CN1170630C - 催化法制备氨以及制备和回收氨合成催化剂的方法 - Google Patents
催化法制备氨以及制备和回收氨合成催化剂的方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 13
- 238000011084 recovery Methods 0.000 title abstract description 5
- 238000006555 catalytic reaction Methods 0.000 title description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 30
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 11
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000002681 magnesium compounds Chemical class 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 3
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000005189 flocculation Methods 0.000 claims 1
- 230000016615 flocculation Effects 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 239000011149 active material Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
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- B01J23/462—Ruthenium
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- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
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Abstract
一种在氨合成中呈活性的、具有改进的活性的催化剂，和一种从催化剂中回收有用的组分的方法。
Description
技术领域
本发明涉及一种改进的、在由氨合成气来制备氨时呈活性的催化剂。而且，本发明还涉及从废催化剂中回收有用的催化组分。
背景技术
在20世纪里，按吨数计，氨的制备已经显著地增加，以使氨处于最重要的工业化学产品之列。现在，超过1％的全球能量消耗是用于用传统的哈伯-勃赤法来制备氨。目前，多促进的铁催化剂到目前为止是工业上使用的最重要的催化剂。
最近，已将负载于碳上的促进的钌(Ru)催化剂引入到工业操作中。钌催化剂一般的缺点是在工业条件下使用的碳载体，因为所有形式的碳在这些条件下对氢化作用是敏感的。通过形成甲烷，氢化作用导致碳载体的逐渐损失，并最终造成严重的操作困难。因此，在工业合成氨的条件下，即，在300℃和500℃之间的温度下和超过50bar(50×105KPa)的压力下，呈热力学稳定的载体材料，可预期成为碳载体的重要的替换物。
在此作为参考引入的美国专利4309311，公开了一种在大约325-430℃的温度下，通过加热氰基络合物的组合物而得到的、用于合成氨的催化剂。该催化剂是基于例如氧化镁的载体上的碱金属或碱土金属六氰基钌酸盐。该催化剂的活化形式是氰基络合物的盐，并且载体的性质未表明有任何特殊的意义。
美国专利4588705公开了一种用于包括氨生产的多重目的的凝胶或悬浮液，是基于具有可还原的过渡金属和不可还原的金属的、含氰基的阴离子络合物，与一种或多种含有多价金属离子的溶液的混合物。
美国专利4698325公开了一种用于制备氨的催化剂。催化剂前体的实例显示出，该前体是基于含有0.3％重量/重量的氧化镁的氧化物的熔融混合物，并且使用钌的碱金属盐的促进剂。
例如，在US5756421和5336655及SE507226中提到了在诸如制备合成气的其它方法中使用的各种含钌的催化剂。
在此作为参考引入上述专利公开的全部内容。
由于钌基氨合成催化剂与铁基催化剂相比是非常昂贵的，有必要确保钌在催化剂中的最佳使用。因此，这种钌催化剂可达到的表面积，必须适合于给出该催化剂的高催化活性和较长的操作时间。而且，重要的是可以以低成本从催化剂中回收钌，以确保重复利用钌金属。最近，我们已经研究了载体材料的应用，它允许用高分散的Ru来制备催化剂，并使Ru和所需的促进剂都能容易回收。我们业已发现在这方面(和如上所述的关于对氢化作用的敏感性)氧化镁(MgO)是非常理想的载体。以前，在氨的合成中呈活性的、负载于MgO上的促进的Ru催化剂，在文献中已有记载。
当催化剂载体具有超过40m2/g的比表面并且该催化剂中的钌含量在3％重量和20％重量之间，并且促进剂含量是0.2-0.5mol的钌时，我们发现与早期记载的那些催化剂相比，在由氨合成气来制备氨时，负载于MgO上的促进的Ru催化剂出乎意外地显示出更高的催化活性。而且，已发现一种适用于回收有用的催化组分，尤其是适用于从废催化剂中回收钌的方法。
