CN1599696A - 氨合成用催化剂 - Google Patents
氨合成用催化剂 Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 27
- 239000010439 graphite Substances 0.000 claims abstract description 27
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 17
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011591 potassium Substances 0.000 claims abstract description 6
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- KFIKNZBXPKXFTA-UHFFFAOYSA-N dipotassium;dioxido(dioxo)ruthenium Chemical compound [K+].[K+].[O-][Ru]([O-])(=O)=O KFIKNZBXPKXFTA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000008188 pellet Substances 0.000 claims description 3
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 238000011010 flushing procedure Methods 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 238000002203 pretreatment Methods 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract 2
- 229910003481 amorphous carbon Inorganic materials 0.000 abstract 1
- 230000007717 exclusion Effects 0.000 abstract 1
- 238000011282 treatment Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 238000004513 sizing Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- WECIKJKLCDCIMY-UHFFFAOYSA-N 2-chloro-n-(2-cyanoethyl)acetamide Chemical compound ClCC(=O)NCCC#N WECIKJKLCDCIMY-UHFFFAOYSA-N 0.000 description 1
- ADHFMENDOUEJRK-UHFFFAOYSA-N 9-[(4-fluorophenyl)methyl]-n-hydroxypyrido[3,4-b]indole-3-carboxamide Chemical compound C1=NC(C(=O)NO)=CC(C2=CC=CC=C22)=C1N2CC1=CC=C(F)C=C1 ADHFMENDOUEJRK-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 102100039851 DNA-directed RNA polymerases I and III subunit RPAC1 Human genes 0.000 description 1
- 101710112289 DNA-directed RNA polymerases I and III subunit RPAC1 Proteins 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241001482237 Pica Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 210000004534 cecum Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000311 lanthanide oxide Inorganic materials 0.000 description 1
- -1 mentioned Chemical compound 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J21/18—Carbon
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- B01J23/462—Ruthenium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- 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
我们要求基于钌的氨合成用催化剂，该催化剂直接负载于石墨上，该石墨的BET比表面积超过10m2/g，优选超过100m2/g，更优选超过280m2/g，所述石墨的特征在于X－射线衍射图样仅包含结晶石墨的衍射线特征，而不包括由于活性炭产生的相关谱带，钡、铯和钾作为助催化剂加到该催化剂中。该石墨载体可以避免已知的预处理和后处理，而这些处理在通过活性炭的部分石墨化获得载体的情况下是必需的，并在使用期间它们可以忽略被甲烷化作用影响，而由活性炭得到的载体表现出该甲烷化作用。而且，本发明的催化剂特征在于非常高的活性，即使钌加载量低于已知的加载量。
Description
本发明的主题是氨合成用催化剂，其特征尤其在于一种新型的有利的载体类型。此外，本发明涉及关于制备载体和催化剂以及其预处理和后处理的创新方法。
自一个世纪以来，工业上通过用氢气催化还原氮气(Haber-Bosch方法)而生产氨，最常用的催化剂是铁，同时添加助催化剂例如氧化钾、氧化铝和其他非还原性氧化物。为了达到在热力学和动力学因素之间最佳折衷，已经发现特别有利的是在120～220巴和380～520℃下处理(参见例如J.R.Jennings(编者)，《催化的氨合成》(Catalytic Ammonia Synthesis)，Fundamentals and Practice，Plenum Press，纽约，1991年和A.Nielsen，《氨催化剂和制备》Ammonia Catalysts and Manufacture，Springer Verlag，Heidelberg，1995年)。
为了在比以前指出的压力低的压力下操作(从装置设计、经济和安全的角度考虑其可以具有显而易见的优点)，已经考虑了几种其他的催化材料，并发现钌特别有希望。然而，这种金属的高成本导致高表面积的载体，以允许较高的金属分散，即使用较少量的金属。为此目的，已经研究了几种载体，例如：
·SiO2：参见Lopez等，React.Kinet.Catal.Lett.，
41(1990)217；
·Al2O3：Y.Kadowaki等，J.Catal.，.
161.(1996)178；和S.Murata等，J.Catal.，.
