JPS61256904A - Purifying method for liquid sulfur - Google Patents
Purifying method for liquid sulfurInfo
- Publication number
- JPS61256904A JPS61256904A JP60096805A JP9680585A JPS61256904A JP S61256904 A JPS61256904 A JP S61256904A JP 60096805 A JP60096805 A JP 60096805A JP 9680585 A JP9680585 A JP 9680585A JP S61256904 A JPS61256904 A JP S61256904A
- Authority
- JP
- Japan
- Prior art keywords
- liquid sulfur
- catalyst
- h2sx
- gas
- 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.)
- Granted
Links
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- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
発明の目的
産業上の利用分
この発明はＨ２Ｓ （硫化水素）とＳＯ２（亜硫酸ガス
）から製造された液体硫黄の精製方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION OBJECTS OF THE INVENTION Industrial Application This invention relates to a method for purifying liquid sulfur produced from H2S (hydrogen sulfide) and SO2 (sulfur dioxide gas).
Ｈ２Ｓと５０２とのクラウス反応による元素硫黄の生成
は、硫黄製造を主目的として、あるいはＨ２Ｓ又はＳＯ
２を含有するガスの精製を主目的として広〈実施されて
いるが、このようにして生成した液体硫黄にはＨ２Ｓ換
算で２００〜８００ｐｐｍ（７）ＨｚＳ及びＨ２Ｓｘ（
ポリ硫化水素）が溶存している。The production of elemental sulfur by the Claus reaction between H2S and 502 can be used primarily for sulfur production, or for the production of H2S or SO
The liquid sulfur produced in this way contains 200 to 800 ppm (7) HzS and H2Sx (7) in terms of H2S.
Polyhydrogen sulfide) is dissolved.
かかる液体硫黄の貯蔵又は輸送中に、溶存しているＨ２
Ｓは気化・拡散し、人出荷時の人体への影響、ガス爆発
の危険を伴なう。またＨ２Ｓｘは徐々に分解してＨ２Ｓ
となるので同様に有害である。During storage or transportation of such liquid sulfur, dissolved H2
S vaporizes and diffuses, which poses a risk of impact on the human body during shipping and a risk of gas explosion. In addition, H2Sx gradually decomposes into H2Sx.
Therefore, it is equally harmful.
従来の技術
液体硫黄に溶存しているＨ２Ｓ及びＨ２Ｓｘを除去する
方法としては、液体硫黄を障害物に吹きつけて物理的衝
撃によりＨ−３結合を破壊する方法、スイープガスと呼
ばれる空気と液体硫黄を無触媒で接触させＨ２Ｓ及びＨ
２Ｓｘを気化して除去する方法があるが、いずれも長時
間を要し除去効率が悪い、ことにＨ２Ｓｘは分解が遅く
、スイープガスの利用だけでは一日以上の処理時間を要
する。ＮＨ３やアミンを添加し、Ｈ２Ｓ及びＨ２Ｓｘと
反応させて除去する方法もあるが、製品硫黄中に不純物
が混入するので好ましくない。Conventional technology Methods for removing H2S and H2Sx dissolved in liquid sulfur include a method in which liquid sulfur is sprayed onto obstacles to destroy H-3 bonds by physical impact, and a method in which H2S and H2Sx dissolved in liquid sulfur are removed is a method in which H-3 bonds are destroyed by physical impact, and a method in which air and liquid sulfur called a sweep gas is used. are brought into contact with each other without a catalyst and H2S and H
There are methods for removing 2Sx by vaporizing it, but all of them take a long time and have poor removal efficiency. In particular, H2Sx decomposes slowly, and the use of sweep gas alone requires more than a day's processing time. There is also a method of adding NH3 or amine and reacting it with H2S and H2Sx to remove it, but this is not preferred because impurities are mixed into the product sulfur.
