CN101970106A - 脱硫材料 - Google Patents

脱硫材料 Download PDF

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CN101970106A
CN101970106A CN2009801085470A CN200980108547A CN101970106A CN 101970106 A CN101970106 A CN 101970106A CN 2009801085470 A CN2009801085470 A CN 2009801085470A CN 200980108547 A CN200980108547 A CN 200980108547A CN 101970106 A CN101970106 A CN 101970106A
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nickel
compound
oxide
sulfur removal
weight
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CN101970106B (zh
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G·波特
G·E·维尔森
N·麦克里奥德
A·C·拉尔拉
A·C·加诺斯
Y·S·洛佩兹
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Johnson Matthey PLC
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Johnson Matthey PLC
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Abstract

描述了一种颗粒脱硫材料，其包含一种或多种镍化合物、氧化锌载体材料、和一种或多种碱金属化合物，其中该材料的镍含量为0.3-10重量％，该材料的碱金属含量为0.2-10重量％。还描述了制备该脱硫材料的方法，该方法包括步骤：(i)使镍化合物与颗粒锌载体材料和碱金属化合物接触以形成掺杂碱金属的组合物，(ii)将该掺杂碱金属的组合物成型，和(iii)干燥、煅烧以及任选还原所得材料。该脱硫材料可以用于以降低的烃氢解水平使烃气体料流脱硫。

Description

脱硫材料
技术领域
本发明涉及脱硫材料，特别是包含镍的脱硫材料。
背景技术
必须首先对欲用于产生合成气的烃进料进行脱硫以便保护敏感的下游催化剂不遭受失活。使用加氢脱硫(HDS)催化剂(典型地基于CoMo或NiMo催化剂)和氧化锌基吸收剂的组合按照常规进行除硫。在该方法中，HDS催化剂将进料中的任何有机硫物质转变为硫化氢，硫化氢随后可以通过与ZnO的反应被除去。为了进行加氢脱硫反应，在进料中必须存在氢气。作为上述两阶段方法的替代方案，还可以使用兼具有加氢脱硫活性和吸收硫化氢能力的单一材料。
以前已提出用于各种脱硫应用的含有镍的脱硫材料。
SU959821公开了用于气体脱硫的催化剂，该催化剂包含0.6-5.0重量％氧化镍、5.4-10.0重量％氧化铜、5-16重量％氧化铝和其余的氧化锌。宣称可以使用该材料进行脱硫的气体是天然气，原油精炼和裂化期间产生的气体，以及含有H2、CO和CO2的工艺气体。所述催化剂通过以下制备：将氧化锌、氧化铜、碱式碳酸镍和氧化铝在碳酸铵溶液中合并，并且在45-85℃范围内的温度下老化所得混合物。将所得物料在100-110℃下干燥并在350-400℃下煅烧。
