CN107442164A - 挤出式分子筛蜂窝催化剂及其制备方法 - Google Patents
挤出式分子筛蜂窝催化剂及其制备方法 Download PDFInfo
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- CN107442164A CN107442164A CN201710503096.7A CN201710503096A CN107442164A CN 107442164 A CN107442164 A CN 107442164A CN 201710503096 A CN201710503096 A CN 201710503096A CN 107442164 A CN107442164 A CN 107442164A
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- Prior art keywords
- molecular sieve
- preparation
- bake
- kiln
- honeycomb
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 28
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- YOWAEZWWQFSEJD-UHFFFAOYSA-N quinoxalin-2-amine Chemical compound C1=CC=CC2=NC(N)=CN=C21 YOWAEZWWQFSEJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 iron ion Chemical class 0.000 claims abstract description 3
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 11
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- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 5
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims 1
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- 238000004886 process control Methods 0.000 abstract 1
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical class [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
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- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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Abstract
本发明涉及一种挤出式分子筛蜂窝催化剂及其制备方法,其特征在于将制备得到的蜂窝陶瓷体,在一定温度下浸渍在含有铜离子、铁离子、过渡金属离子及氨基甲酸铵混合液中,使活性液中的金属离子与蜂窝陶瓷体中的分子筛部分活性位发生反应,然后经高温燃烧在氨基甲酸铵作用下使剩余分子筛活性位、多组分金属离子充分反应,在载体表面实现活性组分分布均匀、高效率负载;其具有活性组分负载均匀、涂层脱落率低的优点,在215~520℃的温度区间内NOx的转化率均高于75%,显示了宽温度窗口下较好的De‑NOx效果。本发明制备方法简单、易于过程控制。
