CN103447063B - 重油高效转化催化裂化催化剂及其制备方法 - Google Patents
重油高效转化催化裂化催化剂及其制备方法 Download PDFInfo
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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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- 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
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Abstract
本发明涉及一种重油催化裂化催化剂及制备方法,催化剂中含2~50重量%的含磷超稳稀土Y型分子筛,0.5~30重量%的一种或几种其它分子筛、0.5~70重量%的粘土、1.0~65重量%的耐高温无机氧化物和0.01~12.5%重量的氧化稀土。含磷超稳稀土Y型分子筛是以NaY分子筛为原料,经过稀土交换、分散预交换后,分子筛浆液再经过滤、水洗和第一次焙烧,获得“一交一焙”稀土钠Y分子筛,其中稀土交换、分散预交换的先后次序不限;然后经“二交二焙”获得,该制备过程包含了铵盐交换、磷改性,其中铵盐交换、磷改性的先后次序不限,铵盐交换、磷改性过程是连续进行或不连续进行的,第二次焙烧是在铵盐交换降钠后进行的,磷改性既可以在第二次焙烧前进行,也可在第二次焙烧后进行。本发明提供催化剂具有重油转化能力强、总液收和轻质油收率高的特点。
Description
技术领域
本发明涉及一种高重油转化能力的重油催化裂化催化剂及其制备方法,更具体地,是一种适用于掺炼渣油催化裂化催化剂及其制备方法。
背景技术
催化裂化装置作为原油重要的二次加工手段,其综合产品分布决定着炼厂的经济效益。近年随着原料油重质化、劣质化趋势的加剧,要求FCC催化剂具有更强的重油转化能力和高价值产品选择性。Y型分子筛作为重油裂化催化剂裂化活性的主要提供者,其活性稳定性优劣和裂化活性高低是决定FCC催化剂重油转化能力的关键因素。
因此围绕如何提高Y型分子筛的裂化活性和活性稳定性,国内外相关研究机构进行了大量的研究工作。目前较为一致的观点是在分子筛稀土改性过程中使稀土离子尽可能更多的定位方钠石笼,从而抑制水汽老化过程中分子筛骨架脱铝,提高分子筛骨架结构稳定性和活性稳定性。专利ZL200410058089.3介绍了一种稀土改性Y型分子筛制备方法,该方法是在稀土交换反应结束后采用碱液将体系pH值调至8~11,之后再进行常规后续处理过程,按照该方法制备的分子筛稀土离子全部定位于小笼(方钠石笼);在ZL200410058090.6中介绍了专利ZL200410058089.3中分子筛的反应性能,该专利中催化剂反应结果表明,稀土离子定位于方钠石笼提高了分子筛结构稳定性和活性稳定性,表现在催化剂重油转化能力得到明显改善,但是该催化剂焦炭选择性较差。
中国专利ZL97122039.5中介绍了一种超稳Y沸石的制备方法,该方法包括将一种Y型沸石,与一种酸溶液和一种含铵离子的溶液接触,并进行高温水蒸汽处理,所述酸的用量为每摩尔骨架铝1.5~6摩尔氢离子、酸溶液浓度0.1~5当量/升,Y型沸石与酸溶液接触的温度为5~100℃,接触时间0.5~72小时,Y型沸石与铵离子的重量比为2~20。该专利涉及的改性方法中需加入含铵离子溶液,其目的是降低分子筛中的氧化钠含量或是减少焙烧过程中酸性气体对分子筛结构的破坏,采用该分子筛制备的FCC催化剂具有重油转化能力强、轻质油收率高的特点;但是该分子筛改性技术存在以下技术缺陷:1)制备过程加入大量的铵离子,含铵离子最终进入大气或是污水中,增加氨氮污染和治污成本;2)该专利方法不能有效解决分子筛颗粒团聚问题,颗粒团聚降低了分子筛的比表面和孔体积,增加了分子筛交换过程的孔道阻力,使改性元素难以准确定位、定量于分子筛笼内;3)同时该专利还提及Y型沸石与含铵离子溶液接触的同时或是之后,还可以采用离子交换的方式引入稀土离子,在该交换过程中,铵离子与稀土离子存在竞争反应,铵离子会优先占据稀土离子位置,增加了稀土离子交换进入分子筛笼内的阻力,同时降低了稀土离子的利用率。
