CN1915516A - 含分子筛的催化裂解流化床催化剂 - Google Patents

含分子筛的催化裂解流化床催化剂 Download PDF

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CN1915516A
CN1915516A CNA2005100287943A CN200510028794A CN1915516A CN 1915516 A CN1915516 A CN 1915516A CN A2005100287943 A CNA2005100287943 A CN A2005100287943A CN 200510028794 A CN200510028794 A CN 200510028794A CN 1915516 A CN1915516 A CN 1915516A
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molecular sieve
catalyst
fluid bed
catalytic cracking
bed catalyst
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CN100391610C (zh
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谢在库
姚晖
马广伟
肖景娴
陈亮
杨为民
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
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Sinopec Shanghai Research Institute of Petrochemical Technology
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Priority to RU2008109666/04A priority patent/RU2403972C2/ru
Priority to KR1020087006339A priority patent/KR101347189B1/ko
Priority to SG10201506253UA priority patent/SG10201506253UA/en
Priority to PCT/CN2006/002072 priority patent/WO2007019797A1/zh
Priority to US12/063,598 priority patent/US20090288990A1/en
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Abstract

本发明涉及一种含分子筛的催化裂解流化床催化剂，主要解决石脑油催化裂解制乙烯丙烯中反应温度较高、催化剂低温活性低和选择性较差的问题。本发明通过采用在分子筛上负载，以原子比计化学式如下的组合物：AaBbPcOx为催化剂的技术方案，较好地解决了该问题，可用于石脑油催化裂解制乙烯丙烯的工业生产中。

