Method for absorbing CO2 from a gas mixture

The present application is US national stage of international application PCT/EP2013/058288, which had an international filing date of Apr. 22, 2013. Priority is claimed to German application DE 10 2012 207 509.7, filed on May 7, 2012. These related applications are hereby incorporated by reference.

The invention relates to a method of absorbing CO 2 from a gas mixture.

Gas streams which have an undesirable high content of CO 2 which has to be reduced for further processing, for transport or for avoiding CO 2 emissions occur in numerous industrial and chemical processes.

On the industrial scale, CO 2 is typically absorbed from a gas mixture by using aqueous solutions of alkanolamines as an absorption medium. The loaded absorption medium is regenerated by heating, depressurization to a lower pressure or stripping, and the carbon dioxide is desorbed. After the regeneration process, the absorption medium can be used again. These methods are described for example in Rolker, J.; Arlt, W.; “Abtrennung von Kohlendioxid aus Rauchgasen mittels Absorption” [Removal of carbon dioxide from flue gases by absorption] in Chemie Ingenieur Technik 2006, 78, pages 416 to 424, and also in Kohl, A. L.; Nielsen, R. B., “Gas Purification”, 5th edition, Gulf Publishing, Houston 1997.

A disadvantage of these methods, however, is that the removal of CO 2 by absorption and subsequent desorption requires a relatively large amount of energy and that, on desorption, only a part of the absorbed CO 2 is desorbed again, with the consequence that, in a cycle of absorption and desorption, the capacity of the absorption medium is not sufficient.

U.S. Pat. No. 7,419,646 describes a process for deacidifying off-gases in which an absorption medium is used which forms two separable phases upon absorption of the acid gas. 4-Amino-2,2,6,6-tetramethylpiperidine is cited, inter alia, in column 6 as a reactive compound for absorbing an acid gas. The process of U.S. Pat. No. 7,419,646 has the disadvantage that additional apparatus is required for separating the two phases which arise in the absorption.

US 2009/0199709 describes a similar method, in which, following absorption of the acid gas, heating of the loaded absorption medium produces two separable phases which are then separated from one another. Here again, 4-amino-2,2,6,6-tetramethylpiperidine is cited as a reactive compound suitable for the absorption of an acid gas.

FR 2900841 and US 2007/0286783 describe methods for deacidifying off-gases, in which the reactive compound reacted with CO 2 is separated from the loaded absorption medium by extraction. One of the reactive compounds cited for the absorption of an acid gas is 4-amino-2,2,6,6-tetramethylpiperidine.

WO 2010/089257 describes a method of absorbing CO 2 from a gas mixture using an absorption medium that comprises water and a 4-amino-2,2,6,6-tetramethylpiperidine, which amine can be alkylated on the 4-amino group. However, precipitation of the carbamate salt readily occurs during the absorption of CO 2 with absorption media comprising 4-amino-2,2,6,6-tetramethylpiperidine as the absorbent. WO 2010/089257 describes the addition of solvents, such as sulfolane or ionic liquids, in order to maintain the absorption medium single phase and to achieve a higher absorption capacity for CO 2 .

Therefore, there is still a need for a method of absorbing CO 2 from a gas mixture, by which at the same time a high absorption capacity for CO 2 can be achieved at a high rate of absorption and in which a separation into two liquid phases or precipitation of a solid during the absorption of CO 2 and regeneration of the absorption medium can be avoided even without addition of a solvent.

It has now been found that this object can be achieved by using an absorption medium containing a 4-amino-2,2,6,6-tetramethylpiperidine substituted on the 4-amino group with the substituent on the 4-amino group carrying a suitable functional group which improves water-solubility.

The invention therefore provides a method of absorbing CO 2 from a gas mixture by bringing the gas mixture into contact with an absorption medium comprising water and at least one amine of formula (I)

where

R 1 is a —(CH 2 ) n —(XCH 2 CH 2 ) m —Y—R 3 radical where R 3 =hydrogen or an alkyl radical having from 1 to 6 carbon atoms, X and Y are each, independently of one another, NR 3 , oxygen, SO or SO 2 , where in the case of Y═SO and in the case of Y═SO 2 , R 3 is not hydrogen, and Y—R 3 can be an N-morpholinyl radical or an N-piperazyl radical, n=2 to 4, m=0 to 4 and R 2 is hydrogen, an alkyl radical having from 1 to 6 carbon atoms or a radical R 1 .

