CN102256700B - 炔烃向相应的烯烃的选择性催化加氢 - Google Patents
炔烃向相应的烯烃的选择性催化加氢 Download PDFInfo
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- CN102256700B CN102256700B CN2009801507114A CN200980150711A CN102256700B CN 102256700 B CN102256700 B CN 102256700B CN 2009801507114 A CN2009801507114 A CN 2009801507114A CN 200980150711 A CN200980150711 A CN 200980150711A CN 102256700 B CN102256700 B CN 102256700B
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- 150000001345 alkine derivatives Chemical class 0.000 title claims abstract description 33
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 150000001342 alkaline earth metals Chemical class 0.000 description 1
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- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
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- 239000003426 co-catalyst Substances 0.000 description 1
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- 230000009849 deactivation Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
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- 239000003701 inert diluent Substances 0.000 description 1
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- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- 239000007769 metal material Substances 0.000 description 1
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- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种将炔烃选择性加氢成为相应烯烃的方法,所述方法包括将包含氢气和0.1~20质量%炔烃的气体进料与包含在硼改性的载体上的至少一种10族元素的催化剂接触的步骤。所述方法显示了高的转化率和良好的选择性,且如果所述进料包含大于2质量%的炔烃,也能够稳定地运行所述方法。
Description
本发明涉及炔烃向相应烯烃的选择性加氢的方法,所述方法包括将包含氢气和炔烃的气体进料与负载的10族金属催化剂接触的步骤。
从WO2006/105799中可已知这种方法。该文献公开了一种乙炔向乙烯选择性加氢的方法,其中在固定床反应器中将包含乙炔和氢气的进料与TiO2负载的10族金属催化剂接触,且其中利用惰性固体如SiO2、ZrO2、Al2O3或TiO2,优选在稀释剂与负载的催化剂的重量比为约50~约170下,对催化剂进行稀释。据报道,所述催化剂适用于对含有高达20质量%乙炔的气体流股中的乙炔进行转化。
