JPH0735248B2 - Method for removing sulfur compounds contained in residual gas - Google Patents

Method for removing sulfur compounds contained in residual gas

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Publication number
JPH0735248B2
JPH0735248B2 JP61505660A JP50566086A JPH0735248B2 JP H0735248 B2 JPH0735248 B2 JP H0735248B2 JP 61505660 A JP61505660 A JP 61505660A JP 50566086 A JP50566086 A JP 50566086A JP H0735248 B2 JPH0735248 B2 JP H0735248B2
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JP
Japan
Prior art keywords
gas
sulfur
catalyst
temperature
oxidation
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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.)
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JP61505660A
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Japanese (ja)
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JPS63501359A (en
Inventor
クバスニコフ，ジョルジュ
ヌガイレード，ジャン
フイリツプ，アンドレ
Original Assignee
ソシエテ ナシオナル・エルフ・アキテ−ヌ （プロデユクシオン）
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Publication of JPS63501359A publication Critical patent/JPS63501359A/en
Publication of JPH0735248B2 publication Critical patent/JPH0735248B2/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • C01B17/046—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process without intermediate formation of sulfur dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8612—Hydrogen sulfide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • C01B17/0456—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process the hydrogen sulfide-containing gas being a Claus process tail gas
    • 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
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (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、COS、CS2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 , COS and CS 2 .

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方法は既に色々
提案されおり、中でも、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、次いで前記組合わせた処理によ
り生じた排出物を適当な温度に冷却して中に含まれる水
蒸気の大部分を凝縮させ、最後にこの低水蒸気気体排出
物からH2Sを除去すべく処理することからなる方法が知
られている。前記H2S除去処理は再生可能な選択的溶媒
を用いてH2Sを吸収するか、又はH2Sを調整触媒酸化によ
って硫黄に変えることにより実施し得る。Various methods have already been proposed for treating the residual gas in the CLAUS-type sulfur plant. Among them, the residual gas is subjected to a combined treatment of hydrogenation and hydrolysis in order to unify the sulfur compounds contained in it into the H 2 S form. , Then the effluent produced by the combined treatment is cooled to a suitable temperature to condense most of the water vapor contained therein and finally treated to remove H 2 S from this low water vapor gas effluent. A method consisting of things is known. The H 2 S removal treatment can be carried out by absorbing H 2 S with a reproducible selective solvent or converting H 2 S to sulfur by controlled catalytic oxidation.

硫黄への触媒酸化によってH2Sを除去する前述タイプの
方法の１つとして、CLAUS残留ガスを水素化／加水分解
組合わせ処理にかつ且つその結果生じた気体排出物を冷
却してその水分の大部分を凝縮させた後で、この低水蒸
気排出物を調節量の遊離酸素含有ガスと共に、H2Sを硫
黄に酸化する触媒と150℃より高い温度で接触させ、そ
れによってH2S及びSO2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、次いでこのガス流を
160℃未満に冷却し且つその中に含まれる硫黄を任意に
分離した後で、H2SとSO2との反応によって生じる硫黄が
その上に保持されるように十分低い温度で機能するCLAU
S触媒に接触させて硫黄化合物量の極めて小さい残留気
体排出物を発生させ、この気体排出物は大気中に排出す
る前に焼却し、硫黄を含んだCLAUS触媒は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、このようにして触媒を再生し、次い
でこの再生触媒をH2S及びSO2含有ガス、即ち前記酸化反
応の結果生じるガス流と新たに接触させるのに必要な温
度まで冷却することからなる方法がある。As one of the aforementioned types of methods for removing H 2 S by catalytic oxidation to sulfur, CLAUS residual gas is subjected to a combined hydrogenation / hydrolysis treatment and the resulting gaseous effluent is cooled to reduce its water content. After most of the condensation, this low steam effluent is contacted with a controlled amount of free oxygen-containing gas at a temperature above 150 ° C. with a catalyst that oxidizes H 2 S to sulfur, whereby H 2 S and SO 2 almost 2: to generate a gas stream containing elemental sulfur with containing 1 molar ratio, then the gas stream
After cooling to below 160 ° C. and optionally separating the sulfur contained therein, CLAU which functions at a temperature low enough so that the sulfur produced by the reaction of H 2 S and SO 2 is retained on it.
S-catalyst is contacted to generate a residual gas emission with a very small amount of sulfur compounds, which is incinerated before being discharged into the atmosphere, sulfur containing CLAUS catalysts at 200 ° C-500 ° C.
Of the non-oxidizing working gas at regular intervals to evaporate the sulfur retained on the catalyst, thus regenerating the catalyst, and then regenerating the regenerated catalyst in a gas containing H 2 S and SO 2; There is a method which comprises cooling to the temperature required to make fresh contact with the resulting gas stream.

硫黄を保持したCLAUS触媒の前述のごとき再生技術の効
率が、掃気ガスにCO、H2及び特にH2Sのごとき還元作用
ガスを特定量混入することによって向上し得ることも既
に知られている。このようにすれば、再生処理を多数回
行った後でも、再生CLAUS触媒に初期活性に近い活性が
与えられるからである。そのために使用される掃気ガス
は通常、ほぼ不活性のキャリアガス、例えば窒素又は硫
黄工場からの精製された残留ガスの一部分からなるガス
に、適量のH2S含有ガス、特に硫黄工場で処理される酸
性ガスを混合することによって形成される。It is also already known that the efficiency of regeneration technologies such as described above for sulfur-laden CLAUS catalysts can be improved by incorporating specific amounts of reducing gases such as CO, H 2 and especially H 2 S into the scavenging gas. . By doing so, the activity close to the initial activity is given to the regenerated CLAUS catalyst even after the regeneration treatment is performed many times. The scavenging gas used for that purpose is usually treated in an almost inert carrier gas, for example a gas which consists of a portion of the purified residual gas from a nitrogen or sulfur plant, in an appropriate amount of H 2 S-containing gas, in particular a sulfur plant. It is formed by mixing acid gases that

本発明の目的は、特にCLAUS式工場からの残留ガスのご
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
しながら除去する方法であって、硫黄を保持したCLAUS
触媒をH2S含有非酸化作用高温ガスで掃気することによ
って再生する段階を含み、この再生段階を硫黄工場で処
理される酸性ガスの使用を回避するのに適した方法で実
施するような方法を提供することにある。An object of the present invention is a method for removing sulfur compounds contained in a residual gas such as a residual gas from a CLAUS type factory while recovering the sulfur compound in the form of sulfur.
A method comprising regenerating the catalyst by scavenging it with a non-oxidizing hot gas containing H 2 S, such that the regeneration step is carried out in a manner suitable to avoid the use of acid gases treated in sulfur plants. To provide.

