WO2010102653A1 - Process for the abatement of hydrogen sulphide from compositions containing it with simultaneous production of hydrogen - Google Patents
Process for the abatement of hydrogen sulphide from compositions containing it with simultaneous production of hydrogen Download PDFInfo
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Abstract
Process for the abatement of hydrogen sulphide from compositions containing it with the contemporaneous production of hydrogen, comprising: a. treating hydrogen sulphide with methane (reforming) according to the endothermic reaction: 2 H2S + CH4 = CS2 + 4H2 (1) b. cooling the reaction products and separating the carbon disulphide (CS2); c. burning the carbon disulphide; d. feeding at least an aliquot of the hot gases from the combustion of carbon disulphide to the reforming step, as a heat source for maintaining the endothermic reaction (1). e. disposing of the cooled gases from the combustion of carbon disulphide.
Description
PROCESS FOR THE ABATEMENT OF HYDROGEN SULPHIDE FROM COMPOSITIONS CONTAINING IT WITH SIMULTANEOUS PRODUCTION OF HYDROGEN
The present invention relates to a process for the abatement of hydrogen sulphide from compositions containing it with the contemporaneous production of hydrogen.
More specifically, the present invention relates to a process for the abatement/sweetening of hydrogen sulphide contained in gaseous streams . Hydrogen sulphide is a noxious gas present in many refineries as by-product of hydrodesulphuration installations, and in many oil fields as a blend with natural gas and light hydrocarbons (gas sour) or as a blend with natural gas and carbon dioxide (acidic gases) . Hydrogen sulphide is normally separated from gases by means of absorption with an amine solution and is then sent to a Claus plant in which it is transformed to sulphur.
By operating in this way, the hydrogen present in the molecule of hydrogen sulphide is burned to produce water, whereas the sulphur in the H2S molecule is converted into
elemental sulphur.
Hydrogen is a raw material which is highly requested in refineries for all hydrotreatment processes, such as hy- drocracking and hydrodesulphuration, it would consequently be greatly desirable to be able to obtain it from a source at zero value, such as hydrogen sulphide.
A method which allows hydrogen to be obtained from H2S is methane reforming according to the reaction:
2 H2S + CH4 = CS2 + 4H2 (D This reaction can be carried out with high conversions only at high temperatures (higher than 9000C, for example) and it is highly endothermic (ΔH298 = 232 kj/mole), energy must therefore be provided from the outside, by burning a fuel, such as, for example, the same acid methane for H2S, with a considerable increase in the production costs.
Furthermore, the CS2 thus produced has a limited market, which is continuously decreasing due to the progressive elimination from the market of Freon, which represented one of the derivatives with highest added margin. The Applicant has now found, and this represents an object of the present invention, that it is possible to abate hydrogen sulphide from compositions containing it, with the contemporaneous production of hydrogen, by means of an integrated cycle wherein the CS2 produced by the re- forming reaction between methane and H2S is burned to pro-
duce CO2 and SO2, thus obtaining a blend which can be either advantageously used for the synthesis of sulphuric acid or it can be disposed of by means of traditional methods, for example by injecting it into the subsoil. Further- more, by exploiting the large quantity of reaction heat developed during the combustion of CS2 (ΔH298 = -1032 kj/mole) the previous endothermic reaction of H2S reforming with methane can be sustained without burning any valuable fuel . An object of the present invention therefore relates to a process for the abatement of hydrogen sulphide from compositions containing it with the contemporaneous production of hydrogen, comprising: a. feeding a blend comprising methane and hydrogen sulphide to a reforming reactor operating at a tempera- ture ranging from 900 to 1,5000C and at atmospheric pressure or slightly lower, for example between 0.08 and 0.1 MPa, to produce a blend essentially consisting of carbon disulphide (CS2) and hydrogen (H2) ; b. cooling the reaction products and separating the car- bon disulphide from the remaining reaction blend containing hydrogen; c . burning the carbon sulphide with a gas containing oxygen to produce a gaseous blend, essentially consisting of CO2 and SO2, at a high temperature;
d. feeding at least a part of the hot gases of the carbon disulphide combustion to the reforming step, as a heat source for maintaining the endothermic reaction of step (a) ; and e. using the combustion gases of carbon disulphide, coming from step (d) , as intermediate products for downstream chemical syntheses or disposing of them by injection into suitable geological structures. According to the present invention, the reforming reac- tion of methane/H2S preferably takes place at a temperature ranging from 900 to 1,3000C. This type of reaction is known in literature and is described, for example, in the article of s. K. Megalofonos and N. G. Papayannakos in "International Journal of Hydrogen Energy", vol. 16(5) 1991, pages 319-327, and can also be effected in the presence of a catalyst. Typical examples of catalysts are metal sulphides of Group VIB, VIIB and VIIIB of the periodic table of elements and, among these, sulphides of chromium, molybdenum, tungsten, iron, cobalt and nickel are particularly pre- ferred.
