CN1843623A - 一种煤液化供氢溶剂的预加氢催化剂及其制备方法 - Google Patents
一种煤液化供氢溶剂的预加氢催化剂及其制备方法 Download PDFInfo
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Abstract
一种煤液化供氢溶剂的专用预加氢催化剂及其制备方法，采用氧化铝为载体，VIB或VIII族金属为活性组分，通过混捏、挤条、浸渍、干燥、焙烧、硫化、混油等步骤制成含硫化态活性组分的催化剂，满足煤液化溶剂的不完全饱和预加氢反应的特殊要求，在装卸、运输和装填过程不产生粉尘，装填后无需硫化操作即可直接进行加氢反应。
Description
技术领域
本发明涉及一种催化剂及其制备方法，特别是一种煤液化供氢溶剂的预加氢催化剂及其制备方法。
背景技术
煤炭直接液化方法，一般是在高温(400～500℃)高压(10.0～30.0MPa)条件下，将煤炭和溶剂油进行催化加氢，生成氢碳比高的液体燃料产物，用于补充和代替日益短缺的石油燃料产品。在现有各种煤炭直接液化工艺中，有的对溶剂进行了加氢处理，使溶剂具有一定的供氢作用。如Exxon公司的供氢溶剂(EDS)工艺和日本的NEDOL工艺采用固定床加氢技术专门对循环溶剂加氢、德国的IGOR+工艺和中国煤直接液化工艺(CN03102672.9)将液化产物加氢后分离出循环溶剂、俄罗斯低压液化工艺和日本褐煤液化工艺(BCL工艺和NBCL工艺)将加氢和不加氢溶剂混合为循环溶剂使用。尽管上述工艺不同程度地使溶剂具有供氢作用，但溶剂中的可转移氢仍然不能满足较高煤炭转化率的耗氢需要，均需在液化反应中加入大量气体氢。
溶剂供氢作用相对较好的EDS工艺，使用传统的石油加氢催化剂和反应条件进行溶剂加氢。传统的石油加氢催化剂旨在追求饱和和或选择性的加氢效果，虽然通过改变条件可以控制溶剂的加氢深度，但加氢溶剂的饱和度仍然与加氢的石油产品相似，加氢深度较浅的产物基本是饱和烃和不饱和烃的混合物，不能提供更多的游离氢(-H)来完全满足煤液化反应所需。
发明内容
为了使溶剂提供更多的游离氢(-H)来完全满足煤液化反应所需，必须对溶剂进行均匀的不完全饱和加氢，既使溶剂中的高度不饱和物质适度加氢，又使溶剂中的饱和物质适度脱氢。
煤液化循环溶剂中含有大量对催化剂活性有破坏作用的杂质元素和易于缩合结焦的不饱和多环物质。采用单一催化剂和反应条件难以持久进行溶剂的均匀不完全饱和加氢反应。试验表明，采用预加氢催化剂和主加氢催化剂进行溶剂两段加氢的效果较佳。
本发明的目的是提供一种煤液化溶剂加氢专用催化剂，用于煤液化循环溶剂预加氢，脱除溶剂中的大部分杂质元素，并对易于缩合结焦的不饱和多环物质进行浅度加氢，减少杂质元素进入下游的主加氢催化剂起毒化作用，并延缓不饱和多环物质在主加氢催化剂床层结焦。
本发明采用氧化铝为载体，VIB或VIII族金属为活性组分。VIB族元素为5.5～15.5m％(按硫化物计，下同)，最佳9.2～13.5m％；VIII族元素为1.5～10.5m％，最佳3.2～5.5m％；其余部分为氧化铝。催化剂比表面为100～240m2/g，最佳130～180m2/g；孔容为0.40～1.0ml/g，最佳0.55～0.75ml/g。该催化剂孔径在10～20nm之间的孔容占全部孔容的60％以上，孔径＞20nm的孔容占全部孔容的20～35％。
本发明催化剂的活性金属采取混捏和浸渍两步加入，按下述步骤，最终制成含金属硫化物的成品催化剂：
(1)将含有VIB族和/或VIII族金属盐的胶溶溶液与一定比例的氧化铝混捏为均匀的湿料；
(2)对上述湿料进行挤条，制成湿挤条；
(3)对上述湿挤条进行干燥和焙烧，制成具有一定硬度的干挤条；
