CN102574097A - 吸着剂 - Google Patents

吸着剂 Download PDF

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Publication number
CN102574097A
CN102574097A CN2010800364493A CN201080036449A CN102574097A CN 102574097 A CN102574097 A CN 102574097A CN 2010800364493 A CN2010800364493 A CN 2010800364493A CN 201080036449 A CN201080036449 A CN 201080036449A CN 102574097 A CN102574097 A CN 102574097A
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CN
China
Prior art keywords
copper
carrier
sorbent
compound
fluid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2010800364493A
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English (en)
Inventor
A·菲施
L·J·查理斯
M·J·考辛斯
M·R·菲维尔
A·M·瓦格兰德
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Johnson Matthey PLC
Original Assignee
Johnson Matthey PLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Johnson Matthey PLC filed Critical Johnson Matthey PLC
Priority to CN201610824983.XA priority Critical patent/CN106378088A/zh
Publication of CN102574097A publication Critical patent/CN102574097A/zh
Pending legal-status Critical Current

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    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/0237—Compounds of Cu
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
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    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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    • B01D53/46—Removing components of defined structure
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
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Abstract

描述了一种制备吸着剂组合物的方法，包括以下步骤：(i)从溶液或浆料中将铜化合物层施涂在载体材料表面上，和(ii)干燥涂覆的载体材料，其中干燥的载体上的铜化合物层厚度为1-200μm。可以将前体转化成适合于通过施涂一种或多种硫化合物以将铜化合物硫化并形成CuS而从液体或气体中去除重金属的吸着剂。

