CN110038631A - 一种甲醇制烯烃催化剂细粉的回用方法 - Google Patents
一种甲醇制烯烃催化剂细粉的回用方法 Download PDFInfo
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Abstract
一种甲醇制烯烃催化剂细粉的回用方法是将待回用的催化剂细粉、活性组分、基质材料、粘结剂和去离子水按照一定比例混合,制成具有一定固含量的浆料,然后经剪切、喷雾成型和焙烧,制得具有适宜粒度分布和较低磨损指数的甲醇制烯烃流化床微球催化剂。本发明利用甲醇制烯烃催化剂细粉作为原料,减少了甲醇制烯烃催化剂成型过程中原料的加入量,实现了废物的再利用,有利于环境保护,而且降低了甲醇制烯烃催化剂的生产成本。
Description
技术领域
本发明涉及一种甲醇制烯烃催化剂细粉的再利用方法。
背景技术
我国煤炭资源储量丰富,随着石油资源的日益短缺,以煤为原料制备化学品的技术备受关注。其中,低碳烯烃是用途最为广泛的基本有机化工原料,乙烯、丙烯的研究和开发向来是国内外各研究机构开发的热点。经过多年的技术积累和不断发展,由煤经甲醇制取烯烃的工艺已成功实现工业化,并取得了非常好的经济效益和社会效益。该技术的核心在于催化剂,由于甲醇制烯烃反应在流化床反应器中进行,因此催化剂的活性、耐磨性、粒度分布显得尤为重要。
目前,流化床用微球催化剂多采用喷雾干燥方法制备。采用这种方法生产催化剂时,会同时得到粗粉和细粉两种不同粒度分布的产品。而实际应用到工业流化床反应器中的催化剂粒度分布需达到一定的要求。为满足这一要求,需要对粗粉和细粉进行调配,一般情况下,将会有部分细粉剩余。这部分细粉若不加以回收利用,不仅会增加生产成本,对环境也会产生不利影响。
另外,催化剂在循环流化床装置中会发生磨损,其中大多数粉化的催化剂可以通过旋风分离设备回收下来。这些粉化催化剂一方面粒度更小,无法调配到新鲜催化剂中;另一方面由于磨损严重,球形度差,流动性能较新鲜催化剂差,无法满足流化床工艺对催化剂的要求。这部分催化剂若能回收利用,将产生一定的经济价值,降低催化剂生产成本。
专利CN1615177A 提供了一种重新利用含分子筛催化剂的方法,即将含分子筛微球催化剂与去离子水混合,胶磨后重新喷雾干燥,制备具有较低磨损指数和适宜粒度分布的催化剂。其中用于回收的催化剂必须是新鲜未焙烧样品,即分子筛中含有有机胺模板剂。本发明创造所回收的催化剂可以是新鲜未焙烧的催化剂、焙烧后的新鲜催化剂细粉,也可以是循环流化床产生的含碳或焙烧除去碳的催化剂,应用范围更广。
专利CN106540744A报道了一种将回用的催化剂作为合成SAPO类分子筛的部分原料。该方法采用回用的微球催化剂、硅源、铝源、磷源、模板剂及去离子水作为原料,也可添加一定量金属,按比例混合,在一定条件下晶化、干燥得到分子筛原粉。该发明可以将所有不符合指标要求的催化剂及循环流化床产生的废催化剂进行回收利用,应用范围广泛。但相对于本发明方法来说,对喷雾干燥产生的细粉和循环流化床产生的废催化剂直接进行再成型,方法更简单,催化剂收率也更高。
发明内容
本发明的目的在于提供一种甲醇制烯烃催化剂细粉的再利用方法。该方法是将待回用的催化剂细粉、活性组分、基质材料、粘结剂和去离子水按照一定比例混合,制成具有一定固含量的浆料,然后经剪切、喷雾成型和焙烧,制得具有适宜粒度分布和较低磨损指数的甲醇制烯烃流化床微球催化剂。
本发明所述的一种甲醇制烯烃催化剂细粉再利用的制备过程如下。
将回用催化剂作为全部或部分原料替代活性组分分子筛、基质材料和粘结剂,然后与去离子水按照所需比例混合均匀,制成浆料,经剪切混合、喷雾成型、焙烧后制得流化床微球催化剂,其中所述回用催化剂的活性组分是SAPO-34或MeAPSO-34分子筛;
具体操作步骤是:
a)测定回用催化剂的固含量,以及回用催化剂中的氧化硅、氧化铝、五氧化二磷和改性金属氧化物的含量;
b)按比例制备甲醇制烯烃催化剂浆料,以氧化物质量百分比计的主要原料配比是:SiO2:Al2O3:P2O5:MexOy =(10%~45%):(30%~65%):(12%~45%):(0%~10%),以此分别称取回用催化剂、活性组分、基质材料、粘结剂和去离子水,混合均匀制成浆料,固体干基占浆料的质量分数是10%~50%,回用催化剂在总配料中干基质量含量不超过50%;
c)对步骤b)制备的浆料剪切混合10~100min,然后喷雾成型,于500~800℃,空气或氧气气氛中焙烧1~10小时,制得流化床微球催化剂。
