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US007910078B2

(12) Ulllted States Patent

(10) Patent N0.:

Tontiwachwuthikul et al.

US 7,910,078 B2

(45) Date of Patent:

(54)

METHOD OF CAPTURING CARBON
DIOXIDE FROM GAS STREAMS

C07D 211/02
C07D 211/00
C07D 295/00

(75)

Inventory Pait‘m" TOn?WachWuthikul, Regina

(2006.01)
(2006.01)
(2006.01)

(52)

us. Cl. ...... .. 423/228 423/230- 423/238- 544/170

(58)

Field of Classi?cation Search ................ .. 410/210,

(CA); Andrew G- H; Wee’ Regina (CA);
Raphael IdFm’ RegPla (CA3

_

546/184; 546/248; 564/503

Kreaflgkral ManeFmtn Regma (CA),
Gao-Jun Fan, Regma (CA);

(

410/226, 228, 229; 423/228, 230, 238; 544/170;

)

546/248, 564/503

Amornvadee VeaWab, Regina CA ;

-

Amr Henni’ Regina (CA); Adisorn
AroonWilas, Regina (CA); Amit
Chakma, Waterloo (CA)

73

( )

A

_

'

U

_

_

fR

_

_

Not1ce:

_

_

10/1967 Papadopoulos et 31.

4,101,633 A
_

_

Subject to any d1scla1mer, the term ofthis
patent is extended or adjusted under 35

U_S_C_ 154(1)) by 88 days_

7/1978 SaI‘tOrl et a1.

4,112,050 A

9/1978

4,112,051 A
4,112,052 A

9/1978 sartori er a1,
9/ 1978 Sartori et a1.

4,372,925 A

APPL NO‘, 11/843,958

5,209,914 A

SaI‘tOrl et a1.

2/1983 Cornelisse

4,705,673 A *

(21)

- ’

U.S. PATENT DOCUMENTS

3,347,621 A

)
_

-

See appl1cat1on ?le for complete search h1story.
(56)
References Cited

sslgnee' S mljetrs?ty 0 Ceima’ egma’
as a C eWan(

(*)

R

Mar. 22, 2011

*

11/1987

Capobianco et a1. ....... .. 423/226

5/1993 .Peytavy 6t ?1~ ~~~~~~~~~~~~~ ~~ 423/228

(Contmued)
(22) Filed:
(65)

Aug. 23, 2007

OTHER PUBLICATIONS

Pm" PublicatiO“ Data
US 2008/0050296 A1
Feb. 28, 2008

US. Appl. NO. 60/823,313, ?led Aug. 23, 2006, Tontiwachwuthikul
et a1~

Related US. Application Data
(60)

(51)

(Commued)

Provisional application No. 60/ 823,313, ?led on Aug.

Primary Examiner * Jerry Lorengo

23, 2006, provisional application No. 60/893,926,

Assistant Examineri JenniferA Smith

?led on Mar. 9, 2007.

(74) Attorney, Agent,
Henderson LLP

Int. Cl.
B01D 53/14

or

Firm * GoWling

La?eur

(2006.01)

(57)

C013 1 7/16
C01B 31/20
C01 C 3/00
C07C 215/00

(200601)
(2006.01)
2006 01
(
' )
(200601)

The present invention relates to a method for removing car
.
.
.
bon d1ox1de (CO2) from a gas stream. Partlcularly, the present
invention relates to a method for removing CO2 from a gas
stream by a liquid absorbent having an amino alcohol derived

(200601)
(200601)
(200601)

from 4-amino-2-butanol. In comparison to conventional
amines, the amino alcohols of the present invention have been
found to provide a higher CO2 absorption capacity and a

C0 7D 265/32

(200601)

higher cyclic capacity for CO2 removal.

C0 7D 295/08
C07D 295/10

(2006.01)
(2006.01)

B01D 53/56
B01D 53/04
B01D 53/58

ABSTRACT

24 Claims, 5 Drawing Sheets
dry (:02 +N,
Vent to

CO2

h

Flow I

nleter

meter

1

i><l

Valve

Fume hood

Flow

IE Condenser

El

m

E

m:

0

Temp
gauge

Gas disperser
Heating
soil

v

0 water
Saturation cell

solution

Reactor

Water

Bath

pp. 423/228 Peytavy et al. vol. 1994.366. Chem..700.. Energy Sources. Separation Technology... .. 26..500... Appl..S. 5. pp. pp. .348. . A..910... pp..714 A * 5. STN Search in RegistryTM database Feb. .. 2007.. 4/1998 Iijima et al. “Acid Gas Absorption by Means ofAqueous Solutions of Regenerable Phenol-Modi?ed Polyalkylenepolyamines”. 21. 1997. P. 1364-1368.. Tontiwachwuthikul et al... Eng.442 A 1/1995 Fujii et a1.. 2007. . “Formulated Solvents: New Opportunities for Energy Ef?cient Separation of Acid Gases”. J. 2007.. De Filippis.... . J.. “Equilibrium Between Carbon Dioxide and Aqueous Monoethanolamine Solutions”.. Rinaldi.885 A * 5..277. Chakma. 8.. OTHER PUBLICATIONS U. 9. 727-737. ?led Mar. STN Search in RegistryTM database Apr... “Modi?ed Polyamines for COiAbsorption. vol.926. PATENT DOCUMENTS 5..US 7..397 B1 12/2002 Yoshida et al.....165.... Chakma. 423/228 9/1994 Peytavy et al. 60/893.... Lee.161 A 4/2000 Suzuki et al. G. Res. 2000. Ind..437 A 5. pp.840 A 3/1997 Mimura et al.083 A 12/1997 Fujii et a1. et al.. Eng. 3778-3782. vol.432 A 9/2000 Iijima et al..378. 39. No. A.736. 1999.. * cited by examiner . 96/111 6. Appl.115 A 5. Separation of Acid Gases from Power Plant Flue Gas Streams by FormulatedAmines:. 5/1998 Mimura et al. et al. 423/228 5.. 11/1994 . Production Preparation and Characterization”. I. Biotechnol.. 12/2000 Rooney 6. 5.609.117..709 A * 1/1994 Peytavy et al.. 18.876. Res. vol..051.078 B2 Page 2 US. 1 1.404 A 6. 1976. 36. Birbara et al. 5. 51-62. Chem.488 A * 3/1999 6. 541-549.750. Ind. vol. Chem.

US.—l>'Q—-— Flow } Flow tr [5] Condenser T m G [ l 1 '1‘ w wet CO2 +Nz 0 A“ 0 water 2)Pm solution Saturation cell Reactor 7100" W ater Bath Temp gauge Gas disperser . Patent Mar. 22.078 B2 FIGURE 1 dryCOZ +N2 /O\ Fl A NZ A meter Vent to Fume hood l><l Valve me e CO — mg:.910. 2011 Sheet 1 015 US 7.

22. 0.1 .078 B2 FIGURE 2 Solubility of CO 2 in 3.9 CO. Patent Mar._.3 0.813om cw C 1.8 0.4 0.5 0.US. loading (mole CO z/mole amine) _ 4im f.6 0.910.7 0. 2011 Sheet 2 015 US 7.0M Solutions iA?a9t5m8xva w4268 u 0O :-i T .

2 0.078 B2 FIGURE 3 Solubility of CO2 in 3. Patent Mar.6 0. loading (mole CO2/ mole amine) 4! 1.910.0M Solutions 120 g 100 v 2 80 ~ I 2 2 6O — / P.8 1 CO. 22.4 0.‘ E / + MBA at 40 c 40 _ + MBA at 80 c a mi-------‘ Sample 8 at 40 C 9-1 —A—— Sample 8 at 80 C 20 - + Sample 9 at 40c —<>~ Sample 9 at 80 C O 0 l I I l l 0. 2011 Sheet 3 015 US 7.2 .US.