In general, the blends comprising methane and hydrogen sulphide are gaseous streams from refinery plants or they are streams of natural gas from production fields, or gas streams associated with oilfields. These streams can in- elude other inert/acid gases such as nitrogen or carbon di-
oxide. They are preferably gaseous streams in which the H2S concentration ranges from 1 to 65% moles with respect to the total.
When the H2S concentration in the gaseous stream con- taining methane is low, or, in any case, is not such as to satisfy the conditions of the reforming reaction, the stream is preferably treated in an absorption plant of hydrogen sulphide with amines, in order to concentrate and recover it. The hydrogen sulphide stripped from the absorb- ing liquid, can be recombined with a fraction of the gaseous stream containing it so as to have ratios between H2S and CH4 which allow the reforming reaction to be profitably effected.
The reforming reaction preferably takes place with CH4/H2S molar ratios higher than the stoichiometric value of 0.5, for example between 0.51 and 10, so as to reduce the non-reacted hydrogen sulphide concentration in the reaction products, to negligible values.
At the end of the reforming, the reaction products are cooled to an optimal temperature for the subsequent operations, for example to temperatures lower than 500C, in order to recover carbon sulphide, which is liquid at those temperatures, from the gaseous phase essentially consisting of hydrogen, methane and/or residual H2S and possible reac- tion by-products. The gaseous phase can then be treated
with conventional methods, for example by means of the selective adsorption technology, of the PSA type, or membrane treatment, for the recovery of hydrogen.
The cooling phase is preferably effected in heat ex- changers in which the cooling liquid is water which can be transformed into vapour at a temperature of 100-1500C and a pressure of 0.2-10 MPa. The vapour can be used for producing electric energy or as a heat source destined for the running of other plants. Alternatively, before cooling in the heat exchanger, the reaction products can pre-heat the reagents which are to be fed to the reforming reactor.
The carbon sulphide, recovered in the liquid state, is burned in a specific reactor, with air or air enriched in oxygen as comburent . The combustion gases, which leave the combustion reactor at a temperature of 1,000-2,500 0C are partially or totally fed to a further heat exchanger system to heat the reagents, possibly pre-heated, to the right temperature before entering the reforming reactor. In this way, from the integrated cycle described, object of the present invention, the production of hydrogen can be obtained from a stream containing hydrogen sulphide without having to use any external high-quality fuel, and a stream, containing SO2, is also obtained as by-product, which can be advantageously used as raw material for chemi-
cal syntheses, such as, for example, the production of sulphuric acid. Alternatively, if convenient, the stream containing SO2 can be injected into suitable geological structures . If the starting mix is natural acidic gas for H2S, the considerable quantity of heat produced by the combustion of CS2 can also be used for sustaining the separation of methane from H2S by means of the conventional amine process, if the quantity of H2S present in the gaseous stream is con- siderably lower than the H2S/CH4 molar ratio required by the reforming reaction.
An alternative embodiment of the process object of the present invention, again if the starting material is natural gas, envisages that only a portion of the CS2 produced be burned as energy source, whereas the remaining portion is separated and destined for commercialization.
