Chemical apparatus and process disinfecting – deodorizing – preser – Chemical reactor – Waste gas purifier
Reexamination Certificate
2000-02-29
2001-11-13
Tran, Hien (Department: 1764)
Chemical apparatus and process disinfecting, deodorizing, preser
Chemical reactor
Waste gas purifier
C422S168000, C422S170000, C422S173000, C422S234000, C422S235000
Reexamination Certificate
active
06315961
ABSTRACT:
FIELD OF THE INVENTION
The present invention concerns a process and apparatus for purifying a gas containing hydrogen sulphide and sulphur dioxide.
BACKGROUND OF THE INVENTION
A variety of gas mixtures originating from refineries and natural gas contain hydrogen sulphide (H
2
S) which must be eliminated as completely as possible by recovering sulphur so as to be able to discharge into the atmosphere a gas which satisfies regulations fixed by various industrialised countries. While these regulations were relatively easy to satisfy in the very recent past since they were relatively lenient, this is not the current case particularly in countries such as the United States of America or some states in that country and a gas mixture containing more than 500 parts per million (ppm) of sulphur dioxide and hydrogen sulphide can no longer be discharged into the atmosphere.
As long ago as 1970, the Institut Franqais du Petrole developed a process for eliminating hydrogen sulphide as elemental sulphur using the Claus reaction under conditions which were particularly favourable as regards ease of operation and the relatively low cost of the process. The process, which is known under the trade name Claupol 500, employs a homogeneous catalyst in a solvent to transform hydrogen sulphide to elemental sulphur at a temperature of less than 160° C. by reaction with sulphur dioxide (SO
2
). After treating the acidic gas containing hydrogen sulphide in a conventional Claus unit, it produces an overall sulphur yield of more than 98%. This process is used industrially in more than 30 plants in various countries of the world, among them the United States.
The initial process developed in the 70s has recently been improved, at the beginning of the 90s, and can now produce a sulphur yield which is of the order of 99.5%. The initial process is described, for example, in the article by Y. Barthel et al., published in 1974 in n° 136 of the review “Informations Chimie”, pages 235 to 238, and in “Pétrole et Technique”, n°136, October 1993, pages 24 to 39. The improved process normally known as the CLAUSPOL 300 process has been described in the “Revue de l'Institut Francais du Pétrole”, vol. 49, n°5, September-October 1994, pages 491-493.
Those two processes use a liquid phase essentially constituted by glycol which is circulated as a counter-current to the gas mixture to be purified containing hydrogen sulphide and sulphur dioxide in a ratio of close to 2. Such processes use a catalyst dissolved in glycol, which is selected from alkali or alkaline-earth metal carboxylates.
The prior art is also illustrated in the following patents: French patents FR-A-2 216 223, FR-A-2 532 190, FR-A-2 338 738 and Japanese patent JP-A-54 072 762 (WPI Database, Section Ch, Week 7929, Derwent Publications Ltd., London, GB; AN 79-53653 B).
SUMMARY OF THE INVENTION
The present invention concerns the treatment of a gas mixture comprising sulphur dioxide and hydrogen sulphide. Mixtures which can be treated using the process of the present invention may be the gases discharged by sulphuric acid production factories, by combustion plants using fuels containing sulphur, and those originating from the transformation of hydrogen sulphide to elemental sulphur by the Claus process. In all of these cases, in addition to sulphur dioxide, the gas mixture which can be treated using the process of the present invention will also contain hydrogen sulphide, preferably in a quantity which is close to the stoichiometric quantity for the Claus reaction, namely two moles of hydrogen sulphide per mole of sulphur dioxide. If the mixture to be treated does not contain hydrogen sulphide or contains only a little, it will be necessary to add it before introduction into the reactor in which the process of the present invention is carried out. If the mixture to be treated contains too much hydrogen sulphide, a portion of it can, for example, be transformed into sulphur dioxide by oxidation so as to obtain a suitable ratio of the two compounds.
We have, surprisingly, discovered that the process for recovering sulphur from a gas mixture containing hydrogen sulphide and sulphur dioxide can be further improved by reacting these two compounds with each other in a liquid reaction medium comprising a solvent for these two compounds, preferably a glycol type solvent, by bringing the gas mixture containing sulphur dioxide and hydrogen sulphide into co-current contact in the presence of at least one basic compound which is soluble in the solvent used.
In a preferred implementation, the liquid reaction medium will contain at least one alkali metal or alkaline-earth metal carboxylate in the dissolved state but it is also possible to use other basic compounds such as ammonia.
Preferably, the quantity of hydrogen sulphide contained in the liquid medium in which elemental sulphur is formed by reaction with sulphur dioxide is about 1.5 to about 2.5 moles and advantageously about 1.9 to about 2.1 moles of hydrogen sulphide per mole of sulphur dioxide.
The present invention is particular suitable for treating Claus plant tail gases, which still contain a small quantity of hydrogen sulphide and sulphur dioxide. In this case, a small portion of the hydrogen sulphide normally introduced into the Claus reactor inlet is usually extracted without modifying the quantity of air injected. In this way, the gases discharged by the Claus plant comprise H
2
S and SO
2
in an H
2
S/SO
2
molar ratio of a little less than 2. This ratio is then adjusted to obtain a ratio of close to 2 in the solvent by adding a suitable quantity of hydrogen sulphide to the gas mixture which has been removed from the Claus plan inlet.
In a further implementation, a ratio of air/H
2
S introduced into the Claus plant is selected so as to produce a tail gas containing a proportion of hydrogen sulphide and sulphur dioxide such that the H
2
S/SO
2
ratio is close to 2.
In the process of the present invention, the solvents which can be used are those which can dissolve H
2
S and SO
2
and which are stable at the temperature selected for the elemental sulphur formation reaction. These solvents are, for example, those mentioned in our French patents FR-A-2 123 778 and FR-B-1 601 098. A glycol is preferably used, such as ethylene glycol, propylene glycol, a liquid polyethylene glycol and a liquid polypropylene glycol. Advantageously, a polyethylene glycol with a molecular weight of the order of 400 is used.
The basic compound dissolved in the solvent which is used can be one of those mentioned in the patents cited above or one of those mentioned in U.S. Pat. No. 3,598,529, which is hereby incorporated by reference. Advantageously, at least one alkali or alkaline-earth salt of a carboxylic acid is used, preferably at least one alkaline salt of a carboxylic acid containing an aromatic ring in its formula. Thus, for example, an alkaline salt of benzoic acid and/or an alkaline salt of salicylic acid can be used. A sodium salt of salicylic acid is normally used, either by introducing it into the solvent in the form of a salt, or by introducing salicylic acid and a sufficient quantity of an aqueous caustic soda solution into the solvent.
The invention also concerns an apparatus for carrying out the process. More precisely, it comprises at least one substantially vertical reactor
2
containing at least one packing
2
a,
the reactor comprising, proximate its upper end above the packing, at least one means
3
for introducing a gas mixture containing hydrogen sulphide and sulphur dioxide, and located below the packing, at least one means
7
for evacuating a residual gas mixture and at least one means
1
for withdrawing a liquid reaction medium, and at least one means
9
,
13
for separating and recovering liquid sulphur, and at least one means
4
,
14
for recycling liquid reaction medium to proximate its upper end above said packing connected to the withdrawing means
1
, the apparatus further comprising at least one means
10
for indirect heat exchange connected to the means
4
,
14
for recycling the liquid
Boucot Pierre
Viltard Jean Charles
Institut Francais du Pe'trole
Millen White Zelano & Branigan P.C.
Tran Hien
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