TWI435763B - Oxidative desulfurization catalyst, method for producing the same and application thereof - Google Patents
Oxidative desulfurization catalyst, method for producing the same and application thereof Download PDFInfo
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本發明是有關於一種氧化脫硫觸媒及其製造方法暨應用，特別是有關於一種用於克勞氏尾氣處理製程中的氧化脫硫觸媒及其製造方法暨應用。The invention relates to an oxidative desulfurization catalyst and a manufacturing method thereof and application thereof, in particular to an oxidative desulfurization catalyst used in a Crouch tail gas treatment process, a manufacturing method thereof and an application thereof.
從原油提煉燃料油等油料過程中，需利用加氫脫硫製程以去除原油中所含的硫。然而，加氫脫硫製程產生之硫化氫為劇毒氣體，必需再經過硫磺工廠將硫化氫製成硫磺，以從硫化氫回收所含的硫。In the process of refining fuel oil such as fuel oil from crude oil, a hydrodesulfurization process is required to remove sulfur contained in the crude oil. However, the hydrogen sulfide produced by the hydrodesulfurization process is a highly toxic gas, and it is necessary to further convert the hydrogen sulfide into sulfur through a sulfur plant to recover the sulfur contained from the hydrogen sulfide.
一般而言，硫磺工廠係利用克勞氏(Claus)製程回收硫磺。然而近年來，環境保護的意識高漲，環保問題及廢氣排放標準日趨嚴格，有必要發展硫回收率更高的脫硫方法。因此，克勞氏(Claus)製程歷經多次修正後，其中一種修正製程即藉由增設尾氣(tail gas)處理設備，以提高硫的回收率。In general, sulfur plants use the Claus process to recover sulfur. However, in recent years, the awareness of environmental protection has risen, environmental protection issues and emission standards have become stricter, and it is necessary to develop a desulfurization method with a higher sulfur recovery rate. Therefore, after a number of revisions to the Claus process, one of the correction processes is to increase the sulfur recovery rate by adding a tail gas treatment device.
概言之，克勞氏尾氣處理製程通常於約1100℃至約1650℃下，將克勞氏製程之尾氣中的硫化氫，燃燒成二氧化硫。接著，經上述熱處理的尾氣通入觸媒反應器，藉由克勞氏觸媒(例如以氧化鋁為載體之觸媒)，可選擇性使剩餘的硫化氫與二氧化硫反應成硫蒸汽。之後，將硫蒸汽冷凝成元素硫，即可從尾氣中的硫化氫回收所含的硫。經由克勞氏尾氣處理製程處理後，可提高尾氣中元素硫之回收率。In summary, the Claus's tail gas treatment process typically burns hydrogen sulfide in the tail gas of the Claus process to sulfur dioxide at a temperature of from about 1100 ° C to about 1650 ° C. Then, the exhaust gas subjected to the above heat treatment is introduced into the catalytic reactor, and the residual hydrogen sulfide and sulfur dioxide are selectively reacted into sulfur vapor by a Claus catalyst (for example, an alumina-supported catalyst). Thereafter, the sulfur vapour is condensed into elemental sulfur to recover the sulfur contained in the exhaust gas from the hydrogen sulfide in the exhaust gas. The recovery of elemental sulfur in the tail gas can be increased after treatment with the Claus's tail gas treatment process.
然而，經克勞氏尾氣處理製程處理之元素硫的回收率高低，其關鍵之一在於氧化脫硫觸媒的催化活性之良窳。簡言之，氧化脫硫觸媒對硫化氫的選擇性越高，轉化率越佳，則其元素硫(硫磺)之產率就越好。習知氧化脫硫觸媒之製程可包括含浸法、共沉澱法、機械球磨法等，其中含浸法為目前製備氧化脫硫觸媒較簡便的方法。However, one of the keys to the recovery of elemental sulfur treated by the Crow's tail gas treatment process is the catalytic activity of the oxidative desulfurization catalyst. In short, the higher the selectivity of the oxidative desulfurization catalyst to hydrogen sulfide, the better the conversion, the better the yield of elemental sulfur (sulfur). The process of the conventional oxidative desulfurization catalyst may include an impregnation method, a coprecipitation method, a mechanical ball milling method, etc., wherein the impregnation method is a relatively simple method for preparing an oxidative desulfurization catalyst.
在習知含浸法中，其中一種方式係利用γ-氧化鋁為載體，以釩、鉍為活性成分，鑭為助劑，採用含浸法製備而得。此法雖有擔體，然而所得之觸媒使用前需經脫水，且鑭等稀土金屬的原料來源不易掌握，量產時會有困難。In the conventional impregnation method, one of the methods is prepared by using γ-alumina as a carrier, vanadium and ruthenium as active ingredients, and ruthenium as an auxiliary agent by using an impregnation method. Although this method has a support, the obtained catalyst needs to be dehydrated before use, and the source of raw materials such as lanthanum and rare earth metals is difficult to grasp, and it is difficult to mass-produce.
另一種含浸法的方式係利用α-氧化鋁為載體，將氧化鐵、氧化銫或氧化錫等活性成分沉澱於α-氧化鋁上而製得。此法雖有擔體，然而其作為觸媒將硫化氫選擇性氧化為元素硫的轉化率偏低(約74百分比左右)。Another method of impregnation is obtained by precipitating an active ingredient such as iron oxide, cerium oxide or tin oxide onto α-alumina using α-alumina as a carrier. Although this method has a support, its conversion rate of selective oxidation of hydrogen sulfide to elemental sulfur as a catalyst is low (about 74%).