EP1224970公开了用于与煤油对应的矿物油的深度脱硫的催化剂，该催化剂包含5-25重量％氧化镍、30-70重量％氧化锌、和氧化铝。用于生产深度脱硫催化剂的方法包括：将碱性物质与镍盐水溶液和锌盐水溶液中的每一种或者与它们的混合水溶液混合以分别或同时形成沉淀物，并将该沉淀物与氧化铝或氧化铝前体混合，接着进行成型和煅烧。
US6274533公开了用于裂化汽油或柴油燃料的脱硫的吸附剂系统，该吸附剂系统包含在含有氧化锌的颗粒载体上由选自镍、钴、铁、锰、铜、锌、钼、钨、银、锡、锑和钒的至少两种金属形成的经还原的双金属促进剂。优选的双金属促进剂是在由氧化锌、二氧化硅和氧化铝构成的颗粒载体上镍和钴的混合物。所公开的用于制备这些材料的方法包括：在干燥和煅烧之前将双金属促进剂化合物加入到载体组分中，或者用含有所选促进剂系统的单质金属、金属氧化物或含金属化合物的溶液浸渍经干燥和煅烧的载体颗粒。优选的制备途径包括以下步骤：(a)将氧化锌、二氧化硅和氧化铝混合以便按湿混合物、捏塑体、糊料或浆料的形式形成混合物；(b)将所得混合物造粒以形成料粒、挤出物、片块、丸粒、球或微球；(c)干燥所得颗粒；(d)煅烧经干燥的颗粒；(e)用双金属促进剂浸渍所得煅烧颗粒；(f)干燥经浸渍的颗粒；(g)煅烧所得经干燥的颗粒；以及(h)用合适的还原剂还原(g)的煅烧颗粒产物以便产生其中具有基本上还原的双金属促进剂内容物的颗粒组合物。
认为Ni组分催化进料中的任何有机硫物质的加氢脱硫，而ZnO吸收产生的硫化氢(通过反应形成ZnS)。虽然还原形式的镍具有活性，并且能够向用户提供预还原和钝化的材料，但是一般作法是向用户提供氧化物材料，由用户实施原位还原步骤。
虽然这些镍基材料在从烃进料中除去硫物质中显示出是有效的，但它们的适用性受到它们还可催化烃氢解(高度不需要的副反应)的事实的限制。对该反应主要的顾虑是其放热性质，这可在催化剂床中导致发生明显的过热。此外，该反应还消耗贵重的氢气。
发现碱金属化合物能够抑制氢解反应且不显著降低Ni-氧化锌脱硫材料的氢化和硫吸收能力。
发明内容
因此，本发明提供了一种颗粒脱硫材料，该颗粒脱硫材料包含一种或多种镍化合物、氧化锌载体材料、和一种或多种碱金属化合物，其中该材料的镍含量为0.3-10重量％，该材料的碱金属含量为0.2-10重量％。
本发明还提供了制备脱硫材料的方法，该方法包括以下步骤：
(i)将镍化合物与颗粒锌材料和碱金属化合物混合以形成掺杂碱金属的组合物，
(ii)将该掺杂碱金属的组合物成型，和
(iii)干燥和煅烧，以及任选还原所得材料。
本发明还提供了用于工艺流体料流脱硫的方法，该方法包括在氢气存在下使所述料流与脱硫材料接触。
镍化合物可以选自镍金属、氧化镍、氢氧化镍、硝酸镍、乙酸镍和碱式碳酸镍。用于制备所述材料的镍化合物与最终材料中的镍化合物可以相同或不同。在一个实施方案中将碱式碳酸镍与其它组分合并和煅烧所得混合物以提供具有氧化镍形式的镍的材料。在使用中，无论镍是氧化镍形式还是另一种镍化合物，通常将所述材料暴露于还原性气流使得镍化合物可还原为镍金属。材料中存在的还原或未还原状态的镍化合物的量使得镍含量为0.3-10重量％，优选0.7-5重量％。
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。颗粒锌材料还可以包含一种或多种在煅烧时形成氧化锌的前体。煅烧后脱硫材料中的Zn含量(以ZnO计)优选＞55重量％，更优选＞75重量％，特别地＞80重量％。
