USE OF SILICA NANOPARTICLES WITH GLYOXAL FOR H2S SCAVENGING

Abstract

A process to remove H.sub.2S from a stream comprising the steps of adding a glyoxal, a silica nanoparticle composition, and optionally a triazine to the stream. The stream is selected from the group consisting of Oil streams, Gas streams, CO.sub.2 point source purification streams and Geothermal Energy System streams.

Claims

1. A process to remove H.sub.2S from a stream comprising the steps of: a) Adding a fluid comprising glyoxal and one or more types of silica nanoparticles to a stream comprising H2S, wherein the stream is selected from the group consisting of Oil streams, Gas streams, CO.sub.2 point source purification streams and Geothermal Energy System streams.

2. The process of claim 1, wherein a triazine is also present in the fluid.

3. The process of claim 1, wherein the silica nanoparticle is an aluminum oxide functional silica nanoparticle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0022] Glyoxals useful in the instant claimed invention include, but are not limited to, glyoxals that are commercially available from BASF and other companies.

[0023] Glyoxals can be present in the process at a level of from about one (1) unit to about two (2) units per 3 units of H2S.

[0024] For purposes of this patent application, silica nanoparticles include silica nanoparticles, alumina nanoparticles and silica-alumina nanoparticles.

[0025] The silica nanoparticles are sourced from all forms of precipitated SiO.sub.2 [0026] a) dry silica; [0027] b) fumed silica; [0028] c) colloidal silica; [0029] d) surface treated silicas including silicas reacted with organosilanes; [0030] e) metal or metal-oxide with silica combinations; and [0031] f) precipitated silica.

[0032] There are known ways to modify the surface of colloidal silica: [0033] 1. Covalent attachment of Inorganic oxides other than silica. [0034] 2. Non-covalent attachment of small molecule, oligomeric, or polymeric organic materials (PEG treatment, amines or polyamines, sulfides, etc.). [0035] 3. Covalent attachment of organic molecule including oligomeric and polymeric species: [0036] a. Reaction with organosilanes/titanates/zirconates/germinates. [0037] b. Formation of organosilanes/titanate/zirconate/germinate oligomers followed by reaction of these with surface of colloidal silica. [0038] c. Silanization followed by post-reaction formation of oligomeric/dendritic/hyperbranched/polymeric species starting from colloidal silica surface. [0039] d. Formation of oligomeric/dendritic/hyperbranched/polymeric silanes/zirconates/titanates followed by reaction to SiO.sub.2 surface.

[0040] The silica particles included in the colloidal silica may have any suitable average diameter. As used herein, the average diameter of silica particles refers to the average largest cross-sectional dimension of the silica particle. In an embodiment, the silica particles may have an average diameter of between about 0.1 nm and about 100 nm. In an embodiment, the silica particles may have an average diameter of between about 1 nm and about 100 nm. In an embodiment, the silica particles may have an average diameter of between about 5 nm and about 100 nm. In an embodiment, the silica particles may have an average diameter of between about 1 nm and about 50 nm. In an embodiment, the silica particles may have an average diameter of between about 5 nm and about 50 nm. In an embodiment, the silica particles may have an average diameter of between about 1 nm and about 40 nm. In an embodiment, the silica particles may have an average diameter of between about 5 nm and about 40 nm. In an embodiment, the silica particles may have an average diameter of between about 1 nm and about 30 nm. In an embodiment, the silica particles may have an average diameter of between about 5 nm and about 30 nm. In an embodiment, the silica particles may have an average diameter of between about 7 nm and about 20 nm.

[0041] In an embodiment, the silica particles have an average diameter of less than or equal to about 30 nm. In another embodiment, the silica particles may have an average diameter of less than or equal to about 25 nm. In another embodiment, the silica particles may have an average diameter of less than or equal to about 20 nm. In another embodiment, the silica particles may have an average diameter of less than or equal to about 15 nm. In another embodiment, the silica particles may have an average diameter of less than or equal to about 10 nm. In another embodiment, the silica particles may have an average diameter of less than or equal to about 7 nm. In another embodiment, the silica particles may have an average diameter of at least about 5 nm. In another embodiment, the silica particles may have an average diameter of at least about 7 nm. In another embodiment, the silica particles may have an average diameter of at least about 10 nm. In another embodiment, the silica particles may have an average diameter of at least about 15 nm. In another embodiment, the silica particles may have an average diameter of at least about 20 nm. In another embodiment, the silica particles may have an average diameter of at least about 25 nm. Combinations of the above-referenced ranges are also possible.

