WO2010019282A2 - Mercury removal from crude oil - Google Patents
Mercury removal from crude oil Download PDFInfo
- Publication number
- WO2010019282A2 WO2010019282A2 PCT/US2009/034883 US2009034883W WO2010019282A2 WO 2010019282 A2 WO2010019282 A2 WO 2010019282A2 US 2009034883 W US2009034883 W US 2009034883W WO 2010019282 A2 WO2010019282 A2 WO 2010019282A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mercury
- hydrocarbon stream
- liquid hydrocarbon
- stream
- accordance
- Prior art date
Links
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 82
- 239000010779 crude oil Substances 0.000 title claims abstract description 34
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 95
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 95
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 75
- 239000007788 liquid Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000012546 transfer Methods 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000002594 sorbent Substances 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 54
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000011143 downstream manufacturing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/34—Arrangements for separating materials produced by the well
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/401—Further details for adsorption processes and devices using a single bed
Definitions
- the present invention relates to a process for the removal of mercury from crude oil.
- this invention relates to a process for the removal of mercury from crude oil at the well site using produced gas.
- a process including the following: a) extracting a crude oil stream comprising elemental mercury, hydrocarbons and water from a crude oil well; b) separating the crude oil stream into a gaseous hydrocarbon stream comprising hydrocarbons, mercury and water, and a liquid hydrocarbon stream comprising hydrocarbons and elemental mercury, and which can also include water; c) charging a mercury-containing gas feed, including in part at least a portion of the gaseous hydrocarbon stream, to a mercury removal unit for removal of mercury from the mercury-containing gas feed, thereby forming a treated gas stream; d) contacting a recycle gas stream comprising a portion of the treated gas stream with at least a portion of the liquid hydrocarbon stream for transfer of at least a portion of the elemental mercury contained in the liquid hydrocarbon stream to the recycle gas stream; thereby forming a mercury rich gas stream, and a treated liquid hydrocarbon stream; and e) passing the mercury rich gas stream to the mercury removal unit as a
- a process including the following: a) extracting a crude oil stream comprising elemental mercury, hydrocarbons and water from a crude oil well; b) separating the crude oil stream into a gaseous hydrocarbon stream comprising hydrocarbons, mercury and water, and a liquid hydrocarbon stream comprising hydrocarbons and elemental mercury, and which can also include water; c) removing water from a mercury-containing gas feed, including in part at least a portion of the gaseous hydrocarbon stream, prior to charging to a mercury removal unit for removal of mercury from the mercury-containing gas feed, thereby forming a treated gas stream; d) contacting a recycle gas stream comprising a portion of the treated gas stream with at least a portion of the liquid hydrocarbon stream for transfer of at least a portion of the elemental mercury contained in the liquid hydrocarbon stream to the recycle gas stream; thereby forming a mercury rich gas stream, and a treated liquid hydrocarbon stream; and separating water from the liquid hydrocarbon stream; and
- Figure 1 is a simplified schematic flow diagram presenting an embodiment of the present invention.
- Figure 2 is a simplified schematic flow diagram presenting an embodiment of the present invention.
- Figure 3 is a graphic illustration of a temperature vs. pressure curve, resulting from a simulation, above which temperature 90% mercury removal from a crude oil is predicted.
- Figure 4 is a graphic illustration of results from experiments concerning the removal of mercury from decane using methane as a sparging media.
- FIGURE 1 crude oil is removed from a crude oil well by line 100 and is passed to separator 102 for separation into a gaseous hydrocarbon stream comprising, consisting of, or consisting essentially of hydrocarbons, mercury and water, which is removed from separator 102 by line 104, and into a liquid hydrocarbon stream: 1) comprising, consisting of, or consisting essentially of hydrocarbons and elemental mercury, or 2) comprising, consisting of, or consisting essentially of hydrocarbons, elemental mercury and water, which is removed from separator 102 by line 106.
