a crude oil feedstream, an unrefined diesel feedstream, an unrefined naphtha feedstream, an unrefined gas oil feedstream, or an unrefined vacuum gas oil feedstream, is generally in the liquid phase initially, and the permeate and retentate remain in the liquid phase, without conversion into vapors and subsequent condensation, thereby conserving energy.
  • the sequence of a membrane separation zone followed by second stage desulfurization zone is also conducive to integration with existing commercial hydrotreating units.
  • This sequence realizes substantial economic savings, since the cost of operating a hydrotreating unit is proportional to the feed volume and is generally not sensitive to the sulfur content of the feed.
  • the cost of a membrane separation unit is generally much less than the cost of a hydrotreating unit; therefore, technically mature hydrodesulphurization units can be employed with the attendant economic savings.
  • the use of common and well understood processing units in combination will facilitate the capability for rapid scale-up or development of unrefined hydrocarbon feedstream desulfurization.
  • the overall performance of the integrated process and system generally depends on the performance of the membrane separation unit, which in turn is enhanced by the selectivity and permeability of the membrane used.
  • the membrane material is selected based on the permeation rate and selectivity for the range of sulfur compounds that are present in the unrefined hydrocarbon stream.
  • the selection of the type of membrane can also increase efficiency and reliability of the separation unit, and hence increase efficiency and reliability of the overall process.
  • the membrane is generally a substrate coated with a solid or a liquid material that is selective for the sulfur compounds present in the unrefined feedstream.
  • the coating may be upon the major surfaces of the substrate and/or within pores of the substrate. Coating within the pores preferably is a relatively thin layer, to maintain pore openings and minimize mass transfer resistance and thereby increase flux.
  • desired sulfur selective materials used as coatings exhibit effective adhesion to the substrate.
  • Liquid coatings preferably include molecules with functional groups that cause them to be anchored to the substrate, thereby minimizing or avoid the loss of liquid sulfur-selective material over the life of the membrane.
  • Substrate materials upon or within which the selective sulfur compounds can be coated include ultrafiltration and microfiltration membranes, for instance, formed of polymeric materials such as polyethersulfone (PES), polycarbonate, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), including hydrophilic PVDF, polyester, fluorinated polyimide, polyethyl-oxazoline, Nafion®, nylon, hydrophobically modified nylon, and polyether terephthalate (PET).
  • the substrate has pore sizes of about 0.01 to about 2 micrometers, preferably about 0.05 to about 1 micrometer and more preferably about 0.1 to about 0.5 micrometers.
  • Suitable substrates have molecular weight cut-off values of about 5,000 to about 1,000,000, preferably about 30,000 to about 500,000, and more preferably about 30,000 to about 100,000.
  • the substrate can also be hydrophilic, for instance, with the inclusion of wetting agents such as polyvinylpyrrolidone (PVP)).
  • PVP polyvinylpyrrolidone
  • the thickness of the substrate can be from about 100 to about 500 micrometers, preferably about 100 to about 300 micrometers, and more preferably about 100 to about 200 micrometers.
  • the area of the membrane e.g., diameter in the case of circular membranes in flat mounted sheet configurations) can be selected based upon the requisite processing volume demands.
  • the sulfur selective compounds suitable for use as membrane coating materials can include functionalities with affinity to the aromatic sulfur compounds, complexation agents, or acidic functional groups.
  • sulfur selective compounds can comprise ionic liquids including, but not limited to, N-butyl-3-methyl-pyridinium methyl sulfate, imidazolium-based ionic liquids, and methyl-pyridinium based ionic liquids.
  • the sulfur selective compounds are selective to organosulfur compounds including thiophenes, dibenzothiophenes and other refractory sulfur compounds commonly found in untreated hydrocarbon feedstreams.
  • the driving force for separation can be a concentration gradient across the membrane, which is enhanced by a sweep stream on the permeate side.
  • Suitable sweep stream liquids include paraffins such as isooctane, dodecane and hexadecane; or liquid hydrocarbon mixtures such as naphtha and desulfurized diesel.
  • the particular sweep liquid should be low in organic sulfur compounds, of paraffinic origin and be a liquid at room temperature and ambient pressure conditions.
  • the membrane separation system for separating sulfur compounds from unrefined hydrocarbon feeds can operate at temperatures of about 15°C to about 6O 0 C, preferably about 20 0 C to about 50 0 C, more preferably about 25°C to about 35°C, and pressures of 1 pound per square inch (psi) to about 30 psi, preferably about 5 psi to about 20 psi, more preferably about 10 psi to about 15 psi.
  • psi pound per square inch
  • the driving force for separation is a pressure gradient across the membrane.
  • the pressure gradient required is not as severe as that required for pervaporation conditions, as the feed, retentate and permeate are maintained in liquid phase.
  • suitable pressure gradients across the membrane can be about 1 psi to about 15 psi, preferably about 5 psi to about 15 psi, and more preferably about 5 psi to about 10 psi.
  • Operating temperatures in embodiments using a pressure gradient as the driving force for separation can be about 15°C to about 60 0 C, preferably about 2O 0 C to about 5O 0 C, more preferably about 25°C to about 35°C.
  • Suitable liquids coatings for membranes operating under pressure gradients include any of the ionic liquids mentioned above coated after plasma treatment of the mentioned substrates.
  • the membrane unit can be in any suitable configuration.
  • the membrane unit can be in a spirally wound configuration, a hollow fiber configuration, a plate and frame configuration, or a tubular configuration.
  • the membrane unit is in a spirally wound or a hollow fiber configuration.
  • a plurality of membrane units can optionally be operated in parallel or series, hi the parallel configuration, one or more membrane units can be decommissioned for maintenance without disrupting the continuity of the desulfurization process.
  • the stream desulfurized by conventional processes, such as hydrotreating, and the hydrocarbons desulfurized by the membrane separation apparatus can be combined to provide a low sulfur hydrocarbon effluent with minimal or no loss of the original volume.
  • This low sulfur hydrocarbon effluent can serve as a feedstream for subsequent fractioning in a downstream process.
  • the low sulfur hydrocarbon effluent may be sold as sweet crude oil, thereby taking advantage of the price differential between sweet and sour crude oils.
  • the system 50 included a membrane 52 having a retentate side 54 and a permeate side 56.
  • the apparatus included a sulfur-lean portion 58 in for receiving retentate from the retentate side 54, and a sulfur-rich portion 60 for receiving permeate from the permeate side 56.
  • a reservoir 62 initially included the feedstream that is conveyed to the membrane, which was converted into an unrefined sulfur-lean hydrocarbon retentate.
  • a reservoir 64 initially included a sweep solution, and the unrefined sulfur-rich hydrocarbon permeate filled the reservoir 64.
  • the feedstream was pumped to the membrane retentate side 54 with a gear pump 66.
  • the sweep solution was pumped via a gear pump 68 across the permeate side 56 of the membrane 52.
  • a polyethersulfone ultrafiltration filter with a molecular weight cutoff of 100,000 and having a 47 millimeter diameter (commercially available from GE Osmonics Labstore,
  • the membrane was configured in a system schematically shown in FIG. 2.
  • Untreated diesel with 1% total sulfur content (10,000 parts per million) is introduced tangentially to the retentate side of a membrane cell shown in FIG. 2 that included the membrane prepared as described above.
  • a liquid sweep stream of light treated naphtha with 100 ppm sulfur was conveyed across the membrane in the permeate side. After 72 hours of operation, the sweep stream sulfur concentration increased to 1000 ppm, yielding a sulfur- compound flux of 0.1 kg/hr/m .
  • Example 1 was repeated using a feed consisting of Arabian crude oil having an American Petroleum Institute (API) gravity of about 27 and a sulfur concentration of 2.85%. After 72 hours of operation, the average sulfur-compound flux of 0.05 kg/hr/m 2 is achieved.
  • Example 3 A polycarbonate membrane filter with 0.1 micron pores having a diameter of 47 millimeters (GE PCTE commercially available from GE Osmonics Labstore, Minnetonka, Minnesota, USA) was prepared. The membrane included polyvinylpyrrolidone (PVP) as a wetting agent that imparts hydrophilicity. The membrane was coated with ionic liquid and tested with a seven component model feed described in Table 1 , using a dodecane carrier.
  • PVP polyvinylpyrrolidone
  • the receiving side included a dodecane solution to sweep accumulated permeate from the surface of the membrane.
  • a gear pump was connected to each side while samples were extracted from the reservoirs to measure the change in composition on both sides.
  • the samples collected were analyzed by gas chromatography, and for total sulfur by the ASTM D 5453 method. The process was performed at a low flow rate (10 milliliters per min) for 48 hours. TABLE l
  • a PTFE membrane filter with 0.2 micron pores having a diameter of 47 millimeters (OmniporeTM commercially available from Millipore, Billerica, Massachusetts) was prepared.
  • the membrane was coated with ionic liquid and tested with a seven component model feed described in Table 2 using a dodecane carrier.
  • the receiving side (permeate) included a dodecane solution to sweep accumulated permeate on the surface of the membrane.
  • a gear pump was connected to each side while samples were extracted from the reservoirs to measure the change in composition on both sides. The samples collected were analyzed by gas chromatography, and total sulfur methods. The process was performed at a low flow rate (10 milliliters per min) for 48 hours.

