CN113457688A - 一种铜基微通道低温变换催化剂及其制备方法、微通道低温变换反应的方法 - Google Patents
一种铜基微通道低温变换催化剂及其制备方法、微通道低温变换反应的方法 Download PDFInfo
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- CN113457688A CN113457688A CN202010238097.5A CN202010238097A CN113457688A CN 113457688 A CN113457688 A CN 113457688A CN 202010238097 A CN202010238097 A CN 202010238097A CN 113457688 A CN113457688 A CN 113457688A
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- copper
- temperature shift
- catalyst
- low
- shift catalyst
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Links
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Classifications
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
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- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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Abstract
一种铜基微通道低温变换催化剂及其制备方法、微通道低温变换反应的方法。所述铜基微通道低温变换催化剂为表面具有一个大孔的中空微球,所述中空微球内部具有一个中空结构,所述铜基微通道低温变换催化剂包括活性组分、第一助剂,所述活性组分为CuO和ZnO;所述第一助剂为Al2O3和/或Cr2O3。本发明提供的铜基微通道低温变换催化剂应用在微通道低温变换反应时,具有一氧化碳低温变换活性高、热稳定性好的特点,同时其粒度分布均匀,具有较高的机械强度和较好的耐磨性能,以及显著降低的床层压降的特点。
Description
技术领域
本发明涉及微通道变换反应领域,更具体地说,是一种铜基微通道低温变换催化剂及其制备方法、微通道低温变换反应的方法。
背景技术
随着氢气日益广泛地应用,采用CO变换制备氢气的工艺技术逐渐受到重视。CO变换反应为放热反应,当处理高浓度CO时容易出现飞温现象,导致催化剂烧结失活,因此需要加强催化剂床层的传热,控制反应的温度平稳,来保证好的反应效果。
微通道反应器是一种单元反应界面在微米级别的反应器结构,与常规反应器相比,具有传热面积大、传质距离短、单位体积反应器反应负荷高、模块结构易工程放大等特点,特别适用于放热的反应。利用微通道反应技术,可以实现高活性催化剂在等温条件反应,既克服了传统反应器传质扩散的影响,又解决了传热效果差的缺点。
微通道反应器对催化剂粒径和结构都具有特殊要求,因此需开发相应的适用于微通道反应器的特殊催化剂。按照催化剂的形态和填充方式,可将微通道反应器分为填充床反应器、结构催化剂反应器和壁载催化剂反应器三种。填充床反应器是直接将催化剂填充到微通道反应器中,这种方式成本低、催化剂实用性高、重复性好,同时微通道反应器高的传质、传热速率能提高催化剂的性能,从而被广泛使用。填充床反应器所用催化剂颗粒一般为实体微球,在热效应较大的反应中,微球内部易产生热点,导致催化剂失活。并且还存在微通道反应器反应通道内压降较大,以及随着催化剂不断破碎粉化导致压降逐渐上升的问题。