中国专利ZL02103909.7中介绍了一种含稀土超稳Y分子筛制备方法,该方法是将NaY分子筛经一次交换一次焙烧后制得,其特征在于将NaY分子筛置于铵离子溶液中,于25~100℃进行化学脱铝处理,化学脱铝络合剂中含有草酸和/或草酸盐,处理时间0.5~5小时,然后加入稀土溶液,搅拌,使生成包含草酸稀土的稀土沉淀物,经过滤、水洗成为滤饼,再进行水热处理,制得分子筛产品。该方法制备的分子筛虽具有一定的抗钒污染能力,但是其活性稳定性和裂化活性较低,不能满足原料油重质化、劣质化的发展趋势。这主要是与分子筛改性过程中的稀土离子在分子筛超笼和方钠石笼的位置分布有关。该方法明确了稀土离子是以两种形态存在于分子筛体系中,即部分稀土以离子形态进入方钠石笼,另一部分稀土离子是以氧化稀土(其前身物为草酸稀土,后续焙烧转化为氧化稀土)独立相分散于分子筛表面,这降低了稀土离子对分子筛结构的稳定支撑作用;同时该方法中也存在大量的氨氮污染问题,所加的草酸和或草酸盐的对环境和人体毒害较大。
CN200410029875.0中公开了一种稀土超稳Y型沸石的制备方法,其特征在于该方法包括用稀土盐和柠檬酸组成的混合溶液或者无机铵盐、稀土盐和柠檬酸组成的混合溶液处理沸石的步骤。该方法可简化工艺,所制备的沸石作为裂化催化剂的活性组元,具有降低催化裂化汽油产物烯烃含量和明显增加催化裂化轻质油产物收率的优点,但是该方法并未对分子筛稀土离子定位进行说明。
发明内容
本发明的目的在于提供一种新型重油高效转化催化裂化催化剂及其制备方法,该催化剂特点是重油转化能力强,焦炭选择性适中,目的产品收率高。
本发明提供一种新型重油高效转化催化裂化催化剂,其特征在于催化剂组成中含有2~50重量%的含磷超稳稀土Y型分子筛、0.5~30重量%的一种或几种其它分子筛、0.5~70重量%的粘土、1.0~65重量%的耐高温无机氧化物和0.01~12.5%重量的氧化稀土,其中含磷超稳稀土Y型分子筛中含氧化稀土1~20重%,氧化钠不大于1.2重%,磷(以P计)0.1~5重%,结晶度51~69%,晶胞参数2.449nm~2.469nm;该含磷超稳稀土Y型分子筛制备过程包含了稀土交换、分散预交换,其中稀土交换、分散预交换的先后次序不限,稀土交换与分散预交换是连续进行,之间没有焙烧过程;分散预交换是指将分子筛浆液浓度调为固含量为80~400g/L,加入0.2重%~7重%的分散剂进行分散预交换,交换温度为0~100℃,交换时间为0.1~1.5小时;分散预交换过程所述分散剂选自田菁粉、硼酸、尿素、乙醇、聚丙烯酰胺、乙酸、草酸、己二酸、甲酸、盐酸、硝酸、柠檬酸、水杨酸、酒石酸、苯甲酸、淀粉中的任意一种或多种;稀土交换、分散预交换中没有使用铵盐。
本发明中,对稀土交换的方法、条件不加以特别限制,可采用通用方法及条件。
本发明还提供了一种该重油催化裂化催化剂的制备方法,主要包含以下步骤:
(1)制备含磷超稳稀土Y型分子筛:以NaY分子筛(最好硅铝比大于4.0,结晶度大于70%)为原料,经过稀土交换、分散预交换后,分子筛浆液再经过滤、水洗和第一次焙烧,获得“一交一焙”稀土钠Y分子筛,其中稀土交换、分散预交换的先后次序不限;再将“一交一焙”稀土钠Y分子筛经过铵盐交换、磷改性和第二次焙烧,从而获得含磷超稳稀土Y型分子筛,其中铵盐交换、磷改性的先后次序不限,铵盐交换、磷改性过程是连续进行或不连续进行的,第二次焙烧是在铵盐交换降钠后进行的,磷改性既可以在第二次焙烧前进行,也可在第二次焙烧后进行。
(2)重油催化裂化催化剂制备:将含磷超稳稀土Y型上述分子筛组分、粘土和耐高温无机氧化物的前驱物及其它原料进行混合均质,进行喷雾成型、焙烧和水洗,获得催化剂成品。