- a gaseous hydrocarbon stream comprising, consisting of, or consisting essentially of hydrocarbons, mercury and water
- separator 102 for separation into a gaseous hydrocarbon stream comprising, consisting of, or consisting essentially of hydrocarbons, mercury and water, which is removed from separator 102 by line 104, and into a liquid hydrocarbon stream: 1) comprising, consisting of, or consisting essentially of hydrocarbons and elemental mercury, or 2) comprising
- a mercury-containing gas feed including in part at least a portion of the gaseous hydrocarbon stream, is charged to a mercury removal unit (MRU) 108 by line 110 for removal of mercury from the mercury-containing gas feed, thereby forming a treated gas stream, which is removed from MRU 108 by line 112.
- a recycle gas stream comprising a portion of treated gas stream from line 112 is charged to a contactor 114 by line 116 for contact with at least a portion of the liquid hydrocarbon stream charged to contactor 114 by line 106.
- the elemental mercury contained in the liquid hydrocarbon stream is transferred to the recycle gas stream, thereby forming a mercury rich gas stream, which is removed from contactor 114 by line 118, and a treated liquid hydrocarbon stream, which is removed from contactor 114 by line 120.
- the recycle gas stream is charged to contactor 114 by line 116 below the location line 106 charges the liquid hydrocarbon stream to contactor 114.
- the mercury rich gas stream is removed from contactor 114 by line 118 at a location above the location line 106 charges the liquid hydrocarbon stream to contactor 114.
- the treated liquid hydrocarbon stream is removed from contactor 114 by line 120 at a location below the location line 106 charges the liquid hydrocarbon stream to contactor 114.
- the mercury rich gas stream is passed to the MRU 108 as a portion of the mercury-containing gas feed by lines 118 and 110.
- crude oil is removed from a crude oil well by line 200 and is passed to separator 202 for separation into a gaseous hydrocarbon stream comprising, consisting of, or consisting essentially of hydrocarbons, mercury and water, which is removed from separator 202 by line 204, and into a liquid hydrocarbon stream comprising, consisting of, or consisting essentially of hydrocarbons, elemental mercury and water, which is removed from separator 202 by line 206.
- a mercury rich gas stream described later the gaseous hydrocarbon stream is charged to a separator 207 wherein water is removed and exits separator 207 by line 208.
- the overhead gases leaving separator 207 by line 209 are charged to a mercury removal unit (MRU) 210 as a mercury-containing gas feed for removal of mercury from the mercury-containing gas feed, thereby forming a treated gas stream, which is removed from MRU 210 by line 212.
- a recycle gas stream comprising a portion of the treated gas stream from line 212 is charged to a contactor 214 by line 216 for contact with at least a portion of the liquid hydrocarbon stream charged to contactor 214 by line 206.
- the elemental mercury contained in the liquid hydrocarbon stream is transferred to the recycle gas stream, thereby forming a mercury rich gas stream, which is removed from contactor 214 by line 218, and a treated liquid hydrocarbon stream, which is removed from contactor 214 by line 220.
- water is separated from the liquid hydrocarbon stream (and from the recycle gas stream, if water is present in such) and removed from contactor 214 by line 222.
- the recycle gas stream is charged to contactor 214 by line 216 below the location line 206 charges the liquid hydrocarbon stream to contactor 214.
- the mercury rich gas stream is removed from contactor 214 by line 218 at a location above the location line 206 charges the liquid hydrocarbon stream to contactor 214.
- the treated liquid hydrocarbon stream is removed from contactor 214 by line 220 at a location below the location line 206 charges the liquid hydrocarbon stream to contactor 214.
- Water is removed from contactor 214 by line 222 below the location line 220 removes the treated liquid hydrocarbon stream from contactor 214.
- the mercury rich gas stream is passed to the separator 207 along with the gaseous hydrocarbon stream by lines 218 and 204.
- the crude oil stream of the present invention comprises, consists of, or consists essentially of a broad range crude oil. More particularly, the crude oil stream comprises hydrocarbons containing at least one carbon atom per molecule.
- the gaseous hydrocarbon stream comprises, consists of, or consists essentially of hydrocarbons containing from about 1 to about 6 carbon atoms per molecule.
