• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a method and a system for catalytic oxidation of a lean H2S stream. More specifically, the invention concerns a novel way of removing sulfur dioxide (SO2) formed by catalytic oxidation of hydrogen sulfide (H2S) with the purpose of removing H2S from a gas. This catalytic oxidation of H2S yields sulfur dioxide (SO2) through the use of known catalysts, so-called SMC catalysts.
    公开号:DK201900857A1
    申请号:DKP201900857
    申请日:2018-01-11
    公开日:2019-07-12
    发明作者:Trane-Restrup Rasmus；Saadi Souheil；Bengt Jakobsson Niklas；Qiongxiao Wu Hans；Bian Xiang Tommy
    申请人:Haldor Topsøe A/S；
    IPC主号:
    专利说明:

    Title: Method and system for catalytic oxidation of a lean
    H2S stream
    The present invention relates to a method and a system for catalytic oxidation of a lean H2S stream. More specifically, the invention concerns a novel way of removing sulfur dioxide (SO2) formed by catalytic oxidation of hydrogen sulfide (H2S) with the purpose of removing H2S from a gas. This catalytic oxidation of H2S yields sulfur dioxide (SO2) through the use of known catalysts, so-called SMC catalysts, which will be described in the following.
    The process of removing H2S from a gas can be summarized schematically as follows: An optionally pre-heated H2S-containing gas is mixed with air or oxygen, and then the mixture is fed to a catalyst-containing reactor via a heat exchanger. In this reactor, H2S is oxidized to sulfur dioxide (SO2) according to the reaction
    1.5 O2 + H2S SO2 + H2O
    The idea underlying the present invention is to add syngas to a lean H2S stream, which is to be treated by catalytic oxidation as described above, thereby obtaining SO2. The treatment is carried out in an SMC (Sulfur Monolith Catalyst) unit.
    Thus, the present invention relates to a method for the oxidation of hydrogen sulfide, carbonyl sulfide or carbon disulfide to sulfur dioxide, said method comprising the steps of:
    DK 2019 00857 A1
    - providing a feed gas lean in H2S,
    - adding air or O2 to the feed gas,
    - heating the feed gas to the desired inlet temperature,
    - feeding the gas mixture to an oxidation reactor, which contains a catalyst, and
    - recovering a cleaned gas, wherein syngas is added to the gas mixture prior to feeding the gas mixture to the oxidation reactor.
    The catalyst is preferably a sulfur monolith catalyst.
    Preferably the gas mixture is fed to the oxidation reactor via a heat exchanger.
    Furthermore, the invention relates to a system, in which the method for the oxidation of hydrogen sulfide to sulfur dioxide is carried out. This system comprises a gas blower, a heat exchanger and an oxidation reactor, which contains a catalyst, preferably a sulfur monolith catalyst.
    The SMC technology is aimed at sulfur abatement in gases with low fuel value. The conventional way of treating such gases consists in using support fuel in combination with thermal oxidation. Another way is to blend the gas of low fuel value with the feed gas to a Claus plant or a sulfuric acid plant which, however, often will lead to an increased demand for support fuel and a substantial increase of the size of such a unit.
    The core of the SMC technology is the SMC catalyst, which selectively oxidizes H2S and other sulfur compounds, such
    DK 2019 00857 A1 as carbonyl sulfide (COS) and carbon disulfide (CS2), to
    SO2 and oxidizes higher hydrocarbons, hydrogen and CO to CO2 and water. The SMC catalyst can operate at temperatures from 200°C, and the unique design of the catalyst enables operation with a very low pressure drop, a low surplus of oxygen, low formation of SO3 and without formation of NOx.
    If required, the SO2 formed can be removed in a caustic scrubber.
    In the method of the present invention, the oxidation of
    H2S proceeds at an inlet temperature to the catalyst between 200 and 450°C. Preferably, the inlet temperature to the catalyst is between 250 and 400°C, most preferably between 250 and 300°C.
    Fig. 1 illustrates a typical design as used in the conventional way of gas treatment. In addition to the catalytic oxidation reactor, the design includes two gas blowers, a heat exchanger and a burner to raise the temperature of the feed gas before entering the catalytic reactor.
    Fig. 2 illustrates the design of an SMC unit to be used when carrying out the process of the invention. This design comprises only one gas blower, and use of a gas burner to raise the temperature of the feed gas is not needed.
    By adding syngas to a lean H2S stream, which is to be treated by catalytic oxidation, the heating value of the gas will increase. Further, the amount of equipment needed is minimized, which also holds true for the size of the individual pieces of equipment, especially the size of the
    DK 2019 00857 A1 feed/effluent heat exchanger(s) constituting the most expensive part of the SMC unit. In addition, the OPEX (the operating expense) decreases because expensive feed gases or natural gas can be replaced by cheaper fuel gases, which also are oxidized at a lower air surplus. This decreases the air requirement and the duty of the blowers.
