CN1156555C - 一种催化裂化助剂及其制备方法 - Google Patents

一种催化裂化助剂及其制备方法 Download PDF

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CN1156555C
CN1156555C CNB001242164A CN00124216A CN1156555C CN 1156555 C CN1156555 C CN 1156555C CN B001242164 A CNB001242164 A CN B001242164A CN 00124216 A CN00124216 A CN 00124216A CN 1156555 C CN1156555 C CN 1156555C
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zeolite
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molecular sieve
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王龙延
魏小波
刘丹禾
郝代军
刘金龙
龚旭辉
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中国石油化工集团公司
中国石化集团洛阳石油化工工程公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline 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
    • B01J29/405Crystalline 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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04Oxides
    • C10G11/05Crystalline alumino-silicates, e.g. molecular sieves
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10After treatment, characterised by the effect to be obtained
    • B01J2229/26After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30After treatment, characterised by the means used
    • B01J2229/42Addition of matrix or binder particles

Abstract

本发明公开了一种降低催化裂化汽油烯烃含量并同时提高辛烷值的助剂及其制备方法,该助剂由5~65重量%的ZSM-5分子筛、15~60重量%载体和10~40重量%粘结剂组成,其中ZSM-5分子筛为氢型,且是经改性元素磷、锌和至少一种稀土元素改性的;助剂的制备是先将氢型ZSM-5分子筛用Zn和稀土元素改性,将改性后的ZSM-5分子筛和载体加入到磷酸铝溶胶粘结剂中混合打浆并均质,后经过滤、喷雾干燥、焙烧制得。

Description

一种催化裂化助剂及其制备方法

本发明属于石油炼制领域,涉及到催化裂化工艺中所用助剂,尤其是催化裂化工艺中所用的降低催化裂化汽油烯烃含量的助剂及其制备方法。

汽油辛烷值是衡量车用汽油的一项重要指标。为了追求较高的汽油辛烷值,炼油厂的催化裂化装置现在一般都采用高温短接触的操作条件和超稳分子筛催化剂,这种技术在提高汽油辛烷值的同时导致了催化汽油烯烃的提高。汽油中的烯烃是造成汽车尾气排放污染物高的主要原因。为了保护环境必须要降低汽油中烯烃含量。因此,降低催化裂化汽油烯烃含量与同时提高辛烷值成为亟待解决的问题。

采用具有高硅分子筛ZSM-5的催化裂化催化剂提高汽油辛烷值,已有大量专利报导。根据专利介绍,ZSM-5分子筛可以作为活性组分之一加入到催化裂化催化剂中,也可以把ZSM-5分子筛作为单一的活性组分制备成添加催化剂,加入到催化裂化装置中与常规催化裂化催化剂混合使用。  ZSM-5分子筛的加入量,少的仅占催化剂总量的0.01~1重量%,多的可占催化剂总量的5~10重量%或更多,如USP4,929,337采用了Ga改性的ZSM-5分子筛,作为芳构化的活性组分;择形裂化/芳构化组分使烷烃和烯烃裂化/芳构化,择形芳构化组分把烷烃和烯烃转化成芳烃。但是,这些催化剂主要用作催化裂化的催化剂,可以提高汽油辛烷值,对汽油中的烯烃含量没有降低效果。USP4,867,863介绍了一种重油催化裂化提高汽油辛烷值的方法,所用催化剂含0.5~5%的HZSM-5分子筛,采用这种催化剂可以提高汽油的辛烷值,但是汽油烯烃含量降低效果没有说明。

本发明的目的是提供一种既能降低汽油烯烃含量,又能提高汽油辛烷值,还可增加低碳烯烃产率的助剂。另外本发明还提供了这种助剂的制备方法。

本发明中,降低催化裂化汽油烯烃含量并同时提高辛烷值助剂是由ZSM-5分子筛、载体和粘结剂组成的,其中所述ZSM-5分子筛为氢型,且是经改性元素改性的ZSM-5分子筛,其在助剂中含量是5~65重量%,最好是20~50重量%;所述载体是SiO2、Al2O3、Zr2O3、P2O5、白土、硅藻土或海泡石等,或是它们的混合物,含量为15~60重量%;所述粘结剂可以是铝溶胶、硅铝溶胶、磷酸铝溶胶或它们的混合物,含量是10~40重量%。其中所述ZSM-5分子筛所用改性元素是磷、锌和至少一种稀土元素,在ZSM-5分子筛中的含量为0.01~10.0重量%,最佳含量为0.1~5.0重量%。