[0042] Colloidal silica is a flexible technology medium, allowing for customized surface treatment based on application. In an embodiment, the silica is a GlycidoxyPropylTriMethoxySilane-functional silica. GPTMS-functionalized silica includes alkaline sol silica, available from Nissan Chemical America as ST-V3. Another GPTMS-functionalized silica is an acidic type of silica sol, available from Nissan Chemical America as ST-OV3.

[0043] The amount of silica nanoparticle used per unit of H2S is as follows: In an embodiment, 1 unit of silica nanoparticle per 3 units of H2S, in another embodiment, 1 unit of silica nanoparticle per 5 units of H2S and in another embodiment, 1 unit of silica nanoparticle per 10 units of H2S.

[0044] The alumina nanoparticles are sourced from all forms of precipitated Al.sub.2O.sub.3 [0045] a) dry alumina; [0046] b) fumed alumina; [0047] c) colloidal alumina; [0048] d) surface treated aluminas including aluminas reacted with organosilanes; [0049] e) metal or metal-oxide with alumina combinations; and [0050] f) precipitated alumina.
There are known ways to modify the surface of colloidal alumina: [0051] 1. Covalent attachment of Inorganic oxides other than alumina. [0052] 2. Non-covalent attachment of small molecule, oligomeric, or polymeric organic materials (PEG treatment, amines or polyamines, sulfides, etc.). [0053] 3. Covalent attachment of organic molecule including oligomeric and polymeric species: [0054] a. Reaction with organosilanes/titanates/zirconates/germinates. [0055] b. Formation of organosilanes/titanate/zirconate/germinate oligomers followed by reaction of these with surface of colloidal alumina. [0056] c. Silanization followed by post-reaction formation of oligomeric/dendritic/hyperbranched/polymeric species starting from colloidal alumina surface. [0057] d. Formation of oligomeric/dendritic/hyperbranched/polymeric silanes/zirconates/titanates followed by reaction to Al.sub.2O.sub.3 surface.

[0058] The alumina particles included in the colloidal alumina may have any suitable average diameter. As used herein, the average diameter of alumina particles refers to the average largest cross-sectional dimension of the alumina particle. In an embodiment, the alumina particles may have an average diameter of between about 0.1 nm and about 100 nm. In another embodiment, the alumina particles may have an average diameter of between about 1 nm and about 100 nm. In another embodiment, the alumina particles may have an average diameter of between about 5 nm and about 100 nm. In another embodiment, the alumina particles may have an average diameter of between about 1 nm and about 50 nm. In another embodiment, the alumina particles may have an average diameter of between about 5 nm and about 50 nm. In another embodiment, the alumina particles may have an average diameter of between about 1 nm and about 40 nm. In another embodiment, the alumina particles may have an average diameter of between about 5 nm and about 40 nm. In another embodiment, the alumina particles may have an average diameter of between about 1 nm and about 30 nm. In another embodiment, the alumina particles may have an average diameter of between about 5 nm and about 30 nm. In another embodiment, the alumina particles may have an average diameter of between about 7 nm and about 20 nm.

[0059] In an embodiment, the alumina particles have an average diameter of less than or equal to about 30 nm. In an embodiment, the alumina particles have an average diameter of less than or equal to about 25 nm. In an embodiment, the alumina particles have an average diameter of less than or equal to about 20 nm. In an embodiment, the alumina particles have an average diameter of less than or equal to about 15 nm. In an embodiment, the alumina particles have an average diameter of less than or equal to about 10 nm. In an embodiment, the alumina particles have an average diameter of less than or equal to about 7 nm. In an embodiment, the alumina particles have an average diameter of at least about 5 nm. In an embodiment, the alumina particles have an average diameter of at least about 7 nm. In an embodiment, the alumina particles have an average diameter of at least about 10 nm. In an embodiment, the alumina particles have an average diameter of at least about 15 nm. In an embodiment, the alumina particles have an average diameter of at least about 20 nm. In an embodiment, the alumina particles have an average diameter of at least about 25 nm. Combinations of the above-referenced ranges are also possible.

