CN107519917A - 一种无粘结剂分子筛催化剂及其制备方法 - Google Patents
一种无粘结剂分子筛催化剂及其制备方法 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 55
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 54
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 19
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/24—Iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/46—Iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/617—500-1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/60—Synthesis on support
- B01J2229/66—Synthesis on support on metal supports
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Abstract
本发明属于催化剂技术领域，具体为一种无粘结剂分子筛催化剂及其制备方法。本发明催化剂是由装在金属方管内的多孔金属填料和无粘结剂氢型沸石分子筛构成，该分子筛相互粘连并粘附在金属管内壁和多孔金属填料上。其制备方法是在装有多孔金属填料的金属管中，加入含或不含有机导向剂的无定形硅铝酸盐反应物凝胶或干胶，置高压釜内，在120‑200℃，反应20‑100小时水热结晶或蒸汽相转晶制备成分子筛晶体后，原位烘干焙烧除去有机导向剂，再用矿物酸或铵盐溶液交换脱钠、洗涤、干燥后制成。本催化剂具有热传导性能好、强度高、且扩散性能优良之优点。
Description
一、技术领域
本发明属于催化剂技术领域，具体涉及一种无粘结剂分子筛催化剂及其制备方法。
二、背景技术
骨架结构的硅铝酸盐分子筛，作为高效择形催化剂，在石油炼制、石油化工、新能源(煤和天然气)化工、精细化工等领域有极其重要的应用。
分子筛晶体是热的不良导体，而其骨架摩尔硅铝比高于10时，具有迁移性的可交换阳离子很少，此时的分子筛热传导性能接近绝热体。而反应物分子在催化剂上反应时，视反应类型的不同，会放热或者吸热。在工业大型催化反应器中，如果不能及时撤热或补热，催化反应所需合适的反应温度便难以保持稳定，催化剂的活性、选择性和稳定性会受到严重影响。在强放热性反应中，反应器不良撤热可导致催化剂床层急剧升温，反应失控，甚至造成烧毁整个反应器的严重后果。在使用催化剂装填量为数毫升至10多毫升容量的小型催化反应器(通常称为“微反”)评价反应性能时，金属外壁传热尚可对分子筛催化剂及时撤热和补热，催化剂上产生的反应热效应对催化性能影响尚不显著，而在中试装置和大型工业装置中，解决撤热和补热，就成为一个重大问题。
催化剂的分子扩散性对催化剂的活性、选择性和稳定性(寿命)起决定性作用。反应物和反应产物分子在催化剂上的扩散，有内和外扩散二种，前者是分子在分子筛晶体内部孔道中的扩散，由所使用的分子筛本征物性所决定。后者是在催化剂中所含分子筛晶粒之间的扩散，由成型造粒工艺所控制。调变前者的方法：1，选择不同结构类型的分子筛，使反应物和产物能通畅地进入和离开分子筛晶体，避免在分子筛晶内孔道中停留而进一步反应生成其它副产物，降低选择性和堵塞孔道、以至失去活性；2，合成不同尺寸的分子筛晶粒。通常细小晶粒，如亚微米和纳米尺寸的分子筛内扩散性能相对优良；3，结构改性。通过离子交换、脱铝脱硅、部分溶解扩孔等多种方法调节孔道尺寸。而调变外扩散的方法通常是在成型造粒工艺中进行。用于大型工业反应器的催化剂必须具有相当的抗压强度，以防止大量堆积时被压碎或在反应物气流冲击下粉化。增加催化剂强度的普遍做法是在分子筛晶粉中加入粘结剂在一定的机械力作用下成型造粒，此方法虽然可以使其强度明显增加，带来的副作用是分子筛晶粒之间的空隙率降低以致影响外扩散。通常所用方法是在成型造粒工艺中加造孔剂，在粘结剂将分子筛粉晶粘结以挤压或滚球方式造粒成型时，往粘结剂中添加合适的有机高聚物或植物粉(如淀粉、田箐粉)等。在催化剂使用前的加热活化过程中，作为造孔剂的添加物被烧去而留下较多的空隙。但众所周知，造孔剂的加入，虽然可明显改善成型催化剂的外扩散性能，同时也导致催化剂的机械强度下降。
