US20100000910A1 - System and method for separating a trace element from a liquid hydrocarbon feed - Google Patents
System and method for separating a trace element from a liquid hydrocarbon feed Download PDFInfo
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- US20100000910A1 US20100000910A1 US12/167,466 US16746608A US2010000910A1 US 20100000910 A1 US20100000910 A1 US 20100000910A1 US 16746608 A US16746608 A US 16746608A US 2010000910 A1 US2010000910 A1 US 2010000910A1
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- United States
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- liquid hydrocarbon
- hydrocarbon
- trace element
- separation device
- phase separation
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- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 112
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 110
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 97
- 239000007788 liquid Substances 0.000 title claims abstract description 87
- 239000011573 trace mineral Substances 0.000 title claims abstract description 67
- 235000013619 trace mineral Nutrition 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims description 32
- 239000000654 additive Substances 0.000 claims abstract description 54
- 230000000996 additive effect Effects 0.000 claims abstract description 54
- 238000005191 phase separation Methods 0.000 claims abstract description 49
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 28
- 239000012267 brine Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 21
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002569 water oil cream Substances 0.000 claims abstract description 9
- 150000008116 organic polysulfides Chemical class 0.000 claims abstract description 5
- 239000012530 fluid Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 238000011033 desalting Methods 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000011282 treatment Methods 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000011669 selenium Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 230000005684 electric field Effects 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 229910052716 thallium Inorganic materials 0.000 claims description 4
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 235000019476 oil-water mixture Nutrition 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 3
- 229910052742 iron Inorganic materials 0.000 claims 3
- 150000002730 mercury Chemical class 0.000 claims 3
- 229910052720 vanadium Inorganic materials 0.000 claims 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 3
- 229910052725 zinc Inorganic materials 0.000 claims 3
- 239000011701 zinc Substances 0.000 claims 3
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000004508 fractional distillation Methods 0.000 description 14
- 230000002745 absorbent Effects 0.000 description 10
- 239000002250 absorbent Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 7
- 238000004821 distillation Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- -1 diesel Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 239000005077 polysulfide Substances 0.000 description 4
- 229920001021 polysulfide Polymers 0.000 description 4
- 150000008117 polysulfides Polymers 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002731 mercury compounds Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910001848 post-transition metal Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- 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
- 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.
- the following example shows how mercury content is reduced from a liquid hydrocarbon feed to minimal levels, according to the present invention.
- Test results were taken at a plurality of locations, each corresponding to a different stage within a liquid hydrocarbon treatment facility, over four hour intervals to measure the variation in the concentration of mercury within a contaminated liquid hydrocarbon feed.
- 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. While no significant change may be seen at Point B in this example, 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. Considering that a concentration of mercury is continually detected at 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.
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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)
Abstract
Description
- This application is a continuation-in-part of U.S. patent application Ser. No. 12/132,475 filed Jun. 3, 2008, which is hereby incorporated herein in its entirety by reference.
- 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.
- Various successful methods for removal of trace metal contaminates within liquid hydrocarbon feed prior to fractional distillation have nonetheless been developed. For example, U.S. Pat. No. 6,350,372 B1 discloses utilizing a solubilized sulfur compound in combination with an absorbent carrier. In particular, a liquid hydrocarbon feed is mixed with a miscible sulfur compound and then placed in contact with a fixed bed absorbent, thus removing at least 85% of the mercury on an elemental basis. U.S. Pat. No. 4,474,896 claims the use of absorbent compositions, mainly polysulfide based, for removal of elemental mercury from gaseous and liquid hydrocarbon streams. Specifically, 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.
- Another method to remove mercury from liquid hydrocarbon condensate is disclosed in U.S. Pat. No. 4,915,818. In this method, the use of absorbent carriers is eliminated by treating the liquid hydrocarbons with a dilute aqueous solution of alkali metal sulfide salt. Due to the high partition coefficient of the sulfur compounds in the aqueous phase, the risk of contaminating the liquid hydrocarbons with sulfur is limited. However, while this process minimizes the risk of sulfur contamination, mercury present in the organic phase may also be less likely to react to the alkali metal sulfide salt as its chemical dependency may be governed by the phase it resides in. In particular, the organic mercury compounds are soluble in the liquid hydrocarbon feed and typically are far less reactive than elemental mercury or inorganic mercury compounds.