However, m must be different from 0 when R 2 is not a radical R 1 , Y═NR 3 and Y—R 3 is not an N-morpholinyl radical and not an N-piperazyl radical.

Preferably, X and Y in formula (I) are each, independently of one another, NR 3 or oxygen.

In a particularly preferred embodiment, Y in formula (I) is oxygen, and R 3 is then particularly preferably methyl or hydrogen. Amines of formula (I) which are particularly suitable for this embodiment are

4-(2-hydroxyethylamino)-2,2,6,6-tetramethylpiperidine where R 1 =—(CH 2 ) 2 OH and R 2 =hydrogen, 4-[bis(2-hydroxyethyl)amino]-2,2,6,6-tetramethylpiperidine where R 1 , R 2 =—(CH 2 ) 2 OH and R 2 =hydrogen, 4-(2-methoxyethylamino)-2,2,6,6-tetramethylpiperidine where R 1 =—(CH 2 ) 2 OCH 3 and R 2 =methyl, and 4-(2-hydroxyethylaminoethylamino)-2,2,6,6-tetramethylpiperidine where R 1 =—(CH 2 ) 2 NH(CH 2 ) 2 OH and R 2 =hydrogen.

In a further particularly preferred embodiment, Y—R 3 in formula (I) is an N-morpholinyl radical or an N-piperazyl radical. Amines of formula (I) which are particularly suitable for this embodiment are

4-(2-piperazinoethylamino)-2,2,6,6-tetramethylpiperidine where R 1 =—(CH 2 ) 2 Y—R 3 and Y—R 3 ═N-piperazyl and 4-(2-morpholinopropylamino)-2,2,6,6-tetramethylpiperidine where R 1 =—(CH 2 ) 3 Y—R 3 and Y—R 3 ═N-morpholinyl.

In both particularly preferred embodiments, m in formula (I) is preferably 0.

Preferably, amines of formula (I) in which n=2 or 3, with particular preference being given to n=2, are used in the process of the invention.

Amines of formula (I) can be prepared from commercial triacetone amine by reductive amination, in which triacetone amine is reacted with an amine of formula R 1 R 2 NH and hydrogen in the presence of a hydrogenation catalyst. To prepare amines of formula (I) which contain a group X or Y═SO or SO 2 , the reductive amination is preferably carried out using an amine R 1 R 2 NH which has a sulphur atom in place of the group SO or SO 2 and in a subsequent step the thioether group of the resulting product is oxidized to the group SO or SO 2 by means of an oxidant. Suitable oxidants for this purpose are hydrogen peroxide, preferably in the presence of a catalyst such as molybdate, and peroxycarboxylic acids, preferably peroxyacetic acid.

In the method of the invention, the content of amines of formula (I) in the absorption medium is preferably from 10 to 60% by weight, particularly preferably from 20 to 50% by weight. The content is here based on the absorption medium without absorbed CO 2 .

In the method of the invention, in addition to water and amines of formula (I), the absorption medium may further comprise one or more physical solvents which do not lead to any chemical reaction with CO 2 . The fraction of physical solvents in this case may be up to 50% by weight. Suitable physical solvents (C) include sulfolane, aliphatic acid amides, such as N-formylmorpholine, N-acetylmorpholine, N-alkylpyrrolidones, more particularly N-methyl-2-pyrrolidone, or N-alkylpiperidones, and also diethylene glycol, triethylene glycol and polyethylene glycols and alkyl ethers thereof, more particularly diethylene glycol monobutyl ether. Preferably, however, the absorption medium of the invention contains no physical solvent.

In the method of the invention, the absorption medium may additionally comprise further additives, such as corrosion inhibitors, wetting-promoting additives and defoamers.

All compounds known to the skilled person as suitable corrosion inhibitors for the absorption of CO 2 using alkanolamines can be used as corrosion inhibitors in the method of the invention, in particular the corrosion inhibitors described in U.S. Pat. No. 4,714,597. In this case, a significantly lower amount of corrosion inhibitors can be chosen than when using a customary absorption medium containing ethanolamine, since amines of formula (I) are significantly less corrosive towards metallic materials than ethanolamine.

The cationic surfactants, zwitterionic surfactants and nonionic surfactants known from WO 2010/089257 page 11, line 18 to page 13, line 7 are preferably used as wetting-promoting additive.

