CN103298554A - 氧化钛负载的氢化处理催化剂 - Google Patents
氧化钛负载的氢化处理催化剂 Download PDFInfo
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- CN103298554A CN103298554A CN2011800614544A CN201180061454A CN103298554A CN 103298554 A CN103298554 A CN 103298554A CN 2011800614544 A CN2011800614544 A CN 2011800614544A CN 201180061454 A CN201180061454 A CN 201180061454A CN 103298554 A CN103298554 A CN 103298554A
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- Prior art keywords
- catalyst
- carbon monoxide
- molybdenum
- olefin polymeric
- carrier
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- 239000003054 catalyst Substances 0.000 title claims abstract description 156
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 42
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 34
- 239000011733 molybdenum Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 18
- 239000010937 tungsten Substances 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- 239000010779 crude oil Substances 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 120
- 239000011148 porous material Substances 0.000 claims description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 239000004408 titanium dioxide Substances 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
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- 239000010941 cobalt Substances 0.000 claims description 21
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- 238000001354 calcination Methods 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
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- 238000005516 engineering process Methods 0.000 claims description 13
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- 239000001257 hydrogen Substances 0.000 claims description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 9
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- -1 nitrogen-containing compound Chemical class 0.000 claims description 8
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- 239000007864 aqueous solution Substances 0.000 claims description 6
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- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 6
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- 230000008569 process Effects 0.000 abstract description 18
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 abstract description 2
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- 239000000126 substance Substances 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- GVGLGOZIDCSQPN-PVHGPHFFSA-N Heroin Chemical compound O([C@H]1[C@H](C=C[C@H]23)OC(C)=O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4OC(C)=O GVGLGOZIDCSQPN-PVHGPHFFSA-N 0.000 description 4
