CN106799253A - 一种一步水热合成多级孔结构分子筛脱销催化剂的制备方法 - Google Patents
一种一步水热合成多级孔结构分子筛脱销催化剂的制备方法 Download PDFInfo
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 27
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical class CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
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- 125000001246 bromo group Chemical class Br* 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical class [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
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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
- B01J29/40—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
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Abstract
一种一步水热合成多级孔结构分子筛脱销催化剂的制备方法，首先制备长链有机配合物模板剂，然后合成具有多级孔结构的Cu‑ZSM‑5分子筛。本发明通过软模板法，设计制备长链有机配合物模板剂并由此合成出414 m2/g的高比表面积，且同时具有介孔和微孔的多级孔结构的Cu‑ZSM‑5分子筛，然后焙烧除去有机模板剂后用于NH3‑SCR反应。本发明在250‑400℃的宽的温度范围内，在60000 ml/g·h的空速下具有较高的催化消除效果和稳定性。
Description
技术领域
本发明属于环境催化技术领域，涉及一种一步水热法得到多级孔含Cu的分子筛催化剂的制备方法。
背景技术
随着科技的进步，人们生活水平逐渐提高，机动车、工厂日益增多，由此带来的环境问题亟待治理。氮氧化物（NOx）是燃煤电厂和机动车尾气的主要成分，氮氧化物是形成酸雨、光化学烟雾、臭氧层空洞、雾霾等环境问题的主要原因，不仅破坏人类赖以生存的环境同时危害人类健康。选择性催化还原技术是目前最有效的NOx脱除方法。沸石分子筛基催化剂由于成本低、催化转化效率高等特点被广泛应用在氮氧化物选择性催化脱除方面。常规合成分子筛基催化剂的思路是先合成沸石分子筛，再通过离子交换等方法负载活性组分。本发明通过合成长链配合物有机模板剂一步制得Cu-ZSM-5催化剂，N2吸附脱附测试结果显示该催化剂同时具有微孔和介孔的多级孔结构。多级孔结构有利于催化过程的传质和扩散，对催化反应有利。
选择性催化还原技术是指在催化剂的作用下，NOx被还原剂（如氨气、尿素等）选择性的还原为 N2。通过加氨把NOx转化为无毒无害的N2和H2O，其主要化学反应如下：
4NH3 + 2NO + 2O2→ 3N2 + 6H2O
4NH3 + 4NO + O2→ 4N2 + 6H2O
8NH3 + 6NO→ 7N2 + 12H2O
4NH3 + 6NO→ 5N2 + 6H2O
