JPH0832548B2 - Method for removing sulfur compounds contained in residual gas - Google Patents
Method for removing sulfur compounds contained in residual gasInfo
- Publication number
- JPH0832548B2 JPH0832548B2 JP61505667A JP50566786A JPH0832548B2 JP H0832548 B2 JPH0832548 B2 JP H0832548B2 JP 61505667 A JP61505667 A JP 61505667A JP 50566786 A JP50566786 A JP 50566786A JP H0832548 B2 JPH0832548 B2 JP H0832548B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- sulfur
- catalyst
- effluent
- claus
- 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
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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
- 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
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】 本発明は、特にCLAUS式硫黄工場から排出されるよう
な残留ガスの中に含まれる硫黄化合物を除去するための
方法に係わる。この方法では前記硫黄化合物を硫黄の形
態で回収する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for removing sulfur compounds contained in residual gas, especially as discharged from a CLAUS sulfur plant. In this method, the sulfur compound is recovered in the form of sulfur.
CLAUS法という名称で知られているH2S含有酸性ガスの
部分的酸化処理によって硫黄を製造するような硫黄工場
から排出される残留ガスは約0.2〜２容量％の硫黄化合
物と蒸気状及び／又は胞状硫黄とを含む。これら硫黄化
合物の大部分はH2Sからなり、残りはSO2、CS2、COSから
なる。The residual gas emitted from a sulfur plant that produces sulfur by partial oxidation of H 2 S-containing acid gas known as CLAUS method is about 0.2 to 2% by volume of sulfur compounds and vaporous and / or Or vesicular sulfur. Most of these sulfur compounds consist of H 2 S, and the rest consist of SO 2 , CS 2 and COS.
このような残留ガスは通常、大気汚染に関する法律に
よって課せられた基準を遵守しながら焼却後に大気中に
排出できるように、硫黄化合物総含量を最大限に低下さ
せ、それと同時にこれらの硫黄化合物を硫黄工場で処理
される酸性ガスから生成される利用価値のある生成物の
収率増加に寄与するような形態で回収すべく処理され
る。Such residual gases usually maximize the total sulfur compound content while at the same time maximizing the sulfur compounds so that they can be discharged into the atmosphere after incineration, in compliance with the standards imposed by air pollution legislation. It is processed to be recovered in a form that contributes to the increased yield of valuable products produced from acid gases processed in the factory.
CLAUS式硫黄工場の残留ガスを処理するために本出願
人によって開発された公知の方法は、残留ガスを任意に
160℃未満の温度に冷却した後でCLAUS触媒に接触させて
H2SとSO2との反応により硫黄を形成し、硫黄を含んだCL
AUS触媒を200℃〜500℃の非酸化作用ガスで定期的に掃
気して該触媒に保持された硫黄を蒸発させ、それによっ
て触媒を再生し、次いでこの再生した触媒を残留ガスと
新たに接触させるのに必要な温度まで冷却することから
なる。前記触媒は発生した硫黄がこの触媒に保持される
ように十分低い温度で機能する。また、前記触媒冷却処
理は160℃未満の温度の不活性ガスを用いて実施し、こ
の冷却ガスは少なくともその使用の最終段階の間水蒸気
を含む。A known method developed by the applicant for treating residual gas in a CLAUS sulfur plant is that the residual gas is optionally
Contact the CLAUS catalyst after cooling to a temperature below 160 ° C
CL containing sulfur is formed by the reaction of H 2 S with SO 2 .
The AUS catalyst is periodically scavenged with a non-oxidizing working gas at 200 ° C to 500 ° C to evaporate the sulfur retained on the catalyst, thereby regenerating the catalyst and then contacting the regenerated catalyst with fresh residual gas. It consists of cooling to the temperature required to allow it. The catalyst functions at a temperature low enough so that the generated sulfur is retained by the catalyst. Also, the catalyst cooling treatment is carried out with an inert gas at a temperature of less than 160 ° C., the cooling gas containing water vapor for at least the final stage of its use.
硫黄化合物による大気汚染に関する法律によって課さ
れる基準は厳しくなる一方であるため、これらの基準に
対処すべく本出願人は前述の方法に改良を加えた。本発
明はこの改良に係わるものである。この改良された方法
は残留ガス中に存在し且つ前述の公知方法では回収され
なかった硫黄有機化合物を十分に回収せしめると共に、
CLAUS触媒との接触によるH2SとSO2との反応の硫黄収率
を向上させる。その結果、残留ガスに含まれる硫黄化合
物の回収率が全体的に向上し、それに付随して大気中に
排出される硫黄生成物の総濃度が更に低下することにな
る。Since the standards imposed by the legislation on air pollution by sulfur compounds are becoming stricter, the Applicant has modified the above-mentioned method in order to address these standards. The present invention relates to this improvement. This improved method allows sufficient recovery of sulfur organic compounds present in the residual gas and not recovered by the previously known methods,
Improves the sulfur yield of the reaction of H 2 S and SO 2 by contact with CLAUS catalyst. As a result, the recovery rate of the sulfur compounds contained in the residual gas is improved as a whole, and the total concentration of the sulfur products discharged into the atmosphere is further reduced accordingly.
本発明の目的は、特にCLAUS式硫黄工場からの残留ガ
スのごとき残留ガスの中に含まれる硫黄化合物のより完
璧な除去法であって、該化合物の硫黄の形での回収を伴
うものであり、残留ガスに由来しH2SとSO2とを含む160
℃未満のガス流をCLAUS触媒に接触させてH2SとSO2との
反応により硫黄を形成せしめ、但しこの触媒は発生した
硫黄が該触媒に保持されるように十分低い温度で機能
し、次いで硫黄化合物含量の極めて低い精製された残留
ガスを排出し、硫黄を保持したCLAUS触媒を200℃〜500
℃の温度の非酸化作用ガスで定期的に掃気して該触媒に
保持された硫黄を蒸発させ、このようにして触媒を再生
し、その後160℃未満の温度の不活性ガスを用いて、再
生触媒をH2S及びSO2含有ガスと新たに接触させるのに必
要な温度まで冷却することからなり、前記冷却ガスは少
なくともその使用の最終段階の間は水蒸気を含んでいる
のが好ましく、CLAUS触媒に接触させられる前記ガス
が、硫黄工場から排出される残留ガスをそれに含まれる
硫黄化合物をH2Sの形態に統一すべく水素化と加水分解
とを組合わせた処理にかけ、次いで前記処理により生じ
た気体排出物を冷却してその水分を約10容量％未満の値
にし、この低水分気体排出物に調節量の遊離酸素含有ガ
スを加え、これを150℃より高い温度でH2S酸化触媒と接
触させて、H2Sの調整酸化を生起させ且つH2S及びSOをほ
ぼ2:1のモル比で含むと共に硫黄元素を含むガス流を発
生させ、但し前記モル比は前記低水分気体排出物に加え
る遊離酸素含有ガスの流量を連続的に調整することによ
って調節し、次いで前記酸化反応の結果生じた前記ガス
流を冷却して160℃未満の温度にし、その結果このガス
に含まれる硫黄の大部分が凝縮によって分離されるよう
にすることによって形成されることを特徴とする方法を
提供することにある。It is an object of the present invention, in particular a more complete process for the removal of sulfur compounds contained in residual gases such as those from CLAUS sulfur plants, which involves the recovery of said compounds in the form of sulfur. , Derived from residual gas and containing H 2 S and SO 2 160
A gas stream below C is contacted with the CLAUS catalyst to form sulfur by reaction of H 2 S with SO 2 , provided that the catalyst functions at a temperature low enough so that the generated sulfur is retained by the catalyst, Then, the refined residual gas with a very low sulfur compound content was discharged, and the CLAUS catalyst containing sulfur was heated at 200 ° C to 500 ° C.