- the temperature at which the crude oil stream is separated into the gaseous hydrocarbon stream and the liquid hydrocarbon stream is preferably at least about 50 0 C, more preferably at least about 60 0 C.
- the pressure at which the crude oil stream is separated into the gaseous hydrocarbon stream and the liquid hydrocarbon stream is preferably at least about 0.5 Bars, more preferably at least about 1 Bars.
- the mercury removal unit has a fixed bed comprising any mercury sorbent material capable of removing mercury from gases.
- the treated gas stream preferably comprises less than about 20 wt. % of the mercury contained in the mercury-containing gas feed, and more preferably less than about 10 wt. % of the mercury contained in the mercury-containing gas feed.
- the treated liquid hydrocarbon stream preferably comprises less than about 50 wt. % of the elemental mercury contained in the liquid hydrocarbon stream, and more preferably less than about 20 wt. % of the elemental mercury contained in the liquid hydrocarbon stream.
- the liquid hydrocarbon stream typically comprises at least about 10 ppb elemental mercury, and more particularly comprises at least about 200 ppb elemental mercury.
- the recycle gas stream is contacted with the liquid hydrocarbon stream at a temperature in the range of from about 7O 0 C to about 300 0 C, preferably from about 15O 0 C to about 200 0 C, a pressure in the range of from about 0.5 Bars to about 15 Bars, preferably from about IBar to about 10 Bars, and more preferably from about 2 Bars to about 7 Bars; and a gas to liquid ratio in the range of from about 50 to about 300 standard cubic feet of gas/bbl of liquid (SCF/bbl), preferably from about 100 to about 200 SCF/bbl.
- SCF/bbl standard cubic feet of gas/bbl of liquid
- Example 2 An experiment was run to test the removal of Hg (elemental) from a hydrocarbon by sparging with a lighter hydrocarbon Elemental mercury was dissolved in decane at about 1,300 ppbw
- Figure 4 shows the results of the experiment, plotting residual Hg in the decane vs liters of methane sparged through the decane for two different runs, Runs 1 and 2
- FIG. 4 is a plot of the results of a theoretical calculation of the mercury removal process, and shows that the experimental results for Runs 1 and 2 are m good agreement with such, and that the experimental results for Run 3 is m excellent agreement with the theoretical calculations
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Fluid Mechanics (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Gas Separation By Absorption (AREA)
Abstract
A process for decreasing the level of elemental mercury contained in a crude oil at the well site by separating the crude oil stream into a gaseous hydrocarbon stream containing hydrocarbons, mercury and water, and a liquid hydrocarbon stream containing hydrocarbons and elemental mercury; removing mercury from the gaseous hydrocarbon stream in a mercury removal unit, thereby forming a treated gas stream; contacting a recycle gas stream comprising a portion of the treated gas stream with at least a portion of the liquid hydrocarbon stream for transfer of at least a portion of the elemental mercury contained in the liquid hydrocarbon stream to the recycle gas stream; thereby forming a mercury rich gas stream, and a treated liquid hydrocarbon stream; and passing the mercury rich gas stream, along with the gaseous hydrocarbon stream, to the mercury removal unit, is disclosed.
Description
MERCURY REMOVAL FROM CRUDE OIL
The present invention relates to a process for the removal of mercury from crude oil. In another aspect, this invention relates to a process for the removal of mercury from crude oil at the well site using produced gas.
Since the presence of mercury in crude oil can cause problems with downstream processing units, as well as health and environmental issues, there is an incentive to remove mercury from crude oil.
Therefore, development of an improved process for effectively removing mercury from crude oil before downstream processing into products would be a significant contribution to the art.