[0060] Colloidal alumina is a flexible technology medium, allowing for customized surface treatment based on application. In an embodiment, the alumina is a GPTMS-functional alumina. GlycidoxyPropylTriMethoxySilane-functional alumina includes alkaline sol silica, available from Nissan Chemical America as AT-V6. Another GPTMS-functionalized alumina is an acidic type of silica sol, available from Nissan Chemical America as AT-OV6.

[0061] The amount of alumina nanoparticle used per unit of H2S is as follows: 1 unit of alumina nanoparticle per 3 units of H2S, in another embodiment, 1 unit of alumina nanoparticle per 5 units of H2S and in another embodiment, 1 unit of alumina nanoparticle per 10 units of H2S.

[0062] Some examples of nanoparticles can include particles of spherical shape, fused particles such as fused silica or alumina or particles grown in an autoclave to form a raspberry style morphology, or elongated silica particles. The particles being bare, or surface treated. When surface treated may be polar or non-polar.

[0063] The surface treatment is sufficient to allow the nanoparticle to be stable during transportation to the area where a H.sub.2S sorbent is required and for delivery. The stability achieved either by covalent, charge-charge, dipole-dipole, or charge-dipole interactions.

[0064] Triazines useful in the instant claimed invention include, but are not limited to, 1,2,3-triazine; 1,2,4-triazine and 1,3,5-triazine (aka s-triazine). Triazines useful in the instant claimed invention include Hexahydro-1,3,5-tris(hydroxyethyl)-s-triazine.

[0065] Triazines are alkaline and can cause carbonate scaling. Triazines are commercially available.

[0066] Triazines can be present in the process at a level of from about zero point 1 (0.1) units to about 1 unit per 3 units of H2S. Units could mean any quantitative measure, such as grams, pounds, mols, etc. etc.

[0067] CO.sub.2 Point Source Purification is described in Evaluation of CO.sub.2 Purification Requirements and the Selection of Processes for Impurities Deep Removal from the CO.sub.2 Product Stream, Zeina Abbas et al, Energy Procedia, Volume 37, 2013, Pages 2389-2396. Depending on the reference power plant, the type of fuel and the capture method used, the CO.sub.2 product stream contains several impurities which may have a negative impact on pipeline transportation, geological storage and/or Enhanced Oil Recovery (EOR) applications. All negative impacts require setting stringent quality standards for each application and purifying the CO.sub.2 stream prior to exposing it to any of these applications.

[0068] In the Abbas paper, the CO.sub.2 stream specifications and impurities from the conventional post-combustion capture technology are assessed. Furthermore, the CO.sub.2 restricted purification requirements for pipeline transportation, EOR and geological storage are evaluated. Upon the comparison of the levels of impurities present in the CO.sub.2 stream and their restricted targets, it was found that the two major impurities which entail deep removal, due to operational concerns, are oxygen and water from 300 ppmv to 10 ppmv and 7.3% to 50 ppmv respectively. Moreover, a list of plausible technologies for oxygen and water removal is explored after which the selection of the most promising technologies is made. It was found that catalytic oxidation of hydrogen and refrigeration and condensation are the most promising technologies for oxygen and water removal respectively.

[0069] Geothermal Energy System Streams are described as follows: [0070] Hot water is pumped from deep underground through a well under high pressure. [0071] When the water reaches the surface, the pressure is dropped, which causes the water to turn into steam. [0072] The steam spins a turbine, which is connected to a generator that produces electricity. [0073] The steam cools off in a cooling tower and condenses back to water.

EXAMPLES

Materials:

[0074] Stepanquat 200 is a 78.5% actives solution of Hexahydro-1,3,5-tris(hydroxyethyl)-s-triazine available commercially from Stepan Corp.
ST-040, ST-30, ST-OV4, PGM-ST, ST-C, ST-V3, and MT-ST are commercially available colloidal silica products from Nissan Chemical America Corporation.
Organosilanes, Propylene Glycol Monomethyl Ether solvent, NaHCO.sub.3, CuCl.sub.2H.sub.2O, and Glyoxal were procured from Sigma Aldrich Corp.

