BRPI1014380B1 - Process for removing mercury from a mercury-containing hydrocarbon fluid feed - Google Patents

Description

(54) Title: PROCESS FOR THE REMOVAL OF MERCURY FROM A FOOD OF

HYDROCARBON FLUID CONTAINING MERCURY (51) lnt.CI .: C10G 21/27; C10G 25/00; C07C 211/00; C07D 233/00; C10L 3/10 (30) Unionist Priority: 06/04/2009 GB 0905896.7 (73) Holder (s): PETROLIAM NASIONAL BERHAD (PETRONAS) (72) Inventor (s): ROBIN DON ROGERS; JOHN HOLBREY; HECTOR RODRIGUEZ (85) National Phase Start Date: 10/06/2011

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PROCESS FOR THE REMOVAL OF MERCURY FROM A HYDROCARBONET FLUID FEEDING CONTAINING MERCURY [0001] The present invention relates to a process for the removal of metals, and particularly mercury, from hydrocarbon fluids. More specifically, the invention relates to a process in which metals are extracted from gaseous or liquid hydrocarbons using an ionic liquid.

[0002] Liquid and gaseous hydrocarbons obtained from oil and gas fields are often contaminated with mercury. In particular, liquid and gaseous hydrocarbons obtained from oil and gas fields in and around the Netherlands, Germany, Canada, USA, Malaysia, Brunei and the United Kingdom are known to contain mercury. As reported by NS Bloom (Fresenius J. Anal. Chem., 2000, 366, 438-443), the mercury content of such hydrocarbons can take a variety of forms. Although elemental mercury tends to predominate, particles of mercury (mercury bound to particles), organic mercury (for example, diethylmercury-dimethylmercury) and ionic mercury (for example, mercury dichloride) can also be found in natural sources of hydrocarbons. The concentration of mercury in crude petroleum oils can vary from less than 1 part

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2/38 per billion (ppb) up to several thousand ppb, depending on the well and location. Likewise, mercury concentrations in natural gas can range from below 1 ng m ^-3 to greater than 1000 pg m ^-3 .

[0003] The presence of mercury in hydrocarbons is problematic due to its toxicity. In addition, mercury is corrosive to hydrocarbon processing equipment, such as that used in oil and gas refineries. Mercury can react with aluminum components of hydrocarbon processing equipment to form an amalgam, which can lead to equipment failure. For example, pipe welds, cryogenic components, aluminum heat exchangers and hydrogenation catalysts can be damaged by mercury-contaminated hydrocarbons. This can lead to plant shutdown, with serious economic implications, or, in extreme cases, uncontrolled loss of containment or complete failure of the plant, with potentially catastrophic results.

[0004] Furthermore, products with high levels of mercury contamination are considered to be of poorer quality, resulting in a product that achieves only a lower price.

[0005] A number of approaches for removing mercury from hydrocarbons have been proposed. These include: washing techniques using fixed bed columns containing sulfur, transition metal or heavy metal sulfides and iodides on an activated support;

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3/38 oxidation followed by complexation with sulfur-containing compounds; and oxidation followed by solvent extraction.

[0006] In addition, a limited number of approaches have been proposed for the removal of mercury from hydrocarbons using ionic liquids.

[0007] The term ionic liquid, as used herein, refers to a liquid that is capable of being produced by the melting of a salt and, when so produced, consists solely of ions. An ionic liquid can be formed from a homogeneous substance that comprises a species of cation and a species of anion, or it can be composed of more than one species of cation and / or more than one species of anion. Thus, an ionic liquid can be composed of more than one species of cation and one species of anion. An ionic liquid can also be composed of a species of cation, and one or more species of anion. Furthermore, an ionic liquid can consist of more than one species of cation and more than one species of anion.

[0008] The term ionic liquid includes compounds having both high melting points and compounds having low melting points, for example, at / or below room temperature. Thus, many ionic liquids have melting points below 200 ° C, especially below 100 ° C, around room temperature (15 to 30 ° C), or even below 0 ° C. Ionic liquids having melting points below about 30 ° C are commonly referred to as ionic liquids at room temperature and are often derived from nitrogen-containing organic salts having heterocyclic cations, such as cations based on

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4/38 imidazolium and pyridinium. In ionic liquids at room temperature, the cation and anion structures prevent the formation of an orderly crystalline structure and, therefore, salt is liquid at room temperature.

[0009] Ionic liquids are better known as solvents. Many ionic liquids have been shown to have negligible vapor pressure, temperature stability, low flammability and are recyclable.

[00010] Due to the large number of anion / cation combinations that are available, it is possible to adjust the physical properties of the ionic liquid (for example, melting point, density, viscosity and miscibility with water or organic solvents) to meet the requirements of particular application.

[00011] The combination of metalcomplexing binders and ionic liquids coated on an inert support, such as adsorbents, to remove mercury from combustion coal flue gases has been described in US patent application US2007 / 0123660 and by Ji et al. {Water, Air, & Soil Pollution: Focus 2008, 8, 349-358 and Ind. Eng. Chem. Res., 2008, 47, 8396-8400}.

[00012] Halogen reactivity to mercury has been used in flue gas flushing technologies to remove metallic vapor, including mercury vapor, by high temperature reaction with bromine or chlorine to form inorganic mercury species that are easily extracted in an aqueous medium (see, for example, Lui, et al. Environ. Sci. Technol., 2007, 41, 1405-1412).

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5/38 [00013] The partitioning of mercury ions, in the high oxidation state, 2+, into ionic liquids in water was reported by Rogers, et al. (Green Chem., 2003, 5, 129135), which showed that liquid dicationic anionic complexes can be used to partition Hg (II) from aqueous solutions of salt and acid. Prausnitz et al. {Ind. Eng. Chem. Res., 2008, 47, 5080-5086) showed that mercury ions are preferably partitioned from water into hydrophobic ionic liquids.

[00014] The present invention is based on the surprising determination that ionic liquids can be used as effective agents to remove mercury from liquid and gaseous hydrocarbons, without additives and without the need for chemical modification of the mercury. In particular, additional solvents and / or complexing mercury binders are not necessary to obtain efficient partitioning of mercury from liquid and gaseous hydrocarbons into an ionic liquid, although a number of co-solvents and / or additives can be incorporated , if desired. In addition, it has also surprisingly been determined that ionic liquids can be used to remove mercury from liquid and gaseous hydrocarbons, preferably at, or close to, room temperature.

[00015] This property of ionic liquids is not known in the prior art. In particular, the known partitioning of oxidized mercury ions,

Hg (II), between water highly polar and hydrophobic ionic liquids does not suggest that mercury, whether in a state

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6/38 elementary, particles, organic or ionic forms, as commonly found in hydrocarbons, can be extracted directly from substantially non-polar hydrocarbons in an ionic liquid.

[00016] In a first aspect, the present invention provides a process for removing mercury from a mercury-containing hydrocarbon fluid feed, comprising the steps of:

(i) placing the hydrocarbon fluid supply containing mercury in contact with an ionic liquid of the formula:

[Cat +] [X-] where: [Cat +] represents one or more cationic species, and [X-] represents one or more anionic species; and (ii) separating a liquid hydrocarbon product with a reduced mercury content compared to feeding mercury-containing hydrocarbon fluid from the ionic liquid.

[00017] Mercury-containing hydrocarbon fluids that can be processed according to the present invention can comprise from 1 part per billion (ppb) of mercury to an excess of 50,000 ppb of mercury, for example, from 2 to 10,000 ppb of mercury. mercury, or 5 to 1000 ppb of mercury. The naturally occurring content of mercury in hydrocarbon fluids can take a variety of forms, and the present invention can be applied to remove elemental mercury, particulate mercury, organic mercury or ionic mercury from fluids

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7/38 of hydrocarbons. In a preferred embodiment, mercury is found in one or more of the particulate, elemental or organic forms. Even more preferably, the mercury is found in elemental or organic form. Thus, in one modality, mercury is found in elementary form. In an even more preferred embodiment, mercury is in organic form.

[00018] The process of the present invention can be applied to any hydrocarbon feed which substantially comprises mercury, and which is liquid or gaseous under the operating conditions of the process. Thus, hydrocarbon fluids that can be processed according to the present invention include: liquid hydrocarbons, such as liquefied natural gas; light distillates, for example comprising liquefied petroleum gas, gasoline and / or naphtha; condensates of natural gas; medium distillates, for example comprising kerosene and / or diesel; heavy distillates, for example fuel oil and crude petroleum oils. Fluid hydrocarbons that can be processed, according to the present invention, also include gaseous hydrocarbons, such as natural gas and refinery gas. Preferably, the hydrocarbon fluid comprises a liquid hydrocarbon.