(4)将含有VIB族和/或VIII族金属盐的浸渍液对上述干挤条进行浸渍，制成含有足量金属的半干(或全湿)挤条；
(5)对上述半干(或全湿)挤条进行干燥和焙烧，制成含有金属氧化物的半成品催化剂；
(6)对上述半成品催化剂进行硫化，制成干品硫化态催化剂；
(7)对上述硫化态干品催化剂进行混油保护，制成半干硫化态催化剂。
上述(1)所述的胶溶溶液的制备方法为：先将一定量VIB族和/或VIII族金属盐加入一定量的蒸馏水，搅拌溶化，制成金属盐水溶液；再加入一定量的酸(无机酸和/或柠檬酸)搅拌酸化，制成酸化金属盐溶液；然后将所得酸化金属盐溶液加入一定量的氧化铝粉中，搅拌均匀，形成色泽一致的胶溶溶液。所用无机酸为硫酸或硝酸，优选后者，或后者与柠檬酸按mol比5∶1～1∶3的比例混合；所用VIB族金属盐为钼酸铵和/或钨酸铵，也可用其它水溶性钼盐和/或钨盐；所用VIII族金属盐为钴、镍的硫酸盐和/或硝酸盐，也可用其它水溶性盐，优选硝酸盐。胶溶溶液中酸与氧化铝的mol比为0.08～1.2之间，优选0.15～0.35；金属盐含量为总量的5m％～45m％，优选10m％～30m％；水含量为50m％～85m％，优选65m％～75m％。
上述(1)所述的氧化铝为大孔氧化铝，其孔容为0.6～1.3ml/g，最佳为0.65～0.95ml/g。
上述(1)所述的湿料，其含水量为35m％～55m％，优选40m％～50m％。
上述(2)所述的挤条，其截面一般为圆形，直径0.6～1.2mm，优选0.75～0.86mm。
上述(3)所述的湿挤条干燥和焙烧，是先以150～200℃/hr速度升温到105～135℃，恒温干燥1.0～4.0hr，再以同样速度升温到390～500℃，恒温焙烧1.0～4.0hr；优选恒温干燥温度110～120℃，恒温焙烧温度410～450℃，恒温时间2.0～3.0hr。
上述(4)所述的浸渍液含有VIB族金属氧化物0.01～0.60g/ml，优选0.20～0.45；VIII族金属氧化物0.001～0.25g/ml，优选0.075～0.15g/ml。VIB族金属为Mo、W，VIII族金属为Ni、Co。浸渍液的制备方法为：将VIB族金属盐和/或VIII族金属盐按预定含量加入到PH值为7.5～12.5的NH3和H2O2(0.010～0.12g/ml)的水溶液中搅拌溶解。
上述(4)所述的对干挤条浸渍，可浸没浸渍，也可喷淋浸渍，优选后者。浸渍上盐量为总盐量的55～95m％，优选70～90m％。
上述(5)所述的对湿挤条进行干燥，其干燥温度为105～165℃，优选115～135℃；恒温时间1.0～3.5hr，优选2.0～2.5hr。
上述(5)所述的对湿挤条进行焙烧，其焙烧温度为420～465℃，优选430～455℃；恒温时间1.0～3.5hr，优选2.0～2.5hr。
上述(6)所述的对半成品催化剂进行硫化，可干法硫化也可湿法硫化。干法硫化时，以H2混合H2S为硫化介质，H2S浓度为0.5～10.0v％，优选1.0～3.0v％；湿法硫化时，以柴油混合CS2(或二硫化物如CH3-S-S-CH3、硫醇如C4H9SH等)为硫化介质，临氢硫化，液体的硫化物浓度为1.5～15.0v％，优选3.5～7.5v％。实行程序升温硫化：先以3～5℃/hr升到230±5℃，在此温度下维持上述气相H2S浓度并恒温2～3hr，再以4～7℃/hr升到320±5℃，在此温度下维持上述气相H2S浓度并恒温1.5～2.5hr，最后以5～10℃/hr升到370±5℃，在此温度下维持上述气相H2S浓度并恒温1.0～2hr。