该发明中所述的重油催化裂化催化剂制备过程的步骤(1)中,即获得含磷超稳稀土Y型分子筛时,NaY分子筛稀土交换和分散预交换之间,分子筛浆液可以不经洗涤、过滤,也可以进行洗涤、过滤。稀土交换时,其RE2O3/Y沸石(质量)最好为0.005~0.25,最佳是0.01~0.20;交换温度为0~100℃,最佳为60~95℃;交换pH值为2.5~6.0,最佳是3.5~5.5,交换时间为0.1~2小时,最佳为0.3~1.5小时;分散预交换时,分散剂加入量为0.2重量%~7重量%,最佳为0.2重量%~5重量%;交换温度为0~100℃,最佳为60~95℃;交换时间为0.1~1.5小时。改性后的分子筛浆液经过滤、水洗获得滤饼,将所得滤饼闪蒸干燥使其水分含量在30%~50%,最后焙烧,第一次焙烧条件可使用通用条件,如在350℃~700℃、0~100%水汽焙烧0.3~3.5小时,最好是在450℃~650℃、15~100%水汽焙烧0.5~2.5小时,即得“一交一焙”超稳稀土钠Y分子筛。
本发明的分子筛的制备过程还包含了铵盐交换、磷改性,其中铵盐交换、磷改性的先后次序不限,铵盐交换、磷改性过程是连续进行或不连续进行的,之间有或没有焙烧过程。本发明中稀土交换、铵盐交换、磷改性、焙烧(第一次焙烧、第二次焙烧)均可采用行业内所熟悉的交换改性、超稳化过程所用的条件,本发明不特别限制。
磷改性的条件最好是:将分子筛浆液浓度调为固含量为80~400g/L,加入0.1重%~5重%(以单质P计)的含磷化合物进行交换,交换温度为0~100℃,交换时间为0.1~1.5小时;交换过程所述含磷化合物选自磷酸、亚磷酸、磷酸酐、磷酸氢二铵、磷酸二氢铵、磷酸铵、亚磷酸铵、亚磷酸二氢铵、磷酸铝中的任意一种或多种。
本发明中制备含磷超稳稀土Y型分子筛的过程中,在“一交一焙”超稳稀土钠Y分子筛得到后,还要进行铵盐交换、磷改性,铵盐交换,其条件可以采取通用的常规做法,推荐的方法是:将“一交一焙”超稳稀土钠Y分子筛加入去离子水,固含量调配为100~400g/L,NH4+/Y沸石(质量)为0.02~0.40,最好为0.02~0.30,pH值为2.5~5.0,最好为3.0~4.5,在60℃~95℃下反应0.3~1.5小时;磷改性中含磷化合物的加入量为0.1~5重%(以单质P计),最佳为0.2重%~4重%(以单质P计),交换温度为0~100℃,最佳为20~80℃,交换时间为0.1~1.5小时。反应完成后,将分子筛浆液过滤、水洗,将所得滤饼在450℃~700℃、0~100%水汽焙烧0.3~3.5小时,最好是0.5~2.5小时,最终获得本发明提供的高活性含磷超稳稀土Y型分子筛。
本发明中所述的超稳稀土Y型分子筛“一交一焙”过程中,稀土交换和分散预交换的交换过程可以采用罐式交换、带式交换和/或滤饼交换;在进行稀土交换时,可以按以下方式进行,即在稀土总量不变的前提下,可以将稀土化合物溶液分为若干份,进行罐式交换、带式交换和/或滤饼交换,即多次交换。同样,在分散预交换过程时,可以在分散剂总量不变的前提下,可以将分散剂分为若干份,进行罐式交换、带式交换和/或滤饼交换;稀土交换和分散预交换为多次交换时,两类交换可交叉进行。
本发明所述的稀土化合物为氯化稀土或硝酸稀土或硫酸稀土,最好是氯化稀土或硝酸稀土。
本发明所述的稀土可以是富镧或富铈稀土,也可以是纯镧或纯铈。
本发明所述的分散预交换过程中所述分散剂选自田菁粉、硼酸、尿素、乙醇、聚丙烯酰胺、乙酸、草酸、已二酸、甲酸、盐酸、硝酸、柠檬酸、水杨酸、酒石酸、苯甲酸、淀粉中的一种或一种以上,最好是两种或两种以上。
本发明所述的催化剂组成中的其它分子筛为一种或一种以上选自Y型沸石、L沸石、ZSM-5沸石、β沸石、磷酸铝沸石、Ω沸石,优选Y型沸石、ZSM-5沸石、β沸石,或经过常规物理或化学改性的上述沸石,包括HY、USY、REY、REHY、REUSY、H-ZSM-5、Hβ。