炔烃向相应烯烃的选择性加氢在工业上是重要的。大量文献集中于从乙烯中除去乙炔杂质(典型以0.5~1mol%存在)的方法。
乙烯是多种化学品的主要中间体,例如,其可作为用于制备大量聚合物的单体。通常,通过烃的热解或蒸汽裂化法,随后实施分离步骤来得到乙烯。聚合物级乙烯需要具有高的纯度,且可允许的最大乙炔含量为约10或甚至5ppm。使得乙烯不含任何乙炔杂质的一种技术是在负载在合适载体如氧化铝上的钯基催化剂上将乙炔选择性加氢成乙烯。这种金属基催化剂的普遍问题在于,当操作条件为例如完全消除乙炔时,也对一部分乙烯进行加氢并转化成乙烷。另外,这些单金属催化剂通常由于形成大量低聚物而具有相对低的稳定性,通常将所述低聚物称作绿油,其在运行条件下逐渐覆盖催化剂的表面,由此需要通过一些受控氧化方法经常地对催化剂进行再生。另外的缺点在于,如果将这种催化剂用于对含相对高量即高达10或者甚至20质量%乙炔的进料流股中的乙炔进行加氢,则所述催化剂会快速失活。
几个其他文献也致力于提高在炔烃例如乙炔加氢中尤其是Pd基负载催化剂的性能。例如,US5648576公开了一种在负载催化剂上在氢气存在下对含有2或3个碳原子的气相形式的乙炔化合物进行选择性加氢而成为相应乙烯化合物的一种方法,其中已经利用Pd和源自IB族的另一种金属如Ag、以及任选的碱金属或碱土金属对所述负载催化剂进行了表面改性。典型地,在3300小时-1的空速下对含98%乙烯和2%乙炔的进料进行乙炔的选择性加氢。
在US6350717B1中,描述了一种在氧化铝载体上以特定比例包含至少一种10族和至少一种11族金属的催化剂,其中将10族金属浓缩在载体的表面层中。将所述催化剂用于对乙炔/乙烯为1/99的混合物进行加氢。
WO03/106020描述了利用碘化物化合物对负载的Pd-Ag催化剂进行改性,以提高对混合进料流股中的乙炔进行加氢的性能,所述混合进料流股含有高达约1.5质量%的乙炔。
US7153807B2公开了负载的Ni-或Pt-催化剂,所述催化剂还包含选自8~9族和11~12族中的至少两种其他元素,其对包含高达约2质量%乙炔的进料流股显示更好的加氢选择性。
US4906800公开了一种将含有乙炔、乙烯和氢气的进料流股选择性地转化成汽油范围烃的方法,其中通过将乙炔与Pd-Pb/CaCO3催化剂接触对乙炔进行加氢,所述催化剂通过包括特殊的氧化/还原预处理步骤的方法制得。这种催化剂适用于处理含相对高量乙炔的进料混合物,例如热解流出物气体;通过对含2.6质量%乙炔的流股进行实验来例示。
EP0689872A1公开了一种包含钯、银和载体物质的催化剂,所述催化剂可用于选择性的乙炔加氢。在使用之前,将所述催化剂与液体还原剂接触,其中所述液体还原剂可以为硼氢化物等。
WO02/16032公开了一种使用包含无机载体物质、钯组分、银组分和助催化剂组分“XYFn”的催化剂选择性地对乙炔进行加氢的方法,其中所述助催化剂组分为含氟化合物,其还包含碱金属元素和其他元素,其中所述其他元素可以为硼等。
在工业上仍需要一种在对混合进料中、以及含相对高量炔烃的进料中的炔烃进行加氢时显示高活性和高选择性、以及良好稳定性的催化剂体系。
因此,本发明的目的是提供这种选择性催化加氢方法,以对混合进料中的炔烃进行加氢。
根据权利要求书中所限定的本发明实现了所述目的,尤其是利用将炔烃选择性加氢成为相应的烯烃的方法实现了所述目的,所述方法包括将包含氢气和0.1~20质量%炔烃的气体进料与包含在硼改性的载体上的至少一种10族元素的催化剂接触的步骤。
在本发明的上下文中,术语“在硼改性的载体上的元素”是指将所述元素沉积在载体上,所述载体在将所述元素沉积在所述载体上之前用硼改性过。
因此,本发明的方法中所使用的“包含在硼改性的载体上的至少一种10族元素的催化剂”表示这样的催化剂,其特征在于在硼改性的载体上沉积了至少一种10族元素。