[00019] In accordance with the present invention, [Cat +] may include a cationic species selected from: ammonium, benzimidazolium, benzofuranium, benzothiophene, benzotriazolium, borolium, cinolinium, diazabicyclodecene, diazabicyclononium, 1,4-diazabicyclo [2.2.2] octane , diazabicyclo-undecene, dithiazolium, furanium, guanidinium,

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8/38 imidazolium, indazolium, indolium, indolium, morpholium, oxaborol, oxafostrium, oxazinium, oxazolium, iso-oxazolium, oxothiazolium, phosphorus, phosphonium, phthalazinium, piperazinium, piperidinium, pyranium, pyrazinium, pyrazolium, pyridinium, pyridinium, pyridinium, pyridinium, pyridinium, pyridinium , pyrrolium, quinazoline, quinoline, iso-quinoline, quinoxaline, quinuclidinium, selenazolium, sulfonium, tetrazolium, thiadiazolium, iso-thiadiazolium, thiazine, thiazolium, isothiazolium, thiophene, thiuronium, triazine, triazolium and isothiadium.

[00020] In a preferred embodiment of the invention, [Cat +] comprises a cationic aromatic heterocyclic species selected from: benzimidazolium, benzofuranium, benzothiophene, benzotriazolium, cinolinium, diazabicyclodecene, diazabicyclononium, diazabicycloundecene, dithiazolium, indidoline, indidazolium, indidazole, indidazolium, indidazolium, indidazolium, indidazolium, indidazolium, indidazolium, indidazolium, indidium, indidazolium, indidazolium, indidazolium, indidazolium, indidazolium, indidazolium, indidazolium, indidazolium, indidazolium. oxazolium, iso-oxazolium, oxathiazolium, phthalazinium, pyrazinium, pyrazolium, pyridazinium, pyridinium, pyrimidinium, quinazolinium, quinolinium, iso-quinolinium, quinoxalinium, tetrazolium, thiadiazolium, iso-thiadiazolium, thiazium, thiazolium, triazolium, isziozio iso-triazolium.

[00021] More preferably, [Cat +] has the formula:

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where: R ^a , R ^b , R ^c , R ^d , R ^e , R ^f and R ^g are each independently selected from hydrogen, C 1 to C 30 alkyl group, straight or branched chain, C 3 to C 8 cycloalkyl group or aryl group C6 to Ci0, or any two of R ^b , R ^c , R ^d , R ^e and R ^f , when attached to adjacent carbon atoms, form a methylene chain - (CH2) _q where q is 3 to 6 and wherein said alkyl group, cycloalkyl or aryl , or said methylene chain is unsubstituted or substituted by 1 to 3 groups selected from: alkoxy C ₆ alkoxyalkoxy C ₂ to C _i2 cycloalkyl C ₃ to C _8, C ₆ aryl Ci _0, alkaryl C ₇ to Ci _0, aralkyl C ₇ to Ci _0, -CN, -OH, -SH, -N0 _2, -CO ₂ R ^x, -C (O) R ^X , C (O) R ^X , -C (S) R ^X , CS2R ^x -, -SC (S) R ^X , -S (0) alkyl (C1 to C6), S (0) 0 alkyl (C1 to C _6), -OS (0) alkyl (Ci to _C6) alkyl - S (Ci to _C6) alkyl -SS (Ci to _C6) alkyl , -NR ^x C (0) NR ^Y R ^Z,

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NR ^X C (O) OR ^Y , -OC (O) NR ^Y R ^Z , -NR ^X C- (S) OR ^Y , -OC (S) NR ^Y R ^Z , -NR ^X C (S) SR ^Y , -SC (S) NR ^Y R ^Z , -NR ^X C- (S) NR ^Y R ^Z , -C (O) NR ^Y R ^Z , -C (S) NR ^Y R ^Z , NR ^Y R ^Z , or a heterocyclic group, where R ^x , R ^Y and R ^z are independently selected from hydrogen or alkyl

Ci a ϋς.

[00022] R ^a is preferably selected from straight or branched C ₁ to C ₃₀ alkyl, preferably straight or branched C ₂ to C ₂ alkyl, even more preferably straight or branched C ₂ to C ₁₀ alkyl, and more preferably, straight or branched C4 to Cs alkyl. Other examples include cations where R ^a is selected from: methyl, ethyl, n-propyl, n-butyl, n-pentyl, nhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl , ndodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, nhexadecyl, n-heptadecyl and n-octadecyl.

[00023] In cations comprising an R ^g group, R ^g is preferably selected from straight or branched C ₁ to C ₁₀ alkyl, more preferably straight or branched C 1 to C 5 alkyl, and more preferably, R ^g is a methyl group .

[00024] In the cations comprising both an R group as an R ^g group, R ^a and R ^g are each independently selected preferably from: alkyl C linear C30 or branched and one of R ^a and R ^g , they can also be hydrogen. More preferably, one of Ra and ^Rg may be selected from alkyl C2 linear C ₂₀ or branched, most preferably alkyl C ₂ linear Ci ₀ or branched, and more preferably alkyl C 4 to C ₈ linear C4 or branched alkyl, and another of R ^a and R ^g can

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11/38 be selected from straight or branched C ₁ to C ₀ alkyl, more preferably straight or branched C 1 to C 5 alkyl and, more preferably, a methyl group. In an even more preferred embodiment, R ^a and R ^g can each be independently selected, when present, from linear or branched C ₁ to C ₃₀ alkyl and C 1 to C 15 alkoxyalkyl.

[00025] In other preferred embodiments, R ^b , R ^c , R ^d , R ^e and R ^f are independently selected from hydrogen and straight or branched C 1 to C 5 alkyl and, more preferably R ^b , R ^c , R ^d , R ^and and R ^f are hydrogen.

[00026] In this embodiment of the invention, [Cat +] preferably comprises a cation selected from:

where: R ^a , R ^b , above.

R ^c , R ^d , R ^e , R ^f and R ^g are as defined [00027] More preferably, [Cat +] comprises a cation selected from:

and where: R ^a and R ^g are as defined above.

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12/38 [00028] Still according to this modality of the invention, [Cat +] can preferably comprise a cation selected from:

where: R ^a , R ^b , R ^c , R ^d , R ^e , R ^f and R ^g are as defined above.

[00029] Specific examples of preferred nitrogen-containing aromatic heterocyclic cations that can be used according to the present invention include:

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13/38 ^ CH ₂ CH ₃ /%. ⁺ ^ - (CH ₂ ) ₃ CH ₃

Ν Ν Ν ^Χ Ν ^J Ν ^Χ Ν ^{ά JJ} \ = /, \ = /, \ = /, [me] [emim] [bmim]

- ^ _N ^^. J ^ - (CH ₂ ) ₅ CH ₃ '- » _n > ^/ ^^ (CH ₂ ) ₇ CH ₃ - ^. _n /% ^ (CH ₂ ) ₂ OCH ₃ \ = /, \ = /, \ = /.

[hmim] [me _and me] [meOC ₂ me]

[(4-NC) bpir] [C8pir] [00030] In another preferred embodiment of the invention, [Cat +] comprises a saturated heterocyclic cation selected from cyclic ammonium, 1,4-diazabicyclo [2.2.2] octane, morpholium, cyclic phosphonium, piperazinium, piperidinium, quinuclidinium and cyclic sulfonium.

[00031] More preferably, [Cat +] comprises a saturated heterocyclic cation with the formula:

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14/38

, 0. .R “ ^R “ R ^e

R ^to R ' ⁵

where: R ^a , R ^b , R ^c , R ^d , R ^e , R ^f and R ^g are as defined above.

[00032] Even more preferably, [Cat +] comprises a saturated heterocyclic cation with the formula:

and it is, more preferably:

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15/38

where: R ^a , R ^b , R ^c , R ^d , R ^e , R ^f and R ^g are as defined above.

[00033] Still according to this modality of the invention, [Cat +] can preferably comprise a saturated heterocyclic cation selected from:

and [00034] In saturated heterocyclic cations R ^a is preferably selected from: straight or branched C ₁ alkyl, preferably C ₂ to C ₂ o or branched alkyl, even more preferably, above C to linear C ₃₀ alkyl Cio

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16/38 straight or branched and, more preferably, straight or branched C ₄ to Cg alkyl. Other examples include cations where R ^a is selected from: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, ndecyl, n-undecyl , n-dodecyl, n-tridecyl, n-tetradecyl, npentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl.

[00035] In saturated heterocyclic cations comprising an R ^g group, R ^g is preferably selected from straight or branched C 1 to 0 _alqu alkyl, more preferably, a straight or branched C 1 to C ^g alkyl and, more preferably, R ^g is a methyl group.