发明内容
因此，本发明的目的是提供一种用于合成氨的催化剂。
本发明的另一个目的是提供一种比那些先前已知的催化剂显示出更高的催化活性的氨合成催化剂。
而且，本发明的目的是提供一种含有起催化作用的、可容易地从废催化剂中回收的化合物的催化剂。
最后，本发明的目的是提供一种用于从氨合成催化剂中回收催化组分的方法。
通常的概念是，在所述的催化剂的组中，活性(所制备的氨的摩尔数/g催化剂)与催化剂钌含量之间有一种比值关系。通过本发明，该催化剂的活性增加10-20倍，而钌含量增加1.5-8倍。
因而，本发明提供一种在氨合成中呈活性的、具有改进的活性的催化剂。本发明还提供一种用于从该催化剂中回收有用的催化组分的方法，即：
I)一种促进剂组分的溶解的氢氧化物的溶液，
II)一种溶解的镁化合物的溶液，和
III)钌金属。
人们进一步发现，将根据本发明的催化剂的活性，在操作条件下改进，与合成氨反应方案的化学计算法相比，其中氨的浓度高和/或其中该合成气的组合物含氢量低。
在工业应用中，这种增强的活性有几个优点。重要地是，改进的催化剂活性允许使用相对更小的合成塔，或者使用更低的合成压力而不降低氨的生产率。
具体实施方式
实施例1
钌催化剂的制备。
MgO载体是从Johnson-Matthey购买的(纯度99.9955％，表面积51.3m2/g)。通过用Ru3(CO)12在四氢呋喃中浸渍载体，或通过Ru3(CO)12的化学气相沉积(CVD)，将钌引入到载体上。另一方面，可用诸如RuCl3的合适的盐，在非水溶剂中浸渍钌。在将浸渍的催化剂干燥以除去溶剂后或直接使用CVD法沉积的Ru3(CO)12/MgO，通过用氢处理而将该催化剂活化。活化是在30000h-1的空间速度下进行，并且按0.1℃/min加热速率直到它达到550℃，在这种情况下将该催化剂保持12小时并冷却到室温。将该催化剂缓慢地曝露于环境条件下(钝化)，以使小的Ru晶体的氧化达到最低程度。活化还可以在氮-氢-氨混合物中进行。合适的Ru浓度范围是3-20％重量的钌。
实施例2
催化剂的促进。
将来自实施例1的、通过将Ru3(CO)12负载于MgO上的CVD法制备的、随后用氢活化并且钝化的催化剂，在非水溶液中通过合适的促进剂盐的浸渍来促进。合适的促进剂是碱金属、碱土金属、镧系元素以及它们的结合。在促进剂盐的浸渍中，碳酸盐、氢氧化物和硝酸盐属于合适的反离子。在如实施例1所述的分离还原方法中，可将反离子除去，或可将它们直接引入到催化转化器中。促进剂的最佳含量取决于Ru浓度和分散，但对每摩尔钌来说，在0.2-5.0mol的促进剂范围内即可。
实施例3
催化剂的检测。
将促进的Ru/MgO催化剂传送到用于催化活性测量的装置中。将该催化剂加热到所需的检测温度，典型地是400℃，并将压力增加到所需的检测压力，典型地是100bar(100×105KPa)。在所需的空间速度，典型地为30000h-1下，使已知的氢-氮混合物和非必需的氨在催化剂床上通过，并确定出口处氨的浓度。通过系统地改变温度、压力、空间速度和氨入口浓度，在相应的条件下，即在温度为300-550℃、压力在10-140bar(10-140×105KPa)之间、空间速度在10000-100000h-1之间和氨的入口浓度为0-20％体积下，评价该催化剂的特性。
实施例4
从废催化剂中回收催化剂促进剂、Ru和Mg的硝酸盐。
在检测后，使该催化剂按实施例1中所述钝化。然后，用组成为1M氨水的碱性溶剂洗涤该催化剂。可能大量地(＞97％)回收促进剂，而不被钌或镁污染。可使洗液蒸发到干燥以分离促进剂氢氧化物。将从氨的洗涤过程剩余的催化剂，在组成为超过1M硝酸的酸性溶剂中加热到70℃。这样，将氧化镁载体转化为硝酸镁溶液，这就可以通过离心作用或过滤，将该溶液与剩余的钌金属分离。这样，可回收超过94％的Ru。硝酸镁是非常纯的，并且可用于制备其它镁盐或例如经碳酸盐转化成氧化物。
实施例5
单促进的Ru催化剂的活性。
根据实施例1-3制备的、含有4.1％重量的Ru和6％重量的Ba的催化剂的活性，是常规的多促进的铁催化剂KM1的5倍。
实施例6
双促进的Ru催化剂的活性。
将根据实施例1-3制备的、含有3.8％重量的Ru、5.8％重量的Ba和4.1％重量的Cs的催化剂，在等温转换器中检测，该转换器是在温度为400℃和压力为100bar(100×105KPa)、按照氨合成气中H2/N2的比率为3∶1以及催化剂的空间速度为30000h-1的条件下操作的。按容积基位计，该催化剂显示出超过常规的多促进的催化剂KMl(可从Haldor Topsoe A/S买到)5倍的活性。
Claims (3)
1.从包括作为催化活性金属的钌的氨合成催化剂中回收催化组分的方法，所述金属钌用一种或多种组分来促进，所述组分选自碱金属、碱土金属和镧系元素的组，该催化活性金属由氧化镁材料负载，其中氧化镁材料比表面至少为40m2/g，钌浓度在3％重量和20％重量之间，并且以每摩尔的钌计，促进剂含量为0.2-5.0mol，所述方法包括步骤：
a)用能够将促进剂金属转化成氢氧化物的碱性溶剂从催化剂上洗去促进剂，这样制成脱促进剂的催化剂，并得到富含溶解的促进剂氢氧化物的溶液；
b)使来自于脱促进剂的催化剂的氧化镁在硝酸中溶解，其中钌是不可溶的，这样在富含溶解的镁化合物的溶液中得到钌金属残余物；
