CN109201064A - 一种活性态强度高于压片强度的催化剂制备方法 - Google Patents
一种活性态强度高于压片强度的催化剂制备方法 Download PDFInfo
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Abstract
本发明属催化剂制造技术领域,提供了活性态强度高于压片强度的催化剂制备方法。本发明采用共沉淀法制备催化剂,将可溶性金属盐溶液先后与硅交联剂、碱性溶液沉淀剂相混合,共沉淀出不溶性的金属盐混合物,经老化、洗涤、过滤得到催化剂母体,再经干燥、焙烧形成金属氧化物混合物,最后压片成型得到催化剂成品,催化剂活性态强度高于压片强度。
Description
技术领域
本发明属于催化剂制备技术领域,具体涉及一种活性态强度高于压片强度的催化剂制备方法。
背景技术
共沉淀法生产的催化剂,其活性组分含量高,应用广泛,主要用于气、固两相反应中,一些气—液—固多相反应中也有应用,如防老剂IPPD、6PPD、液相丁辛醇等气、液、固多相反应中。
由于结构的原因,共沉淀法所生产的催化剂,在用于上述气—液—固多相反应中,有一个突出的问题,在生产过程中,液体的浸泡以及液相物料在催化剂床层汽化张力,使得催化剂容易粉化。粉化后的催化剂灰分会混入液相产品中,影响产品质量,催化剂也因粉化而造成大量流失,甚至塌床,极大地缩短了催化剂的使用寿命。
催化剂的结构强度好坏,一般可以通过考察其用前、用后强度,根据使用后强度下降比例来评价,可以用“强度下降率”来表示。催化剂的强度变化主要有三个节点,第一,压片时的控制强度,即用前强度;第二,活化后经历物相变化,结构上发生本质改变后的强度,即活性态强度;第三,催化剂钝化卸出后的强度,即用后强度。
试验发现,6PPD生产中所使用的催化剂,检验中用前、用后强度都很好的情况下生产中依然会出现粉化,可见催化剂压片强度和用后的强度都不能客观反映催化剂在使用过程中的强度。催化剂使用中的强度,应该是活性态强度,活性态强度能客观评价催化剂的使用寿命。为准确说明催化剂活性态强度,该发明对活性态强度进行了定义:以催化剂活化后或活性检测后,不经钝化,在溶剂保护下测得的强度,为活性态强度。并依据该定义测定、计算活性态强度,进而得出活性态强度下降率。
众所周知催化剂的机械强度从压片强度,到活性态强度或用后强度是逐步下降的,也就是催化剂的机械寿命。一般共沉淀法制备的催化剂活性态强度降在气固相反应中约为30%~60%,气液固相反应中约为70%~80%,活性态强度降超过80%就有粉化的危险。
发明内容
本发明所要解决的技术问题是,用共沉淀法制备出一种活性态强度高于压片强度的催化剂,解决共沉淀法生产的催化剂在含液相环境中使用时易于粉化的问题,拓宽共沉淀法生产的催化剂应用领域。
本发明方法的主要技术方案:采用共沉淀法制备催化剂,其特征是在沉淀时加入结构助剂,改变晶体粒子间交联结构即交联剂,制备出活性态强度高于压片强度的催化剂,从而得到耐浸泡、耐湍流、耐压力波动的催化剂。
本发明采用共沉淀法制备催化剂,将可溶性金属盐溶液先后与硅交联剂、碱性溶液沉淀剂相混合,共沉淀出不溶性的金属盐混合物,经老化、洗涤、过滤得到催化剂母体,再经干燥、焙烧形成金属氧化物混合物,最后压片成型得到催化剂成品。
本发明方法制备的催化剂还原后活性态强度高于压片强度,用后强度也高于压片强度,也就是催化剂用后比用前还结实。
所述的可溶性金属盐为硝酸盐;沉淀温度10℃~70℃,沉淀过程的pH值为2.0~7.5,沉淀后进行热处理的温度控制在60~380℃。催化剂可以是柱状或其他适宜的形状。
可溶性金属盐的共沉淀过程是:将金属盐溶液配成一定浓度的工作盐溶液,溶液浓度为0.2 mol/L ~1.8 mol/L,最好是0.2 mol/L ~1.0 mol/L;硅交联剂浓度为0.2 mol/L~1.0 mol/L;碱配成一定浓度的沉淀剂溶液,溶液的浓度为0.5 mol/L ~2.2 mol/L,最好为0.9 mol/L ~1.5 mol/L;沉淀温度为10℃~70℃,最好为30℃~70℃;金属盐溶液在加热保温条件下分别与硅交联剂、碱溶液混合并且搅拌,生成沉淀物后,去除上层清液得到沉淀物,经洗涤、干燥得到催化剂母体。
上述沉淀的混合过程是在沉淀反应温度下将沉淀剂加入到工作盐溶液中,或将工作盐溶液加入到沉淀剂中,也可同时将一定温度的沉淀剂和工作盐并流混合并搅拌,在共沉淀前、过程中或沉淀后,加入硅交联剂,利用硅氧化学键的特性,在催化剂还原过程中与生成的还原水作用,形成更为稳固的硅氧键,改变晶体粒子间交联结构,得到意想不到的活性态强度高于压片强度的催化剂产品。
所述的硅交联剂最好是水玻璃,水玻璃的模数为2.2~3.7,能确切地获得活性态强度高于压片强度的催化剂,且不损害催化剂的活性、选择性。