本発明の方法は、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、この組合わせ処理の結果生じた気体排
出物を冷却してその中に含まれる水蒸気を凝縮させ、こ
のようにして得た低水蒸気気体排出物を、必要な温度に
再加熱し且つ調節量の遊離酸素含有ガスを加えた後で、
H2Sの硫黄への酸化触媒に150℃より高い温度で接触させ
て、H2S及びSO2をほぼ2:1に等しいH2S:SO2モル比で含む
と共に硫黄元素も含むガス流を発生させ、このガス流を
160℃未満に冷却し且つその中に含まれる硫黄を任意に
分離した後で、H2SとSO2との反応によって生じる硫黄が
その上に堆積するように十分低い温度で機能するCLAUS
触媒に接触させ、それによって新たな量の硫黄を形成す
ると共に精製された残留ガスを発生させ、この残留ガス
を任意に焼却した後で大気中に排出し、硫黄を保持した
CLAUS触媒を200℃〜500℃のH2S含有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、この再生触媒をH2
S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るタイプの方法であって、遊離酸
素含有ガスの存在下におく前の前記低水蒸気気体排出物
の一部分を掃気ガス、即ち200℃〜500℃の適温に加熱さ
れた後で硫黄保持CLAUS触媒の再生に用いられるガスの
形成に使用し、且つ遊離酸素含有ガスと共に酸化触媒に
接触させる前記気体排出物を、前記再生処理の結果生
じ、中に含まれる硫黄の大部分が凝縮によって任意に除
去された掃気ガス量で構成し、その量は掃気ガスの形成
に使用される低水蒸気気体排出物の量にほぼ等しく、前
記再生処理用掃気ガスの形成に使用されない低水蒸気気
体排出物量があればこれを前記掃気ガス量に加えること
を特徴とする。In the method of the present invention, the residual gas is subjected to a combined treatment of hydrogenation and hydrolysis to unify the sulfur compounds contained in it into the form of H 2 S and the gaseous effluent resulting from this combined treatment is cooled. To condense the water vapor contained therein, reheat the low water vapor gas effluent thus obtained to the required temperature and add a controlled amount of free oxygen-containing gas,
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 also containing elemental sulfur by contacting a catalyst for the oxidation of H 2 S to sulfur at temperatures above 150 ° C. Generate this gas flow
After cooling below 160 ° C and optionally separating the sulfur contained therein, CLAUS which functions at a temperature low enough for the sulfur formed by the reaction of H 2 S and SO 2 to deposit thereon.
Contact with the catalyst, thereby forming a new amount of sulfur and producing a purified residual gas, which is optionally incinerated and then discharged into the atmosphere to retain sulfur
Periodically regenerated by purging at 200 ° C. to 500 ° C. in H 2 S-containing non-oxidizing working gas the CLAUS catalyst, the regenerated catalyst H 2
A method of the type comprising cooling to a temperature necessary for fresh contact with S and SO 2 containing gases, scavenging a portion of said low water vapor gas effluent prior to placing it in the presence of free oxygen containing gases. The gas effluent used to form the gas, i.e., the gas used to regenerate the sulfur-bearing CLAUS catalyst after being heated to a suitable temperature of 200 ° C to 500 ° C, and contacted with the oxidation catalyst along with the free oxygen-containing gas The majority of the sulfur contained in the rejuvenation process is made up of voluntarily removed scavenging gas by condensation, which is approximately equal to the amount of low water vapor gas effluent used to form the scavenging gas. If there is a low water vapor gas discharge amount that is not used in the formation of the scavenging gas for the regeneration process, this is added to the scavenging gas amount.

本発明の実施態様の１つでは、低水分気体排出物の全部
を硫黄保持CLAUS触媒再生用掃気ガスの形成に使用し、
前記再生処理の結果生じる掃気ガスの全部を、その中に
含まれる硫黄の大部分を凝縮によって任意に分離した後
で、遊離酸素含有ガスと共に酸化触媒に接触させる気体
排出物の形成に使用する。In one embodiment of the present invention, all of the low moisture gas effluent is used to form a scavenging gas for regeneration of sulfur bearing CLAUS catalysts,
All of the scavenging gas resulting from the regeneration process is used to form a gaseous effluent which is contacted with the free oxygen-containing gas on the oxidation catalyst, after optional separation of most of the sulfur contained therein by condensation.

本発明の別の実施態様では、低水分気体排出物に遊離酸
素含有ガスを混入する前にこの気体排出物から一部分を
採取し、この採取気体分を用いて硫黄保持CLAUS触媒再
生用掃気ガスを形成し、再生処理の結果生じた掃気ガス
の一部分を、該ガス中に含まれる硫黄の大部分を凝縮に
よって除去した後で、遊離酸素含有ガス添加地点の上流
で前記低水分気体排出物中に再導入する。再生処理の結
果生じる掃気ガスの前記一部分の量は、再生処理用掃気
ガスを構成すべく低水分気体排出物から採取される気体
分の量にほぼ等しい。In another embodiment of the present invention, a portion of a low moisture gas effluent is sampled from the gaseous effluent prior to admixing the free oxygen-containing gas, and the sampled gas fraction is used to provide a scavenging gas for sulfur-bearing CLAUS catalyst regeneration. A portion of the scavenging gas formed and resulting from the regeneration process is removed into the low-moisture gas effluent upstream of the free oxygen-containing gas addition point after the majority of the sulfur contained in the gas has been removed by condensation. Reintroduce. The amount of said portion of the scavenging gas resulting from the regeneration process is approximately equal to the amount of gas extracted from the low moisture gas effluent to constitute the scavenging gas for the regeneration process.

再生処理の結果生じる掃気ガスの前記一部分は、好まし
くは、遊離酸素含有ガス添加地点と再生用掃気ガスの形
成に使用される気体分の採取地点との間で低水分気体排
出物中に再導入する。Said portion of the scavenging gas resulting from the regeneration process is preferably reintroduced into the low moisture gas effluent between the point of addition of free oxygen-containing gas and the point of collection of the gas used to form the scavenging gas for regeneration. To do.

水素化と加水分解とを組合わせた処理は通常触媒の存在
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。この水素化
／加水分解組合わせ処理は約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焼
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
に含まれるSO2のごとき水素化し得る硫黄化合物もしく
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量とする必要がある。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倍にしてよい。The combined treatment of hydrogenation and hydrolysis is usually carried out in the presence of a catalyst, during which operation sulfur compounds such as SO 2 , CS 2 and COS contained in the residual gas as well as vapor and / or Or vesicular sulfur is 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. This combined hydrogenation / hydrolysis treatment is carried out at temperatures which can reach about 140 ° C to 550 ° C, preferably at temperatures 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. One advantageous method of supplying H 2 and CO to the residual gas consists of adding to the residual gas the combustion gas produced by a fuel gas burner operating below stoichiometry. The amount of hydrogen used is such that sulfur compounds or products capable of being hydrogenated such as SO 2 contained in the residual gas subjected to the hydrogenation / hydrolysis treatment, vaporous and / or vesicular sulfur are almost completely converted to H 2 S.
Should be sufficient to convert to. In the actual operation, the amount of hydrogen used is 1 to 1 of the stoichiometric amount necessary to convert the hydrogenatable sulfur product present in the residual gas into H 2 S.
May be 6 times.

残留ガスが硫黄有機化合物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 a sufficient amount of water vapor required for hydrolysis organosulfur compounds COS and CS 2, the residual required amount of water vapor prior to carrying out the hydrogenation / hydrolysis combination treatment Can be added to gas.

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 catalysts 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, such as cobalt, molybdenum, chromium, vanadium, thorium, nickel, tungsten, and uranium. Examples thereof include those containing metal compounds. 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、その中に含まれる水蒸気の大部分
が凝縮されるようにする。この冷却処理は、有利には、
冷却された気体排出物の水蒸気含量が約10容量％未満の
値になるように実施する。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. , So that most of the water vapor contained in it is condensed. This cooling process is advantageously
It is carried out such that the water vapor content of the cooled gaseous effluent is less than about 10% by volume.

このようにして冷却した水蒸気含量低下気体排出物は、
次いでH2Sの酸化を生起させる時の温度に適合した温度
まで再加熱される。この加熱処理は特に、凝縮によって
水蒸気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
記水蒸気含量低下気体排出物と150℃より高い温度で機
能する酸化触媒との接触処理の間に、又は好ましくはこ
の接触処理の前に実施する。The water vapor content reduced gas effluent cooled in this way is
It is then reheated to a temperature compatible with the temperature at which H 2 S oxidation occurs. This heat treatment may in particular be carried out by indirect heat exchange with the hot gas effluent which is cooled to separate the water vapor 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 steam-depleted gaseous effluent with an oxidation catalyst which functions above 150 ° C., or preferably before this contact treatment.

