CN115155659B - 一种用于焚化和热解处理固废危废的复合催化剂及其制备方法 - Google Patents
一种用于焚化和热解处理固废危废的复合催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于焚化和热解处理固废危废的复合催化剂及其制备方法。该复合催化剂由原料溶剂、催化剂、催化加强剂、催化辅剂、金属络合剂、有机酸和表面活性剂组成,各原料之间的质量配比为100~200:10~30:5~10:1~5:30~60:10~50:5~10。将表面活性剂、有机酸和溶剂混合均匀,得到混合溶液;向混合溶液中依次加入催化剂、催化加强剂、催化辅剂和金属络合剂混合均匀,得到复合催化剂原液。使用时,直接在固废危废中加入复合催化剂原液,或者将复合催化剂原液稀释后加入危废固废中使用。将本发明复合催化剂作用于焚烧或热解过程,能够达到节能减排、抗结焦、尾渣或飞灰提标、尾气提标等目的。
Description
一、技术领域:
本发明涉及一种复合催化剂及其制备方法,具体涉及一种用于焚化和热解处理固废危废的节能减排抗结焦复合催化剂及其制备方法。
二、背景技术:
焚化或热解的物料一般都是成分复杂且分布组成不均一;焚烧过程是一种强氧化过程,焚化过程同时又伴随着解聚和缩聚;而热解过程是一种在惰性或还原环境下的高温分解过程,此过程同时也伴随着缩聚和解聚反应;综合而言,这些反应过程复杂多变,而且同时存在并且不可控。
因为有些物料含水率高不易燃烧或是着火点过高,或是分解反应起点温度较高,各种反应化学过程反应缓慢;缩聚反应会产生焦质,焦质会使设备结垢或堵塞管道,影响设备换热或物料流动。
现有解决方案就是在物料中加入供氧剂(高锰酸钾、氯酸钾等),但此类方案只适用焚化工艺,而且添加氧化剂并不能减少缩聚反应的发生,不能减小焦块的产生;部分厂家为阻止结焦在物料中加入大量的砂子,加入砂子虽然可以减小设备结焦,但是会由于砂子与物料一同加热时砂子会吸收大量的热,导致能耗极高;所以研发一种适用广泛、功能多样的添加剂尤为重要。
选择添加有机盐金属盐类的复合催化剂去引导反应过程朝着预设方向进行,降低各种反应起始温度,减小尾气中污染物浓度、减小尾渣中污染物的含量、提高物料热失重率,利用反应过程产生或自身携带的水分提高反应环境中的自由基含量。
危废固废焚烧或热解是无害化处理的重要方法,由于固废危废成分的复杂、不均匀,焚烧或热解过程中发生了许多不同的化学反应,并产生很多气态、固体污染物;这些气态或固体污染物其产量和性质对环境都有不同程度的危害。同时危废固废焚化或热解过程中伴随着高能耗,较高的反应起始温度,飞灰、尾渣燃烧或热解不充分、重金属不达标、含油率不达标、热失重率不达标、炉体等主要设备结焦严重等问题。为此,本发明经过研究,提供一种利用有机金属盐类制作的复合催化剂,并将该复合催化剂应用于危废固废的焚化、热解领域,使其上述问题得以解决。
三、发明内容:
本发明要解决的技术问题是:根据现有用于焚烧或热解危废固废所用催化剂生产技术中存在不足,本发明提供一种用于焚化和热解处理固废危废的节能减排抗结焦复合催化剂及其制备方法,即本发明提供一种用于焚化和热解处理固废危废的复合催化剂及其制备方法。本发明利用各种有机金属盐类复配成复合催化剂,并将所得复合催化剂作用于焚烧或热解过程,从而达到节能减排、抗结焦、尾渣或飞灰提标、尾气提标等目的。
为了解决上述问题,本发明采取的技术方案是:
