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
  • C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
  • B01D17/02—Separation of non-miscible liquids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
  • B01F23/40—Mixing liquids with liquids; Emulsifying
• • 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
  • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
  • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
  • C10G21/12—Organic compounds only
  • C10G21/27—Organic compounds not provided for in a single one of groups C10G21/14 - C10G21/26
• • 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
  • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
  • C10G29/20—Organic compounds not containing metal atoms
  • C10G29/28—Organic compounds not containing metal atoms containing sulfur as the only hetero atom, e.g. mercaptans, or sulfur and oxygen as the only hetero atoms

Definitions

• This invention relates generally to separating a trace element from a liquid hydrocarbon feed within a phase separation device, such as a desalting unit or oil- water separator.
• Liquid hydrocarbon feeds generally contain an assortment of trace elements in amounts generally ranging from several parts per billion (ppb) to several thousand ppb depending on the feed source. These elements often cause corrosion within equipment and may deteriorate or poison a catalyst of a subsequent treatment process. For example, mercury may amalgamate with a surface metal, such as copper or aluminum, collecting with time in piping, valves and even in larger structures such as fractional distillation columns. Equipment replacement or abstraction of this deleterious metal from the equipment can be very expensive and potentially hazardous. Therefore, it may be preferable to remove the trace elements as early as possible during processing, such as removal prior to distillation of the feed or even while still at the hydrocarbon recovery site. However, due to the liquid hydrocarbon state of the feed prior to distillation being more chemically complex, current technologies for removing the trace elements prior to hydrocarbon distillation tend to be less developed.
• the absorbent compositions comprise a polysulfide, a support material and metal cation capable of forming an insoluble metal polysulfide. While the approach of using fixed bed absorbents to extract trace elements, including mercury, from a hydrocarbon feed have shown to be successful, they also include a number of less than desirable attributes. Absorbent beds tend to get clogged by solid particulates in the crude, thus impeding the flow of the feed. Absorbents can also be very costly due to the large quantity needed, especially if there is a high concentration of the trace element or elements being extracted. In addition, stripping the absorbent is generally necessary prior to disposal or recycling of the absorbent.
• the present invention comprises removing a trace element from a liquid hydrocarbon, such as crude oil, natural gas, and other petroleum products.
• the liquid hydrocarbon is mixed or emulsified with water and a hydrocarbon-soluble additive.
• the additive chemically reacts with the trace element forming a compound.
• This compound is typically an aqueous insoluble compound, such that the compound may easily be separated and removed in subsequent treatment processes.
• a phase separation device such as a desalter or an oil-water separator, resolves, i.e., separates, the oil-water emulsion containing the compound.
• the resolved mixture produces the compound formed by mixing the additive with the trace element, effluent brine, and effluent liquid hydrocarbon with a reduced concentration of the trace element as compared to the liquid hydrocarbon feed.
• the compound may be dispensed from the phase separation device with the effluent brine or the effluent liquid hydrocarbon and may later be filtered out.
• the present invention is directed to removing elemental mercury from a liquid hydrocarbon feed.
• a sulfiir-containing hydrocarbon-soluble additive is mixed with the liquid hydrocarbon feed and water to produce an emulsified solution.
• the liquid hydrocarbon is already emulsified with the water prior to injection of the additive and in other scenarios the additive may be added directly to either the liquid hydrocarbon or water and then can all be mixed together.
• an organic polysulfide can be injected directly into the liquid hydrocarbon stream prior to being emulsified with water or it can be injected into an emulsified oil-water mixture.
• the sulfur-containing additive reacts with the mercury, concentrated within the liquid hydrocarbon, rapidly forming an agglomeration of mercuric sulfide which is then dispensed with the effluent brine or the effluent liquid hydrocarbon for subsequent filtering.
• a system is employed to remove a trace element from a liquid hydrocarbon.
• the system includes first and second fluid lines fluidly communicating with a phase separation device.
• the phase separation device may comprise a desalting unit
• the first fluid line can contain a liquid hydrocarbon feed and the second fluid line can contain wash water.
• a hydrocarbon-soluble additive can be mixed with either the liquid hydrocarbon feed or the wash water, such that it chemically reacts with the trace element as the fluids are emulsified.
• the phase separation device may comprise an oil-water separator.
