JPH08187430A - Sulfur dioxide oxidizing catalyst composing material - Google Patents
Sulfur dioxide oxidizing catalyst composing materialInfo
- Publication number
- JPH08187430A JPH08187430A JP7000826A JP82695A JPH08187430A JP H08187430 A JPH08187430 A JP H08187430A JP 7000826 A JP7000826 A JP 7000826A JP 82695 A JP82695 A JP 82695A JP H08187430 A JPH08187430 A JP H08187430A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- ratio
- reaction
- diameter
- sulfur dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 230000001590 oxidative effect Effects 0.000 title abstract description 4
- 239000000463 material Substances 0.000 title abstract 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 14
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、二酸化硫黄を三酸化
硫黄に酸化するのに用いられる五酸化バナジウムベース
の粒状触媒の新規構造に関する。FIELD OF THE INVENTION This invention relates to a novel structure of a vanadium pentoxide-based particulate catalyst used to oxidize sulfur dioxide to sulfur trioxide.
【０００２】[0002]
【発明の背景】二酸化硫黄酸化触媒は、静止触媒層を通
る二酸化硫黄含有ガスの流れ方向が周期的に反転する非
定常型二酸化硫黄酸化装置（以下、単に「非定常型」と
いう）において用いられる。この種の二酸化硫黄酸化触
媒としては、通常の硫酸製造装置に用いられている直径
５ｍｍ〜２５ｍｍの円柱粒状あるいはリング状の触媒が
使用できる。BACKGROUND OF THE INVENTION Sulfur dioxide oxidation catalysts are used in unsteady sulfur dioxide oxidizers (hereinafter simply referred to as "unsteady") in which the flow direction of the sulfur dioxide-containing gas through the stationary catalyst layer is periodically reversed. . As this type of sulfur dioxide oxidation catalyst, a cylindrical granular or ring-shaped catalyst having a diameter of 5 mm to 25 mm, which is used in an ordinary sulfuric acid production apparatus, can be used.
【０００３】そして、非定常型の場合、触媒層内での効
率的な熱の移動が最終的な反応率に大きな影響を与える
ため、普通、原料二酸化硫黄の濃度によって触媒を大き
さにより使いわけている。すなわち、二酸化硫黄の濃度
が４％以下である場合、直径４ｍｍ〜１２ｍｍの触媒を
使用し、濃度４〜１５％のときにはさらに大きな直径の
ものを使用する。これは、発生する反応熱を効率的に触
媒層中を移動させるためには、充填物の大きさが大きい
ほど有効であるためである。一方、反応率は反応器に充
填された触媒の全表面積に依存し、触媒表面積が大きい
ほど高い反応率が得られることは周知の事実である。従
って、非定常型の場合、高い反応を得るためには触媒の
充填量を従来の量よりも増加する必要がある。In the case of the unsteady type, since efficient heat transfer in the catalyst layer has a great influence on the final reaction rate, the catalyst is usually used depending on the size depending on the concentration of the raw material sulfur dioxide. ing. That is, when the concentration of sulfur dioxide is 4% or less, a catalyst having a diameter of 4 mm to 12 mm is used, and when the concentration is 4 to 15%, a catalyst having a larger diameter is used. This is because the larger the size of the packing, the more effective it is to efficiently transfer the generated heat of reaction in the catalyst layer. On the other hand, it is a well-known fact that the reaction rate depends on the total surface area of the catalyst packed in the reactor, and the higher the catalyst surface area, the higher the reaction rate. Therefore, in the case of the non-steady type, in order to obtain a high reaction, it is necessary to increase the packing amount of the catalyst as compared with the conventional amount.
【０００４】[0004]
【従来技術および解決すべき課題】通常の硫酸製造工程
では、総合反応率９９．５〜９９．７％を得るために二
段接触二段吸収という手法を用いている。これは、一段
目の反応操作でＳＯ2 が８９〜９２％までＳＯ3 に酸化
されたガスを一度反応系から取り出し、生成したＳＯ3
を硫酸に吸収させたのち、さらに二段目の反応器で反応
を行って高い反応率を得ようとするものである。2. Description of the Related Art In a normal sulfuric acid production process, a two-step contact two-step absorption method is used to obtain a total reaction rate of 99.5 to 99.7%. This is because the gas in which SO 2 was oxidized to SO 3 by 89 to 92% in the first stage reaction operation was once taken out from the reaction system, and the generated SO 3
Is absorbed in sulfuric acid, and then the reaction is further carried out in the second-stage reactor to obtain a high reaction rate.