Synthesis example 1

[0075] 1000 mL Snowtex ST-30 from Nissan Chemical America Corporation (Aqueous alkaline colloidal silica dispersion, 30 wt % SiO.sub.2 solids, 10-15 median particle size) was placed into a 2000 mL 4 neck glass reactor assembled with addition funnel, thermometer, heating mantle connected to voltage regulator, and mixer with 2 inch diameter trifoil mixing blade. Mixing was activated at 150 rpm and silicasol was brought to 50 C. Into the addition funnel was weighed 49.98 g of Aminoethylaminoethylaminopropyl Trimethoxysilane (CAS #35141-30-1, Sigma-Aldrich). Addition funnel was assembled to reactor top and silane was slowly added to stirring silicasol at a drop rate of 2 drops per second. After all organosilane had been added to reaction the mixture was allowed to stir at 50 C. for a period of 3 hours. Finished surface-treated alkaline silica was poured off to a 2 L Nalgene bottle for storage and use.

Synthesis Example 2

[0076] 1.4 L Snowtex O-XS (Aqueous acidic colloidal silica dispersion, 10 wt % colloidal silica median particle size 5 nm) was transferred to a 4-neck reaction kettle. To this vessel were also added 9.6 L distilled water. Copper (II) Chloride dehydrate (CuCl.sub.2H.sub.2O, Sigma Aldrich), 13.87 g were added to the reaction flask and allowed to dissolve at room temperature under light agitation. A stock solution (Solution A) of NaHCO.sub.3(Sigma Aldrich ACS reagent grade, >99.7% was prepared (47.04 g NaHCO.sub.3 dissolved in 12.6 L distilled water, 0.04 M final concentration). The stir rate in the reaction vessel was increased to 9500 rpm to achieve vigorous agitation. Solution A was added slowly 10-15 mL per minute to the reaction via addition funnel. After Solution A was added completely the reaction was allowed to stir at room temperature for 30 minutes and contents were removed for storage and use.

Synthesis Example 3

[0077] Snowtex PGM-ST (Solvent borne dispersion of acidic colloidal silica, 30 wt % SiO.sub.2 median particle size 10-15 nm dispersed in Propylene Glycol Monomethyl ether), 450 g were placed into a 1000 mL 4-neck reaction flask. Similar to Synthesis Example 1 the reactor was assembled with mixer, thermometer, and heating mantle/voltage regulator. A 4.05 g portion of 3-Mercaptopropyl Trimethoxysilane (Sigma Aldrich) were added to an addition funnel and assembled to the reactor. PGM-ST was brought to 50 C. under mild agitation and Mercaptopropyl trimethoxysilane was added dropwise via addition funnel at 1 drop/second until addition was complete. Reaction was kept at 50 C. for a period of 3 hours, then the surface-treated silicasol was poured off to a Nalgene container for storage and use.

Example 1, Comparative

[0078] Into a 1000 mL Nalgene bottle were placed 300 g distilled H.sub.2O, 300 g Propylene Glycol Monomethyl Ether (PGM) solvent, and 300 g Stepanquat 200. Contents were mixed thoroughly by shaking container vigorously for 30 seconds.

Example 2

[0079] Into a 1000 mL Nalgene bottle were placed 300 g distilled H.sub.2O, 300 g Propylene Glycol Monomethyl Ether solvent, and 300 g Synthesis Example 1 fluid. Contents were mixed thoroughly by shaking container vigorously for 30 seconds.

Example 3, Comparative

[0080] Into a 1000 mL Nalgene bottle were placed 700 g distilled H.sub.2O, and 300 g Stepanquat 200. Contents were mixed thoroughly by shaking container vigorously for 30 seconds.

Example 4

[0081] Into a 1000 mL Nalgene bottle were placed 300 g distilled H.sub.2O, 300 g ST-040 (Aqueous acidic colloidal silica available from Nissan Chemical America Corporation), and 300 g Stepanquat 200. Contents were mixed thoroughly by shaking container vigorously for 30 seconds.