• the first fluid line can contain a contaminated oil-in- water mixture and the second fluid line can contain a hydrocarbon-soluble additive that can be directly injected into the first fluid line to treat the mixture.
• the additive chemically reacts with the contaminant or trace element forming a compound.
• the liquid hydrocarbon is recovered such that it has a reduced concentration of the trace element.
• FIG. 1 is a flow chart depicting steps for removing trace elements from liquid hydrocarbon feed, according to one embodiment of the present invention.
• FIG. 2 is a schematic diagram depicting a system for removing trace elements from liquid hydrocarbon feed, according to one embodiment of the present invention.
• FlG. 3 is a schematic diagram depicting a system for removing trace elements from liquid hydrocarbon feed, according to one embodiment of the present invention.
• Hydrocarbon feeds generally a conglomeration of hydrocarbon chains with approximate lengths ranging between CsHi 2 and C4 2 H86, typically contain a variety of trace elements.
• the trace elements range from alkaline earth metals, transition metals, post-transition metals, and nonmetals and generally consist of calcium (Ca), vanadium (V), chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As), selenium (Se), molybdenum (Mo), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), barium (Ba), mercury (Hg), thallium (Tl), lead (Pb), and/or bismuth (Bi).
• Ca calcium
• V vanadium
• Cr chromium
• Fe iron
• Co cobalt
• Ni nickel
• Cu copper
• Zn zinc
• FIG. 1 depicts steps, according to one method of the present invention, for removal of a trace element from a liquid hydrocarbon.
• a hydrocarbon-soluble additive is mixed with a liquid hydrocarbon having a concentration of a trace element and with water.
• the hydrocarbon-soluble additive chemically reacts with the trace element forming a compound.
• this compound will be insoluble in both the hydrocarbon and aqueous phase so that it may easily be removed during future processing.
• the oil-water emulsion containing the compound is formed, it is resolved into phases in a phase separation device, as shown in step 20.
• the effluent phases are then dispensed separately from the phase separation device, as depicted in step 30.
• the compound formed by the hydrocarbon-soluble additive chemically reacting with the trace element is dispensed along with the effluent phases.
• the compound then can easily be extracted out of the effluent, as shown in step 40. Therefore, once this process has been completed, the effluent liquid hydrocarbon that is dispensed from the phase separation device has a reduced concentration of the trace element.
• concentration of the trace element as used herein, is meant to describe the concentration of the trace element within the liquid hydrocarbon when it is in an elemental state; that is, disregarding the content of the trace element once it has chemically reacted with the additive or when it is in a compound state.
• mercury is the trace element targeted for extraction and a hydrocarbon-soluble additive, such as an organic polysulfide such as Di- Tertiary-Nonyl Polysulfide (TNPS), is utilized to form a compound with the mercury.
• a hydrocarbon-soluble additive such as an organic polysulfide such as Di- Tertiary-Nonyl Polysulfide (TNPS)
• TNPS Di- Tertiary-Nonyl Polysulfide
• R is any hydrocarbon or hydrogen
• S is Sulfur
• X and x are the same whole number, typically between 3 and 8.
• mercuric sulfide has essentially no vapor pressure and with the conversion to an ionic salt, makes the mercury more readily available for removal by various techniques already known in the art.
• mercurous sulfide may also be formed from the reaction of the sulfur-based additive with the mercury in the liquid hydrocarbon feed.
• FIG. 1 depicts a schematic flow process, according to one embodiment of the present invention, for removing trace elements from liquid hydrocarbon feed, such as in an oil refinery setting.
• Treatment system 100 includes liquid hydrocarbon feed, commonly referred to as petroleum or crude oil, which is routed via piping 104 from storage container 102. The feed is then heated in a furnace 106 to a temperature above its boiling point, typically ranging from about 500 to 600 degrees Celsius. The heated liquid hydrocarbon feed continues within piping 104 and a hydrocarbon- soluble additive is introduced to the liquid hydrocarbon feed through line 108.
• liquid hydrocarbon feed commonly referred to as petroleum or crude oil
• the feed is then heated in a furnace 106 to a temperature above its boiling point, typically ranging from about 500 to 600 degrees Celsius.
• the heated liquid hydrocarbon feed continues within piping 104 and a hydrocarbon- soluble additive is introduced to the liquid hydrocarbon feed through line 108.