All compounds known to the skilled person as suitable defoamers for the absorption of CO 2 using alkanolamines can be used as defoamers in the method of the invention.

In the method of the invention, the gas mixture may be a natural gas, a methane-containing biogas from a fermentation, composting or a sewage treatment plant, a combustion off-gas, an off-gas from a calcination reaction, such as the burning of lime or the production of cement, a residual gas from a blast-furnace operation for producing iron, a gas stream in a refinery, or a gas mixture resulting from a chemical reaction, such as, for example, a synthesis gas containing carbon monoxide and hydrogen, or a reaction gas from a steam-reforming hydrogen production process. The gas mixture is preferably a combustion off-gas, a natural gas or a biogas.

Before being brought into contact with the absorption medium, the gas mixture preferably has a CO 2 content in the range from 0.1 to 60% by volume, particularly preferably in the range from 1 to 40% by volume.

The gas mixture can contain further acid gases from the series COS, H 2 S, CH 3 SH or SO 2 , in addition to CO 2 . A combustion off-gas is preferably desulphurized beforehand, i.e. SO 2 is removed from the gas mixture by a desulphurization method known from the prior art, preferably by a gas scrub using milk of lime, before the method of the invention is carried out.

For the method of the invention, all apparatus suitable for contacting a gas phase with a liquid phase can be used to contact the gas mixture with the absorption medium.

Preferably, absorption columns or gas scrubbers known from the prior art are used, for example membrane contactors, radial flow scrubbers, jet scrubbers, venturi scrubbers, rotary spray scrubbers, random packing columns, ordered packing columns or tray columns. With particular preference, absorption columns are used in countercurrent flow mode.

In the method of the invention, the absorption of CO 2 is carried out preferably at a temperature of the absorption medium in the range from 0 to 80° C., more preferably 20 to 60° C. When using an absorption column in countercurrent flow mode, the temperature of the absorption medium is more preferably 30 to 60° C. on entry into the column, and 35 to 80° C. on exit from the column.

The absorption of CO 2 is preferably carried out at a pressure of the gas mixture in the range from 0.5 to 90 bar, particularly preferably from 0.9 to 30 bar. The partial pressure of CO 2 in the gas mixture before absorption is preferably in the range from 0.1 to 10 bar. Absorption of CO 2 from natural gas is preferably carried out at a pressure of the gas mixture in the range from 5 to 90 bar, particularly preferably from 10 to 80 bar. Absorption of CO 2 from a combustion off-gas is preferably carried out at a pressure of the gas mixture in the range from 0.8 to 1.5 bar, particularly preferably from 0.9 to 1.1 bar, in order that the combustion off-gas does not have to be compressed beforehand.

In a preferred embodiment of the method of the invention, CO 2 absorbed in the absorption medium is desorbed again by increasing the temperature and/or reducing the pressure and the absorption medium after this desorption of CO 2 is used again for absorbing CO 2 . By such cyclic operation of absorption and desorption, CO 2 can be entirely or partially separated from the gas mixture and obtained separately from other components of the gas mixture.

As an alternative to the increase in temperature or the reduction in pressure, or in addition to an increase in temperature and/or a reduction in pressure, it is also possible to carry out a desorption by stripping the absorption medium loaded with CO 2 by means of a gas.

If, in the desorption of CO 2 , water is also removed from the absorption medium, water may be added as necessary to the absorption medium before reuse for absorption.

All apparatus known from the prior art for desorbing a gas from a liquid can be used for the desorption. The desorption is preferably carried out in a desorption column. Alternatively, the desorption of CO 2 may also be carried out in one or more flash evaporation stages.

The desorption is carried out preferably at an absorption medium temperature in the range from 50 to 200° C., more particularly 80 to 180° C. The temperature during desorption is then preferably at least 20° C., more preferably at least 50° C., above the temperature during absorption. The absorption is particularly preferably carried out at a temperature in the range from 0 to 80° C. and the desorption is particularly preferably carried out at a higher temperature in the range from 50 to 200° C.

In the case of desorption by lowering the pressure, the desorption of CO 2 is preferably carried out at a total pressure in the gas phase in the range from 0.01 to 10 bar, in particular from 0.1 to 5 bar. The pressure in the desorption is preferably at least 1.5 bar below, particularly preferably at least 4 bar below, the pressure in the absorption and is most preferably atmospheric pressure. The absorption is particularly preferably carried out at a pressure in the range from 0.8 to 90 bar and the desorption is carried out at a lower pressure in the range from 0.01 to 10 bar.

