JP4336225B2 - Flue gas desulfurization method - Google Patents
Flue gas desulfurization method Download PDFInfo
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- JP4336225B2 JP4336225B2 JP2004059704A JP2004059704A JP4336225B2 JP 4336225 B2 JP4336225 B2 JP 4336225B2 JP 2004059704 A JP2004059704 A JP 2004059704A JP 2004059704 A JP2004059704 A JP 2004059704A JP 4336225 B2 JP4336225 B2 JP 4336225B2
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- 238000006477 desulfuration reaction Methods 0.000 title claims description 51
- 230000023556 desulfurization Effects 0.000 title claims description 51
- 238000000034 method Methods 0.000 title claims description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims description 17
- 239000003546 flue gas Substances 0.000 title claims description 17
- 239000003054 catalyst Substances 0.000 claims description 140
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 82
- 239000007789 gas Substances 0.000 claims description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 60
- 239000007788 liquid Substances 0.000 claims description 36
- 239000008235 industrial water Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 230000002940 repellent Effects 0.000 claims description 5
- 239000005871 repellent Substances 0.000 claims description 5
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 3
- 239000007921 spray Substances 0.000 description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 229910052815 sulfur oxide Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Description
本発明は、活性炭系ハニカム形状触媒を用いて、排ガス中に含まれる亜硫酸ガス等の硫黄酸化物を接触硫酸化反応によって硫酸として回収除去する排煙脱硫方法に関するものである。 The present invention relates to a flue gas desulfurization method for recovering and removing sulfur oxides such as sulfurous acid gas contained in exhaust gas as sulfuric acid by catalytic sulfation reaction using an activated carbon-based honeycomb-shaped catalyst.
従来より、排ガス中に含まれる亜硫酸ガス等の硫黄酸化物を触媒および酸素の共存下に低温で酸化し、最終的に硫酸として回収する排煙脱硫方法が知られている（例えば、特許文献１参照）。
また、この排煙脱硫方法に用いられる触媒として、活性炭にフッ素樹脂を混合、担持した活性炭触媒が高い脱硫性能を有することが知られている（例えば、特許文献２および特許文献３参照）。この触媒は、燃焼排ガス、例えば石炭燃焼排ガス等では長時間に渡って安定な性能を示すことが確認されている。
Conventionally, there has been known a flue gas desulfurization method in which sulfur oxide such as sulfurous acid gas contained in exhaust gas is oxidized at a low temperature in the presence of a catalyst and oxygen and finally recovered as sulfuric acid (for example, Patent Document 1). reference).
Moreover, as a catalyst used for this flue gas desulfurization method, it is known that the activated carbon catalyst which mixed and carried the fluororesin on activated carbon has high desulfurization performance (for example, refer
このような排煙脱硫方法においては、工水、希硫酸などで触媒を洗浄すると、生成した硫酸が希釈されて触媒表面からの離脱速度が増加し、高性能となると共に性能が安定する効果があり、各種の具体的な方法が提案されている。この際、洗浄液としては、硫酸濃度が低い水溶液、もしくは工水が好適であると言われている（例えば、特許文献１および特許文献４参照）。
In such a flue gas desulfurization method, when the catalyst is washed with industrial water, dilute sulfuric acid, etc., the generated sulfuric acid is diluted to increase the separation rate from the catalyst surface, resulting in high performance and stable performance. There are various specific methods proposed. At this time, it is said that an aqueous solution having a low sulfuric acid concentration or industrial water is suitable as the cleaning liquid (see, for example,
しかしながら、高脱硫率を得るためには、触媒量を多くする必要があり、そのため触媒層高が高くなる。
本発明者らは、活性炭系ハニカム形状触媒を用いたときに、触媒層高を高くすると、低い触媒層高での脱硫率から予想される性能と比べて低下することを見出した。被処理ガス中の亜硫酸濃度が高く、処理ガス中の亜硫酸濃度を低くする時、つまり高脱硫率を得ようとした場合に、この両者の差が大きくなる。また、被処理ガスが水分不飽和の場合に特に顕著である。その原因を検討した結果、次のことがわかった。ラシヒリング等を充填した吸収塔ではスプレー等による初期の液分散が不十分でも充填層内で徐々に液分散が改善されていくのに対し、ハニカム形状触媒では横方向の混合均一化が起こらないため、触媒層内では改善されない。このため、洗浄液の導入量の少ないハニカムセル内では硫酸が高濃度となり、脱硫性能が低下する。特に、被処理排ガス中の水分濃度が低いと、高濃度の硫酸が生成しやすい。ハニカムセル内の硫酸濃度が上昇しないように、スプレー液量を増加させると、触媒表面を液が覆ってしまい、触媒と排ガスの接触を妨げ、脱硫性能を低下させる。
また、洗浄液の偏りは、被処理ガスの偏流を引き起こし、これによってさらに脱硫性能が低下する。
However, in order to obtain a high desulfurization rate, it is necessary to increase the amount of catalyst, so that the catalyst layer height becomes high.