脱硫材料还可以包含选自铜金属、氧化铜(copper oxide)、氢氧化铜、硝酸铜、乙酸铜和碱式碳酸铜的铜化合物。用于制备所述材料的铜化合物与最终材料中的铜化合物可以相同或不同。在一个实施方案中将碱式碳酸铜与其它组分合并和煅烧所得混合物以提供具有氧化铜形式的铜的材料。在使用中，无论铜是氧化铜形式还是另一种铜化合物，通常将所述材料暴露于还原性气流使得铜化合物还原为铜金属。材料中存在的还原或未还原状态的铜化合物的量使得铜含量为0.3-10重量％，优选0.7-5重量％。在一个特别优选的实施方案中脱硫材料中Ni∶Cu的摩尔比为0.8∶1-1.2∶1。
碱金属化合物可以是钠化合物、钾化合物、锂化合物或铯化合物。优选地，碱金属化合物是氧化物、碳酸盐或碳酸氢盐。更优选的碱性化合物是氧化钠或碳酸钠。所述材料中存在的碱金属化合物的量使得材料中碱金属的含量为0.2-10重量％，优选0.2-5重量％。
脱硫材料可以使用已知的方法制备，所述方法例如用镍和碱金属化合物浸渍颗粒载体材料，接着进行干燥，或者挤出包含载体材料、镍化合物和碱金属化合物的糊料，接着进行干燥；或者通常通过在粘合剂存在下，将粉未状镍化合物、锌载体材料和碱金属化合物进行造粒，接着进行干燥。合适的粘合剂包括铝酸钙水泥和粘土粘合剂例如绿坡缕石粘土或海泡石粘土。优选通过造粒制备脱硫材料。在该技术中，在少量水存在下将粉末状镍化合物、锌载体材料、碱金属化合物和粘合剂混合以形成直径为1-10mm的粗略球形的团聚体。将造粒的材料干燥且煅烧以形成氧化物形式的脱硫材料。
因此制备根据本发明的脱硫材料的方法可包括以下步骤：
(i)在水存在下将粉末状镍化合物与颗粒锌材料和粉末状碱金属化合物混合以形成掺杂碱金属的细合物，
(ii)将该掺杂碱金属的组合物成型，和
(iii)干燥和煅烧成型的掺杂碱金属的组合物。
成型可以是造粒本身的作用，或者可以是根据本领域技术人员已知的方法通过成型模将所述材料单独粒化或挤出。因此脱硫材料可以是成型单元形式例如球体、丸粒、圆柱体、环或多孔洞丸粒，其可以是多叶形或是有槽纹的(fluted)，例如具有三叶草形截面。
干燥和煅烧可以在一个或两个阶段中进行。干燥典型地在40-120℃下进行。煅烧可以在250℃-750℃下进行高达24小时，但是优选在250-550℃下进行1-10小时。
为使脱硫材料具有活性，应将Ni组分在还原性气体流中还原以将Ni转化为单质形式。如果存在铜化合物，也可以将其还原。还原可以在掺杂碱金属的镍化合物和载体材料的干燥成型混合物上，或者在掺杂碱金属的镍化合物和载体材料的煅烧成型混合物上进行。优选在煅烧材料上进行还原。还原可以在器外或原位(即在待用于脱硫的容器中)进行。可以使用使Ni组分还原的已知方法。所述还原性气流可以是待脱硫的工艺流体，其中其含有氢气和/或一氧化碳。优选地，使用含氢气流将脱硫材料原位活化。活化通常在提高的温度例如250-500℃和1-100巴的绝对压力下进行。
在优选的实施方案中，脱硫材料包含0.3-10重量％的镍，0-10重量％的铜，1-15重量％的Al2O3，0.2-10重量％的钠，0-10重量％的粘合剂和余量的ZnO。
通过本发明方法获得的脱硫材料可以适用于许多含硫液体和气体的脱硫，所述含硫液体和气体包括烃例如天然气、液体天然气、天然气液体、煤油、裂化石脑油、柴油燃料；二氧化碳、一氧化碳、氢气和这些的混合物，包括具有多种组成的合成气混合物。特别地，该脱硫材料可以适用于气态料流例如气态烃或合成气混合物。优选地，本发明的脱硫材料适用于气态烃料流，特别是天然气料流。
在使用中，用于工艺流体脱硫的方法包括：在氢气存在下，在10-450℃的温度下和1-100巴的绝对压力下将液体或气态工艺流体与脱硫材料例如颗粒脱硫材料的固定床接触。使用中需要氢气，并且其可以典型地在料流中以0.1-25体积％的最小水平提供。