Periodically scavenging with a non-oxidizing working gas at a temperature of ℃ to evaporate the sulfur retained on the catalyst and thus regenerate the catalyst, followed by regeneration with an inert gas at a temperature below 160 ° C. Preferably, the catalyst comprises cooling to a temperature required for fresh contact with the H 2 S and SO 2 containing gas, said cooling gas containing water vapor for at least the final stage of its use, CLAUS The gas contacted with the catalyst is subjected to a combined treatment of hydrogenation and hydrolysis of the residual gas emitted from the sulfur plant in order to unify the sulfur compounds contained therein into the form of H 2 S, and then by said treatment The resulting gaseous effluent is cooled to bring its water content to a value of less than about 10% by volume, and a controlled amount of free oxygen-containing gas is added to this low-moisture gas effluent, which is then oxidized to H 2 S at temperatures above 150 ° C. Contact with a catalyst for controlled oxidation of H 2 S A gas stream containing H 2 S and SO in a molar ratio of approximately 2: 1 and containing elemental sulfur, the molar ratio being a continuous flow rate of the free oxygen-containing gas added to the low moisture gas effluent. The gas stream resulting from the oxidation reaction is then cooled to a temperature below 160 ° C. so that most of the sulfur contained in this gas is separated by condensation. It is to provide a method characterized by being formed by
残留ガスを水素化と加水分解とを組合わせた処理にか
ける操作は通常触媒の存在下で実施されるが、この操作
の間に、残留ガスに含まれるSO2、CS2、COSのごとき硫
黄化合物並びに蒸気状及び／又は胞状硫黄がH2Sに変換
される。この変換はSO2並びに蒸気状及び／又は胞状硫
黄の場合には水素の作用で実施され、COS及びCS2の場合
には残留ガス中に存在する水蒸気の作用で加水分解によ
って実施される。触媒の存在下での、水素化と加水分解
とを組合わせた処理は約140℃〜550℃に達し得る温度、
好ましくは約200℃〜400℃の温度で実施する。水素化反
応に必要な水素は残留ガスに既に含まれているものを使
用してもよく、又は残留ガスが例えばCO及びH2Oを含む
場合にはCO及びH2Oの反応によって水素化及び加水分解
ゾーン内にその場で発生させてもよく、又は外部の水素
源から残留ガスに加えるようにしてもよい。残留ガスに
H2及びCOを供給する有利な方法の１つは、化学量論量以
下で機能する燃料ガスバーナーによって生じる燃料ガス
を前記残留ガスに添加することからなる。使用する水素
量は、水素化／加水分解処理にかけられる残留ガスに含
まれ水素化し得るSO2のごとき硫黄化合物もしくは生成
物、蒸気状及び／又は胞状硫黄をほぼ完全にH2Sに変換
するのに十分なものにする必要がある。実際の操作では
使用する水素量を、残留ガス中に存在する水素化可能硫
黄生成物のH2Sへの変換に必要な化学量論量の１〜６倍
にすることができる。The operation of subjecting the residual gas to a combined treatment of hydrogenation and hydrolysis is usually carried out in the presence of a catalyst, and during this operation, sulfur such as SO 2 , CS 2 and COS contained in the residual gas is included. Compounds and vaporous and / or vesicular sulfur are converted to H 2 S. This conversion is carried out by the action of hydrogen in the case of SO 2 and vaporous and / or vesicular sulfur, and in the case of COS and CS 2 by hydrolysis by the action of water vapor present in the residual gas. The combined treatment of hydrogenation and hydrolysis in the presence of a catalyst can reach temperatures of about 140 ° C to 550 ° C,
It is preferably carried out at a temperature of about 200 ° C to 400 ° C. Hydrogen required in the hydrogenation reaction may be used which is already included in the residual gas, or when the residual gas contains, for example, CO and H 2 O is hydrogenation and the reaction of CO and H 2 O It may be generated in situ within the hydrolysis zone or it may be added to the residual gas from an external hydrogen source. To residual gas
One of the advantageous ways of supplying H 2 and CO consists of adding to the residual gas a fuel gas produced by a fuel gas burner which operates below stoichiometry. The amount of hydrogen used is such that the sulfur compounds or products such as SO 2 which can be hydrogenated contained in the residual gas subjected to the hydrogenation / hydrolysis treatment, vapor and / or vesicular sulfur are almost completely converted into H 2 S. Need to be enough. The amount of hydrogen used in the actual operation, can be 1-6 times the stoichiometric amount required for conversion to H 2 S hydrogenatable sulfur products present in the residual gas.
残留ガスが化合物COS及びCS2の加水分解に必要とされ
る十分な量の水蒸気を含んでいない場合には、水素化／
加水分解組合わせ処理を実施する前に必要量の水蒸気を
残留ガスに加え得る。If the residual gas does not contain sufficient water vapor needed for the hydrolysis of the compounds COS and CS 2 , hydrogenation /
The required amount of water vapor may be added to the residual gas before carrying out the hydrolytic combination treatment.