136(1992)118；
·沸石：C.T.Fishel等，J.Catal.，
163(1996)148；和J.Wellenbüscher等，Stud.Surf.Sci.Catal.，第84卷，B部分，Elsevier 1994年，941；
·MgO：O.Hinrichsen等，Chem.Eng.Sci.，
51(1996)1983；
·碳覆盖的氧化铝：K.S.Rama Ra0等，Appl.Catal.，
62(1990)L19；和S.K.Mashtan等，J.Molec.Catal.，
67(1991)L1；
·MgAlO4尖晶石：B.Fastrup，Catal.Lett.，
48(1997)111；
·镧系氧化物：Y.Niwa等，Chem.Lett.，1996，3；和特别地
·石墨化的碳：Z.Kowalczyk等，Appl.Catal.，A：General，
138(1996)83。
最适宜的载体必须满足一系列要求：a)其必须不是酸性的，b)其必须具有高表面积，以促进金属分散，c)其在所采用的反应条件下必须是化学稳定的，和d)其必须具有良好的机械强度。
就要求a)和b)而言，最有希望的材料是活性碳。然而，在反应环境下，钌可以催化碳的甲烷化作用。为了避免这种不利情况并提高催化剂的机械强度，已经采用在高温下预处理，其由于碳或多或少的深度石墨化而可以提高载体的稳定性，但同时这种处理大大地降低了表面积(L.Forni，D.Molinari，I.Rossetti，N，Pernicone，Appl.Catal.，A：General，
185(1999)269)。已经建议在空气中于425℃下进一步处理，旨在恢复至少部分表面积和孔隙率(美国专利US 4,163,775)，然而Z.Zhong等(J.Catal.，
173(1998)535)建议另外在流动的氢气中加热到至多900℃，以除去碳中存在的杂质和/或在制备催化剂期间加入的杂质。
为了改进Ru/C催化剂通常的低活性(K.S.Rama Rao等.，Appl.Catal.，73(1991)L1)，已经建议加入助催化剂，例如碱金属(S.Murata等，Chem.Lett.，1990，1067)；碱土金属(K.Aika等，J.Catal.，
136(1992))；镧系元素(Y.Kadowaki等，同上；Y.Niwa等，同上和J.Catal.，
162(1996)138)。此外参见美国专利US 4,142,996、US 4,163,775、US 4,250,057和US 4,600,571)。
正如已经提到的那样，本发明的主题是新型的基于钌的氨合成用催化剂，特征在于直接承载于特殊的石墨类型上，这相对于以前基于碳的载体而言可提供具有高度科技和经济重要性的许多优点。实际上，由于它们的使用，不再需要使活性碳经受热预处理而使其至少部分地石墨化，而且不再需要使其经受随后的氧化后处理以达到恢复表面积和孔隙率的目的(见上文)。实际上，本发明中采用的石墨已经具备使它们成为氨合成催化剂用的最佳载体的特征。
此外，根据本发明所用的石墨具有的抵抗甲烷化(即，在反应环境中由碳形成甲烷，这会导致损害载体性能)性质比负载于预处理的活性碳上的催化剂所表现出的这种性质高得多：实际上，用本发明的催化剂形成甲烷的作用仅仅可以在温度到达600℃后检测到，并且在大约700℃下还保持最小。
另外，本发明的催化剂特别活泼：相对于负载于预处理的活性碳上的催化剂而言，如所提及的那样，本发明的催化剂比采用其他载体的那些好，它们表现出较高的活性以及低得多的钌加载量。如果给出钌的高成本，甚至不必强调该结果的重要性。
用作根据本发明催化剂的载体的石墨必须具有超过10m2/g，优选超过100m2/g，更优选超过280m2/g的BET比表面积。此外，它们的特征必须是仅包含结晶石墨的特征衍射线(不包括由于无定形碳产生的相关谱带)的X-射线衍射图样。这意味着石墨表现出亲油特性。在本发明的催化剂中使用亲油性石墨的优点是令人惊奇的，因为以前的专利(US 4,600,571)中声明要避免使用亲油性石墨。特别合适的石墨的非限定性实例是由TimcalS.A.，Bodio，瑞士提供的微细粉末HSAG 300，其具有约300m2/g的BET比表面积。根据本发明，用钌酸钾的水溶液浸渍石墨，所述溶液在浸渍所需的最小量水中含有获得最终催化剂中希望的钌浓度所需的准确量的钌。在旋转蒸发器中(在大约30-90℃，优选大约70℃下)除去大部分水后，使固体在烘箱中于大约50-100℃，优选大约80℃下干燥过夜。然后在管式烘箱中在流动氢气下于300-340℃，优选大约320℃将钌酸盐还原成金属钌，并使其在流动氮气中冷却到室温。然后用蒸馏水处理该固体以除去残余的钾，直到洗液的pH变为中性，并在大约50-100℃，优选80℃下再次干燥。
