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CN103687667B - 包含负载在氧化锌上的铜的脱硫材料 - Google Patents

包含负载在氧化锌上的铜的脱硫材料 Download PDF

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CN103687667B
CN103687667B CN201280036034.5A CN201280036034A CN103687667B CN 103687667 B CN103687667 B CN 103687667B CN 201280036034 A CN201280036034 A CN 201280036034A CN 103687667 B CN103687667 B CN 103687667B
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sulfur removal
removal material
copper
zinc oxide
sulfur
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CN103687667A (zh
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N·麦克里奥德
G·E·维尔森
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Johnson Matthey Davy Technologies Ltd
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Abstract

描述了一种颗粒脱硫材料，其包含一种或多种负载在氧化锌载体材料上的铜化合物，其中该脱硫材料的铜含量在0.1‑5.0wt%的范围内，振实堆密度≥1.55kg/l。

Description

包含负载在氧化锌上的铜的脱硫材料
本发明涉及脱硫材料，特别是包含铜和氧化锌的脱硫材料。
计划用于生成合成气的烃原料必须首先经过脱硫，以保护敏感的下游催化剂以免失活。脱硫常规上使用加氢脱硫(HDS)催化(通常基于CoMo或NiMo催化剂)和氧化锌基吸收剂。锌基吸收剂设计用来根据下式捕获H2S：
ZnO+H2S→ZnS+H2O
用于捕获硫的ZnO基吸收剂的性能是密度和孔隙率之间的折中。高密度允许更多ZnO装载到单位体积的容器中，因此增大了理论上可捕获硫的量并可能地延长了更换的时间。然而，实践中这种致密材料的低孔隙率和相关的低表面积对硫化过程造成动力学上的阻碍，这阻止了反应器中存在的大量ZnO得到有效利用。
这种考虑为用于商业操作中的当前的ZnO基产品的密度设置了事实上的上限。该上限处于1.5kg/l的区间。
已经令人惊奇地发现，低水平的铜可以显著提高硫化过程的速度，结果是显著更高密度的材料可以得到有效利用。
因此，本发明提供一种颗粒状脱硫材料，其包含一种或多种负载在氧化锌载体材料上的铜化合物，其中该脱硫材料以CuO表示的铜含量在0.1-5.0wt%的范围内，振实堆密度(tapped bulk density)≥1.55kg/l。
本发明还提供一种制备脱硫材料的方法，和工艺流体物流脱硫的方法，其包括任选在氢存在下使该物流与该脱硫材料接触。
产品的高密度提供了就每单位体积安装的吸收剂的脱硫(例如kgS/m3)而言的高硫容量。使用铜促进剂确保硫化速率足够快，以使反应区(传质区)保持合理的床长度。这种组合使吸收剂床的有效性最大化，增长了更换的时间，极大地改进了采用该产品的装置的操作效率。
铜的存在也将为吸收剂提供一些氢化能力，这在去除逃逸过上游HDS催化剂的痕量级的有机硫化合物方面是有利的。对于COS更是如此，其在HDS催化剂上的转化率经常受到平衡的限制。
本发明脱硫材料的物理性质增强了硫吸着能力。通常作为颗粒催化剂和吸着剂的度量的振实堆密度≥1.55kg/l，优选≥1.60kg/l。振实堆密度(TBD)度量可以如下来进行：用颗粒脱硫材料填充1升量筒，并振实直到获得恒定的体积。记录振实体积。然后称重该材料并计算它的密度。脱硫材料的粒度(即颗粒直径或宽度)优选为1-10mm，更优选为1.5-7.5mm，最优选为2.5-5.0mm。纵横比(即直径或宽度除以颗粒高度)优选≤2。
脱硫材料的孔体积可以≤0.22cm3/g。孔体积优选≥0.05cm3/g，更优选≥0.10cm3/g以提供可接受的表面积。BET表面积可以≤23m2/g。BET表面积优选≥5m2/g，更优选≥10m2/g。BET表面积可以通过氮物理吸附来确定。孔体积可以使用水银孔率法来确定。