本发明所述的粘土为一种或一种以上选自高岭土、埃洛石、蒙脱土、海泡石、珍珠岩等;所说的耐高温无机氧化物为一种或一种以上选自Al2O3、SiO2、SiO2-Al2O3、AlPO4,其前驱物可选自硅铝凝胶、硅溶胶、铝溶胶、硅铝复合溶胶、拟薄水铝石中的一种或多种。
本发明所述的喷雾条件为常规的制备裂化催化剂的操作条件,本发明不做任何限制;后处理过程与现有技术相同,包含催化剂焙烧、水洗、干燥等,其中焙烧最好是喷雾微球样品在200℃~700℃下焙烧,优选300℃~650℃,时间0.05~4小时,优选0.1~3.5小时;水洗条件最好为:水/催化剂重量为0.5~35,水洗温度为20℃~100℃,时间为0.1~0.3小时。
本发明所述的新型重油催化剂的主活性组分之一是高裂化活性稳定含磷性稀土超稳Y型分子筛,该分子筛在稀土改性制备过程中采用分散剂将NaY分子筛进行预分散,降低了分子筛颗粒间的团聚度,使分子筛表面更多的与稀土离子接触,降低了稀土离子在交换过程的阻力,使稀土离子更多的交换进入分子筛笼内,并在后续水汽焙烧过程中迁移至方钠石笼,提高了分子筛的结构稳定性和活性稳定性。稀土离子定位于方钠石笼,超笼和分子筛表面没有稀土离子,降低了该位置的酸性强度和密度,减少了该活性位的生焦机率,较好地解决了催化剂的重油转化能力和焦炭选择性的矛盾。
具体实施方式
下面的实施例对本发明的特点做进一步说明,但这些实施例并不能限定本发明。
(一)实例中所用的分析及评价方法。
1.晶胞常数(a0):X-光衍射法。
2.结晶度(C/C0):X-光衍射法。
3.硅铝比:X-光衍射法。
4.Na2O含量:火焰光度法。
5.RE2O3含量:比色法。
6.P含量:分光光度法。
7.微反活性:样品预先在800℃、100%水蒸气条件下处理4小时。反应原料为大港轻柴油,反应温度460℃,反应时间70秒,催化剂装量5.0克,剂油重量比3.2,以总转化率作为微反活性。
8.ACE重油微型反应器:反应温度530℃,剂油比为5,原料油为新疆油掺炼30%的减压渣油。
(二)实例中所用原料规格
1.NaY分子筛:NaY-1(硅铝比4.8,结晶度92%),NaY-2(硅铝比4.1,结晶度83%),兰州石化公司催化剂厂生产。
2.超稳一交一焙分子筛样品:结晶度60%,氧化钠4.3m%,兰州石化公司催化剂厂生产。
3.稀土溶液:氯化稀土(氧化稀土277.5克/升),硝酸稀土(氧化稀土252克/升),均为工业品,采自兰州石化公司催化剂厂。
4.田菁粉、硼酸、尿素、乙醇、聚丙烯酰胺、草酸、已二酸、乙酸、甲酸、盐酸、硝酸、柠檬酸、水杨酸、酒石酸、淀粉均为化学纯;氯化铵、硝酸铵、硫酸铵、草酸铵,磷酸、亚磷酸、磷酸酐、磷酸氢二铵、磷酸二氢铵、磷酸铵、亚磷酸铵、亚磷酸二氢铵、磷酸铝均为工业品。
5.拟薄水铝石(灼减36.2%)、高岭土(灼减16.4%)、埃洛石(灼减21.4%)、蒙脱土(灼减15.8%)、珍珠岩(灼减17.6%),固体;铝溶胶,含氧化铝23.0重%;硅溶胶,含氧化硅24.5重%,均为工业合格品。
6.REY、REHY、USY、REUSY分子筛,均为合格工业品,兰州石化公司催化剂厂生产;β沸石,工业合格品,抚顺石化公司生产;H-ZSM-5,工业合格品,上海复旦大学生产。
实施例1
在带有加热套的反应釜中,依次加入3000gNaY-1分子筛(干基)和一定量的去离子水,调配成固含量为220g/L的浆液,加入82g硼酸和105克田菁粉,然后升温至85℃,在搅拌下交换反应0.5小时,之后过滤、洗涤,将所得滤饼放置反应釜中,之后再加入1.67升的氯化稀土,调节体系pH=4.0,升温至80℃,交换反应0.3小时,将所得滤饼闪蒸干燥使其水分含量在30%~50%,最后在70%水汽和670℃下焙烧1.0小时,制得“一交一焙”稀土钠Y。在带有加热套的反应釜中,加入“一交一焙”超稳稀土钠Y分子筛500克(干基)和一定量的去离子水,制成固含量为120g/L的浆液,加入120g硫酸铵,调节体系pH=4.2,升温到90℃,交换0.8小时,然后过滤、洗涤,将滤饼打浆后加入磷酸氢二铵115g,混合均匀后在80%水汽和560℃下焙烧2.5小时,制得本发明所述的含磷稀土超稳Y分子筛活性组分,记做改性分子筛A-1。