【０００５】非定常型二酸化硫黄酸化装置を用いた硫酸
製造方法は、低コストおよび省エネルギー型として従来
の硫酸製造方法よりも優れたものである。しかし、この
方法では、その反応機構の特殊性の故に、二段接触二段
吸収法で総合反応率９９．７％を得るために一段目の反
応操作で８９〜９２％の反応率を得ようとすると、特殊
な形状の触媒が必要である。The method for producing sulfuric acid using the unsteady type sulfur dioxide oxidizing apparatus is superior to the conventional method for producing sulfuric acid as a low cost and energy saving type. However, in this method, due to the peculiarity of the reaction mechanism, in order to obtain a total reaction rate of 99.7% in the two-step contact two-step absorption method, a reaction rate of 89 to 92% should be obtained in the first-step reaction operation. If so, a catalyst with a special shape is required.
【０００６】この発明の目的は、上記のような実情に鑑
み、非定常型二酸化硫黄酸化装置に用いる有効な触媒構
造物を提供することにある。In view of the above situation, an object of the present invention is to provide an effective catalyst structure for use in an unsteady type sulfur dioxide oxidation device.
【０００７】[0007]
【課題を解決するための手段】この発明による二酸化硫
黄酸化触媒構造物は、上記目的を達成すべく工夫された
のものであって、二酸化硫黄を三酸化硫黄に酸化するの
に用いられる五酸化バナジウムベースの粒状触媒であっ
て、その高さ（Ｈ）と直径（Ｄ）の比（Ｈ／Ｄ）が０．
９〜１．５で、かつ表面積（Ａ）と直径（Ｄ）の比（Ａ
／Ｄ）が１１０ｍｍ〜４４０ｍｍであることを特徴とす
るものである。The sulfur dioxide oxidation catalyst structure according to the present invention has been devised to achieve the above object, and is a vanadium pentoxide base used for oxidizing sulfur dioxide to sulfur trioxide. Granular catalyst, the ratio (H / D) of the height (H) and the diameter (D) of which is 0.
9 to 1.5 and the ratio of surface area (A) to diameter (D) (A
/ D) is 110 mm to 440 mm.
【０００８】[0008]
【実施例】つぎに、この発明の実施例を幾つか挙げる。EXAMPLES Next, some examples of the present invention will be described.
【０００９】実施例１ 二酸化硫黄を三酸化硫黄に酸化するのに通常用いられる
五酸化バナジウムベースの触媒をいろいろな形状に成型
した。こうして図１から図１０の触媒構造物を得た。Example 1 A vanadium pentoxide-based catalyst commonly used to oxidize sulfur dioxide to sulfur trioxide was molded into various shapes. Thus, the catalyst structures shown in FIGS. 1 to 10 were obtained.
【００１０】図１の触媒は円柱状であり、図２、図３お
よび図６の触媒は軸心部に空筒を有する円柱状であり、
図４、図５、図７および図８の触媒は軸方向に４つの空
筒を有する円柱状であり、図９および図１０の触媒は軸
方向に５つの空筒を有する円柱状である。The catalyst shown in FIG. 1 has a cylindrical shape, and the catalysts shown in FIGS. 2, 3 and 6 have a cylindrical shape having an empty cylinder at its axial center.
The catalyst of FIGS. 4, 5, 7 and 8 is a cylinder having four hollow cylinders in the axial direction, and the catalyst of FIGS. 9 and 10 is a cylinder having five hollow cylinders in the axial direction.
【００１１】なお、図１、図２および図３の触媒は公知
の触媒であり、本発明品との比較のために示したもので
ある。The catalysts shown in FIGS. 1, 2 and 3 are known catalysts, and are shown for comparison with the products of the present invention.
【００１２】これらの触媒について、高さ（Ｈ）と直径
（Ｄ）の比（Ｈ／Ｄ）、表面積（Ａ）と直径（Ｄ）の比
（Ａ／Ｄ）などを表１に示す。Table 1 shows the ratio (H / D) of height (H) to diameter (D) and the ratio (A / D) of surface area (A) to diameter (D) of these catalysts.