上述沉淀得到的滤饼经干燥、焙烧得到氧化物的混合物,再与一定量的成型助剂混合经压片得到催化剂成品。
本发明所制备的催化剂活性组份初始为氧化态,使用前需还原,还原介质可以是氢,一氧化碳,异丙醇,甲醇,最好是采用异丙醇浸泡下通氢进行还原。
本发明方法制备的催化剂经过活化后,其强度高于压片强度,不易粉化,寿命长,将其用于6PPD生产中,能够将使用诱导期大大缩短,并且初始6PPD浓度高,产品质量有所提高。
具体实施方式
下面通过实施例进一步说明本发明。
本发明所公开的一种活性态强度高于压片强度的催化剂制备方法,广泛适用于共沉淀法制备催化剂,在此仅以铜-锌-铝系催化剂为例进行实例说明,方便比较说明。
比较例1
以中国专利200610161327.2的方法制备铜-锌-铝系催化剂。将206gCu(NO3)2、250gZn(NO3)2和24gAl2(NO3)3配成2L混合溶液,将225g乙二酸配成2L溶液,分别将两种溶液置于高位槽,同时加热到50℃。在保温和搅拌条件下,将两者同时加入到低位槽,终点PH值为4.2,然后在搅拌条件下老化0.3h,过滤,滤饼在110℃下干燥8h,在400℃下焙烧4h,然后加入适量石墨混合均匀后压片成型,即得催化剂。制得的催化剂中铜锌摩尔比为0.8∶1,并且铝铜摩尔比为0.10,比表面积为51.32m2/g,孔容积为0.11ml/g。
比较例2
以中国专利GK85100599的方法制备铜-锌-铝系催化剂。将167.3g硝酸铜、194.3g硝酸锌和39.4g硝酸铝溶解在1.8L去离子水中形成混合盐溶液,加热到80℃,将碳酸钠130g溶解于3L去离子水中,加热到80℃。在沉淀槽中加入1L去离子水并加热到80℃,边搅拌边加入上述盐溶液,控制沉淀PH值为7.5~7.8,保持温度为80℃。
沉淀完成后,继续搅拌10分钟,滤去清液,然后用去离子水洗涤2h,过滤后的滤饼在110℃下干燥8h,在400℃下焙烧4h,然后加入适量石墨混合均匀后压片成型,即得所述铜-锌-铝催化剂。该催化剂的比表面积为76.47m2/g,孔容积为0.18ml/g。
实施例1
将370gCu(NO3)2、410gZn(NO3)2和110gAl2(NO3)3.9H2O配成3L混合溶液,将400g碳酸钠配成2L溶液,分别将两种溶液置于高位槽,同时加热到60℃。向盐溶液中加入90g 模数为3.7的水玻璃,将盐溶液放入低位槽中,在保温和搅拌条件下,将碱溶液加入到盐溶液中,终点PH值为6.8,然后在搅拌条件下老化0.3h,过滤,滤饼在110℃下干燥8h,在350℃下焙烧2h,然后加入适量石墨混合均匀后压片成型,即得催化剂。制得的催化剂比表面积为44.25m2/g,孔容积为0.11ml/g。
实施例2
将300gCu(NO3)2、410gZn(NO3)2和100gAl2(NO3)3.9H2O配成3L混合溶液,将480g碳酸钠配成2L溶液,分别将两种溶液置于高位槽,同时加热到55℃。向盐溶液中加入100g模数为2.2的水玻璃,将盐溶液放入低位槽中,在保温和搅拌条件下,将碱溶液加入到盐溶液中,终点PH值为7.2,然后在搅拌条件下老化0.3h,过滤,滤饼在80℃下干燥8h,在320℃下焙烧2h,然后加入适量石墨混合均匀后压片成型,即得催化剂。制得的催化剂比表面积为52.36m2/g,孔容积为0.12ml/g。
实施例3
将320gCu(NO3)2、410gZn(NO3)2和120gAl2(NO3)3.9H2O配成3L混合溶液,将500g碳酸钠配成2L溶液,分别将两种溶液置于高位槽,同时加热到70℃。向盐溶液中加入110g 模数为2.5的水玻璃,将盐溶液放入低位槽中,在保温和搅拌条件下,将碱溶液加入到盐溶液中,终点PH值为7.5,然后在搅拌条件下老化0.3h,过滤,滤饼在90℃下干燥8h,在360℃下焙烧1h,然后加入适量石墨混合均匀后压片成型,即得催化剂。制得的催化剂比表面积为49.36m2/g,孔容积为0.13ml/g。
将实施例1、实施例2、实施例3、比较例1、比较例2所述的催化剂分别装入固定床反应器中。催化剂装量:100ml ,MIBK与RT培司的分子比为5.0,液空速0.15h-1,反应压力5MPa、反应温度170℃的条件下进行6PPD合成反应。
比较例1、比较例2所述的催化剂在该条件下100h内,6PPD含量均低于95%,未达到合格品要求,比较例1所述的催化剂在工业使用中,6PPD含量达到95%以上的时间为9天。比较例2所述的催化剂在工业使用中,6PPD含量达到95%以上的时间为15天以上。本发明所述制备方法得出的三个催化剂不合格品转化期缩短为零,6PPD起始含量高于96.5%。该制备方法能缩短催化剂的使用诱导期。
表1 实施例和比较例催化剂用前、用后、活性态强度对照
