CN1832801A - 再生氢化催化剂的方法 - Google Patents
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Abstract
一种再生包括至少一种在惰性载体上的选自Ru，Rh，Pd，Os，Ir和Pt的催化金属的废氢化催化剂的方法，所述方法主要包括在氧气存在下在300和700℃之间进行热处理。
Description
本发明涉及再生特异性氢化催化剂的方法以及利用这种再生催化剂的工业方法。
很多工业方法利用催化氢化步骤。非常适于此目的的催化剂为包括在惰性载体(硅石，矾土等)上的元素周期表VIII族的选自元素Ru，Rh，Pd，Os，Ir和Pt的金属的催化剂。
这种方法的实例为通过将乙烯(C2H4)的直接氯化作用和氧氯化结合形成1，2-二氯乙烷(DCEa)来制备氯乙烯单体(VCM)，将其进行热分解来一方面形成VCM并且另一方面形成HCl。在热分解过程中，同时生成约2000ppm(相对于的HCl体积)数量级的少量乙炔(C2H2)，但其由于具有与HCl具有非常类似的挥发性而不能从HCl中被很容易地分离。在C2H2反应产生多种对方法的收益不利的无价值的副产物的过程中，热分解HCl再生来进行氧氯化。一种已知的用于除去所存在C2H2的非常优良的方法包括利用适当的催化剂氢化将其转化为乙烯(C2H4)。在专利申请DE 24 38 153中描述了这种催化剂，其尤其阐述了一种基于无孔硅石上的Pd催化剂。然而在使用中，这种催化剂渐渐失活且，尽管上述的应用记录了理论上再生的可能性，在实践中这种再生被证明是失败的，尤其是由于重金属将这种催化剂污染(H.Muller等，Chem.-Ing.-Tech.59(1987)No.8，pp.645-7)。
然而，本申请人令人惊讶地发现如果这种污染的催化剂在氧气的存在下，在足以除去杂质而不是过高的温度(以免得削弱催化剂)下处理，所述催化剂可以令人满意地再生。
本发明因此提供了一种再生包括至少一种选自在惰性载体上的Ru，Rh，Pd，Os，Ir和Pt的催化金属的氢化催化剂的方法，所述方法主要包括在氧气存在下在300和700℃之间进行热处理。
上述的催化金属优选为Pt和Pd。Pd是尤其优选的，由于其高氢吸附能力。催化剂中催化金属的浓度通常按重量计大于或等于0.01％(相对于催化剂的总重量)，优选地大于或等于0.05％，甚至大于或等于0.1％。然而浓度通常小于或等于，或甚至小于或等于5％，或甚至小于或等于1％。
本发明方法可再生的催化剂的惰性载体优选地选自多孔和无孔硅石，矾土和硅-矾土。主要基于硅石的载体(换句话说由超过50％，优选地超过95％的SiO2组成)产生良好的结果。载体优选为无孔的或低孔隙率的，换句话说具有小于5m2/g，且优选地小于3m2/g，或甚至小于1m2/g的比表面积(根据BET法用氮气测定)。载体的平均孔隙体积优选小于0.01ml/g。其粒度优选在1和20mm之间，或甚至在2和10mm之间，且优选地在3和7mm之间。在此载体上催化金属通常存在于小于或等于微米的层中。其通常为具有0.1和0.5μm之间大小的微晶形式。尤其是，上述参考文献(DE 24 38 153和Müller的文章)中所述描述的无孔硅石产生良好的结果。
本发明“主要包括热处理”的方法的事实是指通过热处理实现了大部分催化剂的再生(换句话说获得至少50％的选择性和/或转化率)。热处理结果优选为至少75％的再生，或甚至至少90％，且尤其优选为全部再生，表明在所述热处理之前或之后没有任何再生处理(用例如蒸汽或H2)的情况下可以进行本发明方法，因此获自热处理的催化剂被再使用在其原来的氢化反应中。
然而，通常需要考虑在根据本发明热再生之前除去仍然存在于催化剂表面上的反应物(例如，通过氮气冲洗)。
类似地，通过“催化剂的再使用”是指等同于新鲜催化剂使用那些催化剂。这种使用可包括例如在通过H2冲洗激活之前。
热处理包括在氧气存在下维持在高温(300和700℃之间)。热处理期间的温度优选地大于等于400℃，或甚至大于等于500℃，以增加再生的效率。然而其优选小于等于600℃，或甚至小于等于550℃，以免损坏催化剂(因为众所周知，在过高温度下载体上的催化剂可能“烧结”，或催化金属凝聚，由于有效表面的减少导致活性降低)。热处理可在纯氧存在下进行。然而，优选地，氧气用例如惰性气体稀释。因此空气产生良好的结果。
因此所述的处理的问题事实上通常包括氧化气体通常是指什么，其可以是静态的或动态的(也就是说包含氧气的气流流经待再生的催化剂)。流动的氧化气体产生良好的结果。在火炉或电烘箱中简单地驻留，优选地用风扇，可用作本发明的热处理。产生良好结果的另一方式包括使氧化气体在加氢反应器中例如原位流经催化剂床。
当处理过程中分散催化剂时，通常获得较好的结果：也就是，当最大的表面积暴露于氧化气体时。因此催化剂优选在层中分散，从催化剂单层(其厚度取决于催化剂的粒度)到约20cm的层，不过优选地，层的厚度不超过10cm，或甚至5cm。
所述处理的时间很容易由技术人员确定且随再生的期望程度而变化。它通常大于或等于1小时，或甚至5小时。然而持续时间通常小于或等于48小时，或甚至24小时。通风流速也是如此，其优选地大于或等于0.011/分钟，kg催化剂(或升，每分钟，每kg催化剂)，或甚至大于或等于0.11/min.kg催化剂，但通常小于或等于100l/min.kg催化剂，或甚至小于等于10/min.kg催化剂。
预通过本发明方法再生的催化剂为“废”催化剂，(即已用于氢化反应中的催化剂)其催化活性(按照选择性和/或转化率)已经下降。此种催化活性的下降通常是由于含碳物质的沉淀和/或氯化合物和/或至少一种痕量重金属的污染。术语“重金属”是指下述的一种金属：Al，As，Cd，Cr，Ni，Cu，Sn，Fe，Mn，Hg，Pb，Zn和Ti(不过后者通常不被认为是重金属，然而其构成对加氢催化剂的破坏性污染且，因而，在本发明上下文中被视为重金属)。痕量重金属尤其具有破坏性且，在它们之中，尤其是Fe和Ti，因为它们通常存在于工业液体中，取决于用于运输/处理它们的设备的特性。类似地，痕量Hg，其遇到特定来源的H2也是破坏性的。“痕量”是指的数量级，或甚至几十倍ppm的数量级。通常起始催化剂已包含痕量的某些重金属(尤其是Fe，但通常小于50ppm)，但使用过程中增加其量(例如铁的情况，大于或等于50ppm)通常有助于降低催化活性。