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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)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention porte sur un procédé de désulfuration d'un flux d'hydrocarbures non raffiné contenant du soufre avec un appareil de séparation par membrane, des composés soufre étant concentrés dans un flux riche en soufre sur un côté de perméat de la membrane, et un flux pauvre en soufre étant récupéré sous forme de rétentat. Le flux riche en soufre, qui a un petit volume par rapport au flux d'hydrocarbures non raffiné initial, est transporté vers un appareil ou système de désulfuration ultérieur, tel qu'un système d'hydrotraitement, pour récupérer les hydrocarbures associés aux composés organosoufre. Le flux désulfuré par des procédés classiques, tels qu'un hydrotraitement, et les hydrocarbures désulfurés par l'appareil de séparation par membrane peuvent être combinés pour fournir un effluent d'hydrocarbures à faible teneur en soufre avec une perte minimale ou pas de perte du volume initial.
PCT/US2008/014075 2007-12-24 2008-12-23 Désulfuration par membrane de flux d'alimentation d'hydrocarbures liquides WO2009082493A1 (fr)

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US12/741,261 US20100264065A1 (en) 2007-12-24 2008-12-23 Membrane desulfurization of liquid hydrocarbon feedstreams

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US901607P 2007-12-24 2007-12-24
US61/009,016 2007-12-24

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