[00036] In cations heterocyclic unsaturated comprising both an R group as an R ^g group, R ^a and R ^g are each independently selected preferably from: alkyl C linear C30 or branched and one of R ^a and R ^g can also be hydrogen. More preferably, one of Ra and ^Rg may be selected from alkyl C2 to _C2 linear or branched, more preferably alkyl Ci to Ci ₀ straight or branched, more preferably alkyl C ₄ linear Cs or branched, and the other from R ^a and R ^g can be selected from: linear or branched C 1 to C 6 alkyl, more preferably linear or branched C 1 to C 5 alkyl and, more preferably, a methyl group. In an even more preferred embodiment, R ^a and R ^g can each be independently selected, when present, from: linear or branched C ₁ to C ₃₀ alkyl and C 1 to C 15 alkoxyalkyl.

[00037] In other preferred embodiments, R ^b , R ^c , R ^d , R ^e and R ^f are independently selected from among

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17/38 hydrogen and C 1 to C ₅ alkyl linear or branched and, more preferably R ^b , R ^c , R ^d , R ^e and R ^f are hydrogen.

[00038] In another preferred embodiment of the invention, [Cat +] comprises an acyclic cation selected from:

[N (R ^a ) (R ^b ) (R ^c ) (R ^d )] ⁺ , [P (R ^a ) (R ^b ) (R ^c ) (R ^d )] ⁺ , [S (R ^a ) (R ^b ) (R ^c )] ⁺ , and

where: R ^a , R ^b , R ^c and R ^d are each independently selected from: straight or branched chain C ₁ to C ₃₀ alkyl, a C ₃ to C ₈ cycloalkyl group, or a C aryl group

ΊΟγ and wherein said alkyl groups, cycloalkyl and aryl are unsubstituted or may be substituted by 1 to 3 groups selected from: alkoxy C ₆ alkoxyalkoxy C ₂ to C _i2 cycloalkyl C ₃ to C ₈ aryl C ₆ to C ₁₀ , C ₇ to C ₁₀ alkaryl, C ₇ to C ₁₀ aralkyl, -CN, -OH, -SH, NO ₂ , -CO ₂ R ^x , -OC (O) R ^x , -C (O) R ^x, -C (O) R ^{x, x} -CS2R, -SC (S) R ^x, S (O) (Ci to C6) alkyl, -S (O) O) (Ci to _C6) alkyl, - OS (O)) (Ci a

C ₆ ) alkyl, -S) (Ci to C ₆ ) alkyl, -SS (Ci to C ₆ ) alkyl, NR ^X C (O) NR ^Y R ^Z , -NR ^X C (O) OR ^Y , -OC ( O) NR ^Y R ^Z , -NR ^X C- (S) OR ^Y ,

OC (S) NR ^Y R ^Z , NR ^X C- (S) SR ^Y , -SC (S) NR ^Y R ^Z , -NR ^X C (S) NR ^Y R ^Z , C (O) NR ^Y R ^Z , -C (S) NR ^Y R ^Z , -NR ^Y R ^Z or a heterocyclic group, where R ^x , R ^Y and R ^z are independently selected from hydrogen or C 1 to C ₆ alkyl.

[00039] More preferably, [Cat +] comprises a cation selected from:

[N (R ^a ) (R ^b ) (R ^c ) (R ^d )] ⁺ , [P (R ^a ) (R ^b ) (R ^c ) (R ^d )] ⁺ , [S (R ^a ) <R ^b ) (R ^c )] \ where: R ^a , R ^b , R ^c and R ^d are each independently selected from: straight or branched chain C ₁ to C ₅ alkyl, a C ₃ a cycloalkyl group C ₆ , or a C ₆ aryl group, and wherein said alkyl groups,

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18/38 cycloalkyl or aryl are unsubstituted or may be substituted by 1 to 3 groups selected from: Ci to _C6 alkoxy, alkoxyalkoxy C ₂ to C _i2 cycloalkyl C ₃ to C _8, C ₆ to Cio aryl, alkaryl C ₇ to C ₁₀ aralkyl C ₇ to C _10, -CN, -OH, -SH, N0 _2, -CO ₂ R ^x, -OC (O) R ^x, -C (O) R ^x, -C ( S) R ^{x, x} -CS2R, -SC (S) R ^x, S (0) (Ci to C6) alkyl, -S (0) 0) (Ci to _C6) alkyl, -OS (0)) ( Ci a

C ₆ ) alkyl, -S) (Ci to C ₆ ) alkyl, -SS (Ci to C ₆ ) alkyl, NR ^X C (0) NR ^Y R ^Z , -NR ^X C (0) 0R ^Y , -0C ( 0) NR ^Y R ^z , -NR ^X C- (S) 0R ^Y ,

OC (S) NR ^Y R ^Z , NR ^X C- (S) SR ^Y , -SC (S) NR ^Y R ^Z , -NR ^X C (S) NR ^Y R ^Z , C (O) NR ^Y R ^Z , -C (S) NR ^Y R ^Z , -NR ^Y R ^Z or a heterocyclic group, where R ^x , R ^Y and R ^z are independently selected from hydrogen or C 1 to C ₆ alkyl.

[00040] Other examples include cations where R ^a , R ^b , R ^c and R ^d are independently selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, nhepty, n -octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, nheptadecyl and n-octadecyl. More preferably, two or more and, more preferably, three or more, from R ^a , R ^b , R ^c and

R ^d are selected butyl.

[00041] Still starting from methyl, ethyl, propyl and more preferably, [Cat +] comprises a cation selected from:

[N (R ^a ) (R ^b ) (R ^c ) (R ^d )] ⁺ , where: R ^a , R ^b , R ^c and R ^d e are as defined above. [00042] In an even more preferred embodiment, [Cat +] preferably comprises a cation selected from:

[S (R ^a ) (R ^b ) (R ^c )] ⁺ , where: R ^a , R ^b , R ^c and R ^d e are as defined above.

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19/38 [00043] Specific examples of preferred ammonium and phosphonium cations suitable for use in accordance with the present invention include:

[00044]

+ + NBu ₄ , PBu ₄ , (IN4 4 4 4]) (^ 4.4.4.4]) + + (C ₈ Hi ₇ ) ₃ NMe, NBuMe ₃ ([Ng.e.ej]) ¢ 1 ^ 4,1,1,1]) + / Me ₃ N

+ (C ₈ H ₁₇ ) NMe ₃

I

+ NHBu ₃ , + Et ₃ NMe, + NMeBu ₃ ([NH ₄₄₄ ]) ([N2.2.2.1]) (] N ₄₄₄ 1])

+

Me ₃ N

OH ([^ 8.1 1.ll) .1, 20h1)

([Ni, i, i, 3Oh]) (1 ^ 1.1, 1.40h1) [00045] In an additional embodiment of the invention, [Cat +] comprises a cation selected from: guanidinium, cyclic guanidinium, uronium, cyclic uronium, thiuronium and cyclic thiuronium. More preferably, [Cat +] comprises a cation having the formula:

NR ^and R ^f II + OR ^and Ϊ II RdRbN ^ ^ NR ^C R ^Ü 5 R ³ R ^b í \ TU \ JR ^: R ^rJ

or +

SR ^and

R ^a R ^b N ^ NR ^c R ^d where: R ^a , R ^b , R ^c , R ^d , R ^e and R ^f are each independently selected from: straight chain C ₃ to C ₃₀ alkyl or branched, a C ₃ cycloalkyl group at

C ₈ , or a C ₆ to Ci ₀ aryl group, or any two of R ^a ,

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20/38

R ^b , R ^c e R ^d , When attached to atoms nitrogen many different, form a methylene chain - (CH ₂ ) _q - where q is 2 to 5, and in that the said alkyl group cycloalkyl or arila or The said methylene chain are non- replaced or replaced by 1 to 3 groups

selected from: Ci to _C6 alkoxy, alkoxyalkoxy C ₂ to C _i2 cycloalkyl C ₃ to C _8, C ₆ aryl Ci _0, alkaryl C ₇ to Ci _0, aralkyl C ₇ to Ci _0, -CN, -OH, -SH, -NO ₂ , -CO ₂ R ^X , -C (O) R ^X , C (O) R ^X , -C (S) R ^X , CS2R ^x -, -SC (S) R ^X , -S (O) alkyl (Ci to C6), S (O) O alkyl (Ci to C ₆ ), -OS (O) alkyl (Ci to C ₆ ), -S alkyl (Ci to C ₆ ), -SS alkyl ( Ci to C ₆ ), -NR ^X C (O) NR ^Y R ^Z , NR ^X C (O) OR ^Y , -OC (O) NR ^Y R ^Z , -NR ^X C- (S) OR ^Y , -OC (S) NR ^Y R ^Z , -NR ^X C (S) SR ^Y , -SC (S) NR ^Y R ^Z , -NR ^X C- (S) NR ^Y R ^Z , -C (O) NR ^Y R ^Z , -C (S) NR ^Y R ^Z , NR ^Y R ^Z , or a heterocyclic group, where R ^x , R ^Y and R ^z are independently selected from hydrogen or C 1 to C ₆ alkyl.