其中,所述回用催化剂的粒度分布是D50为0.5~50μm;所述基质材料选自高岭土、蒙脱土、拟薄水铝石、氧化硅、氧化铝中的一种或几种的混合;粘结剂选自硅溶胶、铝溶胶、水玻璃中的一种或几种的混合;MeAPSO-34分子筛中所包含金属是镁、钙、钡、锶、镍、钴、锌、锰、铁等中的一种或任意几种的混合,且该金属形成的盐易溶于水。
与现有技术相比,本发明具有以下特点。
(1)回收的催化剂可以是未焙烧的新鲜催化剂细粉、焙烧后的新鲜催化剂细粉,也可以是循环流化床的旋风分离装置回收的催化剂细粉,包括含碳的或焙烧除去碳的催化剂。且旋风分离回收的催化剂细粉中分子筛的含量可以小于新鲜催化剂。
(2)成型后的微球催化剂的粒度分布在20~300 μm,平均粒径为60~120 μm。
(3)成型后的微球催化剂的磨损指数小于1.0% / h。
(4)重新成型后的催化剂应用于甲醇制烯烃反应,其反应性能不低于新鲜催化剂。
附图说明
图1 是循环流化床旋风分离装置回收的催化剂细粉的SEM 照片。
图2 是图1所示催化剂细粉再成型后的微球催化剂,即实施例3的SEM 照片。
具体实施方式
下面的实施例将对本发明予以进一步的说明,但不因此而限制本发明。以下实施例中所述磨损指数采用沈阳科汇仪器仪表制造有限公司KMS-D型磨耗仪测量,粒度分布采用英国马尔文Mastersizer 2000型激光粒度仪测量。
对比例1
全部采用新鲜原料制备的甲醇制烯烃流化床微球催化剂见已公开的专利CN107185587A中实施例2所述的催化剂样品C-2。
实施例1
以喷雾干燥未焙烧的新鲜催化剂细粉作为待回用催化剂,D50为14.3μm。按照固体干基占浆料的50wt%,回用催化剂在总配料中干基占比10wt%,氧化物质量百分比计SiO2:Al2O3:P2O5 =18%:50%:32%,分别称取回用催化剂、SAPO-34分子筛、拟薄水铝石、硅溶胶和去离子水,混合均匀制成浆料。然后对浆料剪切混合60min,于喷雾干燥装置上成型为微球催化剂。将此催化剂置于马弗炉中于600℃焙烧5个小时,制得甲醇制烯烃催化剂,记作M1。
实施例2
以喷雾干燥焙烧后的新鲜催化剂细粉作为待回用催化剂,D50为43.2μm。按照固体干基占浆料的10wt%,回用催化剂在总配料中干基占比50wt%,氧化物质量百分比计SiO2:Al2O3:P2O5:NiO = 10%:43.2%:45%:1.8%,分别称取回用催化剂、NiAPSO-34分子筛、高岭土、铝溶胶和去离子水,混合均匀制成浆料。然后对浆料剪切混合100min,于喷雾干燥装置上成型为微球催化剂。将此催化剂置于马弗炉中于500℃焙烧10个小时,制得甲醇制烯烃催化剂,记作M2。
实施例3
以循环流化床旋风分离装置回收的含碳催化剂粉末作为待回用催化剂,D50为4.05μm。按照固体干基占浆料的25wt%,回用催化剂在总配料中干基占比35wt%,氧化物质量百分比计SiO2:Al2O3:P2O5 = 45%:30%:25%,分别称取回用催化剂、SAPO-34分子筛、氧化硅、铝溶胶和去离子水,混合均匀制成浆料。然后对浆料剪切混合10min,于喷雾干燥装置上成型为微球催化剂。将此催化剂置于马弗炉中于800℃焙烧1个小时,制得甲醇制烯烃催化剂,记作M3。
实施例4
将循环流化床旋风分离装置回收的含碳催化剂于650℃焙烧4小时,以此粉末作为待回用催化剂,D50为4.05μm。按照固体干基占浆料的37wt%,回用催化剂在总配料中干基占比15wt%,氧化物质量百分比计SiO2:Al2O3:P2O5:CaO = 20%:58%:12%:10%,分别称取回用催化剂、CaAPSO-34分子筛、拟薄水铝石、水玻璃和去离子水,混合均匀制成浆料。然后对浆料剪切混合30min,于喷雾干燥装置上成型为微球催化剂。将此催化剂置于马弗炉中于550℃焙烧6个小时,制得甲醇制烯烃催化剂,记作M4。
实施例5
以循环流化床旋风分离装置回收的含碳催化剂粉末作为待回用催化剂,D50为4.05μm。按照固体干基占浆料的30wt%,回用催化剂在总配料中干基占比20wt%,氧化物质量百分比计SiO2:Al2O3:P2O5 = 17%:65%:18%,分别称取回用催化剂、SAPO-34分子筛、高岭土、铝溶胶和去离子水,混合均匀制成浆料。然后对浆料剪切混合50min,于喷雾干燥装置上成型为微球催化剂。将此催化剂置于马弗炉中于700℃焙烧3个小时,制得甲醇制烯烃催化剂,记作M5。
