CN115487860B - 一种复合负载型β分子筛催化剂的制备方法及应用 - Google Patents
一种复合负载型β分子筛催化剂的制备方法及应用 Download PDFInfo
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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
- 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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- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
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Abstract
本发明涉及一种复合负载型β分子筛催化剂的制备方法及应用,属于分子筛催化剂领域。复合负载型β分子筛催化剂的制备方法,包括如下步骤:(1)焙烧;(2)制备浸渍液;(3)搅拌;(4)水浴条件下浸渍;(5)干燥;(6)焙烧,得到复合型Co‑Zn/β分子筛。本发明采用Co和Zn元素作为活性组分,制得复合负载型β分子筛催化剂,并将复合负载型β分子筛催化剂用于异丁烯选择性齐聚反应,异丁烯的转化率可达到95%以上,C8的选择性能达到80%以上,相比于传统的分子筛催化剂催化效率大大提高。
Description
技术领域
本发明属于分子筛催化剂领域,具体涉及一种复合负载型β分子筛催化剂的制备方法及应用。
背景技术
混合碳四是含有4个碳的烷烃、单烯烃和二烯烃的总称,是重要的石油化工资源。其来源较为广泛,可以通过天然气、原油提炼等多种途径获得,可以作为家用煤气,也可作为化工原料生产高附加值化工产品。目前,正丁烯主要用于生产甲乙酮、丁二烯,通过催化歧化与催化裂解转化为附加值较高的产品。
近年来,随着人类对环境保护的日益重视,汽油法规变得越来越严格。混合碳四中异丁烯的主要用途是生产汽油添加剂MTBE(甲基叔丁基醚),提高汽油的辛烷值。但是MTBE极易溶于地下水,进而污染环境。由于社会的发展以及人们对美好环境的需求,MTBE使用量降低甚至禁用是不可避免的,这种现象也会导致作为MTBE原料的异丁烯大量剩余。因此,开发异丁烯的新用途以及混合碳四中异丁烯反应分离方法具有重要意义。
异丁烯选择性齐聚技术,可以分离混合碳四中的异丁烯,替代之前依靠醚化反应生产MTBE分离混合碳四中异丁烯的生产工艺。异丁烯的齐聚反应可生成C8和C12,C8中DIB(二异丁烯)加氢可制得高辛烷值、低硫、抗爆震性能好的异辛烷,也可进行氢甲酰化反应生成异戊醛等产品。考虑到分子筛催化剂具有骨架状结构可以对反应原料进行择形催化,并且具有催化效率高、无腐蚀、环境友好、抗毒化能力强和可再生等优点,且通过负载过渡金属可以增加催化剂活性组分,从而提高异丁烯选择性反应转化率以及二聚产物收率。
发明内容
本发明针对上述现有技术存在的不足,提供一种复合负载型β分子筛催化剂的制备方法及应用,采用Co和Zn元素作为活性组分,制得复合负载型β分子筛催化剂,并将复合负载型β分子筛催化剂用于异丁烯选择性齐聚反应,异丁烯的转化率可达到95%以上,C8的选择性能达到80%以上,相比于传统的分子筛催化剂催化效率大大提高。
本发明的第一个目的在于,一种复合负载型β分子筛催化剂的制备方法,包括如下步骤:
(1)将β分子筛进行焙烧,以去除β分子筛中的模板剂;
(2)取Co(NO3)2·6H2O和Zn(NO3)2·6H2O放入烧杯中,滴加蒸馏水,充分混合、溶解,得浸渍液;
(3)将步骤(1)焙烧后的β分子筛加入步骤(2)所得浸渍液中,搅拌;
(4)搅拌均匀后,在水浴条件下浸渍;
(5)浸渍完成后,将步骤(4)所得产品进行干燥;
(6)干燥后,再将步骤(5)干燥后的产品进行焙烧,得到复合型Co-Zn/β分子筛。
进一步,所述的步骤(1)中,在4004600℃下焙烧246h。
进一步,所述的步骤(3)中,搅拌3410min。