特公昭５９−４０７６２号には、液体硫黄をアルミナ又
はコバルト−モリブデン含浸アルミナからなる触媒に接
触せしめ、空気又は酸素富化空気でパージすることによ
りＨ２Ｓ及びＨ２Ｓｘを除去する方法が記載されている
が、Ｈ２Ｓｘを半減するのになお数時間を要し、工業的
に改良の余地がある。Japanese Patent Publication No. 59-40762 describes a method for removing H2S and H2Sx by bringing liquid sulfur into contact with a catalyst made of alumina or cobalt-molybdenum impregnated alumina and purging with air or oxygen-enriched air. , it still takes several hours to reduce H2Sx by half, and there is still room for industrial improvement.
発明が解決しようとする問題点
本発明は上記従来法の欠点を解決し、液体硫黄中のＨ２
Ｓ及びＨ２Ｓｘを迅速に除去する方法を提供することを
目的とする。Problems to be Solved by the Invention The present invention solves the above-mentioned drawbacks of the conventional method, and solves the problem of H2 in liquid sulfur.
The purpose of the present invention is to provide a method for quickly removing S and H2Sx.
発明の構成
間 点 るための
本発明は、Ｈ２Ｓ及びＨ２Ｓｘを含有する液体硫黄をＮ
ｉ−Ｍｏ系触媒の存在下、酸素含有ガス及び窒素ガスよ
りなる群から選ばれるスイープガスと接触させることよ
りなる。According to the present invention, liquid sulfur containing H2S and H2Sx is converted into nitrogen.
It consists of contacting a sweep gas selected from the group consisting of an oxygen-containing gas and a nitrogen gas in the presence of an i-Mo catalyst.
Ｎ ｆ −Ｍ ｏ系触媒は通常脱硫触媒として使用され
ているものであればよく、シリカ、アルミナ又は酸化チ
タンに担持された状態で使用される。担持触媒中のＮｉ
含有量はＮｉＯとして約０．５〜２０重景％、ＭＯ含有
量はＭ ｏ ０３として約１〜３５重量％のものが使用
される。Ｎｔ及びＭｏは酸化物または硫化物の形態で用
いられる。The N f -Mo catalyst may be any catalyst that is normally used as a desulfurization catalyst, and is used in a state supported on silica, alumina, or titanium oxide. Ni in supported catalyst
The content used is about 0.5 to 20% by weight as NiO, and the MO content is about 1 to 35% by weight as Mo03. Nt and Mo are used in the form of oxides or sulfides.
反応温度は１２０〜１６０℃の範囲とするのが好ましい
、圧力は常圧でも加圧でもよい。The reaction temperature is preferably in the range of 120 to 160°C, and the pressure may be normal pressure or increased pressure.
本発明でスイープガスとして使用する酸素含有ガスは、
空気又は酸素富化空気はもとより使用できるが１例えば
クラウス法硫黄回収装置におけるインシネレータ−オフ
ガスのように、酸素を１〜２％程度しか含有していない
ガスでも使用することができる。インシネレータ−オフ
ガスを利用することは、既にガスが高温になっているの
で、スイープガスとして反応温度まで予熱する熱エネル
ギーを節約することができることを意味する。The oxygen-containing gas used as the sweep gas in the present invention is
Although air or oxygen-enriched air can be used, it is also possible to use a gas containing only about 1 to 2% oxygen, such as incinerator off-gas in a Claus process sulfur recovery device. Utilizing incinerator off-gas means that the gas is already at a high temperature, so thermal energy can be saved in preheating it to reaction temperature as a sweep gas.
さらに窒素もスイープガスとして使用することができる
。これは本発明におけるＮｉ−Ｍｏ系触媒が酸化触媒と
してではなく、Ｈ２ＳｘのＨ２Ｓへ゛の分解触媒として
作用し、スイープガスによるパージ効果を高めるためと
推定される。Additionally, nitrogen can also be used as a sweep gas. This is presumed to be because the Ni--Mo catalyst in the present invention acts not as an oxidation catalyst but as a decomposition catalyst for H2Sx to H2S, thereby enhancing the purging effect by the sweep gas.
