SELECTIVE ABSORBTION OF SULFUR DIOXIDE FROM GASES CONTAINING SULFUR DIOXIDE AND CARBON DIOXIDE

Abstract: Sulfur dioxide is selectively removed and recovered from a gas stream containing the same by contacting the gas with an aqueous solution of a piperazinone or a morpholinone as absorbent. The rich absorbent is thermally regenerated to release the sulfur dioxide for reuse in the contacting step.

Description: SELECTIVE ABSOkBTION OF SULFUR DIOXIDE FhGM GASES CONTAINING SULFUR DIOXIDE AS CARBON DIOXILE The present invention concerns a process for selectively removing sulfur dioxide gas from a gas stream in the presence of carbon dioxide. The absorbent, which removes the sulfur dioxide, is regenerated thereby enabling its reuse and a continuous operation of the process. Numerous patents and literature describe techniques for removing sulfur compounds from a gas stream containing the sulfur compounds. By far the most common technique is that used to treat natural gas having one or more of the acid gases, hydrogen sulfide (H2S), sulfur dioxide (SO2), carbonyl sulfide (COS), and carbon dioxide (CO2) with an aqueous liquid lean (with respect to the acid gases) absorbent to produce a rich absorbent stream and regenerate the rich absorbent stream by thermal treatment to produce a recycleable lean stream. Many compounds leave been suggested and used as the absorbent, some to selectively remove or CO, and other absorbents more general in nature to remove as much of each of the acid gases present as is possible. Now, with the renewed interest in coal fired boilers and the like, coupled with the greater concern for the environment, there is a need to provide a low pressure (at or below atmospheric), low temperature selective process to remove sulfur dioxide from the flue gases emitted from such plants without removal of any major portion of the carbon dioxide. A commercially desirable feature for the absorbent would be its regeneration from the absorbed gases enabling its reuse. One process for removing the SO2 widely in use today is the limestone scrubbing process. The disadvantage of this process is the formation of a large volume of solid waste, calcium sulfite-sulfate, often contaminated with fly ash, which requires disposal. In areas of the country where paper pulp operations are being carried out, the waste is oftentimes usable, but such situations are not widespread. Another process recently in the forefront is the use of potassium or sodium citrate as disclosed in U.S. Patent No. 4,366,134. -While the absorbent is regener ted and recycled, the make-up costs can be high due to thermally stable salts being formed. In addition, it is necessary to employ stainless steel for the entire plant to prevent excessive corrosion of the metals. It would be advantageous to have a process which: (a) selectively absorbs sulfur dioxide to the exclusion of the other acid gases, particularly carbon dioxide; (b) has low chemical make-up cost; (c) has reduced operating costs; and (d) permits economical construction of equipment, to process low pressure, high volume, gas streams, such as flue gas, which results in the reduction or elimination of the sulfur dioxide content of such gases. Surprisingly, the present process meets the above stated purposes. The process selectively removes sulfur dioxide from a gas stream containing sulfur dioxide and carbon dioxide by contacting the gas with an aqueous solution of a compound of the general formula EMI3.1 wherein X is an oxygen atom or NR'; R' is a hydrogen atom or C1-C5 alkyl; and R is a hydrogen atom or Cl-C5 alkyl. The gas stream may also contain one or more of the other acid