Chemistry of inorganic compounds – Sulfur or compound thereof – Elemental sulfur
Reexamination Certificate
1999-10-07
2001-08-21
Griffin, Steven P. (Department: 1754)
Chemistry of inorganic compounds
Sulfur or compound thereof
Elemental sulfur
C423S575000, C423S576200
Reexamination Certificate
active
06277352
ABSTRACT:
FIELD OF THE INVENTION
The object of the present invention is a method for processing, by means of a solvent, a gaseous effluent containing at least hydrogen sulfide and sulfur dioxide, during which by-products formed during the solvent processing method are extracted.
The method according to the invention can notably be applied in processing units used after the Claus process.
BACKGROUND OF THE INVENTION
The Claus process is widely used, notably in refineries (after hydrodesulfurization or catalytic cracking units) and for processing of natural gas, to recover elemental sulfur from gaseous feeds containing hydrogen sulfide. However, the fumes produced by Claus plants contain, even after several catalytic stages, appreciable amounts of acid gases. It is then necessary to process these Claus plant effluents (tail gas) to remove most of the toxic compounds so as to abide by antipollution standards. Since these standards become increasingly severe, it is essential to permanently improve the existing technology.
It is for example well-known to recover about 95% by weight of the sulfur present from a Claus plant.
Processing this Claus plant effluent with a Clauspol plant allows for example to reach 99.8% by weight of solvent recovered, from the exothermic Claus reaction:
2 H
2
S+SO
2
→3 S+2 H
2
O (reaction 1)
Such processing requires a reaction medium consisting of an organic solvent and a catalyst comprising an alkaline or alkaline-earth salt of an organic acid. Contacting the gas to be processed and the organic solvent containing the catalyst can be carried out countercurrent or cocurrent, in a vertical or horizontal gas-liquid contactor reactor whose temperature is controlled by passage of the solvent that has been extracted at one end of the contactor reactor by a circulation pump into a heat exchanger so as to favour the highest sulfur conversion coefficient while preventing formation of solid sulfur. It is well-known that, in this type of plant, the solvent that has a limited capacity for dissolving elemental sulfur becomes loaded with free liquid elemental sulfur that can be separated from the solvent by simple decantation This liquid sulfur—solvent decantation is carried out in a liquid-liquid decantation zone that can be situated at the bottom of the contactor reactor. The sulfur is thus recovered in liquid form.
Operation of such a plant is for example described in one of the following reference books:
Y. BARTHEL, H. GRUHIER, The IFP Clauspol 1500 process: eight years of industrial experience, Chem Eng. Monogr., 10 (Large Chem. Plants), 1979, pp.69-86;
HENNICO A., BARTHEL Y., BENAYOUN D., DEZAEL C., Clauspol 300: the new IFP TGT process, For presentation at AICBE Summer National Meeting, Denver (Colo.), Aug. 14-17, 1994.
It is also well-known that the desulfurization rate of a plant of this type can be improved by desaturating the solvent in sulfur according to a process described in patent FR-2,735,460 filed by the applicant. In this case, part of the single-phase solvent and sulfur solution extracted at the end of the contactor reactor is cooled in order to crystallize the sulfur. This crystallized sulfur is then separated from the solvent by various known solid-liquid separation means such as filtration, decantation or centrifugation. A sulfur-depleted solvent that can be recycled to the contactor reactor is obtained on the one hand, and a suspension enriched in solid sulfur that can be reheated to melt the sulfur, then sent to a solvent-sulfur liquid-liquid decantation zone where the liquid sulfur is recovered is obtained on the other hand.
Although such methods prove to be very effective, they can however be limited by constraints.
For example, side reactions occur in the contactor reactor, leading to formation of solid by-products, mainly salts such as alkaline or alkaline-earth sulfates or thiosulfates, due for example to the slow degradation of the catalyst. These solids tend to accumulate and to increase in the decantation zone at the interface between the organic solvent and the liquid suffer, which makes decantation of sulfur difficult.
One way allowing to overcome this problem is described in patent FR-2,735,460, which discloses the possibility of passing a solvent containing such salts through a filter. The salts settle on the filter, and the sulfur-containing solvent is sent to a sulfur-desaturation stage. Such processing of the circulating solvent is however not sufficient to entirely remove any accumulation of these salts at the liquid sulfur-solvent interface, including the liquid sulfur-solvent decantation zone situated downstream from the zone intended for sulfur desaturation of the solvent.
SUMMARY OF THE INVENTION
The object of the present invention is a method and its associated device wherein a liquid fraction F containing the solid by-products formed during side reactions is extracted, and this fraction is processed so as to remove said by-products and to obtain a solvent practically free of said by-products.
These by-products are for example the result of the slow degradation of the catalyst.
Extraction can be continuous or discontinuous, and accumulation of these by-products is controlled. The by-products are removed for example when this accumulation leads to sulfur decantation difficulties.
The solvent practically free of solid by-products can be advantageously recycled to the contactor reactor where the gas is processed.
The invention relates to a method for processing a gas containing at least hydrogen sulfide (H
2
S) and at least sulfur dioxide (SO
2
), wherein said gas is contacted, at a suitable temperature, with an organic solvent containing at least one catalyst, a gaseous effluent substantially containing no hydrogen sulfide and no sulfur dioxide any more is recovered, liquid sulfur separated from the solvent by liquid-liquid decantation.
It is characterized in that:
a layer comprising by-products is situated between the liquid sulfur and the solvent that have been separated,
a liquid fraction F containing at least solid by-products is extracted from said layer, and
said liquid fraction F is sent to a processing stage distinct from the contacting stage, after which at least a stream F
1
comprising most of the byproducts and a stream F
2
mostly comprising solvent nearly free of by-products are recovered.
The processing stage is for example carried out by implementing at least one of the following procedures:
a) sending an aqueous phase such as water under temperature, pressure and flow rate conditions selected to solubilize at least most of the solid by-products in said aqueous phase, and to obtain at least liquid-liquid demixing between this aqueous phase and an organic phase containing most of the solvent extracted, and/or
b) carrying out at least one filtering stage, and/or
c) carrying out a stage of capture, on a solid support, of the by-products so as to recover at least two phases, a phase mainly consisting of solvent depleted in solid by-products and a phase, resulting from regeneration of the capture bed, containing most of the by-products.
At least a third phase mainly consisting of sulfur is for example recovered during procedure a).
It is possible to carry out:
procedures a) or b) or c) at a temperature ranging for example between 120 and 180° C., and/or
procedure a) at a pressure ranging for example between the atmospheric pressure and 1.5 MPa
Procedure a) is for example carried out at a selected temperature and/or pressure so as to prevent formation of a gas phase.
The position and/or the thickness of the layer containing the solid by-products are for example controlled.
At least part of stream F
2
mainly consisting of solvent is for example sent to a stage of sulfur desaturation of the solvent and the sulfur-depleted solvent phase is partly or totally recycled to the contacting stage.
The method can also comprise a heating stage for favouring crystallization of the by-products formed.
The invention also relates to a device allowing to remove or to recover by-products formed during a process for
Barrere-Tricca Cecile
Benayoun Daniel
Lecomte Fabrice
Streicher Christian
Antonelli Terry Stout & Kraus LLP
Griffin Steven P.
Institut Francais du Pe'trole
Vanoy Timothy C
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