Description

含分子筛的催化裂解流化床催化剂
                               技术领域
本发明涉及一种含分子筛的催化裂解流化床催化剂，特别是关于一种含分子筛的石脑油催化裂解制乙烯丙烯的流化床催化剂。
                               背景技术
目前制乙烯丙烯的最主要的方法是蒸汽热裂解。所采用最多的原料是石脑油。但蒸汽热裂解石脑油存在着反应温度高，工艺条件苛刻，对设备尤其是炉管材料要求高，损耗大的缺点。为此人们开展了各种有意义的研究，其中催化裂解是最有吸引力，也是最有前途的一项。目标在于寻找一种合适的裂解催化剂，提高乙烯丙烯的选择性，降低反应温度，同时可以在乙烯丙烯的收率上有一定的灵活性。
从现有的文献来看，多数催化裂解研究者多用高硅铝比的分子筛作催化材料，而且用高价态的金属离子进行交换和浸渍。但分子筛催化剂具有水热稳定性差，难以再生的缺点。
美国专利USP6211104和国内专利CN1504540A采用一种含10～70重量％粘土，5～85重量％无机氧化物，1～50重量％分子筛组成催化剂，对传统蒸汽热裂解的各种原料，显示出了很好的转化为轻烯烃的活性，尤其是乙烯。用的分子筛，是由高硅铝比的0～25重量％Y沸石或具有MFI结构的ZSM分子筛，由磷/Al、Mg或Ca浸渍而成，基本上也属于单纯分子筛类催化剂。
除此以外，人们用氧化物作催化剂。
美国Phillips公司的专利US4620051和US4705769采用了以氧化锰或氧化铁为活性组分，添加了稀土元素La，以及碱土金属Mg的氧化物催化剂，裂解C3、C4原料。Mn，Mg/Al2O3催化剂在实验室的固定床反应器中，700℃，水与丁烷的摩尔比为1∶1，丁烷的转化率可达80％，乙烯，丙烯的选择性为34％和20％。该两个专利声称也可以用石脑油和流化床反应器。
意大利恩尼切姆公司的专利CN1317546A涉及化学式为12CaO·7Al2O3的蒸汽裂解反应催化剂。原料可以用石脑油，操作温度720～800℃，在1.1～1.8个大气压下，接触时间0.07～0.2秒，乙烯和丙烯的产率可达43％。
前苏联专利USSR Pat1298240.1987用负载于浮石或陶瓷上的Zr2O3和钒酸钾，温度660～780℃中型装置上空速为2-5小时-1，水/直馏汽油重量比1∶1。以正构烷烃C7～17，环己烷，直馏汽油为原料，乙烯产率可达到46％，丙烯8.8％。
中国专利CN1480255A介绍一种氧化物催化剂，用石脑油为原料，在780℃下催化裂解制乙烯丙烯，双烯收率可达到47％。
综上所述，分子筛作为主要的裂解催化剂受到了人们的重视，但与氧化物混合使用的例子，还未见报道。
                               发明内容
本发明所要解决的技术问题是现有技术催化裂解制乙烯丙烯中反应温度较高、催化剂低温活性低和选择性较差的问题，提供一种新的含分子筛的催化裂解流化床催化剂。使用该催化剂催化裂解石脑油制乙烯丙烯，不但可以降低催化裂解温度，还可以提高催化剂的选择性的优点。
为解决上述技术问题，本发明采用的技术方案如下：一种含分子筛的催化裂解流化床催化剂，含有选自ZSM-5、Y、β、MCM-22、SAPO-34或丝光沸石中至少一种的分子筛和载于分子筛上以原子比计化学式如下的组合物：
AaBbPcOx
式中A选自镧系稀土元素中的至少一种；
B选自VIII、IB、IIB、VIIB、VIB、IA或IIA中的至少一种元素；
a的取值范围为0.01～0.5；
b的取值范围为0.01～0.5；
c的取值范围为0.01～0.5；
X为满足催化剂中各元素化合价所需的氧原子总数；
其中催化剂中分子筛的用量以重量百分比计为催化剂重量的0～60％。
上述技术方案中，a的取值优选范围为0.01～0.3；b的取值优选范围为0.01～0.3；c的取值优选范围为0.01～0.3。稀土元素的优选方案为选自La或Ce中的至少一种。VIII族元素的优选方案为选自Fe、Co或Ni中的至少一种；IB元素的优选方案为选自Cu或Ag中的至少一种；IIB元素的优选方案为选自Zn；VIIB元素的优选方案为选自Mn；VIB元素的优选方案为选自Cr、Mo或其混合物；IA元素的优选方案为选自Li、Na或K中的至少一种；IIA元素的优选方案为选自Mg、Ca、Ba或Sr中的至少一种。分子筛优选方案为选自ZSM-5、Y或丝光沸石中的至少一种；分子筛的硅铝摩尔比SiO2/Al2O3优选范围为10～500，更优选范围为20～300；催化剂中分子筛的用量以重量百分比计优选范围为催化剂重量的30～50％
本发明涉及的是含分子筛的催化裂解石脑油的流化床催化剂。本发明涉及的催化剂制备，所用的原料A类元素用的是相应的硝酸盐、草酸盐、或氧化物。B类元素用的是相应的硝酸盐、草酸盐、乙酸盐或可溶性卤化物。所用的磷元素来源于磷酸、磷酸三铵、磷酸氢二铵、磷酸二氢铵。
制备催化剂的成形方式是将加入了各组分元素和载体的浆液，在70～80℃的水浴上加热回流5小时后进行喷雾干燥。得到的粉末在马福炉中焙烧，温度为600～750℃，焙烧时间为3～10小时。
本发明由于采用了具有酸性、择形性和高比表面积的分子筛作为裂解助剂，有利于烃类原料按正碳离子机理裂解，多产低碳烯烃，同具有氧化还原性的活性组份配合，产生协同作用，在相对较低温度(580～650℃)下，达到较好的催化裂解效果，获得了较高的乙烯丙烯收率，取得了较好的技术效果。
为了考评本发明所涉及的催化剂活性，用石脑油(具体指标见表1)为原料。反应的温度范围为580～650℃，催化剂负荷为0.5～2克石脑油/克催化剂·小时，水/石脑油重量比为0.5～3∶1。流化床反应器的内径为39毫米，反应压力0～0.2MPa。
        表1  石脑油原料指标
  项目   数据
  密度(20℃)千克/米3   704.6
  馏程 初馏程℃   40
  终馏程℃   160
  饱和蒸汽压(20℃)千帕   50.2
