TWI781956B - 一種清潔黏液製造排氣的方法及用於該方法的催化劑 - Google Patents
一種清潔黏液製造排氣的方法及用於該方法的催化劑 Download PDFInfo
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Abstract
一種清潔來自黏液製造之排氣(基本上含有H2S及CS2)的方法包含使該氣體穿過含有直接氧化型催化劑(諸如V2O5/於二氧化矽上)之催化反應器以經由存在於氣體中之氧氣或經由向氣流中添加之氧氣來將該氣體中之H2S轉化為元素硫、SO2或其混合物。自來自催化反應器之廢氣移除元素硫及SO2,且將未經轉化之CS2再循環至黏液製造過程中。
Description
本發明係關於一種清潔來自黏液製造之排氣的方法及用於該方法的催化劑。
黏液嫘縈為再生纖維素之纖維;其在結構上與棉花類似,但可由多種植物(諸如大豆、竹子及甘蔗)製造。纖維素為具有經驗式(C6H10O5)n的β-D-葡萄糖單元之線性聚合物。為了製備黏液,用氫氧化鈉水溶液(典型地16%-19% w/w)處理溶解中之紙漿以形成「鹼金屬纖維素」,其具有大致式[C6H9O4-ONa]n。隨後用二硫化碳處理鹼金屬纖維素以形成黃原酸纖維素鈉:[C6H9O4-ONa]n+nCS2→[C6H9O4-OCS2Na]n
纖維素與經組合之硫的比率愈高,黃原酸纖維素之溶解度愈低。將黃原酸酯溶解於氫氧化鈉水溶液(典型地2%-5% w/w)中,且如由溶液黏度所指示,使其解聚合達到所需程度。解聚合(熟化或陳化)之速率取決於溫度,且受各種無機及有機添加劑(諸如金屬氧化物及氫氧化物)之存在影響。空氣亦影響熟化過程,此係因為氧氣造成解聚合。
嫘縈纖維藉由用無機酸(諸如硫酸)處理來由經熟化之溶液
製造。在此步驟中,使黃原酸酯基團水解以使纖維素再生且釋放二硫碳酸,該二硫碳酸稍後分解為二硫化碳及水:[C6H9O4-OCS2Na]2n+nH2SO4→[C6H9O4-OH]2n+2nCS2+nNa2SO4H2COS2→H2O+CS2
除再生纖維素以外,酸化得到硫化氫、硫及二硫化碳。洗滌由再生纖維素製成之線以移除殘餘酸。隨後藉由添加硫化鈉溶液來移除硫,且藉由用次氯酸鈉溶液漂白來使雜質氧化。
因此在黏液工業中,存在若干含有硫組分之排氣。常常回收含有高水準之H2S的物流且將其轉化為硫酸,如所提及,該硫酸為用於製造黏液纖維之原料。亦存在來源於煙霧收集之氣體,該等氣體含有少於2%之H2S及相關硫化合物。H2S之水準常常在200至2000ppm範圍內,且CS2水準為約200至1000ppm。在當今仍在運作之大部分黏液工廠中處理此更貧乏之排氣。在最常見過程中,將氣體傳送至鹼洗氣器(用NaOH操作)中,其中自氣相移除H2S,從而形成跟隨液體排放之NaHS及Na2S。
在洗氣器下游應用再生性活性碳過濾器,其中在過濾器床中吸收及濃縮CS2。隨後,使用輕度溫度擺動過程使其解吸附,且視情況在高度濃縮之後以寶貴原料之形式返回至黏液工廠中。若H2S存在於用於活性碳步驟之進口氣體中,則其將佔用活性碳之容量且破壞對於工廠整體經濟情況極其重要之CS2再循環過程。此為在活性碳床上游使用基於NaOH之鹼洗氣器的主要原因。
H2S洗氣器將使用顯著過量之苛性材料以捕集H2S,此係因為在此類洗氣器中需要高pH來捕集H2S。在水相中,將存在NaHS及Na2S
之混合物,在廢水處理廠中對該混合物進行處理為繁瑣且昂貴的,且若溫度或pH未得到小心控制,則該混合物在釋放H2S方面亦不穩定。
US 2005/0147554 A1描述使用濕式氧化製程以控制來自黏液製程之經還原硫化合物的濃度。濕式氧化製程使經還原硫化合物氧化以將其轉化為鹼金屬硫酸鹽和/或硫代硫酸鹽物種。將鹼金屬硫酸鹽物流再循環至黏液製程中。氧化在高溫及高壓條件下進行,以使得排氣之氧氣濃度在約2%與約18%之間,且鹼金屬硫酸鹽物流之pH為約2至10。
在US 6.416.725 B1中,加工包含H2S及CS2之含硫氣體物流(諸如以嫘縈形成過程之副產物形式製造的含硫氣體物流)來以可用形式回收該等組分。首先使氣流與NaOH水溶液接觸以溶解出H2S及一些CS2。自溶液去除經溶解之CS2,且使其以液體濃縮物形式冷凝出來。回收氣流中殘餘之任何CS2,諸如藉由冷凝來回收。使自移除CS2殘留之鈉硫化物水溶液濃縮,且視需要將pH調節至鈉硫化物佔優勢地呈氫硫化鈉形式之值。經濃縮之氫硫化鈉溶液能夠與CS2液體濃縮物一起再用於嫘縈形成過程中。
用於來自黏液纖維製造之廢氣的廢氣回收及吸附系統的各種具體實例描述於中國實用新型及專利申請案CN 204107303 U、CN 204134460 U、CN 201115810 Y及CN 101219319 A中,其一般採用鹼金屬清潔/吸附及冷凝方法。然而,當相關時,此等CN申請案並不預測本發明。
本發明之想法為在活性碳過濾器上游使用直接氧化型催化劑,且因此將H2S轉化為元素硫、SO2或其混合物。可在冷凝器中移除元素
硫,且在鹼洗氣器中使用與化學計算需求量相比輕度過量之標準苛性劑(諸如NaOH或CaCO3)容易地移除SO2,由此產生可在液體排放系統中容易地處置之硫酸鹽。
