EP2547423A1

EP2547423A1 - Removal of co2 from gases having low co2 partial pressures, using 1,2 diaminopropane

Info

Publication number: EP2547423A1
Application number: EP10798964A
Authority: EP
Inventors: Johannes Menzel; Olaf Von Morstein
Original assignee: ThyssenKrupp Uhde GmbH
Current assignee: ThyssenKrupp Industrial Solutions AG
Priority date: 2010-01-05
Filing date: 2010-12-20
Publication date: 2013-01-23
Also published as: AU2010341129A8; CN102834161A; JP2013516311A; KR20120124062A; RU2012130909A; DE102010004073A1; CA2786323A1; US20130055895A1; WO2011082807A1; AU2010341129A1

Abstract

Use of an absorption agent for removing acid gases from a fluid flow, comprising an aqueous solution of 1,2-diaminopropane.

Description

C0 ₂ removal from gases with low C0 ₂ partial pressures by means of 1,2

diaminopropane

The invention relates to the use of an absorbent for removing C0 ₂ from industrial gases.

The removal of C0 ₂ from industrial gases is of particular importance for the reduction of C0 ₂ emissions, since C0 _{2 is} considered as the main cause of the greenhouse effect.

In the industry, for the removal of acid gas components, aqueous solutions of organic bases, e.g. Alkanolamines used as an absorbent. The absorbent is regenerated by supplying heat, pressure reduction, or stripping by means of suitable auxiliary media. After regeneration, the absorbent is a regenerated solvent for the absorption of

Sour gas components available again. Flue gases from the combustion of fossil fuels, now fall approximately at atmospheric pressure. Since the C0 ₂ content in the flue gases is typically about 3 to 13% by volume, the C0 ₂ partial pressure is correspondingly only 0.03 to 0.13 bar. In order to achieve a sufficient removal of C0 ₂ 's from the flue gases at these low C0 ₂ partial pressures, a suitable

Absorbents have a very high binding capacity for C0 ₂ . In particular, the highest possible absorption capacity should already be available even at low C0 ₂ partial pressures.

By the absorption capacity of the absorbent is essentially the required Absorptionsmittelumlaufmenge and thus determines the size and cost of the equipment required for it. Since the energy needed to heat and cool the absorbent is proportional to the amount of recirculation, the regeneration energy needed to regenerate the solvent is also substantially reduced if it succeeds in reducing the recirculating amount of the absorbent. In addition to a high absorption capacity should be a suitable

Absorbent in particular but also have the highest possible stability to oxygen, since in particular in flue gases always a certain amount of oxygen is present. It is known from the literature that many amine compounds, which otherwise have favorable absorption properties, are easily decomposed in the presence of oxygen, which leads to a high level of

Absorbent consumption and other leads to correspondingly high costs. The resulting decomposition products usually lead to significantly increased corrosion and can on the other hand significantly reduce the capacity of the absorbent.

Volatile decomposition products, such as ammonia would have the consequence that the C0 ₂ product and leaving the C0 ₂ scrubbing flue gas would be contaminated with impermissible emission components. Avoiding these emissions requires further process steps, which further increase the cost of a C0 ₂ wash.

The use of an absorbent for removing acidic gases from a fluid stream is known, for example, from US 2007/0264180 A1. Here it is taught that 1, 2 diaminopropane (referred to as 1, 2-propanediamine) in a concentration of 0 to 30 wt.% Can be added to the absorbent as an additional activator. The use of an aqueous 1,2-diaminopropane solution, which in itself acts as an absorbent, is in no way suggested.

There is therefore a considerable need for an absorbent, on the one hand the highest possible absorption capacity for C0 ₂ at low

Has partial pressures and at the same time as stable as oxygen stable and thermally stable under the conditions of absorption medium regeneration. The cover of this need, ie the provision of such an absorbent, as well as a method for removing C0 ₂ from industrial gases, the present invention has made the task.

The object is achieved by the use of an absorbent containing 1, 2 diaminopropane in aqueous solution. In general, the absorbent based on the weight of the absorbent 10 to 90% by weight, preferably 30 to 65 wt% of 1.2

Diaminopropane. In one embodiment of the invention, the absorbent to be used also contains at least one other of 1, 2 diaminopropane different amine. Thus, the absorbent of the invention may be e.g. 5 to 45% by weight, preferably 10 to 40% by weight of one or more thereof different amines.