本发明提供一种用于焚化和热解处理固废危废的复合催化剂,所述复合催化剂由原料溶剂、催化剂、催化加强剂、催化辅剂、金属络合剂、有机酸和表面活性剂组成,各原料之间的质量配比为(100~200):(10~30):(5~10):(1~5):(30~60):(10~50):(5~10)。
根据上述用于焚化和热解处理固废危废的复合催化剂,所述溶剂为无水乙醇;
所述催化剂为2-乙基已酸镍、异辛酸钴、丙酸铁和异辛酸锰中的至少一种;
所述催化加强剂为柠檬酸稀土、钨酸铵和钼酸铵中的至少一种;
所述催化辅剂为醋酸铼、柠檬酸镁铵、异辛酸铜和异辛酸铈中的至少一种;
所述金属络合剂为柠檬酸三铵、EDTA铵盐或二者的混合物;
所述有机酸为醋酸、柠檬酸或二者的混合物;
所述表面活性剂为十二烷基苯磺酸钠、含酯基双子季铵盐阳离子表面活性剂或二者的混合物。
根据上述用于焚化和热解处理固废危废的复合催化剂,所述催化剂是由2-乙基已酸镍、异辛酸钴、丙酸铁和异辛酸锰按照质量比2~6:2:1:1混合配制而成;
所述催化加强剂是由柠檬酸稀土、钨酸铵和钼酸铵按照质量比1~4:1:1混合配制而成;
所述催化辅剂是由醋酸铼、柠檬酸镁铵、异辛酸铜和异辛酸铈按照质量比1:1:1:1混合配制成;
所述金属络合剂(铵盐脱酸剂)是由柠檬酸三铵和EDTA铵盐按照质量比1:1混合配制而成;
所述有机酸是由醋酸和柠檬酸按照质量比1:1混合配制成;
所述表面活性剂是由十二烷基苯磺酸钠、含酯基双子季铵盐阳离子表面活性剂按照质量比1:1混合配制而成。
根据上述用于焚化和热解处理固废危废的复合催化剂,所述复合催化剂的制备方法为:
首先将配制的表面活性剂、有机酸和溶剂进行混合,混合均匀后,得到混合溶液;然后向混合溶液中依次加入催化剂、催化加强剂、催化辅剂和金属络合剂进行混合,混合均匀后得到复合催化剂溶液即复合催化剂原液。
根据上述用于焚化和热解处理固废危废的复合催化剂,所述复合催化剂原液的添加量为固废危废质量的0.5~5.5%。
根据上述用于焚化和热解处理固废危废的复合催化剂,所得复合催化剂溶液使用时,需要加入水进行1000倍稀释,得到复合催化剂稀释液。
根据上述用于焚化和热解处理固废危废的复合催化剂,所得复合催化剂稀释液的添加量为固废危废质量的3.0~17.5%。
本发明技术方案中加入有机酸,有助于有机金属盐类溶于有机溶液,防止金属离子与水发生水解产生沉淀;加入的金属络合剂可以减缓金属离子在固废危废中的释放速度;加入的表面活性剂可以加速溶液在固废危废中扩散渗透的速度。一般分子量越大、胶质、沥青质含量越高添加量越大,反之越小。双组分表面活性剂的加入可以提高催化剂在不同性质、成分的物料中的分散效率。
由于焚化或热解过程中,单一种类物料可能只对一种或几种金属有较高的催化作用,所以采用复合配方。本发明原理主要参考、利用与石油炼制过程使用的金属催化剂催化机理,以镍铁钴锰基催化剂为基础,复合其它金属盐协同增强催化效果。
本发明的积极有益效果:
1、危废固废焚化、热解过程伴随着氧化、分解、解聚、缩聚等反应,加入本发明制备的金属复合催化剂,可大幅降低物料的活化能,提高分子活性,从而降低危废固废的着火点,降低分解的温度;提高大分子断链速度及深度,降低断链温度;提高加快解聚反应的发生及程度,减小聚合反应的发生及程度。使燃烧或放热反应更剧烈,从而提高炉内温度、降低其他能源消耗。