令人惊奇地,本发明的方法使得可在更高转化率下将炔烃如乙炔选择性加氢成为烯烃如乙烯,且所述催化剂比使用无硼改性载体的催化剂的现有技术方法显示了更好的稳定性。所述催化剂显示了高的活性,能够使得接触时间相对较短,即高的空速,所述高的空速也称作GHSV,这能够将本方法与其他已知方法例如通常用于乙烯合成的甲烷转化或甲烷热解进行集成,并具有仅非常短的接触时间和由此具有高流速。本发明方法另外的优势在于,本发明的催化剂的活性对进料中存在的一些一氧化碳不敏感。
US6037301也公开了一种含硼的催化剂;其含有VIII族金属和硼的无定形合金、以及多孔载体。在该文献中制备的大部分催化剂为Ni基的并已经将其用于在9000小时-1GHSV下从乙烯流股中除去痕量乙炔(典型地小于2mol%)。在一个实验中,在对4-羧基-苯甲酸中的4-羧基-苯甲醛杂质进行加氢时对Pd-La-B/SiO2无定形合金催化剂进行了试验。该文献未公开或提出将在硼改性的载体物质上的Ni、Pd或Pt催化剂用于炔烃的脱氢。
在根据本发明的方法中,认为炔烃包括具有三键的不饱和烃化合物、尤其是乙炔和丙炔(也称作甲基乙炔)、和具有多于一个双键的不饱和化合物,链二烯如丙二烯或丁二烯;优选地,炔烃为具有三键的不饱和化合物。最优选地,炔烃分别为乙炔或丙炔且相应的烯烃为乙烯或丙烯。
用于根据本发明的方法中的气体进料含有炔烃和氢气、以及任选的其他组分如烯烃尤其是乙烯、烷烃如甲烷或乙烷、液体烃、一氧化碳、二氧化碳、氮气、水或其他惰性气体。优选地,所述进料还包含选自乙烯、甲烷、乙烷、一氧化碳、二氧化碳、氮气和水中的至少一种化合物。
进料气体中炔烃如乙炔的量可以为0.1~20质量%。能够将根据本发明的方法用于从进料流股中除去少量炔烃,典型地,所述炔烃高达约1或2质量%,但是所述方法具有明显的优势,还能够在相对高乙炔浓度下反应。由此,进料气体中乙炔的量优选为至少2质量%,更优选至少4、6、8或10质量%。优选地,进料气体含有至多约18质量%的乙炔,更优选至多约16或14质量%的乙炔(基于进料的总质量计)。在运行根据本发明的方法的优选方式中,通过对烃例如甲烷进行热解而得到了所述进料。
用于根据本发明的方法中的气体进料含有氢气和炔烃,它们可以以广泛变化的量存在,例如以0.5~10的摩尔比存在。其优势在于,能够在高氢气浓度下运行所述方法而不会对选择性带来不利影响。优选地,所述进料含有比完成加氢反应所需要的化学计量更多的氢气,即,氢气与炔烃的摩尔比优选为至少1.0、1.1或1.2,且至多8、6、5、4或3。
本发明人惊奇地发现,如果首先利用硼化合物对合适的载体进行改性,然后利用10族金属进行改性,则应用于根据本发明方法中的催化剂显示了所述优势性能。优选地,利用硼对所述载体进行表面改性,更优选地,主要对载体的表面进行改性。最优选地,在添加Ni、Pd或Pt之前,硼的氧化物B2O3存在于载体的表面上。不期望受到任何理论的束缚,本发明人假定B2O3(和活性金属)存在于载体的表面上不仅使得可在短时间内进行加氢,而且阻止了深度加氢副反应,例如乙烯加氢而成为乙烷。
在负载的催化剂中,硼优选以约0.1~约5质量%、更优选0.3~3质量%的范围存在。催化剂中10族金属组分与硼的质量比优选为10/3~1/6,更优选1/1~1/5。再次,不期望受到任何理论的束缚,本发明人认为,催化剂组合物中过量的B导致活性金属中心的至少一些彼此分离,并由此使低聚反应或聚合反应的风险最小化。
催化剂中10族元素Ni、Pd或Pt的含量优选为约0.001~约2质量%。需要特定的最少含量以达到期望的催化剂活性水平,但是高含量可增加活性位点聚集的机会并降低催化剂的效率。因此,所述催化剂优选含有至少0.01、0.03、0.05或0.1质量%且至多1、0.8或0.5质量%的10族金属(基于负载的催化剂的总质量计,不包括稀释剂)。优选地,所述催化剂含有至少钯作为活性金属。
根据本发明的方法中的催化剂可还含有其他组分,并通过通式M1-M2-M3-B/载体催化剂来表示,其中活性组分M1为选自Ni、Pd和Pt中的至少一种元素,B为硼,M2和M3为任选元素。M2为具有特定基本性质(basic properties)的氧化还原金属元素,其充当助催化剂并选自Cu、Co、Cr、Pt、Ru、Au、Ag或它们的混合物。发现在催化剂中存在这些其他金属改善了活性催化剂组分的分散并降低了活性位点聚集的风险,并阻止副反应。优选地,催化剂中存在的M2的量为0~1质量%,优选0.01~0.5质量%。
