TW382617B - Process for the recovery of sulfur from SO2 containing gases - Google Patents

Process for the recovery of sulfur from SO2 containing gases Download PDF

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Publication number
TW382617B
TW382617B TW086109609A TW86109609A TW382617B TW 382617 B TW382617 B TW 382617B TW 086109609 A TW086109609 A TW 086109609A TW 86109609 A TW86109609 A TW 86109609A TW 382617 B TW382617 B TW 382617B
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sulfur
catalyst
claus
scope
gas
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TW086109609A
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Chinese (zh)
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Jan Adolf Lagas
Johannes Borsboom
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Stork Eng & Contractors Bv
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8603Removing sulfur compounds
    • B01D53/8612Hydrogen sulfide
    • B01D53/8615Mixtures of hydrogen sulfide and sulfur oxides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/02Preparation of sulfur; Purification
    • C01B17/04Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404Preparation 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
    • C01B17/0426Preparation 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 characterised by the catalytic conversion
    • C01B17/0439Preparation 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 characterised by the catalytic conversion at least one catalyst bed operating below the dew-point of sulfur
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/02Preparation of sulfur; Purification
    • C01B17/04Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404Preparation 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
    • C01B17/0456Preparation 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention relates to a process for recovering sulfur from an SO2 containing gas stream through catalytic conversion thereof to elemental sulfur, comprising converting SO2 and H2S in the presence of liquid sulfur and a catalyst system based on a heterogeneous catalyst which catalyzes the Claus reaction, while as promoter for the Claus reaction a basic nitrogen compound is present in the liquid sulfur.

Description

A7 B7 五、發明說明 經濟部智慧財產局貝工消費合作社印製 修正 8& 9. 2 3] 太革 用 T3 * 硫中,然後從通過熱步驟的克勞斯入枓氣體中被抽回。1 8 · 87千莫耳/小時的作為空氣氧氣的02被供應到熱 步驟。另一1.40千莫耳/小時的作為空氣氧氣的〇2 被供應到SUPERCLAUS步驟。SUPERCLAUS步驟之後,尾氣中 H2S體積百分比為0 * 032%,而其中S02含量為 〇 · 189%體積,而其中02含量為0 · 50%體積。 來自SUPERCLAUS步驟數量為1 22千莫耳/小時,溫度為 1 3 0 °C,壓力為1 · 1 3巴(絕對)的尾氣被供應到圖 3所描述的觸媒床。來自接觸容器的液態硫通過該床。對 液態硫添加三級烷醇胺(TEA)。 然後硫返回接觸媒容器。循環流的數量被設定到使充 足的相對於S02的Hz S被供應到觸媒床,使HZ S : S 0 2的比例最小為1 : 1。 出口氣體中的H2 S濃度為0·015%體積,而其 中S0Z體積百分比為0 · 01 1%體積。反應器中Hz S 對硫的轉換率因此為92%,而S〇2轉換率為94%。 • 具備SUPERCLAUS反應器步驟、接著為此反應器步驟( 其中H2 S和S〇2之間的反應在液態硫中進行)克勞斯 工廠的總體硫回收故率超過99·5%。 圖式簡要說明 圖1為自二氧化硫中回'收硫的概要圖式; 圖2為經由克勞斯工廠而自二氧化硫中回收硫的另一 概要圖式;. -14- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁)A7 B7 V. Description of the invention Printed by the Shellfish Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Amendment 8 & 9. 2 3] Tai Ge uses T3 * sulfur, and is then withdrawn from the gas passed by Claus through the thermal step. 1 8 · 87 kmol / h of 02 as air oxygen was supplied to the thermal step. Another 1.40 kmol / h of O2 as air oxygen was supplied to the SUPERCLAUS step. After the SUPERCLAUS step, the volume percentage of H2S in the exhaust gas is 0 * 032%, and the content of S02 is 0. 189% by volume, and the content of 02 is 0. 50% by volume. The number of steps from SUPERCLAUS is 12 22 kmol / h, the temperature is 130 ° C, and the pressure is 1. 13 bar (absolute). The exhaust gas is supplied to the catalyst bed described in FIG. 3. Liquid sulfur from the contact vessel passes through the bed. Add tertiary alkanolamine (TEA) to liquid sulfur. The sulfur then returns to the contact medium container. The number of circulating flows is set so that a sufficient Hz S relative to S02 is supplied to the catalyst bed so that the ratio of HZ S: S 0 2 is at least 1: 1. The H2S concentration in the outlet gas was 0.015% by volume, and the SOZ volume percentage thereof was 0.011% by volume. The conversion rate of sulfur S to sulfur in the reactor was therefore 92%, while the conversion rate of S02 was 94%. • With the SUPERCLAUS reactor step, followed by this reactor step (where the reaction between H2S and S02 is performed in liquid sulfur), the overall sulfur recovery rate of the Claus plant exceeds 99.5%. Brief description of the drawings Figure 1 is a schematic diagram of recovering sulfur from sulfur dioxide; Figure 2 is another schematic diagram of recovering sulfur from sulfur dioxide through a Claus factory; -14- This paper is applicable to China Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page)

經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(/ ) 在很多方法中,例如石油精煉,純化天然氣以及從燐 或石油殘留物製造全成氣等,會釋出含硫氣體,特別是 H2 S。在可以使用上述氣體之前必須先除去此H2 S。 除去H 2 S的最重要的理由是預防在燃燒Η 2 S時會排放 出S〇2 。同時,H2 S是非常毒的氣體且有惡臭也是眾 所周知的。 業界最常用的方法是透過液態吸附劑除去HZ S,藉 此將H2 S形成濃縮形式,之後將H2 S氣體轉換成為無 害的硫元素。 另外,在多種情況下可能省略第一步驟,也就是使 H2 S形成濃縮形式,並直接將Hz S轉換成為硫元素。 將H2 S轉換成為硫元素的一種最廣為人知且最廣受 採用的方法是所謂克勞斯方法(Claus process)。此種克 勞斯方法傜以不同方式進行的,依照入料氣體中的H2 S 含量而定。依照最傳統的具體實施例,一部份H2 S經燃 燒成為S02,然後進一步與殘留的H2 S反應而形成硫 jil 素。 對克勞斯方法的詳細敘述可見於R.N. Maddox ’’Gas and Liquid Sweetening”; Campbell Petroleum Series (1977) 239-243頁以及 H.G. Paskall ^Capabilities of the Modified Claus Process”,pu b 1 . Western Research & Development, Calgary, Alberta, Canada ( 1 9 7 9 ) 〇 克勞斯方法傜以下列反應為基礎: 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閲讀背面之注意事項^^寫本頁)Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (/) In many methods, such as petroleum refining, purification of natural gas, and production of complete gas from plutonium or petroleum residues, sulfur-containing gases are released. Especially H2 S. This H2S must be removed before the above gases can be used. The most important reason for the removal of H 2 S is to prevent the emission of S02 when the plutonium 2 S is burned. At the same time, H2S is a very toxic gas and has a foul odor is well known. The most commonly used method in the industry is to remove HZ S through a liquid adsorbent, thereby converting H2 S into a concentrated form, and then converting the H2 S gas into a harmless sulfur element. In addition, in many cases, the first step may be omitted, that is, H 2 S is formed into a concentrated form, and Hz S is directly converted into sulfur. One of the most widely known and widely used methods to convert H2S to sulfur is the so-called Claus process. This Claus method is performed in different ways, depending on the H2S content in the feed gas. According to the most traditional specific embodiment, a part of H2S is burned to SO2, and then further reacts with the remaining H2S to form sulfur jil. A detailed description of the Claus method can be found in RN Maddox "Gas and Liquid Sweetening"; Campbell Petroleum Series (1977) pp. 239-243 and HG Paskall ^ Capabilities of the Modified Claus Process ", pu b 1. Western Research & Development, Calgary, Alberta, Canada (179 7) 〇 Klaus's method is based on the following reactions: This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the notes on the back first (^^ write this page)

