JP2539711B2 - Method for removing carbonyl sulfide in gas - Google Patents
Method for removing carbonyl sulfide in gasInfo
- Publication number
- JP2539711B2 JP2539711B2 JP3206099A JP20609991A JP2539711B2 JP 2539711 B2 JP2539711 B2 JP 2539711B2 JP 3206099 A JP3206099 A JP 3206099A JP 20609991 A JP20609991 A JP 20609991A JP 2539711 B2 JP2539711 B2 JP 2539711B2
- Authority
- JP
- Japan
- Prior art keywords
- carbonyl sulfide
- gas
- catalyst
- sulfur dioxide
- sulfur
- 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.)
- Expired - Lifetime
Links
Classifications
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Catalysts (AREA)
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、各種のガス中に含有さ
れている硫化カルボニル（ＣＯＳ）を加水分解して除去
するに際し、加水分解触媒の劣化を抑制する方法に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for suppressing deterioration of a hydrolysis catalyst when hydrolyzing and removing carbonyl sulfide (COS) contained in various gases.
【０００２】[0002]
【従来の技術】各種のガス中に含まれているＣＯＳは、
通常水蒸気及び触媒の存在下に加水分解してＨ2 Ｓに転
換した後湿式法により除去することが行われている。2. Description of the Related Art COS contained in various gases is
Usually, it is hydrolyzed in the presence of water vapor and a catalyst to be converted into H 2 S and then removed by a wet method.
【０００３】触媒としては、アルミナ（ JOURNAL OF CA
TALYSIS 32 270, 1947 )及びシリカ、アルミナ上に担持
したコバルト−モリブデート（ JOURNAL CATALYSIS 35
218, 1974 )、アルミナ上に担持された水酸化ナトリウ
ム、水酸化カリウム（特開昭６３−２２４７３６号公
報）、アルミナ上に担持された炭酸カリウム、炭酸ナト
リウム等が用いられている。Alumina (JOURNAL OF CA
TALYSIS 32 270, 1947) and cobalt-molybdate supported on silica and alumina (JOURNAL CATALYSIS 35
218, 1974), sodium hydroxide and potassium hydroxide supported on alumina (JP-A-63-224736), potassium carbonate and sodium carbonate supported on alumina, and the like.
【０００４】[0004]
【発明が解決しようとする課題】上記触媒を用いてガス
中に含まれている硫化カルボニルを加水分解する場合、
処理ガス中に二酸化硫黄、及びまたは三酸化硫黄が共存
する場合、これらによって活性点が被毒され、長期運転
が困難になる。加水分解によって生成した硫化水素は湿
式法で除去するため、これらの加水分解触媒は低温活性
が高いほうが好ましく、アルミナ担持水酸化アルカリあ
るいはアルカリ金属塩は低温活性が高く、加水分解触媒
として特に好ましい反面、二酸化硫黄、三酸化硫黄との
反応性も高く、これらが処理ガス中に共存することは特
に問題となる。アルミナは低温活性が低く、比較的高温
で使用される場合が多いが、高温で使用される場合やは
り二酸化硫黄、三酸化硫黄との反応性が増し長期運転が
困難になる。When the above catalyst is used to hydrolyze carbonyl sulfide contained in gas,
When sulfur dioxide and / or sulfur trioxide coexist in the treated gas, these poison the active sites and make long-term operation difficult. Since hydrogen sulfide generated by hydrolysis is removed by a wet method, it is preferable that these hydrolysis catalysts have a high low-temperature activity, and alumina-supported alkali hydroxide or alkali metal salt has a high low-temperature activity, but is particularly preferable as a hydrolysis catalyst. , Sulfur dioxide, and sulfur trioxide are also highly reactive, and their coexistence in the processing gas is a particular problem. Alumina has low activity at low temperature and is often used at relatively high temperature. However, when used at high temperature, reactivity with sulfur dioxide and sulfur trioxide is increased, and long-term operation becomes difficult.