Brief Summary of the Invention
In accordance with a first embodiment of the present invention, a process is provided including the following: a) extracting a crude oil stream comprising elemental mercury, hydrocarbons and water from a crude oil well; b) separating the crude oil stream into a gaseous hydrocarbon stream comprising hydrocarbons, mercury and water, and a liquid hydrocarbon stream comprising hydrocarbons and elemental mercury, and which can also include water;
c) charging a mercury-containing gas feed, including in part at least a portion of the gaseous hydrocarbon stream, to a mercury removal unit for removal of mercury from the mercury-containing gas feed, thereby forming a treated gas stream; d) contacting a recycle gas stream comprising a portion of the treated gas stream with at least a portion of the liquid hydrocarbon stream for transfer of at least a portion of the elemental mercury contained in the liquid hydrocarbon stream to the recycle gas stream; thereby forming a mercury rich gas stream, and a treated liquid hydrocarbon stream; and e) passing the mercury rich gas stream to the mercury removal unit as a portion of the mercury-containing gas feed.
In accordance with a second embodiment of the present invention, a process is provided including the following: a) extracting a crude oil stream comprising elemental mercury, hydrocarbons and water from a crude oil well; b) separating the crude oil stream into a gaseous hydrocarbon stream comprising hydrocarbons, mercury and water, and a liquid hydrocarbon stream comprising hydrocarbons and elemental mercury, and which can also include water; c) removing water from a mercury-containing gas feed, including in part at least a portion of the gaseous hydrocarbon stream, prior to charging to a mercury removal unit for removal of mercury from the mercury-containing gas feed, thereby forming a treated gas stream;
d) contacting a recycle gas stream comprising a portion of the treated gas stream with at least a portion of the liquid hydrocarbon stream for transfer of at least a portion of the elemental mercury contained in the liquid hydrocarbon stream to the recycle gas stream; thereby forming a mercury rich gas stream, and a treated liquid hydrocarbon stream; and separating water from the liquid hydrocarbon stream; and e) passing the mercury rich gas stream to the mercury removal unit as a portion of the mercury-containing gas feed.
Brief Description of the Drawings
Figure 1 is a simplified schematic flow diagram presenting an embodiment of the present invention.
Figure 2 is a simplified schematic flow diagram presenting an embodiment of the present invention.
Figure 3 is a graphic illustration of a temperature vs. pressure curve, resulting from a simulation, above which temperature 90% mercury removal from a crude oil is predicted.
Figure 4 is a graphic illustration of results from experiments concerning the removal of mercury from decane using methane as a sparging media.
Detailed Description of the Invention
According to the first embodiment of the present invention, the process of the present invention will be described with reference to FIGURE 1.
Referring to FIGURE 1, crude oil is removed from a crude oil well by line 100 and is passed to separator 102 for separation into a gaseous hydrocarbon stream comprising, consisting of, or consisting essentially of hydrocarbons, mercury and water, which is removed from separator 102 by line 104, and into a liquid hydrocarbon stream: 1) comprising, consisting of, or consisting essentially of hydrocarbons and elemental mercury, or 2) comprising, consisting of, or consisting essentially of hydrocarbons, elemental mercury and water, which is removed from separator 102 by line 106. A mercury-containing gas feed, including in part at least a portion of the gaseous hydrocarbon stream, is charged to a mercury removal unit (MRU) 108 by line 110 for removal of mercury from the mercury-containing gas feed, thereby forming a treated gas stream, which is removed from MRU 108 by line 112. A recycle gas stream comprising a portion of treated gas stream from line 112 is charged to a contactor 114 by line 116 for contact with at least a portion of the liquid hydrocarbon stream charged to contactor 114 by line 106. Through such contacting, at least a portion of the elemental mercury contained in the liquid hydrocarbon stream is transferred to the recycle gas stream, thereby forming a mercury rich gas stream, which is removed from contactor 114 by line 118, and a treated liquid hydrocarbon stream, which is removed from contactor 114 by line 120. The recycle gas stream is charged to contactor 114 by line 116 below the location line 106 charges the liquid hydrocarbon stream to contactor 114. The mercury rich gas stream is removed from contactor 114 by line 118 at a location above the location line 106 charges the liquid hydrocarbon stream to contactor 114. The treated liquid hydrocarbon stream is removed from contactor 114 by line 120 at a location below the
location line 106 charges the liquid hydrocarbon stream to contactor 114. The mercury rich gas stream is passed to the MRU 108 as a portion of the mercury-containing gas feed by lines 118 and 110.