Description
技术领域
本发明涉及挤出式分子筛蜂窝催化剂及其制备方法,属于汽车排放技术领域,尤其属于SCR脱硝的催化剂制备领域。
背景技术
为满足NOx排放法规,机内净化及后处理技术必不可少,目前, SCR技术已成为中重型柴油机企业首选降低NOx技术路线,其原理是利用尿素水解产生的氨气和汽车尾气中的NOx经过涂有活性涂层的载体时,NOx快速被氨气还原为氮气和水,氨气和NOx之所以能够在后处理载体上进行快速的化学反应,是与载体组成密不可分的。载体承担着涂层和活性组分,其次还提供合适的催化反应通道,催化剂与载体如何组合使其功能发挥至最大,研究表明,整体式蜂窝催化剂被认为是较为理想的能够将催化效果发挥最大,而整体式蜂窝催化剂主要分为涂覆式和共混挤出式两种。涂覆式是将催化剂粉末与一定的添加剂混合制备成催化剂浆料涂覆在蜂窝陶瓷载体上,形成一定厚度的活性涂层,目前主要使用的催化剂有钒钨钛催化剂和分子筛催化剂。然而此种方法面临着涂层不牢固和催化剂率不高的问题,即随着使用里程的增加,载体上的催化剂会发生脱落,以及部分中毒失活,导致NOx转化率降低,无法满足排放法规要求;共混挤出成型法制备蜂窝催化剂是将催化剂与一定的添加剂混合,通过一系列的工艺步骤挤压成蜂窝状,即催化剂均匀的分布于载体的各个部分,此种方法缩短了SCR整体式蜂窝催化剂制备工艺流程,弥补了传统涂覆式整体催化剂涂层脱落的问题,提高了整体式SCR催化剂的耐久里程。
CN201410038635.0一种蜂窝状脱硝催化剂的制备方法,属于催化剂领域。所述的催化剂由二氧化钛、五氧化二钒、三氧化钨和助剂组成。催化剂的制备方法是将原料组分混合,混合后混炼和堆置陈腐,之后将得到的泥料过滤再次堆置陈腐,陈腐之后挤出成型得到湿胚,将湿胚进行断面切割得到规则端面定长湿胚和端部废料;将规则端面定长湿胚干燥、煅烧和成型;将端部废料与滤料混合,循环使用。相对于现有工艺流程而言,几乎无废料产生,降低了资源消耗,减少了对环境的影响,此外,采用本发明技术方案,能耗降低约6.77%。
CN201110216666.7 公开了一种陶瓷蜂窝式脱硝催化剂及制备方法, 是将催化剂活性成分、催化剂载体和成型助剂经混合、成型和煅烧而成,其中所述催化剂活性成分为硫酸亚铁。在一个实施例中,催化剂活性成分包括20-40重量份的硫酸亚铁,催化剂载体包括60-90重量份的分子筛,成型助剂包括:2-4重量份的柠檬酸、2-6重量份羧甲基纤维素钠、2-6重量份的聚氧化乙烯、0.2-1.0重量份的甘油、2-4重量份的硝酸、90-120重量份的拟薄水铝石、30-40重量份的苏州土、2-6重量份的田箐粉、10-30重量份的玻璃纤维。本发明催化剂的原料成本低,并且可以均无毒性。本发明脱硝催化剂模块具有高脱硝效率,并且具有一定的抗中毒性能和机械强度。
CN200910102190.7 公开了一种以钙铝石为涂层的蜂窝陶瓷型整体催化剂及其制备方法和应用。所述蜂窝陶瓷型整体催化剂是以蜂窝陶瓷为载体,在蜂窝陶瓷表面包覆钙铝石涂层,然后在钙铝石涂层表面负载复合金属氧化物;所述复合金属氧化物为钙钛矿型氧化物或尖晶石型氧化物,所述整体催化剂中,钙铝石涂层与蜂窝陶瓷的质量比为0.02~0.2∶1,复合金属氧化物与蜂窝陶瓷的质量比为0.02~0.2∶ 1。以钙铝石为涂层的蜂窝陶瓷型整体催化剂可用作催化燃烧催化剂,具备良好黏附性、高热稳定性和高催化活性。
上述制备脱硝催化剂及其制备方法存在问题如下:(1)内部的活性组分无法得到利用,造成催化活性组分浪费及制备成本提高;(2)催化剂温度窗口窄;(3)制备工艺复杂;(4)涂层易脱落。
发明内容
本发明的目的在于提供挤出式分子筛蜂窝催化剂及其制备方法,其具有涂层脱落率低、活性组分负载均匀的优点,在215~520℃的温度区间内NOx的转化率均高于75%,显示了宽温度窗口下较好De-NOx效果,同时其制备工艺简单、易于控制。