The inventors have found that when an activated carbon-based honeycomb-shaped catalyst is used, if the catalyst layer height is increased, the performance is expected to be lower than expected from the desulfurization rate at a low catalyst layer height. When the sulfurous acid concentration in the gas to be treated is high and the sulfurous acid concentration in the gas to be treated is low, that is, when a high desulfurization rate is to be obtained, the difference between the two becomes large. This is particularly noticeable when the gas to be treated is water unsaturated. As a result of examining the cause, the following was found. In the absorption tower packed with Raschig rings etc., even if the initial liquid dispersion by spraying etc. is insufficient, the liquid dispersion gradually improves in the packed bed, whereas in the honeycomb-shaped catalyst, horizontal mixing and homogenization does not occur It is not improved in the catalyst layer. For this reason, sulfuric acid becomes a high concentration in the honeycomb cell where the introduction amount of the cleaning liquid is small, and the desulfurization performance is lowered. In particular, when the moisture concentration in the exhaust gas to be treated is low, a high concentration of sulfuric acid tends to be generated. If the amount of spray liquid is increased so that the sulfuric acid concentration in the honeycomb cell does not increase, the liquid covers the surface of the catalyst, preventing contact between the catalyst and the exhaust gas and desulfurization performance.
Further, the unevenness of the cleaning liquid causes a drift of the gas to be processed, which further deteriorates the desulfurization performance.
本発明は、前記事情に鑑みて為されたもので、活性炭系ハニカム形状触媒を用いて、排ガス中の硫黄酸化物を硫酸として回収する排煙脱硫方法において、安定で高い脱硫性能を効率的に得ることができる排煙脱硫方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and in a flue gas desulfurization method for recovering sulfur oxides in exhaust gas as sulfuric acid using an activated carbon-based honeycomb-shaped catalyst, stable and high desulfurization performance is efficiently achieved. An object is to provide a flue gas desulfurization method that can be obtained.
本発明は、発明者らの前述のような知見に基づいて為されたものである。すなわち、請求項１に記載の排煙脱硫方法は、活性炭系ハニカム形状触媒を上下間に空間を有するように積層して触媒層高１〜５ｍに構成した触媒層を上下方向に間隔をおいて複数段設け、
当該触媒層に排ガスを通過させて、排ガス中の硫黄酸化物を硫酸として回収する排煙脱硫方法であって、
排ガスを前記触媒層の活性炭系ハニカム形状触媒と下降流で接触させるとともに、
工水、および前記触媒層で生成した硫酸を含む希硫酸水溶液のうちの少なくとも１つを前記触媒層に上側から噴霧し、
上段の触媒層を流下する液量に対して下段の触媒層を流下する液量を多くするものとし、
前記触媒層に噴霧する液量を、排ガスが最初に通過する最上段の触媒層の液ガス比で０．０５〜５．０Ｌ／ｍ ３ で、かつ排ガスが最後に通過する最下段の触媒層の液ガス比で３０Ｌ／ｍ ３ 以下にすることを特徴とする。
The present invention has been made on the basis of the above-described knowledge of the inventors. That is, in the exhaust gas desulfurization method according to
A flue gas desulfurization method for passing exhaust gas through the catalyst layer and recovering sulfur oxide in the exhaust gas as sulfuric acid,
While contacting the exhaust gas with the activated carbon-based honeycomb-shaped catalyst of the catalyst layer in a downward flow,
Industrial water, and sprayed from above the catalyst layer of at least one of dilute sulfuric acid aqueous solution containing sulfuric acid produced in the catalyst layer,
The amount of liquid flowing down the lower catalyst layer is increased relative to the amount of liquid flowing down the upper catalyst layer,
The amount of liquid sprayed on the catalyst layer is 0.05 to 5.0 L / m 3 in terms of the liquid gas ratio of the uppermost catalyst layer through which the exhaust gas first passes , and the lowermost catalyst layer through which the exhaust gas passes last. The liquid gas ratio is 30 L / m 3 or less .