水素化／加水分解処理に使用できる触媒としては、元
素周期率表の第Va族、第VIa族、及び第VIII族の金属、
例えばコバルト、モリブデン、クロム、バナジウム、ト
リウム、ニッケル、タングステン、ウラニウムのごとき
金属の化合物を含むものが挙げられる。前記化合物はシ
リカ、アルミナ、シリカ／アルミナタイプの支持体上に
配置しても、又は配置しなくてもよい。アルミナ上に配
置された酸化コバルト及び酸化モリブデンをベースとす
る水化脱硫触媒はこの水素化／加水分解処理に特に有効
である。この水素化／加水分解処理では、気体反応媒質
と触媒との接触時間をかなり広範囲で変えることができ
る。この接触時間は普通の圧力及び温度条件の下で有利
には0.5〜８秒、より特定的には１〜５秒である。Examples of the catalyst that can be used in the hydrogenation / hydrolysis treatment include metals of Group Va, Group VIa, and Group VIII of the Periodic Table of Elements.
Examples thereof include those containing a compound of a metal such as cobalt, molybdenum, chromium, vanadium, thorium, nickel, tungsten, and uranium. The compound may or may not be disposed on a silica, alumina, silica / alumina type support. Hydrodesulfurization catalysts based on cobalt oxide and molybdenum oxide deposited on alumina are particularly effective for this hydrotreatment / hydrolysis treatment. In this hydrogenation / hydrolysis treatment, the contact time between the gaseous reaction medium and the catalyst can be varied over a fairly wide range. This contact time is preferably 0.5 to 8 seconds, more particularly 1 to 5 seconds, under normal pressure and temperature conditions.
残留ガスを水素化／加水分解組合わせ処理にかけた結
果生じる気体排出物は任意の公知技術、例えばより低温
の流体との間接的熱交換及び／又は水の噴霧により冷却
して温度を十分低くし、その結果中に含まれる水の大部
分が凝縮されて水含量の低下した水分10容量％未満の気
体排出物が生じるようにする。The gaseous effluent resulting from the combined hydrogenation / hydrolysis treatment of the residual gas is cooled by any known technique, such as indirect heat exchange with cooler fluids and / or water sprays to bring the temperature to a sufficiently low temperature. The result is that most of the water contained therein is condensed to produce a gaseous effluent with a reduced water content of less than 10% by volume of water.
このようにして得た低水分気体排出物は次いで、H2S
の酸化を生起させる時に必要な温度に適合した温度まで
再加熱する。この加熱処理は特に、凝縮によって水を分
離するために冷却される高温気体排出物との間接的熱交
換によって実施し得る。次いでこの排出物に必要量の遊
離酸素含有ガスを加える。この添加操作は前記低水分気
体排出物と150℃より高い温度で機能する酸化触媒との
接触処理の間、又は好ましくはこの接触処理の前に実施
する。The low moisture gas effluent thus obtained is then passed through H 2 S
Reheat to a temperature compatible with the temperature required to cause the oxidation of. This heat treatment may in particular be carried out by indirect heat exchange with the hot gaseous effluent, which is cooled to separate the water by condensation. The required amount of free oxygen-containing gas is then added to this effluent. This addition operation is carried out during the contact treatment of said low-moisture gas effluent with an oxidation catalyst which functions above 150 ° C., or preferably before this contact treatment.
前記気体排出物に含まれるH2Sの酸化に使用される遊
離酸素含有ガスは通常空気であるが、純酸素、酸素含量
の高い空気、又は酸素以外の不活性ガスと酸素との種々
の割合を混合物を使用することもできる。遊離酸素含有
ガスは前述のごとく、H2S及びSO2を約2:1のモル比に等
しいH2S：SO2モル比で含むと共に硫黄元素を或る程度含
むガス流を形成すべく、H2Sを部分的に酸化するのに必
要な最小量に相当する量の酸素が得られるように調整し
た量だけ使用される。The free oxygen-containing gas used for the oxidation of H 2 S contained in the gaseous effluent is usually air, but pure oxygen, air with a high oxygen content, or various proportions of inert gas and oxygen other than oxygen. It is also possible to use mixtures. The free oxygen-containing gas, as previously described, contains H 2 S and SO 2 in a H 2 S: SO 2 molar ratio equal to a molar ratio of about 2: 1 and forms a gas stream containing some elemental sulfur, It is used in an amount adjusted to obtain an amount of oxygen corresponding to the minimum amount required to partially oxidize H 2 S.
遊離酸素含有ガスの量の調節は任意の公知方法、例え
ば酸化の結果生じるガス流のH2S：SO2モル比の値を測定
し、これらの測定の結果に基づいて計算した必要量の大
きさに応じて酸化に使用する遊離酸素含有ガスの流量を
変化させ、それによってH2S：SO2モル比を2:1の値に維
持するような方法で実施する。The adjustment of the amount of free oxygen-containing gas can be carried out by any known method, for example by measuring the H 2 S: SO 2 molar ratio value of the gas stream resulting from oxidation and calculating the amount of the required amount based on the results of these measurements. It is carried out in such a way that the flow rate of the free oxygen-containing gas used for the oxidation is varied accordingly, thereby maintaining the H 2 S: SO 2 molar ratio at a value of 2: 1.
気体反応媒質と酸化触媒との接触時間は、普通の圧力
及び温度条件で0.5〜10秒にし得る。The contact time between the gaseous reaction medium and the oxidation catalyst can be 0.5-10 seconds under normal pressure and temperature conditions.
酸化触媒はCLAUS化学量論量の酸素によるH2Sの酸化、
即ち下記の反応式 1/3 H2S＋1/2 O2 →1/3 SO2＋1/3H2O 2/3 H2S+1/3 SO2 → S +2/3 H2O H2S＋1/2 O2 → S ＋H2O に従う酸化を促進し得る種々の触媒の中から選択し得
る。この反応は、硫黄元素の他にH2S及びSO2をほぼ2:1
に等しいH2S：SO2モル比で含むガス流を発生させる。The oxidation catalyst is the oxidation of H 2 S by CLAUS stoichiometric amount of oxygen,
That is, the following reaction formula 1/3 H 2 S + 1/2 O 2 → 1/3 SO 2 + 1 / 3H 2 O 2/3 H 2 S + 1/3 SO 2 → S +2/3 H 2 O H 2 S + 1 It can be chosen from among various catalysts which can promote the oxidation according to / 2 O 2 → S + H 2 O. This reaction, in addition to elemental sulfur H 2 S and SO 2 almost 2: 1
A gas stream containing H 2 S: SO 2 molar ratio equal to
特に、本発明の方法で使用できる酸化触媒は、有利に
は下記のグループから選択し得る。In particular, the oxidation catalyst which can be used in the process according to the invention may advantageously be selected from the group below.