The balance between the aliquot of CS2 burned and that separated and sold, depends on the quantity of heat to be produced for sustaining the endothermic reforming reaction of methane with H2S. The sufficient quantity of CS2 to be destined for combustion for sustaining the methane reforming with H2S is at least equal to 55% by weight of the total CS2 produced. The remaining part of CS2 can, according to necessity, be separated and sold or burned to provide thermal energy for also sustaining other equipment of the
process, such as for example the amine plant, or it can be used for producing high pressure vapour which can be used in this or other plants.
Another innovative aspect of the process object of the present invention is represented by the fact that the sulphur present in the H2S molecule is transformed into SO2, which, in turn, can be transformed, through reactions and processes which are well-known in literature, into sulphuric acid, for example, requested by the chemical indus- try, instead of into elemental sulphur as in the conventional Claus process .
Elemental sulphur, in fact, has considerable environ- iuencal problems relating to its storage and many nations in which there are oil fields impose heavy economical sanc- tions for sulphur storage.
If, on the contrary, sulphur is transformed into sulphuric acid, an easily transportable liquid product is obtained which can be commercialized as such.
The process for the abatement of hydrogen sulphide from compositions containing it, with the contemporaneous production of hydrogen, object of the present invention, can be better understood with reference to the enclosed figure which represents an illustrative but non- limiting embodiment . With reference to the figure, A is a conventional amine
plant for the sweetening of acid gas, B is a thermal recovery heat exchanger, C is a heat exchanger system useful for providing the energy necessary for the reforming, Rl is the methane/H2S reforming reactor and can be, for example, a fixed- or fluid-bed catalytic reactor, E is a condensation and collection system of the CS2 produced in the reactor Rl, R2 is the combustion reactor of CS2.
A stream of acid gas (1) is provided, essentially consisting of methane and a fraction of H2S equal, for exam- pie, to 10% molar. The stream is fed to an amine treatment plant in order to concentrate the H2S fraction. More specifically, an aliquot (2) of the main stream by-passes the amine plane Ά, wnereas the remaining part is processed in this plant for the recovery of hydrogen sulphide containing (8) . This process step is optional as its existence is linked to whether or not the H2S concentration in the feeding stream (1) is such as to satisfy the conditions of the CH4/H2S reforming reaction.
The stream (2) is recombined with hydrogen sulphide (8) so as to form a stream (3) essentially consisting of methane and H2S with the correct molar ratios for the reforming reaction.
The stream (3) is pre-heated in B, brought to the reforming reaction temperature in C and then fed to the reac- tor Rl.
The hot reaction products (4) are recovered from the reactor Rl, at a temperature of about 900-1,500 0C, for example. These hot gases are fed to B in order to pre-heat the reagents and are then fed to the condenser E, in which the carbon sulphide CS2, in the liquid state, stream (9) , is separated from the gaseous phase essentially consisting of H2, non-reacted H2S and methane, stream (5) . An aliquot of the carbon sulphide produced, stream (12), can be diverted from the cycle, object of the present invention, and can be destined for other purposes.
The carbon sulphide (9) and comburent air (10) are fed to the combustion reactor R2. The combustion gases, stream (11) , comprising CO2 and SO2, leave the reactor at a temperature of about 1,000-2,5000C and are fed directly to the heat exchanger C, where the reagent gases (CH4 and H2S) are heated to a temperature of about 900-1,5000C or slightly higher. The stream of heated reagent gases (13) is fed to the reactor Rl, in which the catalyst is contained, consisting, for example, of one or more metal sulphide (s) of groups VIB, VIIB and VIIIB of the periodic table of elements. Sulphides of chromium, tungsten, molybdenum, iron, cobalt and nickel, used alone or combined, are particularly preferred among these metal sulphides . The temperature inside Rl is uniformly maintained at about 900-1,5000C. After heating the reagents of the reforming reaction to
the reaction temperature, the combustion gases of carbon sulphide can be further cooled, in specific equipment not shown in the scheme of the enclosed figure and then used for chemical processes, for example, the synthesis of sul- phuric acid, or they can be disposed of by injecting them into the ground or into deep seawater.