gases (for example, H2 S or COS) commonly associated with hydrocarbon, natural or synthetic, and/or combustion gases (flue gas). The process employs a lean aqueous absorbent solution of a compound of Formula (I), preferably at a concentration of 0.1 molar to the saturation point. The rich absorbent, containing most of the SO, and little of the CO2, is removed from the absorber (contactor) and thermally regenerated to produce a lean absorbent solution for recycle to the absorber. The absorber is preferably operated at from 50 to 950C under about atmospheric pressure conditions. Higher temperatures and pressures do not materially effect the process although equipment design may require modification to handle the higher temperatures and pressures. The concentration of the sulfur dioxide in the gas streams may vary from about 10 ppm to about 45 percent by volume of the gas stream being treated. The process for regeneration may be one of the conventional methods employed in conventional gas sweetening units as well as by steam stripping. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 represents a schematic diagram of the essential components of a process used to treat gases in accordance with the present invention. An integrated absorber-stripper (contactorregenerator), as illustrated in Figure 1, was constructed by piping a ten tray Oldershaw column, 10, having a one inch (2.54 cm) internal diameter and 1 1/4 inch (3.17 cm) tray spacings in a manner to receive a lean absorbent solution at its upper end, 11, and a con taminated gas stream at its lower end, 12. The top, 13, and bottom, 14, were each independently piped to collect the treated gas at the top and the rich absorbent at the bottom, respectively. Thule rich absorbent was piped to a sllell and tube cooler, 15, which passed the llot lean absorbent on the shell side and the cool rich absorbent on the tube side. The rich absorbent was then delivered to the upper end, 16, of a stripper, 17. The stripper, 17, was a two-foot one-inch (0.635 m) interllal diameter column packed with 1/4 inch (6.35 mm) Berl saddles. The sulfur dioxide exited the top, 18, with some water vapor and was sent to a condenser, 19, wherein the water vapor was condensed and the condensate and sulfur dioxide sent to a degasifier, 20, from which the sulfur dioxide was vented and the condensate returned via pump, 20A, to the top, 18, of the stripper, 17, as reflux. The liquid collecting in the bottom, 21, of the stripper, 17, was substantially lean absorbent, a part of which was passed through a reboiler, 22, and back into the stripper below the packed section. The remainder of the lean absorbent collecting in the bottom, 21, was piped to the cooler, 15, wherein it gave up most of its heat to the rich absorbent. The cool absorbent was drawn to the intake side of a pump, 23, passed through another cooler, 24, and then to the lean feed point of the absorber, 10. To illustrate the present process, the following examples are provided. Example 1 The data collected from several runs is set forth in the table below. The alphabetic headings refer to like alphabetically numerated streams in Figure 1. TABLE 1 1bs/hr (kg/hr) A B C D E F G H Treated Lean Rich Lean Acid Mol Wt Feed Gas Gas Soln Soln Soln Gas/Water Condensate Acid Gas H2O 18.0 0.63 0.63 0.63 0.65 0.65 0.001 (0.285) (0.285) (0.285) (0.295) (0.295) (0.0005) CO2 44.0 0.1908* 0.1908 (0.8655) (0.08655) N2 28.17 0.7105 0.7105 (0.3223) (0.3223) SO2 64.06 0.014 3 ppm 0.0045 0.0185 0.0045 0.014 0.014 (0.0065) 6.6 x 10-6 (0.0020) (0.0085) (0.0020) (0.0065 (0.0065) (3.0 x 10-6) SO3 80.06 0.03 0.03 0.03 (0.015) (0.015) (0.015) NNDP** 128.17 