実施例１
（触媒の調製）
１／８インチに押出成型されたγ−Ａ１２０３（比表面
積：１９０ｍ２／ｇ、細孔容積＝０．６ｍｕ／ｇ）に、
硝酸ニッケル及び硝酸モリブデンを含浸させ、乾燥後５
００℃にて空気中で焼成して、Ｎ ｉ Ｏ： ３ 、２
ｗ ｔ％、ＭＯＯ３：１５．４ｗｔ％のＡｌ２Ｏ３担
持Ｎｉ＊Ｍｏ触媒を得た。Example 1 (Preparation of catalyst) γ-A1203 (specific surface area: 190 m2/g, pore volume = 0.6 mu/g) extruded into 1/8 inch,
Impregnated with nickel nitrate and molybdenum nitrate, after drying 5
Calcinate in air at 00°C to obtain N i O: 3, 2
wt%, MOO3: 15.4 wt% Al2O3 supported Ni*Mo catalyst was obtained.
（触媒の硫化）
この触媒１４１を第１図に示す反応器１（内径８０ ｍ
ｍ ｍ長さ５００ｍｍ）に充填し、配管２からＨ２Ｓ
：５ＶＧ１％、Ｈｚ：９５ｖｏ１％の硫化水素ガスを１
００Ｎ交／ Ｈｒで流し、３００℃まで昇温し維持して
、入口／出口のＨ２Ｓ濃度を分析し、一致した時点をも
って硫化完了とした。(Catalyst sulfurization) This catalyst 141 was placed in the reactor 1 (inner diameter 80 m) shown in FIG.
m m length 500 mm), and connect H2S from piping 2.
:5VG1%, Hz:95vo1% hydrogen sulfide gas 1
The temperature was raised to 300° C. and maintained at 300° C., and the H2S concentrations at the inlet and outlet were analyzed, and when they matched, sulfurization was completed.
（液状硫黄精製）
次いで触媒層温度を１５０℃に調整し、反応器１、の上
部から配管３より液体硫黄１ 、５ Ｋｇ／ ）Ｉｒ、
配管４より空気５ Ｎ ｌ ／ Ｈｒを導入して触媒層
で併流接触させ、次いで分離器５に導入して精製硫黄を
配管６から抜き出し、配管７からオフガスを排出した。(Liquid sulfur purification) Next, the catalyst layer temperature was adjusted to 150°C, and liquid sulfur (1.5 kg/)Ir,
5 Nl/Hr of air was introduced through pipe 4 and brought into cocurrent contact with the catalyst layer, then introduced into separator 5, purified sulfur was extracted from pipe 6, and off-gas was discharged from pipe 7.
原料液体硫黄及び処理後の液体硫黄中のＨ２Ｓｘを赤外
線分析計にて分析したところ原料液体硫黄中３１０ ｐ
ｐｍのものが５ｐｐｍ以下になっていた。Analysis of H2Sx in the raw liquid sulfur and the treated liquid sulfur using an infrared analyzer revealed that the raw liquid sulfur contained 310 p.
pm was below 5 ppm.
実施例２．３及び比較例１
下記のＡ、Ｂ、Ｃを触媒として使用してＨ２Ｓ及びＨ２
Ｓｘを含有する液体硫黄の精製試験を行った。Example 2.3 and Comparative Example 1 H2S and H2 using the following A, B, and C as catalysts
A purification test was conducted on liquid sulfur containing Sx.
Ａ：実施例１で担体として使用したアルミナ自身（比較
例１）
Ｂ：ＡにＮｉＯとして６．７重量％のＮｉ及びＭ ｏ
Ｏｓとして２７重量％のＭｏを担持させ空気中で焼成し
たもの（実施例２）
ＣＡＢの硫化量（実施例３）
触媒１００ｍＩＬを反応器（内径４０ｍｍ・長さ４００
ｍｍ）に充填し、１５０℃に保ち、液体硫黄３００ｍ文
／Ｈｒ、空気Ｉ Ｎ ｆＬ／ Ｈｒを導入し並流接触さ
せてＨ２Ｓ及びＨ２Ｓｘの除去を行った０次いでスイー
プガスの空気Ｉ Ｎ ｌ ／ Ｈｒを窒素ガスｌ Ｎ
ｌ ／ Ｈｒに切り替えて同様の実験をした。その結果
を第１表に示す。A: Alumina itself used as a carrier in Example 1 (Comparative Example 1) B: 6.7% by weight of Ni and Mo as NiO in A
27% by weight of Mo was supported as Os and calcined in air (Example 2) Amount of CAB sulfidation (Example 3) 100ml of catalyst was placed in a reactor (inner diameter 40mm, length 40mm)
mm) and kept at 150°C, liquid sulfur 300 mfL/Hr and air I N fL/Hr were introduced and brought into cocurrent contact to remove H2S and H2Sx. Hr to nitrogen gas lN
A similar experiment was performed by switching to l/Hr. The results are shown in Table 1.