另外，成型工艺中加入的粘结剂降低了有效活性组分-分子筛的含量，堵塞分子筛孔道使外扩散性恶化，为此可采取的方法是将粘结剂通过转晶反应技术将其转变成同类型的分子筛，制成无粘结剂催化剂，提高催化剂中分子筛含量，减轻堵孔情况(石油化工，2007，36(10)，1066)。
三、发明内容
本发明的目的在于提供一种热传导性能好、强度高、且外扩散性能优良的无粘结剂分子筛催化剂及其制备方法。
本发明催化剂是由装在金属方管内的多孔金属填料和无粘结剂氢型分子筛构成，该分子筛相互粘连并粘附在金属管内壁和多孔金属填料上。该金属管及多孔金属填料通常所用金属材料，要求热传导性能好、耐温、且对所进行的催化反应体系呈惰性，通常所用的金属材料型号为304或316L的不锈钢。
本发明催化剂的金属方管横截面边长为20或40mm、容量为50或200mL，装在金属管内的多孔金属填料呈网状。
本发明催化剂所述的无粘结剂氢型分子筛结构类型是MFI型(ZSM-5)、BEA型(Beta)、FER型(镁碱)、以及MOR型(丝光)、FAU型(Y)分子筛。
本发明一种无粘结剂分子筛催化剂及其制备方法是在装有多孔金属填料的金属方管中，加入含或不含有机导向剂的无定形硅铝酸盐反应物凝胶或干胶，置于高压釜内，在120-200℃，反应20-100小时水热结晶或蒸汽相转晶制备成钠型分子筛晶体，此时制成的分子筛晶体会相互粘连并粘附在金属管内壁和金属管内的多孔金属填料上，原位烘干后、于500-600℃焙烧除去有机导向剂，再用矿物酸(如硫酸、硝酸等)或铵盐溶液(如硫酸铵，硝酸铵等)交换脱钠、洗涤、干燥后制成。上述无粘结剂分子筛中，制备MOR型和FAU型时，所加的无定形硅铝酸盐反应物中，不需加入有机导向剂，所以经水热结晶或蒸汽相转晶制成钠型分子筛晶体后不必原位焙烧。上述无粘结剂分子筛中，制备MFI型、BEA型以及FER型时，所加的无定形硅铝酸盐反应物中，需加入有机导向剂，经水热结晶或蒸汽相转晶制成钠型分子筛晶体后，需原位焙烧除去有机导向剂。
上述制备方法中含有机导向剂的无定形硅铝酸盐反应物的摩尔组成是mR·xNa2O·ySiO2·Al2O3·zH2O，R是有机导向剂，可以是四氢呋喃，也可以是有机碱，如季铵碱(四乙基氢氧化铵，四丙基氢氧化铵等)，也可以是烷基胺如伯胺(乙胺，丁胺等)、仲胺(二乙胺，二丙胺等)或叔胺(三甲胺，三丙胺等)中的一种或其混合物，烷基是C1-C4烷基。无定形硅铝酸盐反应物的摩尔配比中，m＝0-30，x＝1-30，y＝10-100，z＝100-2000。
本发明催化剂免去了成型工艺，不需加粘结剂和造孔剂，避免了因加粘结剂会降低催化剂中分子筛晶粒间空隙率而影响外扩散的弊病，同时也克服了因加造孔剂而导致催化剂强度下降之缺点。本发明催化剂特征是由装在金属管内的多孔金属填料及无粘结剂氢型分子筛构成，所以强度高。另由于金属方管壁及多孔金属填料使催化剂具有良好的热传导性能，因而解决了大型催化反应器撤热或补热不及时的问题。本发明催化剂可以集成组装于反应装置中使用，其组装方式可以是串联或并联，也可以是二者兼有。
四、具体实施方式
下面通过实施例进一步说明本发明催化剂的制备。
实施例中制备本发明催化剂的金属管有二种：
A管：材质为304型不锈钢方管，横截面边长为20毫米，有效容量50mL。管内的多孔金属填料为二层材质304的不锈钢制冲孔网，此冲孔网与金属管壁平行呈同心圆均匀分布。
B管：材质为316L型不锈钢，横截面边长为40毫米，有效容量200mL。管内的多孔金属填料为五层材质316L的不锈钢制冲孔网，此冲孔网与金属管壁平行呈同心圆均匀分布。