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五、發明說明(/3 ) 圖3為說明本發明的較佳具體實施例。 中要元件符號說明 經濟部智慧財產局員工消費合作社印製 1 管線 2 反應器 3 觸媒 4 管線 5 管線 6 管線 7 冷卻器 8 泵 9 管線 1 0 克勞斯工廠 1 1 管線 1 2 管線 1 3 管線 1 4 管線 1 5 超级克勞斯工廠 1 6 管線 1 7 管線 1 8 管柱 1 9 管線 2 0 管線 2 1 泵 -15- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) .0裝 · d. 經濟部中央標準局員工消費合作社印製 A7 ___B7_ 五'發明説明(l) 2Hz S + 3〇2 分 2H2 0 + 2S02 (1) 4H2 S + 2S0Z<->4H2 〇 + 6/ nSn (2) 反應(1)和反應(2)造成以下總反應 2Hz S + 〇2;^>2H2 〇 + 2/ nSn ( 3 ) 適合處理H2 S含介於50和100%的氣體的傳統 克勞斯廠包括熱步驟(燃燒器,燃燒室,尾氣容器和硫 冷凝器),接著多値,一般是二或三値反應器步驟(氣體 加熱,填充著觸媒的反應器以及硫冷凝器)。在熱步驟産 生反應(1)和反應(2),而在反應器步驟中只有習知 為克勞斯反應的反應(2)。然而,在克勞斯方法中, H2 S並不完全被轉換成為硫元素,主要是因為克勞斯平 衡反應(2)並不反應完全。 所以會有某數量的H2 S和S02殘留。有鑑於愈來 愈駸格環保規定,燃燒上述殘留氣體的作法已不再被允許 。所諝尾氣必須進一步予以脱硫。尾氣方法對習知此 技藝人士傜熟知的,例如記載於B.G. Goar, Tail Gas Clean-up Processes, a review, paper at the 33rd Annual Gas Conditioning Conference , Norman, Oklahoma, March 7- 9, 1 9 8 3 〇 最著名者且至今是最有效的為尾氣脱硫的方法為 SCOT 方法在 Maddox 之” Gas and liuqid sweetening” (1977)有記載。SCOT方法達到99. 8至99. 9% 的硫回收率。SCOT方法的缺點是過高的投資成本以及 -4- 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X 297公釐) (請先閲讀背面之注意事項\$^寫本頁)V. Description of the Invention (/ 3) FIG. 3 illustrates a preferred embodiment of the present invention. The description of the symbol of the essential components is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 1 Pipeline 2 Reactor 3 Catalyst 4 Pipeline 5 Pipeline 6 Pipeline 7 Cooler 8 Pump 9 Pipeline 1 0 Claus Factory 1 1 Pipeline 1 2 Pipeline 1 3 Pipeline 1 4 Pipeline 1 5 Super Klaus Plant 1 6 Pipeline 1 7 Pipeline 1 8 String 1 9 Pipeline 2 0 Pipeline 2 1 Pump -15- This paper size applies to China National Standard (CNS) A4 (210 X 297 male) (%) (Please read the notes on the back before filling in this page) .0 Pack · d. Printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 ___B7_ Five' Invention Description (l) 2Hz S + 3〇2 points 2H2 0 + 2S02 (1) 4H2 S + 2S0Z <-> 4H2 〇 + 6 / nSn (2) Reaction (1) and reaction (2) cause the following total reaction 2Hz S + 〇2; ^ > 2H2 〇 + 2 / nSn ( 3) A conventional Claus plant suitable for processing H2S containing between 50 and 100% gas includes a thermal step (burner, combustion chamber, exhaust gas container, and sulfur condenser) followed by multiple reactions, typically two or three reactions Reactor step (gas heating, reactor filled with catalyst, and sulfur condenser). Reaction (1) and reaction (2) occur in the thermal step, while only reaction (2), which is known as the Claus reaction, is used in the reactor step. However, in the Claus method, H2S is not completely converted to sulfur, mainly because the Claus equilibrium reaction (2) does not react completely. So there will be a certain amount of H2 S and S02 remaining. In view of the increasingly stringent environmental protection regulations, the practice of burning the above-mentioned residual gases is no longer allowed. The exhaust gas must be further desulfurized. The exhaust gas method is well known to those skilled in the art, such as documented in BG Goar, Tail Gas Clean-up Processes, a review, paper at the 33rd Annual Gas Conditioning Conference, Norman, Oklahoma, March 7- 9, 1 9 8 3 〇The most famous and by far the most effective method for exhaust gas desulfurization is the SCOT method described in Maddox's "Gas and liuqid sweetening" (1977). The SCOT method achieves a sulfur recovery of 99.8 to 99.9%. The disadvantages of the SCOT method are the high investment cost and the -4- paper size applicable to the Chinese National Standard (CNS) A4 size (210 X 297 mm) (Please read the precautions on the back first \ $ ^ write this page)

+° A7 B7 丨修正, 本年月日 五、發明說明(/〆) 2 2 冷卻器 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部中央標準局員工消費合作社印製 A7 __B7___ ,五、發明説明(3 ) 過高的能量消粍。 另一種提高克勞斯方法的效率的方法為SUPERCLAUS® 方法。此方法可以使克勞斯方法的效率從94 - 97%提 高到9 9 %以上。 SIIP E R C L A U S ® 方法記載於” S U P E R C L A U S ® , t h e a n s w e r to Claus plant limitations” pub 1 . 38th Canadian Chem. Eng. Conference, Oct, 25,1 9 88 , Edmonton, Alberta, Canada» SUPERCLAUS®方法的成本比其它習知尾氣處理方法低 。熱步驟及克勞斯反應器步驟的反應(2)係在過量H2 S 之下作業的,所以在來自最後克勞斯反應器步驟的氣體中 ,H2 S含量約為1%體積,S02含量約為0. 02% 體積。在連接下游反窿器步驟中,在使用特殊選擇性氣化 觸媒之下,H2 S依以下反應選擇性地氣化成為硫元素 2 H z S + 〇z ^2Hz O + 2/ nSn (4) 這些觸媒在歐洲專利0242920和0409353 中有記載。 來自SUPERLCAUS®反應器步驟的尾氣仍然含有H2 S 含量為0. 02%體積及約0. 2%體積的SOz ,以及 0. 2至0. 5%體積的02。 另一種克勞斯方法在美國專利4, 280, 990 (Jagodzinski等人)中有記載,克勞斯反應(2)傷在標準 克勞斯觸媒存在下於高壓之下在液態硫中進行,而沒有冷 -5- (請先路讀背面之注意事項+ ° A7 B7 丨 Amendment, this month and day 5. Description of the invention (/ 〆) 2 2 Cooler (Please read the precautions on the back before filling out this page) Printed on the paper. Applicable to the paper by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs China National Standard (CNS) A4 (210 X 297 mm) A7 __B7___ printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention (3) Excessive energy dissipation. Another method to increase the efficiency of the Claus method is the SUPERCLAUS® method. This method can increase the efficiency of the Claus method from 94-97% to more than 99%. The SIIP ERCLAUS ® method is described in "SUPERCLAUS ®, the answer to Claus plant limitations" pub 1. 38th Canadian Chem. Eng. Conference, Oct, 25, 1 9 88, Edmonton, Alberta, Canada The exhaust gas treatment method is low. The reaction in the thermal step and the Claus reactor step (2) is operated under excess H2S, so in the gas from the last Claus reactor step, the H2S content is about 1% by volume and the S02 content is about 02% volume. In the step of connecting the downstream reactor, under the use of a special selective gasification catalyst, H2 S is selectively gasified to sulfur element 2 H z S + 〇z ^ 2Hz O + 2 / nSn (4 These catalysts are described in European patents 0429920 and 0403353. The tail gas from the SUPERLCAUS® reactor step still contains an SO2 content of 0.02% by volume and about 0.2% by volume of SOz, and 0.2 to 0.5% by volume of 02. Another Claus method is described in U.S. Patent 4,280,990 (Jagodzinski et al.). The Claus reaction (2) is performed in liquid sulfur under high pressure in the presence of a standard Claus catalyst, Without cold-5- (Please read the precautions on the back first