又一種含浸法的方式則是將含有釩、釔、釤及鑭等金屬離子的水溶液混合，加熱形成漿體後，再予以煅燒而製得。由於此法並未使用擔體，且釔、釤及鑭等稀土金屬的原料來源不易掌握，量產時會有困難。Another method of impregnation is to obtain an aqueous solution containing metal ions such as vanadium, niobium, tantalum and niobium, and then heat to form a slurry, followed by calcination. Since the carrier is not used in this method, and the source of raw materials of rare earth metals such as lanthanum, cerium and lanthanum is difficult to grasp, it is difficult to mass-produce.
其次，上述習知共沉澱法的方式則是將含有釩、錳、鉬等金屬離子的水溶液混合，共沉澱形成沉澱膠體(paste)後，再予以煅燒而製得。然而此法並未使用擔體，量產時會有困難。Next, the conventional coprecipitation method is obtained by mixing an aqueous solution containing metal ions such as vanadium, manganese, molybdenum, and coprecipitating to form a precipitated paste, followed by calcination. However, this method does not use the carrier, and there will be difficulties in mass production.
另外，上述習知機械混合法的方式則是將含有釩、鎂、銻等金屬先氧化成金屬氧化物之固態顆粒後，繼之以機械混合上述固態顆粒而製得物理混合物。由於此法並未使用擔體，亦未經過煅燒，且銻等稀土金屬的原料來源不易掌握，量產時會有困難。Further, the above-described mechanical mixing method is a method in which a metal containing vanadium, magnesium, ruthenium or the like is first oxidized to a solid particle of a metal oxide, followed by mechanical mixing of the solid particles to prepare a physical mixture. Since the method does not use the support and has not been calcined, and the raw material source of the rare earth metal such as ruthenium is difficult to grasp, it is difficult to mass-produce.
綜言之，上述習知所得之氧化脫硫觸媒，其原料來源取得不易、製程較複雜又不易量產，且所得之氧化脫硫觸媒的轉化率亦不一。有鑑於此，亟需提供一種氧化脫硫觸媒之製造方法，以改善習知氧化脫硫觸媒及其製程之種種缺點。In summary, the oxidative desulfurization catalyst obtained by the above-mentioned conventional materials has a difficult source of raw materials, is complicated in process, and is not easy to mass-produce, and the conversion rate of the obtained oxidative desulfurization catalyst is also different. In view of the above, there is a need to provide a method for producing an oxidative desulfurization catalyst to improve various disadvantages of the conventional oxidative desulfurization catalyst and its process.
因此，本發明之一態樣是在提供一種氧化脫硫觸媒之製造方法，其係將還原脫硝觸媒(A)與多重金屬鹽促進劑(B)經捏拌混合後，再經熱處理而製得氧化脫硫觸媒。由於此製造方法的原料來源取得容易、容易量產且所得之觸媒的轉化率高，因此可改善習知氧化脫硫觸媒之製程之種種缺點。Therefore, one aspect of the present invention provides a method for producing an oxidative desulfurization catalyst by kneading a mixed denitration catalyst (A) and a multiple metal salt promoter (B), followed by heat treatment. An oxidative desulfurization catalyst is produced. Since the raw material source of the production method is easy to obtain, easy to mass-produce, and the conversion rate of the obtained catalyst is high, various disadvantages of the conventional oxidative desulfurization catalyst can be improved.
本發明之另一態樣則是在提供一種氧化脫硫觸媒，其係利用上述方法製得。Another aspect of the present invention provides an oxidative desulfurization catalyst which is obtained by the above method.
本發明之又一態樣則是在提供一種催化煙道尾氣之硫化氫選擇性氧化為元素硫的製程，其特徵在於此製程利用上述之氧化脫硫觸媒將催化煙道尾氣之硫化氫選擇性氧化為元素硫。Still another aspect of the present invention provides a process for selectively oxidizing hydrogen sulfide of a flue gas to elemental sulfur, characterized in that the process utilizes the above-described oxidative desulfurization catalyst to catalyze the hydrogen sulfide of the flue gas. Sexual oxidation to elemental sulfur.
根據本發明之上述態樣，提出一種氧化脫硫觸媒之製造方法。在一實施例中，此方法包括將還原脫硝觸媒(A)與多重金屬鹽促進劑(B)混合，以形成混合物。其中，前述之還原脫硝觸媒(A)至少包含釩金屬銨化合物(A-1)、鉬金屬銨化合物(A-2)以及鈦金屬氧化物(A-3)但不含釔、銻或鑭。前述之多重金屬鹽促進劑(B)可包括但不限於IIb族金屬鹽(B-1)、IIIa族金屬鹽(B-2)或上述之任意組合，且基於前述之混合物之總量為100重量百分比計，多重金屬鹽促進劑(B)之含量為0.1重量百分比至7.0重量百分比。接著，將前述之混合物於100℃至550℃之溫度下進行熱處理30分鐘至360分鐘，以形成氧化脫硫觸媒，其中所得之氧化脫硫觸媒為顆粒狀。According to the above aspect of the invention, a method of producing an oxidative desulfurization catalyst is proposed. In one embodiment, the method comprises mixing a reduced denitration catalyst (A) with a multiple metal salt promoter (B) to form a mixture. Wherein the aforementioned reduced denitration catalyst (A) comprises at least a vanadium metal ammonium compound (A-1), a molybdenum metal ammonium compound (A-2) and a titanium metal oxide (A-3) but does not contain ruthenium, osmium or lanthanum. The aforementioned multiple metal salt promoter (B) may include, but is not limited to, a Group IIb metal salt (B-1), a Group IIIa metal salt (B-2), or any combination thereof, and the total amount based on the foregoing mixture is 100. The content of the multiple metal salt promoter (B) is from 0.1% by weight to 7.0% by weight based on the weight percentage. Next, the foregoing mixture is subjected to heat treatment at a temperature of from 100 ° C to 550 ° C for 30 minutes to 360 minutes to form an oxidative desulfurization catalyst, wherein the obtained oxidative desulfurization catalyst is in the form of particles.