【０００５】本発明は、これらの硫化カルボニル加水分
解触媒が、処理ガス中に含まれている二酸化硫黄又は三
酸化硫黄によって劣化されるのを防止する方法を提供す
ることを目的とする。An object of the present invention is to provide a method for preventing these carbonyl sulfide hydrolysis catalysts from being deteriorated by sulfur dioxide or sulfur trioxide contained in the process gas.
【０００６】[0006]
【課題を解決するための手段】本発明は、 １．二酸化硫黄及び／又は三酸化硫黄を含むガス中の硫
化カルボニルを加水分解触媒の存在下に加水分解して除
去する方法において、二酸化硫黄及び／又は三酸化硫黄
を除去した後、硫化カルボニルを加水分解することを特
徴とするガス中の硫化カルボニルを除去する方法。The present invention includes: A method for hydrolyzing and removing carbonyl sulfide in a gas containing sulfur dioxide and / or sulfur trioxide in the presence of a hydrolysis catalyst, the method comprising hydrolyzing carbonyl sulfide after removing sulfur dioxide and / or sulfur trioxide. A method for removing carbonyl sulfide in a gas, comprising:
【０００７】２．加水分解触媒床の上流側のクラウス反
応活性を有する触媒を充填した触媒床上に、二酸化硫黄
及び／又は三酸化硫黄、硫化水素並びに硫化カルボニル
を含むガスを通じた後加水分解触媒上に通ずることを特
徴とする前記ガス中より二酸化硫黄及び／又は三酸化硫
黄を除去した後硫化カルボニルを除去する方法。2. Characterized by passing through a gas containing sulfur dioxide and / or sulfur trioxide , hydrogen sulfide and carbonyl sulfide on a catalyst bed packed with a catalyst having Claus reaction activity on the upstream side of the hydrolysis catalyst bed, and then passing on a post-hydrolysis catalyst. A method of removing carbonyl sulfide after removing sulfur dioxide and / or sulfur trioxide from the gas.
【０００８】３．前記１記載の方法において、二酸化硫
黄及び／又は三酸化硫黄を吸着する能力を有する吸着剤
を充填した層を用いるガス中の二酸化硫黄及び／又は三
酸化硫黄を除去した後硫化カルボニルを除去する方法。
である。3. In the method of the first aspect, the removal of sulfur dioxide and / or trisulfide carbonyl After removal of sulfur dioxide and / or sulfur trioxide in the gas to use a layer packed with an adsorbent having the ability to adsorb sulfur oxides Method.
Is.
【０００９】以下、本発明を詳しく説明する。本発明で
用いるクラウス反応用触媒としては、市販されているい
ずれの触媒でも良いが、低温活性の高いチタニア、ジル
コニア等を触媒成分とするものがより好ましい。クラウ
ス反応条件としては次の条件が用いられる。 温度：８０〜３５０℃好ましくは１１０〜２５０℃ 圧力：０．３〜２０KG ＧＨＳＶ：２５０〜２０，０００hr-1 Ｈ2 Ｓ／ＳＯ2 ：量論比以上The present invention will be described in detail below. The catalyst for Claus reaction used in the present invention may be any commercially available catalyst, but it is more preferable to use titania, zirconia or the like having high low temperature activity as a catalyst component. The following conditions are used as Claus reaction conditions. Temperature: 80 to 350 ° C., preferably 110 to 250 ° C. Pressure: 0.3 to 20 KG GHSV: 250 to 20,000 hr −1 H 2 S / SO 2 : above stoichiometric ratio
【００１０】本発明で用いうる二酸化硫黄及び／又は三
酸化硫黄の吸着剤としては、活性炭、又はリチウム、カ
リウム、ナトリウム、カルシウムの炭酸塩あるいはこれ
らをアルミナに担持したもの等が挙げられる。Examples of the sulfur dioxide and / or sulfur trioxide adsorbent that can be used in the present invention include activated carbon, carbonates of lithium, potassium, sodium and calcium, or those obtained by supporting these on alumina.