除上述主要基本反应外，NH3-SCR 反应还会随反应温度、反应气氛等条件的变化发生多种副反应。低温时，NH3与 NO2发生反应，生成硝酸铵（NH4NO3），硝酸铵的存在会堵塞孔道，不利于传质，同时挡住活性位点使催化活性降低甚至导致催化剂失活；高温时，NH3与O2发生非选择性氧化反应，生成N2O 和 NO等二次污染物。主要副反应有：
4NH3 + 3O2→ 2N2 + 6H2O
4NH3 + 5O2→ 4NO + 6H2O
3NH3→ N2 + 3H2
8NH3 +4NO2 + 5O2→ 6NH3NO3
目前，分子筛催化剂因其具有很高的比表面积、高的热稳定性和水热热稳定性、高的反应活性等优点受到广泛关注。分子筛骨架的基本单元为硅氧四面体和铝氧四面体，四面体中心分别为硅和铝，它们通过共用氧原子连接。由于分子筛具有高的比表面积、孔径可调、活性位易于调变、吸附容量高、热稳定性和水热稳定性高等特点，分子筛具有良好的吸附分离、催化、离子交换等性能。含Cu、Fe、Co等的沸石分子筛在氮氧化物脱除中表现出良好的催化活性。氮氧化物的脱除过程中易产生硝酸铵、硫酸铵等结晶，这些副产物会堵塞微孔分子筛的孔道导致反应物分子接触不到活性位点而失活，而微孔分子筛孔径小、颗粒大，不利于传质从而对催化活性带来不利影响。具有微孔-介孔的多级孔结构的沸石分子筛可以有效防止氮氧化物脱除过程产生的颗粒物堵塞孔道，同时减少空间位阻利于大分子的扩散和传输，增加客体分子在沸石分子筛内部的扩散速率，减缓分子筛失活。
发明内容
本发明的目的是提出一种一步水热合成多级孔结构分子筛（Cu-ZSM-5）脱销催化剂的制备方法，得到含活性组分Cu物种的多级孔结构的ZSM-5分子筛，以期降低氮氧化物脱除过程中所产生的硝酸铵、硫酸铵、金属硝酸盐等结晶体对对微孔孔道的堵塞问题，同时促进反应物和产物分子在大颗粒分子筛中的传质性能，增加反应物分子与活性位点的可接近性以提高催化剂活性。本发明具有温度窗口宽，选择性高副产物少等特点，将其运用氨选择性催化还原时，其催化活性以及选择性均能很好的满足氨选择性催化还原技术的需要。
本发明所述的一种一步水热合成多级孔结构脱销催化剂的制备方法，其特征在于包含以下步骤。
（1）长链有机配合物模板剂的制备：取8.00 g 2',4'-二羟基苯乙酮溶于50 ml甲醇中，加入1.58 g乙二胺，70 ℃下回流3 h，冷至室温后先用冷甲醇洗再用甲醇重结晶得中间体1。取2.62 g中间体1溶于150 ml甲醇，取1.60 g醋酸铜溶于30 ml去离子水内，待醋酸铜完全溶解后将醋酸铜溶液加入中间体1的溶液中85 ℃回流4 h，所得产物先用热水洗再用冷甲醇洗涤，真空干燥后得中间体2。取52.19 g N,N,N’,N’-四甲基-1,6-己二胺和5.00g溴代正己烷于300 ml乙腈、甲苯的混合液（乙腈、甲苯的体积比为1：1）中，65 ℃回流1 d，所得产物旋蒸除去溶剂后用冷的无水乙醚洗涤、真空干燥后得中间体3。取8.50 g中间体3溶于150 ml乙腈中，加入6.15 g 1,6-二溴己烷，95 ℃下回流1 d，冷至室温后旋蒸除去溶剂，用冷的无水乙醚洗涤，充分干燥，得中间体4。取1.50 g氢氧化钾溶于150 ml乙醇中，在N2保护下加入4.66 g中间体2，完全溶解后加入20.94 g中间体4，85 ℃下回流20 h，冷至室温后洗涤，充分真空干燥后得最终产物长链有机配合物模板剂。
（2）分别取0.556 g长链有机配合物模板剂、9.9 g去离子水、0.02 g偏铝酸钠于烧杯中，60 ℃下水浴加热，在搅拌下快速滴入2.08 g正硅酸四乙酯。60 ℃下搅拌四小时，然后转入15 ml反应釜中150 ℃下旋转晶化四天，所得晶化物过滤、洗涤、干燥，550 ℃焙烧6 h，所得产品即为具有多级孔结构的Cu-ZSM-5分子筛。
本发明催化剂的特点是：通过长链模板剂一步水热法即可得到同时具有微孔和介孔的多级孔结构的含Cu的Cu-ZSM-5分子筛，且分子筛结构未遭到破坏。合成分子筛的步骤简单，常规合成分子筛基催化剂在制得分子筛后还需通过离子交换等手段负载活性物种。
