CN108579812B - 一种复合型液化气脱硫催化剂及其制法 - Google Patents
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Abstract
本发明公开了一种复合型液化气脱硫催化剂及其制法,属于石油加工过程中液化气精制技术领域,所述催化剂由如下重量份数的原料复合而得:4,4‑二氨基二苯甲烷,0.5‑2份;乙酰丙酮钴,1‑3份;磺化酞箐钴,5‑8份;二甘醇,3‑8份;甲醇,2~5份;草酸钠,0.2~0.5份;聚丙烯酸钠,0.1~0.3份。本发明的催化剂性能稳定,可增长碱液使用周期,降低碱液消耗量,且制备方法适于工业生产,对产品脱硫及后续加工无不良影响。
Description
技术领域
本发明涉及一种炼油过程助剂,具体涉及一种复合型液化气脱硫催化剂及其制法。属于石油加工过程中液化气精制技术领域。
背景技术
炼油厂液化气主要来源于催化裂化和延迟焦化装置。催化裂化液化气是生产炼油丙烯和MTBE(甲基叔丁基醚)的主要原料。近年来,随着资源综合利用不断加深的要求,焦化液化气也被作为生产炼油丙烯和MTBE的原料。在MTBE的生产过程中,像甲醇一样,硫醇与异丁烯也能发生醚化反应,同时还可能发生自醚化反应;再加上MTBE对硫化物比碳四烃有更高的溶解性等因素,在MTBE与醚后碳四蒸馏分离时,碳四原料中的硫化物几乎全部被MTBE产品所富集。由于焦化液化气中异丁烯含量较低,如若液化气脱硫精制不完善的话,MTBE产品的硫含量就会高得惊人。加入脱硫催化剂的目的,就是参与反应的各种物质化学及物理特性,加速脱硫醇过程向有益的反应方向进行。脱硫催化剂目前主要为磺化酞箐钴,其确定存在为单一形态的磺化酞箐钴效果差、碱耗大、排渣多。已经不适合用于现代高含硫液化气的脱硫工艺过程。复合型脱硫催化剂技术是近年来新发展起来的一种适合高含硫液化气脱硫的技术,相比于单纯使用磺化酞箐钴,由于其使用方便、经济高效、脱硫效果好。更加适合我国高含硫原油产品的精制和深加工利用,因此更加具有适用性和发展前景。
发明内容
本发明要解决的技术问题是提供一种复合型液化气脱硫催化剂及其制法,其具有良好的储存使用稳定性能,降低碱耗、减少排渣、提高脱硫醇效果的优良作用。
为实现上述目的,本发明采用下述技术方案:
一种复合型液化气脱硫催化剂,主要由如下重量份数的原料复合而得:
优选的,所述聚丙烯酸钠的分子量选择为1000~10000;进一步优选为1000~3000。
本发明中,4,4-二氨基二苯甲烷是良好的硫化剂及硫化促进剂,硫醇与强碱(NaOH)反应生成硫醇钠,利用硫醇钠溶于碱的特性,实现了硫醇向碱液的转移;在4,4-二氨基二苯甲烷的作用下,碱液中的硫醇负离子加速被溶解氧氧化为二硫化物,从碱相脱出,使NaOH得以再生。
磺化酞箐钴是脱除轻质油、液化气中硫醇的高效催化剂;乙酰丙酮钴为有机反应催化剂,能够脱除未能参与反应的有机硫向碱液转移;
4,4-二氨基二苯甲烷不溶于水,需经过甲醇溶解后加入;
草酸钠是碱性条件下的优良络合剂,能使反应生成的金属离子络合,稳定的新的离子;
聚丙烯酸钠作为分散剂,能使生成的离子和其他杂质稳定的悬浮在液相中,避免沉淀。
本发明还提供一种复合型液化气脱硫催化剂的制法,包括如下步骤:
1)取工艺质量的甲醇、4,4-二氨基二苯甲烷,混合搅拌溶解,去离子水稀释,得到混合物Ⅰ;
2)将工艺质量的乙酰丙酮钴、磺化钛氰钴、草酸钠、二甘醇依次溶解于无离子水中,得到混合物Ⅱ;
3)将步骤1)的混合物Ⅰ倒入步骤2)的混合物Ⅱ中,混合均匀;
4)滴加工艺质量的聚丙烯酸钠,搅拌均匀,即得。
优选的,步骤1)所述离子水的质量为甲醇和4,4-二氨基二苯甲烷混合物质量的5倍。
优选的,步骤2)所述离子水的质量为乙酰丙酮钴、磺化钛氰钴、草酸钠、二甘醇质量和的3倍。
本发明的有益效果:
1)储存、使用性能稳定,在-30-60℃范围内反复升降温100天,催化剂性能稳定,无分层现象,使用效果没有变化,具有优良的稳定性;
2)增长碱液使用周期,降低碱液消耗量,对产品脱硫及后续加工无不良影响;
3)制备方法简单,适于工业生产,且达到了工业使用要求;
4)本发明添加的二甘醇是良好的气体脱水剂,在液化气碱洗催化精制过程中,能有效避免液化气向后路携带水分,保证了产品质量及后续加工的安全;所添加的聚丙烯酸钠,在产品储存过程中,其能起到产品稳定、分散的作用,避免产品中的高分子有机物被紫外光分解,造成沉淀引起质量下降,使得产品可长时间存放。
具体实施方式
下面结合实施例对本发明进行进一步的阐述,应该说明的是,下述说明仅是为了解释本发明,并不对其内容进行限定。
实施例1
一种复合型液化气脱硫催化剂的制备
1)按表1中各组分里的重量,称取30kg甲醇、10kg4,4-二氨基二苯甲烷,混合、搅拌至溶解,用5倍质量的去离子水稀释,得到混合物Ⅰ;