2、本发明制备的金属复合催化剂,能够加速二恶英等有毒、有害气体在炉体内分解,抑制二恶英等有害气体的生产;加快并利用焚化炉内O2,分解产生或物料自身携带的H2O等物质分解产生自由基,加速自由基与固废危废物料、及气体当中有害物质的氧化、分解过程;有机铵盐在热解或焚化过程中会分解产生氨气,氨气与热解或焚化过程产生的NOx等酸性气体中和产生氮气,以降低烟气、尾气中污染物NOx含量。
3、由于现有危废固废焚化或热解时会产生焦块,焦块粘结在设备表面产生焦层后影响设备热交换,堵塞设备管口、管道。本发明制备的金属复合催化剂由于可以抑制缩聚反应过程,加快焦体分解成短链物质并挥发,使已经产生的焦块变成蜂窝状,使已经产生的焦块变得松散且易碎,而且抑制新焦产生,从而减小设备结焦结垢的问题,提高设备维护周期,降低设备维护费用。
4、本发明金属复合催化剂可以和硫化氢、硫醇等过程产物产生金属硫化物,以起到固硫的作用,金属硫化物也可以持续起到催化作用。金属催化剂加入到碱性的固废、危废中可以中和其碱性并产生金属氢氧化物,金属氢氧化物受热分解产生金属氧化物也具有催化功能,金属催化剂的加入最终调节了碱性固废、危废的尾渣或飞灰的pH值。
综上所述,本发明制备的金属有机盐类复合催化剂具有节能减排的功效。
四、具体实施方式:
以下结合实施例进一步阐述本发明,但并不限制本发明技术方案保护的范围。
实施例1:
本发明用于焚化和热解处理固废危废的复合催化剂,该复合催化剂由原料溶剂、催化剂、催化加强剂、催化辅剂、金属络合剂、有机酸和表面活性剂组成,各原料之间的质量配比为200:15:7:2:30:25:10。
采用的溶剂为无水乙醇;催化剂是由2-乙基已酸镍、异辛酸钴、丙酸铁和异辛酸锰按照质量比4:2:1:1混合配制而成;催化加强剂是由柠檬酸稀土、钨酸铵和钼酸铵按照质量比1:1:1混合配制而成;催化辅剂是由醋酸铼、柠檬酸镁铵、异辛酸铜和异辛酸铈按照质量比1:1:1:1混合配制成;金属络合剂(铵盐脱酸剂)是由柠檬酸三铵和EDTA铵盐按照质量比1:1混合配制而成;有机酸是由醋酸和柠檬酸按照质量比1:1混合配制成;表面活性剂是由十二烷基苯磺酸钠、含酯基双子季铵盐阳离子表面活性剂按照质量比1:1混合配制而成。
实施例2:
本发明用于焚化和热解处理固废危废的复合催化剂,该复合催化剂由原料溶剂、催化剂、催化加强剂、催化辅剂、金属络合剂、有机酸和表面活性剂组成,各原料之间的质量配比为200:20:8:2:35:25:10。
采用的溶剂为无水乙醇;催化剂是由2-乙基已酸镍、异辛酸钴、丙酸铁和异辛酸锰按照质量比4:2:1:1混合配制而成;催化加强剂是由柠檬酸稀土、钨酸铵和钼酸铵按照质量比3:1:1混合配制而成;催化辅剂是由醋酸铼、柠檬酸镁铵、异辛酸铜和异辛酸铈按照质量比1:1:1:1混合配制成;金属络合剂(铵盐脱酸剂)是由柠檬酸三铵和EDTA铵盐按照质量比1:1混合配制而成;有机酸是由醋酸和柠檬酸按照质量比1:1混合配制成;表面活性剂是由十二烷基苯磺酸钠、含酯基双子季铵盐阳离子表面活性剂按照质量比1:1混合配制而成。
实施例3:
本发明用于焚化和热解处理固废危废的复合催化剂,该复合催化剂由原料溶剂、催化剂、催化加强剂、催化辅剂、金属络合剂、有机酸和表面活性剂组成,各原料之间的质量配比为200:30:8:5:35:35:10。