c)通过液-固分离，从富含溶解的镁化合物的溶液中回收钌金属残余物，由此获得所述富含溶解的镁化合物的溶液和钌金属。
2.根据权利要求1的方法，其中碱性溶剂是氨水。
3.根据权利要求1或2的方法，其中钌金属是通过过滤、离心分离、沉淀或絮凝来回收的。
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| ATE348075T1 (de) * | 2000-07-06 | 2007-01-15 | Haldor Topsoe As | Rückgewinnung des ammoniaksynthesekatalysators |
| EP1605202B1 (fr) * | 2004-06-09 | 2016-10-05 | Valeo Vision | Dispositif projecteur multifonctions |
| US20060058174A1 (en) * | 2004-09-10 | 2006-03-16 | Chevron U.S.A. Inc. | Highly active slurry catalyst composition |
| JP4777670B2 (ja) * | 2005-02-25 | 2011-09-21 | 本田技研工業株式会社 | アンモニア合成触媒及びその製造方法 |
| US7485267B2 (en) * | 2005-07-29 | 2009-02-03 | Chevron U.S.A. Inc. | Process for metals recovery from spent catalyst |
| CN100493700C (zh) * | 2005-10-28 | 2009-06-03 | 厦门大学 | 一种钌基氨合成催化剂制备方法 |
| CN100421788C (zh) * | 2006-03-03 | 2008-10-01 | 厦门大学 | 混合钌基氨合成催化剂及其制备方法 |
| US7674369B2 (en) | 2006-12-29 | 2010-03-09 | Chevron U.S.A. Inc. | Process for recovering ultrafine solids from a hydrocarbon liquid |
| CN100448530C (zh) * | 2007-05-23 | 2009-01-07 | 浙江工业大学 | 一种复合氧化物负载钌基氨合成催化剂及其制备方法 |
| EA016893B1 (ru) * | 2007-10-31 | 2012-08-30 | Шеврон Ю.Эс.Эй. Инк. | Объемный катализатор гидрогенизации и его применение |
| US7846404B2 (en) * | 2007-11-28 | 2010-12-07 | Chevron U.S.A. Inc. | Process for separating and recovering base metals from used hydroprocessing catalyst |
| US7837960B2 (en) * | 2007-11-28 | 2010-11-23 | Chevron U.S.A. Inc. | Process for separating and recovering base metals from used hydroprocessing catalyst |
| US8221710B2 (en) * | 2007-11-28 | 2012-07-17 | Sherritt International Corporation | Recovering metals from complex metal sulfides |
| US7658895B2 (en) * | 2007-11-28 | 2010-02-09 | Chevron U.S.A. Inc | Process for recovering base metals from spent hydroprocessing catalyst |
| US8187561B2 (en) * | 2007-12-05 | 2012-05-29 | Ames Goldsmith Corporation | Processes and systems for recovering catalyst promoter from catalyst substrates |
| JP5039631B2 (ja) * | 2008-04-08 | 2012-10-03 | 日立造船株式会社 | 貴金属担持触媒の製造方法 |
| JP4252616B2 (ja) * | 2008-05-07 | 2009-04-08 | Ｊｆｅエンジニアリング株式会社 | アンモニア合成触媒 |
| US8976913B2 (en) * | 2008-09-17 | 2015-03-10 | Lsi Corporation | Adaptive pattern dependent noise prediction on a feed forward noise estimate |