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- 230000015572 biosynthetic process Effects 0.000 description 4
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- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000010412 oxide-supported catalyst Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
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- 239000002585 base Substances 0.000 description 3
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- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 3
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
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- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及用于氢化处理工艺的成形的TiO2负载的催化剂,其至少含有钼或钨作为活性组分,具体涉及从原油馏分中去除含硫化合物和含氮化合物以及金属,还涉及氧化硫的氢化。
Description
技术领域
本发明涉及用于氢化处理工艺的成形的TiO2负载的催化剂,其至少含有钼或钨作为活性组分,具体涉及从原油馏分中去除含硫化合物和含氮化合物以及金属,还涉及氧化硫的氢化。
背景技术
通常来说,氢化处理反应涉及在存在催化剂的情况下,通常在提升的温度和压力下,向基材施加氢,所述催化剂的目的是导致基材的物理或化学变化。大多数的此类氢化处理反应在精炼操作中发生,其中,所述基材是烃进料。
常规氢化处理催化剂通常是耐火氧化物材料的载体的形式,在该耐火氧化物材料上沉积了提供氢化组分的金属化合物,根据目标用途来对每种组分进行选择和确定用量。本领域中常用的耐火氧化物材料是无定形或者晶体形式的氧化铝、二氧化硅,或者它们的组合。这些氧化物材料会具有部分内在催化活性,但是通常仅提供其上存在活性金属化合物的载体。
金属通常是元素周期表第VIII族和第VIB族的碱金属或者稀有金属,它们在制造过程中以氧化物的形式发生沉积,在碱金属的情况下,在使用前氧化物发生硫化,以增强它们的活性。
根据本领域的现有技术,采用基于钼或钨的催化剂同时钴或镍作为促进剂,从原油馏分中去除含硫化合物和含氮化合物并去除金属。此类催化剂称作氢化处理催化剂。对于此类氢化处理催化剂,几乎普遍采用氧化铝作为载体。通过挤出可以容易地对氧化铝负载的催化剂进行成形,并在煅烧之后提供机械牢固的催化剂主体。
在两种类型的反应器中进行原油馏分的氢化处理。第一种反应器类型称作沸腾床反应器。催化剂主体在液流和气流中保持浮动。对流动进行控制,从而催化剂主体保持浮动,不会被液体的向上流动带走,也不会沉淀到反应器底部。
其他类型的反应器采用滴流工艺。气流和液流向下通过反应器。反应器主要被气相填充,而要处理的液态原油馏分作为催化剂上的薄层进行流动。两种类型的反应器都要求机械牢固的催化剂主体。对于沸腾床,催化剂主体以液流移动,这容易导致机械强度不足的催化剂主体发生磨损。对于滴流工艺,在非常大型的固定床反应器中使用催化剂。
由于催化剂床的重量相当大,因此催化剂主体必须非常牢固以避免催化剂床的下部中的催化剂主体发生碎裂。催化剂主体的碎裂导致流过固定床的气流的压降上升,这在技术上是不可接受的。
氧化铝可以提供高表面积和高本体密度,这对于给定尺寸的反应器中能够负载的催化剂的量是重要的,并且可以容易地挤出催化剂主体,使其在煅烧之后具有高机械强度。通常,需要勃姆石(AlOOH)或者假勃姆石生产的氧化铝来提供最优结果。假勃姆石具有如同勃姆石一样的针形晶粒,但是晶粒小得多。在煅烧过程中维持氧化铝晶粒的形状,但是氧化铝反应生成立方体γ-氧化铝小晶粒,或者取决于煅烧过程生成其他过渡氧化铝。
尽管作为氢化处理催化剂的载体,γ-氧化铝具有有利的性质,但是该载体具有一些明显缺陷。首先,钴和镍有可能与过渡氧化铝反应生成尖晶石、铝酸钴或铝酸镍,因而在上述氢化处理反应中导致任意明显的活性损失。用氢处理或者用氢和硫化氢处理无法从铝尖晶石中释放大部分的钴和镍。推测可能是由于钼和钨也与氧化铝表面发生反应。相互作用导致更难以降低负载的氧化钼和氧化钨,并反应生成Mo(IV)S2和W(IV)S2。
氧化铝负载的氢化处理催化剂的另一个缺陷涉及废催化剂的处理。虽然钼和钴是昂贵的,但是难以从氧化铝载体中回收金属。将氧化铝载体溶解在碱中产生许多碱,并导致发泡溶液。钼和铝一起溶解,而作为对比,钴作为氢氧化钴沉积。难以从铝酸盐溶液过滤和分离所得到的钼酸盐。因此,通常排掉氢化处理的废催化剂。
氧化铝负载的氢化处理催化剂的最后一个问题在于难以令人满意地控制催化剂的孔径分布。由于催化反应涉及固体催化剂和液相,因此传输通过催化剂孔进行地非常缓慢。固定床反应器中的催化剂主体不能小于约1mm,因为更小的尺寸会导致难以接受的过高压降。由于需要大催化剂主体,从而对于长孔而言,仅催化剂主体的外边缘对催化反应起明显贡献作用。因此必须采用具有宽孔的催化剂主体。但是高孔体积(这是宽孔的特征)导致低机械强度。对于机械强度和孔宽之间的妥协,机械强度是最重要的。因此常用的氧化铝负载的氢化处理催化剂具有高机械强度和较窄的孔。
特别是对于从原油馏分中去除金属,常用的氧化铝负载的氢化处理催化剂的窄孔开口是一个缺陷。从原油馏分中除去的金属沉积在孔开口中,这导致窄孔的快速堵塞,因而使催化剂失活。
因此对于氢化处理催化剂,高孔体积是诱人的。但是,催化剂主体的高孔体积难以与高机械强度相结合。由于在非常大型的固定床反应器中采用氢化处理催化剂,催化剂床的重量要求催化剂主体具有高机械强度。