采用的溶剂为无水乙醇;催化剂是由2-乙基已酸镍、异辛酸钴、丙酸铁和异辛酸锰按照质量比4:2:1:1混合配制而成;催化加强剂是由柠檬酸稀土、钨酸铵和钼酸铵按照质量比4:1:1混合配制而成;催化辅剂是由醋酸铼、柠檬酸镁铵、异辛酸铜和异辛酸铈按照质量比1:1:1:1混合配制成;金属络合剂(铵盐脱酸剂)是由柠檬酸三铵和EDTA铵盐按照质量比1:1混合配制而成;有机酸是由醋酸和柠檬酸按照质量比1:1混合配制成;表面活性剂是由十二烷基苯磺酸钠、含酯基双子季铵盐阳离子表面活性剂按照质量比1:1混合配制而成。
实施例4:
本发明用于焚化和热解处理固废危废的复合催化剂,该复合催化剂由原料溶剂、催化剂、催化加强剂、催化辅剂、金属络合剂、有机酸和表面活性剂组成,各原料之间的质量配比为200:18:10:5:22:25:10。
采用的溶剂为无水乙醇;催化剂是由2-乙基已酸镍、异辛酸钴、丙酸铁和异辛酸锰按照质量比4:2:1:1混合配制而成;催化加强剂是由柠檬酸稀土、钨酸铵和钼酸铵按照质量比4:1:1混合配制而成;催化辅剂是由醋酸铼、柠檬酸镁铵、异辛酸铜和异辛酸铈按照质量比1:1:1:1混合配制成;金属络合剂(铵盐脱酸剂)是由柠檬酸三铵和EDTA铵盐按照质量比1:1混合配制而成;有机酸是由醋酸和柠檬酸按照质量比1:1混合配制成;表面活性剂是由十二烷基苯磺酸钠、含酯基双子季铵盐阳离子表面活性剂按照质量比1:1混合配制而成。
实施例5:
本发明用于焚化和热解处理固废危废的复合催化剂,该复合催化剂由原料溶剂、催化剂、催化加强剂、催化辅剂、金属络合剂、有机酸和表面活性剂组成,各原料之间的质量配比为120:30:10:5:32:30:10。
采用的溶剂为无水乙醇;催化剂是由2-乙基已酸镍、异辛酸钴、丙酸铁和异辛酸锰按照质量比4:2:1:1混合配制而成;催化加强剂是由柠檬酸稀土、钨酸铵和钼酸铵按照质量比4:1:1混合配制而成;催化辅剂是由醋酸铼、柠檬酸镁铵、异辛酸铜和异辛酸铈按照质量比1:1:1:1混合配制成;金属络合剂(铵盐脱酸剂)是由柠檬酸三铵和EDTA铵盐按照质量比1:1混合配制而成;有机酸是由醋酸和柠檬酸按照质量比1:1混合配制成;表面活性剂是由十二烷基苯磺酸钠、含酯基双子季铵盐阳离子表面活性剂按照质量比1:1混合配制而成。
本发明上述实施例具体应用情况如下:
1)本发明实施例1的应用具体情况:按照实施例1所述的复合催化剂配比比例称取各种原料,将称取的表面活性剂、有机酸和溶剂进行混合,混合均匀后,得到混合溶液;然后向混合溶液中依次加入催化剂、催化加强剂、催化辅剂和金属络合剂进行混合,混合均匀后得到复合催化剂溶液即复合催化剂原液。
将所得复合催化剂原液加入水进行1000倍稀释,得到复合催化剂稀释液,然后按照3%的添加量加入生活垃圾中进行热解处理,添加后热解垃圾焦油产量较之前降低21.2%,可燃气产量较之前升高38.1%,热解炭渣含油率小于0.3%;炉体除焦效果明显,炉体结焦情况得到明显改善。
2)本发明实施例2的应用具体情况:按照实施例2所述的复合催化剂配比比例称取各种原料,将称取的表面活性剂、有机酸和溶剂进行混合,混合均匀后,得到混合溶液;然后向混合溶液中依次加入催化剂、催化加强剂、催化辅剂和金属络合剂进行混合,混合均匀后得到复合催化剂溶液即复合催化剂原液。
将所得复合催化剂原液加入水进行1000倍稀释,得到复合催化剂稀释液,然后按照5%的添加量加入油泥中进行热解处理,处理后油泥含油率小于0.3%,热解轻质组分比例较高,热解可燃气产量少量增加,运行期间炉体无结焦产生。