【００１３】触媒を反応器に充填し、ＳＯ2 を約８モル
％、Ｏ2 を約１０モル％含有するガスを反応器に流通さ
せ、ＳＯ2 をＳＯ3 に酸化する反応を行い、各触媒につ
いて酸化反応率を求めた。その結果を表１に示す。The catalyst is filled in a reactor, and a gas containing about 8 mol% of SO 2 and about 10 mol% of O 2 is passed through the reactor to oxidize SO 2 to SO 3 to carry out a reaction. Then, the oxidation reaction rate was determined. Table 1 shows the results.
【００１４】[0014]
【表１】 実施例２ この実施例では、ＳＯ2 濃度を１０〜１２モル％にし、
その他の点を実施例１と同様にして各触媒について酸化
反応率を求めた。これらの触媒について、高さ（Ｈ）と
直径（Ｄ）の比（Ｈ／Ｄ）および表面積（Ａ）と直径
（Ｄ）の比（Ａ／Ｄ）、求めた反応率、ならびに反応条
件を表２に示す。[Table 1] Example 2 In this example, the SO 2 concentration was 10-12 mol%,
Otherwise in the same manner as in Example 1, the oxidation reaction rate was determined for each catalyst. For these catalysts, the ratio of height (H) to diameter (D) (H / D) and the ratio of surface area (A) to diameter (D) (A / D), the obtained reaction rate, and reaction conditions are shown. 2 shows.
【００１５】ＳＯ2 濃度が１０％以上の高濃度の場合、
酸化反応の進行に伴って発生する時間当りの反応熱が多
量であるため、非定常型反応器の熱の移動を良好にする
ためには実施例１で用いた触媒よりも比（Ａ／Ｄ）をさ
らに大きくする必要があることが判る。When the SO 2 concentration is as high as 10% or more,
Since the reaction heat generated per unit time with the progress of the oxidation reaction is large, in order to improve the heat transfer in the unsteady reactor, the ratio (A / D) is higher than that of the catalyst used in Example 1. ) Needs to be further increased.
【００１６】[0016]
【表２】 実施例１および実施例２の結果から以下の結論が得られ
た。[Table 2] From the results of Example 1 and Example 2, the following conclusions were obtained.
【００１７】ＳＯ2 濃度が８％である場合、実験No. ４
において最もよい効果が得られた。When the SO 2 concentration was 8%, Experiment No. 4
The best effect was obtained.
【００１８】比較のために行った実験No. １−１、１−
２、２−１、２−２、２−３、３−１および３−２で
は、比（Ａ／Ｄ）が１００以下である場合、非定常型で
は高い反応率が得られないことが判明した。Experiments conducted for comparison No. 1-1, 1-
In the case of 2, 2-1, 2-2, 2-3, 3-1 and 3-2, when the ratio (A / D) is 100 or less, it was found that a high reaction rate cannot be obtained in the unsteady type. did.
【００１９】実験No. １−１および１−２では、実験N
o. ４と同じ反応率を得るためには１．５倍量の触媒を
必要とした。また、実験No. ２−１、２−２および２−
３ではガスは流通速度を低下することによって反応率が
上昇したが、いずれも実際的ではない。In Experiment Nos. 1-1 and 1-2, Experiment N
o 1.5 times the amount of catalyst was needed to obtain the same conversion as o. In addition, Experiment Nos. 2-1, 2-2 and 2-
In No. 3, the reaction rate of the gas was increased by decreasing the flow rate, but neither was practical.
【００２０】実験No. ５−１および５−２では最も高い
反応が得られたが、実験No. ４と同じ触媒量では反応率
が悪く、実際に採用することは困難である。The highest reaction was obtained in Experiment Nos. 5-1 and 5-2, but the reaction rate was poor with the same amount of catalyst as in Experiment No. 4, and it was difficult to actually adopt it.
【００２１】実験No. ６の結果は実験No. ４とほぼ同じ
であった。The results of Experiment No. 6 were almost the same as those of Experiment No. 4.
【００２２】実験No. ７−１および７−２では、必要触
媒量、反応率ともに、実験No. ４、６と、実験No. ５−
１および５−２との中間であった。In Experiment Nos. 7-1 and 7-2, the required amount of catalyst and the reaction rate were both Experiment Nos. 4 and 6 and Experiment No. 5-.