本发明中,推荐助剂的制备方法是先将氢型ZSM-5分子筛用Zn和稀土元素改性,将改性后的ZSM-5分子筛和载体加入到磷酸铝溶胶粘结剂中,混合打浆并均质,控制PH值为2.5~4.8,经过滤、喷雾干燥、洗涤、干燥制得的。

本发明所述粘结剂铝溶胶也可以采用金属铝溶解于盐酸而制得;或者是采用拟薄水铝石,加热溶解于盐酸或硝酸溶液制备得到。

在分子筛中引入新元素的方法很多,例如,离子交换法,浸渍法和如在CN 1057408A中介绍的高温处理法等。采用不同的方法,新引入的元素离子在分子筛中所处的位置不同,因此其作用也不同。本发明改性分子筛是用浸渍法制备的。浸渍法简单易行,浸渍过的分子筛或催化剂,经干燥、焙烧后,改性元素就沉积并结合在分子筛上,起到调节分子筛酸性的作用。本发明中,分子筛改性的典型方法是用改性元素的水溶液浸渍HZSM-5分子筛,浸渍过的分子筛经干燥和焙烧后而得,其水溶液的浓度以所需改性元素的含量确定。

本发明所用的ZSM-5分子筛,为市售的ZSM-5分子筛,其SiO2/Al2O3比为20~500,最好为30~200,约束指数为1~2。

以ZSM-5为代表的Z SM系列分子筛是一种高硅、具有三维交叉直通道结构的新型分子筛,它具有亲油、疏水、热稳定性高等特点。其绝大多数孔径为5.5左右,它的催化活性依赖于表面酸性,这些酸中心绝大部分位于分子筛的孔腔内。由于特殊的孔道结构和酸中心的共同作用,使其具有特殊的择形催化作用。对酸催化反应来说,不同的反应要求不同的酸中心强度并且酸中心的强度对反应选择性有直接影响。为了促进理想反应,必须适当调整分子筛酸中心的数量、强度和分布。所谓分子筛改性就是达到上述目的的有效方法,本发明采用在分子筛中引入新元素来达到改性目的的。

本发明之催化裂化助剂适用于催化裂化工艺,包括馏分油催化裂化和常压渣油或掺炼减压渣油的重油催化裂化。

在常规催化裂化的反应条件下,向催化裂化装置中加入少量本发明所提供的助剂,即可以促进催化汽油中烯烃的裂化反应、氢转移反应、芳构化反应以及烃类的异构化反应,因而本发明与现有技术相比,不仅可降低催化汽油中的烯烃含量,而且可以提高汽油辛烷值,并可适量增加低碳烯烃的产率。

经工业实验证明,在常规催化裂化条件下,加入本发明助剂占催化裂化催化剂总重量的1-15重量%,可以降低催化裂化汽油烯烃含量3-25个百分点,研究法辛烷值提高0.5-3个单位,丙烯产率提高1-4个百分点。

实施例1取硅铝比为60的市售HZSM-5分子筛1500克,分别用0.15M的Zn(NO3)2溶液4000ml和0.6M的混合稀土元素(铈、镧和铷)的硝酸盐溶液1300ml中进行浸渍。即依次在40℃下,快速搅拌打浆2小时,然后过滤浆液,110℃下干燥2小时,粉碎后再浸渍。经干燥、粉碎后,备用。简称F改性分子筛,即FMZSM-5,其中含Zn2.6%,混合稀土7.28%。

实施例2取硅铝比为60的市售HZSM-5分子筛1500克,分别用0.1M的Zn(NO3)2溶液4000ml和0.6M的混合稀土元素(铈、镧和铷)的硝酸盐溶液1000ml中进行浸渍。即依次在40℃下,快速搅拌打浆2小时,然后过滤浆液,110℃下干燥2小时,粉碎后再浸渍。经干燥、粉碎后,备用。简称G改性分子筛,即GMZSM-5,改性分子筛中含Zn1.73%,混合稀土5.6%。

实施例3取硅铝比为3 5的市售HZSM-5分子筛1500克,分别用0.55M的Zn(NO3)2溶液4000ml和0.1M的混合稀土元素(铈、镧和铷)的硝酸盐溶液500ml进行浸渍。即依次在40℃下,快速搅拌打浆2小时,然后过滤浆液,110℃下干燥2小时,粉碎后再浸渍。经干燥、粉碎后,备用。简称H改性分子筛,即HMZSM-5,改性分子筛中含Zn9.53%,混合稀土0.47%。