2011 Sheet 4 0f 5 US 7.US.078 B2 FIGURE 4 Cyclic Capacity of Solutions at 15 kPa CO 2 at 40-80 °C 0.7 - CO(Lalom2iodnleg) 0. Patent Mar.9 — 0.3 — 0.1 40 50 60 Temperature (°C) 70 80 90 .5 - 0. 22.910.

at 40-80 °C L2(COo/mad0oilng Temperature (°C) . Patent Mar. 2011 Sheet 5 015 US 7. 22.910.US.078 B2 FIGURE 5 Cyclic Capacity of Solutions at 15 kPa CO.

No. this route may not .052). F. they have been 30 Sartori. thus alloWing the use of highly concentrated absorbing solutions.. Iijima. pp. one of the dehyde or With formaldehyde and phenol (Rinaldi.112. 36. S. To achieve this target. Res. Production. S. etc. the pro 60 cess e?iciency of removing acid gases from liquid and gas streams can be enhanced signi?cantly as compared to the use tions. 4. Karasaki. “Separation of Acid Gases from PoWer Plant Flue Gas Streams by Formulated Amines”. Preparation and 55 advantages of using alkanolamines is that they contain at least one hydroxyl group. 60/823. pp. 3778-3782. 5. Thus. L. A. E.. intensive research efforts have been made in recent years to develop methods for recovering the CO2 50 Conventionally. Gas Puri?cation. formulated amines are broadly de?ned as amines of about 39% of greenhouse gas emissions from the projected that have been speci?cally formulated to perform a speci?c levels by 2010 or about 240 million tonnes of CO2. Chem. 6. E. Particularly. 4. 5th ed. and Filippis. A commonly used alkanolamine is mono ethanolamine.051. In addition to the sterically hindered amines described above. these hindered The production and use of fossil fuels contribute to an increase in emissions of greenhouse gases (GHGs). G. Pat. ence in their entirety. Besides its greenhouse effects. 1997). or sec ondary. decrease solvent losses and improve air and Water qualities have resulted in several modi ?cations to upgrade the process. No. C. Another advantage of using alkanolamines is that the presence of the hydroxyl group increases the solubility of the alkanolamines in aqueous solu 115) or 2-(diethylamino)-ethanol (DEAE) (Yoshida. and Mitsuoka. such as diisopropanolamine (DIPA). Houston. has thus been introduced as commercially attractive amines. 1364 1368. there needs to be a reduction Generally. for example. US.. B. the basic alkanolamine process for CO2 capture has remained unchanged but current demands to reduce energy consumption.926 ?led onAug. and Mitsuoka. such as in the enhanced oil recovery processes. large point sources of CO2 emissions such as coal-?red poWer plants. Gulf Publishing Co.. and Leder. the present invention relates to a method for removing carbon dioxide from a gas stream by an amine-containing liquid absorbent. bulk separation of CO2. FIELD OF THE INVENTION The present invention relates to a method for capturing or removing carbon dioxide from a gas stream. 313 and 60/893. G. T. Gas Puri?cation. and Nielsen.078 B2 1 2 METHOD OF CAPTURING CARBON DIOXIDE FROM GAS STREAMS Gulf Publishing Co. Vol. in particular sterically hindered amines. and Leder. Kohl.. for example. Canada is com mitted to cap greenhouse gas emissions by 6% beloW the amines are useful as promoters and as components of organic physical solvent/amine systems... Vol. cement manufacturers and the like need to 35 be monitored and stringently regulated. aqueous alkanolamine solutions have been used to absorb CO2 from loW-pressure streams such as ?ue gases emitted from poWer plants. A.. Ind. to reach a desired target for CO2 capture. Thus. (Chakma. and they have been found to require much less energy for regeneration than conventional alkanolamines. respectively. 11.. US.. Sartori. M. CO2 is also blamed for climate changes and global Warming. In 25 Canada. Vol.. US. M. as Well as in the 40 (DMAPD) (Iijima. Eng. 727-737. Separation Technology.. Furthermore. aqueous alkano lamine solutions are the most Widely used solvents for CO2 CROSS-REFERENCE TO RELATED APPLICATIONS and H2S absorption. Pat. In fact. Pat. No. G. G. 45 cess of capturing CO2 e?iciently from gas streams is dif?cult to perform.500. 1999). 2007. several options for alkanolamine-based treating solvents With vary ing compositions are available. Ind. Accordingly. some of the gas process that the presence of the amino group provides the necessary technology in an economical manner can be easily handled With formulated amines. ing problems that cannot be dealt With using the conventional 65 capture using formulated alkanolamines. 4. choice of a formulated amine or an amine mixture. Shimojo.397) or a solvent mix ture such as a mixture of modi?ed polyamines With formal emitted from industrial gas streams and for storing the recov ered CO2 Without discharging it into the atmosphere. MEA. provisional patent applications Nos. accounting for about 80% of the total green house gases emitted. A neW class of amines. 1985. Energy Sources..112.. Vol. D. and Silla. C. Res.US 7. Eng. Recently. A formulated amine may consist of a single solvent such as 3-(dimethylamino)-1. L. Pat. By judicious product during hot regeneration. Seto. C. 21. Maggi.. CO2 constitutes the largest fraction of greenhouse found to be useful in selective absorption of H2S in the pres ence of CO2 (Sartori.. E. 1990 level. From a structural standpoint. G. Yet another advantage of using alkanolamines is of traditional amines.910. S. Depending on the process requirements. alkanolamines have long been the solvent of choice for CO2 removal on a commercial scale. some companies have developed proprietary hin 20 BACKGROUND OF THE INVENTION dered amines for use in removing acid gases from liquid and gas streams. “Modi?ed Polyamines for CO2 absorption. “Acid Gas Absorption by Means of Aqueous Solutions of Regener able Phenol-Modi?ed Polyalkylenepolyamines”. Although captured CO2 can be used in a Wide variety of industrial applications. Furthermore. While it is possible to obtain a cost reduction in CO2 alkalinity to absorb CO2 (Kohl.. and Leder. M. and Reisenfeld. Tex. selective removal of H2S and/ or CO2-bulk removal. some companies have developed formulated amines. 2006 and Mar. Rinaldi. As a result.112. The most important The present application claims the bene?t under 35 USC §119(e) to US. R. and Chakma. 4th ed.. 1997. US. T... for over 70 years. and gas emissions. 51-62. No. in Which recovered CO2 can be used to produce more oil from petroleum reservoirs While part of the CO2 is simultaneously sequestered in the reservoir. R. US. 2000) in aqueous solution. 39. P. 1994. These hindered amines can be either pri mary such as 2-amino-2-methyl-1-propanol (AMP)..2-propanediol manufacturing of commodity chemicals. “Formulated Solvents: NeW Opportunities for Energy Ef? cient Separation ofAcid Gases”. A. Tex. Giavarini.736. selective separation of H2S from light hydrocarbons in the presence of CO2. K. A.. 23. Chem. pp. the contents of Which are incorporated by refer improvement is the introduction of specially formulated sol vents. Most of the proprietary solvents marketed by the major solvent manufacturers for CO2 capture are based on formulated amines. Pat. Which helps to reduce the vapor pres sures of alkanolamines and thus minimiZe the losses of the Characterization”. 9. espe cially carbon dioxide (CO2) and other pollutants such as oxides of sulfur (SOX) and oxides of nitrogen (NOX). No. the pro task. in Which recovered CO2 can be used as a potential chemical feedstock. pp. Through rati?cation of the Kyoto protocol. 050. For many years. Mimura... Houston. re?neries.