【００１１】ＣＯＳ加水分解条件としては次の条件が用
いられる。 温度：４０〜２５０℃好ましくは１００〜２００℃ 圧力：０．３〜２０KG 水蒸気量：１〜３０ vol％好ましくは２〜２０ vol％ ＧＨＳＶ：２５０〜１０，０００hr-1 The following conditions are used as COS hydrolysis conditions. Temperature: 40 to 250 ° C., preferably 100 to 200 ° C. Pressure: 0.3 to 20 KG Water vapor amount: 1 to 30 vol%, preferably 2 to 20 vol% GHSV: 250 to 10,000 hr −1
【００１２】クラウス触媒とＣＯＳ加水分解触媒は同じ
反応器中に充填するのが経済的であるが、必ずしも両触
媒を同一反応器に充填する必要はない。同一反応器に両
触媒を充填して反応を行う場合、反応条件は同一とす
る。Although it is economical to pack the Claus catalyst and the COS hydrolysis catalyst in the same reactor, it is not always necessary to pack both catalysts in the same reactor. When both catalysts are charged in the same reactor to carry out the reaction, the reaction conditions are the same.
【００１３】本発明で処理するガスとしては、硫化カル
ボニルを含有している各種の化学プロセスの排ガス、石
炭ガス化ガス、重質油分解ガスその他石油精製における
各種発生ガスで、硫黄化合物のほかに窒素酸化物、炭化
水素等を含んでいてもよい。As the gas to be treated in the present invention, exhaust gases of various chemical processes containing carbonyl sulfide, coal gasification gas, heavy oil cracking gas and various other gases generated in petroleum refining, in addition to sulfur compounds, It may contain nitrogen oxides, hydrocarbons and the like.
【００１４】[0014]
【実施例】以下、比較例及び実施例を示して本発明を具
体的に説明する。EXAMPLES The present invention will be specifically described below with reference to Comparative Examples and Examples.
【００１５】比較例１ 硫化カルボニル１８０ppm 及び水蒸気２容量％を含む窒
素ガス５．７Nm3 ／時を、含浸法により調製した水酸化
カリ含量が１０重量％の水酸化カリ／γ−アルミナ触媒
（５〜１０φ）５００mlを充填した内径５３．５mmステ
ンレス製反応器に、常圧下、１１０℃で１０時間、１０
０時間及び３００時間通した後の硫化カルボニルの転化
率は各々７６％、７５％、７６％であった。Comparative Example 1 5.7 Nm 3 / hr of nitrogen gas containing 180 ppm of carbonyl sulfide and 2% by volume of steam was prepared by an impregnation method, and a potassium hydroxide / γ-alumina catalyst (5 having a potassium hydroxide content of 10% by weight) was prepared. -10φ) 500ml inner diameter 53.5mm stainless steel reactor, under normal pressure at 110 ℃ for 10 hours, 10
The conversion rates of carbonyl sulfide after 0 hour and 300 hours were 76%, 75% and 76%, respectively.
【００１６】比較例２ 二酸化硫黄８０ppm 、三酸化硫黄３２０ppm 及び酸素
０．１３容量％を含む窒素ガス１．５Nm3 ／時と硫化カ
ルボニル２４０ppm 及び水蒸気２．７容量％を含む窒素
ガス４．２Nm3 ／時を混合しながら、含浸法により調製
した水酸化カリ含量が１０重量％の水酸化カリ／γ−ア
ルミナ触媒（５〜１０φ）５００mlを充填した内径５
３．５mmステンレス製反応器に常圧、１１０℃で１０時
間、１００時間及び３００時間通した後の硫化カルボニ
ルの転化率は各々６４％、１８％、４％であった。Comparative Example 2 Nitrogen gas containing 80 ppm of sulfur dioxide, 320 ppm of sulfur trioxide and 0.13% by volume of oxygen, 1.5 Nm 3 / hour and 240 ppm of carbonyl sulfide and 4.2 Nm 3 of nitrogen gas containing 2.7% by volume of steam. The inner diameter was 5 filled with 500 ml of potassium hydroxide / γ-alumina catalyst (5 to 10φ) having a potassium hydroxide content of 10 wt% prepared by the impregnation method while mixing
The carbonyl sulfide conversions after passing through a 3.5 mm stainless steel reactor at 110 ° C. for 10 hours, 100 hours, and 300 hours at atmospheric pressure were 64%, 18%, and 4%, respectively.