这样一种载体是极有价值的,它能够通过挤出催化剂主体得到,在与氧化铝相同或者更高的机械强度情况下具有提升的孔体积,不会与钴或镍发生反应。
代替氧化铝作为载体的一个替代品是二氧化硅。但是,众所周知二氧化硅难以通过挤出成形。模头很快被二氧化硅磨损。此外,二氧化硅的本体密度明显小于氧化铝的本体密度。难以在二氧化硅表面细分散且均匀分布地最终施涂合适的钼或钨化合物。因此二氧化硅负载的氢化处理催化剂是不可用的。
已经提出氧化钛作为氢化处理催化剂的载体。通常通过钛铁矿、钛酸铁(II价)、FeTiO3与硫酸反应产生氧化钛。硫酸钛的稀释导致钛(IV价)水解成水合二氧化钛。非常小的二氧化钛颗粒是高度水合的。去除水会导致钛氧化物严重烧结成较大氧化钛颗粒。氧化钛的比表面积小于50m2/g,这明显低于用作氢化处理催化剂载体的氧化铝,即,约为130-250m2/g。
氧化钛的一种替代生产过程是通过四氯化钛进行的。使四氯化钛进入氢氧焰,在其中,四氯化钛反应生成约30nm的氧化钛颗粒。所得到的(火成)氧化钛颗粒总是锐钛矿和金红石相的氧化钛的混合物,具有约50m2/g的表面积,孔体积约为0.50cm3/g。通常认为金红石相的氧化钛对于涉及碱金属的任意催化剂配方是有害的,因为金红石相非常容易通过形成金属钛酸盐与这些金属结合,而金属钛酸盐不具有催化活性。实际上,金属氧化物例如氧化镍和氧化铬的反应导致形成黄色颜料,而非活化催化剂。
无法明确地建立氧化钛对于氢化处理催化剂的催化活性的影响。首先,市售可得的火成氧化钛的氧化钛载体的表面积约为50m2/g,这远小于常用于生产氢化处理催化剂的γ-氧化铝的表面积,即,约为200-300m2/g。另一个差异在于,镍和钴促进了氧化铝负载的钼催化剂和钨催化剂的活性,而对于氧化钛负载的催化剂的活性没有明显影响。
1989年,McCormick等,研究了载体对于煤液氢化处理催化剂的性能的影响[Robert L.McCormick,Julia A.King,Todd R.King和Henry W.Haynes Jr.,Ind.Eng.Chem.Res.(1989),28,940–947]。作者研究了许多不同的载体,包括氧化铝、氧化钛以及氧化钛-氧化铝。氧化铝负载的催化剂的表面积为167m2/g,通过汞孔隙率法测得的孔体积为0.75cm3/g,通过77K的氮冷凝测得的(小孔)孔体积为0.43cm3/g。氧化钛负载的钴-钼催化剂的表面积为68m2/g,孔体积为0.27cm3/g,小孔体积为0.11cm3/g。通过三氯化铝和四氯化钛的氨共沉淀制备氧化钛-氧化铝载体。将镍和钼施涂到氧化钛-氧化铝载体上。虽然氧化铝负载的催化剂以及氧化钛-氧化铝负载的催化剂具有高活性和优异的活性维持,但是氧化钛负载的催化剂显示出差活性和低稳定性。
Prins等对氧化铝、氧化钛和碳上负载的钴-钼催化剂以及镍-钼催化剂进行了仔细和广泛的研究。氧化钛载体的表面积为46m2/g,孔体积为0.5cm3/g,而氧化铝显示具有233m2/g的表面积[S.P.A.Louwers,M.W.J.Crajé,A.M.vander Kraan,C.Geantet和R.Prins,J.Catalysis(1993),144,579-596]。氧化铝负载的催化剂的活性比氧化钛负载的催化剂的活性高约3.6倍。
Lecrenay等对氧化钛-氧化铝载体进行了研究[E.Lecrenay,K.Sakanishi,T.Nagamatsu,I.Mochida和T.Suzuka,Applied Catalysis B Environmental(应用催化B环境)(1998)18325–330]。作者研究了许多模拟化合物以及汽油和轻质循环油的加氢脱硫。采用纯氧化铝载体和通过烷氧基钛和烷氧基铝的水解生产的两种商用氧化钛-氧化铝载体。催化剂的表面积在240-252m2/g之间,孔体积在0.54-0.60cm3/g之间。将镍、钼以及钴-钼施涂到载体上。重要的是,对于汽油加氢脱硫的活性随着氧化钛含量下降而下降,对于轻质循环油,8重量%的氧化钛的活性约等于纯氧化铝的活性,而25重量%的氧化钛的活性较低。因此很明显,对于汽油和轻质循环油的加氢脱硫,向氧化铝中加入氧化钛的影响并不明显。
对于纯氧化钛载体,Inoue等发表了关于氧化钛载体的新型制备过程的论文[S.Inoue,H.Kudou,A.Muto和T.Ono,Fuel Division Preprints(燃料学科预印本)(2003)48(1)88–89]。在授予日本横滨千代田区化工建筑有限公司(ChiyodaChemical Engineering and Construction Co.,Ltd.,Yokohama,Japan)的US4,422,960中对所采用的过程进行了详细描述。该过程的目的是为了生产具有宽孔体积和大表面积的载体。原理是基于受控的奥斯特瓦尔德催熟(Ostwaldripening);在避免形成更小颗粒的条件下,小颗粒的载体生长成较大颗粒。从而得到相当均匀的颗粒,其尺寸导致大孔的高体积。该过程已被用于氧化铝、氧化硅、氧化钛以及海泡石。如此生产的氧化钛的表面积在133-175m2/g之间,元素氧化钛颗粒尺寸的孔的相当均匀的尺寸变化在6-20nm之间。但是,孔径分布必须由相当复杂的过程来描述,并且没有提及氧化钛主体的强度改善。
WO2004/073854描述了一种催化剂组合物,其包含一种或多种元素周期表第VIB族金属,一种或多种第VIII金属,描述了一种耐火氧化物材料,其包含大于或等于50重量%的氧化钛(基于氧化物),它是通过沉淀技术制备的,还描述了它们在烃类原料的氢化过程中的使用。
可以通过EP-A1-1748033描述的过程来得到替代氧化钛载体,以及通过US2010/0069233描述的过程得到稍有不同的氧化钛载体。所述过程涉及在100-300°C的温度用碱溶液(优选氢氧化钠)对氧化钛进行处理,所述氧化钛是无定形的、或者由锐钛矿构成或由金红石构成。反应产物具有不同于锐钛矿、金红石或者板钛矿的特殊晶体结构,并且由拉长形状、纳米丝、纳米纤维或纳米管的非均匀颗粒组成。该材料含有氢或者氢和钠的组合。制备氧化钛导致较大表面积(最高至300m2/g)和孔体积(最高至0.70cm3/g)。
