CN1048196C - 一氧化碳耐硫变换催化剂的再生方法 - Google Patents
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- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
一种钴钼系一氧化碳耐硫变换催化剂的再生方法,将失活后的废催化剂作为载体,以可溶性钴盐,钼酸铵和碱金属可溶性盐,在氨水溶液或水溶液中进行分浸或组成混合溶液共浸,然后烘干,制得产品,再生后的催化剂强度好,活性高,同时减少了催化剂制备工序,可降低生产成本,减少废催化剂带来的环境污染,再生后的催化剂可满足工业生产的需要。
Description
本发明涉及一种一氧化碳耐硫变换催化剂的再生方法。具体的说是涉及一种钴-钼系一氧化碳耐硫变换催化剂的再生方法。
目前,中、小合成氨厂使用的一氧化碳耐硫变换催化剂的失效,多是因为催化剂活性下降所致,而催化剂强度不是催化剂失效的主要原因。由于耐硫变换催化剂价格较昂贵,加之失效的催化剂大多作为垃圾处理掉,造成环境的污染,因此,很有必要研制出一种耐硫变换催化剂的再生方法。
国外氨厂多以大型合成氨厂为主,对耐硫变换催化剂活性要求比较严格,对废的一氧化碳耐硫变换催化剂的处理,一般是回收其中的钴、钼以减少污染为目的(美国专利US5066469,US5013533),而我国有很多中、小合成氨厂,相比之下对一氧化碳耐硫变换催化剂性能要求不很苛刻,目前国内对该催化剂的再生方法报导不多,如杂志《河南化工》,1992年第12期的《EB-1型低变触媒钝化降温初探》一文中公开了一种触媒回收使用方法,是把低变炉内的催化剂先用半水煤气降温,将低变炉御至常压,再用惰性气(CO+H2+O2<6%)置换低变炉,然后再通入空气钝化触媒后御出,筛除其中的粉尘,再装炉使用,此方法只能降低变换炉阻力,使其恢复正常运行,并不能增加催化剂的活性,催化剂的活性只能保持原有水平,并且操作比较麻烦。杂志《氮肥设计》1992年第1期的《失活性EB-1型触媒的复活》一文中公开的方法是对使用一定时间后失活性的触媒,通过筛选,除去炉内被氧化的触媒,保留还能继续使用的触媒,按坏触媒损失量增补新触媒,然后将新旧触媒在原变换炉内硫化后使用。此法只能对失硫而失活的催化剂有一定复活作用,不能普遍用于失活催化剂的再生。
本发明的目的是提供一种新的催化剂再生方法,使失活的一氧化碳硫变换催化剂通过重新浸渍活性组分而恢复其活性,即可延长催化剂的使用寿命,又可降低生产成本,同时减少环境污染。
本发明是通过下述方法实现的,采用一种可溶性的钴盐[如Co(NO3)2·6H2O,Co(AC)2,Co(HCOO)2等],钼酸铵及选用一种碱金属(Na.K.Cs)的硝酸盐,碳酸盐,醋酸盐,在氨水溶液或水溶液中,对失活的废一氧化碳耐硫变换催化剂采用浸渍法进行分浸或组成混合溶液共浸,然后烘干即得产品。浸渍上的钴以CoO计为0.01%-2%,最好为0.1%-1%,钼以MoO3计为0.5%--5%,最好为1%-3%,碱金属含量以K2O计为1%-13%,最好为5%-10%,(均为重量百分比)浸渍后烘干。可在变换炉内原位进行再生,也可将催化剂卸出,在炉外部再生。如果变换炉内不衬保温材料,可在炉内原位再生,即把浸渍液用泵喷入炉内,进行催化剂浸渍,然后升温烘干,即得产品。催化剂的硫化方法采用常规的硫化方法即可,如用CS2进行硫化。
本发明方法制备的再生后催化剂的活性评价及对比实验,在常压微反评价装量上进行。催化剂装置0.3g,粒度40--60目,H2O/CO比为2.0,干气空速为10000h-1,H2S浓度0.3%(V/V),硫化时间为4小时,硫化温度为400℃,变换反应温度400℃,原料气组成为:CO46%,CO2 5%,CH4 0.3%,(均为体积比),活性以一氧化碳变换率表示。
本发明的效果:用本发明方法再生后的一氧化碳耐硫变换催化剂,其活性明显提高(见表1),由于采用废催化剂直接作为载体浸渍活性组份,减少了环境污染,复活后的催化剂可满足国内中,小合成氨厂的使用要求。
实施例1.
