# Patent

## Title
Process for partial dehydration of a gas by absorption on a solvent that can be regenerated by segregation at ambient temperature

## Abstract

A process for partial dehydration of a gas by contact with a solvent that can be regenerated by: a) A stage for absorption of H2O by contact of the gas to be treated and regenerated solvent producing a dehydrated gas effluent and a liquid solvent effluent that is charged with H2O and absorbed gas, b) A stage for cooling the solvent charged with H2O at ambient temperature, c) A stage for separation by segregation during which liquid H2O and the solvent are separated at ambient temperature, d) A stage in which the regenerated solvent that is obtained at the end of stage c) is heated, e) A stage in which the regenerated and heated solvent that is obtained at the end of stage d) is recycled to the absorption stage a).

## Background
The invention relates to a process for partial dehydration by means of an organic solvent of a gas that contains H2O in a large quantity. The invention relates more particularly to a process that makes possible the regeneration of said solvent by a simple and economical means that does not involve any pollution of the environment. More specifically, the regeneration of the solvent is performed by separating the H2O that is extracted from the gas that is to be treated and said solvent by liquid-liquid segregation at ambient temperature. The term “ambient temperature” is defined as a temperature of between 10 and 30° C.
The process according to the invention applies particularly to the treatment of a Claus unit tail gas, natural gas, or refinery gas.
In a general way, the process according to the invention advantageously applies to any process that requires the partial dehydration of a gaseous feedstock for the purposes of improving the operation and the yield.
According to rival processes, it is common to put the gas that is to be dehydrated into contact with a hydrophilic liquid solvent. The glycols and polyglycols are part of these solvents because of their strong affinity to H2O, their chemical stability, and their low cost; the triethylene glycol (TEG in abbreviated form) is used the most.
In a standard unit for dehydration of gas by a liquid solvent, for example a glycol, the wet gas enters, in a first step, the lower part of an absorption column in which it is brought into contact in counter-current with the solvent. The dehydrated gas is then extracted at the top of the absorption column and the solvent at the bottom. The solvent is then generally successively cooled, expanded and then heated before being sent into a distillation zone that makes it possible to separate H2O and solvent. The regenerated solvent is then cooled and sent to the top of the absorption column.
Different configurations that are based on this diagram have been the object of patent applications, as described in particular in the documents U.S. Pat. No. 3,105,748, FR-B-2 698 017, and U.S. Pat. No. 4,332,643.
Patent EP 1 035 904 describes a process for dehydration of a wet gas that includes two absorption zones and one zone for regeneration by distillation, whereby the regenerated solvent leaving the second absorption zone is recycled to the first zone.
The processes of the prior art are therefore based on a stage for the regeneration of solvent by thermal means, inevitably requiring a distillation stage and other expensive equipment.
The invention relates to a new process for dehydration of a gas, whereby said process comprises:

    
    
        a) A stage for absorption of H2O by contact of the gas that is to be treated and the regenerated solvent that is obtained from stage e), producing a dehydrated gas effluent and a liquid solvent effluent that is charged with H2O and absorbed gas,
        b) A stage for cooling said solvent charged with H2O to ambient temperature,
        c) A stage for separation by segregation during which the H2O and the solvent are separated at ambient temperature,
        d) A stage in which the regenerated solvent that is obtained at the end of stage c) is heated,
        e) A stage in which the regenerated and heated solvent that is obtained at the end of stage d) is recycled to the absorption stage a).
    
    


The applicant developed an economical dehydration process that implements a minimum amount of equipment while having very good efficiency.
Another advantage of the process according to the invention is that it uses less expensive solvents.
The process of the invention can be applied to any humid gas, advantageously gases having a H2O content is generally between 20 and 80 mol %, especially between 30 and 80 mol %.
The implementation of the process according to the invention makes it possible to obtain a gas whose molar content of H2O is in general reduced by 10 to 50% relative to the molar content of initial H2O, most often from 15 to 40%.
The solvent used in the process of the invention is any solvent that can absorb H2O at a given temperature and desorb H2O at a lower temperature, e.g. ambient temperature advantageously from any of diethyl phthalate of the chemical formula C12H14O4 (DEP in abbreviated form), diethyl sebacate of the chemical formula C14H26O4 (DES in abbreviated form), diethyl azelate of the chemical formula C13H24O4, and diethyl suberate of the chemical formula C12H22O4, preferably diethyl phthalate and diethyl sebacate, and particularly diethyl phthalate.



BRIEF DESCRIPTION OF DRAWING
The attached FIG. 1 is a schematic flowsheet of an embodiment of the invention.