these terms refer to processes that provide any measurable reduction in the levels of CO2 in a gas 60 stream. I. The present invention also includes CO2 absorbers. As used herein. and 80° C. it has been shoWn that there is a removing CO2 from a gas stream comprising contacting the 40 gas stream With a liquid absorbent comprising an amino alco hol of the formula I: absorbent as de?ned above. Thus. E. 2 shoWs a graph illustrating the solubility of CO2 in MEA. “capturing”. 4-(diethylamino)-2-butanol. Other features and advantages of the present invention Will become apparent from the folloWing detailed description. including the ease of stripping of CO2 from the absorbent. D. pp. A. the amino alcohol of formula I is selected from 4-(diethylamino)-2 4-isopropylamino-2-butanol and 4-(ethyl-methyl-amino)-2 structure-performance relationship betWeen amino alcohols and CO2 capturing. than the conventionally used amine. When unsatur . The term “alkyl” includes straight and branched chain saturated and unsaturated alkyl groups. 4-isopropylamino-2-bu cess. Desirable characteristics of these amino alcohols include their capacity to absorb a large amount of CO2 per butanol. FIG. 1976). There is a need for developing an ef?cient and cost effec tive method for capturing or removing CO2 from gas streams. that the detailed description OH R1 R2/ 50 and the speci?c examples While indicating preferred embodi ments of the invention are given by Way of illustration only. In an embodiment of the present invention.078 B2 4 3 necessarily present the most optimum scenario for the pro FIG. and 80° C. “removal” and “remov ing” as they apply to CO2 in gas streams are used interchange ably herein. 4-propylamino-2-butanol and 4-(ethyl-methyl amino)-2-butanol at 40° C. 1 shoWs a schematic diagram of the apparatus for Appl. and 80° C. 4-(di SUMMARY OF THE INVENTION ethylamino)-2-butanol... novel amino alco hols for promoting CO2 capture can be developed. It has been shoWn that certain amino 2-butanol com absorbent and thereby.. 4-(piperidino)-2-butanol. 60° C. hoWever. R1 and R2 in the amino alcohol 65 of the formula I are independently selected from H and Cl_4alkyl. or BRIEF DESCRIPTION OF THE DRAWINGS The invention Will noW be described in relation to the (I) 45 embodiment of the invention.US 7. monoethanolamine.9l0. The terms “capture”. draWings in Which: evaluating the performance of amino alcohols on CO2 absorp tion capacity. Chem. As shoWn hereinafter in the experimental examples. absorbent and thereby. Further. 541-549. FIG. and 80° C. 5 shoWs a graph illustrating the cyclic capacity and the effect of temperature on the solubility of CO2 in MEA.. the present invention includes a method for butanol. 35 tion columns and absorption toWers comprising a liquid unit mole and to permit the separation of CO2 and the recov ery of the absorbing solution With a loW amount of heat energy. MEA. 26. removal of CO2 from the gas stream. The data obtained from the speciation and kinetic studies on the interaction of the amino alcohols With CO2 as Well as from the evaluation of the performance of the amino alcohols in liquid absorbents provide a basis for struc R1 and R2 are independently selected from H and Cl_loalkyl. absorp tural re?nement and optimization of synthetic amino alco hols. 4-propylamino-2-butanol. R1 and R2 are linked to form a 5 to l2-membered carbocyclic ring system under conditions for absorption of CO2 by the 55 It is an embodiment of the invention that the amino alco hols of the formula I include those in which R1 and R2 are independently selected from H and Cl_6alkyl. 60° C. also referred to as CO2 solubility (Lee. It has been shoWn that the placement of functional groups Within the amino alcohols affects the performance of the amino alcohols in CO2 capturing. F. It should be understood. In a further embodiment the liquid absorbent further com prises a solvent. the present invention includes a method for removing CO2 from a gas stream comprising contacting the 4-(piperidino)-2-butanol at 40° C. 3 shoWs a graph illustrating the solubility of CO2 in MEA. 4-pro pylamino-2-butanol and 4-(ethyl-methyl-amino)-2-butanol at 40° C. J.. Otto. Biotechnol. 4-isopropylamino-2-butanol and It has been found that certain amino 2-butanol compounds are highly effective reagents for removing carbon dioxide (CO2) from gas streams. Accordingly. gas stream With a liquid absorbent comprising an amino alco hol of the formula I: OH (I) DETAILED DESCRIPTION OF THE INVENTION 20 R1 R2/ 25 wherein or R1 and R2 are linked to form a 5 to l2-membered carbocyclic 30 pounds are highly effective reagents for capturing CO2 from gas streams. the tanol and 4-(piperidino)-2-butanol at 40° C. 4 shoWs a graph illustrating the cyclic capacity and the effect of temperature on the solubility of CO2 in MEA. the liquid absorbents comprising the amino alcohol of the for mula I as de?ned above provide far superior CO2 absorption and cyclic capacity. ring system. removal of CO2 from the gas stream. “Equilibrium betWeen Carbon Dioxide and Aqueous Monoethanolamine Solutions”. under conditions for absorption of CO2 by the It has been demonstrated that by Way of rational molecular design and placement of functional groups. since the amines Which are required for formu lation are typically those that are commercially available. and Mather. Accordingly. scope for optimization is thereby limiting to existing amines. In a further FIG. FIG. wherein R1 and R2 are independently selected from H and C 1_ l0alkyl. Vol. J. since various changes and modi?cations Within the spirit and scope of the invention Will become apparent to those skilled in the art from this detailed description.

In a further embodiment of the invention. absorption column or absorption toWer comprising a liquid absorbent as de?ned hereinabove. an amine aging inhibitor and other additives knoWn in the art may be included in the 60 NH J liquid absorbent. components. methanol or ethanol. are intended to be open ended terms that specify the presence of desired concentration. The folloWing non-limiting examples are illustrative of the invention: EXPERIMENTAL EXAMPLES It is an embodiment of the present invention that the con ditions for absorption of CO2 by the absorbent and thereby. In addition to the above In a further embodiment of the invention. a particulate ?lter and a carbon bed puri?er. the method further comprises releasing the absorbed CO2 from the absorbent. The method of the present invention can be carried out in any conventional equipments for the removal of CO2 from gas streams and the detailed procedures are Well knoWn to those skilled in the art. groups. In an embodi ment of the invention. Depending on the siZe of the equip ment. more speci?cally about 9% to about 15% by volume CO2. components. integers. plate or spray toWers. In yet another embodiment of the invention. and at a pressure ofabout1 to about 120 kPa. Although certain speci?c conditions may favour one type of absorber over another. the solvent is Water. soluble in the solvent. 0. gas composition. the The term “solubilize” as used herein means that. Such peripheral equipment may include. the ring may con indicated conventional absorbers. The present invention also includes a C02 absorber. Examples of suitable solvents include Water. suitably CO2 gas as Would be knoW to those skilled in the art. elements. The method according to the present inven tion can be conveniently carried out in any suitable absorbers or absorption columns/toWers. the amino alcohol is 4-propylamino-2-butanol. The 25 rying out the method of the present invention Will be knoWn to a person skilled in the art. alcohol and combinations thereof. terms of degree such as “substantially”. Solvents that are suitable for use in the method of the absorbers. ment-plate scrubbers and turbulent contact scrubbers. suitably deioniZed Water. The gas stream may be any gaseous feed for Which it is desirable to remove CO2. elements. the gas stream comprises from about 1% to about 100% by volume CO2. The term “absorbent” as used herein means a liquid in Which CO2 is captured or removed from a gas stream. the gaseous feed is combustion exhaust gas from. a treated gas coalescor. features. these absorbers are inter changeable to a considerable extent. ?ue gas streams of coal ?red poWer plants and other poWer plants. strippers and peripheral equipment useful for car alcohol is 4-(diethylamino)-2-butanol. total pressure and the speci?cation of the It is an embodiment that the liquid absorbent comprises a solvent. a corrosion inhibitor. the cooling bath Was . 65 Methyl vinyl ketone (65 mL. When unsaturated. and/or steps. removal of CO2 from the gas stream com prise contacting the gas stream With the liquid absorbent at a 1) temperature of about 40° C. speci?cally. It is a more particular embodiment of the present inven tion that the conditions for absorption of CO2 by the absor 55 bent and thereby. In another embodiment of the present invention. “including”. specialiZed absorption tain 1 to 3 double bonds suitably 1-2 double bonds. a solvent ?ash tank. In a particular embodiment of the present invention. 0. In an embodiment.078 B2 6 5 ated. 30 In understanding the scope of the present disclosure. but do not exclude the presence of other unstated 35 meanings such as the terms. about 5% to about 30% by volume CO2. the amino alcohol is substantially the stated features. absorbent. the amino toWers are also available to meet speci?c process require ments. the alkyl group may contain 1 to 3 double bonds suitably 1-2 double bonds. integers and/or steps. By “car bocyclic ring system” it is meant a saturated or unsaturated carbon-containing ring. In an embodiment of the present invention. re?neries and cement manufacturers. to about 80° C. The solvent circulation rate Will depend on the amine concentration. In an embodiment. The concentration of amino alcohol Will generally be in the range of about 1 mol/L to about 10 mol/L. The foregoing also applies to Words having similar “about” and “approximately” as used herein mean a reason 40 able amount of deviation of the modi?ed term such that the end result is not signi?cantly changed. the amino alcohol is 4-(piperidino)-2-butanol. groups. at the term “comprising” and its derivatives. The absorbers suitable for use With the method of the present invention may also contain other peripheral equipment Which may enhance the method of the invention. the amino alcohol is 4-isopropylamino-2-butanol. the inlet gas ?oW rate Will vary. After addition Was completed in 1 h. Finally. the amino present invention include those that solubiliZe the amino alco hol and that act as an absorbent for CO2. suitably about 3 mol/L to 5 mol/L. the gas stream further comprises oxygen. such as packed. an inlet gas separator. These terms of degree should be construed as including a deviation of at least 15% of the modi?ed term if this deviation Would not negate the 45 meaning of the Word it modi?es. to about 90° C. the CO2 is released by heating the absorbent.US 7. for example. the solvent is an alcohol.68 mol). In another embodiment of the invention. “having” and their derivatives. Suitably the alkyl group is saturated It is another embodiment of the invention that the amino alcohols of the formula I include those in which R1 and R2 are linked to form a 5 to 10-membered carbocyclic ring system.71 mol) Was added drop optionally collecting the CO2 and optionally regenerating the Wise to ice-Water cold neat diethylamine (70 mL. These specialiZed absorption toWers include impinge alcohol is 4-(ethyl-methyl-amino)-2-butanol. 0 OH N /\N/\)\ Me 2) NaBH4 ) In an embodiment of the invention.910. removal of CO2 from the gas stream comprise contacting the Example 1 50 Synthesis of the amino alcohol 4 -(diethylamino) -2 -butanol (1) gas stream With the liquid absorbent at a temperature of about 25° C. for example. Suitably the ring is saturated. the gas ?oW rate. as used herein. 20 In still another embodiment of the invention. In another embodiment of the invention. R1 and R2 are linked to form a 5 or 6-membered carbocyclic ring system. Optionally. but not limited to. and at a pressure of about 15 to about 110 kPa.