通过表1,我们可以看出,比较例2在实施例2所述的气—液—固三相反应中,活性态强度严重下降,很多催化剂颗粒强度为0N/cm,在试验中就已粉化,比较例1活性态强度能达到40.9N/cm以上,活性态强度下降率77.6%(该催化剂工业使用寿命能达到1年以上),而本发明所述的催化剂,实现了催化剂在气—液—固三相反应中活性态强度,以及用后强度都高于用前压片强度的突破。取得了意想不到的有益效果,具有突出的实质性特点和显著的进步。
Claims (10)
1.一种活性态强度高于压片强度的催化剂制备方法,其特征是:在共沉淀法进行催化剂制备的过程中加入硅交联剂,具体方法是将可溶性金属盐溶液先后与硅交联剂、碱性沉淀剂溶液相混合,共沉淀出不溶性的金属盐混合物,经老化、洗涤、过滤得到催化剂母体,再经干燥、焙烧形成金属氧化物混合物,最后压片成型得到催化剂成品。
2.如权利要求1所述活性态强度高于压片强度的催化剂制备方法,其特征在于所述方法制备的催化剂用后强度高于压片强度。
3.如权利要求1所述活性态强度高于压片强度的催化剂制备方法,其特征在于所述硅交联剂为水玻璃,模数为2.2~3.7。
4.如权利要求1所述活性态强度高于压片强度的催化剂制备方法,其特征在于所述硅交联剂浓度为0.2mol/L~1.0mol/L。
5.如权利要求1所述活性态强度高于压片强度的催化剂制备方法,其特征在于所述可溶性金属盐为硝酸盐混合物,总盐浓度为0.2mol/L ~1.8mol/L。
6.如权利要求5所述活性态强度高于压片强度的催化剂制备方法,其特征在于所述可溶性金属盐为硝酸盐混合物,总盐浓度为0.2 mol/L ~1.0 mol/L。
7.如权利要求1所述活性态强度高于压片强度的催化剂制备方法,其特征在于所述碱性沉淀剂溶液,浓度为0.5mol/L ~2.2mol/L。
8.如权利要求7所述活性态强度高于压片强度的催化剂制备方法,其特征在于所述碱性沉淀剂溶液,浓度为0.9 mol/L ~1.5 mol/L。
9.如权利要求1所述活性态强度高于压片强度的催化剂制备方法,其特征在于所述方法制备的催化剂活性组份初始为氧化态,使用前需还原,还原介质包括氢,一氧化碳,异丙醇,甲醇。
10.如权利要求1所述活性态强度高于压片强度的催化剂制备方法,其特征在于所述方法制备的催化剂用于6PPD生产。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5932949A (ja) * | 1982-08-13 | 1984-02-22 | Mitsubishi Gas Chem Co Inc | メタノ−ル合成用触媒 |
CN101204658A (zh) * | 2006-12-21 | 2008-06-25 | 南化集团研究院 | 缩合还原烷基化催化剂及其制备方法和用途 |
CN102247866A (zh) * | 2011-07-26 | 2011-11-23 | 烟台大学 | 一种用于环己醇脱氢制备环己酮的催化剂及其制备方法 |
CN102626631A (zh) * | 2012-03-20 | 2012-08-08 | 中国石油化工股份有限公司 | 一种对苯二胺类防老剂合成催化剂及其制备方法 |
CN106268827A (zh) * | 2015-06-08 | 2017-01-04 | 中国石油化工股份有限公司 | 一种用于辛烯醛气相加氢制2-乙基己醇的催化剂及制备方法 |
-
2017
- 2017-06-29 CN CN201710514528.4A patent/CN109201064A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5932949A (ja) * | 1982-08-13 | 1984-02-22 | Mitsubishi Gas Chem Co Inc | メタノ−ル合成用触媒 |
CN101204658A (zh) * | 2006-12-21 | 2008-06-25 | 南化集团研究院 | 缩合还原烷基化催化剂及其制备方法和用途 |
CN102247866A (zh) * | 2011-07-26 | 2011-11-23 | 烟台大学 | 一种用于环己醇脱氢制备环己酮的催化剂及其制备方法 |
CN102626631A (zh) * | 2012-03-20 | 2012-08-08 | 中国石油化工股份有限公司 | 一种对苯二胺类防老剂合成催化剂及其制备方法 |
CN106268827A (zh) * | 2015-06-08 | 2017-01-04 | 中国石油化工股份有限公司 | 一种用于辛烯醛气相加氢制2-乙基己醇的催化剂及制备方法 |
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