CN113842920B - 一种二氧化碳加氢制甲醇催化剂及其成型方法和用途 - Google Patents
一种二氧化碳加氢制甲醇催化剂及其成型方法和用途 Download PDFInfo
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Abstract
本发明提供一种二氧化碳加氢制甲醇催化剂及其成型方法和用途,所述成型方法包括如下步骤:1)将催化剂粉体与成型助剂混合均匀;2)经粒度预处理;3)将预处理后的粉体再压制成片,最后焙烧。该成型方法获得的催化剂活性高,CO2单程转化率可达35%,有效避免了成型后催化剂活性降低的问题,同时解决了成型后催化剂侧压强度的均一性问题。
Description
技术领域
本发明涉及化工催化剂领域,特别是涉及一种二氧化碳加氢制甲醇催化剂及其成型方法和用途。
背景技术
甲醇是重要的化工基础原料和清洁液体燃料,在世界范围内的化工产品中,其产量仅次于乙烯、丙烯和苯,居第四位。目前,甲醇被广泛用于精细化工、石油化工、染料、涂料、医药、农药、汽车和国防等工业中。随着自然环境的不断恶化,化石燃料的日渐枯竭,未来能源结构将转向清洁可再生能源。甲醇便于贮存和运输,是良好的液态储氢载体,并且甲醇具有较高的含氧量,燃烧热值高,将成为未来主要燃料的候补燃料,大规模推广应用和全球布局生产甲醇燃料,对于我国积极参与全球环境治理,落实减排承诺,发展生态文明建设具有极其重要的意义。将二氧化碳转化成甲醇等有用化学品或者燃料,可同时解决可再生能源的存储问题、大气二氧化碳浓度增加导致的环境安全问题和过度依赖化石燃料的能源安全问题,不仅提升我国能源多元化保障能力,同时为我国“3060”双碳目标提供技术支撑。
发明内容
鉴于现有催化剂成型技术的缺点,本发明的目的在于提供一种二氧化碳加氢制甲醇催化剂及其成型方法和用途,用于解决现有技术中的问题。
为实现上述目的及其他相关目的,本发明是通过以下技术方案获得的。
本发明提供一种二氧化碳加氢制甲醇催化剂的成型方法,包括如下步骤:
1)将催化剂粉体与成型助剂混合均匀;
2)经粒度预处理;
3)将预处理后的粉体再压制成片,最后焙烧。
优选地,所述催化剂粉体的粒径为2~20μm。
优选地,所述成型助剂包括粘合剂和润滑剂中的一种或两种。
优选地,所述粘合剂选自糊精、淀粉和粘土中的一种或多种。
优选地,以所述催化剂粉体的质量为基准计,所述粘合剂的添加量为不超过10wt%,优选为不超过5wt%,更优选地,所述粘合剂的添加量为0.5~5wt%;更优选地,所述粘合剂的添加量为0.5~4.5wt%。
优选地,所述润滑剂包括硬脂酸镁、硬脂酸、滑石粉、石墨和炭黑中的一种或多种。优选地,以催化剂粉体的质量为基准计,所述润滑剂的添加量为0.5~10wt%,优选1wt%~5wt%,更优选为1~4.5wt%。
优选地,所述粒度预处理是压片破碎。
优选地,所述粒度预处理后获得的粉体的粒度为0.05~0.65mm,如可以为0.05~0.15mm、0.1~0.2mm、0.15~0.25mm、0.2~0.3mm、0.25~0.35mm、0.3~0.4mm、0.35~0.45mm、0.4~0.5mm、0.45~0.55mm、0.5~0.6mm或0.55~0.65mm。优选为0.30~0.60mm。
优选地,经粒度预处理后获得的粉体堆密度为0.6~1.2kg/L,优选为0.7~1.1kg/L。
优选地,所述压制成片时的压力为2t~5t机械压力。
优选地,所述压制成片后为圆柱体,所述圆柱体的直径3.5mm~6mm,长度为3.5~6mm。