其中已经使用催化剂的氢化反应优选为乙炔加氢反应。优选应用存在于流体中，并且优选存在于主要包含HCl的气体混合物中，并且获自如上所述的DCEa的热解的痕量乙炔。这种混合物通常包含1500以及2500ppm之间的乙炔。常常也包含数量级为几十到数百ppm的氯化有机产品诸如VCM以及氯甲烷或者氯乙烷，和/或非氯化有机产品诸如乙烯(C2H4)，甲烷以及丁二烯。这些杂质源于从HCl分离热解产物操作期间的不完全分离，所述分离通常由蒸馏进行。对于这类反应，如上所述，无孔硅基载体上基于Pd的催化剂产生良好的结果并且根据本发明的加工可以很容易再生。
由本发明加工再生的催化剂可用于任何其可具有催化活性的氢化反应。优选地，在类似于预先使用其的方法中再利用。因此本发明同样提供了通过将乙烯的直接氯化作用以及氧氯化结合形成DCEa合成VCM的方法，所述DCEa通过热解主要转化为VCM以及HCl，所述HCl包含痕量乙炔，并且这些痕量乙炔在如上所述的方法再生的催化剂存在下氢化后，再循环到氧氯化。
本发明通过下列实施例进行非限制性描述。
催化剂E39H(3到5mm直径的硅石珠，0.15％的Pd提供在表面，比表面积小于1m2/g)，由Degussa出售，并由Müller描述在上述文章中，与包含大约2000ppm的C2H2在10bars以及120和180℃之间的温度下与HCl接触四年半(54个月)。驻留时间(HCl的m3数(s.t.p.)/h和m3表示的催化剂床的体积的比率)是1680h-1。采用的H2的量为每mole C2H2 3.8mol。
分析该废催化剂并与新催化剂相比较。这些分析结果提供在下表中：
| 分析的成分(内含物) | 新鲜催化剂 | 废催化剂 |
| Pd(重量％) | 0.15 | 0.14 |
| Cl(重量％) | 0.015 | 1.090 |
| Fe(ppm) | ＜50 | 84 |
| 痕量 | - | Co，Zn，Cu，Ti，Pb，Zr |
一批150kg的该废催化剂覆盖在18个板上，每一板的表面积为0.3m2。烘箱温度设定在500℃并保持18小时。通过100l/分钟的进气量控制烘箱的通风。
随后在类似于如上所述的条件下，在173℃温度下再利用这些批料，将其催化活性与使用寿命终止时(180℃使用)的废催化剂的催化活性相比较，结果如下表所示：
| 废催化剂 | 再生的催化剂 | |
| C2H2的转化率(％) | 82 | 94.6 |
| 产率(摩尔％C2H4/C2H2) | 48.7 | 62.9 |
结果发现催化活性被高度再生(尽管在较低的操作温度下仍然提高了转化氯并且提高了产率)。
Claims (9)
1.一种再生包括至少一种在惰性载体上的选自Ru，Rh，Pd，Os，Ir和Pt的催化金属的废氢化催化剂的方法，其特征在于废催化剂已被用于痕量乙炔的氢化反应中，所述痕量乙炔存在于主要包括HCl的气体混合物中且获自1，2-二氯乙烷(DCEa)的热分解，且所述方法主要包括在氧气存在下在300和700℃之间的温度下进行热处理。
2.根据前述权利要求的方法，其特征在于催化金属为Pd。
3.根据前述权利要求任一项的方法，其特征在于惰性载体主要基于硅石。
4.根据前述权利要求任一项的方法，其特征在于惰性载体具有小于5m2/g的BET表面积。
5.根据前述权利要求任一项的方法，其特征在于热处理过程中的温度在400和600℃之间。
6.根据前述权利要求任一项的方法，其特征在于热处理在空气存在下进行。
7.根据前述权利要求的方法，其特征在于热处理包括驻留在火炉或通风电烘箱中。
8.根据前述权利要求任一项的方法，其特征在于催化剂被痕量重金属污染。
9.合成氯乙烯单体(VCM)的方法，通过将乙烯的直接氯化作用和氧氯化结合形成DCEa，所述DCEa通过热解主要转化为VCM以及HCl，所述HCl包含痕量乙炔，并且这些痕量乙炔在通过前述权利要求任一项的方法再生的催化剂存在下氢化后，再循环到氧氯化。
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| CN102471699A (zh) * | 2009-07-09 | 2012-05-23 | 吉坤日矿日石能源株式会社 | 再生氢化处理用催化剂的制造方法及石油制品的制造方法 |
| CN104399492A (zh) * | 2014-11-17 | 2015-03-11 | 张立军 | 一种钯催化剂焙烧再生工艺 |
| CN105712835A (zh) * | 2014-12-03 | 2016-06-29 | 青岛海晶化工集团有限公司 | 一种平衡氧氯化法制备vcm的方法 |
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| US7838708B2 (en) | 2001-06-20 | 2010-11-23 | Grt, Inc. | Hydrocarbon conversion process improvements |
| WO2005021468A1 (en) | 2003-07-15 | 2005-03-10 | Grt, Inc. | Hydrocarbon synthesis |
| US20050171393A1 (en) | 2003-07-15 | 2005-08-04 | Lorkovic Ivan M. | Hydrocarbon synthesis |
