• 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 method relates to a two-stage catalytic oxidation of sulfur compounds in humid gases, in which 98 wt% sulfuric acid is recovered in a condensation tower in countercurrent with concentrated sulfuric acid and the heat is transferred via a heat exchanger system to the raw gas and the gases after the first Reactor stage, quench, filtration and post-reactor with> 99.8% desulfurized.
    公开号:AT513414A1
    申请号:T1082/2012
    申请日:2012-10-08
    公开日:2014-04-15
    发明作者:Walter Dipl Ing Kanzler
    申请人:Kanzler Walter；
    IPC主号:
    专利说明:

    Process for the two-stage catalytic oxidation of sulfur compounds in moist gases.
    Exhaust gases from roasting processes, kiln exhaust gases in metallurgy, acid gases, etc. often contain sulfur compounds such as sulfur dioxide, hydrogen sulfide, carbon disulfide, mercaptans and the like. in concentrations so high that their deposition as sulfuric acid and its economic use is profitable.
    In the presently conventional method, this object is achieved in that brings the exhaust gases through heat exchanger systems and the heat of reaction to the required reaction temperature of 300 - 450 ° C, the gases passes through one or more catalysts and thereby reaches degrees of conversion up to 99%. Thereafter, the gases are cooled to just above the dew point {normally 200-260 ° C), wherein the sulfur trioxide formed from the sulfur dioxide has already converted to vaporous sulfuric acid and this gas stream is then in a glass tube heat exchanger to 60-100 * C directly or indirectly cooled with the raw gas. The further treatment of the gas consists of an aerosol separator.
    The disadvantage of this method is that, on the one hand, the glass tube heat exchangers cause high investment costs and break glass tubes and also the maximum inlet temperature for the glass tubes is limited because of their sealing with PFA and PTFE materials at 250 ° C, on the other hand the usual doped with vanadium pentoxide catalysts only conversion levels for sulfur dioxide of about 99% can be achieved.
    In order to achieve today usual concentrations of the sulfuric acid product of> 98% by weight, the condensation temperature must be at least 250 eC, whereby the relatively large glass tube exchangers have reached the end of their capacity.
    Furthermore, at high concentrations of sulfur compounds in the exhaust gases dew points of 250 ° C and more and thus the temperature window for the safe operation of the system is getting smaller.
    On the other hand, the already worldwide requirements of the legislation are so high that for emission concentrations of sulfur dioxide from 50 to 100 mg / Nm3 a degree of conversion of 99% is often no longer sufficient.
    Therefore, a method must be found which avoids these disadvantages mentioned above.
    It has already been proposed to switch a second oxidation state with vanadium pentoxide catalyst after the condensation of the sulfuric acid. As a result, the investment and operating costs for such a system increase significantly.
    The post-treatment of the gases after the condensation stage can be carried out in various ways. Alkaline scrubbers cause costs for neutralizers and landfills, peroxide scrubbers cause significant operating costs.
    The task can be divided into two parts: • to find materials that are resistant to high acid concentrations and high temperatures, • to find a second post-oxidation stage that operates at low temperatures and does not significantly increase operating costs or investment costs ,
    This object is therefore inventively achieved in that in a first stage, the majority of the sulfur components of the gas stream is reacted in a reactor / catalyst, in a heat exchanger from 380 to SOO'C, preferably 430 - 450 ° C, to 250 to 330 " C, preferably from 270 to 290 ° C, is cooled in a condensation tower (K) with concentrated sulfuric acid in countercurrent to 60 to 160 ° C, preferably 100 to 140 ° C, wherein the ratio between gas flow and sulfuric acid in the condensation tower ( K) is chosen so that the sulfuric acid in the bottom of the condensation tower reaches a temperature of 220 to 280 ° C, preferably 250 to 270 "C, the heat content of the hot sulfuric acid stream in Gegenstromwärmetäuscher (W1, W2) to a heat transfer medium, preferably thermal oil transferred and this is used in the heat exchanger (W4) for preheating the crude gas stream, while the cooled sulfuric acid ester m after the countercurrent heat exchanger with the sulfuric acid pump (PI) at the top of the condensation column (K) is charged and only the condensed each amount of concentrated acid is withdrawn from the system and then the gas stream via a quencher (Q) and an aerosol ( F) is passed to a second stage, consisting of an activated carbon reactor (AR), in which the unreacted
    Sulfur components are oxidized and separated, wherein the activated carbon is regenerated with dilute sulfuric acid and the diluted sulfuric acid from the activated carbon regeneration in the quencher (Q) is used to cool the gas stream to 40 to 60'C.