2.75 3. 2966. for another 1 hour and at room temperature for 3 hours. 1454 cm_l.15-1. parafonnaldehyde (33 g.). the ketone (90 g.58 (m.4 (CH2).54-2. The color of the solution turned from green dark into Wine red. 3H.20-1. 1. 1707.16 (m. 1H). The stirring Was continued at room temperature for 3 h. 4H.69 (m.1 HZ. 62. J:7.80 1. 1. 1H).50 (m. 2. 1H). 2H). 13C NMR (CDCI3. 1:38. 500 MHZ) 53.2 (CH). 2.62 (m. 6H).54 (m. 2H). 500 MHZ) 6 2.45-2. 13. 3. ?ltered and concentrated under reduced pressure. IR (neat) 3383 (br./50-55 mmHg. 1:62 HZ. and the organic layers Were dried With Na2SO4. 2.70 (m. 20 Example 2 25 Expansion of the protocol in Example 1 to 4-(piperidino) 2-butanol (4) Was accomplished by simply changing the diethyl amine to piperidine. 0. 15.10 (d. it Was ?ltered through a short pad of CeliteTM and Washed With diethyl ether. 6. The formed solid Was ?ltered off through Buchuel funnel.56 (m.92 (m.52 (dt. 6H). 1H NMR. The solvent Was removed under reduced pressure.910. 66%): bp 110° C. 0.18 (s. 3. 1H NMR (CDCI3. The combined organic layers Were dried (Na2SO4). After stirring continuously at 0° C.48-1. 3H). 1:35. CDCl3): 0. Sodium boron hydride (26 g.8 (CH2). 1H). 6H). The remaining material Was cooled in an ice Water bath and treated With an Example 3 Synthesis of the amino alcohol aqueous solution of 40% sodium hydroxide (50 mL).89 (tq.US 7. 1.15 mol). 2.15-2.04 (d. 1.00 (t.1. The organic layer Was sepa rated and the aqueous layer Was extracted With dichlo Example 4 Synthesis of the amino alcohol 4-(piperidino)-2-butanol (4) 10 OH romethane (><3). 125 MHZ) 6 214. A total of four batches of bench reaction products Were com bined and fractionally distilled using a viqreux column to afford 4-(diethylamino)-2-butanol (260 g. and Washed With dichloromethane. the .16 (d.10-2. 1.8 g.85 (d.60-3. 1H).31 (sex. 1465 cm_l.0 HZ. Synthesis of the amino alcohol Example 5 4-(morpholino)-2-butanol (2)4Comparative Example Synthesis of the amino alcohol 1 -dimethylamino-2-methyl-3 -pentanol (5) 30 Me 2) NaBH4 0y Expansion of the protocol in Example 1 to 4-(morpholino) 2-butanol (2) Was accomplished by simply changing the diethyl amine to morpholine.90 (d. ice Water. 2.80 (m. 1H). 7. 14. 34. J:7.85-4. 6 (200 MHZ. 1:8 HZ). 1H). 1 H). 1:62 HZ).58-2./52 mmHg.2 HZ. 1. The mixture Was then thoroughly extracted With diethyl ether (x2). 2766.0 (CH3).60 (m.78 (m. IR 60 (neat) 2966.94 (m. 44. It Was diluted With 30 mL of methanol and then cooled in 3H. 2H). 1H NMR. 2.00 (m.2 (C).19 (s. 1H).45 (m. 6 (200 MHZ.078 B2 7 8 removed and the solution Was stirred at room temperature for 3 h.10 mol) and concentrated hydrochloride acid (1 mL) in 45 anhydrous ethanol (90 mL) Was heated at re?ux for 1 day.2 HZ.70-2. ?ltered and evaporated. J:2.36 (br s. 3H). fol loWed by solid sodium hydroxide (30 g). at Which time 30 mL of saturated sodium chloride Was added and the mixture Was stirred for additional 1 h. 2. 5.63 mol) Was diluted With methanol (30 mL) and cooled in an ice Water bath.44-2. 45. 3H). The mixture Was 50 stirred for 30 minutes.80 (m. IR vmax: 3075-3600 cm_l. 1H).4 HZ. 0. 1H) (NH and OH not observed).35-1.39 (dq. IR vmax: 3075-3600 cm_l.0 mol). 3. 2. 1H NMR (CDCI3. 6H). dimethylamine hydrochloride (93.05-2.68 mol) Was added slowly.22-5. CDCl3): 0. 3H). 1. 2. Subsequently. 72%) as a colorless oil: bp 1050 C. 6 (200 MHZ. 2H). 2942. The remaining material Was puri?ed by frac 4-(isopropylamino)-2-butanol (3) 55 tional distillation under vacuum to give the amino ketone (102.76 mol) over a period of 1 hour. 3H.42 (t. CDCl3): 1. 4H). Cooling Was removed after the addition Was com pleted in 1 h.3 (CH3) Expansion of the protocol in Example 1 to 4-(isopropy lamino)-2-butanol (3) Was accomplished by simply changing the diethyl amine to isopropylamine. 1H NMR. 2.8 g. 1:46 HZ). 0.41-2. 1:6 HZ). 3H). 2 H). 1. IR vmax: 3075-3600 cm_l. 2. The solu tion Was sloWly treated With NaBH4 (29 g. 1. 1. 8H). Comparative Example 35 40 A solution of 3-pentanone (87 g. 3.6 (CH3).38 (m. 65 Subsequently. 1.