依據本發明一實施例，上述之還原脫硝觸媒為選擇性催化還原(selectively catalytic reduction；SCR)脫硝觸媒。According to an embodiment of the invention, the reduced denitration catalyst is a selective catalytic reduction (SCR) denitration catalyst.
依據本發明一實施例，上述之IIb族金屬鹽(B-1)包括氧化鋁，且上述之IIIa族金屬鹽(B-2)包括氧化鋅。According to an embodiment of the invention, the Group IIb metal salt (B-1) comprises alumina, and the Group IIIa metal salt (B-2) comprises zinc oxide.
依據本發明一實施例，上述之混合步驟係利用一捏拌裝置進行。According to an embodiment of the invention, the mixing step described above is carried out using a kneading device.
根據本發明之另一態樣，提出一種氧化脫硫觸媒，其係利用上述之方法製得。According to another aspect of the present invention, an oxidative desulfurization catalyst is proposed which is obtained by the above method.
根據本發明之其他態樣，提出一種催化煙道尾氣之硫化氫選擇性氧化為元素硫的製程，其特徵在於此製程利用上述之氧化脫硫觸媒將催化煙道尾氣之硫化氫選擇性氧化為元素硫，其中當煙道尾氣的硫化氫與氧之莫耳比([H2 S]/[O2 ])為2.0、反應溫度為160℃至240℃且水氣含量為35百分比至45百分比時，硫化氫氧化為元素硫之轉化率為93百分比至98百分比。According to another aspect of the present invention, a process for selectively oxidizing hydrogen sulfide of a flue gas to elemental sulfur is proposed, characterized in that the process oxidizes hydrogen sulfide of a catalytic flue gas by using the above oxidative desulfurization catalyst. It is elemental sulfur, in which the hydrogen sulfide to oxygen molar ratio ([H 2 S]/[O 2 ]) of the flue gas is 2.0, the reaction temperature is 160 ° C to 240 ° C and the water vapor content is 35 to 45 In percentage, the conversion of hydrogen sulfide to elemental sulfur is from 93% to 98%.
應用本發明之氧化脫硫觸媒及其製造方法暨應用，其係以現有不含釔、銻或鑭之SCR脫硝觸媒為主體，與多重金屬鹽促進劑捏拌混合再經熱處理後，即可製得顆粒狀之氧化脫硫觸媒，而所得之氧化脫硫觸媒將硫化氫氧化為元素硫的轉化率為93百分比至98百分比。由於氧化脫硫觸媒之原料來源取得容易，製程簡化且其轉化率高，因而有利於量產。The oxidative desulfurization catalyst of the invention and the preparation method and application thereof are mainly based on the existing SCR denitrification catalyst containing no antimony, bismuth or antimony, and are mixed with the multiple metal salt promoter and then heat treated. A granular oxidative desulfurization catalyst can be obtained, and the resulting oxidative desulfurization catalyst converts sulfuric acid to elemental sulfur by a conversion of 93% to 98%. Since the source of the raw material of the oxidative desulfurization catalyst is easy, the process is simplified, and the conversion rate is high, it is advantageous for mass production.
承前所述，本發明提供一種氧化脫硫觸媒及其製造方法暨應用，其係以不含釔、銻或鑭之選擇性催化還原(SCR)脫硝觸媒為主體，與多重金屬鹽促進劑捏拌混合再經熱處理後，即可製得顆粒狀之氧化脫硫觸媒。As described above, the present invention provides an oxidative desulfurization catalyst, a method for producing the same, and an application thereof, which are mainly based on a selective catalytic reduction (SCR) denitrification catalyst containing no ruthenium, osmium or iridium, and a multi-metal salt promotion. After the agent is kneaded and mixed and then heat treated, a granular oxidative desulfurization catalyst can be obtained.
在一實施例中，本發明方法的特徵之一在於利用現有之SCR脫硝觸媒為主體進行改質，由於不含釔、銻或鑭，因此原料來源取得容易且又簡化製程。In one embodiment, one of the features of the method of the present invention is that the existing SCR denitrification catalyst is used for the main body modification. Since the crucible, the crucible or the crucible is not contained, the source of the raw material is easily obtained and the process is simplified.