然后按照以前由I.Rossetti，N.Pernicone和L.Forni(最后两个是本发明的发明人)在Appl.Catal.，A：General，
208(2001)271-278中公开的结果，加入由钡、铯和钾组成的助催化剂。该促进作用包括：首先用硝酸钡的水溶液浸渍先前获得的固体，接着在旋转蒸发器中在真空下于大约35-40℃除去过量的水，然后用CsOH+KOH的水溶液浸渍，接着除去水(见上文)。三种助催化剂的量应当使得助催化剂和钌的原子比为Ba/Ru＝0.4-0.8；Cs/Ru＝0.8-1.2；K/Ru＝3.0-4.0。优选这些比率是Ba/Ru＝0.6；Cs/Ru＝1；K/Ru＝3.5。根据情况，成品催化剂中钌的加载量可以为约1wt％～10wt％。
最后，通过施加2-4吨/厘米2的压力使催化剂成形为适当尺寸的粒料[例如2×2～6×6mm，优选3mm(直径)×2mm(高)]。就活性试验而言，粉碎和筛分所得到的催化剂，以收集0.10-0.35mm，优选0.15-0.25mm的筛分级份，如本领域技术人员已知的，采用相同筛分级份的惰性固体(例如采用石英)以催化剂/惰性固体的体积比为1∶10-1∶30稀释该催化剂；此外，在氨合成实验之前，通过在3/2体积比的流动氢气/氮气(420～470℃、25～35巴、空速(GHSV)为15000-25000h-1)中通过加热数小时(通常为4-6)活化这样稀释的催化剂。
下列实施例意在说明本发明。进行的其中三个实施例旨在证明根据本发明的载体相对首先经过氧化然后进行还原的石墨载体(实施例2)和分别按照已知方法通过活性碳的部分石墨化而得到的载体(实施例7和8)的优越性。
实施例1
由Timcal S.A.，Bodio，瑞士生产的标记为HSAG 300的细微粉末状、BET比表面积超过290m2/g的商购石墨样品，其X-射线衍射图样没有表现出任何由于无定形碳的相关谱段，用钌酸钾的溶液浸渍该石墨样品，在浸渍所需的最小量水中，该溶液含有获得最终催化剂中所希望的金属加载量所需的确切数量的钌。然后在真空中，在70℃，在旋转蒸发器中除去水，在烘箱中于80℃将所得到的固体干燥过夜。然后在流动氢气中，在管式加热炉中，在320℃下通过处理将钌酸盐还原成金属Ru，然后在流动氮气中冷却到室温。
冷却后，用蒸馏水重复清洗固体，以除去残余的钾，直到洗液的pH达到中性值。在烘箱中于80℃另外干燥4小时后，通过使用水溶液浸渍而加入助催化剂(Ba、Cs和K)，在浸渍所需的最小量水中，该溶液依次含有确切数量的BaNO3，和CsOH+KOH。在每次浸渍后，在真空中，在35-40℃，在旋转蒸发器中除去过量的水。
在成品催化剂中Ru加载量为8.9wt％，助催化剂和Ru的原子比分别为Ba/Ru＝0.6，Cs/Ru＝1和K/Ru＝3.5。
然后通过采用3吨/厘米2的压力1.5分钟，将成品催化剂成形为尺寸是4×4mm，具有最佳机械强度的圆柱形粒料，然后粉碎和筛分，收集0.15-0.25mm的筛分级份。
通过9mm内径的连续管式反应器在430℃和100巴下由下列方式测定催化活性：通过将由体积比为3/2的氢气和氮气组成的，空速(GHSV)为60000h-1的反应物气体混合物送入穿过0.15-0.25mm颗粒的催化剂床，该颗粒用以催化剂/石英体积比＝1/22，具有相同颗粒尺寸的石英稀释。在该流程之前，在相同反应物气体混合物氢气/氮气＝3/2，空速(GHSV)为20000h-1的流体中，在30巴的压力和在450℃将催化剂原位活化5小时。通过由在过量的已知浓度的硫酸溶液中鼓泡并用已知浓度的NaOH溶液返滴定过量的酸来估计流出气体中氨的体积浓度而测定活性。活性测试的结果报导于表1中。
然后在活性测试的相同条件下，通过测量从反应器中出来的气体中甲烷的浓度，同时以2℃/min提高温度直到700℃，而使催化剂经受抗甲烷化测试。在相同的表1中报导了抗甲烷化测试的结果。
实施例2(比较)
在流动空气中，在管式加热炉中，在425℃将实施例1的相同商购石墨HSAG300样品氧化12小时。在于流动的惰性气体中冷却以除去空气之后，损耗了原始重量的约20％的该样品，在流动氢气中，在900℃还原3小时，接着在流动的惰性气体中冷却到室温。在这些处理后，该石墨表现出BET比表面积为169m2/g和孔隙率为0.51cm3/g。