优选地,所述焙烧的温度300~600℃,优选400~500℃。优选地,所述焙烧时间至少为3h。更优选地,所述焙烧时间控制在3~10h。
本发明还提供了如上述所述的成型方法获得的催化剂。
本发明还提供了如上述所述的催化剂在二氧化碳加氢制甲醇中的用途。
本发明还提供了一种二氧化碳加氢制甲醇的方法,采用如上述所述的二氧化碳加氢制甲醇催化剂,反应温度在230~280℃,反应压力5.0~10.0Mpa。
优选地,在二氧化碳加氢制甲醇反应中,作为原料气的H2与CO2的摩尔比为(2~5):1。
本发明与现有技术相比具有如下特点:
(1)本申请中经粒度预处理,提升粉体堆密度同时增加了粉体流动性,有利于连续填充至压制成片设备如压片机中,避免堵料,并且有效地提高了成型后催化剂强度的均一性。
(2)该成型方法获得的催化剂能够保持高活性,CO2单程转化率可达35%,有效避免了成型后催化剂活性降低的问题;而且成型后,非常利于工业化大规模使用。
附图说明
图1显示为对比例1中催化剂侧压强度图。
图2显示为实施例2中成型方法获得的催化剂的侧压强度图。
具体实施方式
以下由特定的具体实施例说明本发明的实施方式,熟悉此技术的人士可由本说明书所揭露的内容轻易地了解本发明的其他优点及功效。
在进一步描述本发明具体实施方式之前,应理解,本发明的保护范围不局限于下述特定的具体实施方案;还应当理解,本发明实施例中使用的术语是为了描述特定的具体实施方案,而不是为了限制本发明的保护范围。下列实施例中未注明具体条件的试验方法,通常按照常规条件,或者按照各制造商所建议的条件。
当实施例给出数值范围时,应理解,除非本发明另有说明,每个数值范围的两个端点以及两个端点之间任何一个数值均可选用。除非另外定义,本发明中使用的所有技术和科学术语与本技术领域技术人员通常理解的意义相同。除实施例中使用的具体方法、设备、材料外,根据本技术领域的技术人员对现有技术的掌握及本发明的记载,还可以使用与本发明实施例中所述的方法、设备、材料相似或等同的现有技术的任何方法、设备和材料来实现本发明。
本申请中申请人基于长期实践发现,目前工业甲醇催化剂的成型中存在缺陷,无法有效的同时满足高活性、高选择性,高稳定性,高使用寿命,具有必要强度及适宜形状的情况,从而导致成型后的催化剂催化效果变差如活性变低、选择性变低或者稳定性变低的问题,或使用效果变差如在使用时容易有碎渣导致堵料或堵气的问题。
而申请人发现,通过如本申请中的成型方法就可以有效解决上述问题,由此形成的催化剂粒径一致,质量均匀;催化剂堆密度高,强度好;圆柱体外表光滑,便于填装。
催化剂成型工艺中涉及很多控制因素,包括原粉堆密度、粒径;成型粘结剂、润滑剂等。在成型过程中,如果催化剂原粉堆密度较低,粒径较小,会导致粉体流动性较差,在成型过程中粉体很难均匀进入模具,导致催化剂成型压力不够,同时催化剂堆密度及强度分布不均匀,达不到工业催化剂使用标准。同时成型过程中粘结剂和润滑剂适量添加也很重要,对成型后催化剂活性及堆密度、强度影响较大。如果粘结剂添加量较少,导致成型片剂容易断裂。粘结剂添加量较大,会导致催化剂原粉粘度增加,粉体流动性较差,也导致催化剂活性位减少,降低催化剂性能。同样对于润滑剂而言,添加量较少,催化剂脱模困难,模具摩檫力大,模具容易发热,导致损耗模具,同时催化剂脱模片剂易起毛刺,毛刺在后期使用过程中容易形成碎渣从而导致堵料或堵气。对于成型后的催化剂颗粒来说,如果侧压强度过低,工业填装时容易破碎,如果侧压强度过高,催化剂活性会降低。
由此,申请人提供一种通过干法压制成型的方法成型,其先将干态原料混合,然后经粒度预处理,再经压片机等设备压制成型。