根据本发明的方法中催化剂M1-M2-M3-B/载体可还含有组分M3,其为选自碱金属和碱土金属中的至少一种元素。优选地,M3为钠或钾。发现催化剂中存在这些其他金属进一步提高了性能。优选地,催化剂中存在的M3的量为0~1质量%,优选0.01~0.5质量%。
用于根据本发明的方法中的催化剂包含具有合适粒度和几何形状的载体或载体物质。合适的载体包括在应用于本发明方法中的反应条件下具有良好稳定性的那些物质,且对于催化剂领域中的技术人员是已知的。优选地,所述载体物质为选自SiO2、ZrO2、Al2O3、TiO2以及它们的混合物中的至少一种。TiO2由于其基本特性而成为尤其优选的载体。在根据本发明方法中使用的催化剂中存在的载体物质的量可在宽范围内变化;合适的范围为40~99.87质量%(基于催化剂的总质量)。优选地,所述载体占总催化剂组合物的50~95质量%。优选地,所述载体(和负载的催化剂)的粒度为约45~60目。
在根据本发明的方法中,优选将所述催化剂与惰性固体粘接剂或稀释剂进行混合,所述粘接剂或稀释剂优选选自选自SiO2、ZrO2、Al2O3、TiO2以及它们的混合物。在固定床反应器中对包含多于2质量%的炔烃实施所述方法时,这具有特殊的优势,可通过抑制烯烃加氢成烷烃而提高选择性。基本原理在于,稀释剂改善了放热反应的热量的传递或耗散。在运行根据本发明的方法的优选方式中,稀释剂与催化剂之比为2~250,更优选5~200,或25~175(按质量计)。在优选实施方案中,稀释剂与应用于催化剂中的载体不同;例如,在催化剂含有优选载体TiO2的情况中,所述稀释剂可以为SiO2(二氧化硅或石英)。
能够在宽温度范围内例如30~500℃下实施根据本发明的方法。优选地,在至少约120℃、或150、200、250或甚至275℃但低于450、400、350或甚至低于325℃的温度下实施所述方法。温度越高,通常导致转化率增大,但是也有利于副反应例如形成绿油。能够在等温或非等温下实施所述方法。
能够在宽的压力范围内例如约大气压条件到3MPa下实施根据本发明的方法。可以在不同类型的反应器例如固定床反应器中实施根据本发明的方法,所述反应器能够由玻璃、石英、陶瓷和金属材料制成;如同本领域中所已知的。固定床反应器典型地具有管状结构,内径为约4~50mm,优选4~25mm。
在根据本发明的方法将包含乙炔和氢气的进料混合物与催化剂接触的步骤中接触时间可广泛变化,但优选为约0.3~0.0005秒,更优选0.001~0.0036秒。这些非常短的接触时间可在几个其他反应的相同范围内。由此,这是根据本发明的方法的另一个优势,使其能够与诸如甲烷转化的其他方法进行集成。在根据本发明的方法中,由于GHSV高,其为10000小时-1~7000000小时-1,优选约1000000~4000000小时-1,更优选约1800000~3600000小时-1,所以能够应用相对小的反应器尺寸,进而导致设备的资本成本下降。
本发明还涉及如上所限定的制备催化剂M1-B/载体的方法,所述方法包括步骤:(a)利用硼对载体进行改性,和(b)在含硼载体上沉积选自Ni、Pd和Pt的至少一种元素M1。
优选地,步骤(a)利用硼对所述载体进行改性通过以下操作来实施:(a1)利用硼化合物的水溶液对载体进行处理;(a2)对处理过的载体进行干燥;和(a3)对干燥过的载体进行煅烧以在表面处形成硼的氧化物。用于步骤(a)的合适的硼化合物为导致在步骤(a3)中形成硼的氧化物的那些物质例如硼酸(H3BO3),这对本领域技术人员是已知的。可在本领域技术人员所已知的合适条件下、优选在约75~125℃下实施干燥,除去水。用于对干燥过的载体进行煅烧的步骤(a3)中的温度能够广泛变化,但优选为约200~400℃,更优选225~275℃。
优选地,通过(b1)利用M1的水溶液对煅烧的载体进行浸渍,和(b2)对浸渍的载体进行干燥来实施在根据本发明的方法的步骤(b)中在含硼载体上沉积选自Ni、Pd和Pt中的至少一种元素M1。技术人员知道如何选择合适的有机或无机盐如乙酸盐、硝酸盐或氯化物。或者能够应用其他方法如化学气相沉积法或电化学法。