Ｉ） Fe、Ni、Co、Cu、及びZnの中から選択した金属の
少なくとも１種類の化合物とシリカ及び／又はアルミナ
からなる支持体とを組合わせた触媒。1975年10月17日付
仏国特許第7,531,769号（公開番号第2,327,960号）に開
示。I) A catalyst in which at least one compound of a metal selected from Fe, Ni, Co, Cu, and Zn is combined with a support made of silica and / or alumina. It is disclosed in French Patent No. 7,531,769 (publication number 2,327,960) dated October 17, 1975.
II） 酸化チタンをベースとする触媒、特に酸化チタン
とアルカリ土類金属の硫酸塩、例えば硫酸カルシウムと
を組み合わせたもの。1981年３月13日付仏国特許第81,0
5029号（公開番号第2,501532号）に開示。II) Titanium oxide based catalysts, in particular titanium oxide in combination with alkaline earth metal sulphates such as calcium sulphate. French Patent No. 81,0 dated March 13, 1981
No. 5029 (Publication No. 2,501532).
III） Fe、Cu、Cd、Zn、Cr、Mo、Ｗ、Co、Ni及びBiの
中から選択した金属の少なくとも１種類の化合物、並び
に場合によってはPd、Pt、Ir及びRhのごとき貴金属の少
なくとも１種類の化合物をシリカ及び／又は酸化チタン
からなる支持体と組合わせた触媒。前記支持体は任意に
少量のアルミナを含み得る。1981年８月19日付仏国特許
第8115900号（公開番号第2,511,663号）に開示。III) at least one compound of a metal selected from Fe, Cu, Cd, Zn, Cr, Mo, W, Co, Ni and Bi, and at least a noble metal such as Pd, Pt, Ir and Rh. A catalyst in which one compound is combined with a support made of silica and / or titanium oxide. The support may optionally contain a small amount of alumina. It is disclosed in French Patent No. 8115900 (Publication No. 2,511,663) dated August 19, 1981.
IV） III）に挙げたグループから選択した金属の少な
くとも１種類の化合物と、特に少なくとも１種類の希土
類酸化物少量によって熱的に安定化された活性化アルミ
ナからなる支持体とを組合わせて形成した触媒。独国特
許公開第3,403,328号に開示。IV) Formed in combination with at least one compound of a metal selected from the group mentioned in III) and in particular with at least one support of activated alumina thermally stabilized by a small amount of a rare earth oxide. Catalyst. Disclosed in German Patent Publication No. 3,403,328.
酸化触媒は有利には、タイプＩの触媒とタイプII、II
I又はIVの触媒とを続けて使用して構成し、利点とし
て、酸化の結果生じるガス流がもはや酸素を含まないよ
うにし得る。これは処理の後段階でCLAUS触媒の不活性
化を回避するのに必要なことである。The oxidation catalyst is advantageously a type I catalyst and a type II, II
It may be constructed using I or IV catalysts in sequence, with the advantage that the gas stream resulting from the oxidation is no longer oxygen-containing. This is necessary to avoid deactivation of the CLAUS catalyst in the later stages of the process.
CLAUS化学量論量でのH2Sの酸化反応は150℃〜1000℃
の温度で実施し得、酸化触媒は保持温度で十分な熱的安
定性を示す触媒の中から選択する。例えばタイプＩ）の
触媒は約400℃まで使用可能であり、タイプII）の触媒
は約500℃まで、タイプIII）の触媒は約700℃まで、タ
イプIV）の触媒は約1000℃まで使用できる。CLAUS Stoichiometric H 2 S oxidation reaction is 150 ℃ ~ 1000 ℃
The oxidation catalyst is selected from catalysts that exhibit sufficient thermal stability at the holding temperature. For example, type I) catalysts can be used up to about 400 ° C, type II) catalysts up to about 500 ° C, type III) catalysts up to about 700 ° C, type IV) catalysts up to about 1000 ° C. .
酸化処理の結果生じるガス流は蒸気状の硫黄を含むと
共に、H2S及びSO2を約2:1に等しいモル比で含む。この
ガス流は例えば硫黄凝縮器のごとき凝縮器内での操作に
より冷却して温度を160℃未満の値にし、その結果中に
含まれる硫黄の大部分が凝縮によって分離されるように
し、次いでCLAUS触媒に接触させる。この触媒はH2SとSO
2との反応によって生じる硫黄がその上に堆積されるの
に十分な低い温度で機能する。この温度は有利には約12
0℃〜140℃である。The gas stream resulting from the oxidation treatment contains vaporous sulfur and H 2 S and SO 2 in a molar ratio equal to about 2: 1. This gas stream is cooled, for example by operation in a condenser such as a sulfur condenser, to bring the temperature to a value below 160 ° C. so that most of the sulfur contained therein is separated by condensation and then CLAUS. Contact the catalyst. The catalyst is H 2 S and SO
It functions at a temperature low enough that the sulfur produced by the reaction with 2 is deposited on it. This temperature is advantageously about 12
It is 0 to 140 ° C.
CLAUS触媒との接触の結果得られる精製残留ガスは通
常、大気中に排出される前に、まだ極めて少量含まれて
いる可能性のある硫黄化合物を総てSO2に変換させるべ
く、熱的焼却又は触媒焼却にかけられる。The purified residual gas resulting from the contact with the CLAUS catalyst is usually thermally incinerated in order to convert all sulfur compounds, which may still be present in very small amounts, into SO 2 before being discharged into the atmosphere. Or, it is subjected to catalyst incineration.
硫黄を含んだCLAUS触媒は、該触媒に保持された硫黄
を蒸発させるべく200℃〜500℃の温度の非酸化作用ガス
で掃気することによって定期的に再生し、再生された触
媒は酸化の結果生じるガス流と新たに接触させるのに必
要な温度まで冷却する。この冷却は160℃未満の温度の
不活性ガスを用いて行う。この冷却ガスは有利には、触
媒冷却処理の少なくとも最終段階の間水蒸気を保持す
る。The CLAUS catalyst containing sulfur is periodically regenerated by purging with a non-oxidizing working gas at a temperature of 200 ° C. to 500 ° C. to evaporate the sulfur retained on the catalyst, and the regenerated catalyst is the result of oxidation. Cool to the temperature required to make fresh contact with the resulting gas stream. This cooling is done with an inert gas at a temperature below 160 ° C. This cooling gas advantageously retains water vapor during at least the final stage of the catalyst cooling process.
