CN108722451B - 一种催化活性衰耗慢的低汞触媒的制备方法 - Google Patents
一种催化活性衰耗慢的低汞触媒的制备方法 Download PDFInfo
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- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明涉及一种催化活性衰耗慢的低汞触媒的制备方法,包括浸碱、活化、酸化和氯化汞一次吸附,所述浸碱,加入30%氢氧化钾溶液中浸渍10h,然后在转炉中干燥,加热到100℃,开启真空系统,真空度为0.06MPa,干燥;所述活化,炭化料与无水氢氧化钾的质量比为3:4,温度为385℃;本发明得到的催化活性衰耗慢的低汞触媒,表面规整,外观为黑色,无气泡,光泽性好,呈颗粒状,空隙发达;性能上,硬度为2H,比表面积3070㎡/g;耐水性好,在水中浸泡15‑25天后:无变化:光泽性好,零起粉、无脱落碎屑;具有优良的抗腐蚀性能,耐化学腐蚀性强,耐盐雾性试验的腐蚀率为0.08‑0.28%;使用4000小时后活性保持率为90.2%。
Description
技术领域
本发明涉及低汞触媒技术领域,涉及一种催化活性衰耗慢的低汞触媒的制备方法,具体涉及一种催化活性衰耗慢的低汞触媒的制备方法及其回收方法。
背景技术
随着科技的进步,人们越来越多的关注到能源浪费问题,要求日益提高,目前工业上的乙炔氢氯化反应,主要使用的是氯化汞负载量为12-15%的高汞催化剂,其对汞的用量占国内汞使用量的60%,并对环境和人类的健康造成严重的危害。
现有的低汞触媒催化剂,存在的不足:催化活性衰耗快,耐化学腐蚀性、耐盐雾性弱,使用一段时间后载体容易起粉,使用寿命相对短,消耗往往较大,这在一定程度上限制了低汞触媒的应用空间。因此,急需改变现有低汞触媒,改进性能,以适应产业发展的需求。
发明内容
为了解决背景技术中存在的技术问题,本发明提供一种催化活性衰耗慢的低汞触媒的制备方法及其回收方法,可以实现以下发明目的:
本发明的一种催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒催化剂表面规整,外观为黑色,无气泡,光泽性好,呈颗粒状,空隙发达;性能上,碘吸附值、比表面积、堆比重、机械强度等性能指标都得到提高,具有优良的抗腐蚀性能,耐化学腐蚀性强,耐盐雾性试验的腐蚀率为0.08-0.28%;使用4000小时后活性保持率为90.2%。
为解决上述技术问题,采用以下技术方案:
一种催化活性衰耗慢的低汞触媒的制备方法,其特征在于,包括浸碱、活化、酸化和氯化汞一次吸附。
作为本发明优选的技术方案,所述浸碱,加入30%氢氧化钾溶液中浸渍10h,然后在转炉中干燥,加热到100℃,开启真空系统,真空度为0.06MPa,干燥。
作为本发明优选的技术方案,所述活化,炭化料与无水氢氧化钾的质量比为3:4,温度为385℃。
作为本发明优选的技术方案,所述氯化汞一次吸附,压力为0.5MPa,温度为550℃,质量空速为7.5h-1。
作为本发明优选的技术方案,还包括浸辅助液,所述浸辅助液,包括微波-超声波处理,微波频率320MHz,超声波频率为125KHz,微波-超声波处理时间为15min。
作为本发明优选的技术方案,所述酸化,用酸液浸泡6小时,酸液与碱化后的炭化料中固定碳的的质量比为3:1。
作为本发明优选的技术方案,所述的酸液,为磷酸、硫酸和硼酸,质量比例为17:5:1。
作为本发明优选的技术方案,还包括喷雾,所述喷雾,抽真空处理至72KPa,喷雾3.5%的吡咯。
本发明采用以上技术方案,与现有技术相比,具有以下优点:
本发明的一种催化活性衰耗慢的低汞触媒的制备方法形成的产品外观上表面平整,外观为黑色,光泽性好,空隙发达;催化活性持久,安全环保;具体如下:
(1)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,碘吸附值1000mg/g;
(2)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,硬度为2H;
(3)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,比表面积3070㎡/g;
(4)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,堆比重478g/L;
(5)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,pH值6.5-7;
(6)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,耐水性好,在水中浸泡15-25天后:无变化:光泽性好,零起粉、无脱落碎屑;