本发明的方法还包括分别添加组分M2和M3的步骤(c)和(d),以通过技术人员所已知的技术、优选通过利用水溶液进行的浸渍来制备由如上所限定的M1-M2-M3-B/载体表示的组合物。
根据本发明制备催化剂的方法包括用于如上所述催化剂的所有变化和优选组合物。所述方法优选还包括步骤(e):将所述浸渍的载体与固体稀释剂进行混合,所述稀释剂能够与所述载体相同或不同。在根据本发明制备催化剂的优选方式中,所述稀释剂与所述载体不同。
优选地,根据本发明的方法还包括步骤(f):将所述浸渍的载体与还原剂接触。用于这种还原步骤的合适条件为约200~400℃、优选225~275℃,并在约1~3小时的时间内、优选约2小时内使用氢气或其他合适还原剂。
在优选实施方案中,通过如下操作来制备用于本发明加氢方法中的催化剂:首先利用硼酸对TiO2载体的表面进行处理,在120℃下干燥除水,随后在250℃下对处理过的载体进行煅烧以形成硼的氧化物,然后利用溶于过量水中的硝酸钯对B改性的载体进行浸渍,随后在120℃下进行干燥并将粒度降至40/60目,将所述催化剂与作为惰性稀释剂的二氧化硅混合,和最后在约250℃的温度下利用氢气对催化剂体系还原2小时。
在一个实施方案中,本发明涉及将炔烃选择性加氢成为相应烯烃的方法,所述方法包括将包含氢气和0.1~20质量%炔烃的气体进料与通过本文中所述的方法制备的催化剂进行接触的步骤。
现在利用下列非限制性实验对本发明做进一步说明。
实施例1
通过如下操作来制备凝胶形式的TiO2载体:按本领域中技术人员所已知的将一定量的TiO2与水混合而形成凝胶或稠密的悬浮液,然后在8小时期间内在80℃下利用硼酸(H3BO3)溶液进行浸渍,随后在120℃下进行干燥并在约250℃下进行煅烧以形成B2O3。然后,在80℃下利用1%的硝酸钯水溶液对得到的固体物质进行浸渍。在约120℃下在12小时期间内对浸渍的载体进行干燥以除去水,并压碎和过筛以获得40~60目的粒度。由此获得的催化剂含有0.5质量%的Pd和1质量%的B。在装载入具有10mm内径的固定床玻璃反应器时,将0.2g催化剂颗粒与10.5g SiO2混合,所述SiO2具有与所述催化剂相同范围的粒度。然后,通过在约350℃的温度下通入氢气并持续约2小时来还原催化剂体系。
通过在1720毫升/分钟的流量下并在大气压下向反应器中供应9.8mol%C2H2、9.5mol%N2和80.7mol%H2的初始气体混合物来对乙炔进行加氢。随后,对添加CO和空气处理的效果进行了试验。利用气相色谱对气体流股的组成进行了测量并以mol%的单位进行了报道。在这些实验期间的空速为约540000小时-1(按以毫升/小时计的气体的流量除以以毫升计的催化剂的量而计算;假定催化剂的密度为约1)。将结果总结于表1中。
比较例2
与实施例1类似,在相同条件下进行实验,但是使用未实施硼浸渍步骤制备的0.5%Pd/TiO2催化剂。
总结于表1中的结果显示,这种不含硼的催化剂的转化率和稳定性较低。
表1
实施例3
以与实施例1类似的方式进行实验,但不同之处在于,反应器中催化剂的量不同,即利用10.4g石英对0.057g催化剂进行稀释;进料流量为1800毫升/分钟;导致约1900000小时-1的空速。示于表2中的结果显示了良好的转化率、选择性和催化剂稳定性。
实施例4
以与实施例1和3类似的方式实施实验,但利用使用10.4g石英稀释的0.03g 0.5%Pd-1%B/TiO2催化剂;进料流量为1800毫升/分钟;导致约3600000小时-1的空速。示于下表2中的结果显示,在这种短接触时间下仍获得了高的转化率,并保持了选择性和稳定性。在利用空气处理1560小时之后,能够对催化剂的活性至少部分地进行再生。
表2
比较例5
使用与上述相同的条件来实施实验,但使用利用10.4g石英稀释的0.035g商购获得的Pd-Ag/Al2O3催化剂;进料流量为1800毫升/分钟。在表3中给出了结果。这些实施例显示,与未经B-改性的负载的Pd催化剂或商购的Pd-Ag/Al2O3催化剂相比,根据本发明的Pd-B/载体催化剂具有更高的乙炔转化率和更好的稳定性。