Description

吸着剂
本发明涉及吸着剂和特别是适合于从流体物流中捕集重金属例如汞、砷和锑的金属硫化物吸收剂。
在流体物流例如烃或其它气体和液体物流中发现少量的汞。在烃物流中也可以发现少量砷。除了它的毒性之外，汞可以导致铝换热器和其它处理设备的失效。因此，需要从流体物流中、优选尽可能早地在工艺流程中有效去除这些金属。
US 4094777公开了利用含硫化铜的预硫化吸收剂从含汞的天然气物流中吸收汞。通过混合铜化合物例如粉末化碱式碳酸铜(也称为碱式碳酸铜)与载体或分散体材料例如水泥(cement)，和形成挤出物或颗粒，从而制备吸着剂。作为替代，通过用可溶性铜化合物例如硝酸铜的溶液浸渍载体例如氧化铝小球，制备吸着剂。利用硫化氢或水中或有机溶剂中的硫化物溶液硫化颗粒、挤出物或载体中的铜化合物。
尽管将微粒碳酸铜与微粒载体或水泥组合提供了有效的吸着剂，但是所得挤出物或颗粒中仍然可能有相当大比例的铜不可用。目前，铜是昂贵的金属，希望提供具有低Cu水平的、保留在造粒或挤出产品中观察到的高重金属容量的吸着剂。浸渍材料例如硝酸铜浸渍材料可能需要高的硫化温度或添加银化合物以被完全硫化，这两种情况都是不希望的。
申请人已经发现了克服前述制备路线的问题的方法。
因此，本发明提供制备吸着剂组合物的方法，包括以下步骤：
(i)从溶液或浆料中将铜化合物层施涂在载体材料表面上，和
(ii)干燥涂覆的载体材料，
其中干燥的载体上的铜化合物层厚度为1-200μm。
所述方法可以进一步包括施涂一种或多种硫化合物以实现铜化合物的硫化从而形成硫化铜(II)，CuS的步骤。
本发明还提供通过该方法可获得的吸着剂组合物，包含载体材料表面上的层形式的硫化的铜化合物。
本发明还提供从工艺流体中去除重金属的方法，包括使含重金属的工艺流体与硫化的吸着剂接触。
术语“吸着剂”包括吸附剂和吸收剂。
本文使用的“重金属”指汞，砷，铅，镉和锑，但是本发明吸着剂特别用于从流体物流中去除汞和砷，特别是汞。
铜化合物应该是可硫化的，即与硫化合物反应形成硫化铜(II)，CuS。适合的铜化合物是以下的一种或多种：碱式碳酸铜，硝酸铜，硫酸铜，乙酸铜，它们的氨络物，即碳酸氨铜、硝酸氨铜、硫酸氨铜和乙酸氨铜，硫化铜(II)和氧化铜。优选铜化合物是碳酸铜化合物，例如碱式碳酸铜。硝酸铜和硫酸铜是较次优选的，因为在任何后续硫化步骤期间产生HNO3或H2SO4。
不同于造粒或挤出产品，本发明吸着剂的铜含量相对低和优选为0.5-20重量％(以未硫化材料中存在的铜表示)，更优选0.75-10重量％，最优选0.75-5.0重量％。虽然该水平小于造粒材料中铜的一半，和在一些情况下小于1/3，但是出人意料地发现关于捕集汞的效力与这些产品相称。
本发明中，除了铜之外，吸着剂的可硫化的金属的总含量优选≤5重量％。这使得以充分低的水平形成相应的水-可溶性金属硫酸盐，不因为当工艺流体含有游离水时使用期间的溶解-再沉积和附聚而造成压降升高和减活。优选除了铜之外，硫化的吸着剂中金属硫化物的总含量为≤1wt％，更优选≤0.5wt％，特别是≤0.1wt％。杂质金属硫化物可以是以下的一种或多种：硫化钙，硫化锌，硫化铁，硫化镍，硫化铬和硫化锰。它们可以通过铜化合物或载体材料的污染而引入。低杂质金属硫化物水平可以通过选择高纯铜化合物和载体和通过从组合物中排除杂质金属化合物而实现。
铜化合物在载体表面上作为层存在。干燥的材料中层的厚度为1-200μm(微米)，但优选1-150微米，更优选1-100微米，特别是1-50微米。较薄的层实现更有效地利用施涂的铜。取决于铜化合物，硫化将通常留下不变或略微较薄的层厚度。本发明吸着剂中的铜化合物层可以容易地完全硫化。
