Removal of carbonyls from liquid phase hydrocarbon streams

Abstract

Disclosed are methods and systems for removing a highly reactive polymer precursor such as carbonyls from a liquid hydrocarbon stream. Embodiments may disclose a method for removal of carbonyls from a liquid hydrocarbon stream comprising the steps of providing a liquid hydrocarbon stream containing carbonyls, providing a liquid bisulfite stream comprising an alkali metal bisulfite, and contacting the liquid hydrocarbon stream and the liquid bisulfite stream in a mass transfer device wherein at least a portion of the carbonyl reacts with the alkali metal bisulfite to form a solid adduct that is soluble in the bisulfite solution.

Claims

1. A method for treatment of carbonyls comprising: cracking a hydrocarbon stream in an FCC unit to produce a cracked hydrocarbon stream; separating the cracked hydrocarbon gas stream in a debutanizer column and forming an overhead liquid LPG stream wherein the liquid LPG stream comprises about 50 to about 54 mol % propylene, about 8 to about 12 mol % propane, about 0.15 to about 0.5 mol % 1,3-butadiene, about 14 to about 16 mol % butanes, about 15 to about 25 mol % butenes, about 10 to about 20 ppm H2S, about 100 to about 200 ppm mercaptans, about 200 to about 300 ppm acetaldehyde, and about 200 to about 300 ppm acetone; introducing the liquid LPG stream into a bottom of an extraction column; introducing an aqueous bisulfite stream comprising an alkali metal bisulfite into a top of the extraction column; counter-currently contacting the liquid LPG stream and the aqueous bisulfite stream in the extraction column such that the acetaldehyde and acetone are extracted into and reacted with the alkali metal bisulfite in the aqueous bisulfite stream to form a solid adduct and wherein a an amount of acetaldehyde and acetone are reacted such that a treated liquid LPG stream leaving the extraction column contains less than 0.1 ppm acetaldehyde and greater than 95% of the acetone is removed as compared to the liquid LPG stream, and wherein an amine extractor or a caustic extractor unit downstream from the extraction column is essentially free of aldol condensation products, and sending the treated liquid LPG stream to the amine extractor unit or the caustic extractor unit.

2. The method of claim 1, wherein the extraction column comprises a packed extraction column or a trayed extraction column; and wherein the treated Liquid LPG stream leaves the top of the extraction column and a depleted bisulfite stream containing the solid adduct leaves the bottom of the extraction column.

3. The method of claim 2, wherein the packed extraction column comprises random packing, structured packing, plastic packing, or stoneware packing.

4. The method of claim 2, further comprising contacting the treated hydrocarbon stream with an H.sub.2S removing agent.

5. The method of claim 4, wherein the H.sub.2S removing agent comprises a caustic solution.

6. The method of claim 4, wherein the H.sub.2S removing agent comprises an amine solution.

7. The method of claim 1, further comprising controlling a volumetric ratio between the Liquid LPG stream and the aqueous bisulfite stream.

8. The method of claim 1, wherein the alkali metal bisulfite is selected from the group consisting of sodium bisulfite, potassium bisulfite, magnesium bisulfite, strontium bisulfite, and combinations thereof.

9. A method for treatment of carbonyls comprising: introducing a liquid LPG stream from an FCC Gas Plant Debutanizer Overhead into a bottom of a packed extraction column, wherein the Liquid LPG steam comprises about 50 to about 54 mol % propylene, about 8 to about 12 mol % propane, about 0.15 to about 0.5 mol % 1,3-butadiene, about 14 to about 16 mol % butanes, about 15 to about 25 mol % butenes, about 10 to about 20 ppm H2S, about 100 to about 200 ppm mercaptans, about 200 to about 300 ppm acetaldehyde, and about 200 to about 300 ppm acetone; introducing an aqueous bisulfite stream comprising an alkali metal bisulfite into a top of the packed extraction column; counter-currently contacting the Liquid LPG stream and the aqueous bisulfite stream in the packed extraction column such that at least a portion of the acetaldehyde and acetone are extracted into and reacted with the alkali metal bisulfite to form a solid adduct wherein an amount of acetaldehye and acetone react such that a treated Liquid LPG stream leaving the packed extraction column contains less than 0.1 ppm acetaldehyde and greater than 95% of the acetone is removed as compared to the liquid LPG stream, and wherein an amine extractor or a caustic extractor unit downstream from the mass transfer device is essentially free of aldol condensation products, wherein the liquid bisulfite stream is circulated from a bottom of the packed extraction column to a top of the packed extraction column until a concentration of alkali metal bisulfite in the aqueous bisulfite stream reaches approximately 1% by weight and thereafter discharging the aqueous bisulfite stream and introducing a fresh bisulfite; and sending the treated Liquid LPG stream to an amine extractor unit.