The process of the invention is described in more detail below, in relation to FIG. 1.
In stage a), the wet gas that is to be treated, arriving via a line (1) at a temperature that is generally between 110 and 200° C., and preferably between 130 and 180° C., is brought into contact in an absorption column (2) with the stream of regenerated liquid solvent, arriving via a line (11), and a dehydrated gaseous effluent is extracted from the column via a line (12) to be sent, for example, to a tail gas treatment unit. The contact between the solvent and the gas is operated equally at counter-current or co-current. In general, the absorption column operates at a pressure of between 0.1 and 1 MPa, and preferably between 0.1 and 0.5 MPa. The molar ratio of the solvent/gas to be treated is generally between 0.1 and 20, and preferably between 1 and 15.
Leaving the column, a stream of H2O-saturated solvent is extracted via a pipe (3) and sent into stage b) which comprise cooling the solvent that is charged with H2O at so-called ambient temperature, i.e., at a temperature of between 10 and 30° C., and preferably between 15 and 25° C. The cooling is ensured by any means that is known to one skilled in the art, preferably using an exchanger (4). The cooled gas returns via a line (5) into a separation zone (stage c)), where a liquid-liquid segregation or separation takes place in a piece of separation equipment (6), for example a sedimentation tank or any equipment that is known to one skilled in the art that makes it possible to separate a H2O-rich liquid phase and a solvent-rich liquid phase. The H2O-rich liquid phase is extracted via a line (7) and advantageously can be used in part as a coolant for the exchanger (4). It is then conveyed via a line (8), for example to a H2O treatment unit. The other part of the coolant that supplies the heat exchanger (4) is directed via the pipe (13).
The solvent-rich phase, also called “solvent,” is extracted from the separation equipment (6) via a line (9) and is sent to a heat exchanger (10) to be brought to the operating temperature of the absorption column (2), generally operating at a temperature of between 110 and 200° C., preferably between 130 and 180° C. (stage d)). Leaving the exchanger (10), a line (11) makes it possible to recycle the regenerated and heated solvent to the absorption column (2) (stage e)). In general, the temperature difference between the operating temperature of the absorption column and that of the heated solvent is less than 10° C., and preferably less than 5° C.
The invention is further illustrated by the following non-limiting examples.
EXAMPLE 1
According to the Invention
A Claus unit effluent at a temperature of 170° C. and containing 35 mol % of H2O and the remainder incondensable gases is introduced into an absorption column according to the configuration that is described in FIG. 1, whereby the dehydrating solvent is diethyl phthalate of the chemical formula C12H14O4. The pressure of the absorption column is 0.1 MPa. The molar ratio of solvent/gas to be treated is set at 10, and the solvent (recycled from a sedimentation tank and heated to 170° C.) contains 10 mol % of H2O.
Leaving the absorption column, the solvent is cooled to a temperature of 20° C. At this temperature, a liquid-liquid separation occurs, allowing, on the one hand, the aqueous phase to be recovered, and, on the other hand, the solvent to be recovered.
Table 1 below sums up the primary compositions of the different streams: gas entering the absorption column, (recycled) solvent entering the column, dehydrated gas leaving the column, and solvent leaving the column.












TABLE 1







Gas to be

Dehydrated
Solvent



Dehydrated that
Solvent
Gas
Leaving



is Entering the
Entering the
Leaving the
the



Column
Column
Column
Column



(Line 1)
(Line 11)
(Line 12)
(Line 3)




















Total No. of
1.00
10.00
0.84
10.16


Moles


No. of Mols of
0.35
1.00
0.19
1.16


H2O


H2O Content
35.0
10.0
22.6
11.4


(Mol %)









It is demonstrated in Table 1 that it is possible, by the implementation of the process of the invention, to dehydrate a Claus unit tail gas (35 mol % of H2O) and to bring it to a H2O content that is reduced by 35.4% (relative) in relation to the initial H2O content. The thus dehydrated gaseous feedstock is sent to a Clauspol® unit after having been cooled in advance to the operating temperature of this process, and the sulfur yield of the unit that is obtained is 94% by weight. The latter with a non-dehydrated feedstock by the process of the invention is 93% by weight.
EXAMPLE 2
According to the Invention
A gaseous effluent at a temperature of 160° C., containing 70 mol % of H2O and the remainder incondensable gases is introduced into an absorption column according to the configuration that is described in FIG. 1, whereby the dehydrating solvent is diethyl sebacate of the chemical formula C14H26O4.
The pressure of the absorption column is 0.1 MPa. The molar ratio of the solvent/gas to be treated is set at 10, and the solvent (recycled from a sedimentation tank and heated to 160° C.) contains 8.5 mol % of H2O.
Leaving the absorption column, the solvent is cooled to the temperature of 20° C. At this temperature, a liquid-liquid segregation occurs, and on the one hand, the aqueous phase is recovered, and, on the other hand, the solvent is recovered.
Table 2 below sums up the primary compositions of the different streams: gas entering the absorption column, (recycled) solvent entering the column, dehydrated gas leaving the column, and solvent leaving the column.