这种方法不仅保持了催化剂的活性,而且催化剂表面光滑,无裂痕和毛刺,侧压强度适当且均一。
本申请中,所述侧压强度的测试方法为:将单颗粒催化剂以径向放置测试强度机器平台中间,均匀对其施加负载直至催化剂破碎,记录催化剂破碎负载压力,即为该单颗粒催化剂径向侧压强度。
本申请成型方法中涉及的催化剂粉体不受限制,只要是现有技术中用于二氧化碳加氢制甲醇的催化剂均可。本申请实施例中所采用的催化剂粉体组成为,Cu:30~60wt%;Zn:18~42wt%;Al:8~25wt%;M:0.1~5wt%;其中,M选自Fe、Ni、Zr、Co和Y中的至少一种。
实施例1
本实施例中二氧化碳加氢制甲醇催化剂的成型方法如下:
将100g二氧化碳加氢催化剂粉体与1.5g淀粉和1g滑石粉混合均匀,通过预处理将混合原粉造粒至0.45-0.52mm,堆密度控制在0.82g/mL,再将处理后粉体加入干压成型机压制成片,压成Φ5×5mm圆柱体,再将圆柱状催化剂在350℃焙烧4h。
成型后催化剂表面光滑,无裂痕和毛刺,其堆密度1.3g/mL,侧压强度为220N/颗。
实施例2
本实施例中二氧化碳加氢制甲醇催化剂的成型方法如下:
将100g二氧化碳加氢催化剂粉体与2.2g粘土和1.5g石墨粉混合均匀,通过预处理将混合原粉造粒至0.50-0.60mm,堆密度控制在0.94g/mL,再将处理后粉体加入干压成型机压制成片,压成Φ5×5mm圆柱体,再将圆柱状催化剂在400℃焙烧8h。
成型后催化剂表面光滑,无裂痕和毛刺,其堆密度1.42g/mL,侧压强度为246N/颗。
实施例3
本实施例中二氧化碳加氢制甲醇催化剂的成型方法如下:
将100g二氧化碳加氢催化剂粉体与3.2g石墨粉混合均匀,通过预处理将混合原粉造粒至0.3-0.4mm,堆密度控制在0.7g/mL,再将处理后粉体加入干压成型机压制成片,压成Φ5×5mm圆柱体,再将圆柱状催化剂在500℃焙烧5h。
成型后催化剂表面光滑,无裂痕和毛刺,其堆密度1.24g/mL,侧压强度为217N/颗。
实施例4
本实施例中二氧化碳加氢制甲醇催化剂的成型方法如下:
将100g二氧化碳加氢催化剂粉体与4.5g淀粉和4.5g炭黑混合均匀,通过预处理将混合原粉造粒至0.55-0.60mm,堆密度控制在1.1g/mL左右,再将处理后粉体加入干压成型机压制成片,压成Φ5×5mm圆柱体,再将圆柱状催化剂在500℃焙烧10h。
成型后催化剂表面光滑,无裂痕和毛刺,其堆密度1.51g/mL,侧压强度为305N/颗。
应用例1
采用5mL固定床反应器,将实施例1~4成型后催化剂破碎至40-60目,催化剂装填量为1.5g,以1.5g细石英砂稀释,还原气氛为5%H2-95%N2,流量为80mL/min,还原温度为230℃,还原时间为8h。还原过程结束后,降温至180℃,用N2将压力冲至9.0MPa,进原料气空速4000h-1,原料气组分H2:CO的摩尔比为3:1,升温至反应温度250℃开始反应,反应尾气产物由在线色谱分析。在5mL装置评价必须破碎至40-60目,该装置催化剂评价反应管管径较小,但在放大工业化生产中,其效果相当,本申请实施例中固定床反应器的反应管直径约为0.13cm,而催化剂的填充高度为1.5cm。
尾气分析条件为:色谱柱为Porapak-T,柱温90℃,载气为氩气,流速25mL/min,电流60mA,液相产物由冷阱收集,取出经色谱分析,分析条件为:谱柱为TDX-01,柱温160℃,载气为氩气,流速30mL/min,电流60mA。
实施例1~4中成型方法获得的催化剂评价结果见表1,从表1中看出,采用该发明成型工艺,催化剂活性高,有效避免了成型后催化剂活性降低的问题。