发明内容
本发明的目的是提供一种铜基微通道低温变换催化剂及其制备方法,以及应用方法。
本发明提供一种铜基微通道低温变换催化剂,所述铜基微通道低温变换催化剂为表面具有一个大孔的中空微球,所述中空微球内部具有一个中空结构,所述大孔与所述中空结构贯通形成一端开口的空腔;
所述铜基微通道低温变换催化剂的粒径为20~300μm;
所述铜基微通道低温变换催化剂内部中空结构的直径为1~250μm;
所述铜基微通道低温变换催化剂包括活性组分和第一助剂,所述活性组分为CuO和ZnO;所述第一助剂为Al2O3和/或Cr2O3。
在优选的情况下,所述铜基微通道低温变换催化剂的粒径为60~250μm;所述铜基微通道低温变换催化剂内部中空结构的直径为30~150μm。
在优选的情况下,所述大孔的孔径为0.5~200μm。
在优选的情况下,所述铜基微通道低温变换催化剂的球形度为0.50~0.99。
所述的球形度由式
σ=4πA/L2
计算得出。式中:σ为球形度;A为微球的投影面积,m2;L为微球的投影周长,m;A和L由微球的SEM照片,通过图片处理软件Image-Pro Plus处理得出。
在优选的情况下,所述的铜基微通道低温变换催化剂中各组分的质量百分比组成为:CuO 30%~75%,ZnO 15%~40%,Al2O3和/或Cr2O3 0.5~30%。
在优选的情况下,所述铜基微通道低温变换催化剂包括任选的第二助剂,所述的第二助剂为选自Ti、Zr、La、Ce、K、Ca、Mg、W、P、Ni、Mo、V、Fe、Si、Pt、Mn、Sn、Ru、Re中至少一种元素的氧化物。
在优选的情况下,所述的铜基微通道低温变换催化剂中各组分的质量百分比组成为:CuO 30%~75%,ZnO 15%~40%,Al2O3和/或Cr2O3 0.5~15%,第二助剂0~15%。
进一步优选,所述的铜基微通道低温变换催化剂中各组分的质量百分比组成为:CuO 35%~65%,ZnO 20%~35%,Al2O3和/或Cr2O3 1~12%,第二助剂0~10%。
本发明还提供一种上述任一铜基微通道低温变换催化剂的制备方法,该方法包括以下步骤:
(1)将活性组分CuO和ZnO以及第一助剂和任选的第二助剂的可溶性金属盐均匀分散到去离子水中,用沉淀剂进行沉淀,沉淀反应后浆液pH值在6.8~7.2之间,然后将沉淀反应后物料进行过滤、洗涤,得到催化剂前驱体;
(2)将步骤(1)得到的催化剂前驱体与分散剂、粘结剂、造孔剂和/或爆破剂混合制浆,得到胶体浆液;
(3)将步骤(2)得到的胶体浆液与表面活性剂混合乳化,然后经喷雾干燥成型并焙烧后,制得铜基微通道低温变换催化剂。
在优选的情况下,步骤(1)中所述的活性组分CuO的可溶性金属盐选自氯化铜、硫酸铜、硝酸铜中的一种或几种,所述的活性组分ZnO的可溶性金属盐选自氯化锌、硫酸锌、硝酸锌中的一种或几种。
本发明对CuO和ZnO的可溶性金属盐的来源没有特殊要求,采用本领域技术人员所熟知的相应市售商品即可。
在优选的情况下,步骤(1)中所述的沉淀剂选自氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、氨水中的一种或几种。
在本发明中,优选的沉淀过程中适宜的沉淀温度为65~95℃,沉淀反应后浆液pH值在6.8~7.2之间。本发明在沉淀过程结束后,将沉淀反应后物料进行过滤、洗涤,得到催化剂前驱体。在优选的情况下,对沉淀反应后物料进行充分洗涤,直到洗涤后滤液pH值在7左右。
在优选的情况下,步骤(2)中所述的分散剂选自去离子水、醇类、酮类、酸类中的一种或几种,进一步优选醇类选自甲醇、乙醇、丙醇中的一种或几种,进一步优选酮类选自丙酮和/或丁酮,进一步优选酸类选自甲酸、乙酸、丙酸中的一种或几种。
在优选的情况下,步骤(2)中所述的粘结剂选自铝溶胶、硅溶胶、硅铝溶胶、酸化的拟薄水铝石、高岭土、凹凸棒粉、水泥、石膏中的一种或几种。
