CN108465482B - 一种由fcc废催化剂制备高效蒽醌加氢催化剂的方法 - Google Patents
一种由fcc废催化剂制备高效蒽醌加氢催化剂的方法 Download PDFInfo
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Abstract
本发明涉及一种由FCC废催化剂制备高效蒽醌加氢催化剂的方法,该方法的步骤如下:将FCC废催化剂、NaOH及少量水混合均匀于一定温度下焙烧一段时间;将焙烧后得到的物料研磨充分后过筛;向焙烧得到的物料中加入一定量去离子水,升温至一定温度搅拌老化一段时间;老化结束后将温度升至一定温度搅拌晶化一段时间;过滤洗涤干燥后所得滤饼即为4A沸石;用H2PdCl4溶液等体积浸渍上述4A沸石,接着用NaOH溶液过量浸渍,然后依次经过洗涤、干燥、焙烧后制得所述催化剂。本发明以FCC废催化剂为原料,在较低的活化温度下制得了纯度较高的沸石,并且以其为蒽醌加氢催化剂载体时具有催化剂活性和蒽醌循环回收率高等特点。
Description
技术领域
本发明涉及一种由FCC废催化剂制备高效蒽醌加氢催化剂的方法。
背景技术
流化催化裂化(FCC)是现代石油炼制工艺的重要组成部分,FCC过程是在一定温度及催化剂的作用下使重质原料发生裂解反应,是主要的重油轻质化方法。FCC催化剂在使用过程中,由于催化剂受重金属污染而使催化剂活性下降,导致催化剂的反应选择性变差,因此需要定期卸出一部分保证装置内催化剂的活性和选择性水平,被卸出的部分称为FCC废催化剂。2015年我国废炼油催化剂的产量超过200kt,其中由FCC装置产生的废催化剂占绝大部分。FCC废催化剂活性低,并含有一定量的重金属,污染性强,无害化处理困难。2016年8月1日,新发布的《国家危险废物名录》中,将FCC废催化剂归为HW50类危废。因此,对FCC废催化剂的无害化及绿色资源化利用已迫在眉睫。
目前,FCC废催化剂的主要处理方式还是以填埋为主,但随着环境问题得到重视,其无害化处理方式和再利用引起了关注。中国专利文献CN101219396A提出了一种FCC废催化剂复活再生的方法,该方法采用有机酸无机酸协同处理,脱除FCC废催化剂中的重金属后大幅提高了FCC废催化剂的反应活性,但是存在重金属脱除不彻底和复活后的催化剂活性较低的缺陷。中国专利文献CN1704350A提出了一种由FCC废催化剂制备聚合硅酸铝的方法,该方法先用硫酸浸取FCC废催化剂再用NaOH浸取滤渣之后将两种浸取液混合于一定条件下反应一段时间制得聚合硅酸铝,但该方法存在工艺复杂和未经活化的废催化剂硅铝元素利用率低的缺陷。中国专利文献CN104261424提出了一种由FCC废催化剂与高岭土制备4A沸石的方法,该方法将高岭土、FCC废催化剂加水和分散剂、扩孔剂、助剂、粘结剂中的一种或几种搅拌均匀制成浆料、成型,成型物料在700-1000℃下焙烧一段时间后在一定温度下水热一段时间过滤干燥制得4A沸石,该方法存在活化温度高、能耗大的缺陷。Basaldella等人(Basaldella EI,Sa′nchez RMT,Conconi MS.Conversion of exhausted fluid crackingcatalysts into zeolites by alkaline fusion.Appl.Clay.Sci.2009,42:611–614)提出了一种由FCC废催化剂制备NaA沸石的方法,该方法先将FCC废催化剂与一定质量的碳酸钠混合,于800℃焙烧一定时间后向焙烧物料内补充一定量的偏铝酸钠溶液,进一步水热反应、过滤、干燥后制得NaA沸石,该方法存在需要补加部分化学试剂、活化温度高,能耗大的缺陷。
相比现有FCC废催化剂利用的方法,本发明采用一种温和的工艺从FCC废催化剂制得了高效蒽醌加氢催化剂,在一步利用其中硅铝元素的同时保留了FCC废催化剂部分孔结构,在大幅提高其附加值的同时减少了FCC废催化剂的排放,具有重要的环保和经济意义。
发明内容
本发明所要解决的技术问题是:提供一种由FCC废催化剂制备高效蒽醌加氢催化剂的方法,该方法具有工艺简单,制备条件温和,制得的蒽醌加氢催化剂氢化效率高和蒽醌循环回收率高等优良特性。