10. The method of claim 9, wherein the fresh bisulfite comprises an alkali metal bisulfite in an amount of about 8% to about 15% by weight.

11. The method of claim 9, wherein the alkali metal bisulfite is selected from the group consisting of sodium bisulfite, potassium bisulfite, magnesium bisulfite, strontium bisulfite, and combinations thereof.

12. The method of claim 9, wherein the packed extraction column comprises random packing, structured packing, plastic packing, or stoneware packing.

13. A method for treatment of carbonyls comprising: introducing a Liquid LPG steam from an FCC Gas Plant Debutanizer Overhead into a bottom of a packed extraction column, wherein the Liquid LPG stream comprises 50-54% propylene, 8-12% propane, 0.15-0.5% 1,3-Butadiene, 14-16% butanes, 15-25% butenes, 10-20 ppm H2S, 100-200 ppm mercaptans, 200-300 ppm acetaldehyde, and 200-300 ppm acetone by weight; introducing an aqueous sodium bisulfite stream into a top of the packed extraction column; and counter-currently contacting the Liquid LPG stream and the aqueous sodium bisulfite stream in the packed extraction column such that at least a portion of the acetaldehyde and acetone are extracted into and reacted with the sodium bisulfite to form a solid adduct that is soluble and wherein a sufficient amount of acetaldehyde reacts such that a treated Liquid LPG stream leaving the packed extraction column contains less than 0.1 ppm acetaldehyde such an amine extractor or a caustic extractor unit downstream from the mass transfer device is essentially free of aldol condensation products.

14. The method of claim 13, wherein the treated Liquid LPG stream has 95% of the acetone removed as compared to the Liquid LPG stream.

15. The method of claim 13, wherein the packed extraction column comprises random packing, structured packing, plastic packing, or stoneware packing.

16. The method of claim 13, wherein the step of contacting comprises: circulating the aqueous sodium bisulfite stream from a bottom of the packed extraction column to a top of the packed extraction column until a concentration of sodium bisulfite in the aqeuous sodium bisulfite stream reaches approximately 1% by weight and thereafter discharging the liquid sodium bisulfite stream and introducing a fresh liquid sodium bisulfite.

17. The method of claim 13, wherein the fresh aqueous sodium bisulfite comprises sodium bisulfite in an amount of about 8% to about 15% by weight.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) These drawings illustrate certain aspects of some of the embodiments of the present invention and should not be used to limit or define the invention.

(2) FIG. 1 illustrates a schematic diagram of an FCC gas plant.

(3) FIG. 2 illustrates a schematic diagram of LPG treating unit for removal of carbonyls, H.sub.2S by amine and RSH contaminants.

(4) FIG. 3 illustrates a schematic diagram of LPG treating unit for removal of carbonyls, H.sub.2S by caustic and RSH contaminants.

SUMMARY

(5) Embodiments disclose removal of carbonyls from liquid phase hydrocarbon streams. A method for treatment of carbonyls in a liquid hydrocarbon stream may comprise providing a liquid hydrocarbon stream comprising a carbonyl, providing a liquid bisulfite stream comprising an alkali metal bisulfite, and contacting the liquid hydrocarbon stream and the liquid bisulfite stream in a mass transfer device wherein at least a portion of the carbonyl reacts with alkali metal bisulfite to form a solid adduct that is soluble in the bisulfite solution. A system for treatment of carbonyls in a liquid hydrocarbon stream may comprise a hydrocarbon liquid stream comprising a carbonyl, a liquid bisulfite stream comprising an alkali metal bisulfite, and a mass transfer device configured to counter-currently contact the hydrocarbon liquid stream and the liquid bisulfite stream.