Escobar等[J.Escobar,J.A.Toledo,M.A.Cortés,M.L.Mosqueira,V.Pérez,G.Ferrat,E.Lopez-Salinas和E.Torres-Garcia Catalysis Today(今日催化)(2005)106第222–226页]通过上述专有方法以纳米管的形式制备氧化钛,其表面积大于300m2/g。它的活性是氧化铝负载的钴-钼的两倍。从而相当大地提升了载体的表面积,即,343和335m2/g。孔体积变化更大,即,0.70和0.47cm3/g。令人惊讶的是,应用活性组分(钴和钼)严重影响了表面积,其下降到181和174m2/g,以及浸渍之后的孔体积,其为0.29cm3/g。由于机械或催化性质的不足,无法在负载有活性金属化合物的粉末或纳米管材料的基础上制备具有足够催化活性的成形的氧化钛载体。
上述现有技术文献表明已经进行了许多工作,采用氧化钛作为载体来改进氢化脱硫催化剂的性质。未表明氧化钛-氧化铝负载的催化剂对于催化剂性能具有明显地提升。通过四氯化钛的火焰水解生产的纯氧化钛载体的表面积不够,而根据上文US4.422.960的载体以及Escobar等所述的载体在浸渍之后的活性组分的表面积和孔体积较小。所述的所有催化剂是微米测试单元中测试的粉末材料。
由于缺乏可用的孔结构,氧化钛或二氧化钛作为传统氢化处理催化剂的催化载体的应用受到限制。因此,市场中几乎不存在上文所述的商用氧化钛负载的氢化处理催化剂,其具有低孔体积,因此能装载或负载的氢化金属少于更常用的氧化铝负载的催化剂。通常来说,应当承认,热稳定性、低表面积和较差的机械强度都阻碍了氧化钛负载的催化剂体系的商业开发。
因此,本发明的一个目的是提供氧化钛负载的氢化脱硫催化剂,其具有足够大的表面积、高孔体积以及高机械强度。
发明内容
本发明的发明人发现在氧化钛上单独施加钼或钨,或者与任意钴或镍的组合不会自动导致具有改善的活性的氢化脱硫催化剂。从上文详述的现有技术可以得知,报道了采用氧化钛作为载体使得活性下降和活性上升,原因在于,由于施加了活性组分通常导致表面积和孔体积下降。本发明的发明人认为,每单位反应器体积的氧化钛负载的氢化脱硫催化剂的表面积(这是由表面积/单位重量和本体密度决定的)是最关键的因素,因为表面积/单位体积决定了技术反应器中的催化剂的活性。
令人惊讶的是,本发明的发明人发现,可以在购自荷兰阿默斯福特的欧洲载体制造公司(Euro Support Manufacturing,Amersfoort,The Netherlands)的氧化钛载体上施加活性组分(钼或钨,任选地与钴或镍结合),而不会显著影响获得的催化剂主体可达到的表面积、可达到的孔体积以及机械强度。此类载体的机械强度通常为10N/mm,表面积通常为225m2/g,通过汞孔隙率法测得的孔体积通常为0.4cm3/g。
根据发明人的理解,由于汞孔隙率法测得的宽孔对于本发明的脱硫催化剂是最为重要的,因此它们着重于汞孔隙率法测得的孔体积。考虑到上文所述的现有技术,在市售可得的氧化钛载体上施加活性组分之后,所获得的催化剂主体的表面积、孔体积和机械强度仍然非常高是令人惊讶且无法预期到的。
发明详述
本发明涉及氢化处理催化剂以及采用所述催化剂组合物对化学和石油进料进行氢化处理,该催化剂组合物含有Mo和/或W,和可任选的Ni和/或Co,以及惰性耐火氧化物(大于或等于80重量%的氧化钛,余下是二氧化硅)。
更具体地,本发明提供了一种用于氢化处理的成形的氧化钛载体形式的负载催化剂组合物,其在表面上具有至少一种钼和/或钨的氧化物,表面积至少为80m2/g,通过汞孔隙率法测得的孔体积至少为0.25cm3/g,侧压强度大于7N/mm,并且堆积本体密度在600-1200kg/m3范围内。
通常,新鲜煅烧的催化剂的表面积至少为80m2/g,优选至少为125m2/g,甚至更优选至少为135m2/g,最优选至少为150m2/g,通过汞孔隙率法测得的孔体积至少为0.25cm3/g,优选至少为0.30cm3/g,更优选为0.34cm3/g,侧压强度至少为7N/mm,优选至少为8N/mm,更优选至少为10N/mm,并且堆积本体密度在600-1200kg/m3范围内,更优选在800-1200kg/m3范围内。
本领域已知,例如在Martyn V.Twigg的“催化剂手册(第二版)”(1989)或者Robert J.Farrauto和Calvin H.Bartholomew的“工业催化工艺基础”(1997)中,催化剂在侧压强度和本体密度方面的性质对于它们在反应器中用作催化剂是重要的参数。侧压强度定义为形成的催化剂对于压缩力的抗性。测量侧压强度是为了提供在处理和使用过程中,催化剂维持其物理完整性的能力的指示。ASTM D6175-03(2008)中描述了一种挤出的催化剂和催化剂载体颗粒的径向压强度的标准测试方法,其也用于本发明中,如下文中详述。
堆积密度的测量已经形成许多标准方法,例如对于ASTM4146中的催化剂是“形成的催化剂和催化剂载体的机械堆积组装密度的标准测试方法”,其也用于本发明中,如下文中详述。
可以通过在氧化钛载体上施涂钼和/或钨的至少一种盐的水溶液,并煅烧得到的催化剂主体,来得到用于氢化处理的本发明的负载催化剂组合物。
本文所用术语氢化处理用于覆盖烃类进料与氢发生接触,从而改变关键物理和化学性质的许多氢化处理工艺。
对于在氧化钛载体上施加钼和/或钨的至少一种盐的水溶液,通常使用钼和/或钨的水溶性盐形式的溶液;优选钼酸盐和/或钨酸盐或者金属-磷络合物(例如杂多酸)的水溶液。
在施涂步骤中,水合物形式的金属组分沉积到氧化钛载体上。更具体地,在水中溶解合适的前体(例如金属盐),浓度使得在(干)浸渍、干燥和煅烧之后得到所需的金属负载。碱性碳酸钴或碳酸镍、钼酸铵或者钨酸盐是很好的例子。它们转变成例如杂多酸结构。这可以通过加热水中溶解的化合物,可任选地在存在络合剂例如磷酸的情况下,来实现。首先,可以将机械成形的氧化钛载体装载到合适的容器,例如搅拌机如锥形搅拌机中。用浸渍溶液,以0.01-0.1mL/分钟/g载体的速率进行孔体积浸渍。浸渍量可以根据载体的目标负载发生变化。在计量浸渍溶液后,经过浸渍的成形体老化,优选老化至少12小时,更优选老化至少24小时。然后所得材料进行干燥和煅烧步骤。在干燥之前,优选对新鲜浸渍的材料进行最高至36小时,优选为12-24小时之间的老化步骤,从而使得沉积在材料孔中的金属组分更均匀地分布。在100-150°C的温度范围内进行最高至数小时的干燥步骤,从而去除溶剂。之后,通常在300-600°C的温度范围内进行30-240分钟的煅烧。在金属氧化物转化成它们对应的硫化物的硫化步骤之后,得到活性催化剂。可以在氢化处理反应器中装载了催化剂之后,用含硫化合物进行非原位或原位预硫化步骤来完成硫化,该过程是本领域技术人员已知的。