42-3.1.4 (CH). 3. 500 MHZ) 6 2.6 (CH2).68 (dd. NaBH4 (35 g. 4 -dimethyl -3 -pentanol (7)4Comparative Example 20 Example 6 Synthesis of the amino alcohol 1 -diethylamino-2 -methyl -3 -pentanol 1.29 mol) mol) in ethanol (70 mL). The mixture Was then then thoroughly extracted With diethyl ether (x3). 1461.10-2. folloWed by solid sodium hydroxide until the pH the pH Was >10.6 (CH3). 0.28-3.22-1. The reaction mixture Was stirred for 30 minutes.58 (m. 1 H). 87%) as a colorless oil: bp 90° C. The remaining material Was puri?ed by frac 65 extracted With diethyl ether (x3) and the organic extracts Were dried With Na2SO4.70 (m.1 (CH2). l3C NMR(CDCl3.75 (dd.28 (dd. 34. 1:23. 973 cm_l. The remaining 5 material Was puri?ed by fractional distillation to give the amino alcohol 1-dimethylamino-2-methyl-3-pentanol (60 g. 1H).38-3.40 (CH3). for another 2 hours and at room temperature for 2 hours. 15. 2.2 (CH2). 77. 0.14 (s. 1. 24. 57. 2./15 mmHg. 45. diethylamine hydrochloride (63 g. NaBH4 Expansion of the protocol in Example 5 to 1-dimethy A suspension of 3-pentanone (43 g. 7H).02 (dd. 5H). The solid Was cooled in an ice Water bath and treated With an aqueous solution of 30% sodium became solidi?ed. 7. 6H). Example 7 Synthesis of the amino alcohol 1 -dimethylamino-4.3 (CH2).3 (CH2).1366 cm_l. 1. 0. 14. 24.20 (s.3 (CH3). 9H). 44. 3H). 1H). 3213. NaBH4 (12 g. 64%) as a colorless oil: bp 105° reaction Was quenched by the addition of saturated sodium chloride (30 mL).00-2. 1H).04 (d.58 mol).0 g. IR (neat) 3413. dimethylamine hydrochlo ride (46. 2H). 45. The mixture Was Was >10. 2. 0. 2.9 HZ. 3H).48 (m. 2931.910. 3H). 77.9 (CH). 2. 1H). MeZNH-HCI 25 2. 13C NMR (CDCI3.1 (CH3). 7.34 (m. 13 C NMR (CDCl3. 3H).26-3.1.3 (CH3).55 mol) and acetic acid (0. 43. paraformaldehyde (16. 125 MHZ) (tWo diastereomers) 6 80. 34. 1:73 HZ. 1H NMR (CDCI3. 8.55 mol) 40 and acetic acid (0.18 (s. 3H). The reaction mixture Was stirred for 30 minutes.45 (m. The mixture Was thoroughly over 30 minutes. 1H). 1H NMR (CDCI3. Then. The solid Was cooled in an ice Water bath hydroxide (30 mL). 2955.5 (CH). 1461 cm“. 0. 3H).0 (CH3).91 (dt. 1:75 HZ.44 (m. 125 MHZ) (tWo diastereomers) 6 79. ?ltered and concen trated. 1.7 (CH). 1378. 1. 1. The remaining material Was puri?ed by fractional distillation under vacuum to give the amino ketone (68.1 HZ. the reaction Was quenched by the addition of Water. 7. The mixture Was thoroughly extracted With diethyl ether (x3) and the organic extracts Were dried With Na2SO4. it Was ?ltered through a short pad of CeliteTM and Washed With diethyl ether.74 (m. 500 MHZ) 62. 59%) as a colorless oil: bp 1000 C. 1:116 HZ.1 (C). 11.0 HZ.9 (CH3).5 g. and the thoroughly extracted With diethyl ether (x3).9 (CH). 2. 67. 1:67 HZ. 1.80-0.0 g. 28. 500 MHZ) (tWo diastere omers) 6 3. 0.9 (C).0 (CH3). 3 H). 2.24-1. 1. C. 2. 47. 3H). 9. 1:60. After stirring continuously at 0° C. 0.62 (m. The reaction mixture Was stirred overnight. 1:65 HZ. The ?ltrate Was dried With NaZSO4 and NaCl. 0. 50 layers Were Washed With brine. 2 H).2 (CH2).7 (CH3). 1 H). 34. 2H). 14. 0. 0. 63.46 (m. 125 MHZ) 6215.97 (t. 27. 34. The mixture Was ?ltered through a short pad of CeliteTM and Washed With diethyl ether. The solvent Was removed heated at re?ux for 1 day.12 (m.125 MHZ) 6 214. dried With Na2SO4. 11. The mixture Was ?ltered through a short pad of CeliteTM and Washed With diethyl ether.58 mol). 11. 1:19.2 (CH3). 10. 35.8 HZ. 15. ?ltered and concentrated.3 HZ.63-1.52-1. it Was ?ltered through a short pad of CeliteTM and Washed With diethyl ether. paraformaldehyde (16. 1H).0 g.21 (s. 0.38-2. 15. 12.8 (CH3). 2.06 (m. J:7. 0. The remaining material Was puri?ed by fractional distillation to give the .26 (s. EtZNH-HCI 2.5 g.58 (t. IR (neat) 3408 (br).37 (m.1460. J:2. 1.5 mL) in anhydrous ethanol (50 lamino-4.88 (m.90-1.0 (CH).4 (CH3). 1H NMR (CDCI3.8 (CH2). 0. 3H).7 (CH2).93 mol) Was sloWly in ethanol (50 mL).48 (m./18 mmHg.49 (t.4-dimethyl-3-pentanol (7) Was accomplished by simply changing the 3-pentanone to pinacolone.24-2. 0.8 HZ.37-1. 53. J:2. J:12. After stirring continuously at 0° C.34 (m.5 HZ. 1H). 1:20. 1H). for another 1 hour and at room temperature for 2 hours.32 (m.2 (CH2).18 (m. 7. 3. 1H). The solvent Was removed under under reduced pressure.9 g. 6. 1H NMR (CDCI3.3 (CH2).96 (dt. 1H). 6H).8 (CH2). A suspen sion of pinacolone (50 g. 2. 66%) as a colorless oil: bp 125° C. ?ltered and concentrated. The remaining material Was puri?ed by fractional distillation under vacuum to give the amino ketone (50. 13C NMR (CDCl3.32 mol) Was added sloWly added over 1 hour.84 To an ice-Water cold solution of the ketone (50 g. 3H). 1.82 (m.9 (CH2). 1:75 HZ.70 (d. Then.60-1. 500 MHZ) (tWo diastere omers) 6 3.15 (dt. 6. 1H).0 (CH3). cnzo. 1.34-1. ?ltered and evaporated.US 7.19 (s. 1H). 45. the reaction Was quenched by the addition of saturated sodium chloride (30 mL). Then. 6. ?ltered and concentrated. 57. and the organic organic layers Were dried With Na2SO4.2 (C). 3H). IR (neat) 1713.65-2. IR (neat) 55 2966. 2.1 (CH). 1H). cnzo. NaBH4 (6)iComparative Example OH 30 1. folloWed by solid sodium hydroxide until and treated With an aqueous solution of 30% sodium hydrox reduced pressure during Which time the reaction mixture ide (30 mL).078 B2 10 tional distillation to give the amino alcohol 1-diethylamino 2-methyl-3-pentanol (32.76 (d.73 (m. 26. 2.7 (CH3).5 mL) in anhydrous ethanol (50 mL) Was mL) Was heated at re?ux for 1 day.56-2. 34.74-2. 0. 1190.70 (t. 2H). 2. 1:20. 11.1 (CH2). 1.5 (CH3).4 (CH). 0. 47.1 (CH3).0 (CH). 1H). it Was ?ltered through a short pad of CeliteTM and Washed With diethyl ether. 1H).42 (t.5 mol). 0.60 (m. 0.3 HZ. 2.7 (CH2). 1463 cm_l.5 mol). 1H).9 (CH2).70 (m. 6H). 62. 1H). 0. 3H). 18H).5 HZ.53-1.1701.9 (CH3). 2./98 mmHg. 1. 47./15 mmHg. To an ice-Water cold solution of the ketone (132 g.