DETAILED DESCRIPTION

(6) Embodiments disclose removal of carbonyls (e.g., aldehydes, ketones, etc.) from liquid phase hydrocarbon streams. Advantageously, embodiments may remove carbonyls to a much lower trace level from hydrocarbon products and overcome (1) the aldol condensation reaction upon contacting the LPG with caustic solution, and (2) catalytic deactivation by carbonyls during various hydrocarbon conversion processes where catalysts are employed. Another advantage may be that dissolved hydrocarbons and particularly butadiene and carbonyls may be stripped from the caustic solution feed to the caustic oxidizer to avoid fouling the oxidizer and its regenerated caustic solution.

(7) Embodiments may disclose removal of carbonyls from liquid phase hydrocarbons streams that may include contacting the hydrocarbon streams with an alkali metal bisulfite. Examples of suitable alkali metal bisulfites that may be used include, without limitation, sodium bisulfite, potassium bisulfite, strontium bisulfite, magnesium bisulfite, other alkali metal bisulfites, and combinations thereof. The alkali metal bisulfite may react with the carbonyls to form an adduct.

(8) The embodiment depicted in FIG. 1 is one conventional FCC operating technique and processing sequence of the unsaturated gas plant 10 with an amine absorber for the removal of acid gases from the FCC off Gas and an amine extractor to remove H.sub.2S from the LPG. It should be understood that present embodiments should not be limited to the particular implementation shown on FIG. 1, but may be used in any FCC process for removal of carbonyls. In the illustrated embodiment, the FCC heavy feedstock 11 may be fed to the FCC reactor 12 where it may be cracked to hydrogen, light hydrocarbons, naphthas, middle and heavy distillates, as well as acid gases, and minor amounts of oxygenates and nitriles. Light hydrocarbons may include methane, ethylene, ethane, propylene, propane, C4 olefin/saturate, The FCC heavy feedstock 11 may contain heavy gas oil or vacuum gas oil (HVGO). The HVGO may include the portion of the crude oil with an initial boiling point of 340 C. or higher at atmospheric pressure and an average molecular weight ranging from about 200 to 600 or higher. The reactor effluents 13 may be cooled in main fractionator 14 (e.g., a multi-section column with pump arounds, which may be equipped with means for withdrawing a naphtha, light cycle oil and heavy cycle oil). The total Main Fractionator overhead vapor may comprise the raw gasoline product and lighter hydrocarbons together with steam and inert gas from the reactor system. For example, the overhead vapor may comprise about, expressed in mole percent, 25-33% H.sub.2O, 1-2% N.sub.2, 0.2-0.3% CO.sub.2, 0.01-0.02% H.sub.2S, 4-8% Cl, 4-7% ethylene, 1-4% ethane, 10-19% propylene, 4-8% propane, 7-15% C4's, 3-5% C5's and balance C6.sup.+. The main fractionator bottoms product 15 may comprise relatively heavier hydrocarbons, such as heavy cycle oil (HCO) and slurry oil which are recycled back to the reactor for further cracking; one side product from the main fractionator is the light cycle oil (LCO) of TBP cut of 140-370 C. and largely mono/di/tri/poly aromatic 75% by volume. The Main Fractionator reflux 16, a portion of the steam and a small amount of distillate may be condensed in the Main Fractionator Overhead Condenser 17 and passed to overhead accumulator 19 as stream 18 where sour condensate water 20 with dissolved acids, and part of the alcohols, ammonia and HCN is separated, the gas 21 from accumulator 19 may then be compressed in multistage compressor with interstage cooling unit 22, wherein water condensate 23 may be separated that comprises dissolved oxygenates and nitriles. The gas 21 from accumulator 19 may comprise about, expressed in mole percent, 5-6.4% H.sub.2O, 1.8-2.2% N.sub.2, 0.4-0.5% CO.sub.2, 0.015-0.02% H.sub.2S, 9-10.6% Cl, 14-15% C2's, 28-30% C3's, 15-20% C4's, 5-6% C5's and balance C6.sup.+.