在优选的情况下,步骤(2)中所述的造孔剂选自淀粉、合成纤维素、聚合醇、硝酸铵等中的一种或几种,优选的合成纤维素为选自羧甲基纤维素、甲基纤维素、乙基纤维素、羟基纤维脂肪醇、聚乙烯醚中的一种或几种;优选的聚合醇为聚乙二醇、聚丙醇、聚乙烯醇、聚丙烯醇PPG中的一种或几种。
在优选的情况下,步骤(2)中所述的爆破剂选自苦味酸、三硝基甲苯、雷酸汞、硝化甘油、硝化棉、达纳炸药、叠氮化铅中的一种或几种。
在优选的情况下,步骤(3)中所述的表面活性剂选自脂肪醇聚乙烯醚、脂肪醇酰胺及其衍生物、重均分子量为200-2000000的丙烯酸共聚物和顺丁烯酸共聚物中的一种或几种。
在本发明中,将催化剂前驱体与分散剂、粘结剂、造孔剂和/或爆破剂混合制浆,得到胶体浆液。所述的胶体浆液的固含量优选为25~60%,进一步优选为35~45%;所述胶体浆液的固含量是指胶体浆液经干燥后得到的固体质量占胶体浆液质量的百分比。
在本发明中,所述的胶体浆液中催化剂前驱体中氧化物、粘结剂中氧化物、造孔剂和/或爆破剂的质量比优选为(50~80):(5~30):(2~10),进一步优选为(65~75):(15~25):(3~5)。
在本发明中,所述的混合制浆方式没有特殊要求,采用本领域技术人员所熟知的物料混合方式以能实现均匀混合即可。在本发明中,所述的混合制浆时间优选为1~3h。在本发明其中一种实施方式中,所述的混合制浆过程是在高速分散机和砂磨机中进行,先通过高速分散机将混合物料搅拌均匀,然后将浆液送入砂磨机研磨,最终得到均质的胶体浆液;所述的高速分散机中剪切转速优选为2000~5000rpm。
本发明将所述得到的胶体浆液与表面活性剂混合乳化,然后经喷雾干燥成型并焙烧后,制得铜基微通道低温变换催化剂。在本发明中,胶体浆液中催化剂前驱体中氧化物和表面活性剂的质量比优选为(50~80):(1~6),进一步优选为(65~75):(2~4)。
在本发明中,所述的表面活性剂优选包括脂肪醇聚乙烯醚、脂肪醇酰胺及其衍生物、重均分子量为200-2000000的丙烯酸共聚物和顺丁烯酸共聚物中的一种或几种。本发明对所述表面活性剂的来源没有特殊要求,采用本领域技术人员所熟知的相应市售商品即可。
在本发明中,对所述胶体浆液与表面活性剂的混合方式没有特殊要求,以能实现胶体浆液与表面活性剂的均匀混合即可。
在优选的情况下,步骤(3)中喷雾干燥的雾化压力为0.1~3.5MPa;
所述的喷雾干燥的干燥初始温度为150~350℃,喷雾干燥的干燥终止温度为80~200℃。本发明对所述喷雾干燥法的具体实施方式没有特殊要求,采用本领域技术人员所熟知的喷雾干燥方式即可。
步骤(3)中焙烧温度为250~500℃,进一步优选为300~450℃;焙烧时间为1~6h,进一步优选为2~4h。
在本发明中,所述焙烧的温度优选自室温以1~10℃/min速率升温到焙烧温度;所述升温的速率进一步优选为2~5℃/min。
本发明还提供一种微通道低温变换反应的方法,该方法包括在上述任一所述的铜基微通道低温变换催化剂存在下,在微通道反应器的反应通道内,在低温变换反应条件下,使CO和H2O接触进行变换反应。
在优选的情况下,所述微通道反应器的反应通道至少有一个维度的尺寸小于1000μm。
所述铜基微通道低温变换催化剂在使用前优选进行还原,将催化剂中活性组分由氧化态还原为金属单质。铜基微通道低温变换催化剂还原条件:压力为常压,升温速率为5℃/min,气体组成为体积分数10%H2和90%N2,气体空速为2000h-1,还原温度为200~300℃,还原时间为2~4h。
低温变换反应条件为:以体积计,H2O/原料气的比值为2/1~1/2,反应温度160~300℃,压力0.1~3MPa,原料气干气空速为2000~20000h-1。反应气体积百分比为:H2 70%~90%,CO 5%~25%,N2 5%~15%。
本发明提供的铜基微通道低温变换催化剂,具有一氧化碳低温变换活性高、热稳定性好等特点,同时其粒度分布均匀,具有较高的机械强度和较好的耐磨性能,装填于微通道反应器内时能够显著降低床层压降。采用本发明提高的微通道低温变换反应的方法,反应效率高,操作能耗低。