| US20080275284A1 (en) | 2004-04-16 | 2008-11-06 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US20060100469A1 (en) | 2004-04-16 | 2006-05-11 | Waycuilis John J | Process for converting gaseous alkanes to olefins and liquid hydrocarbons |
| US7244867B2 (en) | 2004-04-16 | 2007-07-17 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
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| CN100355718C (zh) * | 2005-09-21 | 2007-12-19 | 扬子石油化工股份有限公司 | 加氢精制对苯二甲酸的催化剂的再生方法 |
| US7718158B2 (en) | 2005-10-13 | 2010-05-18 | Lyondell Chemical Technology, L.P. | Polymer-encapsulated ion-exchange resin |
| EP1993979A4 (en) | 2006-02-03 | 2011-07-06 | Grt Inc | CONTINUOUS PROCESS FOR CONVERTING NATURAL GAS TO LIQUID HYDROCARBONS |
| UA95943C2 (ru) | 2006-02-03 | 2011-09-26 | ДжиАрТи, ИНК. | Отделение легких газов от галогенов |
| KR101236099B1 (ko) * | 2006-12-12 | 2013-02-21 | 주식회사 엘지화학 | 신규한 염화비닐 단량체 제조방법 |
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| US8282810B2 (en) | 2008-06-13 | 2012-10-09 | Marathon Gtf Technology, Ltd. | Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery |
| SG192538A1 (en) | 2008-07-18 | 2013-08-30 | Grt Inc | Continuous process for converting natural gas to liquid hydrocarbons |
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| GB811820A (en) * | 1957-04-30 | 1959-04-15 | Englehard Ind Inc | Catalytic hydrogenation of acetylene |
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| DE2438153A1 (de) * | 1974-08-08 | 1976-02-19 | Degussa | Verfahren zur selektiven entfernung von acetylen aus dem bei der 1,2-dichloraethan-spaltung zu vinylchlorid anfallenden rohchlorwasserstoff enthaltenden gasgemisch |
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| CN102471699A (zh) * | 2009-07-09 | 2012-05-23 | 吉坤日矿日石能源株式会社 | 再生氢化处理用催化剂的制造方法及石油制品的制造方法 |
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| CN104399492A (zh) * | 2014-11-17 | 2015-03-11 | 张立军 | 一种钯催化剂焙烧再生工艺 |
| CN105712835A (zh) * | 2014-12-03 | 2016-06-29 | 青岛海晶化工集团有限公司 | 一种平衡氧氯化法制备vcm的方法 |
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| MY149389A (en) | 2013-08-30 |
| AR045336A1 (es) | 2005-10-26 |
| JP2007501691A (ja) | 2007-02-01 |
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| EG24366A (en) | 2009-03-05 |
| EA008672B1 (ru) | 2007-06-29 |
| WO2005014168A1 (en) | 2005-02-17 |
| CA2534760A1 (en) | 2005-02-17 |
| EA200600378A1 (ru) | 2006-06-30 |
| TW200510062A (en) | 2005-03-16 |
| BRPI0413286A (pt) | 2006-10-10 |
| EP1658137A1 (en) | 2006-05-24 |
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