申言之，在一例示中，首先將還原脫硝觸媒(A)與多重金屬鹽促進劑(B)混合，以形成混合物。上述多重金屬鹽促進劑包括IIb族金屬鹽(B-1)、IIIa族金屬鹽(B-2)或上述之任意組合，其中適用的IIb族金屬鹽包括氧化鋁，IIIa族金屬鹽包括氧化鋅。基於上述混合物之總量為100重量百分比計，此多重金屬鹽促進劑(B)之含量為0.1重量百分比至7.0重量百分比。然而在另一例示中，多重金屬鹽促進劑(B)之氧化鋁的含量可為0.5重量百分比至4.0重量百分比，而氧化鋅之含量可為0.1重量百分比至1.2重量百分比。惟需說明的是，倘若多重金屬鹽促進劑(B)之含量小於0.1重量百分比，後續所得之氧化脫硫觸媒將硫化氫氧化為元素硫之轉化率則無法達到93百分比。倘若多重金屬鹽促進劑(B)之含量大於7.0重量百分比，則後續所得之氧化脫硫觸媒之轉化率亦將降低。In other words, in one example, the reduced denitration catalyst (A) is first mixed with the multiple metal salt promoter (B) to form a mixture. The above multiple metal salt promoter includes a Group IIb metal salt (B-1), a Group IIIa metal salt (B-2) or any combination thereof, wherein a suitable Group IIb metal salt includes alumina, and a Group IIIa metal salt includes zinc oxide. . The content of the multiple metal salt promoter (B) is from 0.1% by weight to 7.0% by weight based on 100% by weight of the total of the above mixture. In still another example, the multiple metal salt promoter (B) may have an alumina content of from 0.5 weight percent to 4.0 weight percent, and the zinc oxide content may range from 0.1 weight percent to 1.2 weight percent. It should be noted that, if the content of the multiple metal salt promoter (B) is less than 0.1% by weight, the conversion ratio of the subsequently obtained oxidative desulfurization catalyst to hydrogen sulfide to elemental sulfur cannot reach 93%. If the content of the multiple metal salt promoter (B) is more than 7.0% by weight, the conversion rate of the subsequently obtained oxidative desulfurization catalyst will also decrease.
其次，前述所稱之「SCR脫硝觸媒」係指目前可取得之任何SCR脫硝觸媒產品，或是本發明所屬技術領域中任何具有通常知識者運用習知知識可製得之SCR脫硝觸媒。在一實施例中，前述之SCR脫硝觸媒至少包含釩金屬銨化合物、鉬金屬銨化合物以及鈦金屬氧化物，但不含釔、銻或鑭。前述之釩金屬銨化合物例如為釩酸銨，前述之鉬金屬銨化合物例如為七鉬酸銨，而前述之鈦金屬氧化物例如為二氧化鈦氧化物或偏鈦酸。在另一例示中，基於上述混合物之總量為100重量百分比計，釩金屬銨化合物之含量為5.0重量百分比至8.0重量百分比，鉬金屬銨化合物之含量為3.0重量百分比至6.0重量百分比，且鈦金屬氧化物之含量為65.0重量百分比至75.0重量百分比。Secondly, the term "SCR denitrification catalyst" as used herein refers to any SCR denitration catalyst product currently available, or any SCR that can be obtained by using conventional knowledge by anyone with ordinary knowledge in the technical field of the present invention. Nitrogen catalyst. In one embodiment, the aforementioned SCR denitration catalyst comprises at least a vanadium metal ammonium compound, a molybdenum metal ammonium compound, and a titanium metal oxide, but does not contain lanthanum, cerium or lanthanum. The vanadium metal ammonium compound is, for example, ammonium vanadate, the above-mentioned molybdenum metal ammonium compound is, for example, ammonium heptamolybdate, and the aforementioned titanium metal oxide is, for example, titanium oxide or metatitanic acid. In another illustration, the content of the vanadium metal ammonium compound is from 5.0 to 8.0 weight percent based on the total amount of the mixture, and the content of the molybdenum metal ammonium compound is from 3.0 to 6.0 weight percent, and titanium The content of the metal oxide is from 65.0% by weight to 75.0% by weight.
在另一實施例中，前述之還原脫硝觸媒更可選擇性包括一結合劑(A-4)。在一例示中，前述之結合劑可包括無機纖維及黏土，其中無機纖維可包括例如玻璃纖維(A-4-1)等之含矽與矽氧化物，而黏土(A-4-2)可包括例如氧化鋁、二氧化矽等無機黏土之含矽與矽氧化物。在另一例示中，基於上述混合物之總量為100重量百分比計，此無機纖維(A-4-1)之含量為4.0重量百分比至10.0重量百分比，且此黏土(A-4-2)之含量為1重量百分比至6重量百分比。In another embodiment, the aforementioned reduced denitration catalyst more selectively comprises a binder (A-4). In an example, the foregoing bonding agent may include inorganic fibers and clay, wherein the inorganic fibers may include cerium- and cerium-containing oxides such as glass fibers (A-4-1), and clay (A-4-2) may be used. Including cerium and lanthanum oxides of inorganic clays such as alumina and cerium oxide. In another illustration, the inorganic fiber (A-4-1) is present in an amount of from 4.0% by weight to 10.0% by weight based on 100% by weight of the total of the above mixture, and the clay (A-4-2) The content is from 1% by weight to 6% by weight.
再者，本發明方法的另一特徵則在於捨棄習知的含浸法、共沉澱法或機械混合法，而是利用一捏拌裝置混合上述還原脫硝觸媒與多重金屬鹽促進劑。在一例示中，前述之混合步驟可利用上述之捏拌裝置以每分鐘400轉(rpm)至800 rpm之轉速進行1至4小時。Further, another feature of the method of the present invention is that the conventional impregnation method, coprecipitation method or mechanical mixing method is discarded, and the above-mentioned reducing denitration catalyst and multiple metal salt promoter are mixed by a kneading device. In one example, the aforementioned mixing step can be carried out at a number of revolutions of 400 revolutions per minute (rpm) to 800 rpm for 1 to 4 hours using the kneading apparatus described above.
