CN108262057A - 非芳烃高效裂解的方法 - Google Patents
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Abstract
本发明涉及一种非芳烃高效裂解的方法,主要解决现有技术存在非芳裂解催化剂裂解活性低、选择性差的问题。本发明通过采用包括在裂解反应条件下,非芳烃原料与催化剂接触生成C2‑C5轻组分的步骤;所述催化剂以重量份数计,包括以下组份:a)20~80份的选自丝光沸石、ZSM‑5、β沸石、Y沸石中的至少一种沸石;b)0.05%~5份选自镍、锌、锶、镁、铱或其氧化物中的至少一种助剂;c)10~40份的粘结剂的技术方案较好地解决了该问题,可用于非芳烃裂解的工业生产中。
Description
技术领域
本发明涉及一种非芳烃高效裂解的方法。
背景技术
对二甲苯是石化工业主要的基本有机原料之一,在化纤、合成树脂、农药、医药、塑料等众多化工生产领域有着广泛的用途。典型的对二甲苯(PX)生产装置通常包括石脑油催化重整、二甲苯分馏、芳烃抽提、甲苯歧化及烷基转移、吸附分离、异构化共六个单元。芳烃抽提需要一套复杂的溶剂抽提装置,而且抽提溶剂在抽提操作过程中需要源源不断地补充进去,该抽提过程费用占据了芳烃成本的极大比例。此外,在传统芳烃联合生产装置中,一般利用甲苯与碳九及其以上重芳烃(C9 +A)为原料,通过烷基转移反应来增产二甲苯。原料中非芳烃对烷基转移催化剂反应性能有显著影响,非芳烃将降低催化剂转化率及苯产品纯度。因此,现有烷基转移单元对原料中的非芳烃含量有严格限定,重整来的甲苯一般需先经过抽提单元去除非芳烃组分后才能作为烷基转移单元的进料,即增大了抽提单元的能耗物耗,也限制了烷基转移单元的扩能规模。
文献US3,729,409提出与芳烃混合的非芳烃在催化剂的存在下通过加氢裂解反应而转化成低碳烷烃,通过汽-液分离器可从非芳烃中分离出芳烃,该催化剂以分子筛为载体,负载Co、Mo、Ni、W等金属。文献US3,849,290和US3,950,241还提出了一种通过使与芳烃混合的直链烃组分在ZSM-5型沸石的存在下经加氢裂解反应转化成气态组分以增加液态组分中的芳烃含量以制备高质量的挥发性油组分的方法。文献CN105272804A公开了一种非芳裂解催化剂,含有至少一种选自MFI、MOR、BEA结构的硅铝分子筛组分。文献CN104557418A公开了一种甲苯与重质芳烃歧化与烷基转移的方法,甲苯与重芳烃歧化和烷基转移反应后的物流与第三层催化剂接触,第三层催化剂对加氢副反应中形成的沸点与苯接近的非芳烃进行选择性裂解生成轻烃组分,从而提高了苯产品质量。第三层催化剂含有至少一种选自ZSM-5、MOR、MCM-22、NU-87的分子筛,并且不强制性含有至少一种选自钼、铼、铅、锡、锗、铋、硫元素或其化合物。但是,现有技术中的非芳裂解催化剂仍旧存在裂解活性低、选择性差的问题。
发明内容
本发明所要解决的技术问题是现有技术存在非芳裂解催化剂裂解活性低、选择性差的问题,提供一种非芳烃高效裂解的方法。该方法具有良好的开环裂解性能,呈现高的活性和选择性。
为解决上述技术问题,本发明采取的技术方案如下:一种非芳烃高效裂解的方法,包括在裂解反应条件下,非芳烃原料与催化剂接触生成C2-C5轻组分的步骤;
所述催化剂以重量份数计,包括以下组份:
a)20~80份的选自丝光沸石、ZSM-5、β沸石、Y沸石中的至少一种沸石;
b)0.05%~5份选自镍、锌、锶、镁、铱或其氧化物中的至少一种助剂;
c)10~40份的粘结剂。
上述技术方案中,优选地,以重量份数计,沸石的用量为40~70份,助剂的用量为0.1~3份,粘结剂的用量为20~40份。
上述技术方案中,优选地,所述沸石选自丝光沸石、ZSM-5中的至少一种。