前記水素化気体排出物に含まれるH2Sを酸化するために
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、又は窒素以外の不活性ガスと
酸素との種々の割合の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も或
る程度含むガス流を形成すべく、H2Sを部分的に酸化し
てSO2に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 to oxidize H 2 S contained in the hydrogenated gas effluent is usually air, but pure oxygen, air with a high oxygen content, or an inert gas other than nitrogen and oxygen. It is also possible to use mixtures of various proportions of.
As described above, the free oxygen-containing gas contains H 2 S and SO 2 in an amount of about 2: 1.
To a minimum amount required to partially oxidize H 2 S to SO 2 in order to form a gas stream containing H 2 S: SO 2 molar ratio equal to It is used only in an amount adjusted to give a corresponding amount of oxygen.

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要求量の大
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 large demands 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 changed 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 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 oxygen, It may be selected from among a variety of catalysts capable of promoting oxidation according to. 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せた触媒。1975年10月17日付仏
国特許第75,31769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. 75,31769 (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 by combining at least one compound of a metal selected from the group (III) and a support comprising activated alumina thermally stabilized by a small amount of at least one rare earth oxide, in particular. A 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、III
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全く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, III
Or, it is constructed by continuously using the catalyst of IV, and as an advantage,
The gas stream resulting from the oxidation may be completely free of oxygen. 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
媒又はこの種の触媒を含む触媒は約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。The oxidation reaction of H 2 S in CLAUS stoichiometry can be carried out at temperatures between 150 ° C. and 1000 ° C. and the oxidation catalyst is selected from catalysts that show sufficient thermal stability at the holding temperature. For example, type I) catalysts or catalysts containing such catalysts can be used up to about 400 ° C., type II) catalysts up to about 500 ° C., type III).
The catalyst can be used up to about 700 ° C, and the type IV catalyst can be used 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H2S:SO2モル比で含む。
このガス流をその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な温度に冷却し、次いでH2SとSO2と
の反応によって生じる硫黄がその上に堆積するように十
分低い温度、有利には約120℃〜140℃で機能するCLAUS
触媒に接触させ、それによって新たな量の硫黄を形成す
る。硫黄を含んだCLAUS触媒は、200℃〜500℃の温度のH
2S含有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。The gas stream resulting from the oxidation treatment contains vaporous sulfur and H 2 S and SO 2 in a H 2 S: SO 2 molar ratio equal to about 2: 1.
This gas stream is cooled to a temperature at which most of the sulfur contained therein is separated by condensation, and then low enough to deposit the sulfur produced by the reaction of H 2 S and SO 2 on it. CLAUS, which advantageously functions at about 120 ° C to 140 ° C
Contact the catalyst, thereby forming a new amount of sulfur. CLAUS catalysts containing sulfur are
It is regenerated periodically by scavenging with a non-oxidizing working gas containing 2 S, and the regenerated catalyst is H 2 S and SO 2 resulting from oxidation.
Cool to the temperature required for fresh contact with the contained gas stream.

CLAUS触媒との接触によるH2SとSO2との反応は通常複数
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
反応の段階で機能するように使用される。あるいは、１
つ以上のゾーンを反応段階に使用し、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 reaction of H 2 S and SO 2 by contact with CLAUS catalyst is usually carried out in multiple catalytic conversion zones. These zones are used such that at least one zone functions in the regeneration / cooling stage and the rest in the reaction stage. Or 1
It is also possible to operate using more than one zone for the reaction stage, at least one zone for the regeneration stage and at least one zone for cooling.

CLAUS触媒はH2SとSO2との反応を促進させ得る任意の触
媒であってよく、特にアルミナ、ボーキサイト、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。The CLAUS catalyst may be any catalyst capable of promoting the reaction of H 2 S with SO 2 , in particular alumina, bauxite, silica, natural or synthetic zeolites, the above-mentioned type I) catalysts, or mixtures of these substances. Alternatively, it may be configured in combination.

CLAUS触媒との接触の結果生じる精製された残留ガスは
通常、その中に極めて少量残留している可能性のある硫
黄化合物を総てSO2に変換すべく、大気中に排出する前
に熱的焼却又は触媒焼却にかけられる。The purified residual gas that results from contact with the CLAUS catalyst is usually thermally converted before it is discharged into the atmosphere in order to convert all sulfur compounds, which may remain in very small amounts, into SO 2. Subject to incineration or catalyst incineration.

硫黄を保持したCLAUS触媒の再生は、前述のごとく形成
し且つ200℃〜500℃の適温に加熱した掃気ガスで触媒を
掃気することによって行い、再生の結果生じた掃気ガス
はその中に含まれる硫黄の大部分を凝縮によって任意に
分離した後で、前述のごとく遊離酸素含有ガスと共に酸
化触媒に接触する気体排出物の形成に使用する。再生が
完了したら、約160℃未満の掃気ガスを用いて再生触媒
を掃気して冷却し、その温度を酸化の結果生じるガス流
との接触に必要な値にする。Regeneration of the sulfur-laden CLAUS catalyst is carried out by scavenging the catalyst with a scavenging gas formed as described above and heated to an appropriate temperature of 200 ° C to 500 ° C, and the scavenging gas generated as a result of the regeneration is contained therein. Most of the sulfur is optionally separated by condensation and then used to form a gaseous effluent that contacts the oxidation catalyst with the free oxygen-containing gas as described above. Once regeneration is complete, the regenerated catalyst is scavenged and cooled with a scavenging gas below about 160 ° C. to bring its temperature to the value required for contact with the gas stream resulting from oxidation.

本発明は、添付図面に示した装置を用いる非限定的一実
施例に関する以下の説明からより良く理解されよう。The present invention will be better understood from the following description of a non-limiting example using the apparatus shown in the accompanying drawings.

添付図面の装置は水素化／加水分解反応器１と、洗浄カ
ラム２と、酸化反応器３と、互いに並列に配置された２
つのCLAUS触媒変換器4a及び4bとを備えている。反応器
１は硫黄工場から排出される処理すべき残留ガスを導入
するための管５とガス排出管９とを有し、管５上にバー
ナー６が挿置され、このバーナーに燃料ガス導入管７と
空気導入管８とが具備されている。管９はガス／ガス交
換器タイプの間接的熱交換器10の高温回路と低圧蒸気発
生熱交換器11と空気冷却器12とを順次介して、洗浄カラ
ム２の下半分に設けられた開口13に接続される。洗浄カ
ルラム２は上半分の部分に配置された水噴霧管14を有す
る他、底に液体排出管15、上部に気体排出管16を備え
る。この気体排出管は熱交換器10の低温回路を介して該
洗浄カラムを酸化反応器３の入口に接続する。酸化反応
器の入口の近傍では管16にガス添加用分岐管17が接続さ
れ、酸化反応器は出口管18を備え、この出口管に凝縮器
19が配置されている。The apparatus shown in the accompanying drawings comprises a hydrogenation / hydrolysis reactor 1, a washing column 2 and an oxidation reactor 3 arranged in parallel with each other.
Two CLAUS catalytic converters 4a and 4b. The reactor 1 has a pipe 5 and a gas discharge pipe 9 for introducing a residual gas discharged from a sulfur factory to be treated, and a burner 6 is placed on the pipe 5, and a fuel gas introduction pipe is installed in this burner. 7 and an air introduction pipe 8 are provided. The pipe 9 is provided with an opening 13 provided in the lower half of the cleaning column 2 through a high temperature circuit of an indirect heat exchanger 10 of a gas / gas exchanger type, a low pressure steam generating heat exchanger 11 and an air cooler 12 in this order. Connected to. The cleaning carrum 2 has a water spray pipe 14 arranged in the upper half portion, a liquid discharge pipe 15 at the bottom, and a gas discharge pipe 16 at the top. This gas discharge pipe connects the washing column to the inlet of the oxidation reactor 3 via the low temperature circuit of the heat exchanger 10. A gas addition branch pipe 17 is connected to the pipe 16 in the vicinity of the inlet of the oxidation reactor, and the oxidation reactor is provided with an outlet pipe 18 to which a condenser is attached.
19 are arranged.