进一步,所述的步骤(4)中,在50480℃水浴条件下浸渍246h。
进一步,所述的步骤(5)中,在1004150℃下干燥246h。
进一步,所述的步骤(6)中,在4004600℃下焙烧246h。
本发明的第二个目的在于,提供一种复合负载型β分子筛催化剂,采用上述的制备方法制备得到。
进一步,所述的复合负载型β分子筛催化剂中,Co:Zn的摩尔比为(1:3)4(1:0.33)。
本发明的第三个目的在于,提供一种上述复合负载型β分子筛催化剂在混合碳四中异丁烯选择性齐聚反应领域的应用。
与现有技术相比,本发明的有益效果如下:
(1)本发明提供的制备方法采用Co和Zn元素作为活性组分,制得复合负载型β分子筛催化剂,相较于传统的分子筛催化剂,本发明获得的复合负载型β分子筛催化剂上,Co3+有很强的氧化能力,可以获得电子,有助于碳正离子的生成;Co2+具有良好的还原能力,可以失电子,防止链增长;Zn元素可以改变β分子筛表面酸性,有利于增加C8的选择性;
(2)本发明提供的复合负载型β分子筛催化剂可用于异丁烯选择性齐聚反应,异丁烯的转化率可达到95%以上,C8的选择性能达到80%以上,相比于传统的分子筛催化剂催化效率大大提高。
附图说明
图1为本申请各实施例与对比例所得催化剂的X-射线衍射光谱图;
图2为本申请各实施例与对比例所得催化剂的傅里叶红外光谱;
图3为本申请中异丁烯选择性齐聚反应的装置图。
附图标记说明:1、N2气瓶;2、混合碳四原料罐;3、原料泵;4、背压阀;5、反应管;6、加热套;7、过滤器;8、气液分离罐;9、皂膜流量计。
具体实施方式
以下结合实例对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。
实施例1
一种复合负载型β分子筛催化剂的制备方法,包括如下步骤:
(1)取5gβ分子筛(购自南开大学催化剂厂)在马弗炉中550℃下焙烧4h,以去除β分子筛中的模板剂;
(2)准确称量15mL蒸馏水、0.532g Co(NO3)2·6H2O和0.543g Zn(NO3)2·6H2O,同时放入烧杯中,充分混合、溶解,得浸渍液;
(3)称取5g步骤(1)焙烧后的β分子筛慢慢加入到步骤(2)所得浸渍液中,搅拌5min;
(4)搅拌均匀后,放入带有加热搅拌的水浴锅中,加入磁子,在60℃水浴条件下搅拌浸渍2h;
(5)浸渍完成后,将步骤(4)所得产品置于干燥箱中,120℃下干燥3h;
(6)干燥后,再将步骤(5)干燥后的产品置于马弗炉中,550℃下焙烧3h,得到复合型Co-Zn/β分子筛,记为催化剂1,Co:Zn的摩尔比为1:1。
实施例2
一种复合负载型β分子筛催化剂的制备方法,参照实施例1,与实施例1的区别在于,步骤(2)中,称量0.723g Co(NO3)2·6H2O和0.369g Zn(NO3)2·6H2O,最终得到复合型Co-Zn/β分子筛,记为催化剂2,Co:Zn的摩尔比为1:0.5。
实施例3
一种复合负载型β分子筛催化剂的制备方法,参照实施例1,与实施例1的区别在于,步骤(2)中,称量0.821g Co(NO3)2·6H2O和0.280g Zn(NO3)2·6H2O,最终得到复合型Co-Zn/β分子筛,记为催化剂3,Co:Zn的摩尔比为1:0.33。
实施例4
一种复合负载型β分子筛催化剂的制备方法,参照实施例1,与实施例1的区别在于,步骤(2)中,称量0.348g Co(NO3)2·6H2O和0.712g Zn(NO3)2·6H2O,最终得到复合型Co-Zn/β分子筛,记为催化剂4,Co:Zn的摩尔比为1:2。
实施例5
一种复合负载型β分子筛催化剂的制备方法,参照实施例1,与实施例1的区别在于,步骤(2)中,称量0.259g Co(NO3)2·6H2O和0.793g Zn(NO3)2·6H2O,最终得到复合型Co-Zn/β分子筛,记为催化剂5,Co:Zn的摩尔比为1:3。
对比例
一种β分子筛催化剂的制备方法,参照实施例1,只进行步骤(1)中的焙烧,取5g焙烧后的β分子筛,记为催化剂0。
催化剂的表征1
X-射线衍射光谱(XRD)表征:各实施例与对比例所得催化剂的X-射线衍射光谱测试数据如图1所示。