ここで、工水等の触媒層への噴霧は、噴霧用ノズルを設置して行うことができ、このような噴霧用ノズルとしては、スプレーノズル、穴空きパイプなど、液を分散できるものであればどのようなものでも良いが、スプレーノズルが好ましい。また、活性炭の種類は、石炭系でもピッチ系でもよく、炭素質を賦活させたものであればよい。使用する形状としてはハニカム形状の触媒であるが、原料活性炭は粒状、ペレット状、繊維状、シート状などであってもよい。 Here, spraying to the catalyst layer such as industrial water can be performed by installing a spray nozzle, and such a spray nozzle may be a spray nozzle, a perforated pipe, or the like that can disperse the liquid. Any type may be used, but a spray nozzle is preferable. Moreover, the type of activated carbon may be either coal-based or pitch-based, and any carbon-activated material may be used. The shape to be used is a honeycomb-shaped catalyst, but the raw activated carbon may be in the form of particles, pellets, fibers, sheets or the like.
請求項１に記載の発明においては、ハニカム形状触媒を一体化せずに、上下方向の途中に空間を有するように積層して触媒層を形成しているので、各触媒層内を通過している時のガス流れが乱流化され、これにより排ガスの混合化が図られるとともに、落下する液中の硫酸濃度が均一化して低下する。さらに、排ガスの偏流が改善される効果を有する。
また、工水および脱硫工程で生成した硫酸を含む希硫酸水溶液のうちの少なくとも１つを、触媒層に噴霧するので、触媒層内の硫酸濃度の上昇が抑えられる。落下する液を混合均一化させて硫酸濃度を低下させる効果は、ハニカム形状触媒の間に空間を設けることによって得られるが、触媒層に工水等を噴霧することにより大きな効果が得られる。
したがって、硫酸濃度の低下とガス流れの混合化の両方を改善し、その効果を効率的に発揮させるため、ハニカム形状触媒を一体化せずに、上下間に空間を有するように積層して触媒層を形成するとともに、各触媒層にそれぞれ工水等を噴霧する。
In the first aspect of the present invention, since the catalyst layers are formed by laminating the honeycomb-shaped catalyst so as to have a space in the vertical direction without integrating the honeycomb-shaped catalyst, the catalyst layers pass through each catalyst layer. The gas flow during turbulence is turbulent, thereby mixing the exhaust gas and making the concentration of sulfuric acid in the falling liquid uniform and lower. Furthermore, it has the effect that the drift of the exhaust gas is improved.
In addition, since at least one of the industrial water and the dilute sulfuric acid aqueous solution containing sulfuric acid generated in the desulfurization step is sprayed on the catalyst layer, an increase in sulfuric acid concentration in the catalyst layer can be suppressed. The effect of mixing and homogenizing the falling liquid to lower the sulfuric acid concentration can be obtained by providing a space between the honeycomb-shaped catalysts, but a great effect can be obtained by spraying industrial water or the like on the catalyst layer.