在带有水浴加热的反应釜中,加入4.381升水、1062克高岭土、986克氧化铝以及63.5毫升盐酸混合均匀,搅拌1小时,然后依次加入448克改性分子筛A-1、63克H-ZSM-5、755克REUSY,混合均匀后缓慢加入1500克铝溶胶进行成胶,经过喷雾成型,将所得微球在400℃焙烧0.5小时。取焙烧微球2千克,加入15千克去离子水在60℃洗涤15分钟,过滤干燥即得本发明制备的裂化催化剂,记做A。
实施例2
在带有加热套的反应釜中,依次加入3000gNaY-1分子筛(干基)和一定量的去离子水,调配成固含量为360g/L的浆液,加入0.82升的硝酸稀土,调节体系pH=3.3,升温至80℃,交换反应1.5小时,之后过滤、洗涤,将所得滤饼放置反应釜中,再加入202g聚丙烯酰胺和30g的水杨酸,然后升温至78℃进行分散交换,在搅拌下交换反应0.5小时,将所得滤饼闪蒸干燥使其水分含量在30%~50%,最后在30%水汽和630℃下焙烧1.8小时,制得“一交一焙”稀土钠Y。在带有加热套的反应釜中,加入“一交一焙”超稳稀土钠Y分子筛500克(干基)和去离子水,制成固含量为370g/L的浆液,加入200g硫酸铵,调节体系pH=3.6,升温到90℃,交换1.2小时,后加入磷酸氢二铵64g,调节体系pH=3.6,升温到90℃,交换1.2小时,然后过滤、洗涤,滤饼在20%水汽和600℃下焙烧0.5小时,然后过滤、洗涤,滤饼在20%水汽和600℃下焙烧0.5小时,制得本发明所述的含磷稀土超稳Y分子筛活性组分,记做改性分子筛B-1。
在带有水浴加热的反应釜中,加入4.620升水、1024克高岭土、971克拟薄水铝石以及90.8毫升盐酸混合均匀,搅拌1小时,然后依次加入338克改性分子筛B-1、129克β沸石、806克REHY,混合均匀后缓慢加入1304克铝溶胶进行成胶,经过喷雾成型,将所得微球在400℃焙烧1.0小时。取焙烧微球2千克,加入20千克去离子水搅拌均匀,在35℃洗涤40分钟,过滤干燥即得本发明制备的裂化催化剂,记做B。
实施例3
在带有加热套的反应釜中,依次加入3000gNaY-1分子筛(干基)和去离子水,调配成固含量为150g/L的浆液,加入43g盐酸,在85℃下反应1小时,之后再加入1.68升的氯化稀土,调节体系pH=3.7,升温至90℃,交换反应1小时,之后再将分子筛浆液过滤,进行分散剂带式交换,带式交换条件为:将35g草酸配置为pH值=3.4的溶液,并升温至85℃,带式滤机真空度为0.04;之后将所得滤饼闪蒸干燥使其水分含量在30%~50%,最后在10%水汽和510℃下焙烧2.0小时,制得“一交一焙”超稳稀土钠Y。在带有加热套的反应釜中,加入“一交一焙”超稳稀土钠Y分子筛500克(干基)和去离子水,制成固含量为145g/L的浆液,加入80g硫酸铵,调节体系pH=3.5,升温到90℃,交换1.2小时,然后过滤、洗涤,滤饼在50%水汽和650℃下焙烧2小时,然后重新打浆加入磷酸二氢铵110g混合均匀,交换1小时后过滤、洗涤、烘干,制得本发明所述的含磷稀土超稳Y分子筛活性组分,记做改性分子筛C-1。
在带有水浴加热的反应釜中,加入4.854升水、1125克埃洛石、825克拟薄水铝石以及51.4毫升盐酸混合均匀,搅拌1小时,然后依次加入406克改性分子筛C-1和903克USY,混合均匀后缓慢加入1224克硅溶胶进行成胶,经过喷雾成型,将所得微球在600℃焙烧0.3小时。取焙烧微球2千克,加入15千克去离子水,在80℃洗涤30分钟,过滤干燥即得本发明制备的裂化催化剂,记做C。
实施例4