It was intermediate between 1 and 5-2.
【００２３】ＳＯ2 濃度が１０％以上である場合、実験
No. ８−１および８−２と、実験No. １１−１および１
１−２との結果から、触媒充填量を増加しても非定常型
酸化反応では一定以上の反応率は得られず、反応率を上
げるために触媒形状をより大きな比（Ａ／Ｄ）を持つも
のに変える必要があることが判明した。When the SO 2 concentration is 10% or more, the experiment
No. 8-1 and 8-2 and Experiment No. 11-1 and 1
From the results of 1-2, even if the catalyst loading was increased, the reaction rate above a certain level could not be obtained in the unsteady-state oxidation reaction, and in order to increase the reaction rate, a larger catalyst ratio (A / D) was used. It turns out that you need to change it to something you have.
【００２４】ＳＯ2 濃度が８％以下である場合、各触媒
について、比（Ａ／Ｄ）と反応率の関係を図１１に示
す。同図から、ＳＯ2 濃度が８％以下である場合、比
（Ａ／Ｄ）の最適な範囲は１１０〜２２０ｍｍであるこ
とが判る。FIG. 11 shows the relationship between the ratio (A / D) and the reaction rate for each catalyst when the SO 2 concentration is 8% or less. From the figure, it is understood that when the SO 2 concentration is 8% or less, the optimum range of the ratio (A / D) is 110 to 220 mm.
【００２５】また、ＳＯ2 濃度が１０％以上である場
合、比（Ａ／Ｄ）と反応率の関係を図１２に示す。同図
から、ＳＯ2 濃度が１０％以上である場合、比（Ａ／
Ｄ）の最適な値は４４０ｍｍ付近であることが判る。FIG. 12 shows the relationship between the ratio (A / D) and the reaction rate when the SO 2 concentration is 10% or more. From the figure, when the SO 2 concentration is 10% or more, the ratio (A /
It can be seen that the optimum value of D) is around 440 mm.
【００２６】[0026]
【発明の効果】この発明によれば、その高さ（Ｈ）と直
径（Ｄ）の比（Ｈ／Ｄ）が０．９〜１．５で、かつ表面
積（Ａ）と直径（Ｄ）の比（Ａ／Ｄ）が１１０〜４４０
（ｍｍ）である最適な触媒形状を選定することにより、
満足できる反応率を得ることができる。According to the present invention, the ratio (H / D) of the height (H) and the diameter (D) is 0.9 to 1.5, and the surface area (A) and the diameter (D) are Ratio (A / D) is 110-440
By selecting the optimum catalyst shape that is (mm),
A satisfactory reaction rate can be obtained.
【図１】触媒の斜視図である。FIG. 1 is a perspective view of a catalyst.
【図２】触媒の斜視図である。FIG. 2 is a perspective view of a catalyst.
【図３】触媒の斜視図である。FIG. 3 is a perspective view of a catalyst.
【図４】触媒の斜視図である。FIG. 4 is a perspective view of a catalyst.
【図５】触媒の斜視図である。FIG. 5 is a perspective view of a catalyst.
【図６】触媒の斜視図である。FIG. 6 is a perspective view of a catalyst.
【図７】触媒の斜視図である。FIG. 7 is a perspective view of a catalyst.
【図８】触媒の斜視図である。FIG. 8 is a perspective view of a catalyst.
【図９】触媒の斜視図である。FIG. 9 is a perspective view of a catalyst.
【図１０】触媒の斜視図である。FIG. 10 is a perspective view of a catalyst.
【図１１】ＳＯ2 濃度８％の場合の（表面積／直径）比
（Ａ／Ｄ）と反応率との関係を示すグラフである。FIG. 11 is a graph showing the relationship between the (surface area / diameter) ratio (A / D) and the reaction rate when the SO 2 concentration is 8%.
【図１２】ＳＯ2 濃度が１０％以上である場合の（表面
積／直径）比（Ａ／Ｄ）と反応率との関係を示すグラフ
である。FIG. 12 is a graph showing the relationship between the (surface area / diameter) ratio (A / D) and the reaction rate when the SO 2 concentration is 10% or more.