本文所用术语“负载”或“载体”应理解为组合物具有预成形的、成形的催化剂载体,然后通过浸渍或沉积用金属化合物装载所述预成形的、成形的催化剂载体。通常,在此类负载催化剂组合物中,载体是组合物中独立不同的材料,即载体通常并非在成形过程中由与金属化合物一起装载的粉末材料制备的。可以机械地,例如通过挤出糊状材料来实现所述成形。成形体的直径尺寸通常为数毫米,1mm至最高为10mm的范围内。主体的形状可以是圆柱形、三叶形、四叶形,只要它们能维持机械性质。
在一个实施方式中,本发明的氧化钛载体可以含有70-100重量%,优选80-100重量%的TiO2,以及最高至30重量%,优选20重量%的氧化硅(它可以提升氧化钛的热稳定性)。
以经煅烧的催化剂的总重量计,本发明的催化剂组合物的一个实施方式含有9.0-25.0重量%,优选为10-16重量%,更优选为12-16重量%的钼和/或钨(以三氧化物计算)。
以负载催化剂组合物的总重量计,本发明的催化剂组合物的另一个实施方式除了含有钼和/或钨之外,还含有钴和镍中的至少一种,范围最高至10重量%,优选6.5重量%,更优选2-4重量%,以Co3O4或NiO计。合适的含镍化合物是碳酸镍、氧化镍、氢氧化镍、磷酸镍、甲酸镍、硫化镍、钼酸镍或者两种或更多种上述物质的混合物,对于钼也基于类似的标准。除此之外,可溶性盐,例如硝酸镍、硫酸镍或者乙酸镍可以与上述一种或多种化合物结合使用,和/或相互结合使用。对应的含钴化合物也是合适的。
优选地,本发明的催化剂组合物含有钼和钴的组合,它们各自的含量范围如上文所述。
虽然本发明涉及装载有前述金属化合物的载体,本发明还涉及用于例如氢化和氧化反应的催化工艺的成形氧化钛载体形式的负载催化剂组合物,其具有至少一种选自下组的催化活性材料:铂、钯、铑、铼、银、金或者它们的混合物,以经煅烧的催化剂的总重量计,所述催化活性材料的含量最高为8重量%,优选为5重量%,所述催化活性材料装载在载体的表面上,所述负载催化剂组合物的表面积至少为80m2/g,通过汞孔隙率法测得的孔体积至少为0.25cm3/g,侧压强度大于7N/mm,并且堆积本体密度范围为600-1200kg/m3。
在氧化钛载体上细分施加活性组分,这使得活性物质的前体(氧化物)优选小于50nm,优选小于20nm。优选地,用具有元素分析的扫描透射电子显微镜来评估活性组分的尺寸。
令人惊讶的发现,本发明的催化剂非常适合二氧化硫氢化成硫化氢,特别是在处理克劳斯尾气的所谓SCOT工艺所需的氢化步骤中。
多步法克劳斯工艺从原料天然气中存在的气态硫化氢并从源自原油精炼的含有硫化氢的副产物气体以及其他工业过程中回收硫。副产物气体主要来自精炼厂、天然气加工厂以及气化或合成气工厂的物理和化学气体处理单元(Selexol、Rectisol、Purisol和胺洗涤器)。这些副产物气体还可能含有氰化氢、烃类、二氧化硫或者氨。H2S含量大于25%的气体适合在直通式克劳斯工厂中回收硫。来自克劳斯工艺的尾气仍然含有可燃性组分和含硫化合物(H2S、H2和CO),它在焚化单元中燃烧或者在下游尾气处理单元中进一步脱硫。
在此类SCOT(壳克劳斯尾气处理)工艺中,对流出最后的催化克劳斯反应器的气体进行冷却,以冷凝元素硫,之后气流再加热以建立将余下的二氧化硫氢化成硫化氢所需的温度。可以通过用含链烷醇胺的液体吸收以选择性去除硫化氢。与硫化氢不同,余下的二氧化硫与链烷醇胺发生不可逆反应,所述硫化氢可以发生热解吸。因此,必须完全去除二氧化硫。
用蒸汽对流出硫冷凝器的气体进行再加热在商业上是非常诱人的,并且令人惊讶的是,本发明的催化剂在200-240°C的温度范围内具有高活性。尤其令人惊讶的是,即使在较低温度例如200°C,也能实现二氧化硫的完全转化。由于通过蒸汽所能建立的温度约为240°C,而本发明的催化剂在200-240°C,特别是215-240°C之间就已经具有足够高的活性,因此本发明的催化剂在SCOT工艺中是特别有利的。
SCOT等工艺的最终硫回收主要由二氧化硫氢化过程中形成的硫醇的量,以及用加工气体中所含的水通过水解对COS和CS2同时去除的效率所决定。发现采用本发明的氧化钛负载的催化剂所产生的硫醇的量明显低于氧化铝负载的催化剂所产生的量。
相比于氧化铝负载的产物以及低孔体积的基于氧化钛的催化剂,本发明的催化剂可以获得非常高的水解效率。
同样,本发明的氧化钛负载的催化剂对于从原油馏分中去除金属也是非常诱人的。由于载体的高孔体积和大孔/中孔性质以及本发明催化剂,在孔堵塞导致活性下降之前,能够在催化剂主体上装载许多金属。此外,要指出的是,由于活性表面组分的高度分散状态,这些催化剂获得金属污垢的数量大大提升。
对于本发明的催化剂,还令人惊讶地发现另一个优点,即,可以以一种非常吸引人的方式对氧化钛负载的废催化剂进行处理来回收金属。本发明的发明人发现,在氢化处理步骤期间,在沉积到催化剂主体中和催化剂主体上的碳燃烧之后,沉积在来自原油馏分的催化剂上的金属(即钼、钨、钴、镍以及钒)可以容易地溶解在浓氨水和碳酸铵的混合物中。为了提升溶解速率,可以在提升的压力下进行反应。氧化钛载体不会溶解于碱溶液,而钼、钨和钒作为钼酸盐、钨酸盐或者钒酸盐进入溶液,并且钴和镍作为氨络合物溶解。
在与氧化钛载体分离后,可以通过氨的热解吸来分离钴和镍,这导致相应碳酸盐的沉淀。其他金属作为氧阴离子存在,留在溶液中,并可在进一步的加工步骤中进行回收。
因此,本发明还涉及一种在本发明的催化剂组合物使用之后从中回收金属,特别是钴和/或钼的方法,所述方法包括以下步骤:在400-700°C的温度范围内,在空气中煅烧催化剂组合物,然后用金属化合物,钴和钼的溶剂,氨和碳酸铵的水溶液处理经煅烧的催化剂组合物,并从溶液回收溶解的金属。