(7)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,具有优良的抗腐蚀性能,耐化学腐蚀性强,耐盐雾性试验的腐蚀率为0.08-0.28%;
(8)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,25℃氯化汞损失率为0.1%;
(9)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,催化剂使用4000小时后的活性保持率为90.2%。
具体实施方式
实施例1一种催化活性衰耗慢的低汞触媒的制备方法
本发明的一种催化活性衰耗慢的低汞触媒的制备方法,主要包括以下步骤:
(1)载体原料的选择
选择优质核桃壳为原料,所述核桃壳,为当年新鲜核桃壳,去掉外层绿色果皮,长径为4-5cm,短径为3-4cm,含水率为10-15%;
(2)浸碱
将上述新鲜核桃壳,加入30%氢氧化钾溶液中浸渍10h,然后在转炉中干燥,加热到100℃,开启真空系统,真空度为0.06MPa,干燥;
(3)炭化
将经过碱化的核桃壳,在N2流量为20ml/min的保护下,进行炭化,炭化温度起始温度为310℃,以3℃/min的升温速率,升至420℃,炭化2.5小时,得炭化料;
所述炭化料,灰分为7-8%,含水率低于3%;
(4)活化
将炭化料以熔融的无水氢氧化钾处理,炭化料与无水氢氧化钾的质量比为3:4,温度为385℃;
(5)酸化
用酸液浸泡,所述的酸液,为磷酸、硫酸和硼酸,质量比例为17:5:1,酸液与碱化后的炭化料中固定碳的的质量比为3:1,浸泡6小时,水洗,干燥;
(6)水洗
用清水冲洗掉酸液,至pH值为6.5-7之间,干燥,过滤掉滤渣,得活性炭载体。
所述的活性炭载体,碘吸附值1000mg/g,比表面积3070㎡/g,堆比重478g/L,pH值6.5-7,灰分3%,水份≤3%,机械强度≥99%。
(7)氯化汞一次吸附
将上述步骤制备得到的活性炭载体用氮气吹扫系统,排出氧气、二氧化碳等杂质气体,将高纯度氯化汞进行加热气化,控制压力为0.5MPa,温度为550℃,质量空速为7.5h-1进行吸附;
(8)浸辅助液
吸附10min后,投入到辅助液中,将以上混合物进行微波-超声波处理,微波频率320MHz,超声波频率为125KHz,微波-超声波处理时间为15min;
辅助液的制备步骤如下:用盐酸和脱盐水配制pH=3的15%的盐酸溶液,加入适量协同促进剂,协同促进剂的质量含量为12%,协同促进剂包括:氯化锌、氯化锰、二氯四氨钯、吡咯、腐植酸钾,质量比例为:5:1:1:1:3;
(9)氯化汞二次吸附
将上述步骤制备得到的活性炭载体再次用氮气吹扫系统,排出氧气、二氧化碳等杂质气体,将高纯度氯化汞进行加热气化,控制压力为0.65MPa,温度为570℃,质量空速为7.5h-1进行吸附;
(10)喷雾
将活性炭载体转移至干燥机,抽真空处理至72KPa,向减压的干燥机内供入氮气,直到活性炭载体内的氧气完全被氮气置换,同时向上述活性炭载体表面缓慢喷雾3.5%的吡咯,接着排出干燥机内的氮气,在减压状态下利用红外线加热,波长为3μm、红外灯功率为1055W,风速为2-3m/s,温度为85℃,加热至恒重。
(11)包装
进行包装,即得。
对比例1:在实施例1的基础上,仅改变步骤(9),删除步骤(9):即浸辅助液之后没有进行氯化汞二次吸附,直接进行喷雾处理。
对比例2:在实施例1的基础上,仅改变步骤(10):即氯化汞二次吸附之后直接进行普通干燥至恒重。
对比例3:在实施例1的基础上,改变步骤(9)和步骤(10),删除步骤(9),即浸辅助液之后采用普通干燥方法至恒重。
本发明的一种催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒
表1:一种催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒的效果指标
备注:耐水性测试采用在水中浸泡15-25天,干燥后的指标,其中,无变化包括的指标为:光泽性好,零起粉、无脱落碎屑;催化剂使用4000、7000小时后的活性保持率数据为采用合成氯乙烯工业方法所收集数据。
由上表的的数据可以看出:
本发明的一种催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒催化剂表面规整,外观为黑色,无气泡,光泽性好,呈颗粒状,空隙发达;
性能上,碘吸附值、比表面积、堆比重、机械强度等性能指标都得到提高,具体如下:
(1)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,碘吸附值1000mg/g;
(2)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,硬度为2H;