According to the second embodiment of the present invention, the process of the present invention will be described with reference to FIGURE 2.
Referring to FIGURE 2, crude oil is removed from a crude oil well by line 200 and is passed to separator 202 for separation into a gaseous hydrocarbon stream comprising, consisting of, or consisting essentially of hydrocarbons, mercury and water, which is removed from separator 202 by line 204, and into a liquid hydrocarbon stream comprising, consisting of, or consisting essentially of hydrocarbons, elemental mercury and water, which is removed from separator 202 by line 206. Along with a mercury rich gas stream described later, the gaseous hydrocarbon stream is charged to a separator 207 wherein water is removed and exits separator 207 by line 208. The overhead gases leaving separator 207 by line 209 are charged to a mercury removal unit (MRU) 210 as a mercury-containing gas feed for removal of mercury from the mercury-containing gas feed, thereby forming a treated gas stream, which is removed from MRU 210 by line 212. A recycle gas stream comprising a portion of the treated gas stream from line 212 is charged to a contactor 214 by line 216 for contact with at least a portion of the liquid hydrocarbon stream charged to contactor 214 by line 206. Through such contacting, at least a portion of the elemental mercury contained in the liquid hydrocarbon stream is transferred to the recycle gas stream, thereby forming a mercury rich gas stream, which is removed from contactor 214 by line 218, and a treated liquid hydrocarbon stream, which
is removed from contactor 214 by line 220. In addition, water is separated from the liquid hydrocarbon stream (and from the recycle gas stream, if water is present in such) and removed from contactor 214 by line 222. The recycle gas stream is charged to contactor 214 by line 216 below the location line 206 charges the liquid hydrocarbon stream to contactor 214. The mercury rich gas stream is removed from contactor 214 by line 218 at a location above the location line 206 charges the liquid hydrocarbon stream to contactor 214. The treated liquid hydrocarbon stream is removed from contactor 214 by line 220 at a location below the location line 206 charges the liquid hydrocarbon stream to contactor 214. Water is removed from contactor 214 by line 222 below the location line 220 removes the treated liquid hydrocarbon stream from contactor 214. The mercury rich gas stream is passed to the separator 207 along with the gaseous hydrocarbon stream by lines 218 and 204.
The crude oil stream of the present invention comprises, consists of, or consists essentially of a broad range crude oil. More particularly, the crude oil stream comprises hydrocarbons containing at least one carbon atom per molecule.
The gaseous hydrocarbon stream comprises, consists of, or consists essentially of hydrocarbons containing from about 1 to about 6 carbon atoms per molecule.
The temperature at which the crude oil stream is separated into the gaseous hydrocarbon stream and the liquid hydrocarbon stream is preferably at least about 50 0C, more preferably at least about 60 0C. The pressure at which the crude oil stream is
separated into the gaseous hydrocarbon stream and the liquid hydrocarbon stream is preferably at least about 0.5 Bars, more preferably at least about 1 Bars.
The mercury removal unit has a fixed bed comprising any mercury sorbent material capable of removing mercury from gases.
The treated gas stream preferably comprises less than about 20 wt. % of the mercury contained in the mercury-containing gas feed, and more preferably less than about 10 wt. % of the mercury contained in the mercury-containing gas feed.
The treated liquid hydrocarbon stream preferably comprises less than about 50 wt. % of the elemental mercury contained in the liquid hydrocarbon stream, and more preferably less than about 20 wt. % of the elemental mercury contained in the liquid hydrocarbon stream.
The liquid hydrocarbon stream typically comprises at least about 10 ppb elemental mercury, and more particularly comprises at least about 200 ppb elemental mercury.
The recycle gas stream is contacted with the liquid hydrocarbon stream at a temperature in the range of from about 7O0C to about 3000C, preferably from about 15O0C to about 2000C, a pressure in the range of from about 0.5 Bars to about 15 Bars, preferably from about IBar to about 10 Bars, and more preferably from about 2 Bars to about 7 Bars; and a gas to liquid ratio in the range of from about 50 to about 300 standard cubic feet of gas/bbl of liquid (SCF/bbl), preferably from about 100 to about 200 SCF/bbl.