(9) In the illustrated embodiment, the gas 21 may continue from compressor with interstage cooling unit 22 to Absorber Stripper 25. As illustrated, the Absorber/Stripper 25 may recover C.sub.3.sup.+ hydrocarbons in the absorber bottoms 27, and the Absorber/Stripper 25 may strip the C2's hydrocarbons and lighter components from the high pressure liquid to form a lights stream 26. Lights stream 26 may comprise on average by mole 95% C2.sup. and 5% C3.sup.+.

(10) The Sponge Absorber 28 may recover most of the C.sub.3+ hydrocarbons entrained in the vapors (e.g., lights stream 26) leaving the Absorber/Stripper 25. In some embodiments, lean oil from the Main Fractionator 14 may be the absorption medium used in the Sponge Absorber 28. Sponge Absorber overhead 31 may be cooled in the off gas Cooler 32 before the cooled stream 33 may be fed into the amine absorber 34 with lean amine stream 35 for removal of CO.sub.2 and H.sub.2S from the refinery off gas (ROG) 33 and producing treated ROG product 37, which may comprise about, expressed in mole percent, 5-6% N.sub.2, 16-20% H.sub.2, 28-32% CH.sub.4, 27-31% ethylene 8-12% ethane, and balance C3.sup.+. Lean amine stream 35 may comprise, for example, Methyldiethanolamine (MDEA) about 30 to 45 wt % in water. A rich amine stream 36 may be removed from the amine absorber 34 and routed to the amine regenerator. The rich amine stream 36 may comprise MDEA, absorbed acid gases and hydrocarbons.

(11) The C.sub.3.sup.+ liquid bottoms stream 27 may be fractionated in a debutanizer (DC4) tower 38 to provide a C.sub.5.sup.+ liquid gasoline product 39 and LPG product 40. The DC4 overhead gas (e.g., LPG product 40) may be condensed in DC4 condenser 41 providing reflux 42 to the DC4 tower 38 and C3/C4 LPG stream 43, which may pass to the amine extractor 56 for removal of H.sub.2S to less than 0.1 mppm. For example, regenerated amine stream 58 which may comprise a solution of 30-45% MDEA and the H.sub.2S loaded amine solution stream 57 may leave the amine unit 56 for regeneration. The H.sub.2S free LPG 59 may be further treated in Mercaptan Extractor Unit 60 for mercaptan removal to produce treated LPG 63. In some embodiments, the Mercaptan Extractor Unit 60 may be a Merichem Extractor Unit, with regenerated caustic stream 61 comprising 18-20% by weight caustic feed to the extractor, and mercaptide loaded caustic solution stream 62 leave the extractor for oxidation and regeneration.

(12) FIG. 2 represents a schematic of an embodiment for treatment of a liquid phase hydrocarbon stream for removal of carbonyls. In the illustrated embodiment, an H.sub.2S and RSH treatment system 100 may be provided in which a liquid hydrocarbon stream 140 contaminated with carbonyls may be introduced. Liquid hydrocarbon stream 140 may comprise liquefied petroleum gas (LPG). Liquid hydrocarbon stream 140 may comprise about, expressed in mole percent, 50-54% propylene, 8-12% propane, 0.15-0.5% 1,3-Butadiene, 14-16% butanes, and 15-25% butenes with 10-20 ppm H.sub.2S, 100-200 ppm mercaptans, 200-300 ppm acetaldehyde and 200-300 ppm acetone by weight. Liquid hydrocarbon stream 140 may comprise C3/C4 LPG stream 43 shown on FIG. 1, for example. For carbonyl removal, embodiments may include a mass transfer device such as a packed extraction column 141 between DC4 tower (e.g. DC4 tower 38 on FIG. 1) and the amine extractor 56 to treat the LPG stream 140. The packed extraction column 141 may comprise any suitable packing such as random material, structured material, plastic material, stoneware material, and combinations thereof. A liquid bisulfite stream 148 may be pumped to the top of the packed extraction column 141 for intimate counter-contact with liquid hydrocarbon stream 140, where the carbonyls (acetaldehyde and acetone) content in the liquid hydrocarbon steam 140 may be reacted with the liquid bisulfite stream 148 forming a soluble adduct product. The liquid bisulfite steam 148 may comprise an alkali metal bisulfite such as sodium bisulfite, potassium bisulfite, other alkali metal bisulfites, and combinations thereof. The alkali metal bisulfite may be present in water in concentration of about 8% to 15% by weight. Packed extraction column 141 may comprise a controller (not shown) to control the volumetric ratio between the liquid hydrocarbon stream 140 and the liquid bisulfite stream 148 entering the packed extraction column 141. The treated hydrocarbons may leave packed extraction column 141 as an overhead hydrocarbon stream 155. Overhead hydrocarbon stream 155 may be essentially free of the acetaldehyde (e.g., less than 0.1 ppm) and have greater than 95% of the acetone removed. Overhead hydrocarbon stream 155 may comprise about 50-54% propylene, 8-12% propane, 0.15-0.5% 1,3-Butadiene, 14-16% butanes, and 15-25% butenes by weight. In addition, the liquid 142 leaving the bottom of the packed extraction column 141 may contain the formed adduct and any unreacted liquid bisulfite solution. Stream 148 may be recirculated back to the top of the packed extraction column 141 via recirculating pump 147. When the bisulfite content in the recirculating solution reaches approximately 1% both valves 144 and 146 may be opened to allow addition of fresh liquid bisulfite stream 145 through valve 143 and the depleted liquid bisulfite solution stream 143 to discharge from the column through valve 144. Fresh liquid bisulfite stream 145, for example, may comprise an alkali metal bisulfite in water in a concentration range of about 8% to 15% by weight.