触媒変換器4a及び4bは夫々第１の管20a、20bと第２の管
21a、21bとを有し、これらの管は当該変換器を挟んで両
側に配置されている。変換器4aの管20aは弁23aを備えた
管22aにより凝縮器19の下流で管18に接続されると共
に、弁25aを備えた管24aによって管26に接続される。管
26は送風器27の吸引口に接続され、その上に硫黄凝縮器
28が配置されている。同様にして、変換器4bの管20bは
弁23bを備えた管22bによって酸化反応器の出口管18に該
管と管22aとの接合点の下流で接続されると共に、弁25b
を備えた管24bを介して管24aと硫黄凝縮器28との間に位
置する地点で管26に接続される。Catalytic converters 4a and 4b are respectively a first tube 20a, 20b and a second tube.
21a, 21b, and these tubes are arranged on both sides of the transducer. The pipe 20a of the converter 4a is connected to the pipe 18 downstream of the condenser 19 by a pipe 22a with a valve 23a and to the pipe 26 by a pipe 24a with a valve 25a. tube
26 is connected to the suction port of the blower 27, on which the sulfur condenser
28 are arranged. Similarly, the pipe 20b of the converter 4b is connected by a pipe 22b with a valve 23b to the outlet pipe 18 of the oxidation reactor downstream of the junction of said pipe and the pipe 22a and a valve 25b.
It is connected to the pipe 26 at a point located between the pipe 24a and the sulfur condenser 28 via a pipe 24b provided with.

変換器4aの管21aは弁30aを備えた管29aによって管31に
接続されると共に、弁33aを備えた管32aによって送風器
27の送出口から延びる管34に接続される。前記管31は精
製された残留ガスを図示されていない焼却器の方向に排
出し、残留ガスはそこから大気中に放出される。管34は
加熱器35と、弁37を備えた前記加熱器を通らない分岐36
とを有し、更に前記加熱器とその上流の前記分岐部分と
の間に配置された弁38を備える。同様にして、変換器4b
の管21bは弁30bを備えた管29bを介して精製残留ガス排
出管31に接続されると共に、弁33bを備えた管32bを介し
て前記分岐と管32aとの間に位置する地点で管34に接続
される。熱交換器10と管17との間で管16に分岐状に接続
された管39は該管16を硫黄凝縮器28と送風器との間に位
置する地点で管26に接続し、管40は管39と管17との間で
管16に分岐状に接続されて、管16を送風器27の送出口と
分岐36との間に位置する地点で管34に接続する。この管
40は流量調整弁41を具備する。The pipe 21a of the converter 4a is connected to the pipe 31 by a pipe 29a provided with a valve 30a, and the blower is provided by a pipe 32a provided with a valve 33a.
It is connected to a pipe 34 extending from the outlet of 27. Said pipe 31 discharges the purified residual gas towards an incinerator, not shown, from which the residual gas is discharged into the atmosphere. The tube 34 comprises a heater 35 and a branch 36 which does not pass through said heater with a valve 37.
And a valve 38 located between the heater and the branch upstream thereof. Similarly, converter 4b
The pipe 21b is connected to the purified residual gas discharge pipe 31 via a pipe 29b equipped with a valve 30b, and at a point located between the branch and the pipe 32a via a pipe 32b equipped with a valve 33b. Connected to 34. A pipe 39 branchingly connected to the pipe 16 between the heat exchanger 10 and the pipe 17 connects the pipe 16 to the pipe 26 at a point located between the sulfur condenser 28 and the blower, and the pipe 40 Is connected to the pipe 16 in a branched manner between the pipe 39 and the pipe 17, and connects the pipe 16 to the pipe 34 at a point located between the outlet of the blower 27 and the branch 36. This tube
40 includes a flow rate adjusting valve 41.

本発明の方法はこの装置で下記のように実施される。The method of the invention is carried out on this device as follows.

変換器4aがCLAUS反応段階にあり、変換器4bが再生段階
にあり、弁23a、25b、30a、33b及び38が開放され、弁23
b、25a、30b、33a及び37が閉鎖されていると想定する。Transducer 4a is in the CLAUS reaction stage, transducer 4b is in the regeneration stage, valves 23a, 25b, 30a, 33b and 38 are open and valve 23
Assume b, 25a, 30b, 33a and 37 are closed.

管５を介して硫黄工場から送られた残留ガスはバーナー
６を通り、その中でこのバーナーにより発生した燃焼ガ
スと混合される。前記バーナーは化学量論量以下で機能
して空気により燃料ガスを燃焼させ、カロリーの他に適
当な量のH2及びCOを発生させる。前記残留ガスはこのバ
ーナーを通過する時に燃焼ガスによって水素化に必要な
温度、例えば200℃〜400℃に加熱され、同時に、燃焼に
よって生じた水素及びCOを受容する。残留ガスとバーナ
ーによる燃焼ガスとの高温混合物は水素化／加水分解反
応器１内に流入する。この反応器内にはSO2及び硫黄元
素のH2Sへの水素化と化合物COS及びCS2の加水分解とを
促進し得る触媒が適量収容されている。この触媒は例え
ばコバルト及びモリブデンをベースとする。反応器１で
は残留ガス中に存在するH2S以外の硫黄化合物がほぼ完
全にH2Sに変換される。管９を介して反応器１から流出
する気体排出物は約300℃〜450℃の温度を有し、熱交換
器10を通って低圧蒸気発生交換器11内に流入し、最後に
冷却のために空気冷却器12を通過し、その後開口13から
洗浄カラム２内に入る。冷却された水素化気体排出物は
このカラムで管14により実施される水の噴霧によって洗
浄され、その結果中に含まれる硫黄の大部分が凝縮され
る。洗浄カラム２の上部からは約10容量％未満の水蒸気
を含む冷却された気体排出物が排出される。この気体排
出物は熱交換器10で150℃より高い値、例えば180℃〜30
0℃であり且つ酸化触媒の最高作用温度に適合するよう
な温度に加熱され、且つ管17を介して調節量の遊離酸素
含有ガス、特に空気を受容した後で、管16を介して酸化
反応器３内に導入され、そこでCLAUS化学量論量のH2Sの
酸化が生起する。即ち、H2Sの1/3がSO2に酸化される。The residual gas sent from the sulfur plant via the pipe 5 passes through the burner 6 in which it is mixed with the combustion gases generated by this burner. The burner functions below the stoichiometric amount and burns the fuel gas with air to generate appropriate amounts of H 2 and CO in addition to calories. When the residual gas passes through the burner, it is heated by the combustion gas to a temperature necessary for hydrogenation, for example, 200 ° C. to 400 ° C., and at the same time, it receives hydrogen and CO generated by combustion. The hot mixture of residual gas and combustion gas from the burner flows into the hydrogenation / hydrolysis reactor 1. This reactor contains an appropriate amount of a catalyst capable of promoting the hydrogenation of SO 2 and elemental sulfur to H 2 S and the hydrolysis of the compounds COS and CS 2 . This catalyst is based on, for example, cobalt and molybdenum. In the reactor 1, sulfur compounds other than H 2 S present in the residual gas are almost completely converted to H 2 S. The gaseous effluent leaving reactor 1 via tube 9 has a temperature of about 300 ° C. to 450 ° C., flows through heat exchanger 10 into low pressure steam generation exchanger 11, and finally for cooling. Through the air cooler 12 and then through the opening 13 into the wash column 2. The cooled hydrogenated gas effluent is scrubbed in this column by a spray of water carried out by means of a tube 14 so that most of the sulfur contained therein is condensed. The cooled gas effluent, which contains less than about 10% by volume of water vapor, is discharged from the top of the washing column 2. This gaseous effluent has a value higher than 150 ° C in the heat exchanger 10, for example 180 ° C to 30 ° C.
Oxidation reaction via tube 16 after being heated to a temperature which is 0 ° C. and adapted to the maximum operating temperature of the oxidation catalyst and after receiving a controlled amount of free oxygen-containing gas, especially air via tube 17. It is introduced into vessel 3 where the oxidation of CLAUS stoichiometry of H 2 S occurs. That is, 1/3 of H 2 S is oxidized to SO 2 .