The following examples are provided to further illustrate this invention and are not to be considered as unduly limiting the scope of this invention.
EXAMPLES Example 1
To test the idea, a simulation of the liquid/gas contactor was constructed using an equation of state thermodynamic prediction model for mercury partitioning between gas and liquid using data for elemental mercury in a commercially obtained crude oil blend. The results of the calculation are shown in Figure 3, wherein the temperature of the crude oil is plotted against the pressure to achieve 90% removal of mercury from the liquid oil feed to the contactor. A gas to oil ratio of 80 SCF/bbl was used in the model.
This simulation shows that 90% mercury removal is achievable at the temperature and pressure conditions commonly present at the crude oil well site. That is, wherein the pressure of the Low Pressure Coalescer/Separator typically present at the well site (which is redeployed in the invention as a gas/oil contactor) ranges from about < 1 to ~ 3 Bars, and the reservoir temperature of high mercury crude oils is normally greater than about 15O0C. Example 2
An experiment was run to test the removal of Hg (elemental) from a hydrocarbon by sparging with a lighter hydrocarbon Elemental mercury was dissolved in decane at about 1,300 ppbw Figure 4 shows the results of the experiment, plotting residual Hg in the decane vs liters of methane sparged through the decane for two different runs, Runs 1 and 2
A third experiment was run wherein, prior to adding the elemental mercury, the decane was water washed and passed over a silica gel column to remove trace levels of chloride, oxide or sulfur compounds that could, at the conditions of the experiment, oxidize the mercury and cause it to form non-spargable mercury compounds
Also shown m Figure 4 is a plot of the results of a theoretical calculation of the mercury removal process, and shows that the experimental results for Runs 1 and 2 are m good agreement with such, and that the experimental results for Run 3 is m excellent agreement with the theoretical calculations
While this invention has been described in detail for the purpose of illustration, it should not be construed as limited thereby but intended to cover all changes and modifications withm the spirit and scope thererof
Claims
1. A process comprising: a) extracting a crude oil stream comprising elemental mercury, hydrocarbons and water from a crude oil well; b) separating said crude oil stream into a gaseous hydrocarbon stream comprising hydrocarbons, mercury and water, and a liquid hydrocarbon stream comprising hydrocarbons and elemental mercury; c) charging a mercury-containing gas feed, including in part at least a portion of said gaseous hydrocarbon stream, to a mercury removal unit for removal of mercury from said mercury-containing gas feed, thereby forming a treated gas stream; d) contacting a recycle gas stream comprising a portion of said treated gas stream with at least a portion of said liquid hydrocarbon stream for transfer of at least a portion of the elemental mercury contained in said liquid hydrocarbon stream to said recycle gas stream; thereby forming a mercury rich gas stream, and a treated liquid hydrocarbon stream; and e) passing said mercury rich gas stream to said mercury removal unit as a portion of said mercury-containing gas feed.
2. A process in accordance with claim 1 wherein water is removed from said mercury-containing gas feed prior to charging to said mercury removal unit in step c).
3. A process in accordance with claim 1 wherein said contacting of step d) occurs in a vessel, and wherein said recycle gas stream is charged to said vessel below the location said liquid hydrocarbon stream is charged to said vessel, and wherein said mercury rich gas stream is removed from said vessel at a location above the location said liquid hydrocarbon stream is charged to said vessel, and wherein said treated liquid hydrocarbon stream is removed from said vessel at a location below the location said liquid hydrocarbon stream is charged to said vessel.
4 A process in accordance with claim 1 wherein said gaseous hydrocarbon stream comprises hydrocarbons containing from about 1 to about 6 carbon atoms per molecule.
5. A process in accordance with claim 1 wherein the temperature of said crude oil m step (a) is at least about 5O0C, and wherein the pressure of said separation step (b) is at least about 0.5 Bars
6 A process in accordance with claim 1 wherein the temperature of said crude oil in step (a) is at least about 6O0C, and wherein the pressure of said separation step (b) is at least about 1 Bars
7 A process m accordance with claim 1 wherein said mercury removal unit has a fixed bed comprising a mercury sorbent material.