硫黄を含んだCLAUS触媒の再生に使用される掃気ガス
はメタン、窒素、CO2、もしくはこれらのガスの混合物
であってよく、又は焼却すべき精製残留ガスの一部分も
しくは処理すべき残留ガスの一部分であってもよい。こ
の掃気ガスはH2、CO及び特にH2Sのごとき還元作用気体
化合物を、少なくとも再生処理の最終段階の間、即ち触
媒上に堆積した硫黄の大部分が蒸発した後で、或る程
度、例えば0.5〜25容量％含み得る。The scavenging gas used to regenerate the sulfur-containing CLAUS catalyst may be methane, nitrogen, CO 2 , or a mixture of these gases, or a portion of the purified residual gas to be incinerated or a portion of the residual gas to be treated. May be This scavenging gas is, to a certain extent, reducing gas compounds such as H 2 , CO and especially H 2 S, at least during the final stage of the regeneration process, i.e. after evaporation of most of the sulfur deposited on the catalyst. For example, it may contain 0.5 to 25% by volume.
酸化処理の結果生じるガス流をCLAUS触媒と接触させ
る操作は通常複数の触媒変換ゾーンで実施される。これ
らのゾーンは少なくとも１つのゾーンが再生／冷却段階
で機能し、残りがCLAUS反応の段階で機能するように使
用される。あるいは、１つ以上のゾーンをCLAUS反応に
使用し、少なくとも１つのゾーンを再生段階に使用し、
少なくとも１つのゾーンを冷却に使用して操作を行うこ
ともできる。The operation of contacting the gas stream resulting from the oxidation treatment with the CLAUS catalyst is usually carried out in multiple catalytic conversion zones. These zones are used so that at least one zone functions in the regeneration / cooling stage and the rest in the CLAUS reaction stage. Alternatively, one or more zones are used for the CLAUS reaction and at least one zone is used for the regeneration step,
It is also possible to operate using at least one zone for cooling.
CLAUS触媒はH2SとSO2との反応、即ち下記の反応 ２ H2S＋SO23/x Sx＋２ H2O による硫黄形成を促進させ得る任意の触媒であってよ
い。The CLAUS catalyst may be any catalyst capable of promoting the reaction of H 2 S with SO 2 , ie the formation of sulfur by the reaction 2 H 2 S + SO 2 3 / x Sx + 2 H 2 O described below.
例えば、前記CLAUS触媒はボーキサイト、アルミナ、
シリカ、天然もしくは合成ゼオライト、前述のタイプ
Ｉ）の触媒、又はこれらの物質の混合物もしくは組合わ
せで構成し得る。For example, the CLAUS catalyst is bauxite, alumina,
It may consist of silica, natural or synthetic zeolites, the type I) catalysts mentioned above, or mixtures or combinations of these substances.
再生ガスは好ましくは加熱ゾーンから再生中のゾーン
と冷却ゾーンとを順次通過し、この冷却ゾーンで該ガス
に含まれる硫黄の大部分が凝縮によって分離され、その
後加熱ゾーンに戻るように閉回路状に循環する。この再
生ガスは勿論開回路状に循環させてもよい。The regeneration gas preferably passes sequentially from the heating zone to the zone being regenerated and the cooling zone, in which most of the sulfur contained in the gas is separated by condensation and then closed circuit to return to the heating zone. Circulate to. This regenerated gas may of course be circulated in an open circuit.
再生した触媒の冷却に使用されるガスは、硫黄を含ん
だ触媒の再生に使用されるガスと同じタイプ、即ちほぼ
不活性のガスである。再生ガス及び冷却ガスの回路は互
いに独立していてもよい。前述のごとき再生ガス回路は
冷却ゾーンの出口と再生中のゾーンの入口とを加熱ゾー
ンを迂回して接続する分岐を有し得る。このようにする
と前記加熱ゾーンを通らずにすむため、再生ガスを冷却
ガスとして使用することが可能になる。The gas used to cool the regenerated catalyst is of the same type as the gas used to regenerate the sulfur-containing catalyst, i.e., a substantially inert gas. The regeneration gas and cooling gas circuits may be independent of each other. The regeneration gas circuit as described above may have a branch connecting the outlet of the cooling zone and the inlet of the zone being regenerated bypassing the heating zone. In this case, since the heating gas does not pass through the heating zone, the regeneration gas can be used as the cooling gas.
前述のごとく、冷却ガスは再生触媒冷却処理の少なく
とも最終段階の間、より特定的には冷却中の再生触媒の
温度が約25℃より低くなった時に水蒸気を含み得る。但
し、この再生ガスは再生触媒冷却処理の最初から水蒸気
を含み得る。冷却ガスが含み得る水蒸気の量はかなり大
幅に変化し得、例えば１〜50容量％であり得る。As mentioned above, the cooling gas may include water vapor during at least the final stage of the regenerated catalyst cooling process, and more particularly when the temperature of the regenerated catalyst during cooling falls below about 25 ° C. However, this regeneration gas may contain water vapor from the beginning of the regeneration catalyst cooling process. The amount of water vapor that the cooling gas may contain can vary considerably and can be, for example, 1 to 50% by volume.
以上記述してきた本発明の方法をより詳細に説明すべ
く、以下に非限定的実施例を挙げる。The following non-limiting examples are provided to illustrate the method of the present invention described above in more detail.
実施例 60.4容量％のH2Sと、36.3容量％のCO2と、3.2容量％
の水と、0.1容量％の炭化水素とを含む酸性ガスの部分
的酸化を行う硫黄工場から排出される残留ガスを処理し
た。Example 60.4 vol% H 2 S, 36.3 vol% CO 2 , 3.2 vol%
Of the residual gas discharged from the sulfur plant, which carries out the partial oxidation of acid gases containing 0.1% by volume of hydrocarbons and 0.1% by volume of hydrocarbons.
処理した残留ガスはモル％で表して下記の組成を有し
ていた。The treated residual gas had the following composition, expressed in mol%.