附图说明
图1是实施例1所得的铜基微通道低温变换催化剂的SEM图像。
具体实施方式
下面的实施例将对本发明做进一步的说明,但不应因此理解为对本发明的限定。
实施例1
(1)催化剂前体制备
将18.22kg三水合硝酸铜、10.23kg六水合硝酸锌、7.36kg九水硝酸铝及1.01kg九水合硝酸铁溶于50L去离子水中,另取1.37kg氢氧化钠溶于50L去离子水中搅拌溶解,将盐溶液和沉淀剂以一定流速滴入沉淀槽中进行沉淀反应,控制沉淀槽pH为6.8~7.2之间,沉淀完全后室温静置老化12h后过滤,并用80L去离子水洗涤两次;
(2)制浆
将滤饼分散到100L去离子水中,剧烈搅拌打浆并依次加入18kg铝溶胶、12.0kgPEG4000和6.5kg硝酸铵,30℃搅拌打浆2h。
(3)喷雾干燥成型
将上述浆液通过Niro Bowen Nozzle Tower型号喷雾干燥装置成型,喷雾干燥压力为0.5至3.5MPa,入口温度350℃以下,出口温度约为200℃。并在400℃空气中焙烧3h,得到平均粒径150μm左右,中空结构的平均直径45μm的树莓形催化剂,记为WGS-1。催化剂化学组成按氧化物计,CuO含量为60重量%,ZnO含量为28重量%,Al2O3含量为10重量%,Fe2O3含量为2重量%。
对比例1
按照实施例1的方法,不同的是,步骤(2)如下:
将滤饼分散到100L去离子水中,30℃搅拌打浆2h。得到平均粒径140μm左右的球形催化剂,记为DB-1。催化剂化学组成按氧化物计,CuO含量为60重量%,ZnO含量为28重量%,Al2O3含量为10重量%,Fe2O3含量为2重量%。
对比例2
按照实施例1的方法,不同的是,步骤(2)和(3)如下:
将滤饼与200g石墨充分混合,然后压片成型,得到尺寸为4*4圆柱型催化剂,记为DB-2。催化剂化学组成按氧化物计,CuO含量为60重量%,ZnO含量为28重量%,Al2O3含量为10重量%,Fe2O3含量为2重量%。
实施例2
(1)催化剂前体制备
将14.58kg三水合硝酸铜、12.42kg六水合硝酸锌、10.3kg九水硝酸铝及2.02kg九水合硝酸铁溶于于50L去离子水中,另取14.48kg氢氧化钠溶于50L去离子水中搅拌溶解,将盐溶液和沉淀剂以一定流速滴入沉淀槽中进行沉淀反应,控制沉淀槽pH为6.8~7.2之间,沉淀完全后室温静置老化6h后过滤,并用150L去离子水洗涤四次;
(2)制浆
将滤饼分散到50L去离子水中,剧烈搅拌打浆并依次加入30kg酸化的拟薄水铝石、10.0kg PEG4000和10.62kg苦味酸,30℃搅拌打浆2h。
(3)喷雾干燥成型
将上述浆液通过Niro Bowen Nozzle Tower型号喷雾干燥装置成型,喷雾干燥压力为2.0MPa,入口温度150℃以下,出口温度约为120℃。并在400℃空气中焙烧4h,得到平均粒径230μm左右,中空结构的平均直径60μm的树莓形催化剂,记为WGS-2。催化剂化学组成按氧化物计,CuO含量为48重量%,ZnO含量为34重量%,Al2O3含量为14重量%,Fe2O3含量为4重量%。
实施例3
(1)催化剂前体制备
将11.54kg三水合硝酸铜、10.96kg六水合硝酸锌、14.72kg九水硝酸铝及6.07kg九水合硝酸铁溶于于50L去离子水中,并加入8.23kg硝酸锰溶液(50重量%),另取38kg碳酸铵溶于50L去离子水中,另取15.94kg氢氧化钠溶于50L去离子水中搅拌溶解,将盐溶液和沉淀剂以一定流速滴入沉淀槽中进行沉淀反应,控制沉淀槽pH为6.8~7.2之间,沉淀完全后室温静置老化6h后过滤,并用80L去离子水洗涤四次;
(2)制浆
将滤饼分散到120L去离子水中,剧烈搅拌打浆并依次加入12kg凹凸棒、10.0kgPEG4000和12.45kg硝化甘油,30℃搅拌打浆2h。
(3)喷雾干燥成型
