CN1234455C - 含铂、锡的多金属重整催化剂及其制备与应用 - Google Patents
含铂、锡的多金属重整催化剂及其制备与应用 Download PDFInfo
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- CN1234455C CN1234455C CNB028090578A CN02809057A CN1234455C CN 1234455 C CN1234455 C CN 1234455C CN B028090578 A CNB028090578 A CN B028090578A CN 02809057 A CN02809057 A CN 02809057A CN 1234455 C CN1234455 C CN 1234455C
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- Prior art keywords
- catalyst
- family metal
- metal
- halogen
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- 239000003054 catalyst Substances 0.000 title claims abstract description 175
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 71
- 239000002184 metal Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000002407 reforming Methods 0.000 title claims abstract description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims description 43
- 229910052697 platinum Inorganic materials 0.000 title claims description 18
- 229910052718 tin Inorganic materials 0.000 title claims description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 19
- 150000002367 halogens Chemical class 0.000 claims abstract description 19
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 14
- 229910052693 Europium Inorganic materials 0.000 claims description 40
- 229910052684 Cerium Inorganic materials 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 36
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- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 22
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- 239000000460 chlorine Substances 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
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- 230000000694 effects Effects 0.000 abstract description 9
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- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 14
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- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 7
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- 238000009835 boiling Methods 0.000 description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
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- 239000000571 coke Substances 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
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- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
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- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
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- 238000010998 test method Methods 0.000 description 1
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
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- 239000011787 zinc oxide Substances 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
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Abstract
一种多金属重整催化剂及其制备方法,所述的催化剂包括质量百分数如下的各组分:Ⅷ族金属0.01~2.0,ⅣA族金属0.01~5.0,Eu0.01~10.0,Ce0.01~10.0,卤素0.10~10.0,耐高温无机氧化物63.00~99.86。该催化剂用于石脑油的重整反应具有较高的活性和选择性,积炭速率低,寿命长。
Description
技术领域
本发明涉及一种具有酸性和加氢脱氢双功能的多金属烃类转化催化剂及其制备方法。具体地说,涉及一种含铂锡的多金属重整催化剂及其制备方法。
背景技术
催化重整是石油加工的重要生产工艺之一,其主要目的是生产高辛烷值汽油、用途广泛的芳烃以及廉价的氢气。目前、工业上广泛应用的重整催化剂多为双金属重整催化剂,主要为Pt-Re、Pt-Sn催化剂。研究表明,相对于Pt-Re催化剂而言,Pt-Sn催化剂具有较好的低压稳定性和较高的芳烃选择性,且催化剂不需预硫化,更适用于移动床重整工艺。在双金属催化剂中异构化酸性功能一般由多孔的酸性无机氧化物载体如氧化铝及卤素提供,加氢脱氢功能由VIII族金属组元,如铂或钯提供。第二金属组元Re或Sn的加入,可使催化剂的稳定性大大提高,贵金属铂含量减少。
在催化重整过程中,同时发生几个竞争反应。这些反应包括环己烷脱氢为芳烃、烷基环戊烷脱氢异构化为芳烃,环烃脱氢环化成芳烃、链烷烃加氢裂解成C5以下的轻烃,以及烷基苯的脱烷基化和链烷烃的异构化。在这些反应中,由于氢化裂解产生轻烃气体,会使汽油收率减少;结焦反应会加快催化剂的失活速率,而频繁的催化剂再生会增加装置的运转费用。因而,开发高选择性、低积炭速率的催化重整催化剂及工艺一直是人们努力的方向。其中向双金属催化剂中加入第三、第四种金属组元制成多金属重整催化剂,是目前应用较多的改性方法之一。
USP3915845公开了一种烃类转化多金属催化组分,包括0.01~2.0重量%的Pt族金属、0.01~5.0重量%的锗、0.1~3.5重量%的卤素和镧系化合物,其中镧系元素与Pt族金属的原子比为0.1~1.25。在催化剂中Pt族金属为金属态,其它金属为氧化态。所使用的镧系元素为镧、铈和钕。
USP4039477公开了一和用镧系金属改性的加氢处理催化剂及其应用。所述的催化剂包括一种难熔金属氧化物、Pt族金属、Sn和至少一种选自Y、Th、U、Pr、Ce、La、Nd、Sm、Dy和Gd的金属。该专利在催化剂中加入镧系金属,使得催化剂的活性稳定性得到提高,而锡的存在能使含镧系金属催化剂的裂解活性降低,有利于提高选择性。在具体的应用实例中,含Pt-Sn-Ce的催化剂在Ce/Pt重量比为0.37时,其己烷转化得到C5 +收率较Pt-Sn催化剂要高。
USSP6059960公开了一种含稀土的Pt-Sn多金属重整催化剂,其引入的镧系组元为Eu、Yb、Sm或Eu与Yb的混合物,并且在催化剂中50%以上的镧系金属以EuO存在。当催化剂为铂-锡-铕组分时,只在铕/铂原子比为1.3~2.0时相对活性和选择性均较好。比值小于1.3时。催化剂的选择性降低,比值失于2.0时,催化活性明显下降。
发明内容
本发明的目的是提供一种稀土改性的铂锡重整催化剂,该催化剂具有较高的活性、较高的选择性和良好的活性稳定性。
本发明的另一个目的是提供上述催化剂的制备方法。
我们发现,用铈和铕改性的双金属重整催化剂可以提高催化剂的选择性和抗积炭能力,从而能使重整反应的液收增加、并使催化剂寿命延长。具体地说,本发明提供的多金属重整催化剂,包括质量百分数如下的各组分:
VIII族金属 0.01~2.0
IVA族金属 0.01~5.0
Eu 0.01~10.0
Ce 0.01~10.0
卤素 0.10~10.0
耐高温无机氧化物 63.00~99.86。
附图说明
图1为本发明催化剂与含Eu的对比催化剂B的选择性比较结果。
图2为本发明催化剂与含Eu的对比催化剂A和C的选择性比较结果。
图3为本发明催化剂与含Eu的对比催化剂A和C的活性比较结果。
图4为本发明催化剂与含Ce催化剂的选择性比较结果。
图5为本发明催化剂与含Ce催化剂的活性比较结果。
图6为本发明催化剂中Ce/Pt原子比与芳烃产率的关系。
具体实施方式
所述的VIII族金属选自Pt、Pd、Ru、Rh、Ir、Os或它们的混合物,优选Pt。VIII族金属组分为本发明催化剂的主要活性组分。Pt族金属在催化剂中的存在形态可为金属、也可为化合物,如以金属氧化物、硫化物、卤化物或氧卤化物的形态存在,也可以与催化剂中的一种或多种其它组分以化学结合的方式存在。该族金属在催化剂中的含量以元素为基准计算,优选的含量为0.05~1.0质量%。
催化剂中的IVA族金属优选Ge或Sn,更优选Sn。IVA族金属组分在催化剂中的存在形态可为金属元素、化合物如氧化物、硫化物、卤化物