(3)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,比表面积3070㎡/g;
(4)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,堆比重478g/L;
(5)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,pH值6.5-7;
(6)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,耐水性好,在水中浸泡15-25天后:无变化:光泽性好,零起粉、无脱落碎屑;
(7)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,具有优良的抗腐蚀性能,耐化学腐蚀性强,耐盐雾性试验的腐蚀率为0.08-0.28%;
(8)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,250℃下焙烧3小时,氯化汞损失率为0.1%;
(9)本发明的催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,催化剂使用4000小时后的活性保持率为90.2%。
以上述依据本发明的理想实施例为启示,通过上述的说明内容,相关工作人员完全可以在不偏离本项发明技术思想的范围内,进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容,必须要根据权利要求范围来确定其技术性范围。
Claims (1)
1.一种催化活性衰耗慢的低汞触媒的制备方法,其特征在于,主要包括以下步骤:
(1)载体原料的选择:选择优质核桃壳为原料,所述核桃壳,为当年新鲜核桃壳,去掉外层绿色果皮,长径为4-5cm,短径为3-4cm,含水率为10-15%;
(2)浸碱:将上述新鲜核桃壳,加入30%氢氧化钾溶液中浸渍10h,然后在转炉中干燥,加热到100℃,开启真空系统,真空度为0.06MPa,干燥;
(3)炭化:将经过碱化的核桃壳,在N2流量为20ml/min的保护下,进行炭化,炭化温度起始温度为310℃,以3℃/min的升温速率,升至420℃,炭化2.5小时,得炭化料;
所述炭化料,灰分为7-8%,含水率低于3%;
(4)活化:将炭化料以熔融的无水氢氧化钾处理,炭化料与无水氢氧化钾的质量比为3:4,温度为385℃;
(5)酸化:用酸液浸泡,所述的酸液,为磷酸、硫酸和硼酸,质量比例为17:5:1,酸液与碱化后的炭化料中固定碳的质量比为3:1,浸泡6小时,水洗,干燥;
(6)水洗:用清水冲洗掉酸液,至pH值为6.5-7之间,干燥,过滤掉滤渣,得活性炭载体;
所述的活性炭载体,碘吸附值1000mg/g,比表面积3070㎡/g,堆比重478g/L,pH值6.5-7,灰分3%,水份≤3%,机械强度≥99%;
(7)氯化汞一次吸附:将上述步骤制备得到的活性炭载体用氮气吹扫系统,排出氧气、二氧化碳杂质气体,将高纯度氯化汞进行加热气化,控制压力为0.5MPa,温度为550℃,质量空速为7.5h-1进行吸附;
(8)浸辅助液:吸附10min后,投入到辅助液中,将以上混合物进行微波-超声波处理,微波频率320MHz,超声波频率为125KHz,微波-超声波处理时间为15min;
辅助液的制备步骤如下:用盐酸和脱盐水配制pH=3的15%的盐酸溶液,加入适量协同促进剂,协同促进剂的质量含量为12%,协同促进剂包括:氯化锌、氯化锰、二氯四氨钯、吡咯、腐植酸钾,质量比例为:5:1:1:1:3;
(9)氯化汞二次吸附:将上述步骤制备得到的活性炭载体再次用氮气吹扫系统,排出氧气、二氧化碳杂质气体,将高纯度氯化汞进行加热气化,控制压力为0.65MPa,温度为570℃,质量空速为7.5h-1进行吸附;
(10)喷雾:将活性炭载体转移至干燥机,抽真空处理至72KPa,向减压的干燥机内供入氮气,直到活性炭载体内的氧气完全被氮气置换,同时向上述活性炭载体表面缓慢喷雾3.5%的吡咯,接着排出干燥机内的氮气,在减压状态下利用红外线加热,波长为3μm、红外灯功率为1055W,风速为2-3m/s,温度为85℃,加热至恒重;
采用所述催化活性衰耗慢的低汞触媒的制备方法得到的低汞触媒,碘吸附值1000mg/g,硬度为2H,比表面积3070㎡/g,堆比重478g/L,pH值6.5-7;耐水性好,在水中浸泡15-25天后:无变化:光泽性好,零起粉、无脱落碎屑;耐盐雾性试验的腐蚀率为0.08-0.28%;250℃下焙烧3小时,氯化汞损失率为0.1%;催化剂使用4000小时后的活性保持率为90.2%。
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