H2S : 0.80 SO2 : 0.40 S1（蒸気） : 0.08 CO2 :16.65 H2O :29.80 N2 :49.75 H2 : 1.93 CO : 0.52 COS : 0.02 CS2 : 0.05 この処理は下記の部材からなる装置を使用して行っ
た。H 2 S: 0.80 SO 2 : 0.40 S 1 (steam): 0.08 CO 2 : 16.65 H 2 O: 29.80 N 2 : 49.75 H 2 : 1.93 CO: 0.52 COS: 0.02 CS 2 : 0.05 Was performed using
空気により燃料ガスを燃焼させるバーナーであって、
処理すべき残留ガスを導入する入口と出口とを有し、化
学量論量以下で機能するバーナー、 −水素化及び加水分解触媒の固定ベッドにより互いに
分離された入口及び出口を有し、その入口が管を介して
前記バーナーの出口に接続される水素化及び加水分解反
応器、 −間接的熱交換器の第１交換回路と、低圧蒸気発生熱交
換器と、空気冷却器（ａrorfrigrant））と、底
に液体用出口を備え上部にガス用出口を備える水噴霧カ
ラムとを直列に含む冷却アセンブリであって、前記第１
交換回路の入口が管を介して前記水素化及び加水分解反
応器の出口に接続されるようなアセンブリ、 −H2Sを硫黄に酸化する触媒の固定ベッドにより互いに
分離された入口及び出口を有する触媒酸化反応器であっ
て、その入口が前記冷却アセンブリの熱交換器の第２交
換回路を介して入口管により前記水噴霧カラムの上部の
出口に接続され、一方出口の先には管が延びてこの管の
上に硫黄凝縮器が配置され、前記入口管が熱交換器の下
流に配置された空気注入口と可変流量弁とを備え、この
弁が該酸化反応器の出口のモル比H2S：SO2を調節する調
整器によって制御されるような触媒酸化反応器、 −互いに並列に配置され且つ各々がCLAUS触媒の固定ベ
ッドにより互いに分離された入口及び出口を有するよう
な２つの触媒変換器からなる触媒変換例。これら２つの
変換器はクロックによりスイッチされる弁を介して、一
方が反応段階、即ち入口が前記触媒酸化反応器に接続さ
れた硫黄凝縮器の出口に接続され且つ出口が焼却器の入
口に接続される状態におかれ、他方が再生／冷却段階に
おかれる、即ち先ず再生回路内に配置され次いで冷却回
路内に配置されるという具合に交互に作動する。尚、前
記再生回路には非酸化作用掃気ガスを前記変換器を介し
て加熱器から硫黄凝縮器まで流し、再び加熱器に戻すよ
うに循環させる手段を含み、前記冷却回路はその回路に
配置された変換器を介して低温不活性ガスを循環させる
べく配置される。A burner that burns fuel gas with air,
A burner having an inlet and an outlet for introducing the residual gas to be treated, which functions below the stoichiometric amount, -an inlet and an outlet separated from each other by a fixed bed of hydrogenation and hydrolysis catalyst, the inlet of which A hydrogenation and hydrolysis reactor connected via a pipe to the outlet of the burner, a first exchange circuit of an indirect heat exchanger, a low pressure steam generating heat exchanger, and an air cooler (arorfrigrant). A cooling atomization column in series having a liquid outlet at the bottom and a gas outlet at the top, said first cooling assembly comprising:
Having an inlet and an outlet which are separated from each other by a fixed bed of catalyst for oxidizing assembly as the inlet of the exchanger circuit is connected to the outlet of the hydrogenation and hydrolysis reactor via a tube, the -H 2 S to sulfur A catalytic oxidation reactor, the inlet of which is connected via a second exchange circuit of the heat exchanger of the cooling assembly by an inlet pipe to an outlet at the top of the water spray column, while a pipe extends beyond the outlet. A sulfur condenser is arranged above the lever tube, the inlet tube is provided with an air inlet arranged downstream of the heat exchanger and a variable flow valve, which valve has a molar ratio H at the outlet of the oxidation reactor. A catalytic oxidation reactor as controlled by a regulator regulating 2 S: SO 2; two catalysts arranged in parallel with each other and each having an inlet and an outlet separated from each other by a fixed bed of CLAUS catalyst Catalyst conversion consisting of converter . These two converters are connected via a clock-switched valve, one to the reaction stage, i.e. to the outlet of a sulfur condenser whose inlet is connected to said catalytic oxidation reactor and whose outlet is connected to the inlet of the incinerator. And the other is placed in the regeneration / cooling stage, ie first placed in the regeneration circuit and then in the cooling circuit, and so on. It should be noted that the regeneration circuit includes means for causing non-oxidizing scavenging gas to flow from the heater to the sulfur condenser via the converter and to circulate back to the heater, and the cooling circuit is arranged in the circuit. Is arranged to circulate the cold inert gas through the converter.
水素化と加水分解とを組合わせた処理で使用する触媒
は、酸化コバルトと酸化モリブデンとを含浸したアルミ
ナからなる直径約5mmの玉で構成した。この玉は比表面
積が250m2/gであり、触媒の重量に対して1.75％のコバ
ルトと８％のモリブデンとを含んでいた。The catalyst used in the combined hydrogenation and hydrolysis treatment consisted of beads of about 5 mm diameter made of alumina impregnated with cobalt oxide and molybdenum oxide. The ball had a specific surface area of 250 m 2 / g and contained 1.75% cobalt and 8% molybdenum based on the weight of the catalyst.
H2Sを硫黄に酸化するための触媒は10重量％の硫酸カ
ルシウムで安定化した酸化チタンからなる直径4mmの押
出し体の層と、硫酸鉄を含浸した活性化アルミナからな
る直径４〜6mmの玉の層とを重ねたもので構成した（触
媒中の鉄含量は５重量％）。The catalyst for the oxidation of H 2 S to sulfur is a layer of extrudate 4 mm in diameter made of titanium oxide stabilized with 10% by weight calcium sulphate and a layer of activated alumina impregnated with iron sulphate of diameter 4-6 mm. It was composed of a stack of balls (the iron content in the catalyst was 5% by weight).
CLAUS触媒は比表面積260m2/g、直径４〜6mmのアルミ
ナからなる玉で構成した。The CLAUS catalyst was composed of beads made of alumina having a specific surface area of 260 m 2 / g and a diameter of 4 to 6 mm.
233kモル／時の流量でバーナー内に注入した残留ガス
はこのバーナー内で約350℃の温度になり、この温度で
水素化／加水分解反応器内に流入した。この反応器では
SO2、Ｓ、CS2及びCOSのH2Sへの変換が実質的に完全に実
施され、この反応器から排出される気体排出物は約380
℃の温度を有し且つ硫黄含有化合物として実質的にH2S
しか含んでいなかった。この気体排出物は冷却アセンブ
リの熱交換器と蒸気発生交換器と空気冷却器とを通して
約80℃まで冷却され、この温度で前記アセンブリの水噴
霧カラム内に流入した。The residual gas, which was injected into the burner at a flow rate of 233 kmoles / hour, reached a temperature of about 350 ° C. in this burner and flowed into the hydrogenation / hydrolysis reactor at this temperature. In this reactor
The conversion of SO 2 , S, CS 2 and COS to H 2 S is carried out virtually completely and the gaseous effluent leaving this reactor is about 380
Has a temperature of ° C and is substantially H 2 S as a sulfur-containing compound.
It only included. The gaseous effluent was cooled to about 80 ° C. through the heat exchanger, steam generator exchanger and air cooler of the cooling assembly and flowed into the water spray column of the assembly at this temperature.