• phase separation device 110 such as a desalting unit or desalter
• wash water introduced through line 112 to form an emulsion within the phase separation device 110.
• the mixture may be passed through a pressure reducing valve (not shown) or stirred by a mixing device (not shown).
• line 112, containing the wash water may be injected directly into piping 104 upstream of the phase separation device 110.
• the hydrocarbon-soluble additive can be injected through the same line as the wash water and only one of lines 108 and 112 will be present.
• the hydrocarbon-soluble additive reacts with one or more trace elements forming compounds, typically insoluble inorganic compounds. Resolving the emulsified solution produces the compound that is formed by a reaction between the hydrocarbon-soluble additive with the trace element, effluent brine, and effluent liquid hydrocarbons with a reduced concentration of the trace element as compared to the liquid hydrocarbon feed.
• the phase separation device 110 may utilize a plurality of baffles 118, a plurality of electrodes (not shown) that create an electric field, and/or a demulsifying agent to assist in separating the mixture into phases. Additionally, a settling agent may similarly be utilized to accelerate the settling of the compound within the hydrocarbon and/or aqueous phase.
• fractional distillation column 120 is comprised of a plurality of spaced plates 122 filled with multiple apertures 124. As the heated effluent hydrocarbon enters the fractional distillation column 120, it separates such that the hydrocarbon vapors continually ascend passing through the apertures 124 within the spaced plates 122.
• hydrocarbons As the hydrocarbon vapors climb in the fractional distillation column 120, they cool down and begin to condense forming liquid fractions that are caught in the plurality of spaced plates 122. Vapors that pass all the way to the top of the fractional distillation column 120 exit through output 126. These vapors are typically very light hydrocarbons and are commonly called naphtha. Heavier hydrocarbons fractions such as gasoline, kerosene, diesel, lubricating oil and heavy gas oil are dispensed through outputs 128 each corresponding to the spaced plates 122 within the fractional distillation column 120. The heaviest hydrocarbon chains collect in the bottom of the fractional distillation column 120 and are dispensed through output 130. These hydrocarbons are commonly referred to as the residual.
• the fractions may pass to subsequent condensers, which cool them further, and then go to storage tanks or be routed to other areas for further chemical processing.
• the naphtha dispensed from the top of the fractional distillation column may further be separated into light ends, such as liquefied natural gases, and heavier or denser ends.
• the compound formed by a reaction between the hydrocarbon-soluble additive with the trace element is dispensed along with the effluent brine or effluent liquid hydrocarbon. Conversion of the trace element to a compound makes it more available for subsequent removal through techniques such as filtration, coagulation, flotation, co-precipitation, ion exchange, reverse osmosis, ultra filtration and other typical treatment processes known in the art.
• the phase separation device 110 may utilize various separation items, already known in the art, to assist in separating the mixture into phases.
• a plurality of baffles 118 are contained within the phase separation device 110 to assist in separating the emulsified solution into phases.
• a series of horizontally spaced baffles are utilized, however, any directional and spatial arrangement of the baffles may be utilized.
• the phase separation device 110 can include a series of charged plates or electrodes (not shown) that operate at relatively high voltages to create an electric field and assist in demulsifying the wash water and the liquid hydrocarbon.
• the charged plates or electrodes comprise any arrangement of anodes and cathodes disposed to create a sufficient electric field for breaking the emulsified mixture into an aqueous phase and an oil phase.
• a chemical demulsifying agent may be additionally added to the phase separation device 110 to aid with phase separation.
• the separated aqueous phase typically consists of effluent brine that flows out of the desalter though first output 114 and can be filtered and recycled back through line 112 as wash water.
• the oil phase typically consists of effluent liquid hydrocarbons that are dispensed into piping 116 and are transported to fractional distillation column 120.
• the compound formed from the reaction of the hydrocarbon-soluble additive with the trace element is produced and dispensed along with either of the effluent brine or effluent liquid hydrocarbon.
• conversion of the trace element to a compound form provides increased opportunity for subsequent removal, as the compound is larger in size than that trace element, has an increased mass, and is typically more stabile.
• a chemical settling agent may be utilized to accelerate the settling of the compound mixed with the hydrocarbon and/or aqueous phase.