为了将工艺流体深度脱硫，可期望在根据本发明制备的脱硫材料的下游引入颗粒氧化锌硫化氢吸收剂床，以便捕获任何逃逸的硫化氢。
根据本发明方法获得的脱硫材料能够除去许多硫化合物，包括硫化氢、羰基硫化物、二硫化碳、硫醇例如叔丁基硫醇、二烷基硫化物例如二甲基硫醚、环硫化物例如四氢噻吩、二烷基二硫化物例如二乙基二硫醚和噻吩类物质。
具体实施方式
现将参考下面实施例进一步描述本发明。
实施例1(对比)
在全生产规模下，向100重量份颗粒锌载体材料加入7份铝酸钙粘合剂，2.2份碱式碳酸铜和2.7份碱式碳酸镍。将所得粉末彻底混合并然后使用轨道行星式混合器将其造粒。然后筛分制得的颗粒并且在300℃下煅烧具有所需尺寸(on-size)的部分(2.8-4.75mm)以形成混合氧化物。成品中NiO和CuO的载量均为1.5重量％。
实施例2(对比)
在实验室规模下，向颗粒锌载体前体(6.00kg)加入铝酸钙粘合剂(0.42kg)，碱式碳酸铜(0.13kg)和碱式碳酸镍(0.16kg)。将所得粉末彻底混合并然后使用实验室规模的轨道行星式混合器将其造粒。然后筛分制得的颗粒并且在300℃下煅烧具有所需尺寸的部分(2.8-4.75mm)以形成混合氧化物。成品中NiO和CuO的载量均为1.5重量％。
实施例3
重复实施例2的方法，不同之处在于还向粉末混合物中加入0.034kg碳酸钠。这在煅烧产物中提供0.5重量％的Na2O载量。
实施例4
重复实施例2的方法，不同之处在于还向粉末混合物加入0.34kg碳酸钠。这在煅烧产物中提供5.0重量％的Na2O载量。
实施例5
重复实施例1的方法，不同之处在于还向粉末混合物加入0.8重量份碳酸钠。这在煅烧产物中提供0.65重量％的Na2O载量。
实施例6：活性测试。
(a)烃氢解
使由天然气中20体积％氢气组成的进料气体以40barg的压力和1800hr-1的GHSV穿过对比例1和2以及实施例3和4中获得的造粒颗粒脱硫材料的床。以1℃/min的加热速率将床温度从环境温度加热到370℃，然后在370℃保持约20小时。
这些试验中所用天然气含有约88体积％甲烷，余量由CO2、N2、乙烷和各种重烃组成。
分析的所有重烃(C2-C7)在氢解方面显示出类似倾向。此处使用正丁烷和正戊烷转化率作为代表性实例。入口进料含有0.330体积％正丁烷和0.025体积％正戊烷。在规定条件下，如气相色谱分析所示，对于各个样品所观测到的正丁烷和正戊烷到甲烷的最大转化率如下：
  催化剂   ％正丁烷转化率   ％正戊烷转化率
  对比例1   57.0   61.2
  对比例2   98.9   99.8
  实施例3   2.8   14.6
  实施例4   0.1   6.8
  实施例5   7.9   26.3
两个对比例均显示出高出相当多的正丁烷和正戊烷转化率。实验室规模的材料显示出较高的转化率，这可能是由于更好的均匀性。铝酸钙粘合剂对氢解没有影响。
(b)加氢脱硫
在第一试验中，使由天然气中2％氢气+2ppm有机硫化合物组成的进料气体以343℃、35barg和4,000h-1的GHSV穿过根据对比例1和实施例3制备的颗粒脱硫材料的床。在该试验中，有机硫化合物由等份数的COS(羰基硫化物)、DMS(二甲基硫醚)和噻吩组成。在这些条件下运行10天后，对于两种样品均观测到COS和DMS的完全转化。噻吩的转化率如下：
  催化剂   ％噻吩转化率
  对比例1   99.3
  实施例3   89.6
