CN114011417A - 一种回收Ni/硅藻土催化剂的方法 - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000009295 crossflow filtration Methods 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
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- 238000004140 cleaning Methods 0.000 claims abstract description 9
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- 238000012216 screening Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004062 sedimentation Methods 0.000 claims abstract description 6
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000012528 membrane Substances 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000005909 Kieselgur Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
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- 238000011084 recovery Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
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- 239000007791 liquid phase Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910052763 palladium Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种回收Ni/硅藻土催化剂的方法,具体步骤为:二硝基甲苯和氢气以镍/硅藻土为催化剂,反应生成甲苯二胺和水,生成物经斜板沉降器连续沉降分离,94‑96%的催化剂连续返回反应体系循环使用,6‑4%的催化剂随产品进入错流过滤***;经错流过滤,不含催化剂的清液,通过滤膜进入产品精馏***,催化剂的高倍浓缩液进入沉降、筛选***;将粒径大、活性高的催化剂连续进入催化剂清洗***,粒径小且已失去活性的催化剂排出***。可实现对流失催化剂的高倍浓缩、分级沉降、连续筛选、循环再利用,催化剂相对活性95.4%,性能完全能满足生产工艺要求。大幅度降低TDA生产过程中催化剂使用成本。
Description
技术领域
本发明属于物理分离领域,涉及一种采用错流过滤技术回收再利用TDA生产过程中镍/硅藻土催化剂的方法。
背景技术
二硝基甲苯(DNT)和氢气(H2)在一定的温度和压力下,加催化剂,反应生成TDA和水。这是复杂的气一液一固三相反应休系,且具有强放热和连续、平行等副反应众多的特点,是TDI生产的重要组成环节之一。所采用的催化剂主要有镍系和钯系两大类,催化剂相对比较昂贵,催化剂回收技术直接影响到TDA的生产成本。目前,该生产工艺镍/硅藻土催化剂的消耗量0.5-0.8kg/吨产品,其主要流失的途径是随产品一起进入精馏***,从精馏塔釜以焦油形式排放、焚烧。
目前,TDA工业化生产所采用的催化剂过滤回收主要有是盲端过滤回收技术(见图3),滤饼中拦截的焦油对催化剂有包覆现象,且滤饼在液相中不易疏散,该技术为间歇式工艺,滤布更换频繁,操作难度较大,催化剂的再利用存在一定难度。
发明内容
本发明的目的是克服现有技术的不足,提供一种回收Ni/硅藻土催化剂的方法。
为实现上述目的,本发明采用的技术方案为:一种回收Ni/硅藻土催化剂的方法,其特征在于:具体步骤如下:
(1)在一定温度和压力下,二硝基甲苯和氢气以镍/硅藻土为催化剂,反应生成甲苯二胺和水,所述催化剂浓度为0.8-1.0wt%;
(2)步骤(1)的生成物(催化剂浓度为0.8-1.0wt%);经斜板沉降器连续沉降分离,94-96%的催化剂连续返回反应体系继续循环使用,6-4%的催化剂随产品一起进入错流过滤***;