  烷烃％(重量)   65.2
  正构烷烃％   32.5
  环烷烃％   28.4
  烯烃％(重量)   0.17
  芳烃％(重量)   6.2
下面通过实施例对本发明作进一步的阐述。
                          具体实施方式
【实施例1】
将2克硝酸铵溶解于100毫升水中，放入20克ZSM-5分子筛(硅铝摩尔比SiO2/Al2O3为400)原粉。90℃交换2小时后，过滤，得滤饼。
取硝酸铁16.2克，硝酸钴7.86克，硝酸铬12.23克，硝酸镧2.4克将它们一起溶解于250毫升水中，得到溶液A。溶解4.65克磷酸氢二铵于100毫升水中，将其倒入A溶液中，搅拌均匀，得到浆液B。
将浆液B置于70～80℃水浴上加热，加入上述交换好的分子筛，回流5小时，用喷雾干燥设备将浆液干燥成型。
将干燥后的粉末，置于马福炉中升温至740℃，灼烧5小时。冷却后得催化剂，再将催化剂过100目筛。
得到催化剂化学式为：Fe0.11Co0.08Cr0.08La0.04P0.05Ox+ZSM-5分子筛31.57重量％
在以下条件下进行催化剂活性评价：39毫米内径的流化床反应器，反应温度650℃，压力0.15MPa。水/石脑油重量比3∶1，催化剂装量为20克，负荷为1克石脑油/克催化剂·小时。收集气体产物，进行气相色谱分析，产物分布及双烯收率见表2。
        表2  气相产物分布及双烯产率
  产品   含量(H2体积％，其余重量％)
  氢气(体积％)   15.5
  甲烷   17.08
  乙烷   1.62
  乙烯   42.23
  丙烷   0.41
  丙烯   14.72
  C4   7.98
  其它   15.96
  转化率   76.37
  乙烯收率   32.25
  丙烯收率   11.24
  双烯收率   43.49
【实施例2】
将2克硝酸铵溶解于100毫升水中，放入20克Y分子筛(硅铝摩尔比SiO2/Al2O3为20)原粉。90℃交换2小时后，过滤，得滤饼。
取硝酸镍7.27克，硝酸铬8.48克，硝酸铈5.44克，溶解于250毫升水中，得溶液A。溶解6.54克磷酸氢二铵于100毫升水中，将其倒入溶液A中，搅拌均匀，得到浆液B。
将交换好的分子筛放入浆液B中，其它同实施例1，得到催化剂化学式为：
Ni0.07Cr0.06Ce0.09P0.08Ox+ZSM-5分子筛41.9％
催化剂评价同实例1，裂解产物分布及双烯收率见表3。
        表3  气相产物分布及双烯产率
  产品   含量(H2体积％，其余重量％)
  氢气(体积％)   15.52
  甲烷   20.46
  乙烷   2.40
  乙烯   44.00
  丙烷   0.37
  丙烯   14.28
  C4   5.60
  其它   12.89
  转化率   75.26
  乙烯收率   33.11
  丙烯收率   10.75
  双烯收率   43.86
【实施例3】
将2克硝酸铵溶解于100毫升水中，放入20克ZSM-5分子筛(硅铝摩尔比SiO2/Al2O3为120)原粉。90℃交换2小时后，过滤，得滤饼。
取硝酸钴5.49克，硝酸锌5.60克，硝酸铈5.44克，硝酸铜6.30克，溶解于250毫升水中，得溶液A。溶解6.54克磷酸氢二铵于100毫升水中，将其倒入溶液A中，搅拌均匀，得到浆液B。
将交换好的分子筛放入浆液B中，其它同实施例1。
得到催化剂化学式为：Co0.06Zn0.06Cu0.08Ce0.09P0.08Ox+ZSM-5分子筛40.5％重量
产物收率见表4。
【实施例4】
将2克硝酸铵溶解于100毫升水中，放入20克ZSM-5分子筛(硅铝摩尔比SiO2/Al2O3为300)原粉。90℃交换2小时后，过滤，得滤饼。
取硝酸铁7.62克，硝酸锌5.60克，硝酸铈5.44克，硝酸钙5.18克，溶解于250毫升水中，得溶液A。溶解6.54克磷酸氢二铵于100毫升水中，将其倒入溶液A中，搅拌均匀，得到浆液B。
将交换好的分子筛放入溶液中，其它同实施例1。
得到催化剂化学式为：Fe0.05Zn0.06Ce0.09Ca0.04P0.08Ox+ZSM-5分子筛39.7％重量
产物收率见表4。
【实施例5】
将2克硝酸铵溶解于100毫升水中，放入20克丝光分子筛(硅铝摩尔比SiO2/Al2O3为25)原粉。90℃交换2小时后，过滤，得滤饼。
取硝酸钴5.49克，50％的硝酸锰溶液10.81克，硝酸铈5.44克，溶解于250毫升水中，得溶液A。溶解6.54克磷酸氢二铵于100毫升水中，将其倒入溶液A中，搅拌均匀，得到浆液B。
将交换好的分子筛放入浆液B中，其它同实施例1。
得到催化剂化学式为：Mn0.08Co0.06Ce0.09P0.08Ox+ZSM-5分子筛46.6％重量
产物收率见表4。
【实施例6】
取硝酸钴5.49克，硝酸铬8.48克，硝酸铈5.44克，硝酸钾1.1克，溶解于250毫升水中，得溶液A。溶解6.54克磷酸氢二铵于100毫升水中，将其倒入溶液A中，搅拌均匀，得到浆液B。
以氧化硅和氧化铝代替分子筛作载体，放入浆液B中，其它同实施例1。
得到催化剂化学式为：Co0.06Cr0.06Ce0.09K0.02P0.08Ox(不含分子筛)
产物收率见表4。
                           表4  不同分子筛助剂的产物收率
  实施例   分子筛类型   乙烯收率   丙烯收率   双烯收率
  实施例3   ZSM-5分子筛(硅铝比120)   36.0％   5.47％   41.47％
  实施例4   ZSM-5分子筛(硅铝比300)   25.37％   15.35％   40.72％
  实施例5   丝光沸石(硅铝比25)   30.71％   9.33％   40.04％
  实施例6   不含分子筛   26.98％   12.49％   39.47％