[00046] Specific examples of guanidinium, uranium and thiuronium cations suitable for use according to the present invention include:

OEt

SMe

SEt

Me ₂ N 'OH

Me ₂ N +

NMe ₂

Me ₂ N +

NMe ₂ [00047] In an even more preferred embodiment, [Cat +] comprises a sulfur cation comprising an electron-rich portion of sulfur or selenium. Examples

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21/38 include cations as defined above comprising pendant thiol and thioether groups or disulfide substituents.

[00048] According to the present invention, [X-] can include one or more anions selected from halides, perhalides, pseudohalides, sulfates, sulfites, sulfonates, sulfonimides, phosphates, phosphites, phosphonates, methids, borates, carboxylates, azolates, carbonates, carbamates, thiophosphates, thiocarboxylates, thiocarbamates, thiocarbonates, xanthates, thiosulfonates, thiosulfates, nitrate, nitrite, perchlorate, halometalates, amino acids and borates.

[00049] Thus, [X-] can represent one or more anions selected from:

The) an anion halide selected from: F-, Cl-, Br- B) an anion perhalide selected from: [i ₃ ] -, [I ₂ Br] -, [IBr ₂ ] -, [Br ₃ ] -, [Br ₂ Cl] -, [BrCl ₂ ] -, [IC1 ₂ ] - , [I ₂ C1] - , [Cl ₃ ] - r ç) a pseudo-selected anion from: [N ₃ ] -, [NCS] -, [NCSe] -, [NCO] -, [CN] -; d) an anion sulphate selected from: [HSO ₄ ] -, [SO ₄ ] ₂ - , [R ² OSO ₂ O] -; and) an anion sulfite selected from: [HSO ₃ ] -, [SO ₃ ] ₂ -,

[R ² OSO ₂ ] -;

f) a sulfonate anion selected from: [R ¹ SO ₂ O] -;

g) a sulfonimide anion selected from: [(R ¹ SO ₂ ) ₂ N]

h) an anion selected from phosphate: [H ₂ PO ₄ ] -, [HPO ₄ ] ₂ -, [PO ₄ ] ₃ -, [R ² OPO3] 2-, [(R ² O) 2PO ₂ ] -, [ H ₂ PO ₃ ] -, [HPO ₃ ] ₂ -, [R ² OPO2] 2-, [(R ² O) 2PO] -;

i) a phosphite anion selected from: [H ₂ PO ₃ ] -, [HPO ₃ ] ₂ -,

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22/38 [R ^ Oals-,

-nitroimidazolate], [4 sulfur selected from: thiocarbamates (eg [R ¹ CS ₂ ] -); thiophosphates (eg [RS (O) ₂ S] -); and [R ² OPO2] 2-, [(R ² O) 2PO] -;

j) a phosphonate anion selected from [R ^ IO) (0R ² ) 0] -;

k) a methyoid anion selected from: [(R ¹ SO ₂ ) ₃ C]

l) a borate anion selected from: [bisoxalatoborate], [bismalonatoborate];

m) a carboxylate anion selected from: [R ² CO ₂ ] -;

n) an azolate anion selected from: [3,5-dinitro-1,2,4-triazolate], [4-nitro-1,2,3-triazolate], [2,4-dinitroimidazolate], [4,5 - dinitroimidazolate ], [4,5diciano-imidazolate], [tetrazolate];

o) an anion containing thiocarbonates (eg [R ² OCS ₂ ] -);

[R ² 2NCS ₂ ] -); thiocarboxylates (eg

(eg [(R ² 0) ₂ PS ₂ ] -); thiosulfonates thiosulfates (eg [ROS (O) ₂ S] -) and

p) a nitrate ([N0 ₃ ]) or nitrite anion ([N0 ₂ ] -);

wherein: R ¹ and R ² are independently selected from the group consisting of alkyl Ci-Ci ₀ aryl C ₆ alkyl Ci-Ci ₀ aryl _(C6) and aryl C ₆ alkyl (Ci-Ci _0), each of which may be substituted by one or more groups selected from: fluorine, chlorine, bromine, iodine, _Ci-C6 alkoxy, alkoxyalkoxy C ₂ -C _2, C ₃ -C ₈ cycloalkyl, aryl alkaryl C ₀ -C _7, aralkyl C ₇ -Ci ₀ , CN, -OH

CO ₂ R ^x , -OC (O) R ^x , -C (O) R ^x , -C (S) R ^x , -CS ₂ R ^x , -SC (S) R ^x ,

S (0) (C 1 -C ₆ ) alkyl, -S (0) 0 (C 1 -C ₆ ) alkyl, -OS (0) (C ₁ -C ₆ ) alkyl, -S alkyl (C 1 -C ₆ ), -SS alkyl (Ci-C ₆ ), -NR ^X C (0) NR ^Y R ^Z , NR ^x C (0) 0R ^Y , -0C (0) NR ^Y R ^z , -NR ^X C (S) OR ^Y , -OC (S) NR ^Y R ^Z ,

C ₆ -Ci ₀ ,, -SH, -N0 ₂ , Petition 870180049814, of 6/11/2018, p. 52/79

23/38

NR ^X C (S) SR ^Y , -SC (S) NR ^Y R ^Z , -NR ^X C (S) NR ^Y R ^Z , -C (O) NR ^Y R ^Z ,

C (S) NR ^Y R ^Z , -NR ^Y R ^Z or a heterocyclic group, where R ^x , R ^Y and R ^z are independently selected from hydrogen or alkyl (Ci-C ₆ ), and where R ¹ can also be fluorine, chlorine, bromine or iodine.

[00050] In a preferred embodiment, [X—] comprises a halide or perhalide anion selected from: [F] -, [Cl] -, [Br] -, [I] -, [I ₃ ] -, [I ₂ Br] -, [IBr ₂ ] -, [Br ₃ ] -, [Br ₂ Cl] -, [BrCl ₂ ] -, [IC1 ₂ ] -, [I ₂ C1] - and [Cl ₃ ] -. More preferably, [X-] comprises a halide or perhalide anion selected from: [F] -, [Cl] -, [Br] -, [I] -, [I ₂ Br] -, [IBr ₂ ] -, [ Br ₂ Cl] -, [BrCl ₂ ] -, [IC1 ₂ ] -, [I ₂ C1] -.

[00051] In an even more preferred embodiment, [X—] comprises an anion containing oxygen selected from: [NO ₃ ] -, [NO ₂ ] -, [H ₂ PO ₄ ] -, [HPO ₄ ] ₂ -, [ PO ₄ ] ₃ -, [R ² OPO ₃ ] ₂ -, [(R ² O) ₂ PO ₂ ] -, [H ₂ PO ₃ ] -, [HPO ₃ ] ₂ -, [R ² OPO2] 2-, [(R ² O) 2PO] -, [R ¹ PO3] 2-, [R ^ -PÍO) (OR ² ) O] - and [R ² CO2] -, where R ¹ and R ² are as defined above. Other examples of anions in this category include: [MeOPO ₃ ] ₂ -, [EtOPO ₃ ] ₂ -, [(MeO) ₂ PO ₂ ] -, [(EtO) ₂ PO ₂ ] -, [MePO ₃ ] ₂ -, [ EtPO ₃ ] ₂ -, [MeP (O) (OMe) O] -, [EtP (O) (OEt) O] -.