脱硫材料以CuO表示的铜含量为0.1-5.0wt%，优选为0.5-4.0wt%，更优选为1.0-3.5wt%。铜化合物可以选自金属铜、氧化铜、氢氧化铜、硝酸铜、醋酸铜和碱式碳酸铜。用于制备该材料的铜化合物可以与最终材料中的相同或不同。在一个实施方案中，将碱式碳酸铜与锌载体材料合并，并煅烧得到的混合物以提供以氧化铜的形式具有铜的脱硫材料。无论铜为氧化铜的形式还是其他铜化合物的形式，在使用中，该材料均可以暴露于还原性气流，以使铜化合物可以还原为金属铜。
颗粒锌材料可以选自氧化锌、氧化锌/氧化铝混合物或锌-氧化铝水滑石材料。颗粒锌材料也可以包含一种或多种经煅烧形成氧化锌的前体。脱硫材料中，煅烧后的Zn含量(以ZnO表示)优选≥80wt%，特别是≥87wt%。
如果需要，脱硫材料可以进一步包含第二载体材料或第二金属化合物，以改变物理性质或改变硫容量。
第二载体材料可以是一种或多种难熔氧化物，特别是氧化物，其在经煅烧的材料中的存在量可以为至多20wt%。
第二金属化合物可以一种或多种铁、锰、钴或镍(优选为镍)的化合物。第二金属化合物可以选自金属、金属氧化物、金属氢氧化物、金属硝酸盐、金属醋酸盐和金属碱式碳酸盐。用于制备该材料的第二金属化合物可以与最终材料中的相同或不同。例如，将金属碱式碳酸盐与其他组分合并，并煅烧得到的混合物以提供以金属氧化物的形式具有该第二金属的材料。对于镍和钴，无论该金属为氧化钴、氧化镍的形式还是其他金属化合物的形式，在使用中，该材料均可以暴露于还原性气流，以使镍化合物或钴化合物可以还原为金属。该材料中以经还原或未还原状态存在的第二金属化合物的量为第二金属含量0.1-5wt%，优选为0.5-5wt%。
脱硫材料可以使用已知方法来制备，例如将颗粒氧化锌载体材料用一种或多种铜化合物浸渍，然后干燥和煅烧，或者对包含氧化锌载体材料和铜化合物的糊剂进行挤出，然后干燥和煅烧；或者通常在粘合剂存在下对粉末状铜化合物和锌载体材料进行粒化，然后干燥和煅烧。
因此，根据本发明的制备脱硫材料的方法包括以下步骤：
(i)将铜化合物与颗粒锌载体材料混合，以形成含铜组合物，
(ii)使该含铜组合物成形，和
(iii)干燥和煅烧得到的材料。
成形步骤可以是根据本领域技术人员已知的方法，通过成形模具进行材料的粒化、造粒或挤出。因此脱硫材料可以为成形装置的形状，例如球形、粒状、圆柱性、环形或多孔粒状，其可以是截面为四叶式交叉的多叶状或多槽状。
脱硫材料优选通过粒化来成形。在这种技术中，在少量水存在下将粉末状铜化合物、锌载体材料和一种或多种粘合剂混合，以形成大致为球形的聚集体。适合的粘合剂包括水泥粘合剂(例如铝酸钙水泥)和粘土粘合剂(例如绿坡缕石或海泡石粘土)。粒化的材料经干燥和煅烧，以形成氧化形式的脱硫材料。
脱硫材料的密度可以通过适当选择所用的ZnO前体材料来控制。物理特性可以使用提供所需产品密度的已知方法来调整。
因此在一个特别优选的实施方案中，脱硫材料包含由一种或多种铜化合物、氧化锌载体材料和一种或多种粘合剂形成的颗粒。该一种或多种粘合剂可以选自粘土粘合剂和水泥粘合剂及其混合物。该颗粒优选粒径为1-10mm，更优选为1.5-7.5mm，最优选为2.5-5.0mm。
干燥和煅烧可以在一个或两个阶段中进行。干燥通常在40-120℃进行。煅烧可以在250℃-750℃进行至多24小时，但优选在250-550℃进行超过1-10小时。煅烧将任何非氧化的铜和锌化合物转化为氧化铜和氧化锌，并使粘合剂(如果存在的话)与该组合物反应，由此增强产品的强度。
然后可以将脱硫材料以其经煅烧的形式提供给最终用户的装置。
本发明包括工艺流体物流的脱硫方法，其包括使该物流与脱硫材料接触。该脱硫材料可以用来对包含液体和气体的宽范围的硫进行脱硫，包括烃，例如天然气、液化天然气、天然气液态产物、炼油厂废气和燃料气、煤油、裂化石脑油、柴油燃料；二氧化碳、一氧化碳、氢和这些的混合物，包括具有宽范围组成的合成气混合物。特别地，脱硫材料可以应用于可能含氢的气态烃物流。优选地，脱硫材料应用于计划用作蒸汽重整装置的进料的液态烃物流。该烃物流包含含硫天然气和伴生气物流以及煤层甲烷和其他甲烷富气。
颗粒脱硫材料可以在250-450℃、优选300-400℃、更优选320-400℃的温度和1-100巴的绝对压力使用。在使用中并不需要氢，但可以通常在物流中提供水平为0.1-25vol%、优选1-5vol%的氢。
脱硫材料主要设计用来通过吸收来去除硫化氢，不过也可以捕获其他硫化合物，例如硫化羰、二硫化碳、硫醇(例如正丁硫醇)、二烷基硫化物(例如甲硫醚)、环状硫化物(例如四氢噻吩)、二烷基二硫化物(例如二乙基二硫化物)和噻吩物类，特别是如果进料流包含氢或其他还原剂时。但是，当进料中存在有机硫化合物时，脱硫材料优选与上游的HDS催化剂(例如常规的CoMo或NiMo基HDS催化剂)组合使用，该HDS催化剂用来在与脱硫材料接触前将原料中的有机硫转化为硫化氢。