前記カラムの上部からは約4.6容量％の水蒸気を含む
約35℃の冷却された気体排出物が流出した。A cooled gaseous effluent at about 35 ° C., containing about 4.6% by volume of water vapor, exited from the top of the column.
この冷却された排出物は冷却アセンブリの熱交換器で
再加熱され、次いでそのために設けた口部を介して空気
が7.61モル／時で加えられた。得られた混合物は200℃
の温度で触媒酸化反応器内に侵入した。酸化反応器内を
通過するガスと安定化した酸化チタンの層及び硫酸鉄含
浸アルミナ層との接触時間は夫々約３秒1.5秒であっ
た。酸化反応器内でのH2Sの交換率は約72％であり、こ
の反応器から流出するガス流は約295℃の温度を有し且
つH2S及びSO2をほぼ2:1に等しいH2S：SO2モル比で含む
と共に、或る程度の量の硫黄元素も含んでいた。The cooled effluent was reheated in the heat exchanger of the cooling assembly and then air was added at 7.61 mol / h via the port provided for it. The resulting mixture is 200 ° C
It entered the catalytic oxidation reactor at the temperature of. The contact time between the gas passing through the oxidation reactor and the stabilized titanium oxide layer and the iron sulfate-impregnated alumina layer was about 3 seconds and 1.5 seconds, respectively. The exchange rate of H 2 S in the oxidation reactor is about 72%, the gas stream exiting this reactor has a temperature of about 295 ° C and the H 2 S and SO 2 are approximately equal to 2: 1. It contained H 2 S: SO 2 molar ratio as well as some amount of elemental sulfur.
前記ガス流は酸化反応器に接続された硫黄凝縮器内で
130℃に冷却され、このガス流に含まれる硫黄の大部分
が凝縮によって分離された。このガス流は次いでCLAUS
反応段階で機能する触媒変換器に注入された。前記変換
器の出口からは、約135℃の温度を有し且つ全体で800容
量p.p.m.に等しい硫黄生成物を含む精製された残留ガス
が排出された。The gas stream is in a sulfur condenser connected to an oxidation reactor.
Cooled to 130 ° C., most of the sulfur contained in this gas stream was separated by condensation. This gas stream is then CLAUS
It was injected into the catalytic converter functioning in the reaction stage. At the outlet of the converter, a purified residual gas having a temperature of about 135 ° C. and containing a total sulfur product equal to 800 ppm by volume is discharged.
再生段階と冷却段階とに順次おかれる前記変換器の中
に収容された硫黄を含む触媒の再生に使用する掃気ガス
は精製された残留ガスの一部分で構成し、再生回路の再
加熱器で300〜350℃にした後2600Nm3／時の流量で再生
段階の変換器に導入した。再生段階の変換器から排出さ
れた硫黄含有掃気ガスは次いで再生回路の硫黄凝縮器内
に流入し、該ガスに含まれる硫黄の大部分が凝縮により
分離されるようにそこで約130℃に冷却され、その後再
加熱器に戻って再生に再使用された。再生段階の変換器
から排出される掃気ガスが硫黄を実質的に含まないよう
になった時点で、処理すべき残留ガスを排出する硫黄ユ
ニットで処理された酸性ガスの一部分をこの掃気ガスに
注入して掃気ガスのH2S濃度を約10容量％にし、H2S含有
ガスによる触媒の掃気処理を該触媒の再活性化に十分な
時間にわたって実施した。The scavenging gas used to regenerate the sulfur-containing catalyst contained in the converter, which is sequentially placed in the regeneration stage and the cooling stage, is composed of a portion of the purified residual gas, and is used in the reheater of the regeneration circuit to generate 300 After being brought to ~ 350 ° C, it was introduced into the converter in the regeneration stage at a flow rate of 2600 Nm 3 / h. The sulfur-containing scavenging gas discharged from the converter in the regeneration stage then flows into the sulfur condenser of the regeneration circuit, where it is cooled to about 130 ° C. so that most of the sulfur contained in the gas is separated by condensation. , Then returned to the reheater and reused for regeneration. When the scavenging gas discharged from the converter in the regeneration stage becomes substantially free of sulfur, a part of the acid gas treated by the sulfur unit that discharges the residual gas to be treated is injected into this scavenging gas. Then, the H 2 S concentration of the scavenging gas was adjusted to about 10% by volume, and the scavenging treatment of the catalyst with the H 2 S-containing gas was performed for a time sufficient to reactivate the catalyst.
次いで、再生触媒を収容する変換器に約130℃のガス
流を通すことによって該触媒を約130℃に冷却した。こ
の冷却ガスは適切な温度に冷却した精製残留ガスの一部
分で精成し、これを2100Nm3／時の流量で冷却回路に流
した。この冷却ガスの水分は約５容量％であった。The catalyst was then cooled to about 130 ° C by passing a gas stream at about 130 ° C through a converter containing the regenerated catalyst. This cooling gas was refined with a part of the purified residual gas cooled to an appropriate temperature, and was passed through the cooling circuit at a flow rate of 2100 Nm 3 / hour. The water content of this cooling gas was about 5% by volume.
触媒変換器は精製段階、即ち反応段階で30時間、再生
／冷却段階で30時間、但しこのうち10時間は冷却用、と
いう状態で交互に作動した。The catalytic converters were alternately operated in the refining stage, ie the reaction stage, for 30 hours, the regeneration / cooling stage for 30 hours, of which 10 hours were for cooling.
H2Sの存在下で実施した再生の最終段階の時間は２時
間であった。The time of the final stage of regeneration carried out in the presence of H 2 S was 2 hours.
排出される残留ガスをこのような残留ガス処理法で処
理する硫黄工場は数箇月で99.70％の合計硫黄収率を示
した。Sulfur plants that treat the residual gas discharged with such a residual gas treatment method showed a total sulfur yield of 99.70% in several months.