在前述混合步驟之後，將所得之混合物於100℃至550℃之溫度下進行熱處理30分鐘至360分鐘，以形成顆粒狀之氧化脫硫觸媒。在另一例示中，所得之混合物亦可於300℃至550℃之溫度下進行前述熱處理60分鐘至300分鐘，以形成顆粒狀之氧化脫硫觸媒。惟需說明的是，倘若熱處理之時間少於30分鐘或低於100℃，則所得之氧化脫硫觸媒催化活性低。倘若熱處理之時間超過360分鐘或高於550℃，則會使得氧化脫硫觸媒燒結甚至降低觸媒活性。After the aforementioned mixing step, the resulting mixture is subjected to heat treatment at a temperature of from 100 ° C to 550 ° C for 30 minutes to 360 minutes to form a particulate oxidative desulfurization catalyst. In another illustration, the resulting mixture may also be subjected to the aforementioned heat treatment at a temperature of from 300 ° C to 550 ° C for from 60 minutes to 300 minutes to form a particulate oxidative desulfurization catalyst. It should be noted that if the heat treatment time is less than 30 minutes or less than 100 ° C, the resulting oxidative desulfurization catalyst has low catalytic activity. If the heat treatment time exceeds 360 minutes or exceeds 550 ° C, the oxidative desulfurization catalyst is sintered and even the catalyst activity is lowered.
在其他實施例中，前述所得顆粒狀之氧化脫硫觸媒可將催化煙道尾氣之硫化氫選擇性氧化為元素硫。在一例示中，當前述煙道尾氣的硫化氫與氧之莫耳比([H2 S]/[O2 ])為2.0且水氣含量為35百分比至45百分比之條件下，前述之氧化脫硫觸媒將硫化氫氧化為元素硫之轉化率為93百分比至98百分比。In other embodiments, the particulate oxidative desulfurization catalyst obtained as described above selectively oxidizes hydrogen sulfide which catalyzes the flue gas of the flue to elemental sulfur. In an example, when the flue gas exhaust gas has a hydrogen sulfide to oxygen molar ratio ([H 2 S]/[O 2 ]) of 2.0 and a water gas content of 35 to 45 percent, the foregoing oxidation The conversion rate of the sulfurized hydrogenation to elemental sulfur by the desulfurization catalyst is from 93% to 98%.
值得一提的是，本發明之方法捨棄習知的含浸法、共沉澱法或機械混合法，使用不含釔、銻或鑭之SCR脫硝觸媒，同時利用捏拌混合上述還原脫硝觸媒與多重金屬鹽促進劑，以製得顆粒狀之氧化脫硫觸媒。如此一來，不僅原料來源取得容易，簡化習知的觸媒製程，更有利於氧化脫硫觸媒之量產。再者，由此製得的顆粒狀之氧化脫硫觸媒應用於克勞氏尾氣處理製程時，當煙道尾氣的硫化氫與氧之莫耳比([H2 S]/[O2 ])為2.0、反應溫度為160℃至240℃且水氣含量為35百分比至45百分比時，此氧化脫硫觸媒將硫化氫氧化為元素硫之轉化率可達93百分比至98百分比。It is worth mentioning that the method of the present invention discards the conventional impregnation method, coprecipitation method or mechanical mixing method, and uses the SCR denitrification catalyst containing no antimony, bismuth or antimony, and simultaneously mixes the above-mentioned reduced denitrification contact by kneading and mixing. The medium and the multiple metal salt promoter are used to prepare a granular oxidative desulfurization catalyst. In this way, not only the source of raw materials is easily obtained, but also the conventional catalyst process is simplified, and the mass production of the oxidative desulfurization catalyst is more favorable. Furthermore, the granular oxidative desulfurization catalyst thus produced is used in the Claude tail gas treatment process when the hydrogen sulfide to oxygen molar ratio of the flue gas is exhausted ([H 2 S]/[O 2 ] When the reaction temperature is from 160 ° C to 240 ° C and the water gas content is from 35 to 45 percent, the oxidative desulfurization catalyst converts the sulfuric acid to elemental sulfur by a conversion of 93% to 98%.
以下利用實施例以說明本發明之應用，然其並非用以限定本發明，本發明技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾。The following examples are provided to illustrate the application of the present invention, and are not intended to limit the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention.
製備氧化脫硫觸媒Preparation of oxidative desulfurization catalyst
實施例1Example 1
此實施例係將68g的釩酸銨(NH4 VO3 ；A-1)、42g的七鉬酸銨[(NH4 )6 Mo7 O24 ‧4H2 O；A-2]、750g二氧化鈦(TiO2 ；A-3)、100g的玻璃纖維(A-4-1)、41g的黏土(A-4-2)、15g的氧化鋁(B-1-1)、5g的氧化鋅(B-2-1)以及385mL的純水中，形成混合物，其配方如第1表所示。接著，利用捏拌裝置以400 rpm至800 rpm之轉速混合此混合物1至4小時，藉此將玻璃纖維碎為細絲，以形成糰料狀之混合物。This example is 68 g of ammonium vanadate (NH 4 VO 3 ; A-1), 42 g of ammonium heptamolybdate [(NH 4 ) 6 Mo 7 O 24 ‧4H 2 O; A-2], 750 g of titanium dioxide ( TiO 2 ; A-3), 100 g of glass fiber (A-4-1), 41 g of clay (A-4-2), 15 g of alumina (B-1-1), 5 g of zinc oxide (B- 2-1) and 385 mL of pure water to form a mixture, the formulation of which is shown in Table 1. Next, the mixture was mixed by a kneading device at a number of revolutions of 400 rpm to 800 rpm for 1 to 4 hours, whereby the glass fibers were broken into filaments to form a dough-like mixture.