对于钴和钼,进一步处理考虑以下步骤:蒸发氨并回收形成的碳酸钴,之后分离碳酸钴,蒸发水以得到作为钼酸盐的钼金属,这可是任意的钼酸铵。
参考以下制备和测试本发明催化剂的实施例来进一步说明本发明。
实施例
实施例1
为了制备本发明的负载催化剂组合物,使用购自欧洲载体制造公司的三叶形TiO2材料,并用金属盐溶液浸渍。通常,本文示例性地使用两种类型的浸渍溶液(A、B),但是也可以使用具有不同金属比的其他溶液,以在载体上得到不同的负载,只要该比例导致的负载属于权利要求书限定的范围。在以下实施例中所使用的浸渍溶液是基于:
A)溶解为聚氧阴离子和硝酸钴的复杂钼酸盐
B)基于钼和磷的杂多酸和硝酸钴
溶液制备:
溶液A的制备:
在60°C的温度下,向52.4mL的去矿物质水中搅拌加入27.86g的(NH4)2Mo2O7。在该温度下搅拌5分钟之后,加入3.81g的MoO3。当MoO3溶解后,溶液冷却至30°C。加入37.6g的Co(NO3)2的溶液(Co含量为13.4%)。所得溶液的最终pH为4.7。溶液的总体积为100mL。
溶液B的制备:
在65°C,向85.9mL的水中搅拌加入42.66g的MoO3。在20分钟后,加入3.27g的H3PO4(浓度为85重量%)。之后逐步加入14.27g的碳酸钴(Co含量为45.3%)。在完成加入碳酸钴总量之后,加入1.19g的HNO3(浓度65%)。溶液冷却至室温。所得溶液的最终pH为4.1。溶液的总体积为100mL。
浸渍过程:
在锥形搅拌机中装载100g的氧化钛载体,记作S-1或S-2(表1),它购自欧洲载体公司,商品名为Mirkat200、300和400。在此处用溶液A和B,以0.5mL/分钟的速率加入42mL的浸渍溶液,来实现孔体积浸渍。浸渍量可以根据载体的目标负载发生变化。在计量浸渍溶液之后,经浸渍的成形体老化24小时。接着,催化剂在120°C干燥(过夜),并在400°C煅烧(1小时)。
载体S-1和S-2以及经浸渍的催化剂的特征详见表1和2所述。表中所用缩写具有如下含义:
BET-SA:总比表面积,根据Brunauer、Emmet和Teller所建立的理论,通过氮吸附确定。
PVHg:孔体积,通过最高至2000巴的汞压入确定。
TBD:堆积本体密度,根据ASTM(美国测试和材料协会)方法D4164-03测得。
CS:侧压强度(N/mm)。以径向方向施加作用力来使得挤出体破裂。所用方法源自ASTM方法D6175-03,其中,在本文的方法中,使用2mm的铁砧板和平板代替两个平板。
表1
向两个载体S-1和S-2施涂溶液B对其进行处理,对于所得到的本发明的催化剂C-1和C-2的以下特性如表2所示。
表2
实施例2
在对照例中,本发明的上述两种基于氧化钛的催化剂C-1和C-2用于分别采用具有低含硫量和含氮量的LGO作为原料和采用具有高含硫量和含氮量的较重进料混合物的HDS/HDN测试中。经浸渍的催化剂的特征以及氧化铝负载的参照催化剂RC-1和RC-2的特征(总结见表3)。
表3
下表4显示测试反应器中每单位体积的可用BET表面积。
表4
测试步骤:
在以下实验中,用100mL的催化剂装载等温反应器(内径30mm)。用DMDS(二甲基二硫醚)对催化剂进行预硫化。预硫化过程是本领域技术人员众所周知的。
实施例3
在另一个对照例中,在预硫化之后,使用表5所列进料对催化剂C-1及其参照RC-1进行测试。
表5
密度15°C | [kg/m3] | 848.3 |
折射率20°C | 1.4716 | |
硫含量 | [mg/kg] | 7990 |
氮含量 | [mg/kg] | 112.7 |
颜色ASTM D1500 | 0.3 | |
溴指数 | [mg Br/100g] | 2958 |
液相色谱法的组成(HPLC) | ||
饱和的 | [%m/m.] | 68.4 |
单芳族 | [%m/m.] | 20.2 |
二芳族 | [%m/m.] | 11.2 |
三芳族 | [%m/m.] | 0.2 |
测试条件如下:压力(H2):3Mpa;WHSV:1.0kg进料/l催化剂/小时;H2/进料:350ln/kg进料(平均);温度:350、360、370°C。
催化剂的HDS和HDN活性总结见表6。
表6
温度(°C) | C-1 | RC-1 | C-1 | RC-1 |
ppm S | ppm S | ppm N | ppm N | |
进料 | 8000 | 8000 | 112 | 112 |
350 | 34 | 30,7 | 5,1 | 16,6 |
360 | 17,3 | 12,5 | 3,4 | 12,6 |
370 | 8,4 | 7,65 | 2,9 | 8,0 |
10ppm的温度(°C) | 367 | 362 | 340 | 370 |
实施例4
在另一个对照例中,在预硫化之后,使用表7所列进料对催化剂C-2及其参照(RC-2)进行测试。
表7
测试条件如下:压力(H2):6Mpa;WHSV:1.0kg/l催化剂/小时;H2/进料-3305m3/m3;温度程序:370-390-405-420°C。
催化剂的HDS和HDN活性总结见表8。
表8
实施例5
制备一系列的催化剂进行SO2氢化和水解反应测试。使用制备方法A或B(实施例1)采用表9和10所列出的各种氧化钛载体材料来制备催化剂。
表9
表10
表11总结了用于克劳斯尾气中的SO2氢化和CS2和COS水解的商用基于氧化铝的CoMo参照催化剂RC-3和RC-4的特性,一个运行温度具体为<240°C,其他的温度为>260°C。
表11
下表显示测试反应器中每单位体积的可用BET表面积。
表12
实施例6
在一定温度范围内,对上文所述的本发明的催化剂C-3至C-8与两种参照催化剂RC-3和RC-4进行对照测试。在测试之前,在375°C的温度,在含有1摩尔%H2S、4摩尔%H2和余量N2,且空速(GHSV)为650Nm3/m3/小时的气流中对催化剂进行16小时预硫化。预硫化之后,进气调节为含有1摩尔%H2S、0.5摩尔%SO2、1.5摩尔%H2、1.1摩尔%CO、16.7摩尔%CO2、0.025摩尔%COS、0.025摩尔%CS2、22摩尔%H2O和余量N2的气体。空速为825或1500Nm3/m3/h。分别在290°C、260°C、230°C、220°C、215°C和200°C的温度对催化剂进行约12小时的测试。用SO2、CS2、COS和CO的转化率以及甲基硫醇(CH3SH)的产量来表征催化剂活性。空速为825Nm3/m3/小时的测试结果总结见表13。该数据涉及各个温度下测试12小时之后的转化率和硫醇产量。