本发明解决其技术问题采用以下的技术方案:
本发明提供的由FCC废催化剂制备高效蒽醌加氢催化剂的方法,包括以下步骤:
(1)取3gFCC废催化剂置于坩埚中,加入一定量固体NaOH及少量去离子水,充分搅拌使其混合均匀,并于400℃下焙烧2h;
(2)将上述焙烧物料充分研磨过200目筛,并向其中加入一定量去离子水,混合后在60℃、180r/min下搅拌老化一段时间;
(3)将老化后悬浮液的温度升至90℃,在180r/min下搅拌晶化一段时间;
(4)将晶化后的悬浮液过滤,用去离子水洗涤至pH≤11,将滤饼在105℃烘干2h,制得4A沸石;
(5)在60℃下,按照理论0.3wt%Pd的负载量,用pH=3的H2PdCl4溶液等体积浸渍1g上述4A沸石,接着用0.1mol/L的NaOH溶液于60℃下稍过量浸渍2h,洗涤该沉淀至无Cl-,然后于60℃下干燥4h、500℃下焙烧2h,制得所述的高效蒽醌加氢催化剂。
上述方法中,步骤(1)所述的固体NaOH的质量为3.437-4.245g。
上述方法中,步骤(1)所述的去离子水的体积为1.5-2.1ml。
上述方法中,步骤(2)所述的去离子水的加入量为34.8-52.3ml。
上述方法中,步骤(2)所述的老化时间为1-2h。
上述方法中,步骤(3)所述的晶化时间为3-5h。
上述方法中,所制得的4A沸石的钙离子交换量为270-305mgCaCO3/g-干基。
本发明提供的上述方法制备的催化剂,其氢化效率达8.12-9.82g/L工作液,蒽醌循环回收率可达87.9-100.0%。
本发明与现有技术相比具有以下主要的优点:
(1)采用FCC废催化剂作为制备4A沸石的原料,在降低成本的同时减少了FCC废催化剂的排放。
(2)采用NaOH作为助融剂活化FCC废催化剂,并采取温和水热法制备4A沸石,大幅降低了活化FCC废催化剂所需的温度,具有制备条件温和、能耗低及设备要求低的特点。
(3)采用FCC废催化剂制备了4A沸石,其保留了部分FCC废催化剂的孔结构,具有良好的织构性质。
(4)采用4A沸石作为蒽醌加氢催化剂的载体,制得的催化剂具有成本低、氢化效率高、蒽醌循环回收率高的特点。
附图说明
图1为FCC废催化剂的XRD图谱;
图2为FCC废催化剂的N2吸附-脱附等温线;
图3为实施例1合成分子筛的XRD图谱;
图4为实施例2合成分子筛的XRD图谱;
图5为实施例3合成分子筛的XRD图谱;
图6为实施例4合成分子筛的XRD图谱;
图7为实施例5合成分子筛的XRD图谱;
图8为各实施例的N2吸附-脱附等温线;
图9为各实施例的孔径分布曲线;
图10为各实施例制备的催化剂的氢化效率图。
具体实施方式
为更方便解释本发明,下面结合以下实施例与附图来进一步解释本发明,但并不局限于下面所述的内容。
实施例1:
称取3gFCC废催化剂置于坩埚中,加入4.25g固体NaOH及2.1ml去离子水,在400℃下焙烧2h。将焙烧后的物料充分研磨过200目筛,向其中加入52.55ml去离子水,先于60℃下180r/min搅拌老化1h,老化结束后,将温度升至90℃,在180r/min下搅拌晶化4h,将混合物过滤,滤饼用去离子水进行洗涤至pH≤11,105℃干燥2h,即得4A沸石。所得4A沸石的钙离子交换量为305mgCaCO3/g-干基、比表面积为9.9m2/g、孔容为0.032cm3/g、平均孔径为10.5nm。
取1.0g上述4A沸石,将0.0050g PdCl2粉末溶解在质量浓度为0.003wt%和pH=3的盐酸中,得到H2PdCl4溶液,盐酸的量要求等于4A沸石的饱和吸水量。用上述H2PdCl4溶液在60℃下等体积浸渍1h,接着用0.1mol/L的NaOH溶液于60℃下稍过量浸渍2h,之后用去离子水洗涤至滤液中无Cl-,然后于60℃干燥4h、500℃下焙烧2h,即得到高效蒽醌加氢催化剂。该催化剂在自制浆态床中所测得最高氢化效率为9.62g/L工作液,蒽醌循环回收率为87.9%。
实施例2:
称取3g FCC废催化剂置于坩埚中,加入3.84g固体NaOH及1.8ml去离子水,在400℃下焙烧2h。将焙烧后的物料充分研磨过200目筛,向其中加入47.54ml去离子水,先于60℃、180r/min下搅拌老化1h,老化结束后,将温度升至90℃,在180r/min下搅拌晶化4h,将混合物过滤,滤饼用去离子水洗涤至pH≤11,进一步在105℃下干燥2h,即得4A沸石。所得4A沸石的钙离子交换量为288mg CaCO3/g-干基、比表面积为10.8m2/g、孔容为0.032cm3/g、平均孔径为10.3nm。
负载过程与实施例1相同。
所得到的催化剂在自制浆态床中的最高氢化效率为9.82g/L工作液,蒽醌循环回收率为100.0%。
实施例3:
称取3g FCC废催化剂置于坩埚中,加入3.84g固体NaOH及1.8ml去离子水,在400℃下焙烧2h。将焙烧后的物料充分研磨过200目筛,向其中加入43.22ml去离子水,先于60℃、180r/min下搅拌老化2h,老化结束后,将温度升至90℃,在180r/min下搅拌晶化3h,将混合物过滤,滤饼用去离子水洗涤至pH≤11,在105℃下干燥2h,即得4A沸石。所得4A沸石的钙离子交换量为285mg CaCO3/g-干基、比表面积为15.3m2/g、孔容为0.041cm3/g、平均孔径为9.4nm。
负载过程与实施例1相同。
所得到的催化剂在自制浆态床中所测得的最高氢化效率为9.53g/L工作液,蒽醌循环回收率为94.0%。
实施例4:
称取3g FCC废催化剂置于坩埚中,加入3.84g固体NaOH及1.8ml去离子水,在400℃下焙烧2h。将焙烧后的物料充分研磨过200目筛,向其中加入38.89ml去离子水,先于60℃、180r/min下搅拌老化1.5h,老化结束后,将温度升至90℃,在180r/min下搅拌晶化5h,将混合物过滤,滤饼用去离子水进行洗涤至pH≤11,在105℃下干燥2h,即得4A沸石。所得4A沸石的钙离子交换量为277mg CaCO3/g-干基、比表面积为16.1m2/g、孔容为0.043cm3/g、平均孔径为8.9nm。
负载过程与实施例1相同。
所得到的催化剂在自制浆态床中所测得的最高氢化效率为8.91g/L工作液,蒽醌循环回收率为100.0%。
实施例5:
称取3g FCC废催化剂置于坩埚中,加入3.44g固体NaOH及1.5ml去离子水,在400℃下焙烧2h。将焙烧后的物料充分研磨过200目筛,向其中加入42.53ml去离子水,先于60℃、180r/min下搅拌老化1.5h,老化结束后,将温度升至90℃,在180r/min下搅拌晶化3h,将混合物过滤,滤饼用去离子水进行洗涤至pH≤11,在105℃下干燥2h,即得4A沸石。所得4A沸石的钙离子交换量为270mg CaCO3/g-干基、比表面积为24.4m2/g、孔容为0.071cm3/g、平均孔径为9.6nm。
负载过程与实施例1相同。所得到的催化剂在自制浆态床中所测得的最高氢化效率为8.16g/L工作液,蒽醌循环回收率为88.0%。
上述实施例中样品的织构性质如比表面积、孔容和孔径分布数据是通过BJH模型计算,所用的N2吸脱附仪器为美国Micromeritics公司生产的TriStarⅡ3020仪器;样品的物相结构和晶粒尺寸数据使用日本Rigaku公司的D/MAX—RB型X射线衍射仪检测。
钙离子交换量的测定方法:沸石分子筛的钙离子交换量以毫克碳酸钙每克无水沸石表示,按照QB/T1768-2003中洗涤用4A沸石钙交换能力测定方法测定,钙离子在pH大于12.5时能与钙指示剂生成酒红色的络合物,用乙二胺四乙酸二钠(EDTA)滴定溶液时会使钙离子与EDTA络合,钙指示剂游离出来,呈现蓝色。具体的测试方法为:用移液管量取50mL、0.05mol/L的氯化钙溶液于500mL容量瓶中,用去离子水稀释至刻度。加入几滴0.5mol/L的NaOH溶液至氯化钙溶液pH为10.2-10.5,然后将此溶液倒入1000mL的三口烧瓶中,放入35℃的恒温水浴中,装上机械搅拌,以大于700r/min的速度搅拌溶液,使溶液不会飞溅,当温度升至35℃时,加入0.5g沸石产品,保温20min后迅速取出用滤膜抽滤,用移液管吸取50mL滤液加入250mL锥形瓶中,再加入2mL、2.5mol/L的NaOH溶液和少许的钙指示剂,用0.01mol/L的EDTA溶液滴定上述溶液,直至该溶液由酒红色变为蓝色停止滴定,记录消耗的EDTA标准溶液的体积,平行滴定三组取平均值。