本发明的技术方案是这样实现的:挤出式分子筛蜂窝催化剂及其制备方法,其特征在于具体步骤如下:(1)泥坯的制备 将粘土、分子筛、莫来石纤维、纤维素、高温粘结剂、润滑剂、增塑剂和水等按照一定质量比放入混泥机中进行混炼捏泥4~8h,得到泥坯;将泥坯放入真空练泥机中进行炼泥1~4h,取出用保鲜膜包住,放入阴凉潮湿的空气中进行陈腐20~24h,制得泥坯。(2)蜂窝陶瓷体定型 将经过陈腐的泥坯放入挤出成型机中进行挤出,挤出压力为23Mpa,用钼丝切割成蜂窝陶瓷湿坯体;坯体挤出后迅速放入微波加热条件下,于95℃~115℃条件下进行定型干燥处理、端面加工,于550~580℃条件下煅烧3~5h。(3)蜂窝催化剂的制备 a. 将一定质量的铜盐,铁盐,金属助剂盐及氨基甲酸铵溶于去离子水中,搅拌溶解得到活性液;b.将(2)中定型后的蜂窝陶瓷体悬置于活性液中,45~60℃,浸渍5~10min后取出,用吹扫气体吹走表面残留液,置于烘箱85~110℃烘干,如此反复,可进行多次浸渍,最后在450℃~530℃煅烧1~3h,即得到蜂窝催化剂成品。
所述金属助剂为La、Ce、Mn盐中的一种或组合。
所述的步骤(1)中的粘土可包括高岭土、膨润土、凹凸棒土或是其中两种或三种粘土的组合,高岭土:凹凸棒土:膨润土的质量比=0~0.5/0~0.25/0~0.25;粘土占蜂窝陶瓷无机组分的30wt%~60wt%;分子筛可包括MFI型、MOR型、CHA型,其占蜂窝陶瓷无机组分的5wt%~30wt%;莫来石纤维占蜂窝陶瓷无机组分的2wt%~5wt%;高温粘结剂可包括磷酸二氢铝、玻璃粉、硅溶胶、铝溶胶,其占蜂窝陶瓷无机组分的10wt%~30wt%。纤维素、润滑剂、增塑剂和水作为蜂窝体无机部分的追加组分,纤维素可包括甲基纤维素、羟甲基纤维素、羟乙基纤维素、羟丙基纤维素,粘结剂的加入量为无机组分的1wt%~4wt%;润滑剂可包括桐油、玉米油、妥尔油、硬脂酸钠或其它合适的润滑剂,润滑剂的加入量为无机组分的1wt%~4wt%。增塑剂可包括甘油、聚乙二醇或是其它合适的增塑剂,增塑剂的加入量为无机组分的1wt%~4wt%;水的加入量为无机组分的15wt%~25wt%。
所述的步骤(3)中活性液中铜盐/铁盐/过渡金属盐/分子筛的质量比为12.8g~23.08g/10.69g~19.23g/5.77g~20g/1g~2.15g。
本发明的积极效果是将粘土、分子筛、莫来石纤维、纤维素、高温粘结剂、润滑剂、增塑剂和水制成泥坯,然后进行定型处理后,将其在一定温度下浸渍在含有铜离子、铁离子、过渡金属离子及氨基甲酸铵混合液中,使活性液中的金属离子与蜂窝陶瓷体中的分子筛部分活性位发生反应,然后经高温燃烧在氨基甲酸铵作用下使剩余分子筛活性位、多组分金属离子充分反应,在载体表面实现活性组分分布均匀、高效率负载;由于金属活性组分是通过化学作用与载体中的分子筛作用,因而活性组分可以牢固地负载在载体表面,克服涂覆式蜂窝催化剂涂层脱落的缺点,同时多组分金属离子,在一定条件下,通过氨基甲酸铵的作用使多组分金属间的协同作用最大化,具有在宽温度窗口下较好的De-NOx活性。
附图说明
图1为实施例1~7脱落率测试的振动试验台安装示意图。
图2为实施例1和某公司蜂窝催化剂产品的NOx转化曲线测试结果。
具体实施方式
在下述的具体事例描述中,给出了大量具体的细节以便于更为深刻的理解本发明。然而,对于本领域技术人员来说显而易见的是,本发明可以无需一个或多个这些细节而得以实施。
实施例1
第一步:泥坯的制备
将5.5kg高岭土、2.0kg Beta25分子筛、0.5kg莫来石纤维、2.0kg磷酸二氢铝、0.3kg甲基纤维素、0.3kg桐油、0.3kg甘油和2kg水放入捏泥机中混炼4h成泥;再将泥坯放入真空练泥机中进行炼泥,混炼时间为4h;之后将经过真空炼泥的泥坯用保鲜膜包住,放入阴凉潮湿的空气中陈腐20h,制得可塑性好的泥坯;
第二步:蜂窝陶瓷体定型
将陈腐好的泥坯放入挤出机中进行挤压成型,挤出压力为23Mpa,使泥坯经过底面直径为18cm,200目的不锈钢模具,然后用钼丝切割成所需要长度的蜂窝陶瓷湿坯体;坯体挤出后迅速放入微波中进行干燥定型,干燥温度为105℃,干透为止、端面加工,550℃煅烧5h,烧结后,用压缩空气对蜂窝孔进行通孔处理;
