CN108126710A - 一种抗硫除萘催化剂的制备及应用 - Google Patents
一种抗硫除萘催化剂的制备及应用 Download PDFInfo
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Abstract
本发明提供一种抗硫除萘催化剂的制备及应用，涉及环境保护催化剂技术领域。该催化剂以Al2O3或蜂窝陶瓷为载体，助剂元素和活性组分经过微波超声浸渍在载体上；助剂元素为铜、铁、锰、铈、镍中一种或者几种，助剂元素负载量为载体质量的2‑12％；活性组分为贵金属钯、金，活性组分负载量为载体质量的0.01‑0.20％，其中钯：金摩尔比为1：(0～3)。本发明可应用于催化氧化法处理含萘含硫有机废气治理领域，对萘转化效率高(高于99％)，而且能够处理含丙酮、苯、甲苯和萘混合废气，处理后废气达到国家排放标准，不生成二次污染物，同时该催化剂有一定的抗硫中毒能力，进一步拓宽了其应用范围。
Description
技术领域
本发明属于催化氧化环境保护领域，特别涉及一种处理含萘含硫有机废气的催化剂及其制备和应用领域。
背景技术
多环芳烃(PAHs)是煤，石油，木材，烟草，有机高分子化合物等有机物不完全燃烧时产生的挥发性碳氢化合物，是重要的环境和食品污染物。他们的分子中含有两个及两个以上的苯环，是环境中普遍存在的一种致癌物，萘就是其中的一种，它在远低于沸点温度下，就具有很大的蒸气压，因而在加热时，固体萘能不经过液态直接变为萘蒸气，而萘蒸气在冷却时又不可经过液态而直接转变为银白色固体。目前治理含萘废气的方法主要是采用喷淋吸收法，一般是盐溶液或者洗油洗涤，这种物理处理方法效率不高(50％～60％)，能耗大，消耗大量的盐溶液和洗油，而萘的挥发性极强，有一些萘蒸汽来不及处理就逸散到大气中，造成环境污染。本发明催化剂对多环芳烃中的萘作进行催化氧化处理后，萘转化率可以达到99％；同时该催化剂还能催化氧化含萘、苯、甲苯和H2S等的废气，处理后苯≦4mg/m3，甲苯≦15mg/m3，非甲烷总烃≦50mg/m3，H2S≦1mg/m3，符合国家排放标准。
CN106732621A公开了一种抗硫催化燃烧催化剂及制备方法和应用，该方法制备的催化剂可以处理含600ppm SO2有机废气，CN105964255A公开了一种一种高抗硫能力的催化燃烧催化剂的制备，制备的催化剂对二氧化硫有较大抗性。有研究表明，二氧化硫和硫化氢同属硫化物，但二氧化硫对催化剂活性的影响较低，S2-发生反应生成硫单质是催化剂中毒、活性下降的主要原因。而本发明提供的催化剂可将H2S高效转化为SO2，降低硫单质的生成量，提高催化剂的抗硫活性。
本发明抗硫除萘催化剂应用范围广，可用于处理VOCs废气和恶臭气体，能够应用在焦化、石油、橡胶加工等众多化工行业。
发明内容
本发明要解决的技术问题是，填补现有技术的空白，提供一种采用催化氧化处理含萘废气的催化剂，同时该催化剂还具有较高的抗硫化氢能力。本发明处理含萘废气具有绿色、高效等优点。
为实现上述目的，本发明采用的技术方案如下：
本发明提供一种抗硫除萘催化剂的制备，具体包括以下步骤：(1)取铜、锰、铈、铁、镍中一种或者两种以上的金属盐溶于水，配置成一定浓度的改性试剂，搅拌均匀后，将经过120℃抽真空处理之后的载体完全浸渍在该溶液中，常温下微波超声浸渍，90℃-120℃烘干2h，400℃-600℃焙烧3h-5h；
(2)按照比例配置贵金属钯、金的金属盐溶液，贵金属钯、金摩尔比为1：(0～3)；将步骤(1)制得的催化剂浸渍于步骤(2)所配置的溶液中，常温下微波超声处理后滤出，90℃-120℃烘干2h，500℃焙烧3h；