    Although condensation towers for sulfuric acid have been customary for many decades, the acid-resistant ceramic materials have also been further developed so that stones and putties with 70 to 99% SiO 2 content are available. However, the acid in the sump always had to be decoupled at low temperatures (below 80 ° C.) so that it could not be used for preheating the raw gases or for obtaining energy.
    So it had to be found the possibility to produce pressure-resistant heat exchangers and pumps that are resistant to sulfuric acid with 98 wt.% Concentration and temperatures of 250 - 260 X resistant. According to the invention, this task can only be fulfilled by silicon carbide materials. In the case of pumps, bearings and sealing elements must be developed accordingly. In the case of heat exchangers, though, there are tube bundle heat exchangers with silicon carbide tubes. These must also be sealed with PTFE / PFA and / or lined the antechambers, so that they are not stable enough against overpressures and the required temperatures. However, it has been found that joined plate heat exchangers made of silicon carbide can accomplish this task.
    Now, if the gas streams from the reactor e.g. cooled to 280 ° C and gives up in the condensation tower so much cool acid on the head (about 50% of the mass flow of the gas flowing through) that at the sump an acid exit temperature of 260 * C is reached, the acid to> 98gew.% and when the acid is cooled to <250 ° C in free flow in a first, smaller heat exchanger, the pump can pump the acid through the main body of the heat exchanger and into the head of the condensation tower.
    The heat can be applied to a heat transfer medium such. B. thermal oil are discharged and transferred with this in a separate heat exchanger to the raw gas.
    Since the heat of condensation and the heat of reaction of the acid formation are released during cooling, the amount of heat that can be transferred to the raw gas is always lower than the usable heat in the raw gas preheating. Therefore, the temperature in the exhaust gas after the condensation tower will become higher depending on the content of sulfur content of the raw gas flow.
    This energy content of the gas stream after the condensation tower is used according to the invention for concentrating the dilute acid from the second reaction stage with activated carbon as catalyst and adsorbent. The activated carbon catalyst is occupied by the sulfur dioxide precipitated and sulfuric acid oxidized and must be desorbed periodically with dilute acid <5wt%. The dilute acid from this reactor gets into the quench and is concentrated there and then fed into the acid cycle in the condensation tower at the top.
    It is customary to install an aerosol separator after the quench, either in the form of a candle filter or a wet electrostatic precipitator.
    Application example: 10000 kg / h of a process gas with a concentration of 8g / Nm3 of hydrogen sulfide, 10 vol% oxygen, carbon dioxide and nitrogen are sucked by a blower with 40 ° C and preheated via the heat exchanger (W4) to 330 ° C and get to the catalyst (RI), where the temperature increases to about 430 ° C by the heat of reaction and the hydrogen sulfide is reacted to 99.9% to sulfur dioxide and this to 99% to sulfur trioxide. In the heat exchanger (W3), the gas flow is cooled from 430 to 270 "C. The gas then passes into the condensation tower (K), where it is cooled from 270 ° C to 120 ° C and in countercurrent about 5000 kg / h 94 wt. % acid is introduced with 100 eC at the top, which heats up to 260 ° C over the column and thereby to 98 wt. % is concentrated. The concentrated acid enters the silicon carbide plate heat exchanger (Wl) at 260 ° C. and is cooled therein to 220 ° C., conveyed by the pump (PI) through the plate heat exchanger (W 2) and cooled to 100 ° C. The amount of acid separated from the gas stream in the condensation tower of about 183 kg / h is discharged as a product, while the remaining 4700 kg / h of sulfuric acid together with the 300 kg / h of 5% by weight dilute acid are re-introduced at the head of the condensation tower. The thermal oil is used to cool the acid in the heat exchangers Wl and W2
    Marlotherm S, which enters the heat exchanger W2 with 60 eC and is heated in countercurrent in the Wl up to 230 ° C, is heated in W3 to 350 ° C and the heat in the finned tube exchanger W4 releases to the raw gas.
    The exhaust gas from the first oxidation stage is passed at 120 ° C in the quencher Q, where it with the 5 wt. % of dilute acid from the 2nd reaction stage is quenched to 50 ° C.
    In a subsequent filter stage F, which is designed as an electrostatic precipitator, the aerosols are separated and in the subsequent activated carbon reactor, the sulfur dioxide is separated to a residual content of 40 mg / Nm3. The regeneration of the activated carbon takes place with 5% dilute acid periodically at intervals of 1 hour.