实施例4取硅铝比为50的市售HZSM-5分子筛1500克,分别用0.01M的Zn(NO3)2溶液4000ml和0.1M的混合稀土元素(铈、镧和铷)的硝酸盐溶液50ml进行浸渍。即依次在40℃下,快速搅拌打浆2小时,然后过滤浆液,110℃下干燥2小时,粉碎后再浸渍。经干燥、粉碎后,备用。简称I改性分子筛,即IMZSM-5,改性分子筛中含Zn0.173%,混合稀土0.05%。

实施例5取硅铝比为120的市售HZSM-5分子筛1500克,分别用0.01M的Zn(NO3)2溶液4000ml和0.1M的混合稀土元素(铈、镧和铷)的硝酸盐溶液200ml进行浸渍。即依次在40℃下,快速搅拌打浆2小时,然后过滤浆液,110℃下干燥2小时,粉碎后再浸渍。经干燥、粉碎后,备用。简称J改性分子筛,即JMZSM-5,改性分子筛中含Zn0.173%,混合稀土0.19%。

实施例6取硅铝比为60的市售HZSM-5分子筛1500克,分别用0.15M的Zn(NO3)2溶液4000ml和0.6M的Ce2(SO4)3溶液1300ml中进行浸渍。即依次在40℃下,快速搅拌打浆2小时,然后过滤浆液,110℃下干燥2小时,粉碎后再浸渍。经干燥、粉碎后,备用。简称K改性分子筛,即KMZSM-5,其中含Zn2.6%,Ce7.2%。

实施例7取硅铝比为60的市售HZSM-5分子筛1500克,分别用0.1M的Zn(NO3)2溶液4000ml和0.6M的Ce2(SO4)3溶液1000ml中进行浸渍。即依次在40℃下,快速搅拌打浆2小时,然后过滤浆液,110℃下干燥2小时,粉碎后再浸渍。经干燥、粉碎后,备用。简称L改性分子筛,即LMZSM-5,改性分子筛中含Zn1.73%,Ce5.5%。

实施例8取硅铝比为35的市售HZSM-5分子筛1500克,分别用0.55MZn(NO3)2溶液4000ml和0.1M Ce2(SO4)3溶液500ml进行浸渍。即在40℃下,快速搅拌打浆2小时,过滤浆液,110℃下干燥2小时,粉碎后再浸渍。经干燥、粉碎后,备用。简称M改性分子筛,即MMZSM-5,改性分子筛中含Zn9.53%,Ce0.47%。

实施例9取硅铝比为50的市售HZSM-5分子筛1500克,分别用0.01MZn(NO3)2溶液4000ml和0.1M Ce2(SO4)3溶液50ml进行浸渍。即在40℃下,快速搅拌打浆2小时,然后过滤浆液,110℃下干燥2小时,粉碎后再浸渍。经干燥、粉碎后,备用。简称N改性分子筛,即NMZSM-5,改性分子筛中含Zn0.173%,Ce0.05%。

实施例10取硅铝比为120的市售HZSM-5分子筛1500克,分别用0.01MZn(NO3)2溶液4000ml和0.1M Ce2(SO4)3溶液200ml进行浸渍。即在40℃下,快速搅拌打浆2小时,过滤浆液,110℃下干燥2小时,粉碎后再浸渍。经干燥、粉碎后,备用。简称P改性分子筛,即PMZSM-5,改性分子筛中含ZnO.173%,Ce0.18%。

实施例11量取蒸馏水1000ml,量取浓硝酸90ml,加入1500ml圆底烧瓶中,搅拌5分钟。称取拟薄水铝石200克,逐步将其加入烧瓶中,并控制温度在80-95℃,搅拌30分钟。将制备好的浆液,倒入均质器中,加入860毫升含白土25%的白土浆液,加入85克磷酸二氢铝溶胶(P2O5含量为35%),混合搅拌5分钟。把380克PMZSM-5分子筛混合,打浆并均质后,搅拌均匀,控制PH值为2.5~4.8,经过滤、喷雾干燥、洗涤、干燥即得助剂,为b。按干基计算,含49.3重量%PMZSM-5,含P2O53.9重量%。

实施例12将980毫升铝溶胶溶液(PH值为3.0含Al2O321%),加入1860毫升含白土25%的白土浆液,加入105克磷酸二氢铝溶胶(PH值为1,P2O5含量为35%),混合搅拌30分钟。把463.1克IMZSM-5分子筛混合,打浆并均质后,搅拌均匀,控制PH值为2.5~4.8,经过滤、喷雾干燥、洗涤、干燥即得助剂,为c。按干基计算,含39.6重量%IMZSM-5,含P2O5为3.1重量%。

