Abstract
The present invention relates to a method (1) for determining a content of H.sub.2S in a process gas comprising H.sub.2S. The method (1) comprises extracting (2) a sample of the process gas, performing oxidation (4) of at least a major portion of H.sub.2S of the sample, whereby oxidation products comprising elemental sulfur are formed, analysing (6) the oxidized sample by optical absorption spectroscopy at wavelengths above 310 nm, and determining (8) the content of H.sub.2S in the process gas based on the analysing. The invention further relates to a system (100) for determining a content of H.sub.2S in a process gas comprising H.sub.2S, and use of system (100).
Claims
1. Method (1) for determining a content of H.sub.2S in a process comprising H.sub.2S, the method comprising: extracting (2) a sample of the process gas, performing oxidation (4) of at least a major portion of H.sub.2S of the sample, wherein the performing oxidation (4) comprises heat treating the sample a temperature of 300° C. to 400° C. in the presence of oxidizing agent and a catalyst, whereby oxidation products comprising elemental sulfur are formed, analysing (6) the oxidized sample by optical absorption spectroscopy at wavelengths from 310 nm to 700 nm, and determining (8) the content of H.sub.2S in the process gas based on the analysing.
2. The method (1) according to claim 1, wherein the analysing (6) the oxidized sample by optical absorption spectroscopy comprises obtaining at least one spectrum, and determining (8) the content of H.sub.2S in the process gas based on the analysing comprises comparing the obtained at least one spectrum with at least one reference spectrum.
3. The method (1) according to claim 1, wherein the heat treating the sample is at a temperature of 300° C. to 310° C.
4. The method (1) according to claim 1, wherein the performing oxidation is catalysed by activated aluminium(III) or titanium(IV) oxide.
5. The method (1) according to claim 1, wherein S.sub.2 is formed during the performing oxidation.
6. The method (1) according to claim 1, wherein the analysing (6) the oxidized sample by optical absorption spectroscopy is performed at between 170° C. and 190° C.
7. The method (1) according to claim 1, wherein the oxidizing agent is present in the process gas or is introduced to the sample after the extracting of the sample.
8. The method (1) according to claim 1, wherein the oxidizing agent is oxygen.
9. The method (1) according to claim 1, wherein the optical absorption spectroscopy is differential optical absorption spectroscopy, DOAS.
10. The method (1) according to claim 1, wherein the sample is extracted as a flow of gas from a flow of process gas.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) This and other aspects of the present disclosure will now be described in more detail, with reference to the appended drawings showing embodiments of the invention, in which:
(2) FIG. 1 schematically illustrates a method for determining a content of H.sub.2S in a process gas comprising H.sub.2S.
(3) FIG. 2 schematically illustrates a spectrum obtained according to an embodiment.
(4) FIG. 3 schematically illustrates a system according to embodiments.
(5) FIG. 4 schematically illustrates a transmission spectrum obtained during an experiment.
(6) As illustrated in the figures, the sizes of parts and portions for example may be exaggerated for illustrative purposes and, thus, are provided to illustrate the general structures of embodiments of the present invention. Like reference numerals refer to like elements throughout.
DETAILED DESCRIPTION
(7) The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which currently preferred embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided for thoroughness and completeness, and fully convey the scope of the invention to the skilled person.
(8) An embodiment will now be described with reference to FIG. 1. FIG. 1 schematically illustrates a method 1 for determining a content of H.sub.2S in a process gas comprising H.sub.2S. The method 1 comprises extracting 2 a sample of the process gas; performing oxidation 4 of at least a major portion of H.sub.2S of the sample, whereby oxidation products comprising elemental sulfur are formed, analysing 6 the oxidized sample by optical absorption spectroscopy at wavelengths above 310 nm, and determining 8 the content of H.sub.2S in the process gas based on the analysing.
