CN1326618C - 制备催化剂微球的方法 - Google Patents
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Abstract
本发明涉及一种制备粒径为20—2000微米的催化剂颗粒的方法，该方法包括搅拌至少两种干燥催化剂成分、在继续搅拌的同时在催化剂成分上喷雾液体粘合剂以及分离具有所需粒径并且包含各催化剂成分的所得催化剂颗粒的步骤。相比于制备这种颗粒的喷雾干燥传统方式，本发明方法能够从高固体含量的浆液形成小颗粒。因此，只需要蒸发较少量的液体，这使本发明方法的能量效率高。
Description
本发明涉及一种制备粒径为20-2000微米的催化剂组合物的方法。在说明书中，术语催化剂组合物还包括催化剂添加剂和吸附剂。
对于一些催化应用领域如流化床工艺，需要小催化剂颗粒。这样的颗粒一般通过喷雾干燥催化剂成分的混合物而制得。例如，流化床催化裂化(FCC)催化剂一般通过喷雾干燥沸石、粘土和二氧化硅和/或氧化铝的水浆液而制备。
喷雾干燥包括通过喷嘴(高压喷嘴或带有喷嘴的回转轮)将含有催化剂成分的浆液泵送到由热空气加热的室中。在该方法中，对浆液施加高剪切力，从而产生在加热室中迅速干燥的小滴。根据采用的喷嘴类型，所得催化剂颗粒的粒度分布取决于喷嘴压力或回转轮的转速，但是一般在30-90微米的范围内。
不利的是，只能对具有低固体含量(即低于大约45重量％的固体)并因而具有高液体含量的浆液进行喷雾干燥。具有较高固体含量的浆液或者太粘而不能泵送通过喷嘴或者在喷雾时不能得到合适的小滴。由于这种低固体含量的局限，需要大量的必须在干燥步骤中蒸发的液体。这是能量效率低的方法。
利用本发明方法解决了这个问题，该方法包括下列步骤：
a)搅拌至少两种干燥催化剂成分，
b)在继续搅拌的同时在催化剂成分上喷雾液体粘合剂，
c)分离具有所需粒径并包含各催化剂成分的所得催化剂颗粒，和
d)任选煅烧分离的催化剂颗粒。
本发明方法需要比喷雾干燥更少的液体。因此，在干燥步骤中需要蒸发更少的液体，这使该方法比喷雾干燥具有更高的能量效率。
本发明的方法需要至少两种单独的催化剂成分以形成催化剂颗粒。它不是如美国专利5286370和5001096所述的仅包括对现有催化剂颗粒进行表面涂布的方法。
合适的搅拌技术包括流化和高剪切混合。
通过在气体流(一般是空气)中流化各催化剂成分而进行流化工艺。将喷嘴置于以这种方式形成的流化床上方。通过这个喷嘴将液体粘合剂喷雾在各催化剂成分上。进行此方法的合适设备是流化床成粒机。气体的流速影响所得催化剂颗粒的尺寸。此气体流速优选是最小流化速度的1-10倍并最优选最小流化速度的1-5倍，其中最小流化速度定义为带动催化剂成分所需的最小气体流速。很明显该最小流速取决于催化剂成分的粒度：颗粒越大，需要的最小气体流速越高。制备FCC催化剂颗粒的催化剂成分一般具有至多大约10微米的粒度。气体的温度优选20-700℃，更优选50-200℃，最优选80-120℃。
高剪切混合在高剪切混合机中进行。在混合机中存在位于催化剂成分之上的喷嘴。通过这个喷嘴，液体粘合剂喷雾在催化剂成分上。优选的剪切速率为250-5000s-1，更优选250-2500s-1，进一步优选250-1000s-1，最优选500-1000s-1。在高剪切混合过程中的温度优选低于100℃，更优选低于50℃，最优选室温。
可用于本发明方法中的催化剂成分包括固体酸、氧化铝、(氢)氧化铁、(变)高岭石、膨润土、(煅烧)阴离子粘土、滑石粉、海泡石、绿土、蒙脱土及其混合物。合适的固体酸包括沸石如β沸石、MCM-22、MCM-36、丝光沸石、八面沸石如X-沸石和Y-沸石(包括H-Y-沸石、RE-Y-沸石和USY-沸石)、pentasil类型的沸石如ZSM-5、非沸石固体酸如二氧化硅-氧化铝、硫酸化氧化物如锆、钛或锡的硫酸化氧化物、锆、钼、钨等的硫酸化混合氧化物以及氯化的氧化铝。合适的氧化铝包括勃姆石、假勃姆石、过渡氧化铝如α-、δ-、γ-、η-、θ-和χ-氧化铝、三水合铝如三水铝石或铝土矿浓缩物(BOC)和快速煅烧的三水合铝。合适阴离子粘土(还称为类水滑石材料或层状双氢氧化物)的例子有Mg-Al阴离子粘土、Fe-Al阴离子粘土、Zn-Al阴离子粘土、Fe-Fe阴离子粘土等。优选至少一种催化剂成分是氧化铝、粘土或沸石。催化剂颗粒是FCC催化剂颗粒或FCC催化剂添加剂颗粒。
在开始本发明方法之前使用的催化剂成分必须是干燥的。在本说明书中术语“干燥”表示这些组分不超过90％的孔体积中填充有水。
大多数用于FCC应用的氧化铝通过沉淀方法制得。这些方法通常包括沉淀、结晶和脱水的顺序步骤。获得用于本发明方法的足够干燥的氧化铝的合适脱水技术采用高压过滤器。通常通过结晶、洗涤/脱水、用NH4和稀土金属(RE)进行离子交换、干燥、煅烧和研磨来制备沸石。