[00052] In an even more preferred embodiment, [X-] comprises a carboxylate anion selected from [R ² CO2] -, where R ² is as defined above. Other examples of anions in this category include: [HCO2] -, [MeCO ₂ ] -, [EtCO ₂ ] -, [CH ₂ (OH) CO ₂ ] -, [CH ₃ CH (OH) CH ₂ CO ₂ ] -, [PhCO ₂ ] -, salicylate, alaninate, argininate, asparaginate, aspartate, cysteine, glutamate glutaminate, glycinate, histidinate, isoleucinate, leucinate, lysinate, methioninate, phenylalaninate, prolinate, serinate,

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24/38 threoninate, tryptophanate, tyrosinate, valinate, Nmethylglycinate, 2-aminobutyrate, 2-aminoisobutyrate, 2 amino-4-aminoxybutyrate, 2- (methylguanidine) -ethanate, 2pyrrolidone-5-carboxylate, piperidine-2-carboxylate and 2-carboxylate and 2-carboxylate 00053] In a still preferred embodiment, the anion [X-] comprises a sulfur compound comprising an electron-rich portion of sulfur or selenium. Examples include: anions as defined above with a pendant thiol and thioether compound or disulfide substituents, [NCS] -, [NCSe] -, [R ² OCS ₂ ] -, [R ² 2NCS ₂ ] -, [R ¹ CS2] - , [(R ² O) 2PS ₂ ] -, [R ¹ S (O) 2S] - and [R ² OS (O) 2S] -, where R ¹ and R ² are as defined above. Other examples of anions in this category include:

[CH ₂ (SH) CO ₂ ] -, [CH ₃ CH ₂ (SH) CO ₂ ] -, [CH ₃ CS ₂ ] -, [PhCS ₂ ] -, [(MeO) ₂ PS ₂ ] -, [( EtO) ₂ PS ₂ ] -, [(CH ₃ ) ₂ NCS ₂ ] -, [(CH ₃ CH ₂ ) ₂ NCS ₂ ] -, [Ph ₂ NCS ₂ ] -, [CH ₃ CH ₂ OCS ₂ ] -, [PhOCS ₂ ] -, [CH ₃ CH ₂ CS ₂ ] -, [(PhO) ₂ PS ₂ ] -, [CH ₃ OCS ₂ ] -,

[00054] In still a preferred embodiment, [X-] comprises a sulfur anion selected from sulfate anions [HSO ₄ ] -, [SO ₄ ] ² -, [R ² OSO2O] -), sulfite anions [HSO3], [ SO3] 2-, [R ² OSO2] -) and sulfonate anions ([R ¹ SO ₂ O] -). Other examples of anions in this category include: [FSO ₂ O] -,

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25/38 [CF ₃ SO ₂ O] -, [MeSO ₂ O] -, [PhSO ₂ O] -, [4-MeC ₆ H ₄ SO ₂ O] [dioctylsulfo-succinate] [MeOSO ₂ O] -, [ EtOSO ₂ O] -, [C ₈ H ₁₇ OSO ₂ O] - and [MeOSO ₂ ] -, [PhOSO ₂ ] -.

[00055] In an additional embodiment of the invention, [X] may include a fluorinated anion selected from: [BF ₄ ], [CF3BF3] -, [CF ₃ CF ₂ BF ₃ ] -, [PF ₆ ] -, [CF ₃ PF ₅ ] -, [CF ₃ CF ₂ PF ₅ ] -, [(CF ₃ CF ₂ ) ₂ PF ₄ ] - and [(CF ₃ CF ₂ ) 3PF3] -. However, fluorinated anions of this type are generally less preferred compared to the previously disclosed types of anion.

[00056] The present invention is not limited to ionic liquids comprising anions and cations having only a single charge. Thus, the formula [Cat +] [X-] is intended to cover ionic liquids comprising, for example, cations and anions that are doubly, triple and quadruple charged. The relative stoichiometric amounts of [Cat +] and [X-] in the ionic liquid are, therefore, not fixed and can be varied to take into account cations and anions with multiple charges. For example, the formula [Cat +] [X-] should be understood as including ionic liquids having the formulas [Cat +] ₂ [X ² -], [Cat ² +] [X-] ₂ ;

[Cat ² +] [X ² -]; [Cat +] 3 [X ³ -], [Cat ³ +] [X-] ₃ and so on.

[00057] It will also be appreciated that the present invention is not limited to ionic liquids comprising a single cation and a single anion. Thus, [Cat +] can, in certain modalities, represent two or more cations, as a statistical mixture of 1,3-dimethylimidazolium, 1-ethyl-3methylimidazolium and 1-3-diethylimidazolium. Likewise, [X] may, in certain modalities, represent two or more

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26/38 anions, as a mixture of tribromide ([Br ₃ ] -) and bistflimide ([N (SO ₂ CF ₃ ) ₂ ] -).

[00058] Ionic liquids for use according to the present invention, preferably have a melting point of 250 ° C or less, preferably 150 ° C or less, even more preferably 100 ° C or less, even more preferably 80 ° C or less and, more preferably, the ionic liquid has a melting point below 30 ° C. However, any compound that meets the criteria of being a salt (composed of a cation and an anion) and that is liquid at the process temperature and pressure, or exists in a liquid state during any phase of the reaction, can be defined as a liquid ionic for the purposes of the present invention. Most preferably, the ionic liquid is chosen to be substantially immiscible with the hydrocarbon fluid, particularly where the hydrocarbon fluid comprises a liquid hydrocarbon.

[00059] The ionic liquid is placed in contact, preferably, with the supply of hydrocarbon fluid containing mercury, at a temperature of -80 ° C to 200 ° C, preferably from -20 ° C to 150 ° C, still more preferably 15 feed liquid at 100 ° C and, more preferably, between 15 ° C and 40 ° C. The ionic liquid and the hydrocarbon fluid supply containing mercury can be contacted at atmospheric pressure (about 100 kPa), although pressures above or below atmospheric pressure can be used, if desired. For example, the process can be conducted at a pressure from 10 kPa to 10,000 kPa, preferably from 20 kPa to 1000 kPa,

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27/38 even more preferably between 5 and 20 kPa and, more preferably, between 80 and 120 kPa.

[00060] As noted above, however, the ionic liquid must be liquid at the temperature and pressure of the process of the present invention. Thus, the operating temperature and pressure ranges above may, in some cases, be further limited by the temperature and pressure at which an ionic liquid is selected in liquid form.

[00061] It is generally more economical for the contact between the ionic liquid and the hydrocarbon fluid feed liquid that contains mercury, that there is no application of heat and that refinery product flows can be conveniently treated at the temperature at which they arise at from the refinery, which is normally up to 100 ° C.

[00062] The ionic liquid and the supply of mercury-containing hydrocarbon fluid are preferably contacted in a volume ratio of ionic liquid for supply of mercury-containing hydrocarbon fluid from 1: 1 to 10,000: 1, more preferably from 20 : 01 to 10,000: 1, preferably from 100: 1 to 10,000: 1 and more preferably 1000: 1 out of 10,000: 1. In general, a lower volume of ionic liquid in relation to the amount of hydrocarbons is preferred, as this prevents the formation of emulsions.

[00063] In an even more preferred embodiment, the volume ratio of ionic liquid for feeding mercury-containing hydrocarbon fluid is selected so that from 1 to 10,000 moles, preferably from 1 to 1000 moles

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28/38 moles, even more preferably from 1 to 100 moles, even more preferably from 1 to 10 moles and, more preferably, from 1 to 5 moles of ionic liquid are contacted with the supply of mercury-containing hydrocarbon fluid per mole of mercury in the supply of mercury-containing hydrocarbon fluid.

[00064] In accordance with the process of the present invention, the ionic liquid extracts at least 60% by weight of the mercury content of the mercury-containing hydrocarbon fluid feed. More preferably, the ionic liquid extracts at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 90% by weight, even more preferably at least 95% by weight and, most preferably, greater than 99% by weight of the mercury content of the mercury-containing hydrocarbon fluid feed.

[00065] Thus, according to the process of the present invention, a liquid hydrocarbon product can be obtained, and this comprises 10% or less of the mercury content of the mercury-containing hydrocarbon fluid feed. More preferably, the hydrocarbon fluid product is composed of 5% or less of the mercury content of the mercury-containing hydrocarbon fluid feed and, more preferably, the hydrocarbon fluid product comprises 1% or less of the mercury content of the fluid feed of hydrocarbons containing mercury. Preferably, the mercury concentration of the liquid hydrocarbon product from the process

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29/38 of the invention is less than 50 ppb, more preferably less than 10 ppb and, more preferably, less than 5 ppb.

[00066] The ionic liquid and the supply of hydrocarbon fluid containing mercury can be contacted by any continuous process or batch processes. Any conventional liquid-liquid or gas-liquid contact apparatus can be used in accordance with the present invention. For example, the ionic liquid and the supply of mercury-containing hydrocarbon fluid can be contacted via a counter-current liquid-liquid contactor, a co-current liquid-liquid contactor, a counter-current gas-liquid contactor, a gas-liquid gas contactor -current, a batch liquid-liquid contactor or a batch gas-liquid contactor.

[00067] In yet another embodiment, the ionic liquid can be supported on a solid support material, preferably porous, before being contacted with the supply of mercury-containing hydrocarbon fluid. Solid support materials suitable for use in this embodiment of the invention include: silica alumina, silicaalumina and activated carbon. In general, supports for ionic liquids for use according to this embodiment of the invention comprise from 50%, by weight, to 1%, by weight, of an ionic liquid and, preferably, from 20%, by weight, to 1% by weight of ionic liquid.

