USE OF MELAMINE CYANURATE NANOPARTICLES AND SILICA NANOPARTICLES FOR H2S SCAVENGING

Abstract

A process to remove H.sub.2S from a stream comprising the steps of adding Melamine cyanurate, optionally a silica nanoparticle composition, and optionally a triazine. 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 adding Adding a fluid comprising (iii) A Melamine cyanurate, (iv) a silica nanoparticle composition, and (iii) a triazine, 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.

Description

EXAMPLES

Materials:

[0085] Stepanquat 200 is a 78.5% actives solution of Hexahydro-1,3,5-tris(hydroxyethyl)-s-triazine available commercially from Stepan Corp. [0086] ST-O40, ST-30, ST-OV4, PGM-ST, ST-C, ST-V3, and MT-ST are commercially available colloidal silica products from Nissan Chemical America Corporation. [0087] Organosilanes, Propylene Glycol Monomethyl Ether solvent, NaHCO.sub.3, CuCl.sub.2H.sub.2O, and Glyoxal were procured from Sigma Aldrich Corp.

[0088] Synthesis example 1: 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

[0089] 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

[0090] Snowtex? PGM-ST (Solvent borne dispersion of acidic colloidal silica, 30 wt % SiO2 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

[0091] 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

[0092] 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

[0093] 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

[0094] Into a 1000 mL Nalgene bottle were placed 300 g distilled H.sub.2O, 300 g ST-O40 (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

[0095] 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

[0096] 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

[0097] 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

[0098] 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

[0099] Into a 1000 mL Nalgene bottle were placed 375 g aqueous solution of Glyoxal (Sigma Aldrich, 37.5 wt %) and 625 g ST-O40 (Aqueous acidic colloidal silica dispersion available from Nissan Chemical America Corporation). Contents were mixed thoroughly by shaking container vigorously for 30 seconds.

Example 10

[0100] 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

[0101] 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

[0102] 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.

[0103] 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

[0104] Each solution tested was equilibrated for weight at 300 g total solution and placed into a vessel with overhead port to measure H.sub.2S content in the vessel headspace. The headspace port was connected to a Dr?ger Pac? 3500 gas monitor (Dr?gerwerk 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

[0105] The Number of minutes is listed is how long the detector detected a value of 0 for H.sub.2S. The Table is ordered from best performance in terms of removal of H2S to worst performance.

TABLE-US-00001 Time to Time to initial H2S 40% H2S reading reading Example (minutes) (minutes) Composition nanoparticle type 2 124 160 Triazine + Water + Amine Amine-Functional func. SiO2 SiO2 1 117 145 Triazine + Water + PGMsolvent none (Comparative Example) 8 107 184 Glyoxal + ST-C Aluminum oxide functional SiO2 4 71 164 Triazine + Water + ST-O40 Aqueous acidic SiO2 10 55 146 Glyoxal + ST-V3 Glycidoxy functional SiO2, alkaline 5 55 139 Triazine + Water + CuOXS Transition Metal functional SiO2 7 55 105 Triazine + Water + Mercapto Mercapto functionalized PGM-ST Functional SiO2 9 51 86 Glyoxal + ST-O40 Aqueous acidic SiO2 3 44 61 Triazine + Water (Comparative none Example) 6 39 153 Triazine + Water + ST-OV4 Glycidoxy functional SiO2, acidic 12 8 14 Glyoxal + Water (Comparative none Example) 11 1 2 Glyoxal + MT-ST Solventborne SiO2, acidic
Observations about the Examples: [0106] 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. [0107] 2. Example 2 (Amine-functional SiO2 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). [0108] 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. [0109] 4. Example 4 (ST-O40, 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. [0110] 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.) [0111] 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). [0112] 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. [0113] 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. [0114] 9. Example 9 (ST-O40+Glyoxal) performed much better than Glyoxal alone. [0115] 10. Example 10 (ST-V3, Aqueous alkaline silica with hydrophilic organic surface treatment+Glyoxal) performed very well compared to Glyoxal alone. [0116] 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 [0117] 12. Example 12 is the solution of Glyoxal and water only, a comparative example with no added nanotechnology.