8 A process in accordance with claim 1 wherein said treated gas stream comprises less than about 20 wt. % of the mercury contained m said mercury-containing gas feed.
9. A process in accordance with claim 1 wherein said treated gas stream comprises less than about 10 wt. % of the mercury contained m said mercury-containing gas feed.
10. A process in accordance with claim 1 wherein said treated liquid hydrocarbon stream comprises less than about 50 wt. % of the elemental mercury contained in said liquid hydrocarbon stream.
11. A process in accordance with claim 1 wherein said treated liquid hydrocarbon stream comprises less than about 20 wt. % of the elemental mercury contained in said liquid hydrocarbon stream.
12. A process in accordance with claim 1 wherein said liquid hydrocarbon stream comprises at least about 10 ppb elemental mercury.
13. A process in accordance with claim 1 wherein said liquid hydrocarbon stream comprises at least about 200 ppb elemental mercury.
14. A process in accordance with claim 1 wherein said contacting of step d) occurs at a temperature in the range of from about 7O0C to about 3000C, and a pressure in the range of from about 0.5 Bars to about 15 Bars, and a gas to liquid ratio in the range of from about 50 to about 300 SCF/bbl.
15. A process in accordance with claim 1 wherein said contacting of step d) occurs at a temperature in the range of from about 1500C to about 2000C, and a pressure in the range of from about 1 Bar to about 10 Bars, and a gas to liquid ratio in the range of from about 100 to about 200 SCF/bbl.
16. A process in accordance with claim 1 wherein said contacting of step d) occurs at a temperature in the range of from about 1500C to about 2000C, and a pressure in the range of from about 2 Bars to about 7 Bars, and a gas to liquid ratio in the range of from about 100 to about 200 SCF/bbl.
17. A process in accordance with claim 3 wherein said liquid hydrocarbon stream comprises hydrocarbons, elemental mercury and water; and wherein water is separated from said liquid hydrocarbon stream and removed from said vessel at a location below the location said treated liquid hydrocarbon stream is removed from said vessel.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/174,816 US20100032344A1 (en) | 2008-08-11 | 2008-08-11 | Mercury removal from crude oil |
| US12/174,816 | 2008-08-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2010019282A2 true WO2010019282A2 (en) | 2010-02-18 |
| WO2010019282A3 WO2010019282A3 (en) | 2010-07-15 |
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Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2009/034883 WO2010019282A2 (en) | 2008-08-11 | 2009-02-23 | Mercury removal from crude oil |
| PCT/US2009/053292 WO2010019510A2 (en) | 2008-08-11 | 2009-08-10 | Mercury removal from crude oil |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2009/053292 WO2010019510A2 (en) | 2008-08-11 | 2009-08-10 | Mercury removal from crude oil |
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| Country | Link |
|---|---|
| US (1) | US20100032344A1 (en) |
| WO (2) | WO2010019282A2 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8489231B2 (en) * | 2009-09-18 | 2013-07-16 | Raf Technology, Inc. | Loop mail processing |
| US8728304B2 (en) | 2010-09-16 | 2014-05-20 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
| US8673133B2 (en) | 2010-09-16 | 2014-03-18 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
| US8663460B2 (en) | 2010-09-16 | 2014-03-04 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
| US8702975B2 (en) | 2010-09-16 | 2014-04-22 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
| US8721873B2 (en) | 2010-11-19 | 2014-05-13 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
| US8721874B2 (en) | 2010-11-19 | 2014-05-13 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
| US8728303B2 (en) | 2010-11-19 | 2014-05-20 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
