CN111744500A - 一种耐高氧的中温水解催化剂及其制备方法 - Google Patents
一种耐高氧的中温水解催化剂及其制备方法 Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
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- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
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Abstract
本发明公开了一种耐高氧的中温水解催化剂及其制备方法。该催化剂以TiO2‑SiO2‑MnO2复合氧化物为载体,以Li‑W‑Cs为活性组分,以Cu为助剂。在一定温度、压力条件下,将钛源、硅源、锰源、模板剂等在高压合成釜内反应制备出载体,然后加入活性组分进行离子交换,过滤焙烧后得到催化剂。催化剂具有水解转化率高、寿命长的特点,可用于水煤气,半水煤气、焦炉气、高炉气等各种含氧工业原料的COS的水解脱除。
Description
技术领域
本发明涉及用于水煤气、半水煤气、焦炉气、高炉气等各种含氧工业原料的一种耐高氧的中温水解催化剂,属于煤化工领域。
背景技术
目前,各种化工原料气中COS、CS2含量很高,必须对其进行脱除才能进行后续的加工利用。市场上广泛使用的脱除方法是使COS、CS2发生水解反应转化为H2S,然后通过湿法脱硫或固体脱硫剂如ZnO、Fe2O3、活性炭等对其进行吸附脱除。在COS和CS2发生水解反应时需要用到水解催化剂,普通的水解催化剂以氧化铝为载体,以碱性金属化合物为其活性组分,在高氧(氧含量大于0.1%)、中温(100-300℃)条件下使用时,容易发生硫酸盐化,即水解产生的H2S与氧反应生产硫酸或亚硫酸,硫酸或亚硫酸与水解催化剂的碱性金属化合物发生中和反应破坏催化剂的碱性中心,致使催化剂中毒失活,同时生成的硫酸或亚硫酸与载体氧化铝发生反应,破坏催化剂的载体结构,造成催化剂活性组分流失、强度显著下降,系统阻力增加。工业应用表明在高氧情况下,正常使用寿命约24个月的普通的水解催化剂只能使用1个月,寿命大大缩减。因此,开发一种耐高氧的中温水解催化剂很有意义。
CN104667926A提供了一种低温羰基硫水解催化剂,以改性γ-FeOOH 为活性组分,改性γ-FeOOH 催化剂采用如下方法制备:亚铁盐与改性剂混合均匀形成溶液,搅拌条件下向溶液中滴加沉淀剂,调节 pH 至 6.5-8,经陈化、 离心水洗,加入成型剂、 粘结剂混捏,成型烘干后得产品。控制所述改性 γ-FeOOH 中所述改性剂与铁盐的摩尔比为0.005-0.1,最佳优选摩尔比为 0.01-0.05。该发明羰基硫水解催化剂在30-80℃的低温条件下,在原料气中 CO2的浓度,高的情况下,可以实现高效脱除COS,且精度高。该发明并未提及如何避免硫酸盐化引起催化剂使用的问题及催化剂的使用寿命。
CN1189394A公开的一种有机硫水解催化剂,是以四水合钼酸铵、碳酸钾及γ-Al2O3制备而成的,该催化剂用来改善常低温条件下COS水解活性。中国专利CN101050389A公开了一种煤制燃气中COS的净化方法,该催化剂是以活性氧化铝载体负载双过渡金属钴-钼,或铁-钼,或镍-钼及碱性金属氧化物的水解转化催化剂。
上述发明均不能解决在高氧、中温条件下的COS的水解问题。
发明内容
为解决现有技术中高氧、中温条件下的COS水解问题,本发明提供一种耐高氧的水解催化剂,以TiO2-SiO2-MnO2复合氧化为载体,以Li-W-Cs为活性组分,以Cu为助剂,可广泛用于水煤气、半水煤气、焦炉气等含氧原料气的COS水解。
本发明通过以下技术方案实现:
一种耐高氧的中温水解催化剂及其制备方法,该催化剂以TiO2-SiO2-MnO2复合氧化物为载体,以Li-W-Cs为活性组分,以Cu为助剂;以催化剂的总质量百分比计,活性组分 Li含量为3-6%, WO3含量为10-20%,Cs含量为0.5-2%,助剂Cu的含量为3-6%;以载体的质量百分含量计,TiO2-SiO2-MnO2复合氧化载体中TiO2含量为50-70%,SiO2含量为10-20%,MnO2含量为10-40%。
催化剂的制备方法:将一定量的钛源、硅源、锰源、模板剂和水混合均匀,然后移入高压合成釜中密封,在压力为9.0MPa、温度为220~320℃的条件下晶化24~48h;将晶体浆液的pH值调节至10,向反应釜中加入一定量的可溶性的锂盐、钨盐、铯盐和铜盐,在温度为80℃条件下,进行离子交换反应4~8h;然后将上述浆液加入絮凝剂沉淀、过滤,过滤后滤液收集用于下次反应,滤饼经洗涤、干燥后挤条成型,经100~150℃干燥2~4h,500~700℃焙烧3~6h后得到耐高氧的中温水解催化剂。
所述的催化剂使用前需要预还原处理,催化剂的比表面积为230~326m2/g,孔容为0.35~0.65mL/g,孔径为4-10nm。
所述的模板剂为季戊四醇、四丙基氢氧化铵、十六烷基三甲基溴化铵中的一种。
所述的催化剂的制备方法中用三乙胺将晶体浆液的pH值调节至10。
所述的催化剂的制备方法中絮凝剂为PSAA、PPFC、PPAC中的一种。
本发明的有益效果:
⑴本发明的催化剂以TiO2-SiO2-MnO2复合氧化物为载体,该载体通过模板剂晶化的方式合成的微晶载体,具有很好的抗酸性,不易受到强酸的侵蚀,活性组分与载体结合牢固,不易流失。β-MnO2可以促使水解反应发生,独有的孔结构可以及时解析出形成的单质S,防止S长期停留在催化剂微孔中而氧化成硫酸盐。经过高压合成釜晶化合成的复合载体,具有良好水热稳定性,水解催化剂通常用在变换反应后面,工况的水蒸气含量约50%,在高水汽情况下,可以保证催化剂骨架结构的完整,强度不受影响,不会产生粉化现象,系统阻力不增加,为催化剂的长期稳定运行提供有力的支撑。
⑵水解催化剂以Li-W-Cs为活性组分,Li、Cs提供水解反应的双碱性中性,Cs的强碱性可以显著提高催化剂的水解活性,优先与硫酸盐化产生的酸发生反应,从而保护碱性相对弱的Li,Li的弱碱性可以保证水解催化剂碱性中心的存在,不易造成水解活性的彻底丧失。W与水解产生的H2S反应转化为WS2,WS2可以催化体中的O2与原料气体中的H2发生反应转化H2O,从而减少硫酸盐化,保护催化剂碱性中心不易被破坏。
⑶助剂Cu可以催化CO与氧的反应,从而达到除氧的目的,反应方程式:CO+O2=CO2。在水解催化剂的初期,系统中H2S较少,W无法转化为WS2,W催化H2与O2的能力很弱,这个阶段容易发生硫酸盐化,而铜可以催化CO与O2反应,达到脱氧的目的,这样水解催化剂前期依靠Cu脱氧,后期靠W和Cu脱氧,全程减少了硫酸盐的发生,另外助剂Cu在反应釜内可以与W结合形成Cu-W键,可以显著增加催化剂脱氧的性能,最大限度的避免硫酸盐化的产生。
实施例
下面结合具体实施案例来详述本发明催化剂的特点、制备方法及其催化性能,但是本发明不仅限于这些例子,也不构成对发明实施范围的任何限定。
实施例1
将35g偏钛酸、28g碱性硅溶胶(SiO2含量25%)、56g软锰矿(MnO2含量50%)、3g模板剂季戊四醇和1000ml去离子水混合均匀,然后移入高压合成釜中密封,在压力为9.0MPa、温度为220℃的条件下晶化24h;用三乙胺将晶体浆液的pH值调节至10,向反应釜中加入29.6g的硝酸锂、24.1g的偏钨酸铵、2.9g的醋酸铯和17.6g的硝酸铜,在温度为80℃条件下,进行离子交换反应4h;然后将上述浆液加入PSAA(聚硅酸絮凝剂)沉淀、过滤,过滤后滤液收集用于下次反应,滤饼经洗涤、干燥后挤条成型,经150℃干燥2h, 700℃焙烧3h后得到耐高氧的中温水解催化剂。该催化剂的比表面积为326m2/g,孔容为0.50mL/g,孔径为7nm。将此催化剂命名为Cat1。
实施例2