(13) Recirculating liquid bisulfite solution in packed extraction column 141 may release small ppm levels of sulfur dioxide (SO.sub.2). The SO.sub.2 may flow up the packed extraction column 141 with liquid hydrocarbon stream 140, and may be purged and vented 154 at the top of the packed extraction column 141.

(14) The overhead hydrocarbon stream 155 essentially depleted of acetaldehyde and acetone may be fed to the amine extractor 156 for further treatment to remove its H.sub.2S content. For example, the overhead hydrocarbon stream 155 may have an acetaldehyde content of less than 1 ppm by weight. Lean amine 158 may flow to the top of the amine extractor 156 and may be contacted counter-currently with the overhead hydrocarbon stream 155 to remove its H.sub.2S content. Lean amine 158 may comprise about 30-45% MDEA. Rich amine solution 157 may leave from the bottom of the amine extractor for regeneration of its acid gas content. Rich amine solution 157 may comprise about 30-45% MDEA loaded with dissolved H.sub.2S.

(15) The treated hydrocarbon stream 159 from the top of the amine extractor 156, may be essentially free of H.sub.2S (e.g., less than 0.1 ppm) and may contain trace acetone (e.g., less than 10 ppm) and butadiene concentration (e.g., less than 0.15 mole %). As illustrated, the treated hydrocarbon stream 159 may flow to the mercaptan extractor 160 for RSH removal by contacting NaOH recirculating solution 161 (e.g., about 18-20 wt % NaOH) at temperature of 30-40 C., for example, where the RSH in the treated hydrocarbon stream 159 may react with the caustic to form mercaptides (RSNa). The rich caustic solution 162 leaves the mercaptan extractor loaded with the formed mercaptide salts while mercaptan free LPG 163 leaves the top of mercaptan extractor 160. Rich caustic solution 162 may comprise about 18% to 20% by weight NaOH, about 0.05% to 0.1% mercaptides and balance may comprise H.sub.2O.

(16) The rich caustic solution 162 from the mercaptan extractor 160 may be stripped of its trace butadiene and residual acetone content by stripping with fuel gas stream 166 or nitrogen in the Butadiene Stripper 165 operated at a temperature of 40 C. or less, for example. Removal of the polymer precursor (butadiene and Acetone) may be advantageous to prevent fouling of the downstream caustic oxidizer 172 which may be operated at a higher temperature of 50-55 C. and with the caustic stream saturated with dissolved oxygen. Stripped gasses 167 may exit at the top of the Butadiene Stripper 165.

(17) In the illustrated embodiment, the rich caustic 168 from the bottom of butadiene stripper may cross the oxidizer heater 169, and may be mixed with process air 170 and makeup cobalt based catalyst 171; the resulting blend may enter the caustic oxidizer 172. In some embodiments, caustic oxidizer 172 may be loaded with charcoal rings packing to promote the homogeneous distribution of the three phases. The mercaptides RSNa present in the rich caustic solution may be oxidized to disulfides RSSR with the aid of Co based catalyst dispersed into the caustic solution.