- In view of the foregoing, previous methods of trace element removal are considered less than desirable and new methods of overcoming the problems associated with trace element extraction from hydrocarbon feed would be extremely useful.
- 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. During mixing, 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.
- In some embodiments, the present invention is directed to removing elemental mercury from a liquid hydrocarbon feed. A sulfur-containing hydrocarbon-soluble additive is mixed with the liquid hydrocarbon feed and water to produce an emulsified solution. In some instances, 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. For instance, 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. Regardless of the mixing strategy, 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.
- According to one embodiment of the present invention, 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. In a refinery setting, where 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 fluid mixture is then resolved within the phase separation device producing effluent liquid hydrocarbons with a reduced concentration of the trace element that can be dispensed through a first output line, effluent brine that can be dispensed through a second output line, and the compound formed by mixing the additive with the trace element, which can be dispensed from the phase separation device with either of the effluent brine or the effluent liquid hydrocarbon. If the trace element is removed at the hydrocarbon recovery site, such as an offshore platform, the phase separation device may comprise an oil-water separator. Here, 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. As the additive is mixed with the contaminated oil-in-water mixture, the additive chemically reacts with the contaminant or trace element forming a compound. As the mixture is separated, the liquid hydrocarbon is recovered such that it has a reduced concentration of the trace element.
- The above mentioned and other features of this invention will become more apparent and better understood by reference to the following detailed description taken in conjunction with the accompanying drawings.
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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. -
FIG. 3 is a schematic diagram depicting a system for removing trace elements from liquid hydrocarbon feed, according to one embodiment of the present invention. - The figures are not necessarily to scale and certain features may be exaggerated in order to better illustrate and explain the present invention. Similarly, the figures have been simplified from a processing standpoint to exclude certain types of equipment, such as mixing devices, not essential for understanding the invention by one skilled in the art.
- Hydrocarbon feeds, generally a conglomeration of hydrocarbon chains with approximate lengths ranging between C5H12 and C42H86, 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). For various reasons, including corrosion prevention and ensuring environmental sustainability, it is often desirable to extract one or more of these trace elements during initial treatment of the feed.
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FIG. 1 depicts steps, according to one method of the present invention, for removal of a trace element from a liquid hydrocarbon. First, as shown instep 10, a hydrocarbon-soluble additive is mixed with a liquid hydrocarbon having a concentration of a trace element and with water. As these fluids are mixed, the hydrocarbon-soluble additive chemically reacts with the trace element forming a compound. Typically, this compound will be insoluble in both the hydrocarbon and aqueous phase so that it may easily be removed during future processing. Once the oil-water emulsion containing the compound is formed, it is resolved into phases in a phase separation device, as shown instep 20. The effluent phases are then dispensed separately from the phase separation device, as depicted instep 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 instep 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. Note that the “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. - In certain embodiments, 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. The hydrocarbon-soluble sulfur-based additive reacts with the mercury rapidly forming an agglomeration of mercuric sulfide through the following reaction:
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R—S—Sx—S—R+XHg→R—S—S—R+XHgS - where R is any hydrocarbon or hydrogen, S is Sulfur, and X and x are the same whole number, typically between 3 and 8. As an inorganic salt, 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. In some instances, mercurous sulfide may also be formed from the reaction of the sulfur-based additive with the mercury in the liquid hydrocarbon feed.