酸化反応器３はCLAUS化学量論量のH2Sの部分的酸化を促
進し得る酸化触媒を収容している。この触媒は例えば前
述のタイプＩ）〜IV）の触媒の中から選択され、有利に
はタイプＩの触媒の層と、これに続くタイプII、III又
はIVの触媒の層とで構成し得る。酸化反応器３からは出
口管18を介して、硫黄の他にH2S及びSO2を約2:1に等し
いH2S:SO2モル比で含むガス流が流出する。このガス流
は凝縮器19で160℃未満の温度、例えば120℃〜140℃に
冷却され、その後管22aを介し弁23aと管20aとを通って
変換器4a内に流入する。Oxidation reactor 3 contains an oxidation catalyst capable of promoting partial oxidation of CLAUS stoichiometry of H 2 S. This catalyst is selected, for example, from the catalysts of the above-mentioned types I) to IV) and can advantageously consist of a layer of a type I catalyst followed by a layer of a type II, III or IV catalyst. From the oxidation reactor 3 is exited via the outlet pipe 18 a gas stream containing, in addition to sulfur, H 2 S and SO 2 in a H 2 S: SO 2 molar ratio equal to about 2: 1. This gas stream is cooled in the condenser 19 to a temperature below 160 ° C., for example 120 ° C. to 140 ° C., and then flows via the pipe 22a through the valve 23a and the pipe 20a into the converter 4a.

この変換器には変換器4bと同様にアルミナ又は前述のタ
イプＩ）の触媒のごときCLAUS触媒が収容されており、
前記ガス流に含まれるH2S及びSO2がこのCLAUS触媒との
接触によって互いに反応し、下記の反応式 2H2S＋SO23/nSn＋2H2O に従って硫黄を形成する。Like the converter 4b, this converter contains a CLAUS catalyst, such as an alumina or type I catalyst described above,
The H 2 S and SO 2 contained in the gas stream react with each other by contact with this CLAUS catalyst to form sulfur according to the following reaction formula 2H 2 S + SO 2 3 / nSn + 2H 2 O.

H2SとSO2との反応の結果生じる硫黄は、CLAUS触媒に接
触するガス流の温度で前記触媒上に堆積する。変換器4a
からは管21aを介して硫黄化合物含量の極めて小さい精
製されたガス流が流出し、管29aを介し弁30aを通って排
出管31方向に流れ、この管によって熱焼却又は触媒焼却
反応器に送られる。Sulfur resulting from the reaction of H 2 S with SO 2 deposits on the CLAUS catalyst at the temperature of the gas stream contacting the catalyst. Converter 4a
From which a purified gas stream with a very low sulfur compound content flows out via a pipe 21a, flows through a pipe 29a through a valve 30a in the direction of an exhaust pipe 31, and is sent to a thermal incineration or catalytic incineration reactor by this pipe. To be

管16を介して酸化反応器３方向に送られる気体排出物
は、熱交換器10での加熱後に且つ遊離酸素含有ガス特に
空気を加える前に、管39を介して一部分が採取され、こ
の採取分は弁38及び加熱器35を介して送風器27により管
34に送られる掃気ガス流を構成するのに使用される。こ
のガスは前記加熱器35で再生処理に適した温度に加熱さ
れる。管34に流れる加熱されたガス流は管32bを介し弁3
3b及び管21bを通って変換器4b内に流入し、この変換器
内に収容された硫黄保持CLAUS触媒を掃気する。この掃
気ガス流は蒸発した硫黄を伴いながら管20bを介して変
換器4bから流出し、管24b内を流れ、弁25bを通り、且つ
管26を通って硫黄凝縮器28に到達し、この凝縮器内で硫
黄の大部分が凝縮により分離される。凝縮器28を出ると
前記掃気ガス流は、酸化反応器内に導入された気体排出
物から管39を介して採取された気体分を受容し、送風器
27により吸引されて管34内に送出される。管34に送出さ
れた前記ガスの一部分は弁38を通過する前に採取され、
管16により酸化反応器３に導入される気体排出物中に、
弁41により調節される流量で管40を介して再導入され
る。The gaseous effluent sent to the oxidation reactor 3 via the pipe 16 is partly taken via the pipe 39 after heating in the heat exchanger 10 and before adding the free oxygen-containing gas, in particular air. Minutes are piped by the blower 27 through the valve 38 and the heater 35.
Used to construct the scavenging gas stream sent to 34. This gas is heated by the heater 35 to a temperature suitable for regeneration treatment. The heated gas flow in tube 34 is routed through valve 32b to valve 3
It flows into the converter 4b through 3b and the pipe 21b, and scavenges the sulfur-containing CLAUS catalyst contained in this converter. This scavenging gas stream exits the converter 4b via the pipe 20b with the vaporized sulfur, flows in the pipe 24b, passes through the valve 25b and through the pipe 26 and reaches the sulfur condenser 28 where it is condensed. Most of the sulfur is separated by condensation in the vessel. Upon exiting the condenser 28, the scavenging gas stream receives the gas fraction taken via line 39 from the gaseous effluent introduced into the oxidation reactor and is blower.
It is sucked by 27 and delivered into the tube 34. A portion of the gas delivered to tube 34 is collected before passing through valve 38,
In the gas effluent introduced into the oxidation reactor 3 by the pipe 16,
It is reintroduced via line 40 at a flow rate regulated by valve 41.

触媒上に堆積した硫黄を完全に除去し且つ掃気ガスに含
まれるH2Sの作用によって前記触媒を再活性化すべく、
加熱器35を通る掃気ガスによって変換器4b内の触媒を十
分な時間にわたり掃気した後、弁37を開放し弁38を閉鎖
して掃気ガスが加熱器35を通らないように、且つその温
度が約160℃未満の値に下がるようにし、変換器4b内の
再生された触媒の冷却に適した時間にわたって掃気を続
ける。In order to completely remove the sulfur deposited on the catalyst and to reactivate the catalyst by the action of H 2 S contained in the scavenging gas,
After the catalyst in the converter 4b has been scavenged by the scavenging gas passing through the heater 35 for a sufficient time, the valve 37 is opened and the valve 38 is closed so that the scavenging gas does not pass through the heater 35 and its temperature is It is allowed to drop to a value below about 160 ° C. and scavenging is continued for a time suitable for cooling the regenerated catalyst in converter 4b.

前記触媒が酸化反応器から排出されるガス流と接触させ
るのに適した温度まで冷却されたら、変換器4a及び4bに
より遂行される役割を切り替える。即ち変換器4bをCLAU
S反応段階におき、変換器4aを弁23a、25b、30a、33b及
び37の閉鎖と弁23b、25a、30b、33a及び38の開放とによ
って再生／冷却段階におき、次いで弁38の閉鎖及び弁37
の開放によって冷却段階におく。変換器4a及び4bの役割
の切り替え遷移期間の間は掃気ガスをこれらの変換器を
迂回する管（図示せず）に流す。Once the catalyst has cooled to a temperature suitable for contact with the gas stream leaving the oxidation reactor, it switches the role performed by converters 4a and 4b. That is, convert converter 4b to CLAU
In the S reaction stage, the converter 4a is placed in the regeneration / cooling stage by closing valves 23a, 25b, 30a, 33b and 37 and opening valves 23b, 25a, 30b, 33a and 38, and then closing and closing valve 38. Valve 37
Put in the cooling stage by opening the. During the transition transition period of the roles of the converters 4a and 4b, the scavenging gas flows through a pipe (not shown) that bypasses these converters.