裝-- 本頁) 訂 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 經濟部中央標準局員工消费合作社印製 A7 B7 五、發明説明(<f ) 凝水。 在此方法中,熱步驟僳在5至50巴壓力下進行,之 後現有的氣體在相同壓力之下通過充填著觸媒的反應器。 H2 S和S02之間的反應因此發生在5至50巴的壓力 ,藉此硫在觸媒上凝結。液態硫通過觸媒床而循環發散反 應熱。來自熱步驟的氣體含有約7. 9%體積的H2 S和 3. 95% 體積的 S02 ,所以 S : S02 為 2 : 1 。設定第一床内的反應器溫度,使出口溫度為2 7 5¾。 第二床的出口溫度被設定在1 9 51C。從本方法的實例當 中,可以推衍到這些高百分比的H 2 S和S Ο 2在提高壓 力之下的轉換率會更好。或者,相同的方法也建議用於克 勞斯尾氣的脱硫。在此情況下,克勞斯尾氣體被置於很高 的壓力之下。 用於克勞斯方法氣體和克勞斯尾氣體的脱硫方法的缺 點分別是H2 S氣體(克勞斯入料氣體)和空氣的壓縮機 的高成本以及高成本的尾氣壓縮機,這些壓縮機.的高能量 消耗,有毒Hz S氣體外漏於壓縮機和其它工廠裝置的危 險,以及這些壓縮機的操作可靠性。 這也就是為什麼此方法至今從未應用於商業上。在美 國專利第4, 280, 990所述方法中,僳使用標準的 克勞斯觸媒。在上述專利的時期中,活性氣化鋁傜作為克 勞斯觸媒,其表面積約為300m2 / gr,平均孔徑約 為50A。此觸媒也記載於美國專利4, 280, 9 9 0 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先蚱讀背面之注意事項t寫本頁) d裝· 寫本 訂 經濟部中央標準局員工消費合作社印製 A7 B7 ' 五、發明説明(亡) 中。 在開發此方法的年代中,克勞斯反應器内慣用標準氣 化鋁觸媒。因此沒有進行其它型態觸媒的任何研究,或者 觸媒尚未問世,又或者尚未開發出來。也没有從事任何關 於依H2 S和SOz濃度而定的工作壓力上的研究。大部 份敘述於美國專利4, 280, 990的試驗偽使用 2· 5%體積Hz S和1. 2%體積S02。 美國專利3, 447, 903掲示另一種方法,也是 以使用液態硫的克勞斯方法的應用為基礎。依照此方法, 反應係在撤量鹼性氮化合物存在下行促進作用。從實例中 看出約使用1至5 0 p pm數量的此化合物。此方法也從 未作商業應用。 本發明的目的是提供一種回收尾氣的硫的方法,藉此 儘可能除去S〇2和^{2 S。更待別的是,本發明的目的 是提供一種方法,藉以改善傳統回收硫的方法,而達到高 轉克 U 劑 相換 媒進 t 進 多轉 觸促 ^ 促 定的 由以 Μ 的 持素 .經及 Μ 應 用元 並硫 U 反 使硫 硫態 Μ 斯 明成 收液 W 勞 發換 回在 ^ 克 本轉 。流括 U 為 現善 率氣包 Ρ 作 發改 效 2 法 而。經顯 收0方 } , 物已明 回 3其0113合 ,到 模含 ,ti2 化是達 規從法acH 氮的以 業種方re和性訝可 Η 一的 2 鹼驚, 的供素uso 有到時 %提元las 中感劑 5 明硫(C換硫人進 .發為應轉態令促 9 本成反下液很的 9 而斯在, 媒 於換勞存時 觸 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) 五、發明説明(έ ) 率。如此,使用液態硫作為反應媒介一直以來都為人所知 。然而,只有使用本發明方法才有可能在低壓,也就是大 氣壓或略高於大氣壓之下進行此方法。 此方法可在多種方式下進行。重要的是觸媒直接與由 外部充分供應的液態硫接觸。較佳的是此液態已經含有卽 將被轉換的H2 S,因為轉換效率明顯更高。所以,可能 以供應氣相的Hz S和S0Z,但是會降低效率。 在本發明的方法中,H2 S和S02反應成為硫和水 僳以H2 S : S02為2 : 1及在合適觸媒及液態硫存在 下,較佳的壓力為1和5巴之間,溫度較佳在120 υ和 250Ϊ:之間進行的。 在本發明的方法中,合適觸媒具備大巨孔(roocropore) 結構。這些包括具備小撤孔和大體積中形和巨孔的活化氧 化鋁。這些活化氣化鋁所具備的中形,巨形和超結構,其 中含有多於65%總體孔體積。也可以使用具備這些作為 載體材料的觸媒,此支撐材料已浸漬活性材料,例如金屬 氧化物。這些觸媒通常被稱為〃促進觸媒〃。 一般而言,可以説那些觸媒可以有用地催化克勞斯反 應。除了已經討論過的活化氣化鋁觸媒之外,其它用於此 反應的習知觸媒也適合使用,例如二氣化鈦,以及在載體 上的金屬氣化物。(Installation-this page) The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm). Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. In this method, the thermal step 僳 is performed at a pressure of 5 to 50 bar, after which the existing gas passes through the reactor filled with catalyst under the same pressure. The reaction between H2 S and S02 therefore takes place at a pressure of 5 to 50 bar, whereby the sulfur condenses on the catalyst. The liquid sulfur passes through the catalyst bed to circulate the heat of reaction. The gas from the thermal step contains about 7.9% by volume of H2S and 3.95% by volume of S02, so S: S02 is 2: 1. The reactor temperature in the first bed was set so that the outlet temperature was 2 7 5¾. The outlet temperature of the second bed was set at 1951C. From the examples of this method, it can be deduced that these high percentages of H 2 S and S 0 2 will have better conversion rates under increased pressure. Alternatively, the same method is recommended for the desulfurization of Claus exhaust gas. In this case, Claus tail gas is placed under high pressure. The disadvantages of desulfurization methods for Claus gas and Claus tail gas are the high cost of H2S gas (Claus feed gas) and air compressors, and the high cost of tail gas compressors. These compressors High energy consumption, the danger of toxic Hz S gas leaking out of compressors and other plant equipment, and the operational reliability of these compressors. This is why this method has never been used commercially. In the method described in U.S. Patent No. 4,280,990, a standard Claus catalyst is used. During the period of the above patent, active gasified aluminum hafnium was used as a Claus catalyst, and its surface area was about 300 m 2 / gr and the average pore size was about 50A. This catalyst is also described in U.S. Patent 4,280,990. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). (Please read the precautions on the back first and write this page.) D Ordered by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs to print A7 B7 'V. Invention Description (Dead). In the years when this method was developed, standard Claus gasified aluminum catalysts were used in Claus reactors. Therefore, no research has been conducted on other types of catalysts, or the catalysts have not yet come out or have not yet been developed. Nor has any research been done on working pressures depending on H2S and SOz concentrations. Most of the tests described in U.S. Patent No. 4,280,990 use 2 · 5% volume Hz S and 1.2% volume S02. U.S. Patent 3,447,903 shows another method which is also based on the application of the Claus method using liquid sulfur. According to this method, the reaction is promoted in the presence of withdrawal of basic nitrogen compounds. It is seen from the examples that this compound is used in an amount of about 1 to 50 ppm. This method has never been used commercially. An object of the present invention is to provide a method for recovering sulfur in exhaust gas, thereby removing S02 and ^ {2S as much as possible. What's more, the purpose of the present invention is to provide a method to improve the traditional method for recovering sulfur, so as to achieve a high-return-gram U-agent phase-change medium, t-to-multi-turn-to-promote, etc. After the application of sulfide and sulfide, the sulfide and sulfide M smine solution were collected and replaced by W Laofa. Include U for the purpose of improving the efficiency of the air bag P for development and reform 2 method. After receiving 0 square}, the material has been cleared back to 3, 0113, to the mold contains, ti2 is the standard method of acH nitrogen and the nature of the 2 basic startle, the supply of uso has When the percentage of las las in the sensation 5 bright sulfur (C for sulfur into the people. Issued as a response to the order to promote the 9 into the liquid 9 is very low, and so on, the media when the labor changes, this paper applies China standards National Standard (CNS) A4 specification (210X 297 mm) 5. Invention description rate. In this way, the use of liquid sulfur as a reaction medium has been known for a long time. However, it is only possible to use low pressure at low pressure using the method of the present invention. That is, the method is carried out at atmospheric pressure or slightly above atmospheric pressure. This method can be carried out in a variety of ways. It is important that the catalyst directly contacts the liquid sulfur that is sufficiently supplied from the outside. It is preferred that this liquid already contains tritium The converted H2 S, because the conversion efficiency is significantly higher. Therefore, it is possible to supply the gas phase Hz S and S0Z, but it will reduce the efficiency. In the method of the present invention, H2 S and S02 react to become sulfur and water hydration with H2 S: S02 is 2: 1 and in the presence of a suitable catalyst and liquid sulfur, The preferred pressure is between 1 and 5 bar, and the temperature is preferably between 120 υ and 250 Ϊ: In the method of the present invention, suitable catalysts have a roocropore structure. These include having a small withdrawal Activated alumina with pores and large volumes of meso and macro pores. The meso, macro and superstructures of these activated gasified aluminum contain more than 65% of the total pore volume. It is also possible to use those with these as support materials Catalysts, this support material has been impregnated with active materials, such as metal oxides. These catalysts are often referred to as 〃promoting catalysts〃. In general, it can be said that those catalysts can effectively catalyze the Claus reaction. Except as already discussed Besides conventional activated gasification aluminum catalysts, other conventional catalysts for this reaction are also suitable for use, such as titanium digasification, and metal vapors on a support.