第三步:蜂窝催化剂的制备
将250g硝酸铜、230g硝酸铁、150g硝酸铈、21.5g氨基甲酸铵溶于去离子水中,搅拌溶解得到活性液;将第二步中烧结定型后的蜂窝陶瓷坯体(陶瓷坯体质量为1kg)置于活性液中,60℃浸渍5min取出,用吹扫气吹走表面残留液体,于110℃烘干,最后经450℃煅烧3h,即得到蜂窝催化剂成品。
将实施例1制备得到蜂窝催化剂成品进行涂层脱落率试验,首先称量质量后将蜂窝催化剂成品安装在振动试验台上,如图1所示。采用振动加速度10g,振动频率为(100±5)Hz,试验时间为5h,实验结束后取下蜂窝催化剂成品称其质量,经计算涂层脱落率为0.8%,这表明活性组分涂层与载体结合的牢固度非常高,与涂覆式蜂窝催化剂相比,本实施例蜂窝催化剂成品具有较好牢固度。
将实施例1制备得到整体蜂窝催化剂切割成截面为1.5cm*1.5cm,长度为2cm的长方体小段,放于固定床反应器中,反应气氛模拟尾气组成,NO:600ppm,NH3:600ppm,O2:5%,平衡气为N2。调节气流量使得反应的空速为50000h-1。分别检测进出口NOx浓度,从而计算出NOx的转化率,得到催化剂的脱硝效率。图2为实施例1以及某公司蜂窝催化剂产品的NOx转化曲线。从测试结果可以看出实施例1的蜂窝催化剂的在215~520℃的温度区间内NOx的转化率均高于75%,显示了很好NOx活性。某商业化蜂窝催化剂在215℃NOx的转化率仅为50%,520℃为65%左右。
实施例2
第一步:泥坯的制备
将5.5kg高岭土、1.7kg Sapo-34分子筛、0.3kg莫来石纤维、2.5kg玻璃粉、0.4kg羟丙基甲基纤维素、0.3kg桐油、0.3kg甘油和2.5kg水放入捏泥机中混炼8h成泥;再将泥坯放入真空练泥机中进行炼泥,混炼时间为1h;之后将经过真空炼泥的泥坯用保鲜膜包住,放入阴凉潮湿的空气中陈腐24h,制得可塑性好的泥坯;
第二步:蜂窝陶瓷体定型
将陈腐好的泥坯放入挤出机中进行挤压成型,挤出压力为23Mpa,使泥坯经过底面直径为18cm,200目的不锈钢模具,然后用钼丝切割成所需要长度的蜂窝陶瓷湿坯体;坯体挤出后迅速放入微波中105℃进行干燥定型,干透为止,进行端面加工。580℃,烧结3h,烧结后,用压缩空气对蜂窝孔进行通孔处理;
第三步:蜂窝催化剂的制备
将300g硝酸铜、250g硝酸铁、260g硝酸镧、28.1g氨基甲酸铵溶于去离子水中,搅拌溶解得到活性液;将第二步中烧结定型后的蜂窝陶瓷坯体(陶瓷坯体质量为1kg)置于活性液中,60℃浸渍5min取出,用吹扫气吹走表面残留液体,于85℃烘干,如此进行2次浸渍,烘干,最后经530℃煅烧1h,即得到蜂窝催化剂成品。
实施例3
第一步:泥坯的制备
将6kg凹凸棒土、0.8kg SSZ-13分子筛、0.2kg莫来石纤维、3.0kg硅溶胶、0.3kg羟乙基纤维素、0.3kg桐油、0.3kg甘油和0.5kg水放入捏泥机中混炼4h成泥;再将泥坯放入真空练泥机中进行炼泥2h;之后将经过真空炼泥的泥坯用保鲜膜包住,放入阴凉潮湿的空气中陈腐20h,制得可塑性好的泥坯;
第二步:蜂窝陶瓷体定型
将陈腐好的泥坯放入挤出机中进行挤压成型,挤出压力为23Mpa,使泥坯经过底面直径为18cm,200目的不锈钢模具,然后用钼丝切割成所需要长度的蜂窝陶瓷湿坯体;坯体挤出后迅速放入微波中110℃进行干燥定型,干透为止,进行端面加工;580℃,烧结4h,烧结后,用压缩空气对蜂窝孔进行通孔处理;
第三步:蜂窝催化剂的制备
将167g硝酸铜、139g硝酸铁、75g硝酸锰、13g氨基甲酸铵溶于去离子水中,搅拌溶解得到活性液;将第二步中烧结定型后的蜂窝陶瓷坯体(陶瓷坯体质量为1kg)置于活性液中,60℃浸渍6min取出,用吹扫气吹走表面残留液体,于100℃烘干,如此进行2,3次浸渍,最后经480℃煅烧2h,即得到蜂窝催化剂成品。
实施例4
第一步:泥坯的制备