载体材料可以是陶瓷或金属，但优选包括氧化物载体例如氧化铝，水合氧化铝，二氧化钛，氧化锆，二氧化硅或硅铝酸盐，或这些中两种或更多种的混合物。优选载体具有相对高的表面积和孔隙率使得所得层的表面积可以最大化。希望载体的BET表面积为10-330m2.g-1，优选100-330m2.g-1，更优选130-330m2.g-1。孔体积优选0.3-0.9cm3.g-1，更优选0.4-0.9cm3.g-1。载体可以是大孔、中孔或微孔的，但是优选是大孔(即它的平均孔径＞50nm)或中孔(即平均孔径为2-50nm)的。在这些材料中，优选＞50％的孔体积来自于这些孔。大孔材料在本发明中是有用的，因为它们能够将铜化合物保持在它们的表面上。BET表面积可以便利地利用氮的物理吸着进行测量。孔体积可以便利地利用氮的物理吸着测定，但是在本发明中，因为孔体积相对大，所以可以更适合地利用压汞法。孔径也可以利用这些技术测定。
优选载体是氧化铝例如γ，θ和δ氧化铝。在特别优选的实施方案中，载体是γ氧化铝。
本发明中，将铜化合物施涂到载体表面。如果载体是多孔的，一些铜化合物可能在载体表面处或附近进入孔。然而，干燥的涂覆载体中铜化合物层的厚度应保持为1-200μm。
载体可以作为泡沫、独石或蜂窝体、或作为整装填料上的涂层提供。与球形造粒吸着剂相比，这些载体提供吸着剂容器中降低的压降。特别适合的泡沫载体描述于EP-A-0260826中。作为替代，载体可以为选自以下的成型微粒单元形式：小球，环(例如拉西环)，三叶体，四叶体和圆柱体，其可以是有裂片或带凹槽的，具有延伸通过其的2-10个孔。优选提供降低的压降与高强度的组合的成型载体。特别优选4个孔的圆柱体，和环。
微粒成型单元希望具有最小尺寸，可以是1-50mm的宽度、直径或长度，和0.5-5的长径比(即宽度或直径/长度)。对于工业规模吸着剂，优选具有3-10mm的直径或宽度的单元，虽然也可以使用1-5mm的单元。
铜化合物层可以以多种方式形成在载体上。在一个实施方案中，通过施涂浆料，例如通过用不可溶性铜化合物例如碱式碳酸铜的浆料(其可以是含水或不含水的)浸涂或喷涂载体，形成碳酸铜层。碱式碳酸铜可以商购获得，或通过利用碱性碳酸盐沉淀剂从铜盐溶液中沉淀出碱式碳酸铜、接着通过洗涤以去除相应的碱性金属盐而新鲜制备。碱式碳酸铜分散在液体介质中，液体介质希望含水。固体含量可以便利地为10-30wt％。粘合剂材料例如氧化铝或水合氧化铝溶胶可以包括在所述层中，并且可以应用其它常规洗涂层制备技术，例如碾磨和混合分散体以在涂覆载体之前实现所需的粒度。载体可以通过将载体浸入浆料分散体中或通过将碳酸铜化合物的浆料分散体喷涂到载体上进行涂覆。可以应用多次浸涂和/或喷涂。浆料可以在10-95℃或更高，优选10-50℃的温度下施涂到载体上。申请人已经发现浆料的pH可以对吸着剂的硫容量和因此汞容量产生影响。优选碱式碳酸铜浆料的pH为5-9。
在替代实施方案中，通过将铜的氨络物化合物的溶液施涂到载体上和同时或随后将载体加热至50-200℃温度，形成铜化合物层。可以通过利用已知方法，任选在铵盐存在下，将铜化合物例如碱式碳酸铜，乙酸铜或硝酸铜溶解在氨水溶液中而形成铜的氨络物化合物。例如，碱式碳酸铜可以溶解在碳酸铵和浓缩氨的溶液中，使得Cu∶NH3摩尔比优选为至少1∶4。加热溶液导致氨释放和铜化合物沉积在载体表面上。不同于浸渍技术，使用加热后的载体使接触时的铜的氨络物化合物不稳定，导致载体表面上形成铜化合物层，而不是允许铜一直扩散通过它。本发明中，优选用含碳酸氨铜的溶液喷涂加热后的载体。作为替代，载体可以浸入铜的氨络物化合物溶液中和移除，其中在浸涂之前或之后加热载体，虽然这是较次优选的。不优选在铜的氨络物化合物溶液中形成载体的浆料，因为通过加热，这可能导致大量未载带的铜化合物从溶液中沉淀出来。在优选方法中，将载体加热至50-200℃的温度，和将铜的氨络物化合物、优选碳酸氨铜的溶液喷涂到加热后的载体上。这在载体表面上立即形成铜化合物的薄蛋壳层，释放出氨。
在硫化前干燥涂覆载体以去除可能干扰硫化反应的任何溶剂，例如水。然而，干燥温度优选保持≤200℃，更优选≤150℃，以避免铜化合物的大量分解。涂覆载体可以便利地在空气中在约70-105℃下干燥1-16小时。