(9) The method 1 efficiently allows the content of H.sub.2S in process gas to be determined, at least in part since the method allows for minimizing detection interference from compounds which are not derived from H.sub.2S. FIG. 2 illustrates a spectrum obtained from analysis of process gas containing H.sub.2S, where a sample has been extracted and oxidized similarly to embodiments. The analysis involved optical absorption spectroscopy on the oxidized sample at wavelengths approximately between 240 and 355 nm. It is evident from the spectrum that between 240 and 310 nm considerable absorption occurs, in part by SO.sub.2. It shall be mentioned that H.sub.2S has absorbance within the interval 240 to 310 nm and would thus be masked by the considerable absorption in this wavelength range. The treatment of the sample by oxidation has resulted in oxidation products from H.sub.2S which is seen as the three peaks within the interval 330 to 360 nm, which peaks are clearly not disturbed by interfering compounds. The three peaks have been identified as corresponding to elemental sulfur compounds.
(10) Performing oxidation of H.sub.2S of the sample will now be discussed. Oxidation of H.sub.2S may, at least in part, be described by what sometimes is referred to as the Claus process, which Claus process describes production of elemental sulfur from gaseous hydrogen sulfide.
(11) An overall reaction describing reactions of the Claus process may be illustrated by reaction (1):
8 H.sub.2S+5 O.sub.2.fwdarw.SO.sub.2+7/2 S.sub.2+8 H.sub.2O (1).
(12) Oxidation of H.sub.2S may, at least in part, further be described by reaction (2):
2 H.sub.2S+SO.sub.2.fwdarw.3 S+2 H.sub.2O (2).
(13) Reaction (2) may be catalysed by a suitable catalyst, for example activated aluminium(III) or titanium(IV) oxide. SO.sub.2 acts as oxidizing agent in reaction 2.
(14) The elemental sulfur obtained in anyone of reactions (1) and (2) may be converted to other forms of elemental sulfur or other sulfur compounds.
(15) The oxidation may be described by anyone of reactions (1) and (2) and combinations of both.
(16) Elemental sulfur formed in the oxidation of H.sub.2S may transform to other sulfur compounds or forms of elemental sulfur. Such transformation may be assisted by light emitted during the optical absorption spectrometry, for example if a Xenon lamp is used during the spectrometry. Particularly, UV light will assist in the transformation.
(17) The use of the invention and embodiments of the invention for determining a content of H.sub.2S in a process gas comprising H.sub.2S comprises performing oxidation of H.sub.2S, according to discussions herein. Any suitable type of process gas may be relevant. The oxidation of H.sub.2S, for example as illustrated by reactions (1) and/or (2) may be realized by compounds acting as oxidizing agents being present in the process gas, and/or may be realized by compounds added to the sample of process gas, depending on the type of process gas. Typically, the process gas comprises small amounts of H.sub.2S and, thus, only small amounts of oxidizing agent(s) are necessary for oxidation. Small amounts of oxidizing agent(s) may be present as for example O.sub.2 and/or SO.sub.2. If a user of the method is uncertain with regard to if a sufficient amount of oxidizing agent is present or not, the method according to an embodiment may be performed without addition of oxidizing agent and the results analysed to find out if oxidation of H.sub.2S occurs, optionally by comparing with performance with addition of oxidizing gas.
(18) For example, if the process gas is a flue gas, the process gas may comprise SO.sub.2. For example, if the process gas is a gas flow from or within a paper mill, or as a mixture with air the process gas may contain SO.sub.2 and/or O.sub.2.
(19) The method may be performed with an addition of oxidizing agent. Addition of oxidizing agent may be based on an expected or estimated amount of H.sub.2S in the process gas.
(20) Addition of oxidizing agent may be in excess in relation to the amount of H.sub.2S. It is not necessary to estimate the amount of H.sub.2S in the process gas.