Example 5

[0082] Into a 1000 mL Nalgene bottle were placed 300 g distilled H.sub.2O, 300 g Synthesis Example 2 fluid, and 300 g Stepanquat 200. Contents were mixed thoroughly by shaking container vigorously for 30 seconds.

Example 6

[0083] Into a 1000 mL Nalgene bottle were placed 300 g distilled H.sub.2O, 300 g ST-OV4 (Aqueous acidic hydrophilic surface treated colloidal silica available from Nissan Chemical America Corporation), and 300 g Stepanquat 200. Contents were mixed thoroughly by shaking container vigorously for 30 seconds.

Example 7

[0084] Into a 1000 mL Nalgene bottle were placed 300 g distilled H.sub.2O, 300 g Synthesis Example 3 fluid, and 300 g Stepanquat 200. Contents were mixed thoroughly by shaking container vigorously for 30 seconds.

Example 8

[0085] Into a 1000 mL Nalgene bottle were placed 375 g aqueous solution of Glyoxal (Sigma Aldrich, 37.5 wt %) and 625 g ST-C (Aqueous alkaline colloidal silica dispersion partially surface treated with Aluminum Oxide available from Nissan Chemical America Corporation). Contents were mixed thoroughly by shaking container vigorously for 30 seconds.

Example 9

[0086] Into a 1000 mL Nalgene bottle were placed 375 g aqueous solution of Glyoxal (Sigma Aldrich, 37.5 wt %) and 625 g ST-040 (Aqueous acidic colloidal silica dispersion available from Nissan Chemical America Corporation). Contents were mixed thoroughly by shaking container vigorously for 30 seconds.

Example 10

[0087] Into a 1000 mL Nalgene bottle were placed 375 g aqueous solution of Glyoxal (Sigma Aldrich, 37.5 wt %) and 625 g ST-V3 (Aqueous alkaline hydrophilic surface treated colloidal silica dispersion available from Nissan Chemical America Corporation). Contents were mixed thoroughly by shaking container vigorously for 30 seconds.

Example 11

[0088] Into a 1000 mL Nalgene bottle were placed 375 g aqueous solution of Glyoxal (Sigma Aldrich, 37.5 wt %) and 625 g MT-ST (Solvent borne acidic colloidal silica dispersed in Methanol, 30 wt % SiO2, 10-15 nm median particle size, available from Nissan Chemical America Corporation). Contents were mixed thoroughly by shaking container vigorously for 30 seconds.

Example 12: Comparative

[0089] Into a 1000 mL Nalgene bottle were placed 375 g aqueous solution of Glyoxal (Sigma Aldrich, 37.5 wt %) and 625 g distilled H.sub.2O. Contents were mixed thoroughly by shaking container vigorously for 30 seconds.
MEA Triazine was kept at a constant concentration across all the Inventive and Comparative examples. Similarly, Glyoxal concentration was kept constant across all Inventive and Comparative examples.

Testing for Removal of H2S

[0090] Each solution tested was equilibrated for weight at 300 g total solution and placed into a vessel with overhead port to measure H2S content in the vessel headspace. The headspace port was connected to a Drager Pac 3500 gas monitor (Dragerwerk AG&Co. KGaA). A mixed gas of 10% H.sub.2S/90% Nitrogen was bubbled through the test solution at a standard rate of 475 mL/minute, solution held at 22 C., and headspace monitored for H.sub.2S content. A reading of 0 means the sensor is not detecting any H.sub.2S in the flow gas stream after the gas has passed through the tested solution. Vessel headspace was monitored for H.sub.2S content once per minute continuously until a H.sub.2S content of 40 reading on gas monitor was reached, at which point the test example in solution reacting with H.sub.2S was considered to be consumed and the experiment stopped. Times to initial H.sub.2S reading and Time to complete H.sub.2S breakthrough were recorded and compared to controls/comparative examples.

Summary of Results

[0091] The Number of minutes is listed is how long the detector detected a value of 0 for H2S. The Table is ordered from best performance in terms of removal of H2S to worst performance.