虽然可以煅烧未干燥或干燥的材料以将铜化合物转化成氧化铜(II)，例如通过将它在空气或惰性气体中加热至250-500℃的温度，但是这不是必须的，因为申请人已经发现沉积的铜化合物可以在没有这个附加步骤的条件下直接进行硫化。
将铜化合物转化成硫化铜(II)CuS的硫化步骤可以使用常规方法进行。因此，可以通过使层中的铜化合物与选自硫化氢、碱金属硫化物、硫化铵、单质硫或多硫化物的硫化合物反应而进行硫化步骤。优选硫化氢。与利用替代品例如硫或硫化合物例如多硫化物的溶液相比，利用含硫化氢的气体混合物是显著更容易和快速的。需要时，气体混合物可以含有其它硫化合物例如硫化羰或挥发性硫醇。硫化化合物优选以与其它气体的混合物的形式进行使用。惰性气体例如氮、氦或氩是控制过程的常规措施。也可以使用二氧化碳。硫化气体混合物优选不含还原气体例如氢和一氧化碳，但当硫化步骤在150℃以下、特别是100℃以下的温度下进行时，这些可以存在。优选将硫化氢以0.1-5体积％的浓度在气体物流中提供至碳酸铜层。可以使用1-100℃的硫化温度。
硫化步骤可以异位在其中通过硫化剂的硫化容器中在干燥的吸着剂前体组合物上进行，或者硫化步骤可以原位进行，在这种情况下，将吸收剂前体装入用于吸收重金属的容器中并经历硫化。原位硫化可以利用硫化剂物流进行或在含重金属的物流也含硫化合物的情况下利用含重金属的物流本身进行。当发生这种伴随的硫化和重金属吸收时，存在的硫化合物量取决于硫化合物类型和使用的金属化合物。通常，使用至少1和优选至少10的如硫化合物(以硫化氢表示)浓度(v/v)与重金属浓度(v/v)的比所定义的浓度比，使得前体充分硫化。如果需要进料物流中硫化合物的初始浓度在建立硫化合物与重金属浓度的希望比所需的水平以下，则优选通过任何适合的方法增加硫化合物的浓度。
当待处理的流体含有游离水时，优选预硫化本发明的吸着剂。预硫化也避免了通过硫化步骤可能伴随的吸着剂的体积和强度变化导致的问题。
硫化的吸着剂的BET表面积理想地是10-330m2.g-1，优选100-330m2.g-1，更优选130-330m2.g-1，和孔体积是0.3-0.8cm3.g-1，更优选0.4-0.7cm3.g-1。
本发明可以用于处理含重金属、特别是汞和砷、特别是汞的液态和气态流体。在一个实施方案中，流体是烃物流。烃物流可以是炼厂烃物流例如石脑油(例如含有具有5或更多个碳原子的烃，和最终大气压力沸点为至多204℃)，中间馏分油或常压粗柴油(例如大气压力沸点为177℃-343℃)，减压粗柴油(例如大气压力沸点为343℃-566℃)，或渣油(大气压力沸点在566℃以上)，或通过例如催化重整从这样的原料产生的含烃物流。炼厂烃蒸汽还包括载体物流例如FCC工艺中使用的“循环油”和溶剂提取中使用的烃。烃物流也可以是原油物流(特别是当原油相对轻时)或例如从焦油或煤提取制得的合成原油(crude)物流。例如，可以利用本发明方法处理气态烃，例如天然气或炼制链烷烃或烯烃。可以特别用本发明的吸收剂处理海上原油和海上天然气物流。也可以处理杂质燃料例如汽油或柴油。作为替代，烃可以是凝析油例如天然气液体(NGL)或液化石油气(LPG)、液化天然气(LNG)或气例如煤层甲烷，掩埋气或生物气。
可以根据本发明处理的非烃流体包括二氧化碳，其可以用于充二氧化碳的饮料、强化油采收工艺中，用于碳捕集和储存，使咖啡脱咖啡因的溶剂，调料和香料提取，提取煤的溶剂等。可以通过本发明方法处理流体，例如用于洗涤过程或干燥过程的醇(包括二醇)和醚(例如三乙二醇，单乙二醇，RectisolTM，PurisolTM和SelexolTM)。也可以从用于酸气脱除单元的胺物流中去除汞。天然油和脂肪例如植物油和鱼油可以通过本发明方法处理，任选在进一步处理例如加氢或酯交换之后，例如用于形成生物柴油。
可以处理的其它流体物流包括来自脱水单元的再生气，例如分子筛废气，或来自二醇干燥剂再生的气体。