2)将20kg乙酰丙酮钴、60kg磺化钛氰钴、5kg草酸钠、50kg二甘醇依次溶解于405kg无离子水中,得到混合物Ⅱ;
3)将步骤1)的混合物Ⅰ倒入步骤2)的混合物Ⅱ中,混合均匀;
4)滴加3kg聚丙烯酸钠,搅拌均匀,即得。
实施例2
一种复合型液化气脱硫催化剂的制备
1)按表1中各组分里的重量,称取30kg甲醇、15kg4,4-二氨基二苯甲烷,混合、搅拌至溶解,用5倍质量的去离子水稀释,得到混合物Ⅰ;
2)将10kg乙酰丙酮钴、70kg磺化钛氰钴、3kg草酸钠、80kg二甘醇依次溶解于489kg无离子水中,得到混合物Ⅱ;
3)将步骤1)的混合物Ⅰ倒入步骤2)的混合物Ⅱ中,混合均匀;
4)滴加3kg聚丙烯酸钠,搅拌均匀,即得。
实施例3
一种复合型液化气脱硫催化剂的制备
1)按表1中各组分里的重量,称取50kg甲醇、20kg4,4-二氨基二苯甲烷,混合、搅拌至溶解,用5倍质量的去离子水稀释,得到混合物Ⅰ;
2)将20kg乙酰丙酮钴、60kg磺化钛氰钴、3kg草酸钠、50kg二甘醇依次溶解于399kg无离子水中,得到混合物Ⅱ;
3)将步骤1)的混合物Ⅰ倒入步骤2)的混合物Ⅱ中,混合均匀;
4)滴加2kg聚丙烯酸钠,搅拌均匀,即得。
实施例4
一种复合型液化气脱硫催化剂的制备
1)按表1中各组分里的重量,称取20kg甲醇、5kg4,4-二氨基二苯甲烷,混合、搅拌至溶解,用5倍质量的去离子水稀释,得到混合物Ⅰ;
2)将30kg乙酰丙酮钴、50kg磺化钛氰钴、2kg草酸钠、30kg二甘醇依次溶解于336kg无离子水中,得到混合物Ⅱ;
3)将步骤1)的混合物Ⅰ倒入步骤2)的混合物Ⅱ中,混合均匀;
4)滴加1kg聚丙烯酸钠,搅拌均匀,即得。
实施例5
一种复合型液化气脱硫催化剂的制备
1)按表1中各组分里的重量,称取30kg甲醇、15kg4,4-二氨基二苯甲烷,混合、搅拌至溶解,用5倍(质量的)去离子水稀释,得到混合物Ⅰ;
2)将10kg乙酰丙酮钴、80kg磺化钛氰钴、4kg草酸钠、70kg二甘醇依次溶解于492kg无离子水中,得到混合物Ⅱ;
3)将步骤1)的混合物Ⅰ倒入步骤2)的混合物Ⅱ中,混合均匀;
4)滴加1kg聚丙烯酸钠,搅拌均匀,即得。
表1复合型液化气脱硫催化剂的原料配方(单位:Kg)
原料成分 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 |
4,4-二氨基二苯甲烷 | 10 | 15 | 20 | 5 | 15 |
乙酰丙酮钴 | 20 | 10 | 20 | 30 | 10 |
磺化酞箐钴 | 60 | 70 | 60 | 50 | 80 |
二甘醇 | 50 | 80 | 50 | 30 | 70 |
甲醇 | 30 | 40 | 50 | 20 | 30 |
草酸钠 | 5 | 3 | 3 | 2 | 4 |
聚丙烯酸钠 | 3 | 2 | 2 | 1 | 1 |
其中,聚丙烯酸钠的分子量选择为1000-3000。
试验例:
1.将上述实施例1~实施例5所得催化剂在-30-60℃范围内反复升降温100天,测试其催化及稳定性能。
2.将上述实施例1~实施例5所得催化剂应用于液化气脱硫生产工艺中,检测其碱液消耗量,对催化剂进行性能评价。
催化剂性能测试结果见表2所示。
表2催化剂性能测试结果
测试结果表明:本发明提供的催化剂性能稳定,无分层现象,使用效果没有变化,表明本发明的催化剂具有优良的稳定性;且可起到增长碱液使用周期,降低碱液消耗量的作用,且对产品脱硫及后续加工无不良影响。
上述虽然对本发明的具体实施方式进行了描述,但并非对本发明保护范围的限制,在本发明的技术方案的基础上,本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。
Claims (5)
2.根据权利要求1所述的一种复合型液化气脱硫催化剂,其特征在于,所述聚丙烯酸钠的分子量选择为1000~10000。
3.根据权利要求2所述的一种复合型液化气脱硫催化剂,其特征在于,所述聚丙烯酸钠的分子量选择为1000~3000。
4.权利要求1所述复合型液化气脱硫催化剂的制备方法,其特征在于,包括以下步骤:
1)取工艺量的甲醇、4,4-二氨基二苯甲烷,混合搅拌溶解,用去离子水稀释,得到混合物Ⅰ;
2)将工艺质量的乙酰丙酮钴、磺化钛氰钴、草酸钠、二甘醇依次溶解于去离子水中,得到混合物Ⅱ;
3)将步骤1)的混合物Ⅰ倒入步骤2)的混合物Ⅱ中,混合均匀;
4)滴加聚丙烯酸钠,搅拌均匀,即得。
5.根据权利要求4所述复合型液化气脱硫催化剂的制备方法,其特征在于,步骤1)所述去离子水的质量为甲醇和4,4-二氨基二苯甲烷混合物质量的5倍;步骤2)所述去 离子水的质量为乙酰丙酮钴、磺化钛氰钴、草酸钠、二甘醇质量和的3倍。
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