フロントページの続き (72)発明者 フィリップ、アンドレ フランス国、エフ‐64300・オルテ、アン パス・デ・ビオレット・２ (56)参考文献 特開 昭57−175710（ＪＰ，Ａ) 特開 昭52−114593（ＪＰ，Ａ) 特開 昭59−182205（ＪＰ，Ａ) 特開 昭60−36309（ＪＰ，Ａ)Front Page Continuation (72) Inventor Philip, Andre F-64300 Orte, France, Ampas de Violet 2 (56) Reference JP-A-57-175710 (JP, A) JP-A-52- 114593 (JP, A) JP 59-182205 (JP, A) JP 60-36309 (JP, A)
Claims (3)
とき残留ガスに含まれる硫黄化合物を硫黄の形態で回収
しながら除去するために、処理すべきガスを水素化と加
水分解を組合せた処理にかけ含まれる硫黄化合物をH2S
の形態に統一し、次いでこの水素化及び加水分解処理の
結果生じる気体排出物を冷却して約10容量％以下の水分
含量を有する低水分気体排出物を製造し、この低水分気
体排出物からH2S及びSO2をほぼ2:1に等しいH2S：SO2モ
ル比で含みかつ160℃未満の温度を有するガス流を発生
させ、該ガス流とCLAUS触媒とを生成した硫黄が該触媒
上に保持されるように十分低い温度で接触してH2SとSO2
との反応により硫黄を形成せしめ、硫黄含量の極めて低
い精製残留ガスを排出し、硫黄を保持するCLAUS触媒を2
00℃〜500℃の温度の非酸化作用ガスで定期的に掃気し
て触媒上に保持された硫黄を蒸発させ、これにより触媒
を再生し、その後160℃未満の温度の不活性ガスを用い
てこの再生触媒を、H2S及びSO2含有ガス流と新たに接触
させるのに必要な温度まで冷却することよりなる方法で
あって、 H2S及びSO2含有ガス流が、全ての低水分気体排出物と該
排出物に加えた調節量の遊離酸素含有ガスとを、150℃
より高い温度でH2S酸化触媒と接触させながら通過させ
てH2Sを部分的に酸化し、H2S及びSO2をほぼ2:1に等しい
H2S：SO2モル比で含むとともに元素硫黄も含むガス流を
形成することにより製造され； 前記モル比が、低水分気体排出物に加える遊離酸素含有
ガスの流量を連続的に調製すること及び酸化により得ら
れた気体排出物を160℃未満の温度に冷却し、この排出
物に含まれる硫黄の大部分を凝縮によって分離すること
により調節され；及び 再生CLAUS触媒の冷却に使用するガスが少なくとも触媒
冷却処理の最終段階の間１〜50容量％の濃度で水蒸気を
含むことを特徴とする方法。1. A process in which the gas to be treated is a combination of hydrogenation and hydrolysis, in order to remove sulfur compounds contained in the residual gas, in particular in the form of sulfur, in the residual gas, such as the residual gas from a CLAUS sulfur plant. The sulfur compounds contained in H 2 S
And then cooling the gaseous effluent resulting from this hydrogenation and hydrolysis process to produce a low moisture gas effluent having a water content of less than about 10% by volume, from which the low moisture gas effluent is produced. Generating a gas stream containing H 2 S and SO 2 in a H 2 S: SO 2 molar ratio approximately equal to 2: 1 and having a temperature of less than 160 ° C., the sulfur forming the gas stream and the CLAUS catalyst H 2 S and SO 2 are contacted at a temperature low enough to be retained on the catalyst.
CLAUS catalyst that retains sulfur by forming sulfur by reaction with sulfur, discharging purified residual gas with extremely low sulfur content, and
Periodically scavenging with a non-oxidizing working gas at a temperature of 00 ° C to 500 ° C to evaporate the sulfur retained on the catalyst, thereby regenerating the catalyst and then using an inert gas at a temperature below 160 ° C. the regenerated catalyst, a method consisting of cooling to a temperature necessary to newly contacted with H 2 S and sO 2 containing gas stream, H 2 S and sO 2 containing gas stream, all of the low moisture Gaseous effluent and a controlled amount of free oxygen-containing gas added to the effluent were heated to 150 ° C.
Partially oxidize H 2 S by passing it through the H 2 S oxidation catalyst at higher temperatures, approximately equal to 2: 1 H 2 S and SO 2.
Produced by forming a gas stream containing H 2 S: SO 2 molar ratio as well as elemental sulfur; said molar ratio continuously adjusting the flow rate of free oxygen-containing gas added to the low moisture gas effluent. And is regulated by cooling the gaseous effluent obtained by oxidation to a temperature below 160 ° C. and separating most of the sulfur contained in this effluent by condensation; and the gas used to cool the regenerated CLAUS catalyst A process comprising steam at a concentration of 1 to 50% by volume during at least the final stage of the cooling treatment of the catalyst.
れる掃気ガスがH2,CO及びH2Sから選択した還元作用化合
物を、少なくとも再生の最終段階の間、即ち触媒上に堆
積した硫黄の大部分が蒸発した後で含むことを特徴とす
る請求の範囲１に記載の方法。2. A scavenging gas used for the regeneration of sulfur-bearing CLAUS catalysts deposits a reducing compound selected from H 2 , CO and H 2 S, at least during the final stage of regeneration, ie on the catalyst. A method according to claim 1, characterized in that most of the sulfur is included after evaporation.
作用化合物の濃度が0.5〜25容量％であることを特徴と
する請求の範囲第２に記載の方法。3. The method according to claim 2, wherein the concentration of the reducing compound contained in the scavenging gas used for regeneration is 0.5 to 25% by volume.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8515906A FR2589082B1 (en) | 1985-10-25 | 1985-10-25 | PROCESS FOR REMOVAL OF SULFUR COMPOUNDS CONTAINED IN A WASTE GAS, PARTICULARLY FROM A CLAUS SULFUR FACTORY, WITH RECOVERY OF SUCH SULFUR COMPOUNDS |
| FR85/15906 | 1985-10-25 | ||
| PCT/FR1986/000365 WO1987002653A1 (en) | 1985-10-25 | 1986-10-24 | Process for removing sulfur compounds contained in a residual gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63501562A JPS63501562A (en) | 1988-06-16 |
| JPH0832548B2 true JPH0832548B2 (en) | 1996-03-29 |
Family
ID=26224791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61505667A Expired - Lifetime JPH0832548B2 (en) | 1985-10-25 | 1986-10-24 | Method for removing sulfur compounds contained in residual gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0832548B2 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5912602B2 (en) * | 1976-03-24 | 1984-03-24 | バブコツク日立株式会社 | Claus sulfur recovery equipment tail gas processing method |
| JPS57175710A (en) * | 1981-03-02 | 1982-10-28 | Standard Oil Co | Improved claus desulfurizing method |
| FR2540092B1 (en) * | 1983-01-31 | 1986-02-21 | Elf Aquitaine | CATALYTIC PROCESS FOR THE PRODUCTION OF SULFUR FROM A H2S-CONTAINING GAS |
| GB8318098D0 (en) * | 1983-07-04 | 1983-08-03 | Shell Int Research | Oxidation of hydrogen sulphide to elemental sulphur |
-
1986
- 1986-10-24 JP JP61505667A patent/JPH0832548B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63501562A (en) | 1988-06-16 |
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