然後，將糰料狀之混合物利用例如塗覆滾輪塗覆於不鏽鋼金屬網上，於500℃之溫度與一大氣壓下，進行熱處理30分鐘至360分鐘或者180分鐘至300分鐘，以形成氧化脫硫觸媒。之後，刮除金屬網上的氧化脫硫觸媒，以形成顆粒狀之氧化脫硫觸媒。Then, the dough-like mixture is coated on a stainless steel metal mesh by, for example, a coating roller, and heat-treated at a temperature of 500 ° C and atmospheric pressure for 30 minutes to 360 minutes or 180 minutes to 300 minutes to form oxidative desulfurization. catalyst. Thereafter, the oxidative desulfurization catalyst on the metal mesh is scraped off to form a particulate oxidative desulfurization catalyst.
實施例2至3Examples 2 to 3
同實施例1之氧化脫硫觸媒的製作方法，不同處在於實施例2至3係改變成份的使用量以及熱處理的溫度與時間，其配方如第1表所示。The method for producing the oxidative desulfurization catalyst of the first embodiment differs in the amounts of the components used in Examples 2 to 3 and the temperature and time of the heat treatment, and the formulation thereof is shown in Table 1.
比較例1Comparative example 1
同實施例1之氧化脫硫觸媒的製作方法，不同處在於比較例1係改變成份的使用量以及熱處理的溫度與時間，其配方亦如第1表所示。The method for producing the oxidative desulfurization catalyst of the first embodiment differs in that the comparative example 1 is the amount of the modified component used and the temperature and time of the heat treatment, and the formulation thereof is also shown in Table 1.
評價方式Evaluation method
1.觸媒氧化脫硫能力之測試系統1. Test system for catalytic oxidative desulfurization ability of catalyst
將模擬克勞氏製程之煙道尾氣(以下簡稱反應氣體)通入第1圖的觸媒氧化脫硫能力之測試系統中，以評估上述觸媒對硫化氫氧化為元素硫之轉化率、對硫化氫之選擇率以及元素硫(硫磺)之產率。The flue gas (hereinafter referred to as the reaction gas) simulating the Claus process is passed into the test system of the catalyst oxidative desulfurization capacity of FIG. 1 to evaluate the conversion rate of the catalyst to sulfuric acid as elemental sulfur. The selectivity of hydrogen sulfide and the yield of elemental sulfur (sulfur).
請參閱第1圖，其係繪示根據本發明一實施例之觸媒氧化脫硫能力之測試系統的示意圖。此觸媒氧化脫硫能力之測試系統100包括管狀石英玻璃反應管105、反應器107、溫度控制器109、氣體混合儲存裝置111、低溫緩衝瓶113以及氣相色層分析儀115。Please refer to FIG. 1 , which is a schematic diagram showing a test system for oxidative desulfurization capability of a catalyst according to an embodiment of the invention. The catalytic oxidation desulfurization capability test system 100 includes a tubular quartz glass reaction tube 105, a reactor 107, a temperature controller 109, a gas mixture storage device 111, a cryogenic buffer bottle 113, and a gas phase chromatography analyzer 115.
進行觸媒氧化脫硫能力之測試時，首先將粒徑12網目(mesh)至16網目的顆粒狀之氧化脫硫觸媒101與直徑約0.4公分之玻璃球103混合均勻後，置於長55公分、直徑2.0公分之石英玻璃反應管105中，觸媒填充高度為約6.0公分，再將裝有上述顆粒狀之氧化脫硫觸媒101及玻璃球103之石英玻璃反應管105置於反應器107(加熱器)中，以進行觸媒氧化脫硫能力之測試。When testing the catalytic oxidative desulfurization ability of the catalyst, firstly, the granular oxidized desulfurization catalyst 101 having a particle size of 12 mesh to 16 mesh is uniformly mixed with the glass ball 103 having a diameter of about 0.4 cm, and then placed in a length of 55. In a quartz glass reaction tube 105 having a centimeter and a diameter of 2.0 cm, the catalyst filling height is about 6.0 cm, and the quartz glass reaction tube 105 containing the above-mentioned granular oxidative desulfurization catalyst 101 and glass ball 103 is placed in the reactor. In 107 (heater), the catalyst is tested for oxidative desulfurization ability.
前述之溫度控制器109係連接至反應器107，以控制反應器107中之反應溫度。前述之石英玻璃反應管105具有入口端121及出口端123，其中入口端121係連接至氣體混合儲存裝置111。硫化氫氣體源131、氧氣氣體源133、氮氣氣體源135經由管線137可提供氣體混合儲存裝置111所需的氣體。The aforementioned temperature controller 109 is connected to the reactor 107 to control the reaction temperature in the reactor 107. The aforementioned quartz glass reaction tube 105 has an inlet end 121 and an outlet end 123, wherein the inlet end 121 is connected to the gas mixing storage device 111. The hydrogen sulfide gas source 131, the oxygen gas source 133, and the nitrogen gas source 135 can supply the gas required for the gas mixing storage device 111 via the line 137.
在進行測試前，先將氮氣氣體源135之氮氣經由管線137與氣體混合儲存裝置111導入石英玻璃反應管105中，以利用氮氣進行清洗。Before the test, the nitrogen gas of the nitrogen gas source 135 is introduced into the quartz glass reaction tube 105 via the line 137 and the gas mixed storage device 111 to be purged with nitrogen.