(18) The resulting oxidizer top effluent 173 (e.g., comprising disulfides+excess air+lean regenerated caustic), may flow to the three disulfides separator which may separate: the excess air 174, the disulfides oil DSO (RSSR) 175, and the lean regenerated caustic solution with the dissolved Co catalyst 176.

(19) The lean regenerated caustic solution 176, from the bottoms of the disulfides separator 181, may be recycled back to mercaptan extractor 160 by the means of the lean caustic circulation pump 179, through the lean caustic water cooler 180. Purged caustic stream 177 may limit sulfides content in the recirculating caustic, and makeup 25 wt % caustic 178 may be added.

(20) FIG. 3 represents an alternative embodiment for treatment of a liquid phase hydrocarbon stream for removal of carbonyls. In the illustrated embodiment, an H.sub.2S and RSH treatment system 200 may be provided as in FIG. 2 except that H.sub.2S removal may be carried out in a caustic extractor 251 in which the overhead hydrocarbon stream 155 may be contacted with 1-10 wt % caustic solution 258, for example. Recirculating caustic stream 250 may pumped to the top of caustic extractor 251 for intimate counter-contact with overhead hydrocarbon stream 155, where the H.sub.2S content in the overhead hydrocarbon stream 155 may react with the caustic in the liquid phase forming a soluble Na.sub.2S product. The overhead treated hydrocarbon stream 259 leaving the caustic extractor 251 may be essentially free of the H.sub.2S, and the recirculating caustic stream 250 leaving the bottom of the column may contain the formed Na.sub.2S and all unreacted NaOH. Liquid 250 may be recirculated back to the top of the column via recirculating pump 252. When the caustic content in the recirculating solution reaches about 1 wt % both valves 254 and 257 may be opened to allow addition of fresh 10% NaOH solution stream 253. NaOH solution stream 253 may enter thought valve 254 and the depleted Caustic solution stream 256 may discharge from the column through valve 257.

EXAMPLES

(21) To facilitate a better understanding of the present embodiments, the following illustrative examples of some of the embodiments are given. In no way should such examples be read to limit, or to define, the scope of the disclosure.

(22) The removal of carbonyls from a liquid phase hydrocarbon stream in the example embodiments may be further illustrated by the following examples wherein all percentages are by weight unless specified otherwise. A gas chromatography (GC) method was used to evaluate the composition of acetaldehyde and acetone in the hydrocarbon stream. Liquid samples were collected by filling sample bottles from the extractor column overhead outlet. Each sample was then analyzed by GC to determine the amount of acetaldehyde and acetone in the hydrocarbon liquid.

(23) The Extraction Column consisted of 1 inch (2.54 cm) inside diameter stainless steel column, packed with 0.24 inch (6.1 mm) Propak stainless steel packing to a height of 36 inches (91.44 cm). Sodium bisulfite solution was allowed to flow down the column packing contacting counter currently against the up flowing iso-octane liquid that contained 200 wppm acetaldehyde and 200 wppm acetone.

(24) The extraction column was operated at 10 psig (0.69 barg) and temperature of 104 F. (40 C.). Temperatures below 50 C. are well suited for the reaction of sodium bisulfite with acetaldehyde and acetone to form solid adduct that is soluble in the aqueous phase.

(25) The iso-octane flow rate to the bottom of the extraction column was targeted at 20 cc/min; while the liquid bisulfite solution flow to the top of the column was targeted at 18.5 cc/min; such flow rates to the column were calculated for operation well below the flooding regime of the packing.

Example 1

(26) The extraction column was operated with iso-octane liquid containing 200 wppm acetaldehyde and 200 wppm acetone which was fed to the bottom of the column, and contacted counter-currently with 1.0 wt % sodium bisulfite solution fed to the top of the packing. The acetaldehyde reacted completely with the sodium bisulfite solution and formed an adduct soluble in the liquid solution. Thus, the acetaldehyde and acetone were depleted from the iso-octane hydrocarbon phase and at the column top outlet stream the concentration measured less than 0.3 wppm acetaldehyde, and less than 9 wppm acetone. Data for Example 1 is shown in Table 2.