合适的液体粘合剂包括水、酸性水溶液或含有硅和/或铝的水溶液或含水悬浮液。优选地，液体粘合剂选自水、酸性水溶液、含硅溶液或悬浮液、包含水合氯化铝和/或水合硝酸铝的悬浮液及其混合物。术语“液体粘合剂”指帮助各催化剂成分粘合以形成催化剂颗粒的液体、溶液或悬浮液。液体粘合剂可以在步骤b)或在随后的步骤如另外的煅烧步骤中引发这种粘合。粘合是否在步骤b)中发生取决于采用的液体粘合剂和催化剂成分。
所需的液体粘合剂取决于所需的基料。例如：如果阴离子粘土是所需的基料，那么水可用作液体粘合剂并且煅烧的阴离子粘土作为催化剂成分之一。所述的水会使煅烧的阴离子粘土再水化，形成阴离子粘土基料。如果氧化铝是所需的基料，酸化的水可用作液体粘合剂并且可胶溶的氧化铝如假勃姆石作为催化剂成分之一。另外的选择是，可以采用含有水合氯化铝(ACH)或水合硝酸铝(ANH)的悬浮液作为液体粘合剂并且形成氧化铝基料，不论使用何种类型的催化剂成分。因此，如果一种催化剂成分是氧化铝并且将ACH或ANH用作液体粘合剂，所得的催化剂会包含两种类型的氧化铝。获得带有氧化铝基料的催化剂颗粒的另一种选择是使用水作为液体粘合剂并且采用快速煅烧的三水合铝作为催化剂成分之一。尽管后一结合方式不在步骤b)中产生颗粒的粘合，但是确实在另外的煅烧步骤(步骤d)中发生粘合。如果二氧化硅是所需的基料，含有硅化合物的溶液或悬浮液可用作液体粘合剂，不论采用何种类型的催化剂成分。合适的硅化合物的实例有硅溶胶、(偏)硅酸钠和沉淀的二氧化硅。
也可以采用多种液体粘合剂，这些粘合剂可顺序喷雾在催化剂成分上。例如，可以采用含硅的溶液或溶胶，或含有水合氯化铝或水合硝酸铝的溶胶作为第一液体粘合剂，而酸化的水可用作第二液体粘合剂。
根据催化剂成分的干燥程度，可优选在喷雾液体粘合剂以前在催化剂成分上喷雾一些水。需要的水量应使催化剂成分大约90％的孔可填充水。
液体粘合剂优选以1-1.5倍于需要量除以停留时间的速率喷雾在催化剂成分上。所述停留时间一般为大约1-30分钟。小滴尺寸优选为1-20μm。
持续搅拌直到获得正确的粒度。在流化床成粒的情况下，选择气体的流速使其只能带动小于所需尺寸的颗粒。因此，一旦颗粒具有所需尺寸，它们就会落下。
本发明方法获得的颗粒具有的尺寸为大约20-2000微米，优选20-600微米，更优选20-200微米，最优选30-100微米。对于流化床催化裂化(FCC)应用，优选30-100微米的粒度。
如果需要，对所得颗粒进行干燥和/或煅烧。如果采用的液体粘合剂在搅拌步骤b)中不产生粘合，则可能需要煅烧步骤d)以引发这种粘合。干燥处理包括优选在100-200℃的温度下加热形成的颗粒。优选在300-1200℃下，更优选在300-800℃下，最优选在300-600℃下煅烧15分钟-24小时，优选1-12小时，最优选2-6小时。
利用本发明方法得到的颗粒可用于各种目的，如作为催化剂、吸附剂等。合适的催化应用包括气体到液体的工艺(如费-脱法)催化、E-床和H-油工艺催化、重整催化、异构化催化、烷基化催化和汽车尾气催化。
实施例
实施例1
这项实施例描述了具有下列组成(基于干燥物质)的FCC催化剂颗粒的制备：15重量％氧化铝、20重量％USY、4重量％二氧化硅、61重量％高岭石。
将大约200g的干燥假勃姆石、干燥高岭石和干燥沸石的混合物填充到流化床成粒机中。将混合物流化，然后以4.8g/min的速率在流化床的顶端喷雾35g硅溶胶。同时，气体的入口温度设定为70℃。然后以4.8g/min的速率在流化床的顶端通过相同的喷嘴喷雾10％的硝酸溶液。在加入100g硝酸溶液后，停止加入液体并将气体入口温度设定为135℃以干燥材料。所得的FCC颗粒具有76微米的平均直径(d50)。SEM分析表明所得颗粒具有各成分的均匀分布。
实施例2
这项实施例描述了具有下列组成(基于干燥物质)的FCC催化剂颗粒的制备：15重量％假勃姆石、20重量％USY、10重量％源于水合氯化铝(ACH)的氧化铝、55重量％高岭石。
将大约200g的干燥假勃姆石、干燥高岭石和干燥沸石的混合物填充到流化床成粒机中。将混合物流化，然后以4.8g/min的速率在流化床的顶端喷雾90g水合氯化铝悬浮液。同时，气体的入口温度设定为70℃。然后以4.8g/min的速率在流化床的顶端通过相同的喷嘴喷雾10％的硝酸溶液。在加入100g硝酸溶液后，停止加入液体并将气体入口温度设定为135℃以干燥材料。所得的FCC颗粒具有78微米的平均直径(d50)。SEM分析表明所得颗粒具有各成分的均匀分布。
实施例3
这项实施例描述了具有下列组成(基于干燥物质)的FCC催化剂颗粒的制备：25重量％假勃姆石、25重量％USY、35重量％高岭石和15重量％Mg-Al阴离子粘土。
首先煅烧Mg-Al阴离子粘土，然后在水热条件(即130℃和自生压力)下在水悬浮液中再水化。将大约200g的干燥假勃姆石、高岭石、阴离子粘土和沸石的混合物填充到流化床成粒机中。将混合物流化，然后以4.8g/min的速率在流化床的顶端通过相同的喷嘴喷雾10％硝酸溶液。同时，气体的入口温度设定为70℃。在加入100g硝酸溶液后，停止加入液体并将气体入口温度设定为135℃以干燥材料。所得的FCC颗粒具有75微米的平均直径(d50)。SEM分析表明所得颗粒具有各成分的均匀分布。