将上述浆液通过Niro Bowen Nozzle Tower型号喷雾干燥装置成型,喷雾干燥压力为2.0MPa,入口温度150℃以下,出口温度约为120℃。并在400℃空气中焙烧3h,得到平均粒径120μm左右,中空结构的平均直径40μm的树莓形催化剂,记为WGS-3。催化剂化学组成按氧化物计,CuO含量为38wt%,ZnO含量为30重量%,Al2O3含量为20重量%,Fe2O3含量为12重量%。
实施例4
按照与实施例1相同的方法制备催化剂,所不同的是以2重量%的CeO2代替2重量%的Fe2O3,得到平均粒径120μm左右,中空结构的平均直径40μm的树莓形催化剂,所得催化剂记为WGS-4。催化剂化学组成按氧化物计,CuO含量为60重量%,ZnO含量为28重量%,Al2O3含量为10重量%,CeO2含量为2重量%。
实施例5
按照实施例1相同的方法制备催化剂,所不同的是不添加第二助剂,得到平均粒径110μm左右,中空结构的平均直径38μm的树莓形催化剂,所得催化剂记为WGS-5。催化剂化学组成按氧化物计,CuO含量为61.2重量%,ZnO含量为28.6重量%,Al2O3含量为10.2重量%。
实施例6
小型微通道反应器(通道横截面最小尺寸1000μm),小型反应器模块具有16条反应通道和36条冷却通道,反应通道长200mm,催化剂最大装量6mL。部分尺寸较大催化剂评价在直径为20mm的固定床微反应器内同条件评价,具体操作包括:取2.0mL上述催化剂,并用4.0mL的100μm石英砂稀释后装填入反应器的恒温区。先在常压条件下通10%(v/v)H2/N2混合气并以2℃/min升温至220℃还原2h;然后升压至1.5MPa,通入H2/CO/N2=77/15/8的原料气,同时按H2O/气=1/1的比例配入水蒸汽进行反应。利用在线色谱进行取样分析并计算反应转化率。
表1
通过上述实施例、对比例和表1的结果可见,本发明提供的微通道低温变换催化剂能够在高空速下高效实现CO转化,适用于微通道反应器,并在低温条件下具有较高的转化率和转化效率。同时,微通道反应器分别装填WGS-1和DB-1催化剂的床层压降为0.13MPa和0.25MPa,由此可以看出,采用具有树莓型结构的催化剂可以显著降低床层压降。
Claims (19)
1.一种铜基微通道低温变换催化剂,其特征在于,所述铜基微通道低温变换催化剂为表面具有一个大孔的中空微球,所述中空微球内部具有一个中空结构,所述大孔与所述中空结构贯通形成一端开口的空腔;
所述铜基微通道低温变换催化剂的粒径为20~300μm;
所述铜基微通道低温变换催化剂内部中空结构的直径为1~250μm;
所述铜基微通道低温变换催化剂包括活性组分、第一助剂,所述活性组分为CuO和ZnO;所述第一助剂为Al2O3和/或Cr2O3。
2.根据权利要求1所述的催化剂,其特征在于,所述铜基微通道低温变换催化剂的粒径为60~250μm;
所述铜基微通道低温变换催化剂内部中空结构的直径为30~150μm;
所述大孔的孔径为0.5~200μm。
3.根据权利要求1所述的催化剂,其特征在于,所述铜基微通道低温变换催化剂的球形度为0.50~0.99。
4.根据权利要求1所述的催化剂,其特征在于,所述的铜基微通道低温变换催化剂中各组分的质量百分比组成为:CuO 30%~75%,ZnO 15%~40%,Al2O3和/或Cr2O3 0.5~30%。
5.根据权利要求1-4任一所述的催化剂,其特征在于,所述铜基微通道低温变换催化剂包括任选的第二助剂,所述的第二助剂为选自Ti、Zr、La、Ce、K、Ca、Mg、W、P、Ni、Mo、V、Fe、Si、Pt、Mn、Sn、Ru、Re中至少一种元素的氧化物。
6.根据权利要求5所述的催化剂,其特征在于,所述的铜基微通道低温变换催化剂中各组分的质量百分比组成为:CuO 30%~75%,ZnO 15%~40%,Al2O3和/或Cr2O3 0.5~15%,第二助剂0~15%。