上述技术方案中,丝光沸石的硅铝摩尔比SiO2/Al2O3=25~80,ZSM-5的硅铝摩尔比SiO2/Al2O3=25~80,β沸石的硅铝摩尔比SiO2/Al2O3=25~80,Y沸石的硅铝摩尔比SiO2/Al2O3=25~80。
上述技术方案中,所述粘结剂选自氧化铝、氧化锆或高岭土。
上述技术方案中,所述非芳烃为含有6~9个碳原子的环烷烃、烷烃或烯烃组分。优选地,所述非芳烃为环己烷、甲基环己烷、甲基环戊烷或二甲基环戊烷中的至少一种。
上述技术方案中,以重量百分比计,原料中非芳烃含量为0.05~50%。
上述技术方案中,优选地,所述裂解反应条件包括:反应温度300~500℃,反应压力1.0~5.0MPa,重量空速1.0~20.0小时-1,氢烃比2~8。
所述C2-C5轻组分包括乙烯、丙烷、丁烷、正戊烷、异戊烷。
本发明中所述催化剂的制备方法包括以下步骤:a)将沸石与粘结剂成型;b)将含助剂金属的前躯体通过浸渍、沉淀、吸附、离子交换方式负载到成型催化剂上;所述浸渍、沉淀、吸附、离子交换方式是为本领域所熟知的;c)将负载助剂组份的成型催化剂在400~600℃的温度下焙烧2~6小时,得到所需催化剂。
本发明在沸石本体上负载了选自镍、锌、锶、镁、铱或其氧化物中的至少一种助剂,有效地调变了催化剂的酸分布,减少了强酸中心,保留了中等强度的酸性位,减少了积碳反应,延长使用寿命。改善了催化剂的裂解活性,非芳转化率可提高至92.9%,选择性可达到88.3%。
下面通过实施例对本发明作进一步阐述。
具体实施方式
[对比例1]
将SiO2/Al2O3为25的丝光沸石195g与γ-Al2O3107.1g均匀混合,然后加入稀硝酸、田菁粉捏合均匀,挤条成型、焙烧制成载体,切粒后置于浸渍容器中。将金属前驱体硝酸镍溶于水,混合均匀后浸渍与载体表面,120℃干燥4小时、500℃焙烧3小时制得催化剂HC-1.
在固定床反应器中,装20克催化剂HC-1,通入氢气,升温至400℃,吹扫两小时还原活化,反应温度为400℃,压力3MPa,按照WHSV=2.5h-1工况进料,氢烃分子比3.0。原料环己烷。催化剂反应性能结果如表1。催化剂反应100小时后逐渐失活。
[对比例2]
将SiO2/Al2O3为25的丝光沸石195g与γ-Al2O3107.1g均匀混合,然后加入稀硝酸、田菁粉捏合均匀,挤条成型、焙烧制成载体,切粒后置于浸渍容器中。将金属前驱体硝酸镍溶于水,混合均匀后浸渍与载体表面,120℃干燥4小时、500℃焙烧3小时制得催化剂HC-2.
在固定床反应器中,装20克催化剂HC-2,通入氢气,升温至400℃,吹扫两小时还原活化,反应温度为400℃,压力3MPa,按照WHSV=2.5h-1工况进料,氢烃分子比3.0。原料环己烷。催化剂反应性能结果如表1。催化剂反应100小时后逐渐失活。
[对比例3]
将SiO2/Al2O3为25的丝光沸石195g与γ-Al2O3107.1g均匀混合,然后加入稀硝酸、田菁粉捏合均匀,挤条成型、焙烧制成载体,切粒后置于浸渍容器中。将金属前驱体硝酸镍溶于水,混合均匀后浸渍与载体表面,120℃干燥4小时、500℃焙烧3小时制得催化剂HC-3.
在固定床反应器中,装20克催化剂HC-3,通入氢气,升温至400℃,吹扫两小时还原活化,反应温度为400℃,压力3MPa,按照WHSV=2.5h-1工况进料,氢烃分子比3.0。原料环己烷。催化剂反应性能结果如表1。催化剂反应100小时后逐渐失活。
[对比例4]
将SiO2/Al2O3为25的丝光沸石195g与γ-Al2O3107.1g均匀混合,然后加入稀硝酸、田菁粉捏合均匀,挤条成型、焙烧制成载体,切粒后置于浸渍容器中。将金属前驱体硝酸镍溶于水,混合均匀后浸渍与载体表面,120℃干燥4小时、500℃焙烧3小时制得催化剂HC-4.