57 (m. Nitrogen and CO2 (obtained from Praxair lnc. 1976). 3H). neat amine — 2. IR (neat) 3260 (br).7 (CH3). NaBH4. 500 MHZ) 6 3. After the 35 mol) Was added portionWise. 1:35.3 (C).98 (t. 1. 14.09 (d.38 (dd.9 (CH2).5 HZ. 1H). 12.4 (CH3). MeOH 65 solutions of these amines/amino alcohols Were prepared using deioniZed Water to achieve a concentration of 3 mol/L of solution. 0. 23.5 HZ./12 mmHg. stability by using a temperature controller Example 9 (Cole-Parmer Polystat Immersion Circulators.38-1. It Was then diluted With 50 mL of methanol and cooled in an ice-Water bath. Synthesis of the amino alcohol 4-propylamino-2-butanol (8) 0. methyl vinyl ketone addition Was completed in 1 hour. 1:29. 51.9 (CH).40 (dt. 12. 1:65 HZ.60 (m. folloWed by another 30 minutes of stirring. Both the cell and the reactor Were immersed in a constant temperature Water bath (Cole 55 Par'mer) maintained at indicated temperatures With an accu racy of :0. 2. 36. 1H). 1. 1:25. 55%) as a colorless oil: bp 120° C. 34. Chem.125 HZ. 10 Example 8 Expansion of the protocol in Example 1 to 4-(ethyl-me thyl-amino)-2-butanol (9) Was accomplished by simply changing the diethyl amine to N-ethylmethylamine. The temperature in the system Was measured by a thermister (Cole-Parmer With an accuracy of :0. pp.35-1.5 HZ.. 1:40. The remaining material Was puri?ed by fractional distillation to give the Example 10 Evaluation of the Performance of Amino Alcohols (1) IO (9) 45 amino alcohol 4-propylamino-2-butanol (35. After the addition Was com pleted in 2 hours.7 g.US 7.01° C. 3H). 2. 1. 1H). 4 H). and at room temperature for 2 hours.5 HZ.2 HZ. The reaction mixture Was continuously stirred at room temperature for 3 hours. 1:75 HZ. Sodium borohydride (45 g.). 125 MHZ) 6 81.91 (dtd. 1125 cm_l. l3CNMR(CDCl3.).85 (s. 34.0 HZ.22 (s. To an ice-Water cold solution of neat N-ethylmethylamine (50 g. Aqueous l. Biotechnol.40-2.42 (dt.15 (s. 0.5.03° C.93 mol) Was added. respectively. 1H). IR (neat) 3282 (br. 2. 25.85 (t. 2.85 mol). 500 MHZ) 6 3. 1. 0. 1. MeOH hydride (18 g. 1. the ice-Water bath Was removed. 12. 2. 125 MHZ) 669. 1:40. 1H). 1:65 HZ. J.1 (CH2). The concentrated solution Was diluted With dichloromethane. 2954. 2962. ?ltered and concentrated under reduced pressure. dried With Na2SO4. 1H). 1:70 HZ. The centrated solution Was diluted With diethyl ether. “Equilibrium BetWeen Carbon Dioxide and Aqueous Monoethanolamine Solutions”. 10. 1462. Which oper Synthesis of the amino alcohol ates Within the temperature range of —20 to 200° C. 1462.4 (CH). 3H). 12. 1H). 6. 1. The remaining material Was puri?ed by fractional distillation to give the amino alcohol 4-(ethyl-methyl-amino)-2-butanol (71. 1. 6. 3H). The ?ltrate Was concentrated under reduced pressure. NaBH4.69 (ddd.).0 HZ.0 HZ.910. 1H). 2.7 (CH2). N-ethylmethylamine 2. 57. 44. 50 A. The ?ltrate Was concentrated under reduced pressure. at Which time 30 mL of saturated sodium chloride Was added. 1H). cooling Was removed and the reaction mixture Was stirred at room temperature for 3 hours.4 (CH2).9 (CH). 1H).. 6H).3 (CH2). 1H NMR (CDCl3. at Which time 20 mL of satu rated sodium chloride Was added. -continued 2. 1H). J:7. 51.48 (m.42 (m. 0. 41. 1125 cm_l. 1H). 500 MHZ) 6 3. The con Expansion of the protocol in Example 1 to 4-propylamino 2-butanol (8) Was accomplished by simply changing the of neat propylamine (82 mL. 11.4 (CH3). 1H).44 (m. 2. 26./12 mmHg.0 mol).25 (dq. and Mather.46-1.0.36-1. IR (neat) 3282 (br.0.85 addition Was completed. 23. 125 MHZ) 6 69. 1H). Appl. 2. the ice-Water bath Was removed. the experimental apparatus con sists of a saturation cell (to control the concentration of solu tion) connected to a reactor (Lee. Otto.).54 (m.0 (CH2). 59.2 (CH2). 4-(ethyl-methyl-amino)-2-butanol (9) (ii) Materials: The solvents evaluated Were MEA at 99+% purity (ob tained from Fisher scienti?c) and the amino alcohols samples v1 (1) to (9) described in Examples 1 to 9.1 (CH2).63 (dt. 49. 12. 9H). 1H). 12. 1:25. J:2.5 HZ. 12.06 (d.50-2. F. folloWed by another 30 minutes of stirring. 5. 1H NMR (CDCI3. To an ice-Water cold solution 30 Was added dropWise (82 mL. E. 1H NMR (CDCI3.46-1.7 (CH2). 2962. freshly distilled methyl vinyl ketone (76 mL. 13C NMR (CDCI3. J. 13C NMR (CDCI3. 1:45. 1460 cm“. D. 1H). ?ltered and concentrated under reduced pressure. The reac tion mixture Was continuously stirred at room temperature for 3 hours. 2.46 mol) Was added portionWise. 1.0./15 mmHg.4-dimethyl-3-pentanol (87 g. 15. 2. 65%): bp 810 C. 27%): bp (i) Apparatus: 1050 C. 2.59 (ddd.2 short pad of CeliteTM and Washed With dichloromethane.0 mol) over 2 hours. 26. 3H).0 HZ. 23.0. 0.078 B2 11 12 amino alcohol 1-dimethylamino-4.55 (m. After the 20 MN/V H 8 25 diethyl amine to propylamine. 541-549.9 (CH3). dried With Na2SO4. the reaction mixture Was stirred at the same temperature for 1 hour.) . solid formed Was ?ltered through a short pad of CeliteTM and Washed With dichloromethane. 110. 1H). 1.4.8 g. 1:70. 1:25. Sodium boron O l. 1.8 (CH3). 12.5 (CH3).45 (ddd.0 (CH3) Vol. As can be seen in FIG. The solid formed Was ?ltered through a 40 (tq. It Was then diluted With 50 mL of methanol and cooled in an ice-Water bath. After the addition Was completed in 1 hour. 1.92 (ddd. 12.