将5kg的高岭土和凹凸棒土(高岭土和凹凸棒土比例为2:1)、1.7kg ZSM-5分子筛、0.3kg莫来石纤维、3kg铝溶胶(质量分数为50%)、0.3kg羟甲基纤维素、0.3kg桐油、0.3kg甘油和0.5kg水放入捏泥机中混炼4h成泥;再将泥坯放入真空练泥机中进行炼泥2h,之后将经过真空炼泥的泥坯用保鲜膜包住,放入阴凉潮湿的空气中陈腐20h,制得可塑性好的泥坯;
第二步:蜂窝陶瓷体定型
将陈腐好的泥坯放入挤出机中进行挤压成型,挤出压力为23Mpa,使泥坯经过底面直径为18cm,200目的不锈钢模具,然后用钼丝切割成所需要长度的蜂窝陶瓷湿坯体;坯体挤出后迅速放入微波中105℃进行干燥定型,干透为止,进行端面加工;580℃,烧结5h,烧结后,用压缩空气对蜂窝孔进行通孔处理;
第三步:蜂窝催化剂的制备
将167g硝酸铜、250g硝酸铁、100g硝酸铈和60g硝酸镧、20.5g氨基甲酸铵溶于去离子水中,搅拌溶解得到活性液;将第二步中烧结定型后的蜂窝陶瓷坯体(陶瓷坯体质量为1kg)置于活性液中,50℃浸渍5min取出,用吹扫气吹走表面残留液体,于105℃烘干,最后经520℃煅烧1h,即得到蜂窝催化剂成品。
实施例5
第一步:泥坯的制备
将6kg的高岭土、凹凸棒土和膨润土(高岭土:凹凸棒土:膨润土=2:1:1)、1.7kg Beta40分子筛、0.3kg莫来石纤维、2kg磷酸二氢铝、0.3kg羟甲基纤维素、0.3kg桐油、0.3kg甘油和2.0kg水放入捏泥机中混炼5h成泥;再将泥坯放入真空练泥机中进行炼泥2h,之后将经过真空炼泥的泥坯用保鲜膜包住,放入阴凉潮湿的空气中陈腐20h,制得可塑性好的泥坯;
第二步:蜂窝陶瓷体定型
将陈腐好的泥坯放入挤出机中进行挤压成型,挤出压力为23Mpa,使泥坯经过底面直径为18cm,200目的不锈钢模具,然后用钼丝切割成所需要长度的蜂窝陶瓷湿坯体;坯体挤出后迅速放入微波中105℃进行干燥定型,进行端面加工;580℃,烧结5h,烧结后,用压缩空气对蜂窝孔进行通孔处理;
第三步:蜂窝催化剂的制备
将300g硝酸铜、139g硝酸铁、50g硝酸铈、50g硝酸锰、50g硝酸镧、18.1g氨基甲酸铵溶于去离子水中,搅拌溶解得到活性液;将第二步中烧结定型后的蜂窝陶瓷坯体(陶瓷坯体质量为1kg)置于活性液中,55℃浸渍6min取出,用吹扫气吹走表面残留液体,于100℃烘干,最后经500℃煅烧2h,即得到蜂窝催化剂成品。
实施例6:
第一步:泥坯的制备
将5.5kg的高岭土、凹凸棒土和膨润土(高岭土:凹凸棒土:膨润土=2:1:1)、1.7kg分子筛(ZSM-5:SSZ-13=2:1)、0.3kg莫来石纤维、2.5kg玻璃粉、0.3kg羟甲基纤维素(粘结剂)、0.3kg桐油、0.3kg甘油和2.5kg水放入捏泥机中混炼5h成泥;再将泥坯放入真空练泥机中进行炼泥2h,;之后将经过真空炼泥的泥坯用保鲜膜包住,放入阴凉潮湿的空气中陈腐20h,制得可塑性好的泥坯;
第二步:蜂窝陶瓷体定型
将陈腐好的泥坯放入挤出机中进行挤压成型,挤出压力为23Mpa,使泥坯经过底面直径为18cm,200目的不锈钢模具,然后用钼丝切割成所需要长度的蜂窝陶瓷湿坯体;坯体挤出后迅速放入微波中105℃干燥定型,进行端面加工,580℃,烧结5h,烧结后,用压缩空气对蜂窝孔进行通孔处理;
第三步:蜂窝催化剂的制备
将250g硝酸铜、186g硝酸铁、150g硝酸铈、19.8g氨基甲酸铵溶于去离子水中,搅拌溶解得到活性液;将第二步中烧结定型后的蜂窝陶瓷坯体(陶瓷坯体质量为1kg)置于活性液中,45℃浸渍8min取出,用吹扫气吹走表面残留液体,于110℃烘干,最后经530℃煅烧1h,即得到蜂窝催化剂成品。
实施例7:
第一步:泥坯的制备
将5kg的高岭土、凹凸棒土和膨润土(高岭土:凹凸棒土:膨润土=2:1:1)、1.7kg分子筛(ZSM-5:SSZ-13:SAPO-34=2:1:1)、0.3kg莫来石纤维、3kg磷酸二氢铝、0.3kg羟甲基纤维素(粘结剂)、0.3kg桐油(润滑剂)、0.3kg甘油(增塑剂)和2.5kg水放入捏泥机中混炼6h成泥;再将泥坯放入真空练泥机中进行炼泥2h,之后将经过真空炼泥的泥坯用保鲜膜包住,放入阴凉潮湿的空气中陈腐24h,制得可塑性好的泥坯;