在固定床反应器中,装20克催化剂HC-4,通入氢气,升温至400℃,吹扫两小时还原活化,反应温度为400℃,压力3MPa,按照WHSV=2.5h-1工况进料,氢烃分子比3.0。原料环己烷。催化剂反应性能结果如表1。催化剂反应100小时后逐渐失活。
[实施例1]
将SiO2/Al2O3为25的丝光沸石195g与γ-Al2O3107.1g均匀混合,然后加入稀硝酸、田菁粉捏合均匀,挤条成型、焙烧制成载体,切粒后置于浸渍容器中。将金属前驱体氯化铱溶于水,混合均匀后浸渍与载体表面,120℃干燥4小时、500℃焙烧3小时制得催化剂HC-5.
在固定床反应器中,装20克催化剂HC-5,通入氢气,升温至400℃,吹扫两小时还原活化,反应温度为400℃,压力3MPa,按照WHSV=2.5h-1工况进料,氢烃分子比3.0。原料环己烷。催化剂反应性能结果如表1。催化剂反应300小时均保持稳定。
[实施例2]
将SiO2/Al2O3为25的丝光沸石195g与γ-Al2O3107.1g均匀混合,然后加入稀硝酸、田菁粉捏合均匀,挤条成型、焙烧制成载体,切粒后置于浸渍容器中。将金属前驱体硝酸镍溶于水,混合均匀后浸渍与载体表面,120℃干燥4小时、500℃焙烧3小时制得催化剂HC-6.
在固定床反应器中,装20克催化剂HC-6,通入氢气,升温至400℃,吹扫两小时还原活化,反应温度为400℃,压力3MPa,按照WHSV=2.5h-1工况进料,氢烃分子比3.0。原料环己烷。催化剂反应性能结果如表1。催化剂反应300小时均保持稳定。
[实施例3]
将SiO2/Al2O3为25的丝光沸石195g与γ-Al2O3107.1g均匀混合,然后加入稀硝酸、田菁粉捏合均匀,挤条成型、焙烧制成载体,切粒后置于浸渍容器中。将金属前驱体硝酸镍溶于水,混合均匀后浸渍与载体表面,120℃干燥4小时、500℃焙烧3小时制得催化剂HC-7.
在固定床反应器中,装20克催化剂HC-7,通入氢气,升温至400℃,吹扫两小时还原活化,反应温度为400℃,压力3MPa,按照WHSV=2.5h-1工况进料,氢烃分子比3.0。原料环己烷。催化剂反应性能结果如表1。催化剂反应300小时均保持稳定。
[实施例4]
将SiO2/Al2O3为25的丝光沸石195g与γ-Al2O3107.1g均匀混合,然后加入稀硝酸、田菁粉捏合均匀,挤条成型、焙烧制成载体,切粒后置于浸渍容器中。将金属前驱体硝酸镍溶于水,混合均匀后浸渍与载体表面,120℃干燥4小时、500℃焙烧3小时制得催化剂HC-8。
在固定床反应器中,装20克催化剂HC-8,通入氢气,升温至400℃,吹扫两小时还原活化,反应温度为400℃,压力3MPa,按照WHSV=2.5h-1工况进料,氢烃分子比3.0。原料环己烷。催化剂反应性能结果如表1。催化剂反应300小时均保持稳定。
[实施例5]
将SiO2/Al2O3为25的丝光沸石195g与γ-Al2O3107.1g均匀混合,然后加入稀硝酸、田菁粉捏合均匀,挤条成型、焙烧制成载体,切粒后置于浸渍容器中。将金属前驱体硝酸锌溶于水,混合均匀后浸渍与载体表面,120℃干燥4小时、500℃焙烧3小时制得催化剂HC-9.
在固定床反应器中,装20克催化剂HC-9,通入氢气,升温至400℃,吹扫两小时还原活化,反应温度为400℃,压力3MPa,按照WHSV=2.5h-1工况进料,氢烃分子比3.0。原料环己烷。催化剂反应性能结果如表1。催化剂反应300小时均保持稳定。
[实施例6]
将SiO2/Al2O3为25的丝光沸石195g与γ-Al2O3107.1g均匀混合,然后加入稀硝酸、田菁粉捏合均匀,挤条成型、焙烧制成载体,切粒后置于浸渍容器中。将金属前驱体硝酸镍溶于水,混合均匀后浸渍与载体表面,120℃干燥4小时、500℃焙烧3小时制得催化剂HC-10.