本発明がより良く理解されるように、以下に本発明の方
法の非限定的一実施例を挙げる。In order that the present invention may be better understood, the following is a non-limiting example of the method of the present invention.

実施例 添付図面に示した装置と類似の装置を使用し且つ前述の
ごとき操作を行うことによって、60.4容量％のH2Sと、3
6.3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 Using an apparatus similar to the one shown in the accompanying drawings and carrying out the operation as described above, 60.4% by volume of H 2 S and 3
Residual gas discharged from a sulfur plant which carries out partial oxidation of acid gases containing 6.3% by volume of CO 2 , 3.2% by volume of water and 0.1% by volume of hydrocarbons was treated.

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 流量223kモル／時、温度約135℃で管５を介して導入さ
れる残留ガスはバーナー６で約350℃に加熱され、この
温度で水素化／加水分解反応器１内に流入した。この反
応器はアルミナからなる支持体上にコバルト／モリブデ
ンタイプの触媒を配置したものを収容していた。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 Flow rate 223 kmol / hr, temperature The residual gas introduced at about 135 ° C. via the tube 5 was heated by the burner 6 to about 350 ° C. and flowed into the hydrogenation / hydrolysis reactor 1 at this temperature. The reactor contained a cobalt / molybdenum type catalyst on a support of alumina.

反応器１ではSO2、Ｓ、COS、及びCS2のH2Sへの変換がほ
ぼ完全に実施され、反応器１から流出する気体排出物は
380℃の温度を有し、硫黄化合物としてH2Sしか含んでい
なかった。この気体排出物は熱交換器10と、凝縮器11
と、空気冷却器12とを順次通過して約80℃まで冷却さ
れ、この温度で水の噴霧により作用する洗浄カラム２内
に流入した。In the reactor 1, the conversion of SO 2 , S, COS and CS 2 into H 2 S is almost completely carried out, and the gaseous effluent flowing out of the reactor 1 is
It had a temperature of 380 ° C. and contained only H 2 S as sulfur compound. This gaseous effluent is heat exchanger 10 and condenser 11
And was cooled to about 80 ° C. by passing through the air cooler 12 in sequence and flowed into the washing column 2 which was acted by spraying water at this temperature.

カラム２の上部からは温度約35℃、水蒸気濃度約4.6容
量％の冷却された気体排出物が流出した。この冷却され
た排出物を熱交換器10で再加熱し、次いで管17を介して
7.61kモル／時の空気を加えた。このようにして得られ
た混合物は200℃の温度で酸化反応器３内に流入した。A cooled gaseous effluent having a temperature of about 35 ° C. and a water vapor concentration of about 4.6% by volume flowed out from the upper part of the column 2. This cooled effluent is reheated in heat exchanger 10 and then via tube 17
7.61 kmole / hour of air was added. The mixture thus obtained flowed into the oxidation reactor 3 at a temperature of 200 ° C.

酸化反応器内で使用する触媒は、10重量％の硫酸カルシ
ウムで安定化した酸化チタンの層と、これに続く硫酸鉄
で含浸した活性アルミナの層とで構成した。酸化反応器
内を通るガスと安定化した酸化チタンの層及び硫酸鉄で
含浸したアルミナの層との接触時間は夫々約３秒及び1.
5秒であった。酸化反応器内のH2Sの変換率は約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2:1に等しいH2S:SO2モル比で含
むと共に或る程度の硫黄元素を含んでいた。The catalyst used in the oxidation reactor consisted of a layer of titanium oxide stabilized with 10% by weight calcium sulfate, followed by a layer of activated alumina impregnated with iron sulfate. The contact time between the gas passing through the oxidation reactor and the layer of stabilized titanium oxide and the layer of alumina impregnated with iron sulfate is about 3 seconds and 1.
It was 5 seconds. The conversion 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 H 2 S and SO 2 equal to 2: 1 H 2. It contained a 2 S: SO 2 molar ratio and also contained a certain amount of elemental sulfur.

前記ガス流は硫黄を凝縮によって分離すべく凝縮器19で
130℃に冷却され、次いで変換器4a内に流入した。この
変換器は変換器4bと同様にCLAUS触媒としてアルミナを
収容していた。The gas stream is in a condenser 19 to separate the sulfur by condensation.
It was cooled to 130 ° C. and then flowed into the converter 4a. Like the converter 4b, this converter contained alumina as a CLAUS catalyst.

反応器4aから流出して焼却器方向に送られる精製された
残留ガスは約135℃の温度を有し、合計して640容量p.p.
m.に等しい量の硫黄化合物を含んでいた。The purified residual gas flowing out of the reactor 4a and sent to the incinerator has a temperature of about 135 ° C. and a total of 640 volume pp
It contained an amount of sulfur compounds equal to m.

触媒を再生処理するために変換器4bに注入される掃気ガ
スは酸化反応器の上流で採取した気体排出物で構成し、
2,500Nm3/時の流量で送風器27により送給した。前記掃
気ガスは再生中の変換器4bに導入される前に、加熱器35
で300〜350℃の温度に加熱した。再生触媒の冷却段階で
は加熱器35を迂回し、そのため掃気ガスの温度は約130
℃であった。The scavenging gas injected into the converter 4b to regenerate the catalyst consists of the gaseous effluent collected upstream of the oxidation reactor,
The air was blown by the blower 27 at a flow rate of 2,500 Nm 3 / hour. Before the scavenging gas is introduced into the regenerating converter 4b, the heater 35
And heated to a temperature of 300-350 ° C. During the cooling stage of the regenerated catalyst, the heater 35 is bypassed, so that the temperature of the scavenging gas is about 130
It was ℃.

酸化反応器の上流で管39を介して気体排出物から採取し
たガスの流量は約250Nm3/時であり、管40を介して前記
気体排出物中に再導入されるガスの流量に相当してい
た。The flow rate of the gas taken from the gas effluent via the pipe 39 upstream of the oxidation reactor is about 250 Nm 3 / h, which corresponds to the flow rate of the gas reintroduced into the gas effluent via the pipe 40. Was there.

変換器4a及び4bは精製段階即ち反応段階で30時間機能
し、再生／冷却段階で30時間機能し、そのうち10時間が
冷却に使用されるという状態で交互に作動した。The converters 4a and 4b operated alternately during the purification or reaction stage for 30 hours and during the regeneration / cooling stage for 30 hours, of which 10 hours were used for cooling.

以上説明してきた本発明の残留ガス処理方法を使用した
硫黄工場は、数箇月で99.80％の総硫黄収率を示した。The sulfur plant using the residual gas treatment method of the present invention described above showed a total sulfur yield of 99.80% in several months.

フロントページの続き (72)発明者 フイリツプ，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・２Front Page Continuation (72) Inventor Filip, Andre France, F-64300 Orte, Ampas de Violet 2

Claims (16)