将工业废催化剂A,以硝酸钴和钼酸铵的氨水溶液进行等体积浸渍,浸渍上的钴以CoO计为1%(wt),钼以MoO3计为3%(wt),在110℃烘干3小时,制得催化剂,在常压微反评价装置上按上述方法进行活性评价,其活性及对比数据见表1。
表1.
催化剂 | 新鲜催化剂活性 | 再生前催化剂活性 | 再生后催化剂活性 |
ABC | 47.4/45.0 | 33.138.339.9 | 49.347.650.4 |
实施例2.
将工业废催化剂B,以硝酸钴溶液进行等体积浸渍,浸渍上的钴以CoO计为0.5%(wt),然后在130℃下烘干3小时,制得催化剂,其活性及对比数据见表1。
实施例3.
将工业废催化剂C,以钼酸铵和碳酸钾的氨水溶液进行等体积浸渍,浸渍上的钼以MoO3计为5%(wt),钾以K2O计为7%(wt),然后在130℃下烘干3小时,制得催化剂,其活性及对比数据见表1。
Claims (4)
1.一种钴钼系一氧化碳耐硫变换催化剂的再生方法,其特征是:用已失活的废钴钼系一氧化碳耐硫变换催化剂作伪载体,用硝酸钴、碳酸钴或醋酸钴的可溶性钴盐、钼酸铵和选自钠、钾或铯的一种碱金属的硝酸盐、碳酸盐或醋酸盐,在氨水溶液或水溶液中分浸或其混合溶液共浸,经烘干制得。
2.按权利要求1所述的方法,其特征是:浸渍上的钴以CoO计为0.01%~2%(wt),钼以MoO3计为0.5%~5%(wt),碱金属含量以K2O计为1%~13%(wt)。
3.按权利要求1或2所述的方法,其特征是浸渍上的钴,以CoO计为0.1%~1%(wt),钼以MoO3计为1%~3%(wt),碱金属以K2O计为5%~10%(wt)。
4.按权利要求3所述的方法,其特征是一氧化碳耐硫变换催化剂的再生,即可在变换炉内直接进行,也可把催化剂从变换炉内卸出,在炉外进行。
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CN1079035C (zh) * | 1998-09-26 | 2002-02-13 | 中国石化齐鲁石油化工公司 | 一种废旧co耐硫变换催化剂的再生方法 |
CN1072730C (zh) * | 1998-12-30 | 2001-10-10 | 王犇 | 钴-钼系废催化剂回收方法 |
CN100534613C (zh) * | 2005-04-13 | 2009-09-02 | 青岛联信化学有限公司 | 一种钴钼系一氧化碳耐硫变换催化剂及其制备方法 |
CN101992128B (zh) * | 2009-08-31 | 2012-09-05 | 中国石油化工股份有限公司 | 氨氧化流化床催化剂的再生方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0009887A1 (en) * | 1978-09-01 | 1980-04-16 | Exxon Research And Engineering Company | Process for regenerating spent hydrofining catalysts |
EP0017285A1 (fr) * | 1979-04-09 | 1980-10-15 | SOCIETE EUROPEENNE DES DERIVES DU MANGANESE en abrégé SEDEMA SOCIETE ANONYME | Procédé de récupération de métaux à partir de catalyseurs d'hydrodésulfuration d'hydrocarbures |
WO1982000961A1 (en) * | 1980-09-20 | 1982-04-01 | Toyoda Y | Method for reactivating catalyst |
US5013533A (en) * | 1990-03-01 | 1991-05-07 | Howard Robert A | Process for recovering valuable metals from spent catalysts |
US5066469A (en) * | 1985-06-26 | 1991-11-19 | Chevron Research And Technology Co. | Leaching cobalt from metal-containing particles |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0009887A1 (en) * | 1978-09-01 | 1980-04-16 | Exxon Research And Engineering Company | Process for regenerating spent hydrofining catalysts |
EP0017285A1 (fr) * | 1979-04-09 | 1980-10-15 | SOCIETE EUROPEENNE DES DERIVES DU MANGANESE en abrégé SEDEMA SOCIETE ANONYME | Procédé de récupération de métaux à partir de catalyseurs d'hydrodésulfuration d'hydrocarbures |
WO1982000961A1 (en) * | 1980-09-20 | 1982-04-01 | Toyoda Y | Method for reactivating catalyst |
US5066469A (en) * | 1985-06-26 | 1991-11-19 | Chevron Research And Technology Co. | Leaching cobalt from metal-containing particles |
US5013533A (en) * | 1990-03-01 | 1991-05-07 | Howard Robert A | Process for recovering valuable metals from spent catalysts |
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