在带有加热套的反应釜中,依次加入3000gNaY-1分子筛(干基)和一定量的去离子水,调配成固含量为320g/L的浆液,加入30g硝酸,然后升温至85℃,在搅拌下交换反应0.8小时,之后再加入0.95升的硝酸稀土,调节体系pH=3.3,升温至80℃,交换反应1.8小时,最后加入62g淀粉在80℃下反应0.5小时,反应之后过滤、洗涤,将所得滤饼闪蒸干燥使其水分含量在30%~50%,最后在60%水汽和560℃下焙烧2小时,制得“一交一焙”稀土钠Y。在带有加热套的反应釜中,加入“一交一焙”超稳稀土钠Y分子筛500克(干基)和去离子水,制成固含量为280g/L的浆液,加入130g硫酸铵,调节体系pH=4.0,升温到90℃,交换0.5小时,然后过滤、洗涤,后加入磷酸氢二铵55g,反应2小时,然后过滤、洗涤,滤饼在50%水汽和650℃下焙烧2小时,制得本发明所述的含磷稀土超稳Y分子筛活性组分,记做改性分子筛D-1。
在带有水浴加热的反应釜中,加入4.577升水、1055克高岭土、983克氧化铝以及63.5毫升盐酸混合均匀,搅拌1小时,然后依次加入892克改性分子筛D-1、63克ZSM-5沸石、118克USY以及188克REY,混合均匀后缓慢加入1500克铝溶胶进行成胶,经过喷雾成型,将所得微球在400℃焙烧0.5小时。取焙烧微球2千克,加入10千克去离子水,在40℃洗涤20分钟,过滤干燥即得本发明制备的裂化催化剂,记做D。
实施例5
在带有加热套的反应釜中,依次加入3000gNaY-1分子筛(干基)和一定量的去离子水,调配成固含量为350g/L的浆液,加入42g柠檬酸和28g田菁粉,然后升温至82℃,在搅拌下交换反应1.3小时,反应结束后加入0.56升硝酸稀土,在85℃下交换反应0.8小时,之后将分子筛浆液过滤,进行带式交换,带式交换条件为:将硝酸稀土溶液升温至88℃,交换pH值为4.7,硝酸稀土加入量为RE2O3/Y沸石(质量)为0.04,带式滤机真空度为0.03;之后将所得滤饼闪蒸干燥使其水分含量在30%~50%,最后在80%水汽和530℃下焙烧1.5小时,制得“一交一焙”超稳稀土钠Y“一交一焙”超稳稀土钠Y。在带有加热套的反应釜中,加入“一交一焙”超稳稀土钠Y分子筛500克(干基)和去离子水,制成固含量为150g/L的浆液,加入100g硫酸铵,调节体系pH=4.0,升温到90℃,交换1小时,然后过滤、洗涤,滤饼在60%水汽和620℃下焙烧2小时,之后将滤饼重新打浆,加磷酸氢二铵55g,混合均匀,在温度为90℃反应1.5小时后,在100%水汽和620℃下焙烧2小时,制得本发明所述的含磷稀土超稳Y分子筛活性组分,记做改性分子筛E-1。
在带有水浴加热的反应釜中,加入6.5升水、995克高岭土、676克氧化铝以及130毫升盐酸混合均匀,搅拌1小时,然后依次加入558克改性分子筛E-1、19克H-ZSM-5、830克REUSY,混合均匀后缓慢加入1359克铝溶胶进行成胶,经过喷雾成型,将所得微球在500℃焙烧0.6小时。取焙烧微球2千克,加入19千克去离子水,在80℃洗涤10分钟,过滤干燥即得本发明制备的裂化催化剂,记做E。
对比例1
制备REUSY分子筛的方法与实施例3所示方法相似,仅是不加入盐酸和草酸,其他与实施例3相同,所得超稳稀土Y型分子筛编号为F-1,所得催化剂编号为F。
对比例2
本对比例使用CN200510114495.1所述的分子筛制备方法,考察该分子筛反应性能,催化剂制备工艺同实施例5。
取3000g(干基)由兰州石化公司催化剂厂水热法生产的超稳一交一焙分子筛样品(Na2O含量1.4重量%、RE2O3含量8.6重量%、晶胞2.468nm,相对结晶度62%),加入到3升2N草酸水溶液中搅拌使其混合均匀,升温至90~100℃反应1小时后,过滤水洗,将所得滤饼至于6升去离子水中,并加入1.46升的硝酸稀土溶液,升温至90~95℃下反应1小时,然后过滤水洗,滤饼于120℃下烘干,即得该对比例分子筛样品,记为H-1。