| CA2756556A1 (en) * | 2009-03-25 | 2010-09-30 | Chevron U.S.A. Inc. | Process for recovering metals from coal liquefaction residue containing spent catalysts |
| CN101580235B (zh) * | 2009-06-17 | 2011-05-04 | 武汉工程大学 | 一种氮化硼纳米管粗产物的提纯与回收工艺 |
| US8372776B2 (en) * | 2009-11-24 | 2013-02-12 | Chevron U.S.A. Inc. | Hydroprocessing bulk catalyst and methods of making thereof |
| US8389433B2 (en) * | 2009-11-24 | 2013-03-05 | Chevron U.S.A. | Hydroprocessing bulk catalyst and methods of making thereof |
| US8815184B2 (en) | 2010-08-16 | 2014-08-26 | Chevron U.S.A. Inc. | Process for separating and recovering metals |
| JP6017777B2 (ja) * | 2011-11-30 | 2016-11-02 | 住友化学株式会社 | アンモニア製造用触媒組成物の製造方法及びアンモニア製造方法 |
| JP5677358B2 (ja) * | 2012-04-13 | 2015-02-25 | 日立造船株式会社 | ルテニウム担持触媒の製造方法 |
| US9321037B2 (en) | 2012-12-14 | 2016-04-26 | Chevron U.S.A., Inc. | Hydroprocessing co-catalyst compositions and methods of introduction thereof into hydroprocessing units |
| US9687823B2 (en) | 2012-12-14 | 2017-06-27 | Chevron U.S.A. Inc. | Hydroprocessing co-catalyst compositions and methods of introduction thereof into hydroprocessing units |
| EP3260526A4 (en) | 2015-02-17 | 2018-11-21 | Ajinomoto Co., Inc. | Production system and production method for organic compounds or microbes |
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| IT1238676B (it) * | 1990-01-26 | 1993-09-01 | Snam Progetti | Sistema catalitico e procedimento per la produzione di gas di sintesi mediante reazione di reforming di idrocarubri leggeri con co2 |
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| EP1170255A2 (en) | 2002-01-09 |
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| ZA200105547B (en) | 2002-02-01 |
| DE60125103T2 (de) | 2007-04-12 |
| US6673732B2 (en) | 2004-01-06 |
| CA2352548A1 (en) | 2002-01-06 |
| NO20013333D0 (no) | 2001-07-05 |
| ATE348075T1 (de) | 2007-01-15 |
| DE60125103D1 (de) | 2007-01-25 |
| US20030158036A1 (en) | 2003-08-21 |
| US6559093B2 (en) | 2003-05-06 |
| NO20013333L (no) | 2002-01-07 |
| JP2002052341A (ja) | 2002-02-19 |
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| EP1170255A3 (en) | 2004-01-07 |
| RU2267353C2 (ru) | 2006-01-10 |
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