已經發現當水蒸氣在低於5巴的壓力下被輸入到即將 處理的氣體,或者當水蒸氣存在於氣體中時,會促進H2 S —8 - 本紙張尺度適用中國國家標準(CNS )八4規格(210X297公釐) 請 kj 閱 背 意 事 項 寫 本 頁 經濟部中央標準局員工消費合作社印製 解 氣 體 A7 B7 五、發明説明(*]) 和SO2之間的反應而成為硫和水。同時,經由適當的選 擇停留時間,可以大大的影響效率。 也已經確定的在低於5巴的壓力之下,當硫中存在有 硫化物時,這些會以與H2 S相同的方式'齒S〇2反應成 為硫和水。發現當氣體含氣時,此氣幾乎不會與H2 S或 存在的硫反應而形成SOz 。 本發明方法的主要優點是在低壓力之下反應,因此 決了美國專利4, 280, 99◦方法的所有缺點。 在本發明方法中,也可以將H2 S氣體添加到這些 體中或者先將H2 S溶解到液態硫中而處理含S02氣 請 閲_ 讀-背_ 之-注 意-事 項 ί 經濟部中央標準局員工消費合作社印製 在本 ,會得到 轉換S 0 Η 2 S依 很令 有少量的 水的轉換 上完金平 合適 Μ E A , ),氨, 較佳 發明方法中, S 0 2的較髙 Z所需要Η 2 然存於硫中, 人感到驚訝的 鹼性氮化合物 效率大大獲得 衡 鹼性氮化合為 D G A , D E 銨鹽,芳香氮 者,使用三級 已確定當先將S 轉換率,並提供一項 S大大簡化,因為溶 之後可加入Hz S而 是,發現到當本發明 時,Hz S 和 S〇2 改善,甚至到在設定 胺(例如烷基胺), A , D I P A , M D 化合物(例如喹啉, 烷醇胺,因為其不會 -9- 溶於液態硫時 使控制所需要 解的未使用 載入硫。 方法中的硫含 反應成為硫和 溫度達到實際 烷醇胺(例如 E A . TEA 嗎啉)。 形成高沸點的 訂 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) A7 B7 五、發明説明(7 ) 氨基磺酸鹽,且因為這些胺相當便宜。 本發明在參考以下圖式會更明瞭。在圖1中,經由管 線1將含H2 S和S〇2的氣體入料到有觸媒3的反應器 2 〇 經由管線4供應液態硫,與入料氣體一起通過觸媒。 液態硫偽經由Hz S和SOz的反應而在觸媒床産生。It has been found that when water vapor is input to the gas to be treated at a pressure of less than 5 bar, or when water vapor is present in the gas, it will promote H2 S — 8-This paper applies the Chinese National Standard (CNS) 8-4 Specifications (210X297 mm) Please read the note and write this page. The Central Government Bureau of the Ministry of Economic Affairs printed the decomposed gas A7 B7. 5. The description between the invention (*)) and SO2 becomes sulfur and water. At the same time, efficiency can be greatly affected by proper choice of dwell time. It has also been determined that under pressures below 5 bar, when sulfides are present in the sulfur, these will react to sulfur and water in the same way as H2S. It was found that when the gas contains gas, the gas hardly reacts with H2S or the sulfur present to form SOz. The main advantage of the method of the present invention is that it reacts under low pressure and therefore resolves all the disadvantages of the method of U.S. Patent 4,280,99. In the method of the present invention, H2S gas can also be added to these bodies or H2S can be dissolved in liquid sulfur to process S02-containing gas. Please read _ read-back _ of-note-matters-Central Bureau of Standards, Ministry of Economic Affairs Employee consumer cooperatives printed on this, will get the conversion S 0 Η 2 S according to the order with a small amount of water conversion Jinping suitable M EA,), ammonia, in the preferred invention method, S 0 2 is better than 髙 Z It needs Η 2 to be stored in sulfur. People are surprised at the efficiency of basic nitrogen compounds. The basic nitrogen compounds are DGA, DE ammonium salts, and aromatic nitrogen. The third conversion rate has been determined. The term S is greatly simplified because Hz S can be added after dissolution. It is found that when the present invention, Hz S and So are improved, even when setting amines (such as alkylamines), A, DIPA, MD compounds (such as Quinoline, alkanolamine, because it will not -9- dissolve unused loaded sulfur needed to control the solution when dissolved in liquid sulfur. The sulfur in the method reacts to sulfur and the temperature reaches the actual alkanolamine (such as EA. TEA morpholine). Forms a high boiling point The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 V. Description of the invention (7) Sulfamate, and because these amines are quite cheap. The present invention will be made clearer by referring to the following drawings. In FIG. 1, a gas containing H2S and S02 is fed to a reactor 2 having a catalyst 3 via a line 1 and a liquid sulfur is supplied via a line 4 to pass through the catalyst together with a feed gas. The reaction of Hz S and SOz is generated in the catalyst bed.