(21) With reference to FIG. 3, a method and a system for determining a content of H.sub.2S in a process gas comprising H.sub.2S will now be discussed. FIG. 3 illustrates a system 100 for determining a content of H.sub.2S in a process gas comprising H.sub.2S. The system 100 comprises: an extractor 102 arranged to extract a sample of the process gas, a reactor 104 arranged for oxidation of at least a major portion of H.sub.2S of the sample, whereby oxidation products are formed, an optical absorption spectrometer 106 arranged to analyse the sample above 310 nm and to output data pertaining to the analysis, and a processing unit 111 arranged to receive the data from the optical absorption spectrometer 106 and to determine the content of H.sub.2S in the process gas based on the data.
(22) As further illustrated in FIG. 3, the optical absorption spectrometer 106 may comprise a light emitter 108, which may be arranged to emit broad spectral light comprising light above 310 nm in wavelength. The optical absorption spectrometer 106 further may comprise a light receiver 110, which is arranged to receive and register or convey light emitted from the light emitter 108 after having passed through an absorption device 112. The absorption device 112 is in the depicted embodiment of FIG. 3 a duct through which the sample gas may be conveyed. The optical absorption spectrometer 106 of FIG. 3, comprises a spectrometer, not shown, for analysing the light having passed through the absorption device 112. The spectrometer may be connected to the light receiver 110 in different ways. The spectrometer may be arranged adjacent to or directly on the light receiver 110. The spectrometer may as an alternative be arranged at a distance from the light receiver 110. In this case light as received by the light receiver 110 may by conveyed or forwarded to the spectrometer through an optical fibre, not shown. The spectrometer may be of any suitable type. The spectrometer may preferably include analysing capabilities used to analyse the light received by the light receiver 110. The spectrometer of the optical absorption spectrometer 106 may produce and output data pertaining to the analysis of the light being carried out. The optical absorption spectrometer 106 of FIG. 3 is connected to the processing unit 111.
(23) According to this example, the sample of process gas is obtained from a stack 114. The reactor 104 may comprise an inlet for oxidizing agent for oxidation of at least a major part of H.sub.2S in the sample. According to an embodiment, at least a part of the system is arranged internally in a stack or pipe arranged for forwarding process gas.
(24) With further reference to FIG. 3 a method 1 for determining a content of H.sub.2S in a process gas comprising H.sub.2S will now be discussed in detail as an exemplary method and with reference to the system also discussed with reference to FIG. 3 where relevant. Suitable pipings may be employed for passing of gas through the system, where relevant. The process gas 102 may be gas from a stack emitting gaseous exhausts from a petroleum industry. A sample is extracted from the process gas. The extracting 2 according to this example is by means of continuous pumping a gas flow from the stack 114 using pump 116 and pipings 118. It is realized that samples alternatively may be provided, for example, batch wise, or as distinct sample volumes. In other applications, for example a pressure differences between the stack and its surrounding may be used instead of a pump 116. The, thus, collected sample is forwarded via pipings 118 to the reactor 104, which may be of any suitable shape and material and according to this example is a vessel made of metal. The reactor 104 of this example contains a catalyst for oxidation of H.sub.2S. In this example, the sample is heated by a heater (not illustrated) such that it is maintained above 300° C., and around 305° C., in the reactor 104. The process gas of this example contains sufficient amount of oxidizing gas to oxidise at least a major part of the H.sub.2S. With other process gasses or examples, oxidizing agent(s) may be needed. Oxidizing agents may be added via a duct 120 suitably connected to or upstream the reactor 104. Therefore, the reactor may be arranged to receive oxidizing agent(s), for example oxygen, air, or any other suitable oxidizing agent. In the reactor 104, H.sub.2S of the sample is contacted with oxidizing agents and at least a major part of the H.sub.2S is oxidized. According to this example, essentially all of the H.sub.2S present in the sample is oxidized. The oxidation results in oxidation products, for example according to anyone of the reactions (1) and (2). The oxidation products may be, for example, elemental sulfur such as S.sub.2. After performing the oxidation 4 the sample is forwarded for sample analysis by absorption spectroscopy, taking