Therefore, in order to improve both the decrease in sulfuric acid concentration and the mixing of the gas flow, and to effectively exert the effect, the catalyst is laminated with a space between the upper and lower sides without integrating the honeycomb-shaped catalyst. A layer is formed, and industrial water or the like is sprayed on each catalyst layer.
また、触媒層の高さは、１〜５ｍが好適である。液の混合均一化には、触媒層の高さが１ｍ以下では、触媒層内を上下で区切って空間を設けてもその効果がなく、一方５ｍ以上では、触媒層内で液が充分に混合均一化されずにすでに脱硫性能の低下が顕著になっており、触媒層間に空間を設けて複層化し、触媒層に工水等を噴霧しても、多量の触媒を必要とし効果がない。活性炭系ハニカム形状触媒の間に設ける空間は、３ｃｍ〜３０ｃｍが好ましい。３ｃｍ未満では、上記の効果が得られず、３０ｃｍを超えても効果は変化しないか、もしくは液分散が悪化して、効果が低下する。
なお、この排煙脱硫方法は、一度脱硫された後の排ガスを２次脱硫する場合にも適用可能である。
Moreover, 1-5 m is suitable for the height of a catalyst layer. For uniform mixing of the liquid, if the height of the catalyst layer is 1 m or less, there is no effect even if a space is provided by dividing the inside of the catalyst layer vertically, whereas if it is 5 m or more, the liquid is sufficiently mixed in the catalyst layer. A reduction in desulfurization performance has already become remarkable without being made uniform, and even if a space is provided between the catalyst layers to form a multi-layer and sprayed with industrial water or the like on the catalyst layer, a large amount of catalyst is required and there is no effect. The space provided between the activated carbon honeycomb-shaped catalysts is preferably 3 cm to 30 cm. If it is less than 3 cm, the above effect cannot be obtained, and if it exceeds 30 cm, the effect does not change, or the liquid dispersion deteriorates and the effect decreases.
The flue gas desulfurization method can also be applied to the case where the exhaust gas once desulfurized is subjected to secondary desulfurization.
複数個の触媒層を上下方向に間隔をおいて設けることにより、落下する液を再分散させ、噴霧された工水等によって硫酸濃度を低下できる。 By providing a plurality of catalyst layers at intervals in the vertical direction, the falling liquid can be redispersed and the sulfuric acid concentration can be lowered by sprayed industrial water or the like.
排ガスを下降流で流すと、触媒層の上部で生成した硫酸が下部に流れるのに伴い、硫酸濃度が上昇し、下部の触媒層での脱硫性能が低下する。その対策として、排ガスを触媒層内を下降流で流し、工水、あるいは脱硫工程で生成した硫酸を含む希硫酸水溶液を流すと、脱硫性能が高く、安定になることが従来から知られている（例えば、特許文献５参照）。しかし、下段の触媒層では、上段の触媒層と比べて排ガス中の亜硫酸ガス濃度が低く、流下する液の硫酸濃度の上昇が脱硫性能に与える影響度が大きい。これに対しては、液量を増やすことによって、硫酸濃度の上昇を抑え、安定した性能を発揮することができる。また、液量を増やすと、液流れがガス流れの乱れを誘い、ガスの混合が改善される効果がある。他方、前述したように、液量を増加させると、触媒表面を液が覆い、触媒と排ガスとの接触を妨げ、性能を低下させる。そのため、請求項３に記載の発明のように、排ガスが最初に通過する触媒層の液ガス比を、０．０５〜５．０Ｌ／ｍ３、好ましくは０．５〜２．０Ｌ／ｍ３とし、かつ排ガスが最後に通過する触媒層の液ガス比を３０Ｌ／ｍ３以下にするのがよい。