The at least one of 1, 2 diaminopropane various other amine is selected for example from:

A) tertiary amines of the general formula:

N (R1) _2-n (R2) _{1 + n}

wherein R 1 is an alkyl group and R 2 is a hydroxyalkyl group or

tertiary amines of the general formula:

(R1) _2-n (R2) _n NXN (R1) ₂ . _m (R2) _m

where R 1 is an alkyl group, R 2 is a hydroxyalkyl group, X is an alkylene group which is interrupted one or more times by oxygen and n and m is an integer from 0 to 2, or two radicals R 1 and R 2 linked to different nitrogen atoms R 2 together represents an alkylene group, B) sterically hindered amines,

C) 5-, 6-, or 7-membered saturated heterocycles having at least one NH group in the ring which may contain one or two additional heteroatoms selected from nitrogen and oxygen in the ring,

D) primary or secondary alkonolamines,

E) alkylenediamines of the formula:

H ₂ N-R2-NH ₂

wherein R2 is a C ₂ to C ₆ alkyl group.

In a preferred embodiment of the invention, the tertiary amines, which are used in addition to 1, 2 diaminopropane, selected from a A group comprising tris (2-hydroxyethyl) amine, tris (2-hydroxypropyl) amine,

Tributanolamine, bis (2-hydroxyethyl) methylamine, 2-diethylaminoethanol, 2-dimethyiaminoethanol, 3-dimethylamino-1-propanol, 3-diethylamino-1-propanol, 2-diisopropylaminoethanol, N, N-bis (2-hydroxypropyl) methylamine

(Methyldiisopropanolamine, MDIPA), Ν, Ν, Ν ', Ν'-tetramethylethylenediamine, N, N-diethyl-N', N'-dimethylethylenediamine, N, Ν, Ν ', Ν'-tetraethylethylenediamine, N, Ν, Ν' , Ν'-tetramethylpropanediamine, N, N, N ', N'-tetraethylpropanediamine, N, N-dimethyl-N', N'-diethylethylenediamine, 2- (2-dimethylaminoethoxy) -N, N-dimethylethanamine; 1, 4-diazabicyclo [2.2.2] octane (DABCO); N, N, N'-trimethylaminoethylethanolamine, N, ΝΓ-dimethylpiperazine and N, N'-bis (hydroxyethyl) piperazine. Other suitable tertiary amines are disclosed in WO 2008/145658 A1, US Pat. No. 4,217,236 and US 2009/0199713 A1.

In a further embodiment, the sterically hindered amines which are used in addition to 1, 2 diaminopropane, selected from a group comprising 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1 -butanol, 3-amino-3-methyl-1-butanol, 3-amino-3-methyl-2-pentanol and 1-amino-2-methylpropan-2-ol. Further suitable sterically hindered amines are mentioned in WO 2008/145658 A1, US Pat. No. 4,217,236, US Pat. No. 2009/0199713 A1, US Pat. No. 5,700,437, US Pat. No. 6,500,397 B1 and US Pat. No. 6,036,931.

Optionally, the 5-, 6-, or 7-membered saturated heterocycles used in addition to 1, 2-diaminopropane are selected from the group comprising, piperazine, 2-methylpiperazine, N-methylpiperazine, N-ethylpiperazine, N-aminoethylpiperazine, homopiperazine, piperidine and morpholine. Other compounds which can be selected are described in WO 2008/145658 A1 and US Pat

2009/0199713 A1.

Advantageously, the primary or secondary alkanolamines used in addition to 1, 2 diaminopropane are selected from a group comprising 2-aminoethanol, N, N-bis (2-hydroxyethyl) amine, N, N-bis (2-hydroxypropyl) amine, 2- (methylamino) ethanol, 2- (ethylamino) ethanol, 2- (n-butylamino) ethanol, 2-amino-1-butanol, 3-amino-1-propanol and 5- Amino-1 pentanol. Also for this purpose, further possible compounds in the documents WO 2008/145658 A1 and US 2009/0199713 A1 are disclosed. In a further embodiment of the invention, the alkyldiamines, which are used in addition to 1, 2 diaminopropane, selected from a group comprising, hexamethylenediamine, 1, 4-diaminobutane, 1, 3-diaminopropane, 2,2-dimethyll, 3rd diaminopropane, 3-methylaminopropylamine, 3- (dimethylamino) propylamine, 3- (diethylamino) propylamine, 4-dimethylaminobutylamine and 5-

Dimethylaminopentylamine, 1, 1, Ν, Ν-tetramethylethanediamine, 2,2, N, N-tetramethyl-1,3-propanediamine, N, N'-dimethyl-1,3-propanediamine, N, N'Bis (2-hydroxyethyl ) ethylene diamine. In addition, all components come into consideration, which are characterized in WO 2008/145658 A1 and US 2009/0199713 A1 as such, in particular MAPA.

Furthermore, the use of the absorbent is characterized in that the fluid flow is brought into contact with a previously characterized absorbent and thereby the absorbent is loaded with C02. This is preferably done at a partial pressure of <200 mbar.

Advantageously, the loaded absorbent is heated by heating,

Relaxation, stripping regenerated by means of stripping vapors generated by internal evaporation of the solvent, stripping with an inert fluid or a combination of two or all of these measures.