Claims (8)

1、一种含分子筛的催化裂解流化床催化剂，含有选自ZSM-5、Y、β、MCM-22、SAPO-34或丝光沸石中至少一种的分子筛和载于分子筛上以原子比计化学式如下的组合物：
AaBbPcOx
式中A选自镧系稀土元素中的至少一种；
B选自VIII、IB、IIB、VIIB、VIB、IA或IIA中的至少一种元素；
a的取值范围为0.01～0.5；
b的取值范围为0.01～0.5；
c的取值范围为0.01～0.5；
X为满足催化剂中各元素化合价所需的氧原子总数；
其中催化剂中分子筛的用量以重量百分比计为催化剂重量的0～60％。
2、根据权利要求1所述含分子筛的催化裂解流化床催化剂，其特征在于a的取值范围为0.01～0.3；b的取值范围为0.01～0.3；c的取值范围为0.01～0.3。
3、根据权利要求1所述含分子筛的催化裂解流化床催化剂，其特征在于稀土元素选自La或Ce中的至少一种。
4、根据权利要求1所述含分子筛的催化裂解流化床催化剂，其特征在于VIII族的元素选自Fe、Co或Ni中的至少一种；IB的元素选自Cu或Ag中的至少一种；IIB的元素选自Zn；VIIB的元素选自Mn；VIB的元素选自Cr或Mo中的至少一种，IA的元素选自Li、Na或K中的至少一种；IIA的元素选自Mg、Ca、Ba或Sr中的至少一种。
5、根据权利要求1所述含分子筛的催化裂解流化床催化剂，其特征在于分子筛选自ZSM-5、Y或丝光沸石中的至少一种。
6、根据权利要求1所述含分子筛的催化裂解流化床催化剂，其特征在于分子筛的硅铝摩尔比SiO2/Al2O3为10～500。
7、根据权利要求6所述含分子筛的催化裂解流化床催化剂，其特征在于分子筛的硅铝摩尔比SiO2/Al2O3为20～300。
8、根据权利要求1所述含分子筛的催化裂解流化床催化剂，其特征在于催化剂中分子筛的用量以重量百分比计为催化剂重量的30～50％。
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CN112322330A (zh) * 2020-10-21 2021-02-05 中国石油大学(北京) 按原料性质的双区分区耦合床层控制多级催化裂解的方法
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