如实施例1中描述的那样加入Ru和助催化剂，成品催化剂的Ru加载量为8.1wt％，并且每种助催化剂和Ru的原子比与实施例1的原子比相等。将成品催化剂粒化，然后如实施例1中描述的那样粉碎和筛分，收集0.15-0.25mm的筛分级份。
如实施例1中描述的那样测定催化剂的活性和抗甲烷化作用，结果于表1中报导。
实施例3-6
还将实施例1的相同商购石墨HSAG 300样品用于实施例3-6的催化剂制备，Ru的加载量分别为1.90，3.06，4.21和4.92wt％，并且每种助催化剂和Ru的原子比与实施例1的原子比相同。将成品催化剂粒化，然后如实施例1中描述的那样粉碎和筛分，收集0.15-0.25mm的筛分级份。
如实施例1中描述的那样测定催化剂的活性和抗甲烷化作用，结果于表1中报导。
实施例7(对比)
将2-4mm颗粒的商购活性碳样品在氩中加热到2000℃ 2小时，该样品由PICA，Levallois(法国)生产，由椰壳制成，BET比表面积为1190m2/g，孔隙率为0.49cm3/g，灰含量为1.3wt％。冷却后，该样品表现出BET比表面积为105m2/g和孔隙率为0.12cm3/g。然后，如实施例2中描述的那样，在流动空气中氧化该样品，重量损耗约为25％。然后接着如实施例2中描述的那样在流动氢气中还原，导致具有BET比表面积为410m2/g和孔隙率为0.21cm3/g的成品碳。如实施例1描述的那样加入Ru和助催化剂，成品催化剂表现出Ru加载量为4.6wt％并且每种助催化剂和Ru的原子比如同实施例1的原子比那样。如实施例1中描述的那样将成品催化剂粒化，然后粉碎和筛分，收集0.15-0.25mm筛分级份。
如实施例1中描述的那样测定催化剂的活性和抗甲烷化作用，结果于表1中报导。
实施例8(对比)
将直径为4mm、圆柱形颗粒的挤出活性碳样品在氩中在1500℃处理2小时，然后如实施例7中描述的那样进行氧化和还原处理，该样品由CECA，Paris la D éfense，法国生产，标记为AC40，BET比表面积为1250m2/g、孔隙率为0.75cm3/g。最后得到BET比表面积为1470m2/g。除了粒化之外，按照实施例1的相同程序采用该载体用于制备催化剂。成品催化剂的Ru加载量为13wt％并且每种助催化剂和Ru的原子比如同实施例1的原子比那样。如实施例1中描述的那样将成品催化剂粉碎和筛分，收集0.15-0.25mm筛分级份。
如实施例1中描述的那样测定催化剂的活性和抗甲烷化作用，结果于表1中报导。
表1
实施例1-8的催化剂在GHSV＝60000h-1，430℃和100巴的活性和抗甲烷化作用。
催化剂 NH3(气体 初始CH4形 700℃CH4信号
(实施例号) 流出物中的Vol.％) 式的温度 (mV×min)的面积
1 10.8 615 1.5
2 2.3 615 2.5
3 9.3 620 1.8
4 11.0 605 1.7
5 11.5 600 1.1
6 10.0 600 1.9
7 10.8 495 8.9
8 11.1 490 20
从该表的数据可以得出下列结论：
·所有负载于如所提供的HSAG 300石墨之上的催化剂(实施例1、3、4、5和6)至少如同负载于在高温下处理然后氧化和还原的活性碳之上的那些催化剂一样活泼，或比那些催化剂更活泼(实施例7和8)；
·通过氧化，接着还原处理HSAG 300石墨(实施例2)极大地损害了催化剂的活性；
·负载于所提供的HSAG 300石墨上的催化剂非常活泼，或者甚至比负载于预处理的活性碳上的那些催化剂更活泼，同样是低得多的Ru加载量(将实施例3、4、5、6与实施例7、8比较)；
·所有负载于如所提供的HSAG 300石墨上的催化剂比负载于预处理的活性碳之上的催化剂高得多的抗甲烷化作用(将实施例1、3、4、5、6与实施例7、8比较)，因为它们在600℃或在更高的温度开始形成甲烷，并且它们即使在700℃形成极少的甲烷，然而实施例7和8的催化剂在低于500℃的温度已经开始形成甲烷并在700℃它们以8-20倍以上的数量形成甲烷；
·通过氧化接着还原处理HSAG 300石墨(实施例2)显著地损害了催化剂的抗甲烷化作用。
Claims (10)
1.基于钌的氨合成用催化剂，其负载于BET比表面积高于10m2/g并且X-射线衍射图样仅包含结晶石墨的特征衍射线而不包括由于无定形碳产生的相关谱带的石墨上。
2.根据权利要求1的催化剂，其特征是负载于BET比表面积高于100m2/g的石墨上。