The present invention will be described in detail below with reference to two examples. Example 1: Test for oxygen stability

The resistance of 1,2-diaminopropane to the action of oxygen was determined as follows:

The investigations were carried out in a glass apparatus consisting of round bottom flask and reflux condenser. The amines were weighed. In this case, at about 110 ° C for 4 days a vorsättigter with steam air flow of about 12 Nl air / h was bubbled into the stirred solution. To monitor the course of the reaction, daily samples were analyzed by means of gas chromatography or acid-base titration (0.1 molar hydrochloric acid) to determine the absolute amine content. At the end, the flasks were weighed for control to determine the total amount of the solution. Due to the presaturation of the air with water vapor found a

Weight gain in the flask over the trial period instead. If the result of the measurement is corrected by the increase in weight due to the water introduced, it was surprisingly found after completion of the experiment that the

Concentration of 1, 2 diaminopropane (50% by weight) in the solution was the same as at the beginning of the experiment. According to measurement technology, no change could be determined. Accordingly, over this period, none

Color change of 1, 2 diaminopropane detected. The color of the 1, 2

Diaminopropane was slightly yellow at the beginning and at the end of the experiment.

In contrast, resulted in the test of the stability of a likewise about 50% by weight monoethanolamine under otherwise the same conditions, a final concentration of 44.89% by weight after 4 days. That corresponds to one

Solvent loss of about 9.6% of the monoethanolamine used within the test period. Accordingly, the color changed from slightly beige to dark orange.

Example 2: Determination of C0 ₂ uptake capacity For the synthetic gas solubility measurements (isothermal Px data), a static phase equilibrium apparatus was used according to the synthetic measuring principle. In this arrangement, the pressure for different

Gross compositions of a mixture measured at constant temperature. The thermostated, purified and degassed solvent is removed by means of

Dosing pumps, which allow to show small volume differences, filled in an evacuated and thermostated measuring cell. Then the gas is added in small steps. That then at a certain pressure in the

Absorption solution C0 ₂ is determined by calculation, taking into account the gas space.

It was the C0 ₂ uptake for a C0 ₂ partial pressure of about 0.1 bar at a temperature of 40 ° C determined.

Tab. 1:

Absorbent absorption capacity in%

MEA (30% by weight) 100

DAP (30% by weight) 149 From the results shown in Table 1 shows that at the same amine concentration 1, 2 diaminopropane (DAP) receives about 50% more C0 ₂ , as compared to the prior art detergent monoethanolamine (MEA).

In the same manner as for 40 ° C and the

Equilibrium concentration of C0 ₂ in aqueous solution at 120 ° C determined. Under the typical regeneration conditions in the desorption column (20 ° C at about 0.09 bar C0 ₂ partial pressure) can then determine the residual charge of C0 ₂ . If the remaining C0 ₂ residual concentration is taken into account, the so-called cyclic absorption capacity, ie the actual C0 ₂ uptake for the particular solvent, wherein the absolute C0 ₂ uptake capacity is reduced by the remaining C0 ₂ residual charge from the solvent regeneration is to determine, so is the cyclic absorption capacity of

1, 2 diaminopropane (DAP) at equal weight proportions of the respective amine in water about 1, 6 times the cyclic absorption capacity of

Monoethanolamine (MEA).

Thus, the cyclic absorption capacity of 1,2 diaminopropane is even greater than the absolute C0 ₂ uptake capacity relative to monoethanolamine. This indicates that the regeneration of 1, 2 diaminopropane, possibly due to the non-straight-chain structure of the hydrocarbon groups, leads to lower residual C0 ₂ loadings than the comparable MEA. This represents a further advantage of the amine according to the invention.

Thus, according to the invention, a solvent for the absorption of C0 ₂ , in particular in the range of low C0 ₂ partial pressures and in the presence of oxygen before, which is significantly more stable on the one hand at these conditions and on the other hand also has a higher cyclic absorption capacity, as a

comparable prior art solvent. This proves the particular suitability for the C0 ₂ removal of the amine of the invention from industrial gases with low partial pressures (<200 mbar).

Claims

claims

Use of an absorbent for removing acidic gases from a fluid stream comprising an aqueous solution of 1,2-diaminopropane.

2. Use of an absorbent according to claim 1, wherein the

Absorbent based on the weight of the absorbent contains 10 to 90% by weight, preferably 30 to 65% by weight of 1, 2 diaminopropane.

3. Use of an absorbent according to any one of claims 1 or 2, wherein the absorbent at least one further of 1, 2 diaminopropane

contains different amine.

4. Use of an absorbent according to claim 3, wherein the

Absorbent 5 to 45 wt%, and preferably 10 to 40 wt% of at least one of 1, 2 diaminopropane different amine.