4A沸石的钙离子交换量E以毫克碳酸钙每克无水沸石表示,按下式计算:
式中:
100.08——碳酸钙的毫摩尔质量,mg/mmol;
VE——在滴定中消耗标准滴定溶液EDTA的体积,mL;
c0——氯化钙标准溶液的浓度,mol/L;
c1——EDTA标准滴定溶液的浓度,mol/L;
m——沸石的质量,g;
W——按QB/T1768-2003中B.1.5a计算的吸湿水量,%;
催化剂活性的评价:采用基于三口烧瓶的微型浆态床反应器,密封反应装置后,检查装置气密性,并用N2置换烧瓶内的空气。催化反应前用摩尔比3:1的H2和N2在60℃下原位还原催化剂2h。催化反应温度为60℃,氢气流速50ml/min,催化剂装量为0.8g,工作液的用量为60ml,每隔30min取2ml氢化工作液,取样至反应体系出现过度氢化。
氢化效率的测定方法:将取的氢化工作液用离心机离心后,取2ml上清液置于分液漏斗中,加入3滴浓磷酸(防止氧化过程中过氧化氢分解),并加入20ml去离子水,在室温下通入35mL/min的O2,直至有机相呈现亮黄色。停止通入O2,静置,将下层水相分离于锥形瓶中,有机相用20mL去离子水萃取5次,水相仍收集于锥形瓶中。萃取结束后,向锥形瓶中加入5mL、20%的硫酸溶液,混合均匀,用0.02mol/L左右的高锰酸钾溶液滴定至溶液颜色变成粉红色且30s不褪色,即为滴定终点。记下高锰酸钾的消耗体积并计算氢化效率。
蒽醌循环回收率的测定方法:采用Agilent HP1260高效液相色谱仪对样品进行液相分析。检测条件为:室温,色谱柱zorbox Eclipse XDB-C18(4.6mm×250mm、5μm),流动相体积比甲醇:水=9:1,流速1mL/min,波长254nm,进样量10μL。采用外标法检测样品中2-乙基蒽醌与四氢-2-乙基蒽醌的含量,以获得催化剂的蒽醌循环回收率数据。
上述实施例中,可以采用老本行400Y多功能粉碎机进行研磨。
上述实施例中,所述自制浆态床是由三口烧瓶、球形冷凝管、橡胶塞、温度计及磁力搅拌器组成,三颈瓶置于磁力搅拌器内。三颈瓶左侧口和右侧口由橡胶塞密封,右侧橡胶塞上插有玻璃管(供氢气氮气进入反应器)、温度计及取样针,上侧口为冷凝管。
表1实施例1-5催化剂载体的钙离子交换量、织构性质及催化剂催化性能数据
Claims (5)
1.一种由FCC废催化剂制备高效蒽醌加氢催化剂的方法,其特征在于包括以下步骤:
(1)取3gFCC废催化剂置于坩埚中,加入质量为3.437-4.245g的固体NaOH及少量去离子水,充分搅拌使其混合均匀,并于400℃下焙烧2h;
(2)将上述焙烧物料充分研磨过200目筛,并向其中加入一定量去离子水,混合后在60℃、180r/min下搅拌老化1-2h;
(3)将老化后悬浮液的温度升至90℃,在180r/min下搅拌晶化3-5h;
(4)将晶化后的悬浮液过滤,用去离子水洗涤至pH≤11,将滤饼在105℃烘干2h,制得4A沸石;
(5)在60℃下,按照理论0.3wt%Pd的负载量,用pH=3的H2PdCl4溶液等体积浸渍1g上述4A沸石,接着用0.1mol/L的NaOH溶液于60℃下稍过量浸渍2h,洗涤沉淀至无Cl-,然后于60℃下干燥4h、500℃下焙烧2h,制得所述的高效蒽醌加氢催化剂。
2.根据权利要求1所述的制备高效蒽醌加氢催化剂的方法,其特征在于步骤(1)所述的去离子水的体积为1.5-2.1mL。
3.根据权利要求1所述的制备高效蒽醌加氢催化剂的方法,其特征在于步骤(2)所述的去离子水的加入量为34.8-52.3mL。
4.根据权利要求1所述的制备高效蒽醌加氢催化剂的方法,其特征在于所制得的4A沸石的钙离子交换量为270-305mgCaCO3/g-干基。
5.根据权利要求1-4之一所述的制备高效蒽醌加氢催化剂的方法,其特征在于所制得的催化剂其氢化效率达8.12-9.82g/L工作液,其蒽醌循环回收率达87.9-100.0%。
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