Claims (7)
1.一种制备粒径为20-2000微米的催化剂颗粒的方法，该方法包括下列步骤：
a)搅拌至少两种干燥催化剂成分，
b)在继续搅拌的同时在催化剂成分上喷雾液体粘合剂，
c)分离具有所需粒径并包含各催化剂成分的所得催化剂颗粒，和
d)任选煅烧分离的催化剂颗粒。
2.如权利要求1所述的方法，其中通过高剪切混合进行搅拌。
3.如权利要求1所述的方法，其中通过流化进行搅拌。
4.如权利要求1-3中任一项所述的方法，其中至少一种催化剂成分是氧化铝、粘土或沸石。
5.如权利要求4所述的方法，其中催化剂颗粒是FCC催化剂颗粒或FCC催化剂添加剂颗粒。
6.如权利要求1-3中任一项所述的方法，其中液体粘合剂选自水、酸性水溶液、含硅溶液或悬浮液、包含水合氯化铝和/或水合硝酸铝的悬浮液及其混合物。
7.如权利要求2所述的方法，其中在高剪切混合过程中作用在催化剂成分上的剪切速率为250-1000s-1。
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| JP4859774B2 (ja) * | 2007-07-17 | 2012-01-25 | 日揮触媒化成株式会社 | 流動接触分解触媒の製造方法 |
| US10064422B2 (en) | 2013-04-05 | 2018-09-04 | D'alcante B.V. | Process for reducing the alcohol and/or sugar content of a beverage |
| CN103736489B (zh) * | 2013-12-24 | 2015-10-28 | 天津众智科技有限公司 | 丁烯氧化脱氢制备丁二烯流化床催化剂的制备方法 |
| GB201504072D0 (en) * | 2015-03-10 | 2015-04-22 | Metalysis Ltd | Method of producing metal |
| US20210015127A1 (en) | 2017-11-28 | 2021-01-21 | Blue Tree Technologies Ltd. | Methods and systems for producing low sugar beverages |
| WO2020012351A1 (en) * | 2018-07-10 | 2020-01-16 | Reliance Industries Limited | Regenerative adsorbent composition for removal of chlorides from hydrocarbon and a process for its preparation |
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| US5001096A (en) * | 1987-12-28 | 1991-03-19 | Mobil Oil Corporation | Metal passivating agents |
| US5286370A (en) * | 1987-12-28 | 1994-02-15 | Mobil Oil Corporation | Catalytic cracking using a layered cracking catalyst |
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| US4946654A (en) * | 1984-04-07 | 1990-08-07 | Bayer Aktiengesellschaft | Process for preparing granulates |
| US5001096A (en) * | 1987-12-28 | 1991-03-19 | Mobil Oil Corporation | Metal passivating agents |
| US5286370A (en) * | 1987-12-28 | 1994-02-15 | Mobil Oil Corporation | Catalytic cracking using a layered cracking catalyst |
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| TW200502039A (en) | 2005-01-16 |
| AU2003294844A1 (en) | 2004-07-09 |
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