易于通过吸收剂处理的进料物流也包括固有地含有重金属和硫化合物的那些例如某些天然气物流，或其中已经加入硫化合物以实现汞和砷的吸收的含汞和/或砷的物流。
当流体含有游离的水、优选0.02-1vol％的低水平时，本发明特别有用。可以短时间内容忍至多5vol％的较高水平。本发明的吸收剂可以在延长的暴露于水之后简单地通过用干气、优选干燥的惰性气体例如氮吹扫而简单地再生。
优选汞的吸收在150℃以下、优选在120℃或以下的温度下进行，在该温度下汞吸收的总容量增加。可以使用低至4℃的温度以在本发明中达到良好的效果。优选温度范围为10-60℃。
汞可以为单质汞、或有机汞化合物、或有机亚汞化合物的形式。本发明对于去除单质汞是特别有效的，虽然可以短时间内去除其它形式的汞。气态进料物流中汞的浓度通常为0.01-1100μg/Nm3，和更通常为10-600μg/Nm3。
使用中，可以将吸着剂材料放置在附着容器中和使含重金属的流体物流通过它。理想地，根据已知方法将吸着剂作为一个或多个固定床放置在容器中。可以利用多于1个床，和床的组成可以相同或不同。通过吸收剂的气时空速可以为通常所利用的范围。
通过以下实施例进一步描述本发明。除非另有说明，使用以下分析工具：
i)硫。硫含量的分析利用LECO SC632、通过燃烧和随后红外测量二氧化硫而进行。
ii)BET表面积和孔结构分析。这些利用常规的氮的物理吸着测定。在140℃下利用氮吹扫1小时使样品脱气，之后进行BET表面积/等温测量。
iii)压汞法。将样品在115℃下干燥16小时，之后在升高的压力下将汞引入孔中，以测定孔体积。
iv)铜含量。Cu利用ICP-OES测量和利用常规标准计算。
v)Cu碳酸盐厚度。利用电子探针微量分析(EPMA)测量层厚度。将样品安放在树脂中、擦亮和真空碳涂覆，之后在20kV的加速电压下采出图像。
实施例1：碱式碳酸铜的洗涂层
洗涂层制备：将碱式碳酸铜(81g)和Sasol Disperal P3[高纯度可分散氧化铝粘合剂](9g)加入210g脱矿质水中。将浆料在高速混合器上混合并研磨以获得所需粒度。碾磨后的pH为5.9和粒度(d90)为4.4微米。
喷涂：将100gγ-，δ-、θ-，或α-氧化铝小球(1mm直径)装入箔内衬的盘式涂覆机中和用12g洗涂层喷涂。始终将载体维持在25-65℃下。
将涂覆的载体在105℃下干燥16小时。干燥的材料的铜含量为2.53-3.66wt％。
硫化：用N2中的1％H2S完全硫化60ml涂覆的材料。气体的流量为42升小时-1，和在环境温度和压力下进行硫化。
对于硫化的材料观察到25-50μm的铜层厚度。
实施例2：碳酸氨铜[Cu(NH3)4CO3)]
在温和加热下将碳酸铵(46.18g，0.294mol)溶解在氨溶液(100ml，1.8mol)中。将碱式碳酸铜(20.22g，9.98gCu，0.17mol)加入碳酸铵/氨溶液中并搅拌以溶解。测定所得溶液含有93.1g.L-1的铜。
将γ-，δ-、θ-或α-氧化铝小球(1mm直径)加热至50℃，80℃或150℃，和用碳酸氨Cu溶液喷涂。
将涂覆的载体在105℃下干燥16小时。干燥的材料的铜含量为0.98-1.46.wt％。
利用实施例1的方法硫化涂覆的材料。
在每种情况下，通过EPMA测量的干燥γ-氧化铝载带材料的铜层厚度为约47μm。干燥的δ-θ氧化铝载体的铜层厚度为41μm和干燥的α氧化铝载体的铜层厚度为28μm。
在120℃下在γ氧化铝载体上重复实验，但是随后在350℃下煅烧2小时以将碳酸铜层转化为氧化铜，之后利用实施例1的方法进行硫化。煅烧的材料的铜含量为3.33wt％。
硫化的氧化物材料上的铜层厚度观察为20-40μm。
实施例3：碳酸/乙酸氨铜
将乙酸铵(22.64g，0.294mol)溶解在氨溶液(100ml，0.9mol)中。在搅拌的条件下按比例加入碱式碳酸铜[Cu2(OH2)2CO3](221g/mol，Alfa Aesar)(20.22g，9.98gCu，0.17mol)。
将氧化铝载体、γ氧化铝小球(1mm直径)加热至150℃和用碳酸/乙酸氨铜溶液喷涂。