[00068] In addition, the process can be repeated on the same supply of hydrocarbon fluid containing mercury in a series of contact steps, for example

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30/38 example, two to ten times, to obtain a successive reduction in the mercury content of the liquid hydrocarbon product at each stage.

[00069] The ionic liquid is allowed to come into contact with the mercury-containing hydrocarbon fluid supply long enough to allow at least a portion of the mercury in the mercury-containing hydrocarbon fluid supply to be transferred to the ionic liquid phase . Suitable timeframes include, from 1 minute to 60 minutes and, preferably, from 2 minutes to 30 minutes.

[00070] The process of the present invention can be used in combination with other known methods for removing mercury from hydrocarbon fluids. However, an advantage of the present invention is that it avoids the need to pre-treat the hydrocarbon liquid to remove solidified species prior to the mercury removal step.

[00071] In an even more preferred embodiment, the present invention provides a process for the preparation of a solution containing mercury, which comprises contacting a hydrocarbon fluid containing mercury with an ionic liquid having the formula:

[Cat +] [X-] where [Cat +] represents a cationic species, and [X-] represents an anionic species.

[00072] In this embodiment of the invention, [Cat +] can be any of the cationic ionic liquids described above, and the cations described as preferred above also

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31/38 are preferred in this embodiment of the invention. Likewise, [X-], in this embodiment of the invention, can be any of the anionic ionic liquids described above, and the anions described as preferred above are also preferred in this embodiment of the invention.

[00073] In yet another embodiment, the present invention provides a process for removing cadmium and / or lead from a liquid hydrocarbon feed containing cadmium and / or lead comprising the steps of:

(i) placing the hydrocarbon fluid supply containing cadmium and / or lead in contact common liquid ionic formula: [Cat +] [X-] Where : [Cat +] represents one or more species

cationic and [X-] represents one or more anionic species; and (ii) separating a liquid hydrocarbon product with a reduced cadmium and / or lead content compared to the supply of cadmium and / or lead hydrocarbon fluid from the ionic liquid.

[00074] In this embodiment of the invention, [Cat +] can be any of the liquid ionic cations described above, and the cations described as preferred are also preferred in this embodiment of the invention. Likewise, [X-], in this embodiment of the invention, can be any of the liquid ionic anions described above, and the anions described as preferred are also preferred in this embodiment of the invention.

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[00075] The present invention will now be described by way of example.

EXAMPLES

Mercury removal from a natural gas condensate [00076] In a test process, equal masses of a condensed natural gas (NGC) liquid and an ionic liquid were stirred for 4 hours at 25 ° C. The stirring was then stopped and the ionic liquid separated as a dense lower phase and the mixtures were left to stand for 15 hours to ensure equilibrium. Several samples of the condensate phases (30 mg each) were taken without disturbing the liquid-liquid interface and the total mercury content determined using a pyrolysis / AA Milestone DMA-80 analyzer. The determined mercury levels are shown in micrograms per kg with standard deviation of duplicate runs in parentheses.

[00077] After the contact of the condensed natural gas with all the ionic liquids described, the mercury content of the condensed natural gas was reduced to less than 14 pg kg U except in the case in which it contacted 1-ethyl3-methylimidazole ethyl sulfate.

Example 1: 1-butyl-3-methylimidazolium bis (trifluoromethane) sulfonimide [00078] NGC (4.1 g) was mixed with 1-butyl-3methylimidazolium bis (trifluoromethane) sulfonimide (4.1 g).

The mercury content of the condensed phase, after contact, was 7 (3) pg kg ¹ when compared to the control sample

NGC which contained 99 (10) pg kg ¹ of mercury.

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33/38

Example 2: 1-butyl-3-methylimidazolium chlorodibromide [00079] NGC (4.2 g) was mixed with 1-butyl-3-methylimidazolium chlorodibromide (4.2 g). The mercury content of the condensed phase, after contact, was 11 (9) pg kg ^-1 when compared to the NGC control sample that contained 99 (10) pg kg ^-1 of mercury.

Example 3: 1-ethyl-3-methylimidazolium sulfate [00080] NGC (4.1 g) was mixed with 1-ethyl-3-methylimidazolium sulfate (4.0 g). The mercury content of the condensed phase, after contact, was 73 (13) pg kg ^-1 when compared to the NGC control sample that contained 99 (10) pg kg ^-1 of mercury.

Example 4: 1-hexyl-3-methylimidazolium bis (trifluoromethane) sulfonimide [00081] NGC (2.0 g) was mixed with 1-hexyl-3methylimidazolium bis (trifluoromethane) sulfonimide (2.0 g). The mercury content of the condensate phase, after contact, was 4 (1) pg kg ^-1 when compared to the control sample

NGC containing 99 (10) pg kg ^-1 of mercury.

Example 5: 1-butyl-4-cyanopyridinium bis (trifluoromethane) sulfonimide [00082] NGC (2.0 g) was mixed with 1-butyl-4-cyanopyridinium bis (trifluoromethane) sulfonimide (2.0 g). The mercury content of the condensate phase, after contact, was 7 (5) pg kg ^-1 when compared to the control sample

NGC containing 99 (10) pg kg ^-1 of mercury.

Example 6: l-butyl-3-methylimidazolium diethyldithiophosphate

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34/38 [00083] NGC (4.0 g) was mixed with 1-butyl-3-methylimidazolium diethyldithiophosphate (4.0 g). The mercury content of the condensate phase, after contact, was 5 (5) pg kg ^-1 when compared to the initial sample containing NGC 532 (23) pg kg ^-1 of mercury.

Example 7: 1-butyl-3-methylimidazolium thiocyanate [00084] NGC (4.0 g) was mixed with 1-butyl-3 methylimidazolium thiocyanate (4.0 g). The mercury content of the condensate phase after contact was 5 (1) pg kg ^-1 when compared to the initial NGC sample, which contained 532 (23) pg kg ^-1 of mercury.

Example 8: methoxy l-butyl-3-methylimidazolium sulfate (propylene glycol) [00085] NGC (4.0 g) was mixed with 1-butyl-3-methylimidazolium methoxy (propylene glycol) sulfate (4.0 g). The mercury content of the condensate phase, after contact, was 9 (4) pg kg ^-1 when compared to the initial NGC sample, which contained 532 (23) pg kg ^-1 of mercury.

Example 9: 1-butyl-3-methylimidazolium acetate [00086] NGC (4.0 g) was mixed with 1-butyl-3-methylimidazolium acetate (4.0 g). The mercury content of the condensate phase, after contact, was 14 pg kg ^-1 when compared to the initial NGC sample, which contained 532 (23) pg kg ^-1 of mercury.

Example 10: 1-ethyl-3-methylimidazolium hydrokenosulfate [00087] NGC (4.0 g) was mixed with 1-ethyl-3-methylimidazolium hydrokenosulfate (4.0 g). The mercury content of the condensate phase, after contact, was

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35/38 of 8 (5) pg kg ^-1 when compared to the initial NGC sample, which contained 532 (23) pg kg ^-1 of mercury.

Mercury removal from elemental mercury-enriched dodecane [00088] In testing processes, known masses of dodecane, which had previously been saturated with mercury and an ionic liquid, were stirred with ionic liquids at a fixed temperature for a period of time measured. The stirring was then stopped and the ionic liquid separated as a dense lower phase and the mixtures were left to stand for 15 minutes to ensure phase separation. Several samples of the condensate phases (30 mg each) were taken without disturbing the liquid-liquid interface, and the total mercury content was determined using a pyrolysis / AA Milestone DMA-80 analyzer. The determined mercury levels are shown in micrograms per kg with standard deviation of duplicate runs in parentheses. Example 11: Removal of dodecane mercury with 1butyl-3-methylimidazolium thiocyanate

[00089] Dodecane (20 g), containing 3978 pg kg ' ¹ in mercury was agitated with thiocyanate in Ι- -butil- -3- methylimidazolium (2.0 g) The 60 ° C for 15 H. Ο content in

mercury from the dodecane phase decreased to 20 (5) pg kg ^-1 and the mercury content of the extracting ionic liquid increased to 53,143 (2,830) pg kg ^-1 .

Example 12: Removal of dodecane mercury with 1butyl-3-methylimidazolium thiocyanate [00090] Dodecane (20 g), containing 3978 pg kg ^-1 of mercury was stirred with l-butyl-3 methylimidazoliumPetition 870180049814, from 11/06/2018, p. 65/79

36/38 thiocyanate (0.2 g) at 60 ° C for 15 h. The mercury content of the dodecane phase decreased to 35 (2) pg kg ^-1 , the dodecane was decanted and an additional batch of dodecane containing 4551 pg kg ^-1 of mercury was added and stirred for 18 h. The mercury content of dodecane has decreased to 43 (4) pg kg ' ¹ .