附图说明
图1为本发明制备的多级孔结构的Cu-ZSM-5和仅含微孔的Cu-ZSM-5催化剂活性测试图。
图2为本发明制备的多级孔结构的Cu-ZSM-5的N2吸附脱附等温线图。
具体实施方式
为了更清楚地说明本发明，列举以下实施例，但其对本发明的范围无任何限制。
实施例1。
分别取0.556 g长链有机配合物模板剂、9.9 g去离子水、0.02 g偏铝酸钠于烧杯中，60 ℃下水浴加热，在搅拌下快速滴入2.08 g正硅酸四乙酯。60 ℃下搅拌四小时，然后转入15 ml反应釜中150 ℃下旋转晶化四天，所得晶化物过滤、洗涤、干燥，550 ℃焙烧6 h，所得产品即为具有多级孔结构的Cu-ZSM-5分子筛。
实施例2。
分别取12.91 g 四丙基氢氧化铵、13.34 g去离子水、0.16 g偏铝酸钠于烧杯中，搅拌下快速滴入8.27 g正硅酸四乙酯。室温下搅拌六小时后转入反应釜中170 ℃下旋转晶化四天，所得晶化物过滤、洗涤、干燥、550 ℃焙烧6 h，得到仅有微孔的Na-ZSM-5。将10 g氯化铵溶于30 ml去离子水中，再取1 g Na-ZSM-5倒入其中，所得混合液于80 ℃下搅拌回流24 h，随后抽滤，110 ℃下干燥12 h，550 ℃焙烧6 h得仅有微孔的H-ZSM-5。配制0.1 mol/L的硝酸铜溶液，将1.0 g H-ZSM-5分子筛倒入100 ml 0.1 mol/L的硝酸铜溶液中，在80 ℃下水浴搅拌4 h，抽滤至滤液为无色，烘干，重复交换交换三次，550 ℃焙烧6 h后，得到成品催化剂离子交换-Cu-ZSM-5。
催化剂活性测试：取50m g催化剂1-4置于内径6 mm的石英管反应器中，通入500ppm NO，500 ppm NH3，5% O2，Ar为平衡气的反应气体，质量空速为60000 ml h-1 gcat.-1，催化剂活性测试以10℃/min的升温速率从100 ℃升温到550 ℃。
Claims (1)
1.一种一步水热合成多级孔结构分子筛脱销催化剂的制备方法，其特征在于包含以下步骤：
（1）长链有机配合物模板剂的制备：取8.00 g 2',4'-二羟基苯乙酮溶于50 ml甲醇中，加入1.58 g乙二胺，70 ℃下回流3 h，冷至室温后先用冷甲醇洗再用甲醇重结晶得中间体1；取2.62 g中间体1溶于150 ml甲醇，取1.60 g醋酸铜溶于30 ml去离子水内，待醋酸铜完全溶解后将醋酸铜溶液加入中间体1的溶液中85 ℃回流4 h，所得产物先用热水洗再用冷甲醇洗涤，真空干燥后得中间体2；取52.19 g N,N,N’,N’-四甲基-1,6-己二胺和5.00 g溴代正己烷于300 ml乙腈与甲苯按体积比1:1的混合液中，65 ℃回流1 d，所得产物旋蒸除去溶剂后用冷的无水乙醚洗涤、真空干燥后得中间体3；取8.50 g中间体3溶于150 ml乙腈中，加入6.15 g 1,6-二溴己烷，95 ℃下回流1 d，冷至室温后旋蒸除去溶剂，用冷的无水乙醚洗涤，充分干燥，得中间体4；取1.50 g氢氧化钾溶于150 ml乙醇中，在N2保护下加入4.66 g中间体2，完全溶解后加入20.94 g中间体4，85 ℃下回流20 h，冷至室温后洗涤，充分真空干燥后得长链有机配合物模板剂；
（2）分别取0.556 g长链有机配合物模板剂、9.9 g去离子水、0.02 g偏铝酸钠于烧杯中，60 ℃下水浴加热，在搅拌下快速滴入2.08 g正硅酸四乙酯；60 ℃下搅拌四小时，然后转入15 ml反应釜中150 ℃下旋转晶化四天，所得晶化物过滤、洗涤、干燥，550 ℃焙烧6 h。
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