上述(7)所述的对硫化态干品催化剂进行混油保护，是用含蜡量10～15m％、馏程250～400℃的馏份油与温度100～150℃的催化剂混合，以阻止催化剂的硫化态活性组分与空气直接接触，防止催化剂在装卸、运输和装填过程产生粉尘。混油量占催化剂重量的5～30％，最佳为15～20％。
有益效果
本发明为在缓和的工艺条件下实现煤液化溶剂的不完全饱和加氢，提供了一种供氢溶剂的专用预加氢催化剂。该催化剂的物化性质满足煤液化溶剂的不完全饱和预加氢反应的特殊要求，在装卸、运输和装填过程不产生粉尘，装填后无需硫化操作即可直接进行加氢反应。
具体实施方式
实施例1：催化剂的制备方法。
(1)胶溶溶液和湿料制备
将10.0g的钼酸铵和7.3g的硝酸镍加入300ml的蒸馏水中溶解，再加入13ml的硝酸搅拌均匀，制得330.0g酸化金属盐溶液。
将全部酸化金属盐溶液倒入80g氧化铝粉中搅拌均匀，制得含水量73％的色泽均匀的含金属盐胶溶溶液410g。
将上述胶溶溶液加入260g的大孔氧化铝中进行均匀捏合，制得含水量44.8m％的湿料670g。
(2)湿料挤条
将上述湿料放入挤条机进行挤条，挤条直径为0.8mm。
(3)挤条干燥和焙烧
将上述湿挤条放入可排气的高温炉中，以150℃/hr速度升温到125℃，恒温干燥2.0hr，再以同样速度升温到450℃，恒温焙烧2.0hr，然后自然降温。
(4)浸渍液配制和催化剂浸渍
将40.0g钼酸铵和16.3g碱式碳酸镍加入60ml含NH3 15m％、H2O2 12m％的水溶液中，搅拌使金属盐完全溶解后，用含NH3 45m％和12m％的氨水调节溶液的PH值为10，制得浸渍液80ml。
采用喷淋浸渍法，将上述80ml浸渍液全部均匀喷洒到步骤(3)所得的干燥挤条中，制得含有足量金属的半干挤条。
(5)含足量金属的半干挤条干燥及焙烧
将上述含足量金属的半干挤条放入可排气的高温炉中，以150℃/hr速度升温到125℃，恒温干燥2.0hr，再以同样速度升温到450℃，恒温焙烧2.0hr，然后自然降温，制成半成品催化剂。
(6)半成品催化剂的硫化
采用湿法硫化，将480mlCS2加入12000ml的柴油中混合均匀，制成硫化柴油。在10MPa压力下保持氢气流量5000ml/hr同时，以15℃/hr将装在管式反应器的400g催化剂升到160℃，恒温2hr后，以150ml/hr的流速使硫化柴油通过催化剂床层，同时以5℃/hr升温到230℃，恒温2.5hr(在此温度下气相H2S浓度达到5.5v％以上)。230℃恒温结束后，以6℃/hr升到320℃，恒温2hr，最后以8℃/hr升到370℃，恒温1.5hr。然后快速降温到150℃，放空硫化柴油，恒温并保持氢气吹扫2hr，完成硫化，制成催化剂400g。
(7)硫化态催化剂的混油保护
上述硫化完毕的催化剂趁热卸出时，用温度80℃的含蜡量12m％、馏程250～400℃的馏份油70g均匀喷洒在催化剂上，然后自然冷却至室温。
实施例2：催化剂的评价。
实施例1制备的催化剂，其物化性质如表1所示。
实施例1制备的催化剂在小型固定床加氢装置进行活性评价，以一种蒽油为原料，反应条件为：
反应压力：10MPa，反应温度：330℃，
体积空速：1.5h-1，氢油比：100(v)。
评价结果如表2所示。
表1 催化剂的物化性质
| 孔容 ml/g | 0.68 |
| 比表面 m2/g | 163 |
| 堆积密度 g/ml | 0.62 |
| 侧压强度 N/mm | 8.2 |
| 孔分布 ％ | |
| ＜10nm | 14 |
| 10～20nm | 66 |
| ＞20nm | 20 |
| 红外酸分布mM/g | |
| 160℃ | 0.161 |
| 250℃ | 0.058 |
| 350℃ | 0 |
| Ni3S2 m％ | 4.02 |
| MoS2 m％ | 12.11 |