Example 13: Removal of dodecane mercury with methylimidazolium camphor sulfonate [00091] Dodecane (2.4 g), containing 3500 pg kg ^-1 of mercury was stirred with methylimidazolium camphor 1-sulfonate (1.2 g) at 21 ° C for 6 h. The mercury content of the dodecane phase decreased to 60 pg kg ^-1 . The concentration of mercury in the dodecane phase remained constant after stirring was continued for 24 hours.

Example 14: Removal of dodecane mercury with tributylammonium lipoate [00092] Dodecane (3.1 g), containing 3500 pg kg ^-1 of mercury was stirred with tributylammonium lipoate (2.2 g) at 21 ° C for 6 h . The mercury content of the dodecane phase decreased to 95 pg kg ^-1 . After stirring for 24 hours, the concentration of mercury in the dodecane phase was reduced to 30 pg kg ^-1 . The concentration of mercury in the dodecane phase remained constant after stirring was continued for more than 24 hours.

Example 15: Removal of dodecane mercury with tricaprilmethylammonium dithiobenzoate [00093] Dodecane (4.5 g), containing 3500 pg kg ^-1 of mercury was stirred with dithiobenzoate of

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37/38 tricaprilmethylammonium (1.2 g) at 50 ° C for 24 h. The mercury content of the dodecane phase decreased to 40 pg kg ^-1 .

Example 16: Removal of dodecane mercury with tetrabutylphophonium dithiobutyrate [00094] Dodecane (1.4 g), containing 3500 pg kg ^-1 of mercury was stirred with tetrabutylphophonium dithiobutyrate (1.1 g) at 50 ° C for 24 h. The mercury content of the dodecane phase decreased to 190 pg kg ^-1 . After stirring for another 24 hours, the concentration of mercury in the dodecane phase was reduced to 80 pg kg ^-1

Example 17: Removal of dodecane mercury with choline lipoate [00095] Dodecane (3.0 g), containing 3500 pg kg ^-1 of mercury was stirred with choline lipoate (0.9 g) at 50 ° C for 2 4 H. The mercury content of the dodecane phase decreased to 2 90 pg kg ^-1 .

Example 18: Removal of dodecane mercury with l-butyl-3-methylimidazolium salicylate [00096] Dodecane (4.0 g), containing 3500 pg kg ^-1 of mercury was stirred with l-butyl-3-methylimidazolium salicylate (2, 9 g) at 50 ° C for 48 h. The mercury content of the dodecane phase decreased to 220 pg kg ^-1 .

Example 19: Removal of dodecane mercury with choline decanoate [00097] Dodecane (3.0 g), containing 3500 pg kg ^-1 of mercury was stirred with choline decanoate (1.5 g) at 50 ° C for 4 8 H. The mercury content of the dodecane phase decreased to 270 pg kg ^-1 .

Example 20: Removal of mercury from dodecane with 1-1 Petition 870180049814, of 11/06/2018, pg. 67/79

38/38 butyl-tris methylpyrrolidinium trifluorophosphate (pentafluoroethi1) [00098] Dodecane (1.57 g) containing 2,200 ppb of elemental mercury was stirred with dodecane with 1-1butyl-tris methylpyrrolidinium trifluorophosphate (pentafluoroethyl) (pentafluoroethyl) (pentafluoroethyl) (pentafluoroethyl)) 60 ° C for 24 h. The mercury content of the dodecane phase decreased to 1587 ppb and the mercury content of the extracting ionic liquid increased to 963 ppm (28% of the available mercury was extracted in the ionic liquid).

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Claims (21)