0.9153 0.901 0.665 0.6785 0.665 0.664 0.65 0.015 (0.4152) (0.409) (0.302) (0.308) (0.302) (0.301) (0.295) (0.007) * Numbers were normalized to Balance ** N,N' methylpiperazinone (or 1,4-dimethylpiperazinone) Example 2 A series of tests were run to screen the efficiency of various compounds known to absorb SO2 witli respect to their absorbent characteristic fOl CO2. The equipment, a steel bomb filled with glass balls, was fitted with a valve at one end through which CO2 and absorbent could be added. The bomb was also fitted with a pressure sensing instrument. The bomb was pressurized to 760 mm Hg with CO2 and filled with a measured quantity of a 1 molar solution of a specific absorbent. The bomb was then left at ambient temperature (about 240C) or heated as indicated in the table below, and the pressure drop measured over a 10 minute period for each condition. The results were as follows: Table II Cell Mols CO2/ Absorbant Temp. C Mol Absorbant Water 24 0.046 1 M triethanolamine 24 0.27 50 none 1 M 1,4-dimethylpiperazinone 23 0.08 75 none 1 M triethylene glycol 24 none2 1 M neutralized citric acid 24 none3 1 M DETA4 24 1.33 65 0.95 74 0.76 1 M Na2SO3 24 0.17 44 0.16 74 0.1 1 High losses due to high vapor pressure. 2 Degrades in presence of oxygen. 3 Solvent used in U.S. 4,366,134, corrosive. 4 Diethylenetriamine Example 3 Using the ten tray Oldershaw column described previously various compounds were tested for CO2 and SO2 absorption characteristics. A synthetic N2/CO2/SO2 gas mixture of the composition set forth in the following table was fed to the bottom of the column at 550C and 4/5 liters/minute. The liquid flow at the top was about 10 cc/minute. The analysis of the gas in and out was obtained and weight percent CO2 and/or SO, absorbed calculated. The results are set forth below. TABLE III ABSORPTION STUDIES WT. % GAS IN FEED WT. % GAS OUT % ABSORBED COMPOUND N2 CO2 SO2 N2 CO2 SO2 CO2 SO2 WATER 78.78 19.85 1.43 79.56 19.27 1.15 3.8 19.5 NNDP 79.01 19.97 1.02 79.58 20.41 ---- ---- 100 74.27 17.60 8.13 80.69 19.31 ---- ---- 100 DETA 73.86 17.94 8.19 83.82 16.17 ---- 20.58 100 K CITRATE 74.44 17.74 7.82 79.83 20.17 ---- ---- 100 69.23 16.86 13.91 80.23 19.77 ---- ---- 100 - pyrrole 78.36 20.19 1.43 78.62 19.90 1.32 1.47 7.7 N,N'-Dimethyl piperazine 79.01 19.51 1.48 79.76 20.24 trace ---- 99 Morpholine 78.16 20.39 1.45 79.78 20.22 trace ---- 99 Tetramethylene sulfone 78.22 20.15 1.63 77.94 19.95 1.35 2.65 17.2 Aminoethylpiper azine +3PO 77.95 20.44 1.61 78.97 21.03 ---- ---- 100 Table IV S02 ABSORPTION; 20 WT % NNDP; HIGH SO2 LOADING 5 cc/min Liquid Feed; 781 mm Hg Pressure Absolute, ca 0.195 ft3/minlgas in and 0.i84 ft3/min2gas out Temperature OC Absorbent Feed In 56 56 57 Gas Feed In 25 25 25 Wt. % Gas In N2 77.17 75.18 73.27 CO2 19.65 19.70 19.00 SO2 3.18 5.12 7.73 Wt. % Gas Out N2 79.78 80.35 78.97 CO2 20.52 19.65 20.76 SO2 .001 .001 .269 ppm SO2by Dryer 10 10 too high to measure This run established that NNDP will absorb in excess of one mol of SO2 per mol of NNDP. STRIPPER 4 cc/min Liquid Feed; 761 mm Hg Pressure Absolute Wt % SO2 Liq (in) 7.5 7.5 7.5 7.5 Liq (out) 2.38 2.29 2.14 2.03 Temperatures, C Feed In 81 81 82 82 Bottoms 104 104 104 103 1 0.0055 m /min 2 0.0052 m3/min TABLE V S02 ABSORPTION; 20 WT % NNDP 5 cc/min Liquid Feed; 781 mm Hg Pressure Cu ft/min (m /min) In 0.173 0.176 0.176 0.177 0.