现在参照以下实施例进一步描述本发明。
通过用颗粒脱硫材料填充1升量筒，轻叩筒壁直到获得恒定的体积，来测量振实堆密度(TBD)。记录振实体积。然后称重该材料并计算它的密度。
所用脱硫材料的硫含量使用LECO SC632仪器来确定。
BET表面积使用Micromeritics ASAP2420和MicromeriticsTristar3000设备来测量。样品在140℃用干燥氮气吹扫至少1小时来除气。所有仪器符合ASTM D3663-03(N2BET面积)和ASTMD4222-03(N2吸附/解吸等温线)。
孔体积来自使用设计来符合ASTM D4282-03的MicromeriticsAutoPore9520水银孔率计的水银孔率法。在分析前，样品在115℃干燥一整夜。在去除颗粒间侵入之后，在60000psia测量孔体积。
光密度分析法：由样品的骨架密度和几何密度计算孔体积。使用Micromeritics Accupyc1330氦比重计来测量骨架密度。使用自带的水银比重计来测量几何密度。同样在分析前，将样品在115℃干燥一整夜。两种方法均符合ASTM D6761-02。
实施例1(比较例)
在第一次测试中，将60ml KATALCOJM TM32-5(2.8-4.75mm，91.5wt%ZnO)样品装载到19mm ID玻璃反应器管中。随后将样品在流动的氮气中加热到370℃。一旦达到温度，则将气体进料切换为以42l/h和大气压输送的5vol%H2S+95vol%H2。然后使用管周期性监测离开吸收剂床的H2S水平，直到离开的H2S水平超过100ppmv时。在此时，继续该测试。随后将硫化的吸收剂释放到6个分散的层中。使用LECO仪器测量每个层上的硫拾取量。随后使用获得的结果来确定床平均硫拾取量(六个子床(sub-bed)硫测量结果的平均值)。获得的结果以kg S/l为单位记录于表1中。
新鲜KATALCOJM32-5相应的振实堆密度、BET表面积、水银孔率法和光密度分析法数据提供于表2中。
实施例2(比较例)
将25份碱式碳酸锌和7.0份铝酸钙粘合剂加入到75份ZnO。将得到的粉末充分混合，然后使用轨道行星式搅拌机添加适当的水来粒化。然后筛分生产出的颗粒，并计算尺寸
(2.8-4.75mm)。通过XRF测量最终产品中的ZnO负载量，并发现为92.7wt%。随后在与实施例1中列出的那些相同的条件下对该材料进行加速的硫化测试。获得的结果同样以kg S/l为单位记录于表1中。
新鲜材料相应的振实堆密度、BET表面积、水银孔率法和光密度分析法数据同样提供于表2中。
实施例3(发明例)
将25份碱式碳酸锌、7.0份铝酸钙粘合剂和2.2份碱式碳酸铜加入到75份ZnO。将得到的粉末充分混合，然后使用轨道行星式搅拌机添加适当的水来粒化。然后筛分生产出的颗粒，并计算尺寸级分(2.8-4.75mm)。通过XRF测量最终产品中的CuO和ZnO负载量，并发现分别为1.7wt%和92.1wt%。随后在与实施例1中列出的那些相同的条件下对该材料进行加速的硫化测试。获得的结果同样以kg S/l为单位记录于表1中。
新鲜材料相应的振实堆密度、BET表面积、水银孔率法和光密度分析法数据同样提供于表2中。
表1加速的硫化测试结果
表2氮物理吸附和水银孔率法数据
表2(续)光密度分析法数据
在实施例1和2结果的比较中，显然仅提高ZnO吸收剂的密度本身并不是提高产品的硫拾取量的有效策略。尽管在单位体积基础上，实施例2中的材料比实施例1中包含明显更多的ZnO，但是由于高密度产品的低表面积和孔隙率，不能有效利用这些另外的ZnO用于捕获硫(在测试的条件下，在100vppm H2S贯穿时，ZnO转化有效性在这两种情况中从46%降至38%)。相比之下，当将铜促进与提高密度相结合时，如实施例3，尽管产品的孔隙率和表面积降低，但是材料能够更有效地利用可用的ZnO用于吸收硫，这使得每单位体积吸收剂的硫捕集显著增加。
这是令人惊奇的，因为通常推测增大密度和因而减小孔体积和表面积会导致硫化合物吸收的降低。
实施例4(比较例)
将两个包含KATALCOJM32-5的85cm3容量的样品篮放置于在升高的温度以领先-滞后模式(lead-leg mode)操作的工业脱硫容器中。将一个篮放置在容器的入口，一个放在出口。联机一段时间后，将篮移开，并使用LECO仪器测量硫摄入。获得的结果记录于表3中。
实施例5(发明例)
重复实施例4的细节，只是同样放置在容器的入口和出口的样品篮填充的是如上述实施例3中所述而制备的脱硫材料。获得的结果记录于表3中。
表3工业反应器硫拾取量结果：入口篮
表3(续)工业反应器硫拾取量结果：出口篮
实施例4和5在相同的脱硫容器中以相同的联机时间长度同时进行测试。实施例4和5显示，在真实的设备条件下也观察到了上面所讨论的改进的性能。