Association of Of?cial Analytical Chemists (AOAC) Methods.) TABLE 2 Solubilities of MBA and the synthetic amino alcohols (1) to (9) at conditions close to the absorption and stripping columns. and 60° C. The presence of CO2 Was evaluated many times.. Then.15%/° C. CO2 loading at 25° C. 2. 12”’ Edition. (4). The sample Was ?rst WithdraWn from the cell using a 2 or 3 mL pipette. 100 kPa CO2 at 80° C. illustrating the ence to What are presently considered to be the preferred examples. (8)21I1d(9) limited to the disclosed examples. the de?nition provided herein is to serve as the de?nition for the term. As shoWn in Table 3. (3). 5. As shoWn in Table 2. 60 and 80 Temperature (° C. the results shoW a cyclic capacity that is by far greater than that for aqueous MEA. and all of the CO2 evolved Was collected in a gas burette for measurement.. From the experimental results. lated. W. Furthermore. ranging from 33 to 72% higher. 45 Solution Concentration (kmol/m3) Partial Pressure ofCO2 (kPa) 3 15 and 100 40. and 14 to 43% higher for synthetic amino alcohol (9). Was calcu (iv) Results and Discussions The experimental results of the synthetic amino alcohols Despite this anomaly. it can be seen tWo consecutive readings shoW only a slight difference from Table 2 and FIG. 35 (1) to (9) as compared to MEA at various conditions are shoWn in Tables 2 and 3. 2 to 5.97 0.9% Were also used in the evaluation. This shoWs a higher cyclic capacity of the synthetic amino alcohols as compared With MEA and indicates an advantage from the vieWpoint of energy ef?ciency in the regeneration of the amines. and 15 kPa and 100 kPa compared With MEA are 30 to 39% higher for synthetic amino alcohol (1).97 0. 33 to 42% higher for synthetic amino alcohol (3).609 0. (mole Concentration of CO2/mole Sample Condition Sample (mole/L) amine) MBA 15 kPa CO2 at 40° C.490 HO/\/ NH2 100 kPa CO2 at 600 C. George temperatures for synthetic amino alcohol (1). the liquid sample Was taken to analyZe for CO2 loading.693 15 kPa coi at 60° c. (5) and (7).05 difference).078 B2 13 14 With purities of 99. 2. both in terms of CO2 absorption capacity and the ease of regenera tion. (3).379 0.586 Comment .0 N HCl acid Was added to the 2-3 mL sample.910. A gas mixture saturated With moisture content in the tion capacity than MEA (ranging from —3% to 5% and —70 to —40% loWer for synthetic amino alcohols (8) and (9). the amino alcohols of Examples 2. the synthetic amino alcohols (1). (4). at a higher tem perature 80° C. the absorption capacity differ TABLE 1 ences at 40° C. To the contrary. The Wetted gas mixture Was then bubbled through the amine test solution and eventually exhausted. 15 kPa CO2 at 80° C. the system Was ture. 1) and the gases Were introduced to the process through ?oW meters (Cole Parrner :0. All the materials Were used Without further puri?cation. excess 1.97 3.99 0. (4). it is to be understood that the invention is not by using the procedure outlined by the Association of Of?cial Analytical Chemists (HorWitZ. (4). (8) and (9) is the high absorption capacity that arises from the unique rela tive positions of the amino and hydroxyl groups in the mol one or tWo hours until the CO2 loading Was constant or until ecule. Com pared With conventional amines. 1975). (8) and (9) provide a much higher CO2 absorption capacity than unexpected and exceptional properties of amino alcohols (1). While the present invention has been described With refer Banta. 2 that there is a phase separation at high (210. the synthetic amino alcohols (1) and (4) have Experimental operating conditions for solubility study. synthetic amino alcohol (3) has a higher CO2 absorption capacity than MEA at this higher tempera saturation cell Was used to maintain the solution concentra tion. as Well as in FIGS. 40 All publications. the ratio of CO2 to amino alcohol in the liquid phase. 10 to 23% higher for synthetic amino alcohol (8). 6 and 7 did not function to capture CO2. HoWever. as given in Table 2.US 7. one of the most important kept in operation for 8-10 hours. The amount 25 of CO2 in g-mol that Was evolved Was measured. 20 The CO2 loading for each liquid sample Was determined as described hereinbeloW. 100 kPa CO at 40° C. a slightly higher CO2 absorption capacity than MEA (ranging (iii) General Procedure: alcohols (1) and (4). To ensure that equilibrium Was reached. The operating conditions for this evalu ation are shoWn in Table 1. the inven tion is intended to cover various modi?cations and equivalent arrangements included Within the spirit and scope of the appended claims. 21 to 37% higher for synthetic amino alcohol (4). for Which the sample Was taken every features of synthetic amino alcohols (1). 2. The sample solution concentration and the CO2 loading Were determined 30 (3). Then. HoWever. full scale accuracy) at the desired partial pressure.97 2.00 2. patents and patent applications are herein incorporated by reference in their entirety to the same extent as if each individual publication. The process Was operated under atmospheric pressure.621 0. patent or patent application Was speci?cally and individually indicated to be incorporated by reference in its entirety. Where a term in the present appli cation is found to be de?ned differently in a document incor porated herein by reference. This is a desired characteristic. From these results. The gas Was sent to the condenser before being vented to the fume hood. MEA. respectively) Whereas the synthetic amino alcohols (8) and (9) have a slightly loWer CO2 absorp from 15 to 24% and 25 to 31% higher for synthetic amino The solvent Was fed into the system (FIG. it can be seen that at loW temperatures. respec tively).

99 0.078 B2 15 16 TABLE 2-c0ntinued Solubilities of MBA and the synthetic amino alcohols (1) to (9) at conditions close to the absorption and stripping columns. 15 kPa CO2 at 80° C.84 0.008 4.23 0.497 (upper part) 4.97 2.437 (upper part) 4.021 (loWer part) 2.919 temperature N 15 kPa CO2 100 kPa CO2 15 kPa CO2 100 kPa CO2 3.593 (upper part) 4. 15 kPa CO2 at 55° C.698 N/A 0.67 0.03 0.747 (upper part) 4.50 0.807 (upper part) 5.07 0. (mole Sample Concentration of COZ/mole Sample (mole/L) amine) Comment 15 kPa CO2 at 40° C.19 0. 100 kPa CO2 at 80° C.80 0.826 Phase separation 100 kPa CO2 at 40° C. 3. (loWer part) 2. No absorption (\N V H 15 kPa CO2 at 40° C.72 0.016 Condition —\ N J OH 15 kPa CO2 at 80° C.724 (upper part) 5.73 0.90 0.000 Phase Separation Does not dissolve in Water Phase separation at high temperature No absorption .US 7.650 0.80 0.72 0.00 0.398 0.962 at high 15 kPa CO2 at 60° C.03 2.07 0.00 N/A 2.37 (upper part) 4.040 (loWer part) 1. OH /\)\ (loWer part) 1.7 0.011 (loWer part) 1.83 0. 2. (loWer part) 2.006 (loWer part) 1. (loWer part) 1.83 0.03 0.83 0. at 80° C.015 (loWer part) 2.000 15 kPa 002 at 80° c.013 2.020 (loWer part) 2. N 100 kPa CO2 at 60° C.947 0.97 0.037 (loWer part) 1. 100 kPa CO2 at 40° C. at 80° C. 2.089 (loWer part) 2.50 0. CO2 loading at 25° C.836 Solid at room I 100 kPa CO2 at 40° C.000 15 kPa CO2 at 40° C.243 (upper part) 3.637 temperature (upper part) 4.97 (loWer part) 1. \ 100 kPa CO2 at 25° C. 2.840 (upper part) 5. OH /\N 15 kPa CO2 at 40° C.27 0.735 (upper part) 4.033 0.000 0.37 0.00 0.566 (upper part) 4.22 0. 100 kPa CO2 at 40° C.17 2. 100 kPa CO2 at 40° C.78 0.545 (upper part) 5.223 (upper part) 5.910.87 0. at 60° C. OH 15 kPa CO2 at 25° C. (loWer part) 1.90 0.00 0.93 0.703 N 15 kPa CO2 at 40° C. 15 kPa CO2 at 60° C.781 OH OH at 60° C. 2. 100 kPa CO2 at 55° C.43 0.013 100 kPa CO2 at 60° C.80 0. 100 kPa CO2 at 80° C.019 (loWer part) 0. 15 kPa CO2 at 40° C.40 0.