在第二试验中，使由天然气中2％氢气+2ppm有机硫化合物组成的进料气体以343℃、35barg和20,000hr-1的GHSV穿过根据对比例1或根据实施例3制备的颗粒脱硫材料的床。在该试验中，有机硫化合物由等份数的COS(羰基硫化物)、DMS(二甲基硫醚)和噻吩组成。运行5天后，在这些条件下对于对比例1和实施例3再次观测到COS的完全转化。DMS和噻吩的相应转化率如下：
  催化剂   ％噻吩转化率   ％DMS转化率
  对比例1   61.2   91.4
  实施例3   49.6   89.4
在第三试验中，使由天然气中2％氢气+2ppm有机硫化合物组成的进料气体以343℃、35barg和8,000hr-1的GHSV穿过根据实施例5制备的颗粒脱硫材料的床。在该试验中，有机硫化合物由等份数的羰基硫化物、二甲基硫醚、叔丁基硫醇和四氢噻吩组成。在线15天后，在这些条件下观测到所有四种有机硫物质的完全转化。
由上述数据清楚的是，向这些材料中适当地加入钠显著降低它们的氢解活性并同时允许高度有效的加氢脱硫活性得到保持。实际上，钠组分对于不期望的烃氢解反应充当选择性毒物。
因此本发明提供了具有适宜活性的脱硫产品，其中烃氢解活性得到有效降低以提供活性和选择性的有利平衡。所需低的碱金属改性剂载量还使ZnO组分的稀释最小化，因此允许硫吸收容量尺可能高地得到维持。

Claims (15)

1.颗粒脱硫材料，其包含一种或多种镍化合物、氧化锌载体材料、和一种或多种碱金属化合物，其中该材料的镍含量为0.3-10重量％，该材料的碱金属含量为0.2-10重量％。
2.根据权利要求1的脱硫材料，其中镍化合物选自镍金属、氧化镍、氢氧化镍、硝酸镍、乙酸镍和碱式碳酸镍。
3.根据权利要求1或权利要求2的脱硫材料，其中氧化锌载体材料选自氧化锌、氧化锌/氧化铝混合物或锌-氧化铝水滑石。
4.根据权利要求1-3中任一项的脱硫材料，其还包含一种或多种选自铜金属、氧化铜、氢氧化铜和碱式碳酸铜的铜化合物。
5.根据权利要求1-4中任一项的脱硫材料，其中碱金属化合物是钠化合物、锂化合物、钾化合物或铯化合物。
6.根据权利要求5的脱硫材料，其中碱金属化合物是氧化物、碳酸盐或碳酸氢盐。
7.根据权利要求1-6中任一项的脱硫材料，其包含0.3-10重量％镍、0.3-10重量％铜、1-15重量％Al2O3、0.2-10重量％钠、0-10重量％粘合剂和余量的ZnO。
8.制备根据权利要求1-7中任一项的脱硫材料的方法，该方法包括以下步骤：
(i)将镍化合物与颗粒锌载体材料和碱金属化合物混合以形成掺杂碱金属的组合物，
(ii)将该掺杂碱金属的组合物成型，和
(iii)干燥和煅烧，以及任选还原所得材料。
9.根据权利要求8的方法，其中镍化合物选自氧化镍、氢氧化镍、硝酸镍、乙酸镍和碱式碳酸镍。
10.根据权利要求8或权利要求9的方法，其中锌载体材料选自氧化锌，氧化锌/氧化铝混合物，或锌-氧化铝水滑石，其还可以包含一种或多种在煅烧时形成氧化锌和/或氧化铝的前体。
11.根据权利要求8-10中任一项的方法，其中将选自氧化铜，氢氧化铜，硝酸铜，乙酸铜或碱式碳酸铜的铜化合物与镍化合物和载体材料混合。
12.根据权利要求8-11中任一项的方法，其中碱金属化合物是钠化合物、锂化合物、钾化合物或铯化合物。
13.根据权利要求8-11中任一项的方法，其中碱金属化合物是选自氧化物、氢氧化物、碳酸盐或碳酸氢盐的钠化合物。
14.根据权利要求8-13中任一项的方法，其中将煅烧的脱硫材料还原。
15.用于工艺流体料流脱硫的方法，该方法包括在氢气存在下使所述料流与根据权利要求1-7中任一项的或者根据权利要求8-14中任一项制备的脱硫材料接触。
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