The products of the reforming reaction which, after cooling in E, are in gaseous phase, stream (5) , essentially consist of methane (the reaction excess) and hydrogen. As they can still entrain considerable traces of non-reacted hydrogen sulphide, they are carefully fed to the plant A7 for the recovery of these traces. In the end, the stream (6) , essentially consisting of methane and hydrogen, is discharged from the plant A. An illustrative and non- limiting example is provided hereunder for a better understanding of the present invention and for its embodiment. EXAMPLE A stream of 1,100 Nm3/h of a methane + hydrogen sul- phide blend, consisting of 1,000 Nm3/h of methane and 100 Nm3/h of H2S, is passed through a conventional amine plant, such as, for example, an MDEA plant, thus separating the hydrogen sulphide from the methane .
The hydrogen sulphide, which is desorbed by means of thermal treatment, is joined to an aliquot of the methane
stream in order to have an H2S concentration equal to 65% moles of the blend, the remaining 35% being methane.
The blend thus obtained, with a total flow-rate of 780 Nm3/h, after being heated (to T = 1,0500C) in a system of two subsequent heat exchangers, is fed to the reforming reactor, consisting, in this example, of a fixed-bed reactor packed with a catalyst consisting of Cr2S3 supported on silica, operating at T = 95O0C.
The outgoing fumes consisting of non-reacted CS2, hy- drogen, H2S and methane, are sent to a condenser in which CS2 is separated as a liquid, whereas the stream mainly consisting of hydrogen with small quantities of non- reacted H2S and methane, is sent back to the amine plant.
The CS2 which is obtained (149.6 1/h) is fed to the combustion plant together with air, obtaining a stream consisting of CO2 and SO2 (at T = 1,1000C) . This stream is used for heating the reagents to be fed to the reforming reactor. After transferring its heat to the reagents of the reforming reaction, it can then be fed to a plant for the production of sulphuric acid or disposed of by injecting it into the ground.
Claims
1. A process for the abatement of hydrogen sulphide from compositions containing it with the contemporaneous production of hydrogen, comprising: a. feeding a blend comprising methane and hydrogen sulphide to a reforming reactor operating at a temperature ranging from 900 to 1,5000C and at atmospheric pressure or slightly lower, for example between 0.08 and 0.1 MPa, to produce a blend essentially consisting of carbon disulphide (CS2) and hydrogen (H2) ; b. cooling the reaction products and separating the carbon disulphide from the remaining reaction blend containing hydrogen; c . burning the carbon sulphide with a gas containing oxy- gen to produce a gaseous blend, essentially consisting of CO2 and SO2, at a high temperature; d. feeding at least an aliquot of the hot gases of the carbon disulphide combustion to the reforming step, as a heat source for maintaining the endothermic reaction of step (a) ; and e. using the combustion gases of carbon disulphide, coming from step (d) , as intermediate products for downstream chemical syntheses or disposing of them by injection into suitable geological structures.
2. The process according to claim 1, wherein the blend comprising methane and hydrogen sulphide is a gaseous stream coming from refinery plants or a stream of natural gas coming from production fields, or a gas stream associated with oil fields.
3. The process according to claim 1 or 2, wherein the concentration of hydrogen sulphide in the blend ranges from 1 to 65% moles with respect to the total amount.
4. The process according to any of the previous claims, wherein the reforming reaction is carried out in the presence of a catalyst selected from sulphides of metals of group VIB, VIIB and VIIIB of the periodic system of elements .
5. The process according to any of the previous claims, wherein the reforming reaction is carried out with CH4/H2S molar ratios higher than 0.5.
6. The process according to any of the previous claims, wherein the products of the reforming reaction are cooled to a temperature lower than 500C.