637 0.217 35.781 0.147 38. 15 kPa CO2 at 80° C.586 NH2 HO/\/ —\ N J 15 kPa c02 at 40° c.63 100 kPa c02 at 40° c.650 0.27 15 kPa c02 at 80° c.323 100 kPa CO2 at 60° C.61 N 15 kPa c02 100 kPa c02 15 kPa c02 100 kPa c02 0.948 0.889 0.92 0. 100 kPa c02 at 80° c. 2. 0.116 0.681 0.227 37.693 N/A N/A 15 kPa CO2 at 60° C.919 0.91 0.US 7.97 (upper part) 4. 0. Difference (mole (mole COZ/mole COZ/mole Sample Condition amine) amine) % Difference MBA 15 kPa CO2 at 40° C. CO2 loading at 25° C.208 N/A 0.00 100 kPa c02 at 60° c.826 0.115 100 kPa CO2 at 80° C.27 | 100 kPa c02 at 40° c.695 0. 0. OH 15 kPa CO2 at 40° C.83 2. 100 kPa CO2 at 40° C.078 B2 17 TABLE 2-c0ntinued Solubilities of MBA and the synthetic amino alcohols (1) to (9) at conditions close to the absorption and stripping columns.698 N/A 0.609 0.264 2. 15 kPa c02 at 60° c. 0. 2. 15 kPa CO2 at 60° C. 100 kPa CO2 at 80° C. \/\N 100 kPa c02 at 60° c.5 0.90 0. c. 2.28 OH 1 OH at at at at 60° 60° 80° 80° c. 100 kPa CO2 at 40° C.87 2.352 8 OH /\N I 9 TABLE 3 Absorption capacity difference of synthetic amino alcohols compared With MEA.565 15 kPa CO2 at 40° C. 2.541 100 kPa CO2 at 55° C. 100 kPa CO2 at 40° C. 15 kPa CO2 at 60° C. (mole Sample OH \ N 7 Concentration of COZ/mole Condition Sample (mole/L) amine) Comment 15 kPa CO2 at 25° C.31 2.962 0. 15 kPa CO2 at 80° C. c.849 0.379 0.772 Does not dissolve in Water 15 kPa CO2 at 40° C.91 2.836 0.138 15. 2. 100 kPa CO2 at 40° C.271 0.195 0.88 0.396 0.81 2.87 0. 2. 0. (loWer part) 0.269 0. 15 kPa CO2 at 55° C.490 100 kPa CO2 at 60° C.403 0.89 0.058 0.729 H 15 kPa CO2 at 80° C. .97 2. CO2 loading Absorption Capacity at 25° C.000 Phase separation at high temperature 2.437 0.226 32. c.279 35.195 42.82 30.00 2.55 H 15 kPa c02 at 40° c.79 0. 2.910. 0. 0.91 3. 0. 100 kPa CO2 at 80° C. 100 kPa CO2 at 25° C.621 0.93 100 kPa CO2 at 40° C.840 0.45 N/A 71.30 23.50 33.96 0. 0.724 0.361 0.

and at a pressure of about gas stream.246 0.264 43.807 0. 0. wherein the gas linked to form a 5 or 6-membered carbocyclic ring system.541 0.149 22. C.103 0. CO2 loading Absorption Capacity at 25° C.49 —3. The method according to claim 1. wherein the amino alcohol is 4-propylamino-2-butanol. wherein R1 and R2 are 60 17. a short-chain alcohol and R1\ M 2/N R combinations thereof.078 B2 19 20 TABLE 3-continued Absorption capacity difference of synthetic amino alcohols compared with MEA. The method according to claim 1. bustion exhaust gas is from gas streams of power plants. The method according to claim 1.086 0. C. wherein the aqueous solvent is selected from water.268 —0.735 0. 100 kPa CO2 at 80° C.747 0. amino alcohol of the formula I: 11. The method according to claim 1.66 36. CO2. wherein R1 and R2 are ture of about 40° C.95 31. wherein the condi independently selected from H and C l_6alkyl.93 9 *negative value (—) means the Absorption is lower than MEA.13 25.82 22. stream is a combustion exhaust gas. The method according to claim 15. C.323 0.65 21. 0.234 —39. and at a pressure of about linked to form a 5 to 10-membered carbocyclic ring system.43 15 kPa CO2 at 40° C. C. The method according to claim 1. wherein R1 and R2 are thereby.US 7.16 —69.497 0. 0.80 —34.565 0. 100 kPa CO2 at 40° C.115 0. wherein the amino 18. 0. wherein the aqueous solvent solubiliZes the amino alcohol and is an absorbent for 40 CO2 OH (I) 12. 0. The method according claim 1.396 0.948 0.41 OH 15 kPa CO2 100 kPa CO2 15 kPa CO2 100 kPa CO2 15 kPa CO2 100 kPa CO2 N at 40° at 40° at 60° at 60° at 80° at 80° % Difference 4 OH \/\N H 8 OH /\N I 100 kPa CO2 at 60° C. wherein the com alcohol is 4—(diethylamino)-2-butanol. removal of CO2 from the gas stream comprise con independently selected from H and C l_4alkyl. A method for removing carbon dioxide (CO2) from a gas stream comprising contacting the gas stream with a liquid 35 10. wherein R1 and R2 are 16.593 0. 15 to about 110 kPa. The method according to claim 1. 13. wherein the amino alcohol is 4-(piperidino)-2-butanol. The method according to claim 1.255 —0. 5. 1. 1 to about 120 kPa. 7.051 10. 14. 6. wherein the aque 45 ous solvent is deionized water. The method according to claim 1. We claim: 9.39 4.108 15 kPa CO2 at 80° C.254 0. wherein the condi tions for absorption of CO2 by the liquid absorbent and R1 and R2 are linked to form a 5 to 12-membered carbocy. tacting the gas stream with the liquid absorbent at a tempera 4.02 29.681 0. 65 19.66 100 kPa CO2 at 80° C.58 15 kPa CO2 at 40° C. 100 kPa CO2 at 40° C.352 —0.849 0. The method according to claim 1. The method according to claim 4.695 0. The method according to claim 1. The method according to claim 2. .910. 55 tions for absorption of CO2 by the liquid absorbent and 3. wherein the aque wherein R1 and R2 are independently selected from H and C l_1Oalkyl.50 thereby.167 14. removal of CO2 from the ture of about 25° C.729 0.12 36. 0.947 0. to about 90° C. The method according to claim 12. 2. wherein the gas stream comprises from about 1% to about 100% by volume 8.08 100 kPa CO2 at 60° C. to about 80° C. The method according to claim 1. 0. The method according to claim 12.138 0.118 0. removal of CO2 from the gas stream comprise con clic ring system under conditions for absorption of CO2 tacting the gas stream with the liquid absorbent at a tempera by the absorbent and thereby. 15 kPa CO2 at 60° C.889 0. C. wherein the amino re?neries or cement manufacturers. wherein the amino absorbent consisting essentially of an aqueous solvent and an alcohol is 4-(ethyl-methyl-amino)—2-butanol.021 17.156 11. 0. The method according to claim 17.51 /\)\ 15 kPa CO2 at 60° C. alcohol is 4—(isopropylamino)—2-butanol. 15 kPa CO2 at 80° C. or ous solvent is methanol or ethanol.072 0.017 —0. Difference (mole (mole COZ/mole COZ/mole Sample Condition amine) amine) C. 15.

24. 21. The method according to claim 22. releasedby heating theliquid absorbent. absorption column or absorption 5 toWer comprising a liquid absorbent as de?ned in claim 1.078 B2 21 22 20. The method according to claim 19. wherein the gas 23. Wherein the gas stream further comprises oxygen. The method according to claim 17. The method according to claim 1. Wherein the CO2 is stream comprises from about 9% to about 15% by Volume CO2. 22. further comprising releasing the absorbed CO2 from the liquid absorbent. A CO2 absorber. optionally collecting the CO2 and optionally regenerating the liquid absorbent.910.US 7. * * * * * .