-
FIG. 2 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 fromstorage container 102. The feed is then heated in afurnace 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 throughline 108. The liquid hydrocarbon feed and hydrocarbon-soluble additive are then inputted into aphase separation device 110, such as a desalting unit or desalter, and blended with wash water introduced throughline 112 to form an emulsion within thephase separation device 110. To obtain an adequate emulsion the mixture may be passed through a pressure reducing valve (not shown) or stirred by a mixing device (not shown). Alternatively,line 112, containing the wash water, may be injected directly into piping 104 upstream of thephase separation device 110. Similarly, the hydrocarbon-soluble additive can be injected through the same line as the wash water and only one of 108 and 112 will be present. While the mixture is emulsifying, 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. As discussed later in more detail, thelines phase separation device 110 may utilize a plurality ofbaffles 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. - Once separated, the effluent brine flows out of the desalter though a
first output 114 and typically is filtered and recycled back throughline 112 as wash water. The effluent liquid hydrocarbon is dispensed from thephase separation device 110 into piping 116 and is transported tofractional distillation column 120.Fractional distillation column 120 is comprised of a plurality of spacedplates 122 filled withmultiple apertures 124. As the heated effluent hydrocarbon enters thefractional distillation column 120, it separates such that the hydrocarbon vapors continually ascend passing through theapertures 124 within the spacedplates 122. As the hydrocarbon vapors climb in thefractional distillation column 120, they cool down and begin to condense forming liquid fractions that are caught in the plurality of spacedplates 122. Vapors that pass all the way to the top of thefractional distillation column 120 exit throughoutput 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 throughoutputs 128 each corresponding to the spacedplates 122 within thefractional distillation column 120. The heaviest hydrocarbon chains collect in the bottom of thefractional distillation column 120 and are dispensed throughoutput 130. These hydrocarbons are commonly referred to as the residual. Depending on the 126, 128, 130, 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. For instance, 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.respective output - As previously mentioned, the
phase separation device 110 may utilize various separation items, already known in the art, to assist in separating the mixture into phases. For example and as shown inFIG. 2 , a plurality ofbaffles 118 are contained within thephase separation device 110 to assist in separating the emulsified solution into phases. As illustrated inFIG. 2 , a series of horizontally spaced baffles are utilized, however, any directional and spatial arrangement of the baffles may be utilized. Similarly, thephase 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 thephase separation device 110 to aid with phase separation. The separated aqueous phase typically consists of effluent brine that flows out of the desalter thoughfirst output 114 and can be filtered and recycled back throughline 112 as wash water. The oil phase typically consists of effluent liquid hydrocarbons that are dispensed intopiping 116 and are transported tofractional distillation column 120. Additionally 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. Again, 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. Depending on the type of settling agent, 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. Additionally, it 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 U.S. Pat. Nos. 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 fromreservoir 202 and routed viapiping 204. The recovered hydrocarbons from thereservoir 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 throughline 206. To obtain adequate mixing with the additive, a pressure reducing valve (not shown) or mixing device (not shown) may be employed. As the additive is sufficiently mixed with the emulsion, the additive chemically reacts with the trace element, which contaminates the recovered hydrocarbons, to form compounds. Again, these compounds can be insoluble such that they can easily be separated in subsequent processes. The mixture is then passed throughphase separation device 210, also known as an oil-water separator, to resolve the emulsion. Similar to thephase separation device 110,phase separation device 210 may also utilizebaffles 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. It can be appreciated by one skilled in the art that neitherphase separation device 110 norphase separation device 210 require such items, and that they are only utilized to expedite the settling time of the emulsified mixture and the compound. Once the mixture has been resolved, the treated liquid hydrocarbon, with reduced contamination of the trace element, passes throughline 214 tostorage tank 220 where it can be transferred to another operation facility, such as the system shown inFIG. 2 . The separated aqueous phase is dispensed throughoutlet 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. - The following example shows how mercury content is reduced from a liquid hydrocarbon feed to minimal levels, according to the present invention. Test results were taken at a plurality of locations, each corresponding to a different stage within a liquid hydrocarbon treatment facility, over four hour intervals to measure the variation in the concentration of mercury within a contaminated liquid hydrocarbon feed. As shown in
FIG. 2 , Point A is located upstream ofphase separation device 110 and in this example upstream of where the hydrocarbon-soluble additive is injected throughline 108, Point B is located downstream of the phase separation device onfirst output 114, Point C is located downstream of the phase separation device onsecond output 116, Point D is located onoutput 130 offractional distillation column 120, and Point E is located onoutput 126 offractional distillation column 120. -
Time Point A Point B Point C Point D Point E (Hours) (ppb) (ppb) (ppb) (ppb) (ppb) 0 109.4 13.2 376.2 0 452.4 4 60.7 8.6 201.9 1 748.2 8 82.5 13.2 140.4 2.2 127.3 12 103 14.2 281.8 1.8 2.6 16 17.7 6.8 102 2 7.6 20 170.6 11.5 259.9 2.8 13.2 24 187.3 8.8 246.6 0.2 7.1
The results above indicate that after the hydrocarbon-soluble additive was injected into the liquid hydrocarbon feed, the mercury concentration began to taper off significantly and stabilize by the twelfth hour of testing to a level of less than 15 ppb at point E, which is located downstream of thephase separation device 110 onoutput 126 offractional 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. While no significant change may be seen at Point B in this example, a settling agent can be used, e.g., by injecting the settling agent at either 108 or 112, to promote an increase of mercury concentration in the effluent brine. Considering that a concentration of mercury is continually detected at 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.Points - Certain terms are defined throughout this description as they are first used, while certain other terms used in this description are defined below:
- The term “sulfur-based” as used herein means any compound containing one or more sulfur atoms.