When exhaust gas is flowed in a downward flow, the sulfuric acid concentration increases as the sulfuric acid generated in the upper part of the catalyst layer flows to the lower part, and the desulfurization performance in the lower catalyst layer decreases. As countermeasures, it is conventionally known that desulfurization performance is high and stable when exhaust gas is allowed to flow downward in the catalyst layer and a dilute sulfuric acid aqueous solution containing sulfuric acid generated in the process water or desulfurization process is flowed. (For example, refer to Patent Document 5). However, in the lower catalyst layer, the concentration of sulfurous acid gas in the exhaust gas is lower than that in the upper catalyst layer, and the increase in the sulfuric acid concentration of the flowing liquid has a great influence on the desulfurization performance. On the other hand, by increasing the liquid volume, it is possible to suppress an increase in sulfuric acid concentration and to exhibit stable performance. Further, when the amount of liquid is increased, the liquid flow invites disturbance of the gas flow, and there is an effect that gas mixing is improved. On the other hand, as described above, when the amount of the liquid is increased, the liquid covers the surface of the catalyst, the contact between the catalyst and the exhaust gas is hindered, and the performance is deteriorated. Therefore, as in the invention described in
請求項２に記載の排煙脱硫方法は、請求項１に記載の発明において、前記活性炭系ハニカム形状触媒は、粒状活性炭系触媒あるいは活性炭素繊維系触媒、または撥水化処理を施した粒状活性炭系触媒あるいは活性炭素繊維系触媒であることを特徴とする。
The flue gas desulfurization method according to
撥水化処理は、撥水性樹脂を添着した活性炭でも、高温焼成した活性炭でも、テフロン（登録商標）を密着させた活性炭でもよい。撥水化処理をした活性炭は、亜硫酸ガスの酸化速度が速いため、ガスの乱れを起こす請求項１または請求項２に記載の発明や、硫酸濃度の低下およびガスの乱れを起こす請求項３に記載の発明において、特に効果的である。
The water repellent treatment may be activated carbon impregnated with a water repellent resin, activated carbon fired at high temperature, or activated carbon with Teflon (registered trademark) adhered thereto. The activated carbon subjected to water repellency treatment has a high oxidation rate of sulfurous acid gas, and therefore, the invention according to claim 1 or 2 that causes gas disturbance, or the invention according to
本発明の排煙脱硫方法によれば、活性炭系ハニカム形状触媒を用いて、排ガス中の硫黄酸化物を硫酸として回収する排煙脱硫方法において、安定で高い脱硫性能を効率的に得ることができる。 According to the flue gas desulfurization method of the present invention, a stable and high desulfurization performance can be efficiently obtained in the flue gas desulfurization method using an activated carbon honeycomb-shaped catalyst to recover sulfur oxides in exhaust gas as sulfuric acid. .
以下、本発明の実施の形態を具体的に説明する。
図１は、本発明の実施の形態に係る排煙脱硫方法に用いる脱硫塔を示す模式図である。この脱硫塔１内には、複数個の触媒層２が、上下に間隔をおいて設けられている。各触媒層２の高さは１〜５ｍに設定されている。また、隣接する触媒層２の上下の間隔は、通常、１．０〜２．５ｍ程度に設定されている。
Hereinafter, embodiments of the present invention will be specifically described.