3)本发明实施例3的应用具体情况:按照实施例3所述的复合催化剂配比比例称取各种原料,将称取的表面活性剂、有机酸和溶剂进行混合,混合均匀后,得到混合溶液;然后向混合溶液中依次加入催化剂、催化加强剂、催化辅剂和金属络合剂进行混合,混合均匀后得到复合催化剂溶液即复合催化剂原液。
然后按照0.5%的添加量将复合催化剂原液加入废旧橡塑中进行热解处理,处理后炭黑含油率小于0.15%,炭黑甲苯透光率合格,热解轻质组分比例较之前提高28.98%,热解可燃气产量较之前增加200%,运行期间炉体无结焦产生。
4)本发明实施例4的应用具体情况:按照实施例4所述的复合催化剂配比比例称取各种原料,将称取的表面活性剂、有机酸和溶剂进行混合,混合均匀后,得到混合溶液;然后向混合溶液中依次加入催化剂、催化加强剂、催化辅剂和金属络合剂进行混合,混合均匀后得到复合催化剂溶液即复合催化剂原液。
然后按照3.5%的添加量将复合催化剂原液加入辽河油田含聚油泥中进行热解处理,处理后炭渣含油率小于0.3%,运行期间炉体无结焦产生。
5)本发明实施例5的应用具体情况:按照实施例5所述的复合催化剂配比比例称取各种原料,将称取的表面活性剂、有机酸和溶剂进行混合,混合均匀后,得到混合溶液;然后向混合溶液中依次加入催化剂、催化加强剂、催化辅剂和金属络合剂进行混合,混合均匀后得到复合催化剂溶液即复合催化剂原液。
然后按照5.5%的添加量将复合催化剂原液加入废漆渣中进行热解处理,处理后炭渣含油率小于0.3%,运行期间炉体无结焦产生。
Claims (5)
1.一种用于焚化和热解处理固废危废的复合催化剂,其特征在于:所述复合催化剂由原料溶剂、催化剂、催化加强剂、催化辅剂、金属络合剂、有机酸和表面活性剂组成,各原料之间的质量配比为(100~200):(10~30):(5~10):(1~5):(30~60):(10~50):(5~10);
所述溶剂为无水乙醇;
所述催化剂是由2-乙基已酸镍、异辛酸钴、丙酸铁和异辛酸锰按照质量比2~6:2:1:1混合配制而成;
所述催化加强剂是由柠檬酸稀土、钨酸铵和钼酸铵按照质量比1~4:1:1混合配制而成;
所述催化辅剂是由醋酸铼、柠檬酸镁铵、异辛酸铜和异辛酸铈按照质量比1:1:1:1混合配制成;
所述金属络合剂是由柠檬酸三铵和EDTA铵盐按照质量比1:1混合配制而成;
所述有机酸是由醋酸和柠檬酸按照质量比1:1混合配制成;
所述表面活性剂是由十二烷基苯磺酸钠、含酯基双子季铵盐阳离子表面活性剂按照质量比1:1混合配制而成。
2.根据权利要求1所述用于焚化和热解处理固废危废的复合催化剂,其特征在于,所述复合催化剂的制备方法为:
首先将配制的表面活性剂、有机酸和溶剂进行混合,混合均匀后,得到混合溶液;然后向混合溶液中依次加入催化剂、催化加强剂、催化辅剂和金属络合剂进行混合,混合均匀后得到复合催化剂溶液即复合催化剂原液。
3.根据权利要求2所述用于焚化和热解处理固废危废的复合催化剂,其特征在于:所述复合催化剂原液的添加量为固废危废质量的0.5~5.5%。
4.根据权利要求2所述用于焚化和热解处理固废危废的复合催化剂,其特征在于:所得复合催化剂溶液使用时,需要加入水进行1000倍稀释,得到复合催化剂稀释液。
5.根据权利要求4所述用于焚化和热解处理固废危废的复合催化剂,其特征在于:所得复合催化剂稀释液的添加量为固废危废质量的3.0~17.5%。
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