Hz S和S02之間反應之後,出口氣體經由管線5排放 請 先 閲^ 讀 背 之- 注After the reaction between Hz S and S02, the outlet gas is discharged through line 5. Please read ^ read back-note

I 經濟部中央標準局員工消費合作社印製 液 反應熱 器2 〇 在 體經由 接著兩 克 驟和反 媒反應 1 3被 硫經由 而形成 管線5 所形成 由管線 態硫從反 。在栗8 所形成的 圖2中, 管線1被 値觸媒反 勞斯反應 應器步驟 器步驟仍 供應到含 管線4被 硫之後, 離開反應 的硫經由 1 4予以 應器經 協助之 硫經由 含有超 供應到 應步驟 所需要 所形成 然含有 有觸媒 供應。 尾氣經 器,且 管線9 添加。 由管線6而到冷郤器7 ,在此排放 下,硫經由管線4被再循環到反應 管線9被排放。 過90%體積H2 S的含Hz S氣 克勞斯廠10,其包括熱步驟以及 〇 的空氣經由管線1 1供應。在熱步 的硫經由管1 2排放。來自第二觸 Η 2 S和S 0 2的尾氣經由管線 3的反應器2中。由觸媒床,液態 在H2 S和S〇2在觸媒床中反應 由管線5離開反應器。液態硫經由 經由冷卻器7被循環到反應器2。 被排放。或者,鹼性氮化合物可經 -10 訂 本纸張尺度適用中國國家標準(CNS ) A4規格(210 X 297公釐) A7 B7 五、發明説明(7 ) 圖3偽敘述本發明方法的較佳具體實施例,經由管線 1將含Η 2 S氣體供應到克勞斯廠1 〇 ,其包括熱步驟, 接著是兩個觸媒反應步驟。 克勞斯反應所需要的空氣經由管線1 1供應。在熱步 驟和反應器步驟所形成的硫經由管12排放。來自第二觸 媒反應器步驟仍然含有Hz S和S02的尾氣經由管線 1 3被供應到SUPERCLAUS廠1 5。 經由管線16供應選擇性氧化的空氣,同時經由管線 17排放液態硫。尾氣傜經由管線13供應到含觸媒3的 反應器2。透過觸媒床,經由管線4供應液態硫。 此液態硫來自管柱18,在其中的硫已經與經由克勞 斯廠管線1的含H2 S的氣體接觸。在管柱1 8中,液態 硫已經合併一部份來自氣體的H2 S。在溶入液態硫的 H2 S和S02在觸媒床中反應成為硫之後,尾氣經由管 線5離開反應器。液態硫經由管線6離開反應器2,且在 泵8協肋之下經由管線1 9循環到管柱1 8。所形成的硫 溶於管線9。 經濟部中央標準局員工消費合作社印製 在管柱中,硫再度吸收H2 S,並經由管線20,泵 2 1 ,冷卻器2 2和管線4再度供應到反應器2。視需要 ,經由管線1 4 ,可將鹼性氮化合物供應到液態硫。 本發明將在以下實例中進一步解說。 賁例1 -11- 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X 297公釐) 經濟部中央標準局員工消費合作社印製 A7 , _B7 _______五、發明^明((。) 使用如圖2所述的工廠,在有二種觸媒步驟的克勞斯 工廠中,進行克勞斯反應。對熱步驟供應含90. 〇%體 積H2 S的克勞斯氣體,相當於36. 0千莫耳/小時, 3. 5%體積C02, 2. 0%體積烴和4. 5%體積 H2 0和作為空氣氣氣的19. 5千莫耳/小時〇2 。第 二觸媒步驟之後尾氣中HZ S體積百分比為〇. 5 8%體 積,而其中S〇2含量為0. 29 %體積,其中水含量為 33. 2%體積。克勞斯廠的硫回收效率為94%。 將數量為120壬莫耳/小時、溫度為15010和颳 力為1. 13巴的尾氣體供應到圖2的觸媒床。觸媒3為 具備高度中形和巨孔結構的活化氣化鋁。數量為5 〇立方 公尺/小時、溫度為15 ου的液態硫被循環過觸媒床。 將所産生的方法反應熱於冷卻器中排放而使循環硫的溫度 保持固定。為了不造成反應器内硫水平升的太高,不時從 条統排放一些硫。觸媒床之後氣體中H2 S體積百分比為 /// 0. 188%,而其中S02體積百分比為0. 088% 。反應器中Hz S轉換成硫的轉換率為68%,而S〇2 為 7 0 %。 依照此反應器步驟(Η 2 S和S ◦ 2間的反應以液態 硫發生)反應的克勞斯工廠的總硫回收效率為97. 7% 以上。 請 先 閱- 背I Printed by the Central Bureau of Standards of the Ministry of Economic Affairs, the consumer cooperative printed a liquid reactor 2 〇 In-vivo via the next two grams and the anti-reaction 1 3 Passed by sulfur to form the pipeline 5 formed by the pipeline state sulfur from the reverse. In Figure 2 formed by chestnut 8, line 1 is still supplied to the catalyst-containing anti-Rolls reactor reactor step after the sulfur containing line 4 is sulfurized, and the sulfur leaving the reaction is supplied to the reactor through the sulfur assisted by 14 Contains a supply of super-supply to the required step and then contains a catalyst supply. Exhaust gas passes through the pipeline, and line 9 is added. From the line 6 to the cooler 7, the sulfur is recycled to the reaction line 9 via the line 4 and discharged. Hz S gas containing 90% by volume of H2S. Claus plant 10, which includes a thermal step and air is supplied via line 11. Sulfur in the thermal step is discharged via pipe 12. The tail gas from the second thorium 2 S and S 0 2 passes through the reactor 2 of the line 3. From the catalyst bed, the liquid reacts in H2S and S02 in the catalyst bed and leaves the reactor through line 5. Liquid sulfur is circulated to the reactor 2 via a cooler 7. Was discharged. Alternatively, the basic nitrogen compounds can be applied to the paper size of -10. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) A7 B7 V. Description of the invention (7) Figure 3 is a pseudo description of the method of the present invention. In a specific embodiment, the Krypton 2 S-containing gas is supplied to the Claus plant 10 via line 1, which includes a thermal step, followed by two catalyst reaction steps. The air required for the Claus reaction is supplied via line 11. The sulfur formed in the thermal step and the reactor step is discharged via the pipe 12. The tail gas from the second catalyst reactor step still containing Hz S and S02 is supplied via line 13 to the SUPERCLAUS plant 15. The selectively oxidized air is supplied through a line 16 while liquid sulfur is discharged through a line 17. The exhaust gas radon is supplied to the reactor 2 containing the catalyst 3 via a line 13. Liquid sulfur is supplied through the catalyst bed via line 4. This liquid sulfur comes from the pipe string 18, where the sulfur has been in contact with the H2S-containing gas passing through the Claus plant line 1. In column 18, liquid sulfur has merged a portion of the H2S from the gas. After H2S and S02 dissolved in liquid sulfur react in the catalyst bed to become sulfur, the tail gas leaves the reactor through line 5. Liquid sulfur leaves reactor 2 via line 6 and is circulated to line 18 via line 19 under the pump 8 ribs. The sulfur formed is dissolved in line 9. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs In the pipe column, sulfur absorbs H2S again and is supplied to reactor 2 via line 20, pump 2 1, cooler 2 2 and line 4 again. Optionally, basic nitrogen compounds can be supplied to the liquid sulfur via line 1 4. The invention will be further illustrated in the following examples. Example 1 -11- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) Printed by A7, _B7 _______, the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs As shown in the plant shown in Figure 2, in the Claus plant with two catalyst steps, the Claus reaction is performed. The heat step is supplied with Claus gas containing 90. 0% by volume H2S, which is equivalent to 36. 0 kmol / h, 3.5% by volume CO2, 2.0% by volume hydrocarbons and 4.5% by volume H2 0 and 19.5 kmol / h as air gas. Second catalyst step After that, the volume percentage of HZ S in the tail gas was 0.5 8% by volume, and the content of S02 was 0.29% by volume, and the content of water was 33.2% by volume. The sulfur recovery efficiency of the Claus plant was 94%. Tail gas at a rate of 120 Nmol / h, a temperature of 15010, and a scraping force of 1.13 bar was supplied to the catalyst bed of Fig. 2. Catalyst 3 was activated gasified aluminum with a highly medium and macroporous structure. The amount of liquid sulfur of 50 m³ / h and temperature of 15 ου was circulated through the catalyst bed. The produced method was heated by reaction and discharged in the cooler, so that The temperature of the episulfur remains fixed. In order not to cause the sulfur level in the reactor to rise too high, some sulfur is emitted from the system from time to time. The volume percentage of H2S in the gas after the catalyst bed is // 188%, and The volume percentage of S02 is 0.088%. The conversion rate of Hz S to sulfur in the reactor is 68%, and S0 2 is 70%. According to this reactor step (the reaction between Η 2 S and S ◦ 2 The total sulfur recovery efficiency of the Claus plant in the reaction of liquid sulfur) is above 97. 7%. Please read first-back