表13
温度: | SO2转化 | CS2转化 | COS转化 | CO转化 | 产物气体中的CH3SH(以 |
290°C | 率(%) | 率(%) | 率(%) | 率(%) | 摩尔ppm干重计) |
C-3 | 100 | 100 | 92 | 99 | 0 |
C-4 | 100 | 100 | 92 | 99 | 0 |
C-5 | 100 | 100 | 91 | 99 | 0 |
C-6 | 100 | 100 | 93 | 99 | 0 |
C-7 | 100 | 100 | 92 | 99 | 0 |
C-8 | 100 | 100 | 92 | 99 | 0 |
RC-3 | 100 | 100 | 92 | 99 | 0 |
RC-4 | 100 | 100 | 92 | 99 | 0 |
260°C | |||||
C-3 | 100 | 100 | 94 | 99 | 0 |
C-4 | 100 | 100 | 95 | 99 | 0 |
C-5 | 100 | 100 | 94 | 99 | 0 |
C-6 | 100 | 100 | 95 | 99 | 0 |
C-7 | 100 | 100 | 95 | 99 | 0 |
C-8 | 100 | 100 | 94 | 99 | 0 |
RC-3 | 100 | 100 | 94 | 99 | 0 |
RC-4 | 100 | 100 | 94 | 99 | 14 |
230°C | |||||
C-3 | 100 | 100 | 95 | 100 | 41 |
C-4 | 100 | 100 | 95 | 100 | 14 |
C-5 | 100 | 100 | 96 | 100 | 23 |
C-6 | 100 | 100 | 97 | 100 | 8 |
C-7 | 100 | 100 | 96 | 100 | 18 |
C-8 | 100 | 100 | 96 | 100 | 22 |
RC-3 | 100 | 100 | 96 | 100 | 34 |
RC-4 | 100 | 100 | 96 | 100 | 57 |
220°C | |||||
C-3 | 100 | 100 | 95 | 100 | 44 |
C-4 | 100 | 100 | 97 | 100 | 31 |
C-5 | 100 | 100 | 97 | 100 | 41 |
C-6 | 100 | 100 | 97 | 100 | 18 |
C-7 | 100 | 100 | 97 | 100 | 33 |
C-8 | 100 | 100 | 97 | 100 | 40 |
RC-3 | 100 | 100 | 96 | 100 | 63 |
RC-4 | 100 | 99 | 94 | 99 | 80 |
215°C | |||||
C-3 | 100 | 100 | 95 | 100 | 59 |
C-4 | 100 | 100 | 97 | 100 | 44 |
C-5 | 100 | 100 | 97 | 100 | 50 |
C-6 | 100 | 100 | 97 | 100 | 39 |
C-7 | 100 | 100 | 97 | 100 | 45 |
C-8 | 100 | 100 | 97 | 100 | 53 |
RC-3 | 100 | 100 | 95 | 100 | 75 |
RC-4 | 100 | 99 | 90 | 99 | 77 |
200°C | |||||
C-3 | 100 | 100 | 95 | 100 | 107 |
C-4 | 100 | 100 | 97 | 100 | 80 |
C-5 | 100 | 100 | 96 | 100 | 101 |
C-6 | 100 | 100 | 98 | 100 | 91 |
C-7 | 100 | 100 | 95 | 100 | 76 |
C-8 | 100 | 100 | 96 | 100 | 99 |
RC-3 | 100 | 98 | 90 | 98 | 109 |
RC-4 | 100 | 98 | 82 | 95 | 90 |
空速为1500Nm3/m3/小时的测试结果总结见表14。
表14
从以上实施例可以看出,本发明的催化剂组合物具有优异的HDS和HDN活性,并且可有利地用于通过氢处理从原油馏分中去除含硫化合物和含氮化合物的工艺。
本发明的催化剂还非常好地适用于SO2氢化和诸如克劳斯尾气的气体的完全转化。在中等温度(215-230°C)下,相比于氧化铝负载的催化剂,具有高氢化和水解活性的催化剂的硫醇产量明显较低。
Claims (14)
1.一种用于氢化处理的呈成形的氧化钛载体形式的负载催化剂组合物,其在表面上具有至少一种钼和/或钨的氧化物,表面积至少为80m2/g,通过汞孔隙率法测得的孔体积至少为0.25cm3/g,侧压强度大于7N/mm,并且堆积本体密度在600-1200kg/m3范围内。
2.如权利要求1所述的催化剂组合物,以负载催化剂组合物的总重计,其载体的二氧化钛含量范围为80-100重量%。
3.如权利要求1或2所述的催化剂组合物,以负载催化剂组合物的总重计,以三氧化物计,其钼含量和/或钨含量的范围为9.0-16.0重量%,优选为10-16重量%,更优选为12-16重量%。
4.如权利要求1-3中任一项所述的催化剂组合物,以负载催化剂组合物的总重计,以Co3O4或者NiO计,其还含有钴和镍中的至少一种,所述钴和镍中的至少一种的总量范围为0-6.5重量%,更优选为2-4重量%。
5.如权利要求1-4中任一项所述的催化剂组合物,其特征在于,在煅烧之后,存在的催化活性氧化物中至少20重量%的负载前体颗粒小于50nm,优选小于20nm。
6.如权利要求1-5中任一项所述用于氢化处理的催化剂组合物,它可通过在成形的氧化钛载体上施涂钼和/或钨的至少一种盐的水溶液,然后对所得到的催化剂主体进行干燥并煅烧来得到。