FIG. 1 is a schematic diagram showing a desulfurization tower used in the flue gas desulfurization method according to the embodiment of the present invention. A plurality of
各触媒層２には、活性炭系ハニカム形状触媒が充填されている。この触媒としては、例えば、粒状活性炭系触媒あるいは活性炭素繊維系触媒、または撥水化処理を施した粒状活性炭系触媒あるいは活性炭素繊維系触媒を挙げることができる。このハニカム形状触媒は、例えば、図２（ａ）に示すように、触媒シートを平板および四角の凹凸板に加工し、これらを積層することにより形成することができるし、あるいは図２（ｂ）に示すように、触媒シートを平板および波板に加工し、これらを積層することなどにより形成することができる。
Each
各触媒層２は、図３に示すように、ＦＲＰ（ガラス繊維入り強化プラスチック）等のケース３内に、活性炭系ハニカム形状触媒４を上部に空間を設けて充填し、このように活性炭系ハニカム形状触媒４を充填したケース３を複数個積層することにより構成されている。なお、活性炭系ハニカム形状触媒４は、ケース３内に、下部に空間を設けて充填するようにしてもよいし、あるいは上部および下部に空間を設けて充填するようにしてもよい。
As shown in FIG. 3, each
各触媒層２の上部にはそれぞれ、工水、および脱硫工程で生成した硫酸を含む希硫酸水溶液のうちの少なくとも１つが導管５により導入され、スプレーノズル等の噴霧用ノズル６によって、各触媒層２に上側から連続的にまたは間欠的に噴霧される。
At least one of the working water and the dilute sulfuric acid aqueous solution containing sulfuric acid generated in the desulfurization process is introduced into the upper part of each
脱硫塔１には、火力発電所用ボイラー等から排出された排ガスが上部から導入される。脱硫塔１内に導入された排ガスは、脱硫塔１内に設置された各触媒層２を通過することにより、排ガス中の亜硫酸ガス等の硫黄酸化物が触媒に吸着され、さらに排ガス中の酸素、水分により酸化されて希硫酸となる。この希硫酸は、脱硫塔１の下部から連続的または完結的に抜き出される。各触媒層２にはそれぞれ、工水、および脱硫工程で生成した硫酸を含む希硫酸水溶液のうちの１つまたは複数が噴霧用ノズル６から噴霧され、これにより各触媒層２内の硫酸濃度の上昇が抑えられる。
Exhaust gas discharged from a boiler for a thermal power plant or the like is introduced into the
次に、本発明を実施例によりさらに具体的に説明する。
（実施例１）
活性炭粉にポリテトラフルオロエチレン（ＰＴＦＥ）分散液を混合、混錬して得た触媒シートを、平板および波形に加工し積層する（図２（ｂ）参照）ことにより、ハニカム形状触媒を得た。この触媒を、幅７００ｍｍ、長さ４００ｍｍ、高さ５００ｍｍの四角のＦＲＰ製ケースに充填した。この際、図３に示すように、ケース３の上部に高さ１０ｍｍの空間ができるようにした。このハニカム形状触媒４が収容されたケース３を５個積層したものを１つの触媒層２とし、図１に示すように、高さ１．５ｍの空間を設けて３段の触媒層２を、角形の反応塔１に設けた。これにより、各触媒層２の高さは、２．５ｍであり、各ハニカム形状触媒４の間にはそれぞれ、上下間に高さ５０ｍｍの空間が形成されている。つまり、各触媒層２には、上下間に高さ５０ｍｍの空間が４つ形成されている。また、各触媒層２の上部にそれぞれ、スプレーノズル６を設置し、液ガス比で１．０Ｌ／ｍ３の生成希硫酸を含む硫酸濃度３ｗｔ％の水溶液を各触媒層２に噴霧した。反応塔１に、下降流で亜硫酸ガス２０００ｐｐｍ、水分１５ｖｏｌ％を含有する排ガスを触媒間ガス流速１ｍ／ｓで通過させた。その結果、脱硫性能は９７％であった。なお、粒状触媒の脱硫性能から推定される脱硫率は９８％である。
Next, the present invention will be described more specifically with reference to examples.