在固定床反应器中,装20克催化剂HC-10,通入氢气,升温至400℃,吹扫两小时还原活化,反应温度为400℃,压力3MPa,按照WHSV=2.5h-1工况进料,氢烃分子比3.0。原料环己烷。催化剂反应性能结果如表1。催化剂反应300小时均保持稳定。
[实施例7]
将SiO2/Al2O3为25的丝光沸石195g与γ-Al2O3107.1g均匀混合,然后加入稀硝酸、田菁粉捏合均匀,挤条成型、焙烧制成载体,切粒后置于浸渍容器中。将金属前驱体硝酸镁溶于水,混合均匀后浸渍与载体表面,120℃干燥4小时、500℃焙烧3小时制得催化剂HC-11.
在固定床反应器中,装20克催化剂HC-11,通入氢气,升温至400℃,吹扫两小时还原活化,反应温度为400℃,压力3MPa,按照WHSV=2.5h-1工况进料,氢烃分子比3.0。原料环己烷。催化剂反应性能结果如表1。催化剂反应300小时均保持稳定。
[实施例8]
将SiO2/Al2O3为25的丝光沸石195g与γ-Al2O3107.1g均匀混合,然后加入稀硝酸、田菁粉捏合均匀,挤条成型、焙烧制成载体,切粒后置于浸渍容器中。将金属前驱体碳酸锶溶于水,混合均匀后浸渍与载体表面,120℃干燥4小时、500℃焙烧3小时制得催化剂HC-12.
在固定床反应器中,装20克催化剂HC-12,通入氢气,升温至400℃,吹扫两小时还原活化,反应温度为400℃,压力3MPa,按照WHSV=2.5h-1工况进料,氢烃分子比3.0。原料环己烷。催化剂反应性能结果如表1。催化剂反应300小时均保持稳定。
[实施例9]
将SiO2/Al2O3为25的ZSM-5沸石195g与γ-Al2O3107.1g均匀混合,然后加入稀硝酸、田菁粉捏合均匀,挤条成型、焙烧制成载体,切粒后置于浸渍容器中。将金属前驱体硝酸镍溶于水,混合均匀后浸渍与载体表面,120℃干燥4小时、500℃焙烧3小时制得催化剂HC-13.
在固定床反应器中,装20克催化剂HC-13,通入氢气,升温至400℃,吹扫两小时还原活化,反应温度为400℃,压力3MPa,按照WHSV=2.5h-1工况进料,氢烃分子比3.0。原料环己烷。催化剂反应性能结果如表1。催化剂反应300小时均保持稳定。
[实施例10]
将SiO2/Al2O3为25的β沸石195g与γ-Al2O3107.1g均匀混合,然后加入稀硝酸、田菁粉捏合均匀,挤条成型、焙烧制成载体,切粒后置于浸渍容器中。将金属前驱体硝酸镍溶于水,混合均匀后浸渍与载体表面,120℃干燥4小时、500℃焙烧3小时制得催化剂HC-14.
在固定床反应器中,装20克催化剂HC-14,通入氢气,升温至400℃,吹扫两小时还原活化,反应温度为400℃,压力3MPa,按照WHSV=2.5h-1工况进料,氢烃分子比3.0。原料环己烷。催化剂反应性能结果如表1。催化剂反应300小时均保持稳定。
[实施例11]
将SiO2/Al2O3为60的β沸石195g与γ-Al2O3107.1g均匀混合,然后加入稀硝酸、田菁粉捏合均匀,挤条成型、焙烧制成载体,切粒后置于浸渍容器中。将金属前驱体硝酸镍溶于水,混合均匀后浸渍与载体表面,120℃干燥4小时、500℃焙烧3小时制得催化剂HC-15.