    Basically the SMC technology is the catalytic oxidation of H2S at temperatures between 200°C and 450°C. The oxidation reactions can increase the temperature across the reactor by 10 to 150°C depending on the gas composition. The feed gas is often delivered at ambient temperatures, and heating of the feed gas can be accomplished by a feed/effluent heat exchanger. However, if the gas is lean (low temperature increase), such heat exchangers will become uneconomically large due to a low driving force for the heat exchange process. The heat exchanger itself will often constitute a large fraction of the overall CAPEX (capital expenditure) of an SMC unit. Therefore, a fired heater using fuel gas or natural gas is sometimes used to raise the temperature.
    This adds to both the CAPEX and the OPEX, since a burner as well as a combustion air blower is needed along with continuous consumption of fuel gas or natural gas. Furthermore, NOx (i.e. NO and/or NO2) may be formed in the burner. As mentioned above, use of a burner is not needed in the process of the invention.
    The method according to the invention, which is especially relevant for coal gasification units, includes adding a small fraction of syngas (containing H2, CO and CO2) to increase the temperature raise across the reactor, since both
    DK 2019 00857 A1
    CO and H2 can be oxidized over the SMC catalyst. This approach has the benefits of decreasing the size of the heat exchangers without adding more equipment to the plant. In addition, the oxygen consumption as well as the air blower power consumption will be lower since the SMC unit operates at a lower air surplus compared with a burner, and formation of NOx is avoided. Syngas is most often cheaper than fuel gas or natural gas, whereby the OPEX is reduced.
    Methods as well as catalysts for oxidative conversion of H2S to SO2 are well-known in the art. Thus, EP 2 878 367 A1, belonging to the applicant, relates to materials consisting of V2O5 on a porous support, that are catalytically active in the oxidation of sulfur compounds, such as oxidation of H2S to SO2, at temperatures between 180 and 450°C.
    US 4.314.983 describes a process for converting H2S to SO2 with a solid catalyst comprising at least 5 wt% of bismuth. Essentially no SO3 is formed in the catalytic process. In this patent it is stated that the bismuth content of at least 5 wt% is necessary to stabilize the catalyst.
    US 2014/0020399 describes a method for generating current from an exhaust gas containing H2S. The exhaust gas is combusted, possibly under addition of supplementary fuel, and the heat released is used for current generation. The SO2 and the SO3 in the gas after combustion of the H2S are delivered for desulfurization.
    In RU 2.276.097 C, a process for selective catalytic oxidation of H2S is disclosed. The catalyst is iron oxide supported by a porous oxide. A similar process, in which a
    DK 2019 00857 A1 different catalyst is used, is disclosed in RU 2.533.140 C.
    In none of these documents the possibility of adding syngas to the feed gas prior to entering the catalyst-containing oxidation reactor is mentioned.
    Usual routes to abatement of sulfur are solutions of absorbent type for low concentrations of H2S, whereas higher concentrations of H2S can be used for production of chemicals, e.g. elemental sulfur or sulfuric acid.
    The present invention utilizes catalytic oxidation of H2S to SO2 at temperatures between 200 and 450°C, preferably between 250 and 400°C and most preferably between 250 and 300°C. In comparison with combustion, which takes place at temperatures above 800°C, catalytic oxidation therefore offers the possibility of reducing the use of supplemental fuel in order to increase the temperature, thereby lowering the operating costs. Furthermore, the catalytic oxidation of H2S can be performed at an oxygen concentration of below 2 vol%, measured at the outlet of the H2S oxidation reactor, whereas combustion of H2S typically requires an oxygen concentration of more than 3 vol% at the outlet of the furnace. This means that the process gas flow is reduced compared to combustion, thereby reducing both investment and operating costs.
    In the process of removing H2S from a gas, an SMC catalyst, i.e. a monolithic type catalyst, is used in the reactor converting H2S to SO2. This catalyst is a corrugated fibrous monolith substrate coated with a supporting oxide. It is preferably coated with TiO2 and subsequently impregnated
    DK 2019 00857 A1 with V2O5 and/or WO3. The channel diameter of the corrugated monolith is between 1 and 8 mm, and the wall thickness of the corrugated monolith is between 0.1 and 0.8 mm.
    The monolith type catalyst is preferably manufactured from a support material comprising one or more oxides of metals selected from aluminium, silicon and titanium, and the active catalytic components preferably comprise one or more oxides of a metal selected from vanadium, chromium, tungsten, molybdenum, cerium, niobium, manganese and copper. Said materials are effective in the catalytic oxidation of hydrogen sulfide at low temperatures.
    Monoliths are increasingly being used, developed, and evaluated as catalyst supports in many new reactor applications such as chemical and refining processes, catalytic oxidation, ozone abatement etc. When the active catalyst has a monolithic structure, it displays a low pressure drop as already mentioned.
    The invention is illustrated further in the examples which follow.