I 之 注I note

訂 實例2 -12 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) 經濟部中央標準局員工消費合作社印製 A7 B7 ' 五、發明説明(f/ ) 在如圖2所述相同工廠中,芳香胺(喹啉)經由管線 1 4被加入循環硫。所供應喹啉的數量使到反應器的硫濃 度為500 ppm重量。 到熱步驟的克勞斯氣體與實例1所述者相同,但是現 在供應19. 85千莫耳/小時〇2作為空氣氣氣,以得Order example 2 -12 This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 'V. Description of the invention (f /) As shown in Figure 2 In the same plant, an aromatic amine (quinoline) was added to the circulating sulfur via line 14. The amount of quinoline supplied was such that the sulfur concentration in the reactor was 500 ppm by weight. The Claus gas to the thermal step is the same as described in Example 1, but now 19.85 kmol / h 02 is supplied as air gas to obtain

到在第二觸媒步驟之後尾氣中的H2 S —樣多的SOz 。 尾氣中Hz S和S02體積百分比各為〇. 46%,而其 中水含量為33. 0%體積。觸媒床之後尾氣中的Hz S 體積百分比為0. 046%,而其中S〇2體積百分比為 〇. 0 1 8%。反應器中H2 S對硫的轉換率因此為90% ,而S02則為96%。 依照此反應器步驟(Hz S和S02間的反應以液態 硫發生)反應的克勞斯工廠的總硫回收效率為99. 0% 以上。 實例3 在如圖3所述的工廠中,SURPERCLAUS反應器步驟被安 排在克勞斯工廠的第二觸媒步驟之後,使來自第二觸媒步 驟的氣體中的H2 S選擇性氣化成為硫。來自SUPERCLAUS 步驟的尾氣被供應到如圖3所描述的觸媒床。在氣體通過 熱步驟之前,克勞斯氣體首先與接觸容器内的硫氣以對流 方式;接阑。流進接觸容器的克勞斯人料氣體與實例1相同 。在接觸容器中,〇· 193千莫耳/小時的Hz S溶於 -1 3- 本纸張尺度適用中國國家標準(CNS ) A4規格(210 X 297公釐) (請先盹讀背面之注意事項^k本頁) 訂_ A7 B7 五、發明說明 經濟部智慧財產局貝工消費合作社印製 修正 8& 9. 2 3] 太革 用 T3 * 硫中,然後從通過熱步驟的克勞斯入枓氣體中被抽回。1 8 · 87千莫耳/小時的作為空氣氧氣的02被供應到熱 步驟。另一1.40千莫耳/小時的作為空氣氧氣的〇2 被供應到SUPERCLAUS步驟。SUPERCLAUS步驟之後,尾氣中 H2S體積百分比為0 * 032%,而其中S02含量為 〇 · 189%體積,而其中02含量為0 · 50%體積。 來自SUPERCLAUS步驟數量為1 22千莫耳/小時,溫度為 1 3 0 °C,壓力為1 · 1 3巴(絕對)的尾氣被供應到圖 3所描述的觸媒床。來自接觸容器的液態硫通過該床。對 液態硫添加三級烷醇胺(TEA)。 然後硫返回接觸媒容器。循環流的數量被設定到使充 足的相對於S02的Hz S被供應到觸媒床,使HZ S : S 0 2的比例最小為1 : 1。 出口氣體中的H2 S濃度為0·015%體積,而其 中S0Z體積百分比為0 · 01 1%體積。反應器中Hz S 對硫的轉換率因此為92%,而S〇2轉換率為94%。 • 具備SUPERCLAUS反應器步驟、接著為此反應器步驟( 其中H2 S和S〇2之間的反應在液態硫中進行)克勞斯 工廠的總體硫回收故率超過99·5%。 圖式簡要說明 圖1為自二氧化硫中回'收硫的概要圖式; 圖2為經由克勞斯工廠而自二氧化硫中回收硫的另一 概要圖式;. -14- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁)H2S in the tail gas after the second catalyst step-so much SOz. The volume percentages of Hz S and S02 in the exhaust gas are each 0.46%, and the water content thereof is 33.0% by volume. The volume fraction of Hz S in the exhaust gas after the catalyst bed is 0.0046%, and the volume fraction of S02 is 0.018%. The conversion rate of H2S to sulfur in the reactor is therefore 90%, while S02 is 96%. 0% 之间。 According to this reactor step (the reaction between Hz S and S02 occurs as liquid sulfur) the total sulfur recovery efficiency of the Claus plant is 99.0% or more. Example 3 In the plant shown in FIG. 3, the SURPERCLAUS reactor step is arranged after the second catalyst step of the Claus plant, and the H2S in the gas from the second catalyst step is selectively gasified to sulfur . The tail gas from the SUPERCLAUS step is supplied to the catalyst bed as described in FIG. 3. Before the gas passes through the thermal step, Claus gas first contacts the sulfur gas in the contact vessel in a convective manner; The Claus gas flowing into the contact vessel is the same as in Example 1. In the contact container, 193 kmol / h Hz S is dissolved in -1 3-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back first Matters ^ k this page) Order _ A7 B7 V. Description of the invention Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, amended 8 & 9. 2 3] Taige uses T3 * sulfur, and then from Claus through the thermal step Into the radon gas was withdrawn. 1 8 · 87 kmol / h of 02 as air oxygen was supplied to the thermal step. Another 1.40 kmol / h of O2 as air oxygen was supplied to the SUPERCLAUS step. After the SUPERCLAUS step, the volume percentage of H2S in the exhaust gas is 0 * 032%, and the content of S02 is 0. 189% by volume, and the content of 02 is 0. 50% by volume. The number of steps from SUPERCLAUS is 12 22 kmol / h, the temperature is 130 ° C, and the pressure is 1. 13 bar (absolute). The exhaust gas is supplied to the catalyst bed described in FIG. 3. Liquid sulfur from the contact vessel passes through the bed. Add tertiary alkanolamine (TEA) to liquid sulfur. The sulfur then returns to the contact medium container. The number of circulating flows is set so that a sufficient Hz S relative to S02 is supplied to the catalyst bed so that the ratio of HZ S: S 0 2 is at least 1: 1. The H2S concentration in the outlet gas was 0.015% by volume, and the SOZ volume percentage thereof was 0.011% by volume. The conversion rate of sulfur S to sulfur in the reactor was therefore 92%, while the conversion rate of S02 was 94%. • With the SUPERCLAUS reactor step, followed by this reactor step (where the reaction between H2S and S02 is performed in liquid sulfur), the overall sulfur recovery rate of the Claus plant exceeds 99.5%. Brief description of the drawings Figure 1 is a schematic diagram of recovering sulfur from sulfur dioxide; Figure 2 is another schematic diagram of recovering sulfur from sulfur dioxide through a Claus factory; -14- This paper is applicable to China Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page)

五、發明說明(/3 ) 圖3為說明本發明的較佳具體實施例。 中要元件符號說明 經濟部智慧財產局員工消費合作社印製 1 管線 2 反應器 3 觸媒 4 管線 5 管線 6 管線 7 冷卻器 8 泵 9 管線 1 0 克勞斯工廠 1 1 管線 1 2 管線 1 3 管線 1 4 管線 1 5 超级克勞斯工廠 1 6 管線 1 7 管線 1 8 管柱 1 9 管線 2 0 管線 2 1 泵 -15- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) .0裝 · d. A7 B7 丨修正, 本年月日 五、發明說明(/〆) 2 2 冷卻器 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)V. Description of the Invention (/ 3) FIG. 3 illustrates a preferred embodiment of the present invention. The description of the symbol of the essential components is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 1 Pipeline 2 Reactor 3 Catalyst 4 Pipeline 5 Pipeline 6 Pipeline 7 Cooler 8 Pump 9 Pipeline 1 0 Claus Factory 1 1 Pipeline 1 2 Pipeline 1 3 Pipeline 1 4 Pipeline 1 5 Super Klaus Plant 1 6 Pipeline 1 7 Pipeline 1 8 String 1 9 Pipeline 2 0 Pipeline 2 1 Pump -15- This paper size applies to China National Standard (CNS) A4 (210 X 297 male) (%) (Please read the precautions on the back before filling this page) .0 packs · d. A7 B7 丨 revised, this year, month and day 5. Description of the invention (/ 〆) 2 2 Cooler (Please read the precautions on the back first (Fill in this page again.) Printed on the paper by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Applicable to China National Standard (CNS) A4 (210 X 297 mm).

Claims (1)