TABLE 2







Gas to be

Dehydrated
Solvent



Dehydrated that
Solvent
Gas
Leaving



is Entering the
Entering the
Leaving the
the



Column
Column
Column
Column



(Line 1)
(Line 11)
(Line 12)
(Line 3)




















Total No. of
1.00
10.00
0.73
10.27


Moles


No. of Mols of
0.70
0.85
0.44
1.11


H2O


H2O Content
70.0
8.5
60.3
10.8


(Mol %)









It is demonstrated in Table 2 that it is possible, by the implementation of the process of the invention, to dehydrate a gas that is heavily charged with H2O (70 mol %) and to bring it to a reduced H2O content of 13.8% (relative).
EXAMPLE 3
For Comparison
A Claus unit effluent at a temperature of 170° C. that contains 35 mol % of H2O and the remainder incondensable gases is introduced into an absorption column. The solvent that is introduced at the top of the column is TEG (triethylene glycol). Its temperature is 170° C. The molar ratio of solvent/gas to be treated is set at 10. The pressure of the absorption column is 0.1 MPa.
Leaving the absorption column, the solvent is cooled to the temperature of 20° C. and sent into a sedimentation tank in which H2O-solvent segregation is not observed, and consequently, it therefore cannot be recycled in the absorption column.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
In the foregoing and in the examples, all temperatures are set forth uncorrected in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated.
The entire disclosures of all applications, patents and publications, cited herein and of corresponding application No. FR 08/07.055, filed Dec. 16, 2008 are incorporated by reference herein.
The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.
From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

## Claims

1. A process for the dehydration of a gaseous effluent that comprises:
a) A stage for absorption of H2O by contact of the gas that is to be treated and heated regenerated solvent obtained from stage e), producing a dehydrated gas effluent and a liquid solvent effluent charged with H2O and absorbed gas,
b) A stage for cooling said solvent charged with H2O at ambient temperature,
c) A stage for separation by segregation during which the H2O and the solvent are separated at ambient temperature,
d) A stage in which the regenerated solvent obtained at the end of stage c) is heated,
e) A stage in which the regenerated and heated solvent obtained at the end of stage d) is recycled to the absorption stage a), in which said solvent is any of diethyl phthalate of chemical formula C12H14O4, diethyl sebacate of chemical formula C14H26O4, diethyl azelate of chemical formula C13H24O4, and diethyl suberate of chemical formula C72H22O4.

2. A process according to claim 1, in which said solvent comprises at least one of diethyl phthalate and diethyl sebacate.

3. A process according to claim 1, wherein said solvent is diethyl phthalate.

4. A process according to claim 1, wherein the gaseous effluent to be treated has an H2O content of between 20 and 80 mol %.

5. A process according to claim 4, in which the H2O content of the gaseous effluent to be treated is between 30 and 80 mol %.

6. A process according to claim 1, wherein in stage b), the solvent is cooled to a temperature of between 10 and 30° C.

7. A process according to claim 6, in which in stage b), the solvent is cooled to a temperature of between 15 and 25° C.

8. A process according to claim 1, in which the gas that is to be treated is introduced in stage a) at a temperature of between 110 and 200° C.

9. A process according to claim 1, in which in stage d), the solvent is at a temperature of between 130 and 180° C.

10. A process according to claim 1, in which the H2O recovered during the separation by segregation provides coolant for stage b).

11. A process according to claim 6, in which in stage d), the solvent is at a temperature of between 130 and 180° C.

12. A process according to claim 11, in which the gas that is to be treated is introduced in stage a) at a temperature of between 110 and 200° C.

13. A process according to claim 12, in which in stage b), the solvent is cooled to a temperature of between 15 and 25° C.

14. A process according to claim 13, in which said solvent comprises at least one of diethyl phthalate and diethyl sebacate.

15. A process according to claim 13, wherein said solvent is diethyl phthalate.

16. A process according to claim 15, in which the H2O content of the gaseous effluent to be treated is between 30 and 80 mol %.

17. A process according to claim 1, wherein in (b) the H2O has a temperature of 10-30° C.