在带有水浴加热的反应釜中,加入6.5升水、995克高岭土、676克氧化铝以及130毫升盐酸混合均匀,搅拌1小时,然后依次加入558克改性分子筛H-1、19克H-ZSM-5、830克REUSY,混合均匀后缓慢加入1359克铝溶胶进行成胶,经过喷雾成型,将所得微球在500℃焙烧0.6小时。取焙烧微球2千克,加入19千克去离子水,在80℃洗涤10分钟,过滤干燥即得对比例的裂化催化剂,记做H。
对比例3
制备REUSY分子筛的方法与实施例5所示方法相似,仅是不加入柠檬酸和田菁粉,其他与实施例5相同,所得超稳稀土Y型分子筛编号为G-1,所得催化剂编号为G。
将本发明实施例及对比例所得超稳稀土Y型分子筛理化性质列于表1。分析结果表明:与对比例相比,新型分子筛具有结构稳定性好、颗粒粒度小的特点。
表1分子筛理化性质分析
实施例1~5和对比例制备的催化剂反应性能评价结果列于表2中。
表2ACE重油微反评价结果
从ACE重油微反评价结果可知,与对比催化剂相比,采用本发明方法制备的催化剂具有优异的重油转化能力和焦炭选择性,总液收和轻质油收率明显高于对比催化剂。表4是催化剂B提升管评价结果,与对比催化剂G相比,本发明催化剂总液收提高0.97个百分点,轻质油收率增加0.77个百分点,汽油性质相当。
表4催化剂提升管评价结果
Claims (25)
1.一种重油催化裂化催化剂,其特征在于催化剂组成中含有2~50重量%的含磷超稳稀土Y型分子筛、0.5~30重量%的一种或几种其它分子筛、0.5~70重量%的粘土、1.0~65重量%的耐高温无机氧化物和0.01~12.5%重量的氧化稀土,其中含磷超稳稀土Y型分子筛中含氧化稀土1~20重%,氧化钠不大于1.2重%,以P计,含磷0.1~5重%,结晶度51~69%,晶胞参数2.449nm~2.469nm,该含磷超稳稀土Y型分子筛制备过程包含了以NaY分子筛为原料,进行稀土交换、分散预交换,其中稀土交换、分散预交换的先后次序不限,稀土交换与分散预交换是连续进行,之间没有焙烧过程;分散预交换是指将分子筛浆液浓度调为固含量为80~400g/L,加入0.2重%~7重%的分散剂进行分散预交换,交换温度为0~100℃,交换时间为0.1~1.5小时;分散预交换过程所述分散剂选自田菁粉、硼酸、尿素、乙醇、聚丙烯酰胺、乙酸、草酸、己二酸、甲酸、盐酸、硝酸、柠檬酸、水杨酸、酒石酸、苯甲酸、淀粉中的任意一种或多种;稀土交换、分散预交换中没有使用铵盐。
2.根据权利要求1所述的重油催化裂化催化剂,其特征在于分散预交换时,分散剂加入量为0.2重量%~5重量%;交换温度为60~95℃;交换时间为0.1~1.5小时。
3.根据权利要求1所述的重油催化裂化催化剂,其特征在于其它分子筛选自Y型沸石、L沸石、ZSM-5沸石、β沸石、磷酸铝沸石、Ω沸石,或经过改性的上述沸石中的一种或多种。
4.根据权利要求1所述的重油催化裂化催化剂,其特征在于其它分子筛选自HY、USY、REY、REHY、REUSY、H-ZSM-5中的一种或多种。
5.根据权利要求1所述的重油催化裂化催化剂,其特征在于粘土选自高岭土、埃洛石、蒙脱土、海泡石、珍珠岩中的一种或多种。
6.根据权利要求1所述的重油催化裂化催化剂,其特征在于耐高温无机氧化物选自Al2O3、SiO2、SiO2-Al2O3、AlPO4中的一种或多种。
7.一种权利要求1所述的重油催化裂化催化剂的制备方法,其特征在于该方法主要包含以下步骤:
(1)制备含磷超稳稀土Y型分子筛:以NaY分子筛为原料,经过稀土交换、分散预交换后,分子筛浆液再经过滤、水洗和第一次焙烧,获得“一交一焙”稀土钠Y分子筛,其中稀土交换、分散预交换的先后次序不限;再将“一交一焙”稀土钠Y分子筛经过铵盐交换、磷改性和第二次焙烧,从而获得超稳稀土Y型分子筛,其中铵盐交换、磷改性的先后次序不限,铵盐交换、磷改性过程是连续进行或不连续进行的,第二次焙烧是在铵盐交换降钠后进行的,磷改性既可以在第二次焙烧前进行,也可在第二次焙烧后进行;
(2)重油催化裂化催化剂制备:将含磷超稳稀土Y型上述分子筛组分、粘土和耐高温无机氧化物的前驱物及其它原料进行混合均质,进行喷雾成型、焙烧和水洗,获得催化剂成品。