对比应用例1
采用5mL固定床反应器,将100g二氧化碳加氢催化剂粉体、2.2g粘土和1.5g石墨粉混合后,直接压片破碎至40-60目,催化剂装填量为1.5g,以1.5g细石英砂稀释,还原气氛为5%H2-95%N2,流量为80mL/min,还原温度为230℃,还原时间为8h。还原过程结束后,降温至180℃,用N2将压力冲至9.0MPa,进原料气空速4000h-1,原料气组分H2:CO的摩尔比为3:1,升温至反应温度250℃开始反应,反应尾气产物由在线色谱分析。尾气分析条件为:色谱柱为Porapak-T,柱温90℃,载气为氩气,流速25mL/min,电流60mA,液相产物由冷阱收集,取出经色谱分析,分析条件为:谱柱为TDX-01,柱温160℃,载气为氩气,流速30mL/min,电流60mA。
表1实施例1~4催化剂性能表
由上述数据可以看出,采用本申请中技术方法形成的催化剂的活性并未降低,并且由此制备获得的催化剂颗粒的侧压强度适当且均一性好,催化剂颗粒的断裂或裂痕及毛刺少,表面光滑圆润,非常有利于工业化大规模填装并长时间稳定运行。
对比例1
本对比例中成型方法未经粒度预处理,包括如下步骤:
将100g二氧化碳加氢催化剂粉体与2.2g粘土和1.5g石墨粉混合均匀,将混合粉体加入干压成型机压制成片,压成Φ5×5mm圆柱体,再将圆柱状催化剂在400℃焙烧8h。
成型后随机抽取10颗催化剂,测试其侧压强度,见图1。
同样随机抽取实施例2成型催化剂10颗,测试其侧压强度,见图2。
对比图1和图2可以看出,通过增加了干法造粒进行粒度预处理,提高了成型后催化剂强度的均一性。
上述实施例仅例示性说明本发明的原理及其功效,而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下,对上述实施例进行修饰或改变。因此,举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变,仍应由本发明的权利要求所涵盖。
Claims (7)
1.一种二氧化碳加氢制甲醇催化剂的成型方法,包括如下步骤:
1)将催化剂粉体与成型助剂混合均匀;
2)经粒度预处理;
3)将预处理后的粉体再压制成片,最后焙烧;
所述粒度预处理是压片破碎;所述粒度预处理后获得的粉体的粒度为0.05~0.65mm;经粒度预处理后获得的粉体堆密度为0.6~1.2kg/L;
所述成型助剂包括粘合剂和润滑剂中的一种或两种;所述粘合剂选自糊精、淀粉和粘土中的一种或多种;以所述催化剂粉体的质量为基准计,所述粘合剂的添加量为不超过10wt%;所述润滑剂包括硬脂酸镁、硬脂酸、滑石粉、石墨和炭黑中的一种或多种;以催化剂粉体的质量为基准计,所述润滑剂的添加量为0.5~10wt%。
2.根据权利要求1所述的成型方法,其特征在于,所述催化剂粉体的粒径为2~20μm。
3.根据权利要求1所述的成型方法,其特征在于,所述压制成片时的压力为2t~5t机械压力;和/或,所述压制成片后为圆柱体,所述圆柱体的直径3.5mm~6mm,长度为3.5~6mm。
4.根据权利要求1所述的成型方法,其特征在于,所述焙烧的温度300~600℃:和/或,所述焙烧时间为至少3h。
5.一种如权利要求1~4任一项所述的成型方法获得的催化剂。
6.如权利要求5所述的催化剂在二氧化碳加氢制甲醇中的用途。
7.根据权利要求6所述的用途,其特征在于,二氧化碳加氢制甲醇反应温度在230~280℃,反应压力5.0~10.0Mpa。
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