7.根据权利要求6所述的催化剂,其特征在于,所述的铜基微通道低温变换催化剂中各组分的质量百分比组成为:CuO 35%~65%,ZnO 20%~35%,Al2O3和/或Cr2O3 1~12%,第二助剂0~10%。
8.一种权利要求1-7任一铜基微通道低温变换催化剂的制备方法,该方法包括以下步骤:
(1)将活性组分CuO和ZnO以及第一助剂和任选的第二助剂的可溶性金属盐均匀分散到去离子水中,用沉淀剂进行沉淀,沉淀反应后浆液pH值在6.8~7.2之间,然后将沉淀反应后物料进行过滤、洗涤,得到催化剂前驱体;
(2)将步骤(1)得到的催化剂前驱体与分散剂、粘结剂、造孔剂和/或爆破剂混合制浆,得到胶体浆液;
(3)将步骤(2)得到的胶体浆液与表面活性剂混合乳化,然后经喷雾干燥成型并焙烧后,制得铜基微通道低温变换催化剂。
9.根据权利要求8所述的制备方法,其特征在于,步骤(1)中所述的活性组分CuO的可溶性金属盐选自氯化铜、硫酸铜、硝酸铜中的一种或几种,所述的活性组分ZnO的可溶性金属盐选自氯化锌、硫酸锌、硝酸锌中的一种或几种。
10.根据权利要求8所述的制备方法,其特征在于,步骤(1)中所述的沉淀剂选自氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、碳酸铵中的一种或几种。
11.根据权利要求8所述的制备方法,其特征在于,步骤(2)中所述的分散剂选自去离子水、醇类、酮类、酸类中的一种或几种,优选醇类选自甲醇、乙醇、丙醇中的一种或几种,优选酮类选自丙酮和/或丁酮,优选酸类选自甲酸、乙酸、丙酸中的一种或几种。
12.根据权利要求8所述的制备方法,其特征在于,步骤(2)中所述的粘结剂选自铝溶胶、硅溶胶、硅铝溶胶、酸化的拟薄水铝石、高岭土、凹凸棒粉、水泥、石膏中的一种或几种。
13.根据权利要求8所述的制备方法,其特征在于,步骤(2)中所述的造孔剂选自淀粉、合成纤维素、聚合醇、硝酸铵等中的一种或几种,优选的合成纤维素为选自羧甲基纤维素、甲基纤维素、乙基纤维素、羟基纤维脂肪醇、聚乙烯醚中的一种或几种;优选的聚合醇为聚乙二醇、聚丙醇、聚乙烯醇、聚丙烯醇PPG中的一种或几种。
14.根据权利要求8所述的制备方法,其特征在于,步骤(2)中所述的爆破剂选自苦味酸、三硝基甲苯、雷酸汞、硝化甘油、硝化棉、达纳炸药、叠氮化铅中的一种或几种。
15.根据权利要求8所述的制备方法,其特征在于,步骤(3)中所述的表面活性剂选自脂肪醇聚乙烯醚、脂肪醇酰胺及其衍生物、重均分子量为200-2000000的丙烯酸共聚物和顺丁烯酸共聚物中的一种或几种。
16.根据权利要求8所述的制备方法,其特征在于,步骤(2)所述的胶体浆液中催化剂前驱体中氧化物、粘结剂中氧化物、造孔剂和/或爆破剂的质量比为(50~80):(5~30):(2~10),优选为(65~75):(15~25):(3~5);
胶体浆液的固含量为25~60%,优选为35~45%;
步骤(3)中胶体浆液中催化剂前驱体的氧化物和表面活性剂的质量比为(50~80):(1~6),优选为(65~75):(2~4)。
17.根据权利要求8所述的制备方法,其特征在于,步骤(3)中喷雾干燥的雾化压力为0.1~3.5MPa;
所述的喷雾干燥的干燥初始温度为150~350℃,喷雾干燥的干燥终止温度为80~200℃;
步骤(3)中焙烧温度为250~500℃,优选为300~450℃;焙烧时间为1~6h,优选为2~4h。
18.一种微通道低温变换反应的方法,该方法包括在权利要求1~7中任意一项所述的铜基微通道低温变换催化剂存在下,在微通道反应器的反应通道内,在低温变换反应条件下,使CO和H2O接触进行变换反应。
19.根据权利要求18所述的方法,其特征在于,所述微通道反应器的反应通道至少有一个维度的尺寸小于1000μm;
低温变换反应条件为:以体积计,H2O/原料气的比值为2/1~1/2,反应温度160~300℃,压力0.1~3MPa,原料气干气空速为2000~20000h-1。
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