将涂覆的载体在105℃下干燥16小时和在350℃煅烧2小时。煅烧的材料的铜含量为0.78wt％。
利用实施例1的方法硫化煅烧的材料。
干燥的γ氧化铝载体上的铜层厚度为10μm。
实施例4：汞静态测试
用30ml干净的己烷将单质汞饱和的30ml正-己烷进行稀释，以获得300-700ppb(w/v)的Hg浓度，转移至具有PTFE磁力搅拌棒的100ml锥形瓶，和在中速搅拌5分钟。称重出0.50g每种测试材料并加入锥形瓶中。在中速上搅拌悬浮体20分钟以避免形成细颗粒。20分钟后采出悬浮体样品并通过在PSA改进Hewlett Packard 6890 GC上的原子荧光分析对单质汞进行定量。通过ln(Hgo/Hgx)相对于反应时间作图的梯度，测定一阶速率常数k(min-1)。
利用上述方法测试根据实施例1-3的方法制备的样品。结果如下。
用γ氧化铝上碱式碳酸铜的喷涂浆料获得了最佳结果。下文给出了随暴露于材料的时间的汞浓度。
Figure BDA0000136272860000102
分析材料1，以评价与市售造粒铜-锌氧化物/氧化铝汞吸着剂相比的孔隙率。结果如下；
Figure BDA0000136272860000111
**源自质量平衡计算
可以清楚看到根据本发明制备的产品的BET表面积的差异。对于测量孔结构，压汞法更适合于中孔，和与N2的物理吸着组合时给出孔结构的更清晰指示。
Figure BDA0000136272860000112
材料1通过该测量是中孔的。
实施例5：流动测试
将用于对比的材料1，6和市售造粒铜-锌氧化物/氧化铝产品在1％H2S/N2中硫化至饱和。将25ml硫化的吸着剂装入管状实验室规模吸收容器(内径19mm)中。将用单质汞饱和至约1.2ppm(w/v)的正-己烷在环境温度(约25℃)下、在7.0hr-1的液时空速(LHSV)下通过床。从反应器出口线路采出样品，通过在PSA改进Hewlett Packard 6890 GC上的原子荧光进行分析，以监控汞的水平。在测试结束时，通过真空将床排入9个相等的独立子床，通过ICP-光发射谱分析这些子床的总汞含量(w/w)。
所有材料运行750小时，在出口物流中观察到不一致的汞减退(slip)。下文给出了回收的材料的分析结果。
Figure BDA0000136272860000121
材料1显示了比市售产品更优异的汞吸收量，在入口床上为4.5-5wt％Hg。分布也是尖锐的，大部分汞通过入口的两个床去除，用于去除汞的剩余部分下降至痕量水平。材料6似乎在约2.5wt％Hg下达到饱和，导致不同的分布形状。
实施例6：pH的作用
根据实施例1的方法，通过将碱式碳酸铜的浆料洗涂层喷涂到1mm γ氧化铝小球上，制备两种吸着剂。两者的铜含量几乎一样，为3.6wt％。仅有的差异在于碱式碳酸铜浆料洗涂层的pH。材料1的pH为6.0-6.5。材料11用氢氧化四甲基铵将pH升高至10.0，以使用于喷涂的浆料变稀。
假定碳酸盐通过硫化100％转化，这应导致两种材料1.8wt％的硫负载量。然而，达到的实际硫负载量：
材料1＝1.57％S(87％转化率)
材料11＝0.69％S(38％转化率)
如下所示，在流动测试期间的床分布也非常不同，材料11似乎在入口床上已经达到了饱和。
Figure BDA0000136272860000131
证明pH 6-6.5的材料比在pH 10下施涂的材料优异。
实施例7：大孔材料
洗涂层制备：根据实施例1的方法制备碱式碳酸铜洗涂层浆料。
涂覆：使用外径为15mm，表面积为0.4m2/g和孔体积为0.09cm3/g的环形式的大孔α氧化铝载体材料。将30g氧化铝载体浸入洗涂层浆料中10分钟，以涂覆表面。将涂覆载体在105℃下干燥16小时。将涂覆的环压碎至1-2mm的粒度。干燥的材料的铜含量为3.5wt％。
硫化：用N2中的1％H2S完全硫化20ml压碎的材料。气体的流量为42升小时-1，和在环境温度和压力下进行硫化。