1. Process for the removal of mercury from a supply of hydrocarbon fluid containing mercury characterized by the fact that it comprises the steps of: (i) placing the hydrocarbon fluid supply containing mercury in contact with an ionic liquid of the formula: [Cat ⁺ ] [X-] where: [Cat ⁺ ] represents one or more cationic species and [X ^- ] represents one or more anionic species; and (ii) separating a liquid hydrocarbon product with a reduced mercury content compared to feeding mercury-containing hydrocarbon fluid from the ionic liquid. 2. Process, according to claim 1, characterized by the fact that mercury is elemental, particulate or in organic form. Process according to either of claims 1 or 2, characterized in that the concentration of mercury in the supply of hydrocarbon fluid containing mercury is in the range of 1 to 50,000 parts per billion. Process according to any one of claims 1 to 3, characterized in that the supply of hydrocarbon fluid containing mercury is a liquid. 5. Process according to claim 4, characterized by the supply of hydrocarbon fluid Petition 870180049814, of 6/11/2018, p. 69/79 2/10 containing mercury comprise one or more of the following: (i) a liquefied natural gas; (ii) a light distillate comprising liquefied petroleum gas, gasoline and / or naphtha; (iii) a condensate of natural gas; (iv) a medium distillate comprising kerosene and / or diesel; (v) a heavy distillate; and (vi) a crude oil. Process according to any one of claims 1 to 3, characterized in that the supply of hydrocarbon fluid containing mercury is a gas. Process according to claim 6, characterized in that the supply of hydrocarbon fluid containing mercury comprises natural gas and / or refinery gas. consisting of benzothiophene, diazabicyclodecene, diazabicycles [2,2,2] 8. Process according to any one of claims 1 to 7, characterized by the fact that [Cat ⁺ ] comprises a cationic species selected from the group ammonium, benzimidazolium, benzofuranium, benzotriazolium, borolium, cinolinium, diazabicyclononene, 1.4 octane, diazabicyclo-undecene, dithiazolium, furanium, guanidinium, imidazolium, indazolium, indolinium, indolium, morpholium, oxaborolium, oxaphostrium, oxazinium, oxazolium, iso-oxazolium, oxothiazolium, phosphorus, phosphonium, phthalazinium, piperazium, piperazinium, piperidium, piperidium, piperazium pyridazinium, pyridinium, pyrimidinium, pyrrolidinium, pyrrolium, quinazolyl, quinoline, isoPetition 870180049814, of 06/11/2018, p. 70/79 3/10 quinoline, quinoxaline, quinuclidinium, selenazolium, sulfonium, tetrazolium, thiadiazolium, iso-thiadiazolium, thiazine, thiazolium, iso-thiazolium, thiophene, thiuronium, triazinium, triazolium, iso-triazolium and uronium. 9. Process, according to claim 8, characterized by the fact that [Cat ⁺ ] comprises a cationic species selected from the group consisting of: Petition 870180049814, of 6/11/2018, p. 71/79 4/10 where: R ^a , R ^b , e R ^c , R ^d , R ^e , R ¹ R ^g are each independently selected from: hydrogen, C 1 to C ₃₀ alkyl group, straight or branched chain, C ₃ to C ₈ cycloalkyl group or C ₆ to C ₀ aryl group, or any two of R ^b , R ^c , R ^d , R ^e and R ^f , when attached to adjacent carbon atoms, form a methylene chain - (CH2) where q is 3 to 6, and wherein said alkyl, cycloalkyl or aryl group or said chain of methylene are unsubstituted or substituted by 1 to 3 groups selected from: Ci to C6 alkoxy, C2 to Ci2 alkoxyalkoxy, C3 to C8 cycloalkyl, C6 to Ci0 aryl, C7 to Ci0 alkaryl, C7 to Ci0 aralkyl, -CN, -OH, -SH, -NO2, -CO2R ^X , -C (O) R ^X , C (O) R ^X , -C (S) R ^X , CS2R ^X -, -SC (S) R ^X , -S (O) alkyl (C1 to C6), S (O) O alkyl (C1 to C6), -OS (O) alkyl (C1 to C6), -S alkyl (C1 to C6), -SS alkyl (C1 to C6) ), -NR ^X C (O) NR ^Y R ^Z , NR ^X C (O) OR ^Y , -OC (O) NR ^Y R ^Z , -NR ^X C- (S) OR ^Y , -OC (S) NR ^Y R ^Z , -NR ^X C (S) SR ^Y , -SC (S) NR ^Y R ^Z , -NR ^X C- (S) NR ^Y R ^Z , -C ( O) NR ^Y R ^Z , -C (S) NR ^Y R ^Z , NR ^Y R ^Z , or a heterocyclic group, where R ^x , R ^Y and R ^z are independently selected from hydrogen or C 1 to C 6 alkyl. 10. Process according to claim 9, characterized by the fact that [Cat ⁺ ] comprises a species Petition 870180049814, of 6/11/2018, p. 72/79 5/10 cationic selected from the group consisting of: where: R ^a , R ^b , R ^c , R ^d , R ^e , R ^f and R ^g are as defined in claim 9. 11. Process, according to claim 9, characterized by the fact that [Cat ⁺ ] comprises a cationic species selected from the group consisting of: Where R ^a , R ^b , R ^c , R ^d , R ^e , R ^f and R ^g are as defined Petition 870180049814, of 6/11/2018, p. 73/79 6/10 in claim 9. 12. Process, according to claim 9, characterized by the fact that [Cat ⁺ ] comprises a cationic species selected from the group consisting of: R · where: R ^a , R ^b , R ^c , R ^d , R ^e , R ^f and R ^g are as defined in claim 9. 13. Process according to claim 8, characterized by the fact that [Cat ⁺ ] is selected from the group consisting of: [N (R ^a ) (R ^b ) (R ^c ) (R ^d )] ⁺ , [P (R ^a ) (R ^b ) (R ^c ) (R ^d )] ⁺ , [S (R ^a ) (R ^b ) (R ^c )] \ e where: R ^a , R ^b , R ^c and R ^d are each independently selected from a chain C ₁ to C ₃₀ alkyl group Petition 870180049814, of 6/11/2018, p. 74/79 7/10 linear or branched, C ₃ to C ₈ cycloalkyl or C ₆ to C ₆ aryl, θ ⁱⁿ which said alkyl, cycloalkyl or aryl group is unsubstituted or can be substituted by 1 to 3 groups selected from: Ci alkoxy to C6, C2 alkoxyalkoxy a. C12, C3 to C8 cycloalkyl, C6 to C10 aryl, C7 to C10 alkaryl, C7 to C10 aralkyl, -CN, -OH, -SH, -NO2, -CO2R ^X , -C (O) R ^X , -C (O ) R ^x, -C (O) R ^x, CS2R ^x -, -SC (S) R ^x, -S (O) alkyl (Ci to _C6), S (O) alkyl (Ci to _C6), -OS (O) alkyl (Ci to C ₆ ), -S alkyl (Ci to C ₆ ), -SS alkyl (Ci to C ₆ ), -NR ^X C (O) NR ^Y R ^Z , NR ^X C (O ) OR ^Y , -OC (O) NR ^Y R ^Z , -NR ^X C- (S) OR ^Y , -OC (S) NR ^Y R ^Z , -NR ^X C (S) SR ^Y , -SC (S) NR ^Y R ^Z , -NR ^X C- (S) NR ^Y R ^Z , -C (O) NR ^Y R ^Z , -C (S) NR ^Y R ^Z , NR ^Y R ^Z , or a heterocyclic group, where R ^x , R ^Y and R ^z are independently selected from hydrogen or C 1 to C ₆ alkyl. 14. Process, according to claim 8, characterized by the fact that [Cat ⁺ ] is selected from the group consisting of: NR ^and R * X R ^a R ^b N ^ ^ NR ^c R ^d OR ^and RaRbN - ^^^ NRhR ⁰ OR R ^a R ^b N SR ^and THE. NR ^c R ^d where: R ^a , R ^b , R ^c , R ^d , R ^e and R ^f are as defined in claim 9. 15. Process according to any one of claims 1 to 14, characterized by the fact that [X ^- ] Petition 870180049814, of 6/11/2018, p. 75/79 8/10 comprise an anion selected from halides, perhalides, pseudohalides, sulfates, sulfites, sulfonates, sulfonimides, phosphates, phosphites, phosphonates, methids, borates, carboxylates, azolates, carbonates, carbamates, thiophosphates, thiocarboxylates, thiocarbonates, thiocarbonates, thiocarbonates, thiocarbons thiosulfonates, thiosulfates, nitrate, nitrite, perchlorate, halometalates, amino acids and borates. 16. Process according to claim 15, characterized by the fact that [X ^- ] comprises an anion selected from [F], [Cl], [Br], [I], [I ₃ ], [bBr], [ IBr ₂ ], [Br ₃ ], [Br ₂ Cl], [BrCl ₂ ], [IC1 ₂ ], [I ₂ C1], [Cl ₃ ], [N ₃ ], [NCS], [NCSe], [ NCO], [CN], [HSO ₄ ], [SO ₄ ] ₂ , [R ² OSO2O], [HSO3] -, [SO3] ² , [R ² OSO2], [R ¹ SO2O], [(R ¹ SO2) ₂ N] [H ₂ PO ₄ ], [HPO ₄ ] ² , [PO4] ³ , [R ² OPO3] ² , [(R ² O) ₂ PO ₂ ], [h ₂ po ₃ ] -, [ HPO ₃ ] ² , [R ² OPO2] ² , [(R ² O) 2PO], [R ¹ PO ₃ ] ² , [R ¹ ? (O) (OR ² ) O], [(R ¹ SO ₂ ) ₃ C], [bisoxalatoborate], [bismalonatoborate], [R ² CO ₂ ], [3,5-dinitro-1, 2,4-triazolate ], [4-nitro-1, 2,3 triazolate], [2,4-dinitroimidazolate], [4,5 dinitroimidazolate], [4,5-dicyanoimidazolate], [4 nitroimidazolate], [tetrazolate], [R ² OCS2], [R ² 2NCS ₂ ], [R ¹ CS2], [(R ² O) 2PS ₂ ], [RS (O) ₂ S], [ROS (O) ₂ S], [NO ₃ ] and [NO ₂ ] r wherein: R ¹ and R ² are independently selected from the group consisting of alkyl Ci-Ci ₀ aryl C ₆ alkyl Ci-Ci ₀ aryl _(C6) and aryl C ₆ alkyl (Ci-Ci _0), each of which it can be replaced by one or more groups selected from: fluorine, chlorine, bromine, iodine, C ~ C ₆ alkoxy, C ₂ -Ci ₂ alkoxyalkoxy, C ₃ -C ₈ cycloalkyl, C ₆ -Ci ₀ aryl, C7 alkaryl -C10, C7-C10 aralkyl, CN, -OH, -SH, -NO ₂ , Petition 870180049814, of 6/11/2018, p. 76/79 9/10 CO ₂ R ^x , -OC (O) R ^x , -C (O) R ^x , -C (S) R ^x , -CS ₂ R ^x , -SC (S) R ^x , S (O) (C 1 -C ₆ ) alkyl, -S (0) 0 (C 1 -C ₆ ) alkyl, -OS (0) (C ₁ -C ₆ ) alkyl, -s (C 1 -C ₆ ) alkyl, -SS alkyl (Ci-C ₆ ), -NR ^X C (0) NR ^Y R ^Z , NR ^x C (0) 0R ^Y , -0C (0) NR ^Y R ^z , -NR ^X C (S) OR ^Y , -OC (S) NR ^Y R ^Z , NR ^X C (S) SR ^Y , -SC (S) NR ^Y R ^Z , -NR ^X C (S) NR ^Y R ^Z , -C (O) NR ^Y R ^Z , C (S) NR ^Y R ^Z , -NR ^Y R ^Z or a heterocyclic group, where R ^x , R ^Y and R ^z are independently selected from hydrogen or alkyl (Ci-C ₆ ), and where R ¹ can also be fluorine, chlorine, bromine or iodine. 17. Process according to any of claims 1 to 16, characterized in that the ionic liquid is immobilized on a solid inert support. 18. Process, of wake up with any an of claims 1 to 17, characterized by the fact of ionic liquid to be immiscible in power fluid in hydrocarbons containing Mercury and in product liquid in Hydrocarbons. 19. Process, of wake up with any an of claims 1 to 18, characterized in that the liquid hydrocarbon product comprises 10% or less of the mercury content of the mercury-containing hydrocarbon feed. 20. Process according to any of claims 1 to 19, characterized in that the supply of hydrocarbons containing mercury and ionic liquids are contacted through a continuous process or a batch process. 21. Process according to claim 17, Petition 870180049814, of 6/11/2018, p. 77/79 10/10 characterized by the fact that the solid inert support is activated carbon. 22. Process according to claim 16, characterized by the fact that the anion is perhalide selected from [I ₃ ], [I ₂ Br] ~, [IBr ₂ ] ~, [Br ₃ ] ^_ , [Br ₂ Cl ] ~, [IC1 ₂ ] -, [I ₂ C1] - and [Cl ₃ ] -. 23. Process according to claim 11, characterized by the fact that the cationic species is: on what: R ^a is selected from a straight or branched C2 to C20 alkyl group (such as methyl, ethyl, n-propyl, n-butyl, npentyl, n-hexyl, h-heptyl, n-octyl, n-nonyl, n-decyl , n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, npentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl) and R ^g is selected from a linear or branched C1 to C5 alkyl group (such as methyl , ethyl, n-propyl, n-butyl and n-pentyl). Petition 870180049814, of 6/11/2018, p. 78/79