本鲁 公 888 8 ABCD 正、一 修^Ben Lu Gong 888 8 ABCD Zheng, Yi Xiu ^ 六、申請專利範圍 1 ♦—種從含S〇2氣體中回收硫的方法,其係Μ觸媒轉 換成硫元素,其方法包括在液態硫及以促進克勞斯反應 (Claus reaction)的多相觸媒為基礎的觸媒系統存在下轉 換S02和H2 S,而作為克勞斯反應的促進劑時,液態 硫中有鹼性氮化合物,其中促進劑係選自包括胺,烷基胺 ,烷醇胺,氨,銨鹽和芳香氮化合物的組群,且觸媒可為 二氧化鈦、活性氧化鋁及被負載之金屬氧化物,且分別地 在1至5巴和1 20¾至2 5.0 °C之壓力和溫度下進行。 2 ·如申請專利範圍第1項的方法,其中促進劑係選自包 括單乙酵ρ,二乙醇胺,DGA,DIPA,M D E A和 三乙醇胺的組群。 3 .如申請專利範圍第1或2項的方法,其中使用三級胺 經濟部智慧財產局員工消費合作社印製 4 .如申請專利範圍第1項的方法,其中使用作為克勞斯 一活性多相觸媒的多孔氧化鋁或設有金屬氧化物的多孔氧 化鋁。 5 .如申請專利範圍第4項的方法*其中氧化鋁的表面積 v 至少為1 5 0平方公尺/克。 本紙張尺度逋用中國國家標準(CNS > A4规格(210X297公釐)6. Scope of Patent Application 1 ♦ A method for recovering sulfur from S02-containing gas, which is to convert the M catalyst into sulfur element. The method includes the method of promoting sulfur content in liquid sulfur and promoting the Claus reaction. In the presence of a catalyst-based catalyst system, S02 and H2S are converted. When used as an accelerator for the Claus reaction, there are basic nitrogen compounds in the liquid sulfur. The accelerator is selected from the group consisting of amines and alkylamines. Group of alkanolamines, ammonia, ammonium salts, and aromatic nitrogen compounds, and the catalysts can be titanium dioxide, activated alumina, and supported metal oxides, respectively at 1 to 5 bar and 1 20 ¾ to 2 5.0 ° C Under pressure and temperature. 2. The method according to item 1 of the scope of patent application, wherein the accelerator is selected from the group consisting of monoacetam, diethanolamine, DGA, DIPA, MDEA and triethanolamine. 3. If the method of applying for the scope of patents 1 or 2 is printed, which is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics of the Tertiary Amine 4. If the method of applying for the scope of patents, the method of claim 1 Catalyst-based porous alumina or porous alumina provided with a metal oxide. 5. The method according to item 4 of the scope of patent application *, wherein the surface area v of the alumina is at least 150 square meters per gram. This paper uses the Chinese national standard (CNS > A4 size (210X297 mm)) 本鲁 公 888 8 ABCD 正、一 修^Ben Lu Gong 888 8 ABCD Zheng, Yi Xiu ^ 六、申請專利範圍 1 ♦—種從含S〇2氣體中回收硫的方法,其係Μ觸媒轉 換成硫元素,其方法包括在液態硫及以促進克勞斯反應 (Claus reaction)的多相觸媒為基礎的觸媒系統存在下轉 換S02和H2 S,而作為克勞斯反應的促進劑時,液態 硫中有鹼性氮化合物,其中促進劑係選自包括胺,烷基胺 ,烷醇胺,氨,銨鹽和芳香氮化合物的組群,且觸媒可為 二氧化鈦、活性氧化鋁及被負載之金屬氧化物,且分別地 在1至5巴和1 20¾至2 5.0 °C之壓力和溫度下進行。 2 ·如申請專利範圍第1項的方法,其中促進劑係選自包 括單乙酵ρ,二乙醇胺,DGA,DIPA,M D E A和 三乙醇胺的組群。 3 .如申請專利範圍第1或2項的方法,其中使用三級胺 經濟部智慧財產局員工消費合作社印製 4 .如申請專利範圍第1項的方法,其中使用作為克勞斯 一活性多相觸媒的多孔氧化鋁或設有金屬氧化物的多孔氧 化鋁。 5 .如申請專利範圍第4項的方法*其中氧化鋁的表面積 v 至少為1 5 0平方公尺/克。 本紙張尺度逋用中國國家標準(CNS > A4规格(210X297公釐)6. Scope of Patent Application 1 ♦ A method for recovering sulfur from S02-containing gas, which is to convert the M catalyst into sulfur element. The method includes the method of promoting sulfur content in liquid sulfur and promoting the Claus reaction. In the presence of a catalyst-based catalyst system, S02 and H2S are converted. When used as a promoter for Claus reaction, there are basic nitrogen compounds in liquid sulfur. The promoter is selected from the group consisting of amines, alkylamines Group of alkanolamines, ammonia, ammonium salts, and aromatic nitrogen compounds, and the catalysts can be titanium dioxide, activated alumina, and supported metal oxides, respectively at 1 to 5 bar and 1 20 ¾ to 2 5.0 ° C Under pressure and temperature. 2. The method according to item 1 of the scope of patent application, wherein the accelerator is selected from the group consisting of monoacetam, diethanolamine, DGA, DIPA, MDEA and triethanolamine. 3. If the method of applying for the scope of patents 1 or 2 is printed, which is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics of the Tertiary Amine 4. If the method of applying for the scope of patents, the method of Clause 1 is used. Catalyst-based porous alumina or porous alumina provided with a metal oxide. 5. The method according to item 4 of the scope of patent application *, wherein the surface area v of the alumina is at least 150 square meters per gram. This paper uses the Chinese national standard (CNS > A4 size (210X297 mm)) 經濟部智慧財產局貝工消費合作社印製 A8 B8 C8 D8 六、申請專利範圍 6. ¾¾請專釦镰圍第5項的方法,其中直徑為5nm或 Μ下的孔中的孔體積(K氮測定)不超過1 2 3 體積。 7. 如申請專利範圍第1項的方法,其中H2 S溶於欣態 硫中,之後與SOz接觸。 8. 如申請專利範圍第7項的方法,其中H2 5含量至少 為0.5%體積的氣體與液態硫接觸’如此使一部BH2 S溶於硫中,之後供應含Hz S的氣流到克勞斯工廠,如 此使一部份H2 S經熱轉換成為SOz ,之後在一或多步 驟中,硫在觸媒克勞斯工廠中形成,得到氣體混合物在分 離硫之後被直接轉換,或視需要在選擇性步驟之後’在含 溶解H2S的液態硫中被轉換。 9 .如申請專利範圍第1項的方法,其中Η 2 S含量至少 為〇·25%體積的克勞斯工廠觸媒步驟的尾氣與流態硫 接觸,如此使至少一部份Hz S溶於液態硫中,之後,含 H2 S液態硫與含S02的氣體接觸,其係在K催化克勞 斯反應的多相觸媒為基礎的觸媒糸統存在下進行,或者是 作為克勞斯反應的促進劑時,液態硫中有鹼性氮化合物。 (請先1讀背面一之注意事項再填寫本頁)A8 B8 C8 D8 printed by the Shelley Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. The scope of patent application 6. ¾¾ Please deduct the method of sickle encirclement 5, where the pore volume in the pores with a diameter of 5nm or M (K nitrogen (Measurement) does not exceed 1 2 3 volume. 7. The method of claim 1 in which the H2S is dissolved in Hind sulfur and then contacted with SOz. 8. The method according to item 7 of the patent application, wherein a gas having an H2 5 content of at least 0.5% by volume is in contact with liquid sulfur 'so that a portion of BH2 S is dissolved in sulfur, and then a gas stream containing Hz S is supplied to Claus Factory, so that a part of H2S is thermally converted into SOz, and then in one or more steps, sulfur is formed in the catalyst Claus factory, and the gas mixture is directly converted after the sulfur is separated, or selected as needed This step is followed by conversion in liquid sulfur containing dissolved H2S. 9. The method according to item 1 of the scope of patent application, wherein the tail gas of the Claus step of the Claus plant catalyst with a Η 2 S content of at least 0.25% by volume is in contact with the fluid sulfur, so that at least a part of the Hz S is dissolved In liquid sulfur, H2 S-containing liquid sulfur is then contacted with S02-containing gas, which is carried out in the presence of a catalyst system based on a K-catalyzed heterogeneous catalyst, or as a Claus reaction When used as an accelerator, there are basic nitrogen compounds in the liquid sulfur. (Please read the precautions on the back first before filling in this page) 1 0 ·如申請專利範圃第1項的方法,其中促進劑的數量 2 (Μ液態硫重量為基準)為1和1〇〇〇 ppm之間,較 3 -2- Α8 Β8 C8 D8 申請專利範圍 佳在1和5 0 P D m之間。 1 1 ·如申請專利範圍第1項的方法,其中反應係在觸媒 粒子固定床或其它設有觸媒的本體中進行,其中這些粒子 或本體都被注人液態硫。 請 先 閱· 讀 背 面 之~ 注 意 事 項 再/ 裝 訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS ) A4现格(210X297公釐)1 0 The method according to item 1 of the patent application, wherein the number of accelerators 2 (based on the weight of the liquid sulfur) is between 1 and 1000 ppm, which is 3-2 Α8 Β8 C8 D8 The range is preferably between 1 and 50 PD m. 1 1 · The method according to item 1 of the scope of patent application, wherein the reaction is performed in a fixed bed of catalyst particles or other bodies provided with a catalyst, wherein these particles or bodies are injected with liquid sulfur. Please read and read the back of the book first ~ Note the matter Re / Binding Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is in accordance with Chinese National Standard (CNS) A4 (210X297 mm)
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