| EP2508243A1 (en) * | 2011-04-06 | 2012-10-10 | Shell Internationale Research Maatschappij B.V. | Method and apparatus for removing mercury from waste water from hydrocarbon well stream |
| WO2013024147A1 (en) | 2011-08-18 | 2013-02-21 | Shell Internationale Research Maatschappij B.V. | System and method for producing a hydrocarbon product stream from a hydrocarbon well stream, and a hydrocarbon well stream separation tank |
| CA2862229A1 (en) * | 2011-12-30 | 2013-07-04 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
| US9447675B2 (en) | 2012-05-16 | 2016-09-20 | Chevron U.S.A. Inc. | In-situ method and system for removing heavy metals from produced fluids |
| SG11201407565SA (en) | 2012-05-16 | 2014-12-30 | Chevron Usa Inc | Process, method, and system for removing mercury from fluids |
| CN104736678A (en) | 2012-05-16 | 2015-06-24 | 雪佛龙美国公司 | Process, method, and system for removing mercury from fluids |
| CN104334692A (en) | 2012-05-16 | 2015-02-04 | 雪佛龙美国公司 | Process, method, and system for removing heavy metals from fluids |
| US9023196B2 (en) | 2013-03-14 | 2015-05-05 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
| US9169445B2 (en) | 2013-03-14 | 2015-10-27 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from oily solids |
| US9234141B2 (en) | 2013-03-14 | 2016-01-12 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from oily solids |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4962276A (en) * | 1989-01-17 | 1990-10-09 | Mobil Oil Corporation | Process for removing mercury from water or hydrocarbon condensate |
| US20050167335A1 (en) * | 2004-02-03 | 2005-08-04 | Japan Petroleum Exploration Co., Ltd. | Mercury-removal process in distillation tower |
| WO2006090597A1 (en) * | 2005-02-24 | 2006-08-31 | Jgc Corporation | Apparatus for removing mercury in liquid hydrocarbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3768865A (en) * | 1972-07-13 | 1973-10-30 | Ppg Industries Inc | Process for the disposal of salt solutions contaminated with azide |
| JP2578514B2 (en) * | 1989-03-03 | 1997-02-05 | 三井石油化学工業株式会社 | Method for removing mercury from liquid hydrocarbon compounds |
| US4983277A (en) * | 1989-04-27 | 1991-01-08 | Mobil Oil Corporation | Process for the production of natural gas condensate having a reduced amount of mercury from a mercury-containing natural gas wellstream |
| US4981577A (en) * | 1989-04-27 | 1991-01-01 | Mobil Oil Corporation | Process for the production of natural gas condensate having a reduced amount of mercury from a mercury-containing natural gas wellstream |
| US5989506A (en) * | 1996-12-18 | 1999-11-23 | Uop Llc | Process for the removal and recovery of mercury from hydrocarbon streams |
| US6350372B1 (en) * | 1999-05-17 | 2002-02-26 | Mobil Oil Corporation | Mercury removal in petroleum crude using H2S/C |
| US6537443B1 (en) * | 2000-02-24 | 2003-03-25 | Union Oil Company Of California | Process for removing mercury from liquid hydrocarbons |
| US6367555B1 (en) * | 2000-03-15 | 2002-04-09 | Corley P. Senyard, Sr. | Method and apparatus for producing an oil, water, and/or gas well |
-
2008
- 2008-08-11 US US12/174,816 patent/US20100032344A1/en not_active Abandoned
-
2009
- 2009-02-23 WO PCT/US2009/034883 patent/WO2010019282A2/en active Application Filing
- 2009-08-10 WO PCT/US2009/053292 patent/WO2010019510A2/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4962276A (en) * | 1989-01-17 | 1990-10-09 | Mobil Oil Corporation | Process for removing mercury from water or hydrocarbon condensate |
| US20050167335A1 (en) * | 2004-02-03 | 2005-08-04 | Japan Petroleum Exploration Co., Ltd. | Mercury-removal process in distillation tower |
| WO2006090597A1 (en) * | 2005-02-24 | 2006-08-31 | Jgc Corporation | Apparatus for removing mercury in liquid hydrocarbon |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010019510A3 (en) | 2010-07-15 |
| WO2010019510A2 (en) | 2010-02-18 |
| WO2010019282A3 (en) | 2010-07-15 |
| US20100032344A1 (en) | 2010-02-11 |
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