(27) TABLE-US-00002 TABLE 2 Feed: 200 ppm/wt acetaldehyde 200 ppm/wt acetone Balance- Isooctane Extracting Solvent: 1 wt % Sodium bisulfite Iso-Octane density = 0.696 gm/cc Bisulfite density = 1.01 gm/cc Top col Btm Col Acetone Run time C8 Feed Bisulfite Temp Temp Acetaldehyde Conc, minutes rate, cc/min rate, cc/min deg C. deg C. Conc, ppm ppm Comments 47 50 start run, start bisulfite pump 9 3.2 52.7 37 41 13 0.0 50.7 37 40 iso pump on 18 57.5 55.4 36 42 28 60.3 53.5 41 45 33 51.7 47.9 42 47 38 51.7 49.3 42 48 42 56.7 42 49 new iso bottle 48 47.9 45.7 42 50 53 57.5 56.0 42 51 60 45.2 43.4 42 50 0.3 9 sx #1 63 57.5 50.2 42 50 68 57.5 56.8 42 50 73 46.0 41.6 42 50 77 57.5 57.7 42 49 0.1 7 sx #2 83 47.9 44.1 42 49 88 51.7 49.1 42 49 94 57.5 49.0 41 49 <0.1 7 sx #3 98 57.5 53.5 41 49 101 switch to run 2 feed Avg 53 50 42 50

Example 2

(28) The extraction column was operated at the same conditions and liquid rates as in Example 1, but the concentration of carbonyls in the iso-octane liquid was increased to 500 wppm acetaldehyde and 500 wppm acetone. The liquid was fed to the bottom of the column, and contacted counter-currently with 1.0 wt % sodium bisulfate solution fed to the top of the packing. In this example, the acetaldehyde and acetone were depleted from the iso-octane hydrocarbon phase and at the column top outlet stream the concentration measured less than 0.1 wppm acetaldehyde, and less than 10 wppm acetone. Data for Example 2 is shown in Table 3.

(29) TABLE-US-00003 TABLE 3 Feed: 500 ppm/wt acetaldehyde 500 ppm/wt acetone Balance- Isooctane Extracting Solvent: 1 wt % Sodium bisulfite Iso-Octane density = 0.696 gm/cc Bisulfite density = 1.01 gm/cc Top col Btm Col Acetone Run time C8 Feed Bisulfite Temp Temp Acetaldehyde Conc, minutes rate, cc/min rate, cc/min deg C. deg C. Conc, ppm ppm Comments start run, pumps on 5 46.0 43.0 44 51 10 57.5 49.9 42 51 15 57.5 53.1 42 51 18 38.3 51.2 42 51 switched bottles 25 53.4 45.7 42 51 30 51.7 48.1 41 50 35 51.7 49.5 42 49 40 57.5 48.7 42 49 45 51.7 49.1 42 49 <0.1 10 sx #1 50 57.5 52.9 42 50 55 51.7 44.8 42 50 60 57.5 49.3 42 50 <0.1 7 sx #2 65 51.7 49.3 42 50 70 51.7 49.7 42 50 75 57.5 47.9 42 50 0.1 7 sx #3 77 57.5 53.0 shut down Avg 54 49 42 50

Example 3

(30) The same extraction column was operated with iso-octane liquid containing 200 wppm acetaldehyde and 200 wppm acetone that was fed to the bottom of the column at the same conditions and liquid rates as in Example 1. The concentration of the aqueous liquid solution was increased to 10 wt % sodium bisulfate solution fed to the top of the packing. The acetaldehyde and acetone similarly were depleted from the liquid hydrocarbon phase and at the column top outlet. The concentration of the acetaldehyde measured less than 0.1 wppm and the acetone concentration measured less than 0.5 wppm. Data for Example 3 is shown in Table 4.