Claims (1)
用いられる五酸化バナジウムベースの粒状触媒であっ
て、その高さ（Ｈ）と直径（Ｄ）の比（Ｈ／Ｄ）が０．
９〜１．５で、かつ表面積（Ａ）と直径（Ｄ）の比（Ａ
／Ｄ）が１１０〜４４０（ｍｍ）であることを特徴とす
る、二酸化硫黄酸化触媒構造物。1. A vanadium pentoxide-based granular catalyst used to oxidize sulfur dioxide to sulfur trioxide, the height (H) to diameter (D) ratio (H / D) of which is 0.1.
9 to 1.5 and the ratio of surface area (A) to diameter (D) (A
/ D) is 110-440 (mm), The sulfur dioxide oxidation catalyst structure characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00082695A JP3314322B2 (en) | 1995-01-06 | 1995-01-06 | Sulfur dioxide oxidation catalyst structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00082695A JP3314322B2 (en) | 1995-01-06 | 1995-01-06 | Sulfur dioxide oxidation catalyst structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08187430A true JPH08187430A (en) | 1996-07-23 |
| JP3314322B2 JP3314322B2 (en) | 2002-08-12 |
Family
ID=11484461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP00082695A Expired - Fee Related JP3314322B2 (en) | 1995-01-06 | 1995-01-06 | Sulfur dioxide oxidation catalyst structure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3314322B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489320A (en) * | 2011-11-15 | 2012-06-13 | 南京云高新型材料有限公司 | Nanometer vanadium catalyst for preparing sulfuric acid through oxidizing SO2 and preparation method thereof |
| CN107081007A (en) * | 2017-06-27 | 2017-08-22 | 福州大学 | A kind of new oxidants prepare functionalization denitration sulfur resistive composite filtering material |
| CN109095441A (en) * | 2017-06-20 | 2018-12-28 | 中国瑞林工程技术有限公司 | The method for preparing sulfuric acid |
| EP3431178A1 (en) | 2017-07-20 | 2019-01-23 | Basf Se | Catalysts and method for the catalytic oxidation of so2 to so3 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3838393A1 (en) | 2019-12-19 | 2021-06-23 | Basf Se | Process for the oxidation of sulfur dioxide to sulfur trioxide involving a structured catalyst bed |
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|---|---|---|---|---|
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| JPS60261539A (en) * | 1984-06-11 | 1985-12-24 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for oxidizing sulfur dioxide |
| JPH06134318A (en) * | 1992-10-06 | 1994-05-17 | Montecatini Tecnol Spa | Cylindrical catalyst granule |
| JPH06170239A (en) * | 1992-12-11 | 1994-06-21 | Mitsubishi Rayon Co Ltd | Catalytic formed body for synthesis of unsaturated aldehyde and unsaturated carboxylic acid and its use |
-
1995
- 1995-01-06 JP JP00082695A patent/JP3314322B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5889946A (en) * | 1981-11-24 | 1983-05-28 | キヤタリスツ・アンド・ケミカルス・ユ−ロプ・ソシエテ・アノニム | Vanadium pentoxide catalyst and production thereof |
| JPS60261539A (en) * | 1984-06-11 | 1985-12-24 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for oxidizing sulfur dioxide |
| JPH06134318A (en) * | 1992-10-06 | 1994-05-17 | Montecatini Tecnol Spa | Cylindrical catalyst granule |
| JPH06170239A (en) * | 1992-12-11 | 1994-06-21 | Mitsubishi Rayon Co Ltd | Catalytic formed body for synthesis of unsaturated aldehyde and unsaturated carboxylic acid and its use |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489320A (en) * | 2011-11-15 | 2012-06-13 | 南京云高新型材料有限公司 | Nanometer vanadium catalyst for preparing sulfuric acid through oxidizing SO2 and preparation method thereof |
| CN109095441A (en) * | 2017-06-20 | 2018-12-28 | 中国瑞林工程技术有限公司 | The method for preparing sulfuric acid |
| CN107081007A (en) * | 2017-06-27 | 2017-08-22 | 福州大学 | A kind of new oxidants prepare functionalization denitration sulfur resistive composite filtering material |
| EP3431178A1 (en) | 2017-07-20 | 2019-01-23 | Basf Se | Catalysts and method for the catalytic oxidation of so2 to so3 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3314322B2 (en) | 2002-08-12 |
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