(3)采用H2-N2混合气(H2体积分数由5％提高至50％)活化还原催化剂，常压下还原5h～8h。
一种抗硫除萘催化剂的应用，其工艺流程如下：催化剂对含萘废气催化氧化流程为空气自空气钢瓶1导出后，经过减压阀2减压后，一路气体经质量流量计3后进入萘蒸气发生装置6；或者该路气体先进入含苯/甲苯汽化罐5，再进入萘蒸汽发生器6；再或者该路气体先进入丙酮汽化罐4，再进入含苯/甲苯汽化罐5，最后进入萘蒸汽发生器6。另一路气体做为稀释气经过质量流量计7后与携带萘蒸气的空气进入缓冲罐8混合，进入缓冲罐8的气体还可以包括来自硫化氢气体钢瓶9中经减压阀14减压后的硫化氢，硫化氢由质量流量计12调节流量，来自缓冲罐8的混合气经过预热器10加热升温至150℃-250℃后进入固定床反应器11，在380-550℃连续反应，尾气经尾气吸收装置13后经通风橱放空处理。固定床反应器11反应前后分别连接气相色谱在线检测。见图1。
相对于现有技术，本发明取得了以下技术进步：
(1)本发明采用浸渍法制备、工艺简单、安全，适合大规模生产，工艺放大风险小；
(2)本发明使用的催化剂克服了传统催化剂易烧结、易结碳、易中毒等特点，不产生二次污染；
(3)本发明使用的催化剂，对含萘废气处理效率高，没有萘蒸汽逃逸，浓度范围广；
(4)本发明使用的催化剂可单独使用处理含萘废气，反应温度低，转化完全；
(5)本发明使用的催化剂既可以单独使用处理含萘废气，也可以用于含萘，芳烃、酮类等混合气体的处理，转化完全，能够达到国家排放标准，填补了现有技术的空白；
(6)本发明使用的催化剂具有良好的抗硫化氢能力。
附图说明
图1为本发明催化剂催化氧化处理含萘废气装置示意图；
其中：1为空气钢瓶，2和14均为减压阀，3、7、12均为质量流量计，4为丙酮汽化罐，5为苯/甲苯汽化罐，6为萘蒸气发生器，8为缓冲罐，9为硫化氢气体钢瓶，10为预热器，11为固定床反应器，13为尾气吸收装置，15为催化剂，16为各储罐伴热，17为管道伴热，18为取样阀门。
具体实施方式
下面结合实施例对本发明进一步详细说明，但本发明包括但不限于这些实例。
本发明中使用的原料均可以通过本领域公知的方法制得，或采用市售产品。
催化剂制备方法实施例如下：
实施例1
称取4.3258g Cu(NO3)2.3H2O，9.5746g Mn(NO3)2-50％wt水溶液，0.7795g Fe2(SO4)3，4.5032g Ni(NO3)2.6H2O溶于30ml去离子水中，搅拌均匀后，将20g经高温抽真空处理后的蜂窝陶瓷完全浸渍在该溶液中，常温下微波超声浸渍60min，90℃烘干，115℃干燥2h，400℃恒温焙烧3h。
按照0.15％的负载量配置PdCl2和AuCl3混合水溶液，其中Pd：Au摩尔比1:1，将上步所得的催化剂快速完全倒入混合盐溶液中，调节pH7-8，常温下微波超声浸渍60min后滤出，110℃烘干2h，500℃焙烧3h。
常压下使用H2体积含量5％～50％的H2-N2混合气，还原2h～5h，得到催化剂0.15％(Pd～Au)/Cu～Mn～Fe～Ni/蜂窝陶瓷。
实施例2
称取1.8875g Cu(NO3)2.3H2O，2.7968g Mn(NO3)2-50％wt水溶液，0.7795g Fe2(SO4)3，2.7756g Ce(NO3)3·6H2O溶于30ml去离子水中，搅拌均匀后，将20g高温抽真空处理后的氧化铝完全浸渍在该溶液中，常温下微波超声浸渍60min，90℃烘干，110℃干燥2h，400℃恒温焙烧3h。
按照0.05％Pd的负载量配置PdCl2水溶液，将上步所得快速完全倒入钯盐溶液中，调节pH7-8，常温下微波超声浸渍60min后滤出，110℃烘干2h，500℃焙烧3h。