在根据实施例5的方法的流动测试中，测试所得材料从正-己烷中去除汞。材料运行750小时，在出口物流中观察到不一致的汞减退。下文给出了回收的材料的分析结果。
  床   累计床体积(ml)   总汞(ppm w/w)
  1   2.95   17530
  2   5.93   10560
  3   8.56   2535
  4   11.93   660
  5   14.51   260
  6   17.02   210
  7   20.07   200
分布是尖锐的，大部分汞通过入口的两个床去除，用于去除汞的剩余部分下降至痕量水平。
实施例8：气相测试
根据实施例1的方法制备硫化的吸着剂材料。硫化的吸着剂的铜含量为大约2wt％。
吸着剂捕集气相中的汞的能力如下测定：将4ml吸着剂材料装入内径5mm的玻璃反应器。使含约17ppb(w/v)单质汞蒸气的氮气在大气压力和环境温度下在400hr-1的GHSV下向下通过吸着剂材料。使测试处于这些条件下1173小时。在测试结束时，用清洁的氮气吹扫反应器，之后从反应器中排出吸着剂材料。通过酸消化接着是ICP-OES分析，对吸着剂的汞含量进行分析。结果显示捕集＞2重量％的汞，具有通过床的尖锐分布。

Claims (28)

1.一种制备吸着剂组合物的方法，包括以下步骤：
(i)从溶液或浆料中将铜化合物层施涂在载体材料表面上，和(ii)干燥涂覆的载体材料，
其中干燥的载体上的铜化合物层厚度为1-200μm。
2.权利要求1的方法，其中干燥的载体中铜化合物层的厚度为1-150微米，优选1-100微米，更优选1-50微米。
3.权利要求1或权利要求2的方法，其中吸着剂包含0.5-20重量％的铜。
4.权利要求1-4任一项的方法，其中除了铜之外，吸着剂的可硫化的金属的总含量≤5重量％。
5.权利要求1-4任一项的方法，其中铜化合物包括以下的一种或多种：碱式碳酸铜，硝酸铜，硫酸铜，乙酸铜，它们的氨络物，硫化铜(II)和氧化铜。
6.权利要求1-5任一项的方法，其中载体材料包括：氧化铝，水合氧化铝，二氧化钛，氧化锆，二氧化硅或硅铝酸盐，或这些中两种或更多种的混合物。
7.权利要求1-6任一项的方法，其中载体材料是氧化铝。
8.权利要求1-7任一项的方法，其中载体的形式为泡沫、独石或蜂窝体或整装填料上的涂层。
9.权利要求1-7任一项的方法，其中载体为选自以下的成型微粒单元形式：小球，环，三叶体，四叶体和圆柱体，其具有延伸通过其的2-10个孔。
10.权利要求1-9任一项的方法，其中载体的BET表面积为10-330m2.g-1和孔体积为0.3-0.9cm3.g-1。
11.权利要求1-10任一项的方法，其中载体是大孔和/或中孔的。
12.权利要求1-11任一项的方法，其中铜化合物层通过用碱式碳酸铜的浆料浸涂或喷涂载体形成。
13.权利要求12的方法，其中浆料的pH为5-9。
14.权利要求1-11任一项的方法，其中铜化合物层通过以下形成：将铜的氨络物化合物溶液施涂至载体上和同时或随后将载体加热至50-200℃的温度。
15.权利要求14的方法，其中铜的氨络物化合物包括碳酸氨铜。
16.权利要求14或权利要求15的方法，其中将载体加热至50-200℃的温度和将铜的氨络物化合物溶液喷涂到加热后的载体上。
17.权利要求1-16任一项的方法，包括煅烧干燥的涂覆载体以将铜化合物转化成氧化铜(II)的步骤。
18.权利要求1-17任一项的方法，还包括将一种或多种硫化合物施涂到所述层上以实现铜的硫化，从而形成硫化铜(II)。
19.权利要求18的方法，其中硫化合物是硫化氢。
20.通过权利要求1-17任一项的方法可获得的吸着剂前体组合物。
21.通过权利要求18或权利要求19的方法可获得的吸着剂组合物，包括载体材料表面上的含有CuS的层形式的硫化的铜化合物。
22.权利要求21的吸着剂组合物，其中除了铜之外，硫化的吸着剂中金属硫化物的总含量≤1wt％。