【００１７】比較例１と２の比較から、処理ガス中に二
酸化硫黄／三酸化硫黄が共存すると、硫化カルボニル加
水分解触媒の劣化が極めて大きいことがわかる。From the comparison between Comparative Examples 1 and 2, it can be seen that the coexistence of sulfur dioxide / sulfur trioxide in the treated gas causes extremely large deterioration of the carbonyl sulfide hydrolysis catalyst.
【００１８】実施例１ 二酸化硫黄８０ppm 、三酸化硫黄３２０ppm 及び酸素
０．１３容量％を含む窒素ガス１．５Nm3 ／時と硫化カ
ルボニル２４０ppm 、硫化水素５００ppm 及び水蒸気
２．７容量％を含む窒素ガス４．２Nm3 ／時を混合しな
がら、含浸法により調製した水酸化カリ含量が１０重量
％の水酸化カリ／γ−アルミナ触媒（５〜１０φ）５０
０ml及びその上流側にチタニア系クラウス触媒５００ml
を充填した内径５３．５mmステンレス製反応器に１１０
℃で１０時間、１００時間および３００時間通した所、
硫化カルボニルの転化率は各々７５％、７０％、６８％
であった。Example 1 Nitrogen gas containing 80 ppm of sulfur dioxide, 320 ppm of sulfur trioxide and 0.13% by volume of oxygen, 1.5 Nm 3 / hr and 240 ppm of carbonyl sulfide, 500 ppm of hydrogen sulfide and 2.7% by volume of steam. Potassium hydroxide / γ-alumina catalyst (5-10φ) 50 having a potassium hydroxide content of 10% by weight, prepared by an impregnation method while mixing 4.2 Nm 3 / hour.
0 ml and 500 ml of titania-based Claus catalyst on the upstream side
110 in a 53.5 mm inner diameter stainless steel reactor filled with
After 10 hours, 100 hours and 300 hours at ℃,
Conversion rate of carbonyl sulfide is 75%, 70%, 68% respectively
Met.
【００１９】比較例２と実施例１の比較から、硫化カル
ボニル加水分解触媒の上流側にクラウス触媒を置き、処
理ガスに硫化水素を添加して二酸化硫黄／三酸化硫黄を
除去することによって、その二酸化硫黄／三酸化硫黄に
よる劣化が大幅に改善されることがわかる。From the comparison between Comparative Example 2 and Example 1, a Claus catalyst was placed upstream of the carbonyl sulfide hydrolysis catalyst, and hydrogen sulfide was added to the treated gas to remove sulfur dioxide / sulfur trioxide. It can be seen that the deterioration due to sulfur dioxide / sulfur trioxide is significantly improved.