在固定床反应器中,装20克催化剂HC-15,通入氢气,升温至400℃,吹扫两小时还原活化,反应温度为400℃,压力3MPa,按照WHSV=2.5h-1工况进料,氢烃分子比3.0。原料环己烷。催化剂反应性能结果如表1。催化剂反应300小时均保持稳定。
表1
Claims (10)
1.一种非芳烃高效裂解的方法,包括在裂解反应条件下,非芳烃原料与催化剂接触生成C2-C5轻组分的步骤;
所述催化剂以重量份数计,包括以下组份:
a)20~80份的选自丝光沸石、ZSM-5、β沸石、Y沸石中的至少一种沸石;
b)0.05%~5份选自镍、锌、锶、镁、铱或其氧化物中的至少一种助剂;
c)10~40份的粘结剂。
2.根据权利要求1所述非芳烃高效裂解的方法,其特征在于,以重量份数计,沸石的用量为40~70份,助剂的用量为0.1~3份,粘结剂的用量为20~40份。
3.根据权利要求1所述非芳烃高效裂解的方法,其特征在于,所述沸石选自丝光沸石、ZSM-5中的至少一种。
4.根据权利要求1所述非芳烃选择性裂解的方法,其特征在于,丝光沸石的硅铝摩尔比SiO2/Al2O3=10~60,ZSM-5的硅铝摩尔比SiO2/Al2O3=10~80,β沸石的硅铝摩尔比SiO2/Al2O3=10~80,Y沸石的硅铝摩尔比SiO2/Al2O3=3~50。
5.根据权利要求1所述非芳烃高效裂解的方法,其特征在于,所述粘结剂选自氧化铝、氧化锆或高岭土。
6.根据权利要求1所述非芳烃高效裂解的方法,其特征在于,所述非芳烃为含有5-10个碳原子的环烷烃、烷烃或烯烃组分。
7.根据权利要求6所述非芳烃高效裂解的方法,其特征在于,所述非芳烃为环己烷、甲基环己烷、甲基环戊烷或二甲基环戊烷中的至少一种。
8.根据权利要求1所述非芳烃高效裂解的方法,其特征在于,以重量百分比计,原料中非芳烃含量为0.05~100%。
9.根据权利要求1所述非芳烃高效裂解的方法,其特征在于,所述裂解反应条件包括:反应温度300~500℃,反应压力1.0~5.0MPa,重量空速1.0~20.0小时-1,氢烃比2~8。
10.根据权利要求1所述非芳烃高效裂解的方法,其特征在于,所述C2-C5轻组分包括乙烯、丙烷、丁烷、正戊烷、异戊烷。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101992120A (zh) * | 2009-08-25 | 2011-03-30 | 中国石油化工股份有限公司抚顺石油化工研究院 | 一种环烷烃加氢转化催化剂及其制备方法和应用 |
CN103785462A (zh) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | 一种环烷烃加氢催化剂及其制备方法和应用 |
CN103864557A (zh) * | 2012-12-14 | 2014-06-18 | 中国石油化工股份有限公司 | 一种催化裂解环烷烃的方法 |
CN103896709A (zh) * | 2012-12-28 | 2014-07-02 | 中国石油化工股份有限公司 | 一种环烷烃开环的催化方法 |
CN105272804A (zh) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | 芳烃烷基转移与非芳烃裂解增产二甲苯的方法 |
-
2017
- 2017-01-04 CN CN201710003422.8A patent/CN108262057B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101992120A (zh) * | 2009-08-25 | 2011-03-30 | 中国石油化工股份有限公司抚顺石油化工研究院 | 一种环烷烃加氢转化催化剂及其制备方法和应用 |
CN103785462A (zh) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | 一种环烷烃加氢催化剂及其制备方法和应用 |
CN103864557A (zh) * | 2012-12-14 | 2014-06-18 | 中国石油化工股份有限公司 | 一种催化裂解环烷烃的方法 |
CN103896709A (zh) * | 2012-12-28 | 2014-07-02 | 中国石油化工股份有限公司 | 一种环烷烃开环的催化方法 |
CN105272804A (zh) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | 芳烃烷基转移与非芳烃裂解增产二甲苯的方法 |
Non-Patent Citations (3)
Title |
---|
张巧玲等: "《化工工艺学》", 31 July 2015, 国防工业出版社 * |
李大东: "《加氢处理工艺与工程》", 31 December 2004, 中国石化出版社 * |
韩文光: "《化工装置实用操作技术指南》", 30 October 2001, 化学工业出版社 * |
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