    Examples :
    The addition of syngas is interesting in situations where the temperature increase over an SMC catalyst is less than 40°C, which corresponds to a concentration of H2S below 2000-3000 ppm H2S (dependent on the remaining constituents and whether other combustible compounds, like CO or H2, are present). The lower heating value (LHV) should be less than roughly 22 kCal/h.
    DK 2019 00857 A1
    Two situations are investigated: One according to the prior art and one according to the invention, illustrated in Fig. 1 and Fig. 2, respectively.
    Example 1
    This example illustrates the prior art as shown in Fig. 1. In this prior art design, a burner is utilized to increase the temperature approach in the feed/effluent heat exchanger (HEX). The basis of the examples is the feed gas, which has the properties and the composition given in Table 1 below:
    Table 1
    Properties and composition of feed gas
    propertiesTemperature [°C]10Pressure [mbar g]150Flow [Nm3/h]100,000compositionN2 [mole%]14CO2 [mole%]84.7H2O [mole%]1H2S [pm]3000
    In this example, the consumption of fuel gas amounts to 541 Nm3/h.
    DK 2019 00857 A1
    Example 2
    This example illustrates the present invention as shown in Fig. 2. In this inventive design, it is not required to use a burner to increase the temperature approach in the heat exchanger (HEX).
    Syngas is added to raise the temperature increase in the SMC reactor, hereby also improving the temperature approach in the feed/effluent heat exchanger.
    The consumption of fuel gas and syngas, as well as an estimated OPEX based on a fuel gas price of 3 RMB/Nm3 and a syngas price of 0.5 RMB/Nm3 can be seen in Table 2 below. More syngas will be required since the heating value is lower. However, the syngas cost will be much lower compared to Example 1.
    Table 2
    Comparison of examples 1 and 2
    Gas consumption[Nm3/h]Price[mRMB/yr]Relative [%]Example 154113100Example 213805.544
    Regarding the equipment, a blower is saved as well as a burner in the design according to the invention, as can be seen in Fig. 1 and Fig. 2.
    权利要求:
    Claims (6)
    [1] Claims:
    1. A method for the oxidation of hydrogen sulfide, carbonyl sulfide or carbon disulfide to sulfur dioxide, said method comprising the steps of:
    - providing a feed gas lean in H2S,
    - adding air or O2 to the feed gas,
    - heating the feed gas to the desired inlet temperature,
    - feeding the gas mixture to an oxidation reactor, which contains an oxidation catalyst, and
    - recovering a cleaned gas, wherein syngas is added to the gas mixture prior to feeding the gas mixture to the oxidation reactor.
    [2] 2. Method according to claim 1, wherein the oxidation catalyst is a sulfur monolith catalyst.
    [3] 3. Method according to claim 1 or 2, wherein the gas mixture is fed to the oxidation reactor via a heat exchanger.
    [4] 4. Method according to any of the claims 1-3, wherein the oxidation of H2S proceeds at an inlet temperature to the catalyst between 200 and 450°C.
    [5] 5. Method according to claim 4, wherein the inlet temperature to the catalyst is between 200 and 400°C, preferably between 250 and 300°C.
    [6] 6. A system for carrying out the method according to any of the claims 1-5 for the oxidation of hydrogen sulfide to
    DK 2019 00857 A1
    sulfur dioxide, said system comprising a gas blower, a heat exchanger and an oxidation reactor, which contains a cata-
    lyst, preferably a sulfur monolith catalyst.
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    同族专利:
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    引用文献:
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    EP2878367A1|2013-12-02|2015-06-03|Haldor Topsøe A/S|Catalyst for the oxidation of sulfur compounds|
    CA2949146C|2014-05-20|2019-03-26|Worleyparsons Europe Ltd.|Method and apparatus for sulfur recovery|
    CA2960919A1|2014-09-16|2016-03-24|Haldor Topsoe A/S|A process for the oxidation of hydrogen sulfide to sulfur trioxide with subsequent sulfur trioxide removal and a plant for carrying out the process|
    CN104475104B|2014-11-05|2018-03-23|杨楠|Selective catalytic oxidation vulcanizes the technique that hydrogen catalyst, tail gas catalyst to burned and treating technology hydrogen sulfide are sulphur|
    WO2017140662A1|2016-02-15|2017-08-24|Haldor Topsøe A/S|A process and a gas treatment system for combined removal of siloxanes and sulfur containing compounds from biogas streams|
    法律状态:
    2019-07-12| PAT| Application published|Effective date: 20190710 |
    优先权:
    申请号 | 申请日 | 专利标题
    CN201710033153|2017-01-16|
    CN201710033153.XA|CN108310964A|2017-01-16|2017-01-16|The poor H of catalysis oxidation2The method and system of S streams|
    PCT/EP2018/050623|WO2018130598A1|2017-01-16|2018-01-11|Method and system for catalytic oxidation of a lean h2s stream|
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