【特許請求の範囲】[Claims] 【請求項１】特にCLAUS式硫黄工場からの残留ガスのご
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
しながら除去する方法であって、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、次いでこの組合わせ処
理の結果生じる気体排出物を冷却して中に含まれる水蒸
気を凝縮させ、このようにして得た低水分気体排出物を
必要な温度に再加熱し且つ調節量の遊離酸素含有ガスを
加えた後で、H2Sを硫黄に酸化させるための触媒に150℃
より高い温度で接触させてH2S及びSO2を2:1にほぼ等し
いモル比で含むと共に硫黄元素も含むガス流を発生さ
せ、このガス流を160℃未満に冷却し且つ中に含まれる
硫黄を任意に分離した後で、H2SとSO2との反応の結果生
じる硫黄がその上に堆積するように十分低い温度で機能
するCLAUS触媒に接触させて新たな量の硫黄を形成する
と共に精製された残留ガスを発生させ、この精製残留ガ
スを任意に焼却処理した後大気中に排出し、硫黄を保持
したCLAUS触媒を温度200℃〜500℃のH2S含有非酸化作用
ガスによって定期的に再生し、再生した触媒を前記酸化
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
まで冷却することからなり、この方法は、遊離酸素含有
ガスの存在下におく前の低水分気体排出物の一部又は全
部を使用して掃気ガス、即ち200℃〜500℃の適切な温度
に加熱した後で硫黄保持CLAUS触媒の再生に使用される
ガスを形成し、且つ遊離酸素含有ガスと共に酸化触媒に
接触させる気体排出物を、前記再生処理の結果生じ、中
に含まれる硫黄の大部分が凝縮によって任意に除去され
た掃気ガス量で構成し、その量は掃気ガスの形成に使用
される低水分気体排出物の量にほぼ相当し、再生用掃気
ガスの形成に使用されない低水分気体排出物量が存在す
ればこれを前記掃気ガス量に加えることを特徴とする方
法。1. A method for removing sulfur compounds contained in a residual gas such as a residual gas from a CLAUS type sulfur plant while recovering the sulfur compound in the form of sulfur, wherein the residual gas contains H 2 S The combined hydrogenation and hydrolysis treatments are then applied to unify the morphology, and the gaseous effluent resulting from this combination treatment is then cooled to condense the water vapor contained therein, thus reducing the After reheating the moisture gas effluent to the required temperature and adding a controlled amount of the free oxygen-containing gas, the catalyst for oxidizing H 2 S to sulfur was heated to 150 ° C.
Contacting at a higher temperature produces a gas stream containing H 2 S and SO 2 in a molar ratio approximately equal to 2: 1 and also containing elemental sulfur, the gas stream being cooled to below 160 ° C. and contained therein. After optional separation of sulfur, a new amount of sulfur is formed by contacting a CLAUS catalyst that functions at a temperature low enough to deposit the sulfur resulting from the reaction of H 2 S and SO 2 on top of it. A residual gas purified with is generated, and the purified residual gas is optionally incinerated and then discharged into the atmosphere, and the CLAUS catalyst holding sulfur is heated by the H 2 S-containing non-oxidizing working gas at a temperature of 200 ° C to 500 ° C. It consists of periodic regeneration and cooling of the regenerated catalyst to the temperature required for fresh contact with the gas stream resulting from said oxidation, the process being carried out at a low temperature before being placed in the presence of a gas containing free oxygen. Scavenging gas, i.e., 200, using some or all of the moisture gas emissions A gas effluent that forms the gas used for the regeneration of the sulfur-bearing CLAUS catalyst after heating to a suitable temperature of ~ 500 ° C and is brought into contact with the oxidation catalyst together with the free oxygen-containing gas, results from said regeneration treatment, Most of the sulfur contained therein is composed of the amount of scavenging gas that has been optionally removed by condensation, and that amount is approximately equivalent to the amount of low-moisture gas emissions used to form the scavenging gas. A low moisture gas effluent amount that is not used to form the gas is added to the scavenging gas amount. 【請求項２】低水分気体排出物の全部を硫黄保持CLAUS
触媒再生用掃気ガスの形成に使用し、且つ前記再生処理
の結果生じる掃気ガスの全部を、それに含まれる硫黄の
大部分を凝縮により任意に分離した後で、遊離酸素含有
ガスと共に酸化触媒に接触させる気体排出物の形成に使
用することを特徴とする請求の範囲１に記載の方法。2. A sulfur-containing CLAUS for all low-moisture gas emissions.
It is used to form a scavenging gas for catalyst regeneration, and all of the scavenging gas resulting from said regeneration treatment is contacted with an oxidation catalyst together with a free oxygen-containing gas after optionally separating most of the sulfur contained therein by condensation. A method according to claim 1, characterized in that it is used to form a gaseous effluent. 【請求項３】遊離酸素含有ガスを導入する前の低水分気
体排出物から一部分を採取し、このようにして採取した
気体分を用いて硫黄保持CLAUS触媒再生用掃気ガスを構
成し、且つ再生の結果生じる掃気ガスの一部分を、それ
に含まれる硫黄の大部分を凝縮によって除去した後で、
遊離酸素含有ガス添加地点の上流で前記低水分気体排出
物中に再導入し、再生の結果生じる掃気ガスの前記一部
分の量が低水分気体排出物から採取され再生用掃気ガス
の形成に使用される分の量にほぼ等しいことを特徴とす
る請求の範囲１に記載の方法。3. A part of a low-moisture gas exhaust gas before introducing a free oxygen-containing gas is collected, and the thus-collected gas component is used to constitute and regenerate a scavenging gas for sulfur-retaining CLAUS catalyst regeneration. After removing a portion of the resulting scavenging gas by condensing most of the sulfur contained therein,
Reintroduced into the low moisture gas effluent upstream of the free oxygen-containing gas addition point, and an amount of the portion of the scavenging gas resulting from regeneration is taken from the low moisture gas effluent and used to form the regeneration scavenging gas. Method according to claim 1, characterized in that it is approximately equal to the quantity. 【請求項４】再生の結果生じる掃気ガスの一部分を遊離
酸素含有ガス添加地点と再生用掃気ガスの形成に使用さ
れる気体分の採取地点との間で低水分気体排出物中に再
導入することを特徴とする請求の範囲３に記載の方法。4. A portion of the scavenging gas resulting from the regeneration is reintroduced into the low moisture gas effluent between the point of addition of the free oxygen-containing gas and the point of collection of the gas used to form the scavenging gas for regeneration. The method according to claim 3, wherein: 【請求項５】H2S酸化触媒がFe、Ni、Co、Cu及びZnの中
から選択した金属の少なくとも１種類の化合物とアルミ
ナ及び／又はシリカからなる支持体との組合わせによっ
て得られることを特徴とする請求の範囲１から４のいず
れかに記載の方法。5. A H 2 S oxidation catalyst is obtained by combining at least one compound of a metal selected from Fe, Ni, Co, Cu and Zn with a support made of alumina and / or silica. The method according to any one of claims 1 to 4, characterized in that: 【請求項６】H2S酸化触媒が酸化チタンをベースとし、
特に酸化チタンとアルカリ土類金属硫酸塩、例えば硫酸
カルシウムとの組合わせによって形成されることを特徴
とする請求の範囲１から４のいずれかに記載の方法。6. A H 2 S oxidation catalyst based on titanium oxide,
Process according to any of claims 1 to 4, characterized in that it is formed in particular by a combination of titanium oxide and an alkaline earth metal sulphate, for example calcium sulphate. 【請求項７】H2S酸化触媒が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
種類の化合物と、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種類の化合物と、シリカ及び
／又は酸化チタンからなる支持体との組合わせからな
り、前記支持体が任意に少量のアルミナを含み得ること
を特徴とする請求の範囲１から４のいずれかに記載の方
法。7. The H 2 S oxidation catalyst is Fe, Cu, Cd, Zn, Cr, Mo,
At least one of the metals selected from W, Co, Ni and Bi
Compound of one kind and at least one compound of at least one noble metal such as Pd, Pt, Ir and Rh, and a support made of silica and / or titanium oxide, wherein the support is arbitrarily small. 5. A method according to any one of claims 1 to 4, characterized in that it can comprise the alumina of 【請求項８】H2S酸化触媒が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
種類の化合物と、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
れた活性アルミナからなる支持体との組合わせによって
形成されることを特徴とする請求の範囲１から４のいず
れかに記載の方法。8. The H 2 S oxidation catalyst is Fe, Cu, Cd, Zn, Cr, Mo,
At least one of the metals selected from W, Co, Ni and Bi
A compound of one kind and optionally at least one compound of a noble metal such as Pd, Pt, Ir and Rh, and in particular a support of activated alumina thermally stabilized by a small amount of at least one rare earth oxide. 5. The method according to claim 1, wherein the method is formed by a combination of 【請求項９】H2S酸化触媒が請求の範囲６から８のいず
れかに記載の触媒の層と、これに続く請求の範囲５に記
載の触媒の層とで構成されることを特徴とする請求の範
囲１から４のいずれかに記載の方法。9. An H 2 S oxidation catalyst comprising a catalyst layer according to any one of claims 6 to 8 and a catalyst layer according to claim 5 following the layer. The method according to any one of claims 1 to 4. 【請求項１０】酸化触媒との接触によるH2S酸化の温度
が約150℃〜400℃であることを特徴とする請求の範囲５
又は９に記載の方法。10. The method according to claim 5, wherein the temperature of H 2 S oxidation by contact with an oxidation catalyst is about 150 ° C. to 400 ° C.
Or the method according to 9. 【請求項１１】酸化触媒との接触によるH2S酸化の温度
が約150℃〜500℃であることを特徴とする請求の範囲６
に記載の方法。11. The method according to claim 6, wherein the temperature of H 2 S oxidation by contact with the oxidation catalyst is about 150 ° C. to 500 ° C.
The method described in. 【請求項１２】酸化触媒との接触によるH2S酸化の温度
が約150℃〜700℃であることを特徴とする請求の範囲７
に記載の方法。12. The method according to claim 7, wherein the temperature of H 2 S oxidation by contact with the oxidation catalyst is about 150 ° C. to 700 ° C.
The method described in. 【請求項１３】酸化触媒との接触によるH2S酸化の温度
が約150℃〜1000℃であることを特徴とする請求の範囲
８に記載の方法。13. The method according to claim 8, wherein the temperature of H 2 S oxidation by contact with an oxidation catalyst is about 150 ° C. to 1000 ° C. 【請求項１４】水素化と加水分解とを組み合わせた処理
の結果生じる気体排出物の水分含量を、この排出物を硫
黄保持CLAUS触媒再生用掃気ガスの形成に使用する前
に、約10容量％未満に低下させることを特徴とする請求
の範囲１から13のいずれかに記載の方法。14. The moisture content of the gaseous effluent resulting from the combined treatment of hydrogenation and hydrolysis is about 10% by volume before the effluent is used to form a scavenging gas for sulfur-bearing CLAUS catalyst regeneration. Method according to any of claims 1 to 13, characterized in that it is reduced to less than. 【請求項１５】再生したCLAUS触媒を、160℃未満の温度
に冷却し且つ中に含まれる硫黄の大部分を凝縮によって
分離した後の再生用掃気ガスによって冷却することを特
徴とする請求の範囲１から14のいずれかに記載の方法。15. The reclaimed CLAUS catalyst is cooled to a temperature of less than 160 ° C. and cooled by a rejuvenating scavenging gas after separating most of the sulfur contained therein by condensation. The method according to any one of 1 to 14. 【請求項１６】CLAUS触媒がアルミナ、ボーキサイト、
シリカ、天然もしくは合成ゼオライト、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
物とアルミナ及び／又はシリカからなる支持体との組合
わせで構成される触媒、又はこれら物質の混合又は組合
わせからなることを特徴とする請求の範囲１から15のい
ずれかに記載の方法。16. The CLAUS catalyst is alumina, bauxite,
Silica, natural or synthetic zeolite, Fe, Ni, Co, Cu
And a catalyst composed of a combination of at least one compound of a metal selected from Zn and Zn with a support made of alumina and / or silica, or a mixture or combination of these substances. 16. The method according to any one of the ranges 1 to 15 of.
JP61505660A 1985-10-25 1986-10-24 Method for removing sulfur compounds contained in residual gas Expired - Lifetime JPH0735248B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR8515905A FR2589141B1 (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
FR85/15905 1985-10-25
PCT/FR1986/000366 WO1987002654A1 (en) 1985-10-25 1986-10-24 Process for removing sulphur-containing compounds from a residual gas