【００２０】[0020]
【発明の効果】一般的に、化学プロセスにおける触媒の
長寿命化は、変動費の低減という意味から重要な因子の
一つであり、硫化カルボニルの除去触媒に対しても例外
ではない。硫化カルボニルの除去対象となるガスは各種
化学プロセスの排ガスであり、その触媒寿命は上流のプ
ロセスに使用されている触媒の寿命と同等以上でなけれ
ばならない。本発明の対象とする処理ガスは、上記のよ
うな各種の化学プロセスの排ガスであり、硫黄酸化物、
窒素酸化物、高級炭化水素等種々の触媒毒を含有してい
るため、その除去プロセスを長期にわたって連続運転す
ることは難しい状況にある。以上のことから、その上流
で触媒毒を除去し、触媒を長期にわたって使用可能な条
件を与えることは極めて有効である。In general, extending the catalyst life in a chemical process is one of the important factors in terms of reducing variable costs, and is not an exception for carbonyl sulfide removal catalysts. The gas for which carbonyl sulfide is to be removed is exhaust gas from various chemical processes, and the catalyst life must be equal to or longer than the life of the catalyst used in the upstream process. The processing gas targeted by the present invention is exhaust gas of various chemical processes as described above, sulfur oxides,
Since it contains various catalyst poisons such as nitrogen oxides and higher hydrocarbons, it is difficult to continuously operate the removal process for a long period of time. From the above, it is extremely effective to remove the catalyst poison upstream of the catalyst and to provide a condition under which the catalyst can be used for a long time.
Claims (3)
ガス中の硫化カルボニルを加水分解触媒の存在下に加水
分解して除去する方法において、二酸化硫黄及び／又は
三酸化硫黄を除去した後、硫化カルボニルを加水分解す
ることを特徴とするガス中の硫化カルボニルを除去する
方法。1. A method for hydrolyzing and removing carbonyl sulfide in a gas containing sulfur dioxide and / or sulfur trioxide in the presence of a hydrolysis catalyst, the method comprising: removing sulfur dioxide and / or sulfur trioxide; A method for removing carbonyl sulfide in a gas, which comprises hydrolyzing carbonyl sulfide.
活性を有する触媒を充填した触媒床上に、二酸化硫黄及
び／又は三酸化硫黄、硫化水素並びに硫化カルボニルを
含むガスを通じた後加水分解触媒上に通ずることを特徴
とする、前記ガス中より二酸化硫黄及び／又は三酸化硫
黄を除去した後硫化カルボニルを除去する方法。2. A post-hydrolysis catalyst is passed through a gas containing sulfur dioxide and / or sulfur trioxide , hydrogen sulfide and carbonyl sulfide on the catalyst bed packed with the catalyst having Claus reaction activity on the upstream side of the hydrolysis catalyst bed. The method for removing carbonyl sulfide after removing sulfur dioxide and / or sulfur trioxide from the gas, characterized in that
及び／または三酸化硫黄を吸着する能力を有する吸着剤
を充填した層を用いるガス中の二酸化硫黄及び／又は三
酸化硫黄を除去した後硫化カルボニルを除去する方法。Wherein the removal of the sulfur dioxide and / or sulfur trioxide in the gas to use a layer packed with an adsorbent having the ability to adsorb sulfur dioxide and / or sulfur trioxide Te method smell of claim 1, wherein Method for removing post-carbonyl sulfide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3206099A JP2539711B2 (en) | 1991-07-24 | 1991-07-24 | Method for removing carbonyl sulfide in gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3206099A JP2539711B2 (en) | 1991-07-24 | 1991-07-24 | Method for removing carbonyl sulfide in gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05115747A JPH05115747A (en) | 1993-05-14 |
| JP2539711B2 true JP2539711B2 (en) | 1996-10-02 |
Family
ID=16517790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3206099A Expired - Lifetime JP2539711B2 (en) | 1991-07-24 | 1991-07-24 | Method for removing carbonyl sulfide in gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2539711B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100228020A1 (en) * | 2006-02-28 | 2010-09-09 | V.B Medicare Pvt. Ltd | Novel Chlorination Reagent and a Novel Process for Chlorination of Sugars Using Thionyl Chloride |
| JP2017003534A (en) * | 2015-06-16 | 2017-01-05 | 理研計器株式会社 | Carbonyl sulfide measurement device |
| CN113426289B (en) * | 2021-06-29 | 2023-04-11 | 松山湖材料实验室 | Hydrolysis adsorbent, blast furnace gas desulfurization method and desulfurization equipment |
-
1991
- 1991-07-24 JP JP3206099A patent/JP2539711B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05115747A (en) | 1993-05-14 |
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