5. Use of an absorbent according to one of claims 3 or 4, wherein the at least one further of 1, 2 diaminopropane different amine is selected from:

A) tertiary amines of the general formula:

N (R1) _2-n (R2) _{1 + n}

wherein R 1 is an alkyl group and R 2 is a hydroxyalkyl group

or

tertiary amines of the general formula:

(R1) ₂ . _n (R2) _n NXN (R1) _2-m (R2) _m

where R 1 is an alkyl group, R 2 is a hydroxyalkyl group, X is an alkylene group which is interrupted one or more times by oxygen and n and m is an integer from 0 to 2, or two radicals R 1 and R 2 linked to different nitrogen atoms R2 together represents an alkylene group,

B) sterically hindered amines, C) 5-, 6-, or 7-membered saturated heterocycles having at least one NH group in the ring which may contain one or two additional heteroatoms selected from nitrogen and oxygen in the ring,

D) primary or secondary alkonolamines,

E) alkylenediamines of the formula:

H ₂ N-R2-NH ₂

wherein R2 is a C ₂ to C ₆ alkyl group.

Use of an absorbent according to claim 5, wherein the tertiary amine is selected from a group comprising bis-dimethylaminoethyl ether, tris (2-hydroxyethyl) amine, tris (2-hydroxypropyl) amine, tributanolamine, bis (2-hydroxyethyl) methylamine , 2-diethylaminoethanol, 2-dimethylaminoethanol, 3-dimethylamino-1-propanol, 3-diethylamino-1-propanol, 2-diisopropylaminoethanol, N, N-bis (2-hydroxypropyl) methylamine

(Methyldiisopropanolamine, MDI PA), Ν, Ν, Ν ', Ν'-tetramethylethylenediamine, N, N-diethyl-N', N'-dimethylethylenediamine, N, Ν, Ν ', Ν'-tetraethylethylenediamine, N, N.N '.N'-tetramethylpropanediamine.NNN'.N'-tetraethylpropanediamine, N, N-dimethyl-N'.N'-diethylethylenediamine, 2- (2-dimethylaminoethoxy) -N, N-dimethylethanamine; 1, 4-diazabicyclo [2.2.2] octane (DABCO); Ν, Ν, Ν'- Trimethylaminoethylethanolamin, N, N'-dimethylpiperazine and Ν, Ν'-bis (hydroxyethyl) piperazine.

7. Use of an absorbent according to claim 5, wherein the steric

hindered amine is selected from a group comprising 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1-butanol, 3-amino-3-methyl-1-butanol, 3-amino-3 - methyl-2-pentanol and 1-amino-2-methylpropan-2-ol.

Use of an absorbent according to claim 5, wherein the 5-, 6- or 7-membered saturated heterocycles are selected from a group comprising piperazine piperazine, 2-methylpiperazine, N-methylpiperazine, N-ethylpiperazine, N-aminoethylpiperazine, Homopiperazine, piperidine and morpholine.

The use of an absorbent according to claim 5, wherein the primary or secondary alkanolamines are selected from the group consisting of 2-aminoethanol, N, N-bis (2-hydroxyethyl) amine, N, N-bis (2-hydroxypropyl ) amine, 2- (Methylamino) ethanol, 2- (ethylamino) ethanol, 2- (n-butylamino) ethanol, 2-amino-1-butanol, 3-amino-1-propanol and 5-amino-1-pentanol.

Use of an absorbent according to claim 5, wherein the alkyldiamines are selected from the group comprising hexamethylenediamine, 1,4-diaminobutane, 1,3-diaminopropane, 2,2-dimethyl-1,3-diaminopropane, 3-methylaminopropylamine, 3 (Dimethylamino) propylamine, 3- (diethylamino) propylamine, 4-dimethylaminobutylamine and 5-dimethylaminopentylamine, 1, 1, N, N-tetramethylethanediamine, 2,2, N, N-tetramethyl-1,3-propanediamine, N, N ' -Dimethyl-1,3-propanediamine, N, N'-bis (2-hydroxyethyl) ethylenediamine.

Use of an absorbent for removing carbon dioxide from a fluid stream according to any one of claims 1 to 10, wherein the fluid stream is contacted with the absorbent and the absorbent is loaded with C0 ₂ .

12. Use of an absorbent for removing carbon dioxide from a fluid stream according to claim 11, wherein the loading of the absorbent with C0 _{2 takes place} at a partial pressure of <200 mbar.

13. Use of an absorbent for removing carbon dioxide from a fluid stream according to any one of claims 1 to 12, wherein the loaded

Absorbent through

i) warming,

ii) relaxation,

iii) stripping by means of internal evaporation of the solvent

generated stripping vapors,

iv) stripping with an inert fluid

or a combination of two or all of these measures is regenerated.