進行測試時，利用氣體流量計141控制硫化氫氣體源131與氧氣氣體源133，以導入硫化氫與氧氣至氣體混合儲存裝置111中，混合成反應氣體。並且，利用氣體流量計141控制反應氣體各成份的流量比例後，將此反應氣體進一步導入石英玻璃反應管105中，以進行選擇性觸媒氧化脫硫反應。進行反應時，另藉由液體幫浦(圖未繪示)於反應器107之入口端121直接打入水，並加熱將水氣化後以進行反應。At the time of the test, the hydrogen sulfide gas source 131 and the oxygen gas source 133 are controlled by the gas flow meter 141 to introduce hydrogen sulfide and oxygen into the gas mixed storage device 111, and mixed to form a reaction gas. Further, after the flow rate ratio of each component of the reaction gas is controlled by the gas flow meter 141, the reaction gas is further introduced into the quartz glass reaction tube 105 to perform a selective catalyst oxidative desulfurization reaction. When the reaction is carried out, water is directly introduced into the inlet end 121 of the reactor 107 by a liquid pump (not shown), and the water is vaporized by heating to carry out the reaction.
反應溫度係由室溫緩慢升溫至預定的反應溫度，並在此反應溫度下進行觸媒對硫化氫之選擇性氧化脫硫反應。The reaction temperature is slowly raised from room temperature to a predetermined reaction temperature, and a selective oxidative desulfurization reaction of hydrogen sulfide with a catalyst is carried out at the reaction temperature.
前述之出口端123連接至低溫緩衝瓶113，用以冷卻反應後之氣體及吸附多餘的水氣。另外，反應器107之出口端123處的低溫緩衝瓶113係連接至氣相色層分析儀115，例如附有火焰光度偵測器(flame photometric detector；FPD)之氣相色層分析儀(gas chromatography；GC)(Model No.6890；Agilent)，以取樣檢測反應物及產物中硫化氫的濃度，並與進料時未反應之硫化氫的濃度進行比對，由此計算出觸媒對硫化氫之選擇性氧化為元素硫的轉化率。The aforementioned outlet end 123 is connected to the cryogenic buffer bottle 113 for cooling the reacted gas and adsorbing excess moisture. In addition, the cryostat bottle 113 at the outlet end 123 of the reactor 107 is connected to a gas phase chromatography analyzer 115, such as a gas chromatograph analyzer equipped with a flame photometric detector (FPD). Chromatography; GC) (Model No. 6890; Agilent), the concentration of hydrogen sulfide in the reactants and products was sampled and compared with the concentration of unreacted hydrogen sulfide at the time of feeding, thereby calculating the catalyst pair vulcanization The selective oxidation of hydrogen is the conversion of elemental sulfur.
上述反應氣體之硫化氫與氧的濃度比([H2 S]/[O2 ])為2.0，氣體空間流量為5000hr-1 ，反應溫度為160℃至240℃，水氣含量為35百分比至45百分比。The reaction gas has a hydrogen sulfide to oxygen concentration ratio ([H 2 S]/[O 2 ]) of 2.0, a gas space flow of 5000 hr -1 , a reaction temperature of 160 ° C to 240 ° C, and a water vapor content of 35 percent. 45 percent.
2.評估觸媒之轉化率、選擇率以及元素硫(硫磺)之產率2. Evaluate the conversion rate of the catalyst, the selectivity and the yield of elemental sulfur (sulfur)
關於觸媒對硫化氫氧化為元素硫之轉化率係根據下式(I)的定義：The conversion rate of the catalyst to sulfuric acid oxidized to elemental sulfur is defined according to the following formula (I):
關於觸媒對硫化氫之選擇率係根據下式(II)的定義：The selectivity of the catalyst for hydrogen sulfide is defined by the following formula (II):
此選擇率即元素硫(硫磺)之生成量除以硫化氫的反應量。當選擇率低於100%時，即表示有二氧化硫生成於煙道尾氣中。This selectivity is the amount of elemental sulfur (sulfur) produced divided by the amount of hydrogen sulfide. When the selectivity is less than 100%, it means that sulfur dioxide is formed in the flue gas.
關於元素硫(硫磺)之產率係根據下式(III)的定義：The yield of elemental sulfur (sulfur) is defined by the following formula (III):
元素硫(硫磺)之產率(百分比)=式(I)之轉化率×式(II)之選擇率 (III)Yield (percentage) of elemental sulfur (sulfur) = conversion rate of formula (I) × selectivity of formula (II) (III)
由第1表之評價結果可知，利用不含釔、銻或鑭之SCR還原脫硝觸媒與0.1重量百分比至7.0重量百分比之多重金屬鹽促進劑(B)經捏拌混合後，將此混合物於100℃至550℃之溫度與一大氣壓下進行熱處理30分鐘至360分鐘，由此製得之氧化脫硫觸媒會具有較佳之轉化率、對硫化氫之選擇率以及元素硫(硫磺)之產率，且原料來源取得容易又簡化製程，故確實可達到本發明之目的。From the evaluation results of the first table, it is known that the SCR reduction denitration catalyst containing no ruthenium, osmium or iridium is mixed with 0.1% by weight to 7.0% by weight of the multiple metal salt promoter (B), and the mixture is kneaded and mixed. The heat treatment is carried out at a temperature of from 100 ° C to 550 ° C under atmospheric pressure for 30 minutes to 360 minutes, whereby the oxidative desulfurization catalyst prepared thereby has a better conversion ratio, a selectivity to hydrogen sulfide, and elemental sulfur (sulfur). The productivity, and the source of the raw materials are easy to obtain and the process is simplified, so that the object of the present invention can be achieved.