TABLE-US-00001 Time to Time to initial 40% H2S H2S Exam- reading reading nanoparticle ple (minutes) (minutes) Composition type 2 124 160 Triazine + Water + Amine- Amine func. SiO2 Functional SiO2 1 117 145 Triazine + Water + none PGMsolvent (Comparative Example) 8 107 184 Glyoxal + ST-C Aluminum oxide functional SiO2 4 71 164 Triazine + Water + Aqueous acidic ST-O40 SiO2 10 55 146 Glyoxal + ST-V3 Glycidoxy functional SiO2, alkaline 5 55 139 Triazine + Water + Transition Metal CuOXS functional SiO2 7 55 105 Triazine + Water + Mercapto Mercapto Functional SiO2 functionalized PGM-ST 9 51 86 Glyoxal + ST-O40 Aqueous acidic SiO2 3 44 61 Triazine + Water none (Comparative Example) 6 39 153 Triazine + Water + Glycidoxy ST-OV4 functional SiO2, acidic 12 8 14 Glyoxal + Water none (Comparative Example) 11 1 2 Glyoxal + MT-ST Solventborne SiO2, acidic
Observations about the Examples:

[0092] 1. Example 1: This is a Triazine controls/comparative examples with MEA Triazine dissolved in a mixture of water and PGM solvent. This example performed very well, much better than MEA Triazine alone at the same concentration dissolved in water. It is believed, without intending to be bound there bye, that it is possible PGM is actually very beneficial in Triazine+H2S reaction.

[0093] 2. Example 2 (Amine-functional SiO.sub.2 combined with Triazine) performed very well compared to the comparative example, with improved/delayed time to initial H2S breakthrough and also time to final breakthrough (when the H2S readings reached a 40% level in the headspace above the sample).

[0094] 3. Example 3 is the Triazine+water control, these times were used comparatively for all the Triazine+nanosilica examples. Example 3 exemplifies the standard field grade fluid of MEA Triazine fluid for treatment of sour gas.

[0095] 4. Example 4 (ST-040, Aqueous acidic silica+Triazine) performed the best of all Triazine+nanosilica examples. It is believed, without intending to be bound thereby, that the solid acidity of the acidic silica surface is likely acting as a catalyst to make the Triazine+H2S reaction more complete, leading to greatly improved/delayed time to initial and complete H2S breakthrough.

[0096] 5. Example 5 (Copper functionalized nanosilica+Triazine) performed relatively well in improved/delayed time to initial and complete H2S breakthrough. This example is the only example of Transition Metal functional silica. (It is noted that the Aluminum present in Example 8 is not considered a true Transition metal, as it is a Post Transition Metal.)

[0097] 6. Example 6 (ST-OV4+Triazine) is aqueous acidic silica functionalized with hydrophilic organic surface treatment and is commercially available from Nissan Chemical America. This example had slightly worse time to H2S initial breakthrough, but had a greatly improved time to complete H2S breakthrough compared to the control (Example 3).

[0098] 7. Example 7 (Mercapto-functional nanosilica dispersed in PGM+Triazine)Slightly improved time to initial H2S breakthrough and much improved time to complete H2S breakthrough. It is believed, without intending to be bound thereby, that the Mercapto surface functionality can disrupt polymer formation in the Triazine+H2S reaction.

[0099] 8. Example 8 is ST-C (Aqueous alkaline colloidal silica with Aluminum Oxide surface) combined with Glyoxal. Compared to Glyoxal alone this combination of ST-C+Glyoxal showed dramatic improvements in both time to initial and time to complete H2S breakthrough. The Glyoxal+nanosilica examples performed relatively well. It is noted that the Aluminum present in Ex. 8 is not considered a true Transition metal, as it is a Post Transition Metal.

[0100] 9. Example 9 (ST-040+Glyoxal) performed much better than Glyoxal alone.

[0101] 10. Example 10 (ST-V3, Aqueous alkaline silica with hydrophilic organic surface treatment+Glyoxal) performed very well compared to Glyoxal alone.

[0102] 11. Example 11 (Acidic silica dispersed in Methanol) did not perform well, this example had the worst results of all. It is believed, without intending to be bound thereby that MT-ST completely deactivated Glyoxal from reacting with H2SJ

[0103] 12. Example 12 is the solution of Glyoxal and water only, a comparative example with no added nanotechnology.