7.一种制备权利要求1-6中任一项所述的催化剂组合物的方法,其特征在于,在存在质子溶剂和任选的碱化合物的情况下,向氧化钛载体施涂钼和/或钨的至少一种盐溶液,回收所形成的催化剂主体,之后对所得到的催化剂主体进行沉淀、干燥和煅烧。
8.权利要求1-6中任一项所述的催化剂组合物在二氧化硫氢化成硫化氢的工艺中的用途,其中,含有二氧化硫的反应气体经过氢化步骤。
9.如权利要求8所述的用途,其特征在于,在小于250°C,优选小于240°C,并且大于200°C,更优选大于215°C的温度下进行所述氢化步骤。
10.权利要求1-6中任一项所述的催化剂组合物在通过氢处理从原油馏分中去除含硫化合物和含氮化合物的工艺中的用途。
11.权利要求1-6中任一项所述的催化剂组合物在通过氢处理从原油馏分中去除金属的工艺中的用途。
12.一种从使用后的权利要求1-6中任一项所述的催化剂组合物中回收选自钴和钼的金属的方法,所述方法包括如下步骤:在400-700°C的温度范围内,在空气中煅烧催化剂组合物,然后用氨和碳酸铵的水溶液处理经煅烧的催化剂组合物。
13.如权利要求12所述的方法,该方法还包括蒸发氨并回收所形成的碳酸钴的步骤。
14.如权利要求13所述的方法,该方法在分离碳酸钴之后,还包括蒸发掉水以得到作为钼酸盐的钼金属的步骤。
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CN111054365A (zh) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | 一种精脱硫剂及其制备方法和脱硫工艺 |
CN113171778A (zh) * | 2021-04-21 | 2021-07-27 | 太原煤炭气化(集团)有限责任公司 | 一种焦炉煤气深度净化脱硫剂及其制备方法和应用 |
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SI3294449T1 (sl) * | 2015-05-15 | 2021-01-29 | Venator Germany Gmbh | Prašnat titanov oksid, postopek za njegovo pripravo in njegovo uporabo |
US10584289B2 (en) * | 2016-12-30 | 2020-03-10 | Advanced Energy Materials | Nanowire-based hydrodesulfurization catalysts for hydrocarbon fuels |
US11306261B2 (en) * | 2016-12-30 | 2022-04-19 | Advanced Energy Materials, Llc | Nanowire-based hydrodesulfurization catalysts for hydrocarbon fuels |
BR112021023284A2 (pt) * | 2019-05-23 | 2022-01-04 | Evonik Operations Gmbh | Catalisadores de hidroprocessamento reativados para uso em abatimento de enxofre |
JP2023524743A (ja) | 2020-05-04 | 2023-06-13 | シェブロン ユー.エス.エー. インコーポレイテッド | 四元金属バルク水素化処理触媒 |
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Cited By (3)
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---|---|---|---|---|
CN111054365A (zh) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | 一种精脱硫剂及其制备方法和脱硫工艺 |
CN111054365B (zh) * | 2018-10-16 | 2023-04-18 | 中国石油化工股份有限公司 | 一种精脱硫剂及其制备方法和脱硫工艺 |
CN113171778A (zh) * | 2021-04-21 | 2021-07-27 | 太原煤炭气化(集团)有限责任公司 | 一种焦炉煤气深度净化脱硫剂及其制备方法和应用 |
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EA201300729A1 (ru) | 2013-12-30 |
US20130294985A1 (en) | 2013-11-07 |
WO2012084800A3 (en) | 2012-10-18 |
JP2014509926A (ja) | 2014-04-24 |
KR20130128423A (ko) | 2013-11-26 |
EP2465605A2 (en) | 2012-06-20 |
EP2654950B8 (en) | 2024-07-03 |
JP5779659B2 (ja) | 2015-09-16 |
KR101572644B1 (ko) | 2015-11-27 |
US9719031B2 (en) | 2017-08-01 |
EP2465605A3 (en) | 2014-04-30 |
BR112013015481A2 (pt) | 2016-09-27 |
WO2012084800A2 (en) | 2012-06-28 |
CN103298554B (zh) | 2017-02-15 |
EA025995B1 (ru) | 2017-02-28 |
BR112013015481B1 (pt) | 2019-12-17 |
EP2654950B1 (en) | 2024-06-12 |
EP2654950A2 (en) | 2013-10-30 |
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