綜言之，本發明之方法提供較簡化且原料來源取得較容易的製程，以製得轉化率高之氧化脫硫觸媒，因而有利於氧化脫硫觸媒之量產。惟在此需補充的是，本發明雖以特定成份、特定反應條件、特定分析方式、特定試驗或特定設備等作為例示，說明本發明之氧化脫硫觸媒及其製造方法暨應用，惟本發明所屬技術領域中任何具有通常知識者可知，本發明並不限於此，在不脫離本發明之精神和範圍內，本發明之氧化脫硫觸媒及其製造方法暨應用亦可使用其他成份、其他反應條件、其他分析方式、其他試驗或其他等級相當的設備等進行。In summary, the method of the present invention provides a process that is relatively simple and has a relatively easy source of raw materials to produce an oxidative desulfurization catalyst having a high conversion rate, thereby facilitating mass production of the oxidative desulfurization catalyst. However, it should be noted that the present invention exemplifies the oxidative desulfurization catalyst of the present invention, a method for producing the same, and the application thereof, with specific components, specific reaction conditions, specific analytical methods, specific tests or specific equipment, and the like. It is to be understood by those skilled in the art that the present invention is not limited thereto, and the oxidative desulfurization catalyst of the present invention, its manufacturing method and application may also use other components, without departing from the spirit and scope of the present invention. Other reaction conditions, other analytical methods, other tests, or other equivalent equipment are performed.
由本發明上述實施例可知，本發明之氧化脫硫觸媒及其製造方法暨應用，其優點在於以現有不含釔、銻或鑭之SCR脫硝觸媒為主體，與多重金屬鹽促進劑捏拌混合再經熱處理後，即可製得顆粒狀之氧化脫硫觸媒，而所得之氧化脫硫觸媒的轉化率為93百分比至98百分比。綜此，本發明之方法不僅原料來源取得容易、簡化製程且所得之氧化脫硫觸媒的轉化率高，因而有利於量產。It can be seen from the above embodiments of the present invention that the oxidative desulfurization catalyst of the present invention and the method and application thereof have the advantages that the existing SCR denitrification catalyst containing no antimony, bismuth or antimony is mainly used, and the multi-metal salt promoter is pinched. After mixing and heat treatment, a granular oxidative desulfurization catalyst can be obtained, and the conversion of the obtained oxidative desulfurization catalyst is 93% to 98%. In summary, the method of the present invention is not only easy to obtain a source of raw materials, but also simplifies the process and has a high conversion rate of the obtained oxidative desulfurization catalyst, thereby facilitating mass production.
雖然本發明已以實施例揭露如上，然其並非用以限定本發明，在本發明所屬技術領域中任何具有通常知識者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。The present invention has been disclosed in the above embodiments, and is not intended to limit the present invention. Any one of ordinary skill in the art to which the present invention pertains can make various changes without departing from the spirit and scope of the invention. The scope of protection of the present invention is therefore defined by the scope of the appended claims.
100．．．觸媒氧化脫硫能力之測試系統100. . . Test system for catalytic oxidative desulfurization ability
101．．．顆粒狀之氧化脫硫觸媒101. . . Granular oxidative desulfurization catalyst
103．．．玻璃球103. . . Glass ball
105．．．石英玻璃反應管105. . . Quartz glass reaction tube
107．．．反應器107. . . reactor
109．．．溫度控制器109. . . Temperature Controller
111．．．氣體混合儲存裝置111. . . Gas mixed storage device
113．．．低溫緩衝瓶113. . . Cryogenic buffer bottle
115．．．氣相色層分析儀115. . . Gas chromatographic analyzer
121．．．入口端121. . . Entrance end
123．．．出口端123. . . Exit end
131．．．硫化氫氣體源131. . . Hydrogen sulfide gas source
133．．．氧氣氣體源133. . . Oxygen gas source
135．．．氮氣氣體源135. . . Nitrogen gas source
137．．．管線137. . . Pipeline
141．．．氣體流量計141. . . Barometer
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂，所附圖式之詳細說明如下：The above and other objects, features, advantages and embodiments of the present invention will become more apparent and understood.
第1圖係繪示根據本發明一實施例之觸媒氧化脫硫能力之測試系統的示意圖。1 is a schematic view showing a test system for oxidizing desulfurization capability of a catalyst according to an embodiment of the present invention.
100．．．觸媒氧化脫硫能力之測試系統100. . . Test system for catalytic oxidative desulfurization ability
101．．．顆粒狀之氧化脫硫觸媒101. . . Granular oxidative desulfurization catalyst
103．．．玻璃球103. . . Glass ball
105．．．石英玻璃反應管105. . . Quartz glass reaction tube
107．．．反應器107. . . reactor
109．．．溫度控制器109. . . Temperature Controller
111．．．氣體混合儲存裝置111. . . Gas mixed storage device
113．．．低溫緩衝瓶113. . . Cryogenic buffer bottle
115．．．氣相色層分析儀115. . . Gas chromatographic analyzer
121．．．入口端121. . . Entrance end
123．．．出口端123. . . Exit end
131．．．硫化氫氣體源131. . . Hydrogen sulfide gas source
133．．．氧氣氣體源133. . . Oxygen gas source
135．．．氮氣氣體源135. . . Nitrogen gas source
137．．．管線137. . . Pipeline
141．．．氣體流量計141. . . Barometer
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