表2 催化剂的评价结果
| 脱Fe率 m％ | 62.3 |
| 脱Ca率 m％ | 65.4 |
| 脱Ni率 m％ | 47.6 |
| 脱V率 m％ | 41.3 |
| 脱残炭率 m％ | 55.2 |
Claims (10)
1.一种煤液化供氢溶剂的专用预加氢催化剂，其特征在于，采用氧化铝为载体，VIB或VIII族金属为活性组分。VIB族元素为5.5～15.5m％(按硫化物计，下同)，最佳9.2～13.5m％；VIII族元素为1.5～10.5m％，最佳3.2～5.5m％；其余部分为氧化铝。催化剂比表面为100～240m2/g，最佳130～180m2/g；孔容为0.40～1.0ml/g，最佳0.55～0.75ml/g。该催化剂孔径在10～20nm之间的孔容占全部孔容的60％以上，孔径＞20nm的孔容占全部孔容的20～35％。
2.根据权利要求1，其特征在于，所述煤液化供氢溶剂的专用预加氢催化剂的制备方法，包括如下步骤：
(1)将含有VIB族和/或VIII族金属盐的胶溶溶液与一定比例的氧化铝混捏为均匀的湿料；
(2)对上述湿料进行挤条，制成湿挤条；
(3)对上述湿挤条进行干燥和焙烧，制成具有一定硬度的干挤条；
(4)将含有VIB族和/或VIII族金属盐的浸渍液对上述干挤条进行浸渍，制成含有足量金属的半干(或全湿)挤条；
(5)对上述半干(或全湿)挤条进行干燥和焙烧，制成含有金属氧化物的半成品催化剂；
(6)对上述半成品催化剂进行硫化，制成干品硫化态催化剂；
(7)对上述硫化态干品催化剂进行混油保护，制成半干硫化态催化剂。
3.根据权利要求1和权利要求2，其特征在于，制备步骤(1)所述的胶溶溶液，酸与氧化铝的mol比为0.08～1.2之间，优选0.15～0.35；金属盐含量为总盐量的5m％～45m％，优选10m％～30m％；水含量为50m％～85m％，优选65m％～75m％。
4.根据权利要求1和权利要求2，其特征在于，制备步骤(1)所述的氧化铝为大孔氧化铝，其孔容为0.6～1.3ml/g，最佳为0.65～0.95ml/g。
5.根据权利要求2，其特征在于，制备步骤(1)所述的湿料，其含水量为35m％～55m％，优选40m％～50m％。
6.根据权利要求2，其特征在于，制备步骤(3)所述的湿挤条干燥和焙烧，干燥温度为105～135℃，优选110～120℃；焙烧温度390～500℃，优选410～450℃。
7.根据权利要求1和权利要求2，其特征在于，制备步骤(4)所述的浸渍液含有VIB族金属氧化物0.01～0.60g/ml，优选0.20～0.45；VIII族金属氧化物0.001～0.25g/ml，优选0.075～0.15g/ml。VIB族金属为Mo、W，VIII族金属为Ni、Co。
8.根据权利要求2，其特征在于，制备步骤(5)所述的对湿挤条进行干燥，其干燥温度为105～165℃，优选115～135℃；对湿挤条进行焙烧，其焙烧温度为420～465℃，优选430～455℃。
9.根据权利要求2，其特征在于，制备步骤(6)所述的对半成品催化剂进行硫化，气相H2S浓度为0.5～10.0v％，优选1.0～3.0v％；液体的硫化物浓度为1.5～15.0v％，优选3.5～7.5v％。分别在230±5℃、320±5℃、370±5℃恒温硫化1.0～3.0hr。
10.根据权利要求2，其特征在于，制备步骤(7)所述的对硫化态干品催化剂进行混油保护，是用含蜡量10～15m％、馏程250～400℃的馏份油与温度100～150℃的催化剂混合。混油量占催化剂重量的5～30％，最佳为15～20％。
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