实施例6
将实施例1,2,3,4,5 中得到的催化剂样品M1,M2,M3,M4,M5进行磨损指数测量,结果列于表1。几个催化剂的磨损指数均小于1.0%。
表1 催化剂的磨损指数结果
。
实施例7
将实施例1,2,3,4,5 中得到的催化剂样品M1,M2,M3,M4,M5进行粒度分布测量,结果列于表2。
表2 催化剂的粒度分布结果
。
实施例8
将催化剂样品M1~M5的进行甲醇制烯烃反应评价。称取5g催化剂样品装入固定床反应器中,氮气气氛下升温至480℃,微量泵进料后停止通氮气,甲醇(80wt%水溶液)重量空速4.0h-1,反应压力0.1MPa(表压)。反应产物由气相色谱进行在线分析。结果见表3。
表3 样品甲醇制烯烃反应结果
。
实施例9
将实施例4所述回用催化剂焙烧除碳(记作X2)和C-2样品分别压片,破碎至40~60目。称取1g样品装入固定床反应器中,进行甲醇制烯烃反应评价。甲醇由氮气携带,氮气流速为35ml/min,反应温度450℃,甲醇(40wt%水溶液)重量空速1.5h-1。反应产物由气相色谱进行在线分析。结果见表4。
从表4中可以看出,对比新鲜原料制备得到的催化剂,循环流化床旋风分离装置回收的粉末催化剂的寿命大大缩短,双烯选择性(100%甲醇转化率时最高(乙烯+丙烯)选择性)也明显降低,特别是乙烯选择性降低更加显著。同时,元素表征结果显示,X1样品的Al :P : Si(摩尔比)是2.40 : 0.61 : 1,C-2样品的Al : P : Si(摩尔比)是2.95 : 0.76 :1,说明经过旋风分离回收的粉末催化剂分子筛含量有一定程度的降低。结合表3的结果可以得出:采用本发明专利的方法对存在粒度分布不合适、形貌不合适,以及催化性能下降等问题的甲醇制烯烃流化床催化剂细粉经过再成型后,其粒度分布、磨损指数、形貌等均能够满足流化床反应器的要求,且反应性能不低于新鲜催化剂。
表4 回用催化剂与新鲜原料制备催化剂的甲醇制烯烃反应结果对比
Claims (8)
1.一种甲醇制烯烃催化剂细粉的回用方法,是将回用催化剂作为全部或部分原料替代活性组分分子筛、基质材料和粘结剂,然后与去离子水按照所需比例混合均匀,制成浆料,经剪切混合、喷雾成型、焙烧后制得流化床微球催化剂,其中所述回用催化剂的活性组分是SAPO-34或MeAPSO-34分子筛;
具体操作步骤如下:
(1)测定回用催化剂的固含量,以及回用催化剂中的氧化硅、氧化铝、五氧化二磷和改性金属氧化物的含量;
(2)按比例制备甲醇制烯烃催化剂浆料,以氧化物质量百分比计的主要原料配比是:SiO2:Al2O3:P2O5:MexOy =(10%~45%):(30%~65%):(12%~45%):(0%~10%),以此分别称取回用催化剂、活性组分、基质材料、粘结剂和去离子水,混合均匀制成浆料,固体干基占浆料的质量分数是10%~50%,回用催化剂在总配料中干基质量含量不超过50%;
(3)对步骤(2)所制备浆料剪切混合10~100min,然后喷雾成型、焙烧后制得流化床微球催化剂。
2.根据权利要求1所述的一种甲醇制烯烃催化剂细粉的回用方法,其特征在于所述回用催化剂是应用甲醇制烯烃催化剂的循环流化床旋风分离装置收集到的细粉,或者是新鲜催化剂喷雾干燥后的细粉。
3.根据权利要求1或2所述的一种甲醇制烯烃催化剂细粉的回用方法,其特征在于所述回用催化剂粒度分布是D50为0.5~50μm。
4.根据权利要求1所述的一种甲醇制烯烃催化剂细粉的回用方法,其特征在于基质材料选自高岭土、蒙脱土、拟薄水铝石、氧化硅、氧化铝中的一种或几种的混合;粘结剂选自硅溶胶、铝溶胶、水玻璃中的一种或几种的混合。
5.根据权利要求1所述的一种甲醇制烯烃催化剂细粉的回用方法,其特征在于MeAPSO-34分子筛中所包含金属是镁、钙、钡、锶、镍、钴、锌、锰、铁等中的一种或任意几种的混合,且该金属形成的盐易溶于水。
6.根据权利要求1 所述的一种甲醇制烯烃催化剂细粉的回用方法,其特征在于微球催化剂焙烧的温度是500~800℃,空气或氧气气氛中焙烧1~10小时。
7.根据权利要求1所述的一种甲醇制烯烃催化剂细粉的回用方法,其特征在于成型微球催化剂的粒度分布控制在20~300 μm,平均粒径为60~120 μm。
8.根据权利要求1所述的一种甲醇制烯烃催化剂细粉的回用方法,其特征在于成型微球催化剂的磨损指数小于1.0% / h。
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