Claims (15)

1.一种颗粒脱硫材料，其包含一种或多种负载在颗粒氧化锌载体材料上的铜化合物，其中该脱硫材料为由一种或多种粉末状铜化合物、氧化锌和一种或多种粘合剂形成的颗粒的形式，并且以CuO表示的铜含量为0.1-5.0wt％，振实堆密度≥1.55kg/l，所述氧化锌包含通过碱式碳酸锌煅烧形成的氧化锌。
2.根据权利要求1的脱硫材料，其中该脱硫材料的粒度为1-10mm。
3.根据权利要求1的脱硫材料，其中该脱硫材料的孔体积≤0.22cm3/g。
4.根据权利要求1的脱硫材料，其中该脱硫材料的BET表面积≤23m2/g。
5.根据权利要求1的脱硫材料，其中该一种或多种铜化合物选自氧化铜、氢氧化铜和碱式碳酸铜。
6.根据权利要求1的脱硫材料，其中该一种或多种粘合剂选自粘土粘合剂和水泥粘合剂及其混合物。
7.根据权利要求1的脱硫材料，其中该脱硫材料进一步包含含量为至多20wt％的第二载体材料，其选自一种或多种难熔氧化物。
8.根据权利要求1的脱硫材料，其中该脱硫材料进一步包含第二金属化合物，其选自铁、锰、钴或镍的一种或多种化合物。
9.制备根据权利要求1的脱硫材料的方法，其包括以下步骤：
(i)将粉末状铜化合物与颗粒锌载体材料和一种或多种粘合剂混合，以形成含铜组合物，该颗粒锌载体材料包含氧化锌和碱式碳酸锌，
(ii)使该含铜组合物通过粒化成形，和
(iii)干燥和煅烧得到的粒化材料。
10.根据权利要求9的方法，其中该铜化合物选自氧化铜、氢氧化铜或碱式碳酸铜。
11.根据权利要求9的方法，其中该铜化合物和氧化锌载体材料与一种或多种粘合剂合并，并粒化形成聚集的直径为1-10mm的球形。
12.工艺流体物流的脱硫方法，其包括使该物流和任选的氢与根据权利要求1或者根据权利要求9制备的脱硫材料接触。
13.根据权利要求12的方法，其中该工艺流体物流包含烃气和氢。
14.根据权利要求12的方法，其中将该工艺流体物流与氢混合，并与加氢脱硫催化剂接触，以形成经处理的工艺物流，然后将该经处理的工艺物流与该脱硫材料接触。
15.权利要求12的方法，其中在250-450℃的温度，将该脱硫材料与该工艺流体物流接触。
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