实施例1
用A管制备无粘结剂氢型丝光分子筛催化剂。
以水玻璃、硫酸铝、硫酸与水按摩尔配比8Na2O·40SiO2·Al2O3·400H2O制备凝胶，将凝胶烘干脱水制得硅铝酸盐干胶，此干胶研磨成细粉后注入A管中。将已注入干胶粉的A管放置于500mL高压釜内，在反应釜底部加入100mL水作为干胶转化蒸汽源，A管所放位置使其与釜底的水不直接接触。干胶经170℃反应24小时，即制得无粘结剂钠型丝光分子筛。随后，在室温下通入0.5摩尔/升浓度的硝酸溶液将所获钠型丝光分子筛离子交换脱钠、洗涤、干燥后制得无粘结剂氢型丝光分子筛催化剂。
将A管中的样品取出，以X射线粉末衍射鉴定，属于纯相丝光；该样品用X射线荧光光谱分析，其硅铝摩尔比(SAR)24.8；样品经低温氮吸附测定，比表面积368m2/g，微孔容积0.19cm3/g，苯吸附量9.1wt％，属于高结晶度的大孔丝光。
实施例2
用B管制备无粘结剂氢型ZSM-5分子筛催化剂。
以有机导向剂正丁胺、氢氧化钠、白炭黑、硫酸铝、与水按摩尔配比30R·15Na2O·50SiO2·Al2O3·150H2O制备凝胶；将凝胶注入B管中。已注入凝胶的B管放置于2000mL高压釜内，在165℃反应48小时，即可制得无粘结剂钠型ZSM-5分子筛。A管内的钠型ZSM-5分子筛原位烘干后，于550℃焙烧4小时除去有机导向剂，冷却至室温。随后，在室温下通入0.5摩尔/升浓度的硫酸溶液将所获钠型ZSM-5分子筛离子交换脱钠、洗涤、干燥制得无粘结剂氢型ZSM-5分子筛催化剂。
将B管中的样品取出，以X射线粉末衍射鉴定，属于纯相ZSM-5；经X射线荧光光谱分析测出其硅铝摩尔比(SAR)为45.3；低温氮吸附测定其比表面积为360m2/g，微孔容积0.18cm3/g，属于高结晶度的ZSM-5。
实施例3
用A管制备无粘结剂氢型Beta分子筛催化剂。
以有机导向剂四乙基溴化胺、氢氧化钠、硅溶胶、偏铝酸钠、与水按摩尔配比15R·25Na2O·100SiO2·Al2O3·1000H2O制备凝胶，将凝胶烘干脱水制得硅铝酸盐干胶。注入了磨细干胶粉的A管，放置于500mL高压釜内。在反应釜底部加入100mL水作为干胶转化蒸汽源，A管所放位置使其与釜底的水不直接接触。在135℃反应80小时，制得无粘结剂钠型Beta分子筛。管内的钠型Beta分子筛原位烘干后，于580℃焙烧6小时除去有机导向剂，冷却至室温。随后，在室温下通人0.5摩尔/升浓度的硝酸铵溶液将所获钠型beta分子筛离子交换脱钠，洗涤、干燥后再于550℃焙烧2小时除去铵离子，即制得无粘结剂氢型beta分子筛催化剂。
将A管中的样品取出，X射线粉末衍射鉴定证明其属于纯相Beta；X射线荧光光谱分析测出其硅铝摩尔比(SAR)97.7；低温氮吸附测定的比表面积586m2/g，微孔容积0.25cm3/g，属于高结晶度的Beta。
Claims (5)
1.一种无粘结剂分子筛催化剂，其特征是由装在金属方管内的多孔金属填料和无粘结剂氢型沸石分子筛构成，该分子筛相互粘连并粘附在金属管内壁和多孔金属填料上。
2.根据权利要求1所述的无粘结剂分子筛催化剂制备方法，其特征是在装有多孔金属填料的金属管中，加入含或不含有机导向剂的无定形硅铝酸盐反应物凝胶或干胶，置高压釜内，在120-200℃，反应20-100小时水热结晶或蒸汽相转晶制备成钠型沸石分子筛晶体后，原位烘干、焙烧除去有机导向剂，再用矿物酸或铵盐溶液交换脱钠、洗涤、干燥后制成。
3.根据权利要求1所述的一种无粘结剂沸石分子筛催化剂，其特征是所述的无粘结剂氢型分子筛结构类型是MFI型、BEA型、FER型、以及MOR型、FAU型。
4.根据权利要求1所述的一种无粘结剂分子筛催化剂，其特征是金属方管横截面边长为20或40mm、容量为50或200mL，装在金属管内多孔金属填料呈网状。
5.根据权利要求1所述的一种无粘结剂沸石分子筛催化剂，其特征是金属方管及多孔金属填料所用金属材料型号为304或316L的不锈钢。
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