3.根据权利要求1的催化剂，其特征是负载于BET比表面积高于280m2/g的石墨上。
4.根据权利要求1-3的催化剂，其中用钡、铯和钾促进催化活性。
5.根据权利要求4的催化剂，其中Ba/Ru、Cs/Ru和K/Ru的原子比分别为0.4-0.8；0.8-1.2和3.0-4.0。
6.根据权利要求3的催化剂，其中Ba/Ru、Cs/Ru和K/Ru的原子比分别为0.6、1和3.5。
7.根据权利要求3的催化剂，其中Ru加载量为成品催化剂的约1-10wt％。
8.制备根据前述权利要求的催化剂的方法，其中用钌酸钾的水溶液浸渍石墨，所述溶液在浸渍所需的最小量水中含有获得最终催化剂中希望的钌浓度所需的准确量的钌；在旋转蒸发器中于大约30-90℃和真空下除去大部分水，并在大约50-100℃下干燥残留固体；在流动氢气下于300-340℃将钌酸盐还原成金属钌，并使其在流动氮气中冷却；用蒸馏水通过冲洗除去钾，直到pH变为中性；然后用BaNO3的水溶液和CsOH+KOH的水溶液浸渍固体(在50-100℃预干燥)，这两种溶液在浸渍所需的最小量水中均含有获得成品催化剂中希望的Ba/Ru、Cs/Ru和K/Ru原子比所需的确切量的试剂，在每次浸渍后，在真空中于约35-40℃除去过量的水；然后使催化剂成形为约2×2-约6×6mm的粒料。
9.根据权利要求8的催化剂，其中粒料尺寸为3mm(直径)×2mm(高)。
10.采用权利要求1-7和9的催化剂由氢气和氮气的气态混合物生产氨的方法。
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| CN102380420A (zh) * | 2011-09-02 | 2012-03-21 | 福州大学 | 一种氨合成催化剂及其制备方法 |
| CN104014336A (zh) * | 2014-06-10 | 2014-09-03 | 福州大学 | 以高比表面石墨为载体的钌系氨合成催化剂及其制备方法 |
| CN105413683A (zh) * | 2015-12-18 | 2016-03-23 | 福州大学 | 一种含钡助剂的炭材料负载钌金属催化剂的制备方法 |
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| EP2391582B1 (de) * | 2009-01-29 | 2016-07-06 | Gert Ungar | Vorrichtung und verfahren zur synthese von ammoniak |
| US8420869B2 (en) | 2010-12-09 | 2013-04-16 | Eastman Chemical Company | Process for the preparation of 2,2,4,4-tetraalkylcyclobutane-1,3-diols |
| US8394997B2 (en) | 2010-12-09 | 2013-03-12 | Eastman Chemical Company | Process for the isomerization of 2,2,4,4-tetraalkylcyclobutane-1,3-diols |
| US9238603B1 (en) | 2014-12-10 | 2016-01-19 | Eastman Chemical Company | Batch process for the preparation of cis-2,2,4,4-tetramethylcyclobutane-1,3-diol |
| US9238602B1 (en) | 2014-12-10 | 2016-01-19 | Eastman Chemical Company | Process for the preparation of cis-2,2,4,4-tetramethylcyclobutane-1,3-diol |
| JP2017001037A (ja) * | 2016-09-29 | 2017-01-05 | 住友化学株式会社 | アンモニア製造用触媒組成物、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 |
| JP6736073B2 (ja) * | 2017-07-19 | 2020-08-05 | 国立研究開発法人産業技術総合研究所 | アンモニア合成触媒 |