8.根据权利要求7所述的制备方法,其特征在于稀土交换时,其RE2O3/Y沸石质量比为0.005~0.25;交换温度为0~100℃;交换pH值为2.5~6.0,交换时间为0.1~2小时。
9.根据权利要求8所述的制备方法,其特征在于稀土交换时,其RE2O3/Y沸石质量比为0.01~0.20;交换温度为60~95℃;交换pH值为3.5~5.5,交换时间为0.3~1.5小时。
10.根据权利要求7所述的制备方法,其特征在于磷改性是指将分子筛浆液浓度调为固含量为80~400g/L;以单质P计,加入0.1重%~5重%的含磷化合物进行交换,交换温度为0~100℃,交换时间为0.1~1.5小时。
11.根据权利要求10所述的制备方法,其特征在于含磷化合物选自磷酸、亚磷酸、磷酸酐、磷酸氢二铵、磷酸二氢铵、磷酸铵、亚磷酸铵、亚磷酸二氢铵、磷酸铝中的任意一种或多种。
12.根据权利要求7所述的制备方法,其特征在于稀土交换和分散预交换之间,分子筛浆液可以不经洗涤、过滤,也可以进行洗涤、过滤。
13.根据权利要求7所述的制备方法,其特征在于稀土交换和分散预交换的交换过程采用罐式交换、带式交换和/或滤饼交换。
14.根据权利要求7所述的制备方法,其特征在于在进行稀土交换时,将稀土化合物溶液分为若干份,进行罐式交换、带式交换和/或滤饼交换,即多次交换。
15.根据权利要求7所述的制备方法,其特征在于在分散预交换过程时,将分散剂分为若干份,进行罐式交换、带式交换和/或滤饼交换,即多次交换。
16.根据权利要求7所述的制备方法,其特征在于稀土交换和分散预交换为多次交换时,两类交换交叉进行。
17.根据权利要求7所述的制备方法,其特征在于第一次焙烧的焙烧条件为350℃~700℃、0~100%水汽焙烧0.3~3.5小时。
18.根据权利要求7所述的制备方法,其特征在于步骤(1)中,获得“一交一焙”稀土钠Y分子筛后,将“一交一焙”稀土钠Y分子筛浆液首先经过磷改性交换,反应结束后过滤、洗涤获得滤饼;将滤饼与铵盐溶液混合均匀进行滤饼交换,反应结束后将滤饼闪蒸干燥后进行焙烧。
19.根据权利要求7所述的制备方法,其特征在于步骤(1)中,获得“一交一焙”稀土钠Y分子筛后,将“一交一焙”稀土钠Y分子筛浆液首先经过磷改性交换,后与铵盐溶液混合均匀进行交换,反应结束后过滤、洗涤获得滤饼;将滤饼闪蒸干燥后进行焙烧。
20.根据权利要求7所述的制备方法,其特征在于步骤(1)中,获得“一交一焙”稀土钠Y分子筛后,将“一交一焙”稀土钠Y分子筛浆液首先经过铵盐交换,反应结束后过滤、洗涤获得滤饼;将滤饼与磷改性溶液充分混合均匀进行滤饼交换,反应结束后将滤饼闪蒸干燥后进行焙烧。
21.根据权利要求7所述的制备方法,其特征在于步骤(1)中,获得“一交一焙”稀土钠Y分子筛后,将“一交一焙”稀土钠Y分子筛浆液首先经过铵盐交换,反应结束后将滤饼与磷改性溶液充分混合均匀进行交换,后过滤、洗涤获得滤饼,最后将滤饼闪蒸干燥后进行焙烧。
22.根据权利要求7所述的制备方法,其特征在于步骤(1)中,获得“一交一焙”稀土钠Y分子筛后,将“一交一焙”稀土钠Y分子筛浆液首先经过铵盐交换,反应结束后将滤饼闪蒸干燥后进行焙烧,之后再将滤饼重新打浆与磷改性溶液充分混合均匀进行交换,后过滤、洗涤获得滤饼,最后将滤饼闪蒸干燥后进行焙烧。
23.根据权利要求7所述的催化剂的制备方法,其特征在于步骤(2)中焙烧条件是将喷雾微球在200℃~700℃下焙烧,时间为0.05~4小时。
24.根据权利要求7所述的催化剂的制备方法,其特征在于步骤(2)中耐高温无机氧化物的前驱物选自硅铝凝胶、硅溶胶、铝溶胶、硅铝复合溶胶、拟薄水铝石中的一种或多种。
25.根据权利要求7所述的催化剂的制备方法,其特征在于步骤(2)中水洗条件为:水/催化剂重量为0.5~35,水洗温度为20℃~100℃,时间为0.1~0.3小时。
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