place in the optical absorption spectrometer 106, whereby continuous light comprising wavelengths in the range of 240 to 360 nm is passed through the sample. The light receiver 110 detects, and processes, light having passed through the sample. A spectrum, similar to the spectrum illustrated in FIG. 2 is obtained from the sample analysis by the spectrometer of the optical absorption spectrometer 106. Compounds in the sample may absorb light within the emitted light range as is known to a skilled person. As described above a spectrometer is typically used for determination of the spectrum of the radiation after absorption in the absorption device 112. The measured spectrum is analysed and/or compared to a known spectrum of the radiation source and the unique absorption spectra for the gas species along the radiation path may thus be identified. It is known that the absorption of light by a compound is proportional to the concentration of the compound and the pass length of the light through the sample containing the compounds. Reference may be made, for example, to Beer's law in this respect. According the Beer-Lambert law the absorption for a specific compound or species may be calculated as follows: A=In(I.sub.0/I.sub.1)=ε.Math.L.Math.c, where ε is absorption cross section of the species is question, L is the absorbing length and c is the concentration of the species. Hence, by knowing the length L of the absorption device 112 and the absorption cross section ε of the species in question, the concentration c of the species may be calculated. The calculation may thus be performed by the processing unit 111, based on the data received form the optical absorption spectrometer 106 in combination with known data pertaining to known cross sections ε for species of interest. In this example, the cross section of sulfur comprising oxidation products originating from the H.sub.2S are typically of interest as this allows for determination of the content or concentration of H.sub.2S in the process gas being extracted from the stack 114.
(25) After the sample analysis, the sample of process gas may be returned back to the flow of process gas or elsewhere.
(26) Determining 8 the content of H.sub.2S in the process gas is in this example made by comparing absorption data obtained from the analysis with data obtained from a reference analysis of a sample with known concentration of H.sub.2S of 1000 ppm, by comparing the spectra. Sample with other known concentrations of H.sub.2S may be used similarly. Peaks in the spectrum above 310 nm from the sample analysis were compared with corresponding peaks from the reference analysis, which enabled quantification of H.sub.2S in the process gas. Several known techniques for quantification of compounds using reference analysis may be used for the determining the content of H.sub.2S in the process gas. It shall be understood from the descriptions herein that it is not necessary to understand which components are formed in the oxidation of H.sub.2S in order to quantify H.sub.2S in the process gas, when taking advantage of reference analysis of a sample with known amount of H.sub.2S.
(27) With reference to FIG. 4, determining a content of H.sub.2S in a process gas will now be described with reference to an experiment. In this experiment the process gas consisted of a mixture of H.sub.2S and air. 4 l/min of the process gas was extracted as a sample. The sample was transferred to a reactor 104 wherein the sample was contacted with a catalyst material composed of HASTELLOY® under heating to 300° C. to allow for oxidation of a major portion of the H.sub.2S in the sample to occur under formation of oxidation products comprising elemental sulfur. After the oxidation, the sample was introduced to a one metre absorption device 112, i.e. an optical cell having a length of one metre. An Opsis AR600 DOAS spectrometer was used to record a transmission spectrum, whereby the spectrum illustrated in FIG. 4 was obtained. The transmission spectrum of FIG. 4 is showing a limited part of the recorded spectrum. More specifically, the transmission spectrum of FIG. 4 is showing the transmission in the wavelength interval of 325 nm to 336 nm. The transmission decreases present at about 327 nm, 331 nm and 334 nm correspond to elemental sulfur formed during the oxidation, and, thus, to the content of H.sub.2S in the process gas. The content of H.sub.2S in the process gas may consequently be determined from the transmission decreases in the spectrum. It shall be appreciated that SO.sub.2 possibly present in the process gas will not interfere with the transmission decreases corresponding to elemental sulfur, as SO.sub.2 has a predominant absorption at wave lengths below those of elemental sulfur. This is evident when comparing with FIG. 2, from which it is clear that SO.sub.2 absorbs in a range of 260-320 nm.