第 １ 表 この結果より、Ａｌ２Ｏ３単独よりＮ１−Ｍ。Table 1 From this result, N1-M is better than Al2O3 alone.
を担持させたものの方がＨ２Ｓｘ除去率、Ｈ２Ｓ除去率
ともに優れていることがわかる。またＮｉ−Ｍ ｏ担持
触媒の中でも硫化処理したもの（実施例３で使用した触
媒Ｃ）は更に活性が向上していることがわかる。It can be seen that the H2Sx removal rate and the H2S removal rate are superior to those on which H2S is supported. Furthermore, it can be seen that among the Ni-Mo supported catalysts, the sulfurized one (Catalyst C used in Example 3) has further improved activity.
発明の効果
液体硫黄中のＨ２Ｓ及びＨ２Ｓｘを迅速に除去すること
ができる。Effects of the Invention H2S and H2Sx in liquid sulfur can be quickly removed.
第１図は実施例１で使用した装置の説明図である。 FIG. 1 is an explanatory diagram of the apparatus used in Example 1.
Claims (1)
ｏ系触媒の存在下、酸素含有ガス及び窒素ガスよりなる
群から選ばれるスイープガスと接触させることよりなる
液体硫黄の精製方法。Ni-M liquid sulfur containing H_2S and H_2Sx
A method for purifying liquid sulfur, which comprises bringing it into contact with a sweep gas selected from the group consisting of an oxygen-containing gas and a nitrogen gas in the presence of an o-based catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60096805A JPS61256904A (en) | 1985-05-09 | 1985-05-09 | Purifying method for liquid sulfur |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60096805A JPS61256904A (en) | 1985-05-09 | 1985-05-09 | Purifying method for liquid sulfur |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61256904A true JPS61256904A (en) | 1986-11-14 |
| JPH0364445B2 JPH0364445B2 (en) | 1991-10-07 |
Family
ID=14174824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60096805A Granted JPS61256904A (en) | 1985-05-09 | 1985-05-09 | Purifying method for liquid sulfur |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61256904A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63222005A (en) * | 1987-03-09 | 1988-09-14 | Jgc Corp | Purification of crude liquid sulfur |
| CN102134061A (en) * | 2010-01-25 | 2011-07-27 | 气体产品与化学公司 | A reactor, a structured packing, and a method for improving oxidation of hydrogen sulfide or polysulfides in liquid sulfur |
-
1985
- 1985-05-09 JP JP60096805A patent/JPS61256904A/en active Granted
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63222005A (en) * | 1987-03-09 | 1988-09-14 | Jgc Corp | Purification of crude liquid sulfur |
| JPH0522642B2 (en) * | 1987-03-09 | 1993-03-30 | Jgc Corp | |
| CN102134061A (en) * | 2010-01-25 | 2011-07-27 | 气体产品与化学公司 | A reactor, a structured packing, and a method for improving oxidation of hydrogen sulfide or polysulfides in liquid sulfur |
| EP2347995A1 (en) * | 2010-01-25 | 2011-07-27 | Air Products and Chemicals, Inc. | A reactor, a structures packing, and a method for improving oxidation of hydrogen sulfide or polysulfides in liquid sulfur |
| AU2011200201B2 (en) * | 2010-01-25 | 2013-08-22 | Fluor Technologies Corporation | A reactor, a structured packing, and a method for improving oxidation of hydrogen sulfide or polysulfides in liquid sulfur |
| US8663596B2 (en) | 2010-01-25 | 2014-03-04 | Fluor Enterprises, Inc. | Reactor, a structure packing, and a method for improving oxidation of hydrogen sulfide or polysulfides in liquid sulfur |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0364445B2 (en) | 1991-10-07 |
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Legal Events
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|---|---|---|---|
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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