第二步:蜂窝陶瓷体定型
将陈腐好的泥坯放入挤出机中进行挤压成型,挤出压力为23Mpa,使泥坯经过底面直径为18cm,200目的不锈钢模具,然后用钼丝切割成所需要长度的蜂窝陶瓷湿坯体;坯体挤出后迅速放入微波中105℃干燥定型,进行端面加工,580℃,烧结3h,烧结后,用压缩空气对蜂窝孔进行通孔处理;
第三步:蜂窝催化剂的制备
将250g硝酸铜、186g硝酸铁、150g硝酸铈、19.8g氨基甲酸铵溶于去离子水中,搅拌溶解得到活性液;将第二步中烧结定型后的蜂窝陶瓷坯体(陶瓷坯体质量为1kg)置于活性液中,45℃浸渍8min取出,用吹扫气吹走表面残留液体,于110℃烘干,最后经530℃煅烧1h,即得到蜂窝催化剂成品。
表1为实施例1-7脱落率测试的结果
实施例 | 脱落率/% |
实施例1 | 0.80 |
实施例2 | 1.21 |
实施例3 | 0.92 |
实施例4 | 1.05 |
实施例5 | 0.88 |
实施例6 | 1.02 |
实施例7 | 1.10 |
Claims (4)
1.挤出式分子筛蜂窝催化剂及其制备方法,其特征在于具体步骤如下:(1)泥坯的制备将粘土、分子筛、莫来石纤维、纤维素、高温粘结剂、润滑剂、增塑剂和水等按照一定质量比放入混泥机中进行混炼捏泥4~8h,得到泥坯;将泥坯放入真空练泥机中进行炼泥1~4h,取出用保鲜膜包住,放入阴凉潮湿的空气中进行陈腐20~24h,制得泥坯;
(2)蜂窝陶瓷体定型 将经过陈腐的泥坯放入挤出成型机中进行挤出,挤出压力为23Mpa,用钼丝切割成蜂窝陶瓷湿坯体;坯体挤出后迅速放入微波加热条件下,于95℃~115℃条件下进行定型干燥处理、端面加工),于550~580℃条件下煅烧3~5h;
(3)蜂窝催化剂的制备 a. 将一定质量的铜盐,铁盐,金属助剂盐及氨基甲酸铵溶于去离子水中,搅拌溶解得到活性液;b.将(2)中定型后的蜂窝陶瓷体悬置于活性液中,45~60℃,浸渍5~10min后取出,用吹扫气体吹走表面残留液,置于烘箱85~110℃烘干,如此反复,可进行多次浸渍,最后在450℃~530℃煅烧1~3h,即得到蜂窝催化剂成品。
2.根据权利要求1中所述的挤出式分子筛蜂窝催化剂及其制备方法,其特征在于所述的所述金属助剂为La、Ce、Mn盐中的一种或组合。
3.根据权利要求1中所述的挤出式分子筛蜂窝催化剂及其制备方法,其特征在于所述的步骤(1)中的粘土可包括高岭土、膨润土、凹凸棒土或是其中两种或三种粘土的组合,高岭土:凹凸棒土:膨润土的质量比=0~0.5/0~0.25/0~0.25;粘土占蜂窝陶瓷无机组分的30wt%~60wt%;分子筛可包括MFI型、MOR型、CHA型,其占蜂窝陶瓷无机组分的5wt%~30wt%;莫来石纤维占蜂窝陶瓷无机组分的2wt%~5wt%;高温粘结剂可包括磷酸二氢铝、玻璃粉、硅溶胶、铝溶胶,其占蜂窝陶瓷无机组分的10wt%~30wt%;纤维素、润滑剂、增塑剂和水作为蜂窝体无机部分的追加组分,纤维素可包括甲基纤维素、羟甲基纤维素、羟乙基纤维素、羟丙基纤维素,粘结剂的加入量为无机组分的1wt%~4wt%;润滑剂可包括桐油、玉米油、妥尔油、硬脂酸钠或其它合适的润滑剂,润滑剂的加入量为无机组分的1wt%~4wt%;增塑剂可包括甘油、聚乙二醇或是其它合适的增塑剂,增塑剂的加入量为无机组分的1wt%~4wt%;水的加入量为无机组分的15wt%~25wt%。
4.根据权利要求1中所述的挤出式分子筛蜂窝催化剂及其制备方法,其特征在于所述的步骤(3)中活性液中铜盐/铁盐/过渡金属盐/分子筛的质量比为12.8g~23.08g/10.69g~19.23g/5.77g~20g/1g~2.15g。
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