常压下使用H2含量5％～50％的H2-N2混合气，120℃～300℃还原2h～5h，得到催化剂0.05％Pd/Cu～Mn～Fe～Ce/氧化铝。
实施例3
称取1.8875g Cu(NO3)2.3H2O，2.7968g Mn(NO3)2-50％wt水溶液，1.5203g Ce(NO3)3·6H2O溶于30ml去离子水中，搅拌均匀后，将20g高温抽真空处理的蜂窝陶瓷完全浸渍在该溶液中，常温下微波超声浸渍60min，90℃烘干，110℃干燥2h，400℃恒温焙烧3h。
按照0.2％的负载量配置PdCl2和AuCl3混合水溶液，其中Pd：Au摩尔比1:3，将上步所得的催化剂快速完全倒入盐溶液中，调节pH7-8，常温下微波超声浸渍60min后滤出，110℃烘干2h，500℃焙烧3h。
常压下使用H2体积分数为5％～50％的H2-N2混合气，120℃～300℃还原2h～5h，得到催化剂0.2％(Pd～Au)/Cu～Mn～Ce/蜂窝陶瓷。
实施例4
称取1.8875g Cu(NO3)2.3H2O，2.5670g Fe2(SO4)3，1.5203gCe(NO3)3·6H2O溶于30ml去离子水中，搅拌均匀后，将20g高温抽真空处理后的蜂窝陶瓷完全浸渍在该溶液中，常温下微波超声浸渍60min，90℃烘干，110℃干燥2h，400℃恒温焙烧3h。
按照0.1％Pd的负载量配置PdCl2水溶液，将上步所得的催化剂快速完全倒入钯盐溶液中，调节pH7-8，常温下微波超声浸渍60min后滤出，110℃烘干2h，500℃焙烧3h。
常压下使用H2体积分数为5％～50％的H2-N2混合气，120℃～300℃还原2h～5h，得到催化剂0.1％Pd/Cu～Fe～Ce/蜂窝陶瓷。
实施例5
将实施例1-4中制备得到的催化剂装填于固定床反应装置中，如图1所示(虚线处装置除外)，在萘浓度5000mg/m3，空速25000h-1条件下进行催化氧化评价，结果见表1所示(T50,T99分别为萘分解率50％和99％的分解温度)。
表1本发明催化剂处理含萘废气催化活性
| 催化剂 | T50/℃ | T99/℃ |
| 实施例1 | 245 | 355 |
| 实施例2 | 250 | 360 |
| 实施例3 | 247 | 352 |
| 实施例4 | 254 | 370 |
由表1可知，对含萘废气进行催化氧化处理时，实施例3中催化剂的T50和T99为四组实施例中的最低值，此时催化剂活性最高，其配比为最优配比。
实施例6
为了进一步考察催化剂对含萘含硫有机废气的处理效果，同时最大限度的模拟工业有机废气的组成，于废气中引入苯、甲苯、丙酮等有机组分，在萘浓度5000mg/m3，苯1000mg/m3、甲苯500mg/m3、丙酮1500mg/m3，H2S 400mg/m3，空速25000h-1，催化氧化温度410℃的条件下对实施例3中制备得到的催化剂进行连续评价，考察其寿命和抗硫活性，已连续评价至1000h，详见表2。
表2含硫有机气体催化氧化处理数据
| 污染物 | 苯 | 甲苯 | 丙酮 | 萘 | H2S |
| 反应前浓度mg/m3 | 1000 | 500 | 1500 | 5000 | 400 |
| 反应后浓度mg/m3 | 2.04 | 0.40 | 0.3 | 5.03 | ≤1 |
| 去除率/％ | 99.79 | 99.92 | 99.98 | 99.89 | ≥99.75 |
由表2可知，经过近1000h的连续运行，催化剂各组分去除率仍高于99％，催化剂活性未收到H2S的影响，抗硫能力强，各污染物反应后浓度后经在线检测分析符合GB31571-2015排放标准。