The method of the invention makes it possible to achieve, at the same time, a high absorption capacity for CO 2 and an absorption rate which is sufficiently high for industrial application by use of amines of formula (I). By the use of amines of formula (I), precipitation of a solid can be reliably prevented in the absorption of CO 2 , even without addition of a solvent, and phase separation of the absorption medium into two liquid phases can be prevented in the desorption of CO 2 . The method of the invention can therefore be used without problems in simply constructed plants as are used in the prior art for gas scrubbing using aqueous solutions of ethanolamine and here achieves an improved absorption performance for CO 2 in comparison with ethanolamine. In addition, discharge of absorbent in the desorption is lower than in the case of ethanolamine.

In a preferred embodiment of the method of the invention, the desorption is carried out first of all by lowering the pressure in one or more successive flash evaporation stages followed by stripping with an inert gas such as air or nitrogen in a desorption column. In the last flash evaporation stages, the pressure is preferably lowered to 1 to 5 bar, more preferably to 1 to 2 bar. The stripping in the desorption column is preferably carried out at a temperature of the absorption medium in the range from 60 to 100° C. Flash evaporation combined with stripping enables a low residual content of CO 2 in the absorption medium after desorption to be achieved with a low energy consumption. Thus the amount of absorption medium required in the overall process may be lowered and the need for thermal energy for the desorption of CO 2 may be reduced.

The following examples illustrate the invention without, however, restricting the subject matter of the invention.

For determining the CO 2 loading, the CO 2 uptake and the relative absorption rate, 150 g of absorption medium consisting of 45 g of amine and 105 g of water were charged to a thermostatable container with a top-mounted reflux condenser cooled at 3° C. After heating to 40° C. or 100° C., a gas mixture of 14% CO 2 , 80% nitrogen and 6% oxygen by volume was passed at a flow rate of 59 l/h through the absorption medium, via a frit at the bottom of the container, and the CO 2 concentration in the gas stream exiting the reflux condenser was determined by IR absorption using a CO 2 analyser. The difference between the CO 2 content in the gas stream introduced and in the exiting gas stream was integrated to give the amount of CO 2 taken up, and the equilibrium CO 2 loading of the absorption medium was calculated. The CO 2 uptake was calculated as the difference in the amounts of CO 2 taken up at 40° C. and at 100° C. From the slope of the curve of CO 2 concentration in the exiting gas stream for an increase in concentration from 1% to 12% by volume, a relative absorption rate of CO 2 in the absorption medium was determined. The amines tested are given in Table 1 with the equilibrium loadings determined in this way at 40° C. and 100° C., in mol CO 2 /mol amine, the CO 2 uptake in mol CO 2 /mol amine, the relative absorption rate of CO 2 , relative to Example 1 with 100%, and the boiling point of the amine.

For determining the phase separation temperatures, the absorption medium was heated slowly in a closed, pressure-rated glass container until a clouding or separation into two liquid phases was discernible. An entry marked with the symbol > means that up to that temperature there was no demixing and that the experiment was ended at the temperature indicated, for safety reasons.

The abbreviations used in Table 1 have the following meanings:

MEA: ethanolamine TAD: 4-amino-2,2,6,6-tetramethylpiperidine Pr-TAD: 4-(n-propylamino)-2,2,6,6-tetramethylpiperidine Bu-TAD: 4-(n-butylamino)-2,2,6,6-tetramethylpiperidine amine 1: 4-(2-hydroxyethylamino)-2,2,6,6-tetramethylpiperidine amine 2: 4-(2-methoxyethylamino)-2,2,6,6-tetramethylpiperidine amine 3: 4-(2-hydroxyethylaminoethylamino)-2,2,6,6-tetramethylpiperidine amine 4: 4-[bis(2-hydroxyethyl)amino]-2,2,6,6-tetramethylpiperidine amine 5: 4-(2-piperazinoethylamino)-2,2,6,6-tetramethylpiperidine amine 6: 4-(2-morpholinopropylamino)-2,2,6,6-tetramethylpiperidine

In addition, the corrosion rate of the steel C22 (material number 1.0402) in contact with the absorption medium was determined for the absorption media of Examples 1 and 8 by measurement of the potentiodynamic polarization resistance and interpretation via a Tafel plot using the method ASTM G59-97 (2009). The results are shown in Table 2.