Example 1
A catalyst sheet obtained by mixing and kneading polytetrafluoroethylene (PTFE) dispersion with activated carbon powder was processed into a flat plate and corrugated and laminated (see FIG. 2B) to obtain a honeycomb-shaped catalyst. . This catalyst was filled in a square FRP case having a width of 700 mm, a length of 400 mm, and a height of 500 mm. At this time, as shown in FIG. 3, a space having a height of 10 mm was formed above the
（実施例２）
被処理排ガスの水分を８ｖｏｌ％とし、各ハニカム形状触媒４の上下の空間高さを２５ｃｍとしたこと以外は実施例１と同一とした時の脱硫率は９０％であった。
(Example 2)
The desulfurization rate was 90% when the same as in Example 1 except that the moisture of the exhaust gas to be treated was 8 vol% and the height of the space above and below each honeycomb-shaped
（比較例１）
実施例と同一のハニカム形状触媒を、上下間に空間を設けずに、実施例と同一の高さに反応塔１に充填して一体的な１層の触媒層とした。スプレーノズル６は、この触媒層の上部に設置し、液ガス比で３．０Ｌ／ｍ３の生成希硫酸をこの触媒層に噴霧した。反応塔１に、実施例１と同様に、下降流で亜硫酸ガス２０００ｐｐｍ含有排ガスを触媒間ガス流速１ｍ／ｓで通過させた。その結果、脱硫率は８４％であった。
(Comparative Example 1)
The same honeycomb-shaped catalyst as in the example was filled in the
（比較例２）
比較例１と同一高さの触媒層が上下方向で３つに分けられ、各触媒層の間にそれぞれ１．５ｍの高さの空間が生じるように、比較例１と同一のハニカム形状触媒を反応塔１に充填した。各触媒層には、実施例１と異なり、触媒の上下方向に空間が形成されていない。また、各触媒層の上部にそれぞれ、スプレーノズル６を設置し、液ガス比で１．５Ｌ／ｍ３の生成希硫酸を各触媒層に噴霧した。反応塔１に、下降流で亜硫酸ガス２０００ｐｐｍ含有排ガスを触媒間ガス流速１ｍ／ｓで通過させた。その結果、脱硫性能は９２％であった。
(Comparative Example 2)
The catalyst layer having the same height as that of Comparative Example 1 was divided into three in the vertical direction, and the same honeycomb-shaped catalyst as that of Comparative Example 1 was formed so that a space of 1.5 m was formed between each catalyst layer. The
（比較例３）
各触媒の上下空間の高さを４０ｃｍとし、スプレー噴霧する各層の液ガス比を０．０１Ｌ／ｍ３とすること以外は実施例２と同一とした時の脱硫率は７２％であった。
(Comparative Example 3)
The desulfurization rate was 72% when the same as in Example 2 except that the height of the upper and lower spaces of each catalyst was 40 cm and the liquid gas ratio of each layer to be sprayed was 0.01 L / m 3 .
１ 脱硫塔
２ 触媒層
３ ケース
４ 活性炭系ハニカム形状触媒
５ 導管
６ スプレーノズル（噴霧用ノズル）
DESCRIPTION OF
Claims (2)
当該触媒層に排ガスを通過させて、排ガス中の硫黄酸化物を硫酸として回収する排煙脱硫方法であって、
排ガスを前記触媒層の活性炭系ハニカム形状触媒と下降流で接触させるとともに、
工水、および前記触媒層で生成した硫酸を含む希硫酸水溶液のうちの少なくとも１つを前記触媒層に上側から噴霧し、
上段の触媒層を流下する液量に対して下段の触媒層を流下する液量を多くするものとし、
前記触媒層に噴霧する液量を、排ガスが最初に通過する最上段の触媒層の液ガス比で０．０５〜５．０Ｌ／ｍ ３ で、かつ排ガスが最後に通過する最下段の触媒層の液ガス比で３０Ｌ／ｍ ３ 以下にすることを特徴とする排煙脱硫方法。 A plurality of layers of catalyst layers each having a catalyst layer height of 1 to 5 m by stacking activated carbon-based honeycomb-shaped catalysts so as to have a space between the upper and lower sides are provided at intervals in the vertical direction;
A flue gas desulfurization method for passing exhaust gas through the catalyst layer and recovering sulfur oxide in the exhaust gas as sulfuric acid,
While contacting the exhaust gas with the activated carbon-based honeycomb-shaped catalyst of the catalyst layer in a downward flow,
Industrial water, and sprayed from above the catalyst layer of at least one of dilute sulfuric acid aqueous solution containing sulfuric acid produced in the catalyst layer,
The amount of liquid flowing down the lower catalyst layer is increased relative to the amount of liquid flowing down the upper catalyst layer,
The amount of liquid sprayed on the catalyst layer is 0.05 to 5.0 L / m 3 in terms of the liquid gas ratio of the uppermost catalyst layer through which the exhaust gas first passes , and the lowermost catalyst layer through which the exhaust gas passes last. The flue gas desulfurization method is characterized in that the liquid gas ratio is 30 L / m 3 or less .
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