本发明催化剂可应用于催化氧化法处理含萘VOCs气体领域，对萘转化效率高(99％)，而且能够处理含苯、甲苯和萘混合废气，处理后废气达到国家排放标准，不生成二次污染物，同时该催化剂有一定的抗硫中毒能力，进一步拓宽了其应用范围。
Claims (7)
1.一种抗硫除萘催化剂的制备，其特征在于：该催化剂以Al2O3或蜂窝陶瓷为载体，助剂元素和活性组分经过微波超声浸渍在载体上；所述助剂元素为铜、铁、锰、铈、镍中一种或者几种，助剂元素负载量为载体质量的2-12％；活性组分为贵金属钯、金，活性组分负载量为载体质量的0.01-0.20％，其中钯：金摩尔比为1：(0～3)。
2.根据权利要求1所述的一种抗硫除萘催化剂的制备，其特征在于，包括以下步骤：
1)载体首先浸渍在助剂元素的金属盐水溶液中，微波超声浸渍，浸渍后，烘干，焙烧；
2)将步骤1)制得的催化剂浸渍在活性组分的金属盐水溶液中，微波超声浸渍，浸渍后，烘干，焙烧；
3)在还原气下，活化还原步骤2)制得的催化剂，即得到抗硫除萘催化剂。
3.根据权利要求2所述的一种抗硫除萘催化剂的制备，其特征在于，步骤1)中，助剂元素的金属盐为氯化盐、草酸盐、硝酸盐、硫酸盐中的一种或几种；浸渍处理前，载体经过120℃抽真空处理，去除载体孔道中吸附的空气和水分，提高浸渍效果。
4.根据权利要求2所述的一种抗硫除萘催化剂的制备，其特征在于，步骤1)和2)中，采用微波超声浸渍：浸渍时间30-60min，频率40kHz；浸渍后，90℃-120℃烘干2h，400-600℃焙烧3h。
5.根据权利要求2所述的一种抗硫除萘催化剂的制备，其特征在于，步骤3)中，还原气为H2-N2混合气，并根据还原进度不断提高混合气中H2含量，其体积分数由5％提高至50％、还原气空速为1000h-1，温度由100℃提升至220℃，常压下还原5h-8h。
6.根据权利要求1-5任一项所述的一种抗硫除萘催化剂的制备得到的催化剂的应用，其特征在于，所述催化剂对含萘废气催化氧化流程为空气自空气钢瓶(1)导出后，经过减压阀(2)减压后，一路气体经质量流量计3后进入萘蒸气发生器(6)；或者该路气体先进入含苯/甲苯汽化罐(5)，再进入萘蒸汽发生器(6)；又或者该路气体先进入丙酮汽化罐(4)，再进入苯/甲苯汽化罐(5)，最后进入萘蒸汽发生器(6)；另一路气体做为稀释气经过质量流量计(7)后与携带萘蒸气的空气进入缓冲罐(8)混合，进入缓冲罐(8)的气体还可以包括来自硫化氢气体钢瓶(9)中经减压阀(14)减压后的硫化氢，硫化氢由质量流量计(12)调节流量，来自缓冲罐(8)的混合气经过预热器(10)加热升温后进入固定床反应器(11)进行连续催化氧化反应，已去除萘、H2S等组分，固定床反应器(11)反应前后分别连接气相色谱在线检测。
7.根据权利要求6所述的应用，其特征在于，萘蒸气发生器(6)及所有流通含萘气体的管道均设有加热保温设施，加热保温设施温度设定在50℃-100℃，以保证萘持续气化并且在管道中不冷凝；苯/甲苯汽化罐(5)上设有保温装置，保温装置温度设定在30℃-40℃，保证苯/甲苯能够持续气化；固定床反应器(11)前后取样位置至气相色谱进样口位置管线连接有伴热装置，伴热装置温度不低于120℃，保证萘呈气体状态。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113522306A (zh) * | 2021-05-13 | 2021-10-22 | 西北矿冶研究院 | 一种去除挥发性有机物复合型催化剂的制备方法 |
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