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- 2002-10-18 WO PCT/EP2002/011707 patent/WO2003048045A2/en active IP Right Grant
- 2002-10-18 DE DE60230665T patent/DE60230665D1/de not_active Expired - Lifetime
- 2002-10-18 CA CA2468909A patent/CA2468909C/en not_active Expired - Lifetime
- 2002-10-18 EP EP02782956A patent/EP1451107B1/en not_active Expired - Lifetime
- 2002-10-18 DK DK02782956T patent/DK1451107T3/da active
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102380420A (zh) * | 2011-09-02 | 2012-03-21 | 福州大学 | 一种氨合成催化剂及其制备方法 |
| CN102380420B (zh) * | 2011-09-02 | 2013-04-17 | 福州大学 | 一种氨合成催化剂及其制备方法 |
| CN104014336A (zh) * | 2014-06-10 | 2014-09-03 | 福州大学 | 以高比表面石墨为载体的钌系氨合成催化剂及其制备方法 |
| CN104014336B (zh) * | 2014-06-10 | 2016-09-07 | 福州大学 | 以高比表面石墨为载体的钌系氨合成催化剂及其制备方法 |
| CN105413683A (zh) * | 2015-12-18 | 2016-03-23 | 福州大学 | 一种含钡助剂的炭材料负载钌金属催化剂的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1451107B1 (en) | 2008-12-31 |
| RU2288891C2 (ru) | 2006-12-10 |
| AU2002346948A2 (en) | 2003-06-17 |
| ITMI20012565A1 (it) | 2003-06-05 |
| PL213569B1 (pl) | 2013-03-29 |
| JP4522704B2 (ja) | 2010-08-11 |
| UA79099C2 (en) | 2007-05-25 |
| CN100387521C (zh) | 2008-05-14 |
| DE60230665D1 (de) | 2009-02-12 |
| DK1451107T3 (da) | 2009-05-04 |
| US20050053541A1 (en) | 2005-03-10 |
| MXPA04005402A (es) | 2005-06-20 |
| RU2004117172A (ru) | 2005-05-20 |
| PL370347A1 (en) | 2005-05-16 |
| AU2002346948B2 (en) | 2007-08-09 |
| AU2002346948A1 (en) | 2003-06-17 |
| CA2468909C (en) | 2012-01-03 |
| CA2468909A1 (en) | 2003-06-12 |
| US7115239B2 (en) | 2006-10-03 |
| ATE419223T1 (de) | 2009-01-15 |
| BR0214722A (pt) | 2004-08-31 |
| BR0214722B1 (pt) | 2011-11-16 |
| EP1451107A2 (en) | 2004-09-01 |
| WO2003048045A2 (en) | 2003-06-12 |
| WO2003048045A3 (en) | 2003-10-09 |
| JP2005511278A (ja) | 2005-04-28 |
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