- The term “mercury salt” as used herein means any chemical compound formed by replacing all or part of the hydrogen ions of an acid with one or more mercury ions.
- The term “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.
- The term “organic polysulfide” as used herein means any chemical compound containing two or more sulfur atoms bonded to any hydrocarbon or hydrogen atom.
- The unit “ppb” as used herein means parts per billion.
- The term “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.
- While this invention has been described as having an exemplary design, the present invention may be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Those skilled in the art will appreciate that the above described embodiments are merely illustrative of the present invention and that many variations of the above described embodiments can be devised without departing from the scope of the invention. For instance, it is contemplated that the hydrocarbon-soluble additive can be introduced into the liquid hydrocarbon or oil-water mixture through multiple injection points as compared to a single injection line. It is therefore intended that such departures from the present disclosure, that come within the known customary practice in the art to which this invention pertains, be included within the scope of the following appended claims and their equivalents.
Claims (20)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/167,466 US20100000910A1 (en) | 2008-07-03 | 2008-07-03 | System and method for separating a trace element from a liquid hydrocarbon feed |
| KR1020117002511A KR20110034658A (en) | 2008-07-03 | 2009-06-03 | Separation System and Method for Trace Elements from Liquid Hydrocarbon Feed |
| PCT/US2009/046065 WO2010005654A2 (en) | 2008-07-03 | 2009-06-03 | System and method for separating a trace element from a liquid hydrocarbon feed |
| NL2002958A NL2002958C2 (en) | 2008-06-03 | 2009-06-03 | System and method for separating a trace element from a liquid hydrocarbon feed. |
| EP09794870A EP2297280A2 (en) | 2008-07-03 | 2009-06-03 | System and method for separating a trace element from a liquid hydrocarbon feed |
| ARP090102003 AR072006A1 (en) | 2008-06-03 | 2009-06-04 | SYSTEM AND METHOD FOR SEPARATING A VESTIGIAL ELEMENT FROM A LOAD OF LIQUID HYDROCARBON |
| ZA2010/08389A ZA201008389B (en) | 2008-07-03 | 2010-11-23 | System and method for separating a trace element from a liquid hydrocarbon feed |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/167,466 US20100000910A1 (en) | 2008-07-03 | 2008-07-03 | System and method for separating a trace element from a liquid hydrocarbon feed |
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| Publication Number | Publication Date |
|---|---|
| US20100000910A1 true US20100000910A1 (en) | 2010-01-07 |
Family
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Family Applications (1)
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| US12/167,466 Abandoned US20100000910A1 (en) | 2008-06-03 | 2008-07-03 | System and method for separating a trace element from a liquid hydrocarbon feed |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20100000910A1 (en) |
| EP (1) | EP2297280A2 (en) |
| KR (1) | KR20110034658A (en) |
| WO (1) | WO2010005654A2 (en) |
| ZA (1) | ZA201008389B (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2297280A2 (en) | 2011-03-23 |
| WO2010005654A3 (en) | 2010-05-06 |
| WO2010005654A2 (en) | 2010-01-14 |
| ZA201008389B (en) | 2012-02-29 |
| KR20110034658A (en) | 2011-04-05 |
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