7. The process according to any of the previous claims, wherein the carbon sulphide burned is at least equal to 55% by weight of the total CS2 produced.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010150063A1 (en) * | 2009-06-24 | 2010-12-29 | Eni S.P.A. | Process for upgrading natural gas with a high hydrogen sulfide content |
| ITMI20102017A1 (en) * | 2010-10-29 | 2012-04-30 | Eni Spa | REFORM PROCEDURE STARTING FROM A RAW ACID GAS CURRENT |
| WO2014149216A1 (en) * | 2013-03-21 | 2014-09-25 | Mocon, Inc. | Reactor for near absolute conversion of alternative moiety-containing species into a select moiety-containing species and analytical instrument employing the reactor |
| CN106115701A (en) * | 2016-08-24 | 2016-11-16 | 张贯彪 | Environment-friendly type Carbon bisulfide reacting furnace |
| CN106715390A (en) * | 2014-07-04 | 2017-05-24 | 阿肯马法国公司 | Method for preparing methyl mercaptan |
| JP2017519790A (en) * | 2014-07-04 | 2017-07-20 | アルケマ フランス | Method for producing dimethyl disulfide |
| CN109250763A (en) * | 2017-07-14 | 2019-01-22 | 中国石油化工股份有限公司 | A kind of method of hydrogen sulfide methane reforming hydrogen manufacturing |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB293172A (en) * | 1927-05-26 | 1928-07-05 | Ig Farbenindustrie Ag | Improvements in the manufacture and production of carbon disulphide |
| US2788262A (en) * | 1953-05-01 | 1957-04-09 | Pan American Petroleum Corp | Process for preparation of carbon disulfide |
| US3388971A (en) * | 1965-06-07 | 1968-06-18 | Seymour C. Schuman | Production of hydrogen |
| GB1126465A (en) * | 1964-09-14 | 1968-09-05 | Ivor Gray Nixon | Manufacture of hydrogen and carbon disulphide |
| US4695443A (en) * | 1985-02-14 | 1987-09-22 | Stauffer Chemical Company | Autothermal process for the production of carbon disulfide and hydrogen sulfide |
| DE102004013283A1 (en) * | 2004-03-18 | 2005-10-13 | Guennadi, Berner | Combined production of carbon disulfide and sulfuric acid from sulfur, without use of natural gas fuel, by using heat from oxidation of sulfur to drive the endothermic carbon disulfide production reaction |
| US20060254769A1 (en) * | 2005-04-21 | 2006-11-16 | Wang Dean C | Systems and methods for producing oil and/or gas |
-
2009
- 2009-03-13 WO PCT/EP2009/001918 patent/WO2010102653A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB293172A (en) * | 1927-05-26 | 1928-07-05 | Ig Farbenindustrie Ag | Improvements in the manufacture and production of carbon disulphide |
| US2788262A (en) * | 1953-05-01 | 1957-04-09 | Pan American Petroleum Corp | Process for preparation of carbon disulfide |
| GB1126465A (en) * | 1964-09-14 | 1968-09-05 | Ivor Gray Nixon | Manufacture of hydrogen and carbon disulphide |
| US3388971A (en) * | 1965-06-07 | 1968-06-18 | Seymour C. Schuman | Production of hydrogen |
| US4695443A (en) * | 1985-02-14 | 1987-09-22 | Stauffer Chemical Company | Autothermal process for the production of carbon disulfide and hydrogen sulfide |
| DE102004013283A1 (en) * | 2004-03-18 | 2005-10-13 | Guennadi, Berner | Combined production of carbon disulfide and sulfuric acid from sulfur, without use of natural gas fuel, by using heat from oxidation of sulfur to drive the endothermic carbon disulfide production reaction |
| US20060254769A1 (en) * | 2005-04-21 | 2006-11-16 | Wang Dean C | Systems and methods for producing oil and/or gas |
Non-Patent Citations (1)
| Title |
|---|
| HUANG ET AL: "Liquid hydrogen production via hydrogen sulfide methane reformation", JOURNAL OF POWER SOURCES, ELSEVIER SA, CH, vol. 175, no. 1, 26 November 2007 (2007-11-26), pages 464 - 472, XP022361662, ISSN: 0378-7753 * |
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