• the settling agent can be added to the liquid hydrocarbon directly with the hydrocarbon-soluble additive, along with the wash water, or through a separate injection port upstream or directly into the phase separation device.
• phase separation device could be added downstream of the phase separation device directly to either the effluent brine or hydrocarbon.
• Types of settling agents that may be utilized are known in that art, and are similar to those characterized in United States Patents 7,204,927, 7,048,847, 5,681,451, 5,593572, 5,481,059 and 5,476988.
• FIG. 3 depicts a schematic flow process, according to another embodiment of the present invention, for removing trace elements from liquid hydrocarbon feed, such as at a hydrocarbon recovery site.
• Treatment system 200 includes recovered contaminated hydrocarbons from reservoir 202 and routed via piping 204.
• the recovered hydrocarbons from the reservoir 202 are normally extracted in an emulsion form and comprise an admixture of hydrocarbons with water.
• the recovered hydrocarbons pass through piping 204 and a hydrocarbon-soluble additive is injected into piping 204 through line 206.
• a pressure reducing valve (not shown) or mixing device (not shown) may be employed.
• phase separation device 210 also known as an oil-water separator, to resolve the emulsion. Similar to the phase separation device 110, phase separation device 210 may also utilize baffles 216, charged plates (not shown), electrodes (not shown), a demulsifying agent, and/or a settling agent to assist in separation of the phases and/or the compound.
• phase separation device 110 nor phase separation device 210 require such items, and that they are only utilized to expedite the settling time of the emulsified mixture and the compound.
• the treated liquid hydrocarbon passes through line 214 to storage tank 220 where it can be transferred to another operation facility, such as the system shown in Figure 2.
• the separated aqueous phase is dispensed through outlet line 212.
• This produced water may still contain an oily residue and/or other contaminates, and therefore, may pass through another phase separation device (not shown) before being recycled or disposed of. In this case, a similar process may be repeated such that the produced water is injected with an additive prior to passing through the separation device such that additional contaminates are removed.
• Point A is located upstream of phase separation device 110 and in this example upstream of where the hydrocarbon-soluble additive is injected through line 108
• Point B is located downstream of the phase separation device on first output 114
• Point C is located downstream of the phase separation device on second output 116
• Point D is located on output 130 of fractional distillation column 120
• Point E is located on output 126 of fractional distillation column 120.
• a more immediate drop at Point E may be realized through proper flushing of the equipment prior to commencing the injection of the additive.
• a settling agent can be used, e.g., by injecting the settling agent at either Points 108 or 112, to promote an increase of mercury concentration in the effluent brine.
• Point C it appears that the compound is carried by the effluent liquid hydrocarbon to the distillation chamber. Note that in this example, detection does not speciate and therefore, the readings include the total mercury concentration present in both an elemental and compound state. It is contemplated that the compound may have collected at the bottom of the distillation chamber, as an increased concentration was not detected at Point D, while a significant drop did occur at point E.
• sulfur-based as used herein means any compound containing one or more sulfur atoms.
• cury salt means any chemical compound formed by replacing all or part of the hydrogen ions of an acid with one or more mercury ions.
• mercury sulfide as used herein means mercuric sulfide, mercurous sulfide, or a mixture thereof. Normally the mercury sulfide is present as mercuric sulfide and thus the stoichiometric equivalent would be one mole of sulfide ion per mole of mercury ion.
• organic polysulfide as used herein means any chemical compound containing two or more sulfur atoms bonded to any hydrocarbon or hydrogen atom.
• oil-water as used herein means any mixture comprising a liquid hydrocarbon with water. Therefore, it is to be understood that the term “oil-water” is inclusive of both oil-in-water emulsions and water-in-oil emulsions.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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• 2008
  • 2008-07-03 US US12/167,466 patent/US20100000910A1/en not_active Abandoned
• 2009
  • 2009-06-03 EP EP09794870A patent/EP2297280A2/de not_active Withdrawn
  • 2009-06-03 WO PCT/US2009/046065 patent/WO2010005654A2/en not_active Ceased
  • 2009-06-03 KR KR1020117002511A patent/KR20110034658A/ko not_active Withdrawn
• 2010
  • 2010-11-23 ZA ZA2010/08389A patent/ZA201008389B/en unknown

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