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JPS63501359A JPS63501359A (en) 1988-05-26
JPH0735248B2 true JPH0735248B2 (en) 1995-04-19

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CA (1) CA1281886C (en)
DE (2) DE3690569T1 (en)
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WO (1) WO1987002654A1 (en)

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GB2215323B (en) * 1988-03-09 1991-12-18 Exxon Research Engineering Co Process for removing sulfur moieties from a sulfurous gas such as claus tail-gas
US5494650A (en) * 1989-01-19 1996-02-27 Societe Nationale Elf Aquitaine (Production) Process for improving the sulphur yield of a complex for producing sulphur from a sour gas containing H2 S, the said complex comprising a sulphur plant and then an oxidation and hydrolysis unit followed by a purification unit
DE4109892C2 (en) * 1991-03-26 1994-12-22 Metallgesellschaft Ag Process for removing hydrogen sulfide from gases using activated carbon
US5494879A (en) * 1993-02-26 1996-02-27 Regents, University Of California Catalyst for the reduction of sulfur dioxide to elemental sulfur
FR2727101B1 (en) * 1994-11-17 1996-12-20 Elf Aquitaine PROCESS FOR OXIDIZING SULFUR DIRECTLY BY CATALYTIC H2S CONTAINED IN LOW CONCENTRATION IN A GAS AND CATALYST FOR CARRYING OUT THIS PROCESS
FR2740703B1 (en) * 1995-11-03 1997-12-05 Elf Aquitaine PROCESS FOR THE TOTAL REMOVAL OF THE SULFUR COMPOUNDS H2S, SO2, COS AND / OR CS2 CONTAINED IN A RESIDUAL GAS OF SULFUR FACTORY, WITH RECOVERY OF THE SAME COMPOUNDS IN THE SULFUR FORM
FR2740704B1 (en) * 1995-11-03 1997-12-26 Elf Aquitaine PROCESS FOR THE QUASI TOTAL ELIMINATION OF THE SULFUR H2S, SO2, COS AND / OR CS2 COMPOUNDS CONTAINED IN A RESIDUAL SULFUR PLANT GAS, WITH RECOVERY OF THE SAID COMPOUNDS IN THE FORM OF SULFUR
DE102009006384A1 (en) * 2009-01-28 2010-08-19 Uhde Gmbh Method for supplying an entrainment gasification reactor with fuel from a reservoir
US9433893B2 (en) 2014-02-28 2016-09-06 Fluor Corporation Configurations and methods for advanced oxygen enrichment for sulfur recovery
US9701537B1 (en) * 2016-01-05 2017-07-11 Saudi Arabian Oil Company Claus process for sulfur recovery with intermediate water vapor removal by adsorption

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GB1211033A (en) * 1968-01-11 1970-11-04 Ontario Research Foundation Treatment of waste gases
NL7006260A (en) * 1969-05-01 1970-11-03
US3702884A (en) * 1970-05-22 1972-11-14 Amoco Prod Co Method for reducing sulfur compounds in sulfur plant effluent
US4035474A (en) * 1976-03-01 1977-07-12 Standard Oil Company (Indiana) CBA for Claus tail gas cleanup
DE2648190C3 (en) * 1976-10-25 1980-02-21 Metallgesellschaft Ag, 6000 Frankfurt Process for the production of sulfur by the Claus process
US4430317A (en) * 1981-03-02 1984-02-07 Standard Oil Company (Indiana) Low temperature Claus process with water removal
FR2511663A1 (en) * 1981-08-19 1983-02-25 Elf Aquitaine CATALYTIC PROCESS FOR THE PRODUCTION OF SULFUR FROM A GAS CONTAINING H2S
US4507275A (en) * 1983-08-30 1985-03-26 Standard Oil Company (Indiana) Process for producing and recovering elemental sulfur from acid gas

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CA1281886C (en) 1991-03-26
DE3690569T1 (en) 1987-11-19
DE3690569C2 (en) 1998-10-01
GB2192871B (en) 1990-08-15
GB8714267D0 (en) 1987-07-22
FR2589141B1 (en) 1987-12-11
GB2192871A (en) 1988-01-27
JPS63501359A (en) 1988-05-26
FR2589141A1 (en) 1987-04-30

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