    权利要求:
    Claims (4)
    [1]
    1. A process for the two-stage catalytic oxidation of sulfur compounds in moist, oxygen-containing gases and exhaust gases with subsequent deposition of the formed concentrated sulfuric acid, characterized in that in a first stage, the majority of the sulfur components of the gas stream in a reactor / catalyst (RI) is reacted, in a heat exchanger of 380 to 500 ° C, preferably 430 to 450 ° C, to 250 to Is cooled in a condensation tower (K) with countercurrent concentrated sulfuric acid at 60 to 160 ° C, preferably 100 to 140 ° C, wherein the ratio between gas flow and sulfuric acid in the condensation tower ( K) is chosen so that the sulfuric acid in the bottom of the condensation tower reaches a temperature of 220 to 280'C, preferably 250 - 270 ° C, the heat content of the he sulfuric acid stream in Gegenstromwärmetäuscher (W1, W2) to a heat transfer medium, preferably thermal oil, and this is used in the heat exchanger (W4) for preheating the crude gas stream, while the cooled sulfuric acid stream after the Gegenstromwärmetäuscher again with the sulfuric acid pump (PI) at the top the Kondensationskoionne (K) is abandoned and only the respectively condensed amount of concentrated acid is withdrawn from the system and then the gas stream via a quencher (Q) and an aerosol (F) in a second stage, consisting of an activated carbon reactor (R2) passed in which the unreacted sulfur components are oxidized and separated, regenerating the activated carbon with dilute sulfuric acid and using the dilute sulfuric acid from the activated carbon regeneration in the quench (Q) to cool the gas stream to 40 to 60 ° C.
    [2]
    2. The method according to claim 1, characterized in that at least coming into contact with the sulfuric acid parts of the / the Gegenstromwärmetäuscher (Wl) (W2) consist of silicon carbide.
    [3]
    3. The method according to claim 1, characterized in that the Gegenstromwärmetäuscher (Wl) (W2) consists of at least two heat exchangers, which are connected in series and the pump (PI) for circulating the concentrated sulfuric acid after the heat exchanger (Wl) in the flow direction is switched.
    [4]
    4. The method according to claim 1, characterized in that the Gegenstromwärmetäuscher are designed as a plate heat exchanger.
    类似技术:
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    同族专利:
    公开号 | 公开日
    AT513414B1|2014-06-15|
    EP2903722B1|2016-11-16|
    WO2014056013A3|2014-06-05|
    EP2903722A2|2015-08-12|
    WO2014056013A2|2014-04-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP2000024461A|1998-07-08|2000-01-25|Chiyoda Corp|Method and system for flue gas desulfurization|
    EP0972746A1|1998-07-17|2000-01-19|L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude|Process and apparatus for producing sulfuric acid|
    US20070110663A1|2005-11-15|2007-05-17|Christensen Kurt A|Process for the production of sulfuric acid|
    WO2011147431A1|2010-05-27|2011-12-01|Haldor Topsoe A/S|Process and apparatus for sulphuric acid production|
    DE1767224A1|1968-04-13|1971-08-12|Metallgesellschaft Ag|Process for the complete conversion of sulfur dioxide to sulfuric acid|
    DE3819417C2|1988-06-07|1990-10-18|Utab Gesellschaft Fuer Umwelttechnischen Anlagenbau Mbh, 4100 Duisburg, De|
    DE102006051899A1|2006-10-31|2008-05-15|Bayer Technology Services Gmbh|Process and apparatus for the catalytic oxidation of SO2-containing gases with oxygen|CN104001455B|2014-06-11|2016-04-06|陕西天宏硅材料有限责任公司|A kind of method preparing high-purity gas|
    CN110124491B|2018-02-02|2021-10-26|中冶长天国际工程有限责任公司|Method and device for multi-pollutant flue gas cooperative treatment and wastewater zero discharge|
    CN110124507B|2018-02-02|2021-10-26|中冶长天国际工程有限责任公司|Method and device for cleaning and treating multi-pollutant flue gas|
    法律状态:
    2018-06-15| MM01| Lapse because of not paying annual fees|Effective date: 20171008 |
    优先权:
    申请号 | 申请日 | 专利标题
    ATA1082/2012A|AT513414B1|2012-10-08|2012-10-08|Process for the two-stage catalytic oxidation of sulfur compounds in exhaust gases|ATA1082/2012A| AT513414B1|2012-10-08|2012-10-08|Process for the two-stage catalytic oxidation of sulfur compounds in exhaust gases|
    PCT/AT2013/050200| WO2014056013A2|2012-10-08|2013-10-07|Method for the two-stage catalytic oxidation of sulphur compounds in wet gases|
    EP13794792.5A| EP2903722B1|2012-10-08|2013-10-07|Method for the two-stage catalytic oxidation of sulphur compounds in wet gases|
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