@@@ 0.17@ 0.177 (0.00490) (0.00499) (0.00499) 0.00501 Out 0.169 0.175 0.175 0.176 (0.00479) (0.00496) (0.00496) (0.00499) Temperatures uc Liquid Feed At Inlet 85 81 80 80 Top of Column 56 55 54 55 Gas In Bottom cf Column 25 24 21 22 Wt. % Gas In N2 77.83 78.11 77.85 77.68 COê 20.56 20.27 20.66 20.75 SO2 1.61 1.62 1.50 1.58 Wt. % Gas Out N2 79.10 79.40 79.03 78.92 CO2 20.90 20.60 20.97 21.08 SO2 too low to measure ppm SO2 by Dräger 8 8 10 2 STRIPPER 761 mm Hg Pressure cc/min Liquid Feed 4 4 5 3 Wt % SO2 Liq (in) 3.12 - 3.09 1.80 1.87 Liq (out) 1.52 ¯1.67 1.44 1.42 Temperatures, C Feed In 84 84 80 90 Bottoms 100 102 102 101 TABLE VI SO2 ABSORPTION ; 20 WT % NNDP 5 cc/min Liquid Feed ; 781 mm Hg Prossure Cu ft/min (m3/min) In 0.195 0.195 0.195 ().195 (0.00552) (0.00552) (0.00552) (0.00552) Out 0.184 0.184 0.184 0.184 (0.00521) (0.00521) (0.00521) (0.00521) Temperatures C Liquid Feed At Billet 80 80 80 80 At Top of Column 55 55 55 55 Gas Bottom of Column 21 22 22 21 Wt. % Gas In N2 78.41 78.93 77.27 78.41 CO2 19.97 19.55 21.11 19.97 SO2 1.62 1.51 1.61 1.62 Wt. % Gas Out N2 78.53 80.15 78.54 79.70 CO2 21.47 19.85 21.46 20.30 SO2 .0003 .0008 .0003 .0003 ppm SO2 by Dräger 3 8 3 3 STRIPPER 4 cc/min Liquid Feed; 761 mm Hg Pressure tt % SO2 Liq (in) 2.94 2.72 2.74 2.74 Liq (out) 0.72 0.72 0.82 0.72 Temperatures, C Feed In 80 .86 87 87 Bottoms 102 103 102 102 These two runs establish that SO2 will be absorb selectively vis-a-vis CO2 at temperatures above 0C, tit' normal water/gas wash temperature, at 5 percent conctrltlation as well as 20 percent concentration. Example 4 In another series of test runs, a 10 percent by weight aqueous solution of l-methyl-2-morpholinone in deionized water was passed down a 1/2" x 2 ft. (1.27 cm x 0.61 m) good (low) packed absorber column at a nominal rate of -5 cc per minute while a mixture of 3.17 liters per minute of N2, 1.2 ton/min. of air, 750 cc/min of CO2 and 70 cc/min of 502 representing 1 percent by weight of SO2 were fed to the bottom of the column. The liquid withdrawn from the bottom of the column was fed to a 1/2" X 2 ft (1.27 cm x 0.61 m) ss stripper column packed with 1/4" (0.6 cm) Berl saddles with a heated bath reboiler. The off gas from the absorber contained 0.45 percent by weight SO2 and the absorber liquid contained 0.63 percent by weight 502 of which 96.8 percent was stripped from the absorbent in the stripper column. This represents a pick-up of 1/2 mole per mole of l-methyl-2-morpholinone vs a 10 percent solution, and the ability to regenerate the absorbent for recycle.

Claims: CLAIMS 1. A process for selectively removing sulfur dioxide trom a gas strtaln containing sulfur dioxide and carbon dioxide which comprises contacting the yas with an absorbent, characterised in that t0O absorbent is an aqueous solution of a compound of the general formula EMI14.1 wherein X is an oxygen atom or NR' ; R is a hydrogen atom or C1-C5 alkyl; and R is a hydrogen atom or Cl-Cs alkyl. 2. A process as claimed in Claim 1, wherein X is oxygen. 3. A process as claimed in Claim 1, wherein X is NR'. 4. A process as claimed in any one of the preceding claims, wherein R and, if present, R' are both C1-C5 alkyl. 5. A process as claimed in Claim 4, wherein the compound of Formula (I) is 1, 4-dimethylpiperazinone. 6. A process as claimed in Claim 4, wherein the compound of Formula I is l-methyl-2-morpholinone. 7. A process as claimed in any one of the preceding claims, wherein the process is continuous. 8. A process as claimed in any one of the preceding claims, which comprises the further step of regeneration of the aqueous solution of a compound of Formula I. 9. A process as claimed in any one of the preceding claims, which comprises the further step of recovering the gas, substantially free of sulfur dioxide, from the aqueous solution.

Inventors: FOWLER, ALLAN E., JONES, MARK B.
Applicants: THE DOW CHEMICAL COMPANY
Application year: 1985
Main classification: B01D53
IPC codes: B01D53