(31) TABLE-US-00004 TABLE 4 Feed: 203 ppm/wt acetaldehyde 200 ppm/wt acetone Balance- Isooctane Extracting Solvent: 10 wt % Sodium bisulfite Iso-Octane density = 0.696 gm/cc Bisulfite density = 1.08 gm/cc Top col Btm Col Acetone Run time C8 Feed Bisulfite Temp Temp Acetaldehyde Conc, minutes rate, cc/min rate, cc/min deg C. deg C. Conc, ppm ppm Comments 52 48 start run, start bisulfite pump 8 0.0 47.3 37 46 13 0.0 45.0 41 51 iso pump on 23 51.7 48.6 41 52 33 54.6 49.5 41 51 41 53.9 50.9 41 51 new iso bottle 53 52.7 47.9 42 50 63 54.6 49.4 42 51 <0.1 0.5 SX #1 68 57.5 56.3 41 50 73 51.7 42.6 41 49 78 51.7 49.8 41 48 <0.1 0.4 SX #2 83 57.5 49.6 41 48 88 51.7 48.9 41 48 93 57.5 49.8 41 48 <0.1 0.4 SX #3 95 switch to run 4 feed Avg 55 50 41 49

Example 4

(32) The same extraction column operated with iso-octane liquid containing 500 wppm acetaldehyde and 500 wppm acetone that was fed to the bottom of the column at the same conditions and liquid rates as in Example 2 but the concentration of the aqueous liquid solution was increased to 10 wt % sodium bisulfite solution fed to the top of the packing. The acetaldehyde and acetone similarly were depleted from the liquid hydrocarbon phase and at the column top outlet. The concentration of the acetaldehyde measured less than 0.1 wppm and the acetone concentration measured less than 8 wppm. Data for Example 4 is shown in Table 5

(33) TABLE-US-00005 TABLE 5 Feed: 506 ppm/wt acetaldehyde 496 ppm/wt acetone Balance- Isooctane Extracting Solvent: 10 wt % Sodium bisulfite Iso-Octane density = 0.696 gm/cc Bisulfite density = 1.08 gm/cc Top col Btm Col Acetone Run time C8 Feed Bisulfite Temp Temp Acetaldehyde Conc, minutes rate, cc/min rate, cc/min deg C. deg C. Conc, ppm ppm Comments 41 48 start run 2 28.7 33.5 41 48 7 63.2 57.8 41 48 12 40.2 40.1 41 48 17 57.5 49.8 41 48 22 51.7 49.6 41 47 27 51.7 53.5 42 48 32 51.7 44.6 42 48 new iso bottle 37 51.7 49.8 42 49 42 51.7 49.3 42 49 47 51.7 49.4 42 49 52 51.7 50.0 42 49 57 51.7 49.3 42 49 62 51.7 49.3 42 49 <0.1 0.5 SX #1 67 46.0 49.6 42 49 72 51.7 49.8 42 49 77 51.7 49.3 42 49 <0.1 0.5 SX #2 82 51.7 49.8 42 49 87 51.7 48.9 42 49 92 51.7 49.4 42 49 <0.1 0.6 SX #3 Shut down Avg 51 49 42 49

SUMMARY OF RESULTS

(34) Results of the Examples 1, 2, 3 and 4 shows that removal of acetaldehyde and acetone are almost complete when using 10 and 1 wt. % sodium bisulfite solution. While when the sodium bisulfite solution reaches one weight percent in the extraction column the removal of acetaldehyde from the hydrocarbon liquid stream is greater than 99.95% and the removal of acetone from the hydrocarbon liquid stream is greater reaches 95%. The results are summarized in Table 6.

(35) TABLE-US-00006 TABLE 6 Inlet Inlet Outlet Outlet Exam- Bisulfite Acetaldehyde Acetone Acetaldehyde Acetone ple Conc. Conc. Conc. Conc. Conc. # wt % wppm wppm wppm wppm 1 1 200 200 <0.3 <9 2 1 500 500 <0.1 <10 3 10 200 200 <0.1 0.5 4 10 506 496 <0.1 <0.6

(36) For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range are specifically disclosed. In particular, every range of values (of the form, from about a to about b, or, equivalently, from approximately a to b, or, equivalently, from approximately a-b) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values even if not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

(37) The foregoing figures and discussion are not intended to include all features of the present techniques to accommodate a buyer or seller, or to describe the system, nor is such figures and discussion limiting but exemplary and in the spirit of the present techniques.