实施例13量取蒸馏水1000ml,量取浓硝酸90ml,加入1500ml圆底烧瓶中,搅拌5分钟。称取拟薄水铝石200克,逐步将其加入烧瓶中,并控制温度在80-95℃,搅拌30分钟。将制备好的浆液,倒入均质器中,加入860毫升含白土25%的白土浆液,加入85克磷酸氢铝溶胶(P2O5含量为35%),混合搅拌5分钟。把105克FMZSM-5分子筛混合,打浆并均质后,搅拌均匀,控制PH值为2.5~4.8,经过滤、喷雾干燥、洗涤、干燥即得助剂,为e。按干基计算,含21.2重量%FMZSM-5,含P2O56重量%。

实施例14量取蒸馏水100ml,量取浓硝酸90ml,加入1500ml圆底烧瓶中,搅拌5分钟。称取拟薄水铝石200克,逐步将其加入烧瓶中,并控制温度在80-95℃,搅拌30分钟。将制备好的浆液,倒入均质器中,加入860毫升含白土25%的白土浆液,加入58克磷酸氢铝溶胶(P2O5含量为35%),混合搅拌5分钟。把56克LMZSM-5分子筛混合,打浆并均质后,搅拌均匀,控制PH值为2.5~4.8,经过滤、喷雾干燥、洗涤、干燥即得助剂,为f。按干基计算,含12.8重量%LMZSM-5,含P2O54.6重量%。

实施例15采用各种不同的改性分子筛和不同分子筛含量制备一系列助剂,用小型提升管催化裂化试验装置进行实验,取得良好的降烯烃效果。小型提升管试验中所采用基本条件如下:原料油      管输蜡油+15%减渣    催化剂活性    61.1催化剂      镇海平衡剂           剂油比        6.5~6.7现将部分典型的提升管实验结果列出:表中空白是指不加入助剂的情况,5%b、5%c、5%e、5%f分别指加入占催化剂总量为5%的上述实施例中制备的b、c、e、f型助剂。

小型提升管试验产品分布表催化剂         空白     5%b     5%c     5%e     5%f改性ZSM-5分子筛含量    0        49.3     39.6     21.2     12.8产品分布,m%裂化气                 17.26    23.98    22.32    19.63    18.1干气                   1.61     2.1      1.86     1.81     1.72液化气                 15.65    21.88    20.46    17.82    16.38C3H66.08     9.01     8.8      7.4      7.39C3H80.6      1.03     0.9      0.69     0.62C4H101.97     3.87     3.41     2.1      1.73C4H86.98     7.97     7.35     7.63     6.64汽油                   35.01    33.13    33.41    34.66    34.81柴油                   22.2     19.22    19.87    20.22    21.52重油                   20.11    18.08    18.47    19.87    19.98焦炭                   4.52     4.89     4.8      4.61     4.58损失                   0.9      0.7      1.13     1.01     1.01总计                   100      100      100      100      100转化率,%             57.69    62.7     61.66    59.91    58.5轻油收率,%           57.21    52.35    53.28    54.88    56.33汽油族组成,v%烷烃              26.6     28.2     29.8     29.9     29.2烯烃              47.7     26.4     28.5     38.7     42.6芳烃              25.7     45.4     41.7     31.4     28.2汽油辛烷值RON          89.4     93.6     91.8     91       89.5

Claims (4)

1.一种催化裂化助剂,其特征在于该助剂由5~65重量%ZSM-5分子筛、15~60重量%载体和10~40重量%粘结剂组成的,其中所述ZSM-5分子筛为氢型,且是经改性元素改性的分子筛;所述载体为SiO2、Al2O3、Zr2O3、P2O5、白土、硅藻土或海泡石,或是它们的混合物;所述粘结剂是铝溶胶、硅铝溶胶、磷酸铝溶胶或它们的混合物;所述ZSM-5分子筛所用的改性元素是磷、锌和至少一种稀土元素,在ZSM-5中的含量为0.01~10.0重量%。
2.根据权利要求1所述的助剂,其特征在于所述的ZSM-5分子筛在助剂中的含量是20~50重量%。
3.根据权利要求1所述的助剂,其特征在于所述的改性元素在ZSM-5中的含量为0.1~5.0重量%。
4.一种制备如权利要求1所述助剂的方法,其特征在于:该方法是先将氢型ZSM-5分子筛用Zn和稀土元素改性,将改性后的ZSM-5分子筛和载体加入到磷酸铝溶胶粘结剂中,混合打浆并均质,控制PH值为2.5~4.8,经过滤、喷雾干燥、洗涤、干燥制得。
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