(3)经错流过滤,不含催化剂的清液(TDA和水),通过滤膜进入产品精馏***,催化剂的高倍浓缩液(其中,催化剂含量7-10%;TDA和水的含量92.5-89.5%;其他组分含量0.5%)进入沉降、筛选***;
(4)通过高效沉降、筛选,将90%左右粒径大、活性高的催化剂连续进入催化剂清洗***,粒径小且已失去活性的催化剂随同焦油类固体物质一起连续排出***。
所述催化剂清洗***为:将回收的催化剂表面进行充分清洗和比表面积再生处理后,连续返回反应体系继续循环使用。
本发明的原理:(见图2)错流过滤回收技术,实现了物料的高倍浓缩,焦油在物料中的浓度,滤后明显减少,过滤工况稳定、操作简便,为连续工艺,能完成在线清洗和催化剂的分级沉降与选择性利用。
本发明具有以下优点:1.可实现催化剂的高倍浓缩、分级沉降、选择性利用的连续化工艺;2.错流过滤工艺可完成在线清洗和催化剂比表面积反复再生,而且操作简便、工况稳定;3.大幅度降低TDA生产过程中镍/硅藻土催化剂的使用成本。
附图说明
图1为本发明工艺流程图;
图2为本发明原理图;
图3为现有技术原理图。
具体实施方式
实施例1:进料为催化剂含量0.8-1.0wt%反应生成物;渗透物为TDA和水;滤饼组成为镍/硅藻土催化剂、少量产品及焦油类物质;浓缩物为催化剂含量7-10%、TDA和水的含量92.5-89.5%、其他组分含量0.5%。
在一定温度和压力下,二硝基甲苯和氢气以镍/硅藻土为催化剂(催化剂浓度0.8-1.0wt%),反应生成甲苯二胺;甲苯二胺反应液(催化剂浓度0.8-1.0wt%)经斜板沉降,95%的催化剂连续返回反应体系继续循环使用,5%的催化剂随产品一起进入错流过滤***;经错流过滤,不含催化剂的产品清液,通过过滤膜进入产品精馏***,含催化剂的高倍浓缩液将进入沉降、筛选***;通过高效沉降、筛选,将90%左右粒径大、活性高的催化剂连续进入催化剂清洗***,粒径小且已失去活性的催化剂随同焦油类固体物质一起排出***;催化剂清洗***,将回收的催化剂表面进行充分清洗和比表面积再生处理后,连续返回反应体系继续循环使用。
研究数据表明:流失催化剂的平均粒径在8~13µm之间、粒径范围0.8~416µm、有效组分镍金属的含量51~54%、催化剂的相对活性95.4%、稳定性无明显衰减,其性能完全能满足生产工艺要求。
Claims (2)
1.一种回收Ni/硅藻土催化剂的方法,其特征在于:具体步骤如下:
(1)在一定温度和压力下,二硝基甲苯和氢气以镍/硅藻土为催化剂,反应生成甲苯二胺和水,所述催化剂浓度为0.8-1.0wt%;
(2)步骤(1)的生成物经斜板沉降器连续沉降分离,94-96%的催化剂连续返回反应体系继续循环使用,6-4%的催化剂随产品一起进入错流过滤***;
(3)经错流过滤,不含催化剂的清液,通过滤膜进入产品精馏***,催化剂的高倍浓缩液进入沉降、筛选***;
(4)通过高效沉降、筛选,将90%左右粒径大、活性高的催化剂连续进入催化剂清洗***,粒径小且已失去活性的催化剂随同焦油类固体物质一起连续排出***。
2.如权利要求1所述的一种回收Ni/硅藻土催化剂的方法,其特征在于:所述催化剂清洗***为:将回收的催化剂表面进行充分清洗和比表面积再生处理后,连续返回反应体系继续循环使用。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH11240855A (ja) * | 1997-12-26 | 1999-09-07 | Kuraray Co Ltd | 反応方法及び反応装置 |
CN103360265A (zh) * | 2012-04-06 | 2013-10-23 | 浙江龙盛化工研究有限公司 | 一种二硝基苯连续加氢及其反应热回收利用方法 |
CN104045569A (zh) * | 2014-05-15 | 2014-09-17 | 赛鼎工程有限公司 | 通过二硝基甲苯低压加氢合成甲苯二胺的工艺及催化剂和催化剂的制法 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11240855A (ja) * | 1997-12-26 | 1999-09-07 | Kuraray Co Ltd | 反応方法及び反応装置 |
CN103360265A (zh) * | 2012-04-06 | 2013-10-23 | 浙江龙盛化工研究有限公司 | 一种二硝基苯连续加氢及其反应热回收利用方法 |
CN104045569A (zh) * | 2014-05-15 | 2014-09-17 | 赛鼎工程有限公司 | 通过二硝基甲苯低压加氢合成甲苯二胺的工艺及催化剂和催化剂的制法 |
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