23.一种从工艺流体中去除重金属的方法，包括使所述流体与权利要求20的吸着剂组合物或根据权利要求1-17的方法制备的吸着剂组合物接触，其中所述流体还包含一种或多种硫化合物，优选硫化氢。
24.一种从工艺流体中去除重金属的方法，包括使所述流体与权利要求21或权利要求22的吸着剂或根据权利要求18或权利要求19的方法制备的吸着剂接触。
25.权利要求23或权利要求24的方法，其中重金属是汞和/或砷。
26.权利要求23-25任一项的方法，其中所述流体是烃物流。
27.权利要求23-26任一项的方法，其中含重金属的流体含有0.02-5vol％的量的游离水。
28.权利要求23-27任一项的方法，其中所述流体是海上烃物流或来自烃脱水单元的再生物流。
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CN105722579B (zh) * 2013-12-18 2019-08-16 庄信万丰股份有限公司 用于制备吸着剂的方法
CN105722587A (zh) * 2013-12-18 2016-06-29 庄信万丰股份有限公司 用于制备吸着剂的方法
CN105722587B (zh) * 2013-12-18 2019-03-29 庄信万丰股份有限公司 用于制备吸着剂的方法
CN104785278A (zh) * 2015-03-25 2015-07-22 江苏佳华新材料科技有限公司 一种脱汞催化剂及其制备方法
CN107787249A (zh) * 2015-06-05 2018-03-09 庄信万丰股份有限公司 制备吸着剂的方法
CN107810052A (zh) * 2015-06-05 2018-03-16 庄信万丰股份有限公司 制备吸着剂的方法
CN107666956A (zh) * 2015-06-05 2018-02-06 庄信万丰股份有限公司 制备吸着剂的方法
CN107810052B (zh) * 2015-06-05 2020-11-03 庄信万丰股份有限公司 制备吸着剂的方法
CN107666956B (zh) * 2015-06-05 2021-04-02 庄信万丰股份有限公司 制备吸着剂的方法
CN107787249B (zh) * 2015-06-05 2021-06-11 庄信万丰股份有限公司 制备吸着剂的方法
CN106215851A (zh) * 2016-09-28 2016-12-14 江苏理工学院 一种铜试剂修饰的纳米氧化铝的制备方法及其应用
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US20160001258A1 (en) 2016-01-07
RU2536989C2 (ru) 2014-12-27
RU2012110239A (ru) 2013-09-27
US9156019B2 (en) 2015-10-13
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AU2010284856A1 (en) 2012-03-15
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JP5778150B2 (ja) 2015-09-16
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SG178312A1 (en) 2012-03-29
US20130053234A1 (en) 2013-02-28
DK2467204T3 (da) 2019-07-22
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BR112012003391A2 (pt) 2016-02-16
GB0914272D0 (en) 2009-09-30

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