将47.4g偏钛酸、47.4g碱性硅溶胶(SiO2含量25%)、39.5g软锰矿(MnO2含量50%)、2g模板剂四丙基氢氧化铵和1000ml去离子水混合均匀,然后移入高压合成釜中密封,在压力为9.0MPa、温度为320℃的条件下晶化48h;用三乙胺将晶体浆液的pH值调节至10,向反应釜中加入59.2g的硝酸锂、12.0g的偏钨酸铵、1.45g的醋酸铯和11.7g的硝酸铜,在温度为80℃条件下,进行离子交换反应8h;然后将上述浆液加入絮凝剂PPFC(聚磷氯化铁)沉淀、过滤,过滤后滤液收集用于下次反应,滤饼经洗涤、干燥后挤条成型,经120℃干燥4h, 500℃焙烧4h后得到耐高氧的中温水解催化剂。该催化剂的比表面积为230m2/g,孔容为0.65mL/g,孔径为10nm。将此催化剂命名为Cat2。
实施例3
将53.6g偏钛酸、61.2g碱性硅溶胶(SiO2含量25%)、61.2g软锰矿(MnO2含量50%)、5g模板剂十六烷基三甲基溴化铵和1000ml去离子水混合均匀,然后移入高压合成釜中密封,在压力为9.0MPa、温度为270℃的条件下晶化36h;用三乙胺将晶体浆液的pH值调节至10,向反应釜中加入49.3g的硝酸锂、18.1g的偏钨酸铵、0.72g的醋酸铯和8.8g的硝酸铜,在温度为80℃条件下,进行离子交换反应6h;然后将上述浆液加入絮凝剂PPAC(聚磷氯化铝)沉淀、过滤,过滤后滤液收集用于下次反应,滤饼经洗涤、干燥后挤条成型,经100℃干燥3h,600℃焙烧6h后得到耐高氧的中温水解催化剂。该催化剂的比表面积为285m2/g,孔容为0.35mL/g,孔径为4nm。将此催化剂命名为Cat3。
实施例4
本实施例对上述实施例1~3的脱氯催化剂和市售的水解催化剂Cat4活性对比测定。
评价方法:将各实施例制备的催化剂分别取30ml装入Φ27×3.5mm的反应管,催化剂床层高度48mm,所用原料气为焦炉气,其组分含量:O2为0.5%、H2为60%、CO为3%、CO2为8%、C2H4为2%、CH4为16%、COS为100mg/Nm3、余为N2。
预还原:先通入10%H2+90%N2的混合气,400℃还原8h。
测试方法:还原结束后降温至300℃并恒温,,将原料焦炉气通入检测系统内并开始计时,每小时用微量硫分析仪测定一次反应器进出口气中COS含量,确定每个催化剂的水解转化率。运行一段时间后的水解转化率如表1所示。
COS水解转化率根据反应器进出口COS含量,按下式计算:
a = (C1-C2)/C1×100%
C1 、C2 —反应器进、出口COS含量,mg/m3;
表1 不同催化剂的水解转化率(%)
从表1的数据可知,Cat1,Cat2,Cat3,Cat4四种水解催化剂水解转化率初期都在95%以上,随着运行时间的延长,Cat1,Cat2,Cat3活性略有下降,特别是运行240h后基本能保持原有的活性,而市售的Cat4随着运行时间的延长水解活性逐步降低,特别是运行到240h,活性出现断崖式的下降,这和其工业运行数据保持一致。通过表1可说明本发明的耐高氧中温水解催化剂具有活性稳定性好,寿命长的特点,完全解决高氧中温条件下COS的水解问题。
Claims (10)
1.一种耐高氧的中温水解催化剂及其制备方法,其特征在于:该催化剂以TiO2-SiO2-MnO2复合氧化物为载体,以Li-W-Cs为活性组分,以Cu为助剂。
2.根据权利要求1所述催化剂,其特征在于:以载体的质量百分含量计,所述的TiO2-SiO2-MnO2复合氧化载体中TiO2含量为50-70%,SiO2含量为10-20%,MnO2含量为10-40%。
3.根据权利要求1所述催化剂,其特征在于:以催化剂的总质量百分比计,活性组分 Li含量为3-6%,WO3含量为10-20%,Cs含量为0.5-2%。
4.根据权利要求1所述催化剂,其特征在于:以催化剂的总质量百分比计,助剂Cu的含量为3-6%。
5.根据权利要求1所述的催化剂,其特征在于:该催化剂的比表面积为230~326m2/g,孔容为0.35~0.65mL/g,孔径为4-10nm。
6.根据权利要求1所述催化剂的制备方法,其特征在于:催化剂的制备方法如下:
将一定量的钛源、硅源、锰源、模板剂和水混合均匀,然后移入高压合成釜中密封,在压力为9.0MPa、温度为220~320℃的条件下晶化24~48h;将晶体浆液的pH值调节至10,向反应釜中加入一定量的可溶性的锂盐、钨盐、铯盐和铜盐,在温度为80℃条件下,进行离子交换反应4~8h;然后将上述浆液加入絮凝剂沉淀、过滤,过滤后滤液收集用于下次反应,滤饼经洗涤、干燥后挤条成型,经100~150℃干燥2~4h,500~700℃焙烧3~6h后得到耐高氧的中温水解催化剂。
7.如权利要求6所述的催化剂的制备方法,其特征在于:所述的模板剂为季戊四醇、四丙基氢氧化铵、十六烷基三甲基溴化铵中的一种。
8.根据权利要求6所述的催化剂的制备方法,其特征在于:用三乙胺将晶体浆液的pH值调节至10。
9.根据权利要求6所述的催化剂的制备方法,其特征在于:所述的絮凝剂为PSAA、PPFC、PPAC中的一种。
10.根据权利要求1或6所述的催化剂,其特征在于:该催化剂使用前需要预还原处理。
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CN85104184A (zh) * | 1983-12-30 | 1986-11-26 | 联合碳化公司 | 以一氧化碳、氢气和烯烃为原料制备醇类的催化过程 |
WO2013135663A1 (de) * | 2012-03-13 | 2013-09-19 | Bayer Intellectual Property Gmbh | Verfahren zur reduktion von kohlendioxid bei hohen temperaturen an mischmetalloxid-katalysatoren umfassend edelmetalle |
WO2013135662A1 (de) * | 2012-03-13 | 2013-09-19 | Bayer Intellectual Property Gmbh | Verfahren zur reduktion von kohlendioxid bei hohen temperaturen an mischmetalloxidkatalysatoren |
CN104169210A (zh) * | 2012-03-13 | 2014-11-26 | 拜耳知识产权有限责任公司 | 在两种操作模式之间交替操作制备co和/或h2的方法 |
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CN85104184A (zh) * | 1983-12-30 | 1986-11-26 | 联合碳化公司 | 以一氧化碳、氢气和烯烃为原料制备醇类的催化过程 |
WO2013135663A1 (de) * | 2012-03-13 | 2013-09-19 | Bayer Intellectual Property Gmbh | Verfahren zur reduktion von kohlendioxid bei hohen temperaturen an mischmetalloxid-katalysatoren umfassend edelmetalle |
WO2013135662A1 (de) * | 2012-03-13 | 2013-09-19 | Bayer Intellectual Property Gmbh | Verfahren zur reduktion von kohlendioxid bei hohen temperaturen an mischmetalloxidkatalysatoren |
CN104169210A (zh) * | 2012-03-13 | 2014-11-26 | 拜耳知识产权有限责任公司 | 在两种操作模式之间交替操作制备co和/或h2的方法 |
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