更具體言之,本發明關注一種清潔來自黏液製造之排氣的方法,該等排氣基本上含有空氣及硫組分(主要為H2S及CS2),該方法包含以下步驟- 使該排氣穿過含有直接氧化型催化劑之催化反應器以經由存在於氣體中之氧氣或經由向氣流中添加之氧氣來將該排氣中之H2S轉化為元素硫、SO2或其混合物,- 自來自該催化反應器之廢氣移除元素硫及SO2,及- 將未經轉化之CS2再循環至該黏液製造過程中。
來自黏液製造之排氣一般含有濃度為約200至2000ppm之H2S及濃度為約200至1000ppm之CS2。
可操作催化反應器以便將H2S轉化為元素硫、SO2或其混合物,且同時保留CS2大體上未經轉化。
較佳地,在冷凝器中移除元素硫,且在鹼洗氣器中移除SO2。使CS2在鹼洗氣器下游之再生性活性碳過濾器中吸附及濃縮。
適合用於該方法中之催化劑包括包含Fe、Cr、Zn、Mn、V、Co、Ti、Bi、Sb、Cu或Mg之氧化物或其混合物負載於二氧化矽、氧化鋁、二氧化鈦、二氧化鈰、碳化矽或活性碳或其混合物上的催化劑,且視情況由鹼金屬(較佳為Na2O)促進。尤其較佳之催化劑包含V2O5負載於二氧化矽上。
操作溫度在100℃至300℃,較佳地160℃至260℃之範圍內。
Claims (9)
- 一種清潔來自黏液製造之排氣之方法,該等排氣基本上含有空氣及包括H2S及CS2的硫組分,該方法包含以下步驟:使該排氣穿過含有直接氧化型催化劑之催化反應器以經由存在於氣體中之氧氣或經由向氣流中添加之氧氣來將該排氣中之H2S轉化為元素硫及SO2,自來自該催化反應器之廢氣移除元素硫及SO2,及將未經轉化之CS2再循環至該黏液製造過程中,其中在冷凝器中移除該元素硫,且在鹼洗氣器中移除該SO2。
- 如申請專利範圍第1項之方法,其中使該CS2在該鹼洗氣器下游之再生性活性碳過濾器中吸附及濃縮,且使經吸收之CS2解吸附並使其以原料之形式返回至黏液製造工廠中。
- 如申請專利範圍第1項之方法,其中來自黏液製造之該排氣含有濃度為200至2000ppm之H2S及濃度為200至1000ppm之CS2。
- 如申請專利範圍第1項至第3項中任一項之方法,其中操作溫度在100℃至300℃範圍內。
- 如申請專利範圍第1項至第3項中任一項之方法,其中操作溫度在160℃至260℃範圍內。
- 一種催化劑之用途,其用於如申請專利範圍第1項至第5項中任一項之方法中,該催化劑為包含Fe、Cr、Zn、Mn、V、Co、Ti、Bi、Sb、Cu或Mg之氧化物或其混合物負載於二氧化矽、氧化鋁、二氧化鈦、二氧化鈰、碳化矽或活性碳或其混合物上的直接氧化型催化劑。
- 一種催化劑之用途,其用於如申請專利範圍第1項至第5項中任一項之方法中,該催化劑為包含Fe、Cr、Zn、Mn、V、Co、Ti、Bi、Sb、Cu或Mg之氧化物或其混合物負載於二氧化矽、氧化鋁、二氧化鈦、二氧化鈰、碳化矽或活性碳或其混合物上的直接氧化型催化劑,且由鹼金屬促進。
- 一種催化劑之用途,其用於如申請專利範圍第1項至第5項中任一項之方法中,該催化劑為包含Fe、Cr、Zn、Mn、V、Co、Ti、Bi、Sb、Cu或Mg之氧化物或其混合物負載於二氧化矽、氧化鋁、二氧化鈦、二氧化鈰、碳化矽或活性碳或其混合物上的直接氧化型催化劑,且由為Na2O促進。
- 如申請專利範圍第6項至第8項中任一項之催化劑之用途,其中該催化劑包含V2O5負載於二氧化矽上。
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CN112121796A (zh) * | 2019-06-25 | 2020-12-25 | 托普索公司 | 一种用于使硫化氢选择性氧化为硫的催化剂 |
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US7850822B2 (en) | 2003-10-29 | 2010-12-14 | Siemens Water Technologies Holding Corp. | System and method of wet oxidation of a viscose process stream |
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US8193114B2 (en) * | 2006-11-15 | 2012-06-05 | Basf Catalysts Llc | Catalysts for dual oxidation of ammonia and carbon monoxide with low to no NOx formation |
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EP3523015A1 (en) | 2019-08-14 |
US20190255484A1 (en) | 2019-08-22 |
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CN109803747A (zh) | 2019-05-24 |
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