表3
Claims (14)
1.将炔烃选择性加氢成为相应烯烃的方法,所述方法包括将包含氢气和0.1~20质量%炔烃的气体进料与包含在硼改性的载体上的至少一种10族元素的催化剂接触的步骤,其中在沉积10族元素时在所述载体表面上存在B2O3。
2.权利要求1的方法,其中在硼改性的载体上沉积至少Pd。
3.权利要求1的方法,其中由通式M1-M2-M3-B/载体来表示所述催化剂,其中所述催化剂含有0.03~1质量%的选自Ni、Pd和Pt中的至少一种元素M1;0~1质量%的选自Cu、Co、Cr、Pt、Ru、Au和Ag中的至少一种元素M2;0~1质量%的选自碱金属和碱土金属中的至少一种元素M3;和0.1~5质量%的硼。
4.权利要求1~3中任一项的方法,其中所述载体选自SiO2、ZrO2、Al2O3和TiO2或它们的混合物。
5.权利要求1~3中任一项的方法,其中所述催化剂还含有选自SiO2、ZrO2、Al2O3和TiO2或它们的混合物中的固体稀释剂,且稀释剂与载体的质量比为2~250,且其中所述稀释剂与所述载体不同。
6.权利要求1~3中任一项的方法,其中所述进料中的所述炔烃为乙炔且相应的烯烃为乙烯。
7.权利要求1~3中任一项的方法,其中所述进料还包含选自乙烯、甲烷、乙烷、一氧化碳、二氧化碳、氮气和水中的至少一种化合物。
8.权利要求1~3中任一项的方法,其中所述气体进料的流股含有4~16质量%的乙炔。
9.权利要求1~3中任一项的方法,其中在所述进料中氢气与炔烃的摩尔比为1.1~5。
10.权利要求1~3中任一项的方法,其中在120~450℃的温度和大气压至3MPa的压力下实施所述加氢。
11.权利要求1~3中任一项的方法,其中在1000000~4000000小时-1的空速下实施所述方法。
12.权利要求1~3中任一项的方法,所述方法包括步骤:
(a)通过如下操作利用硼对所述载体进行改性
(a1)利用硼化合物的水溶液对载体进行处理;
(a2)对处理过的载体进行干燥;和
(a3)对干燥过的载体进行煅烧以在表面处形成硼的氧化物;以及
(b)通过如下操作,利用选自Ni、Pd和Pt中的至少一种元素M1
对所述含硼载体进行改性:
(b1)利用包含选自Ni、Pd和Pt中的至少一种元素的水溶液对煅烧过的载体进行浸渍,和
(b2)对浸渍的载体进行干燥。
13.权利要求12的方法,还包括将所述浸渍的载体与固体稀释剂混合的步骤。
14.权利要求12的方法,还包括将所述浸渍的载体与还原剂接触的步骤。
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US9067851B2 (en) | 2011-08-25 | 2015-06-30 | Exxonmobil Chemical Patents Inc. | Selective hydrogenation of alkynyl-containing compounds |
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CN107175110B (zh) * | 2016-03-11 | 2020-03-31 | 中国石油化工股份有限公司 | 含碳碳三键烃加氢催化剂 |
CN112403460B (zh) * | 2019-08-23 | 2022-05-06 | 中国科学院大连化学物理研究所 | 基于金属-载体强相互作用的铂催化剂及其制备和应用 |
KR102223597B1 (ko) * | 2019-10-10 | 2021-03-05 | 한국화학연구원 | 아세틸렌의 선택적 수소화용 촉매 및 이의 제조방법 |
CN113024340B (zh) * | 2021-03-18 | 2023-10-20 | 长春工业大学 | 一种镍催化水为氢源还原炔烃为烯烃的方法 |
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