由图1中可以看出,本发明实施例1-5制备的催化剂1-5在2θ=7.7°和2θ=22.3°出现了属于β分子筛的特征峰,并且通过负载活性组分Co和Zn并没有改变β分子筛衍射峰的位置。与对比例的原β分子筛(新纯分子筛)相比,负载后的β分子筛的两处特征峰强度略有下降,说明活性组分Co和Zn对β分子筛的晶格强度产生了影响。XRD图中并未出现Co和Zn的特征衍射峰,说明分子筛的骨架不受硝酸盐改性的影响,活性组分Co和Zn均匀的分散在β分子筛的表面,分散度较高。
催化剂的表征2
傅里叶红外光谱(FT-IR)表征:傅里叶红外光谱可表征分子筛的特有的吸收峰,从而判断分子筛的类型和所具有的结构。各实施例与对比例所得催化剂的傅里叶红外光谱测试数据如图2所示。
通过图2的红外光谱可以看出,波数为468.5cm-1、526.7cm-1、791cm-1的三个峰位置满足β分子筛的特征峰,1092cm-1、1228cm-1处的特征峰为β分子筛的骨架吸收峰,1632cm-1处特征峰代表β分子筛表面金属原子上水的O-H振动峰,3432cm-1处特征峰代表β分子筛表面-OH或O-H的振动吸收峰。从表征结果来看,高温焙烧和负载金属会对β分子筛骨架结构带来一定的影响。
催化剂的评价
复合负载型β分子筛催化剂活性评价方法:复合负载型β分子筛催化剂在混合碳四固定床中进行异丁烯选择性齐聚反应测试。异丁烯选择性齐聚反应的装置图如图3所示,具体操作如下:
原料为模拟工业的混合碳四馏分,组成为(丙烷:1.35wt%、丙烯:0.54wt%、异丁烷34.72wt%、正丁烷:11.37wt%、反-2-丁烯:12.06wt%、正丁烯:9.73wt%、异丁烯:22.38wt%、顺-2-丁烯:7.85wt%)。固定床的反应管5直径为9mm,长度为35mm,催化剂颗粒为20440目。实验前,将3g催化剂放入反应管5中,两端为石英砂,使催化剂放置在反应管5的恒温区,反应管5的外部套设有加热套6。安装反应管5后,用N2气瓶1内的N2(纯度为99.999%)对反应系统加压,以达到反应压力。加压期间可通过装置尾部的背压阀4调整压力。实验开始时,混合碳四原料罐2内液相的混合碳四馏分通过原料泵3进入反应管5,在催化剂的作用下进行齐聚反应。产品通过过滤器7进入气液分离罐8,液相产物在气液分离罐8底部直接收集到收集瓶中,通过气相色谱法进行称重分析。用皂膜流量计9测量气相产物,计算物料平衡。
异丁烯选择性齐聚反应中,各实施例与对比例所得催化剂的反应条件及结果如表1所示。
表1催化剂的反应条件及结果
表1结果表明,本发明的复合负载型β分子筛催化剂对工业混合碳四原料中的异丁烯的选择性齐聚表现出较高的转化率和选择性,异丁烯的转化率都在95%以上,C8的选择性都在80%以上,相比于传统的分子筛催化剂(对比例所得的催化剂0)催化效率大大提高。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (3)
1.一种复合负载型β分子筛催化剂在混合碳四中异丁烯选择性齐聚反应领域的应用,其特征在于,所述复合负载型β分子筛催化剂的制备方法,包括如下步骤:
(1)将β分子筛进行焙烧,以去除β分子筛中的模板剂;
(2)取Co(NO3)2·6H2O和Zn(NO3)2·6H2O放入烧杯中,滴加蒸馏水,充分混合、溶解,得浸渍液;
(3)将步骤(1)焙烧后的β分子筛加入步骤(2)所得浸渍液中,搅拌;
(4)搅拌均匀后,在水浴条件下浸渍;
(5)浸渍完成后,将步骤(4)所得产品进行干燥;
(6)干燥后,再将步骤(5)干燥后的产品进行焙烧,得到复合型Co-Zn/β 分子筛;
其中,所述的步骤(1)中,在400~600℃下焙烧2~6 h;所述的步骤(4)中,在50~80℃水浴条件下浸渍2~6h;所述的复合负载型β分子筛催化剂中,Co:Zn的摩尔比为1:1、1:0.5、1:0.33、1:2或1:3。
2.根据权利要求1所述的应用,其特征在于,所述的步骤(3)中,搅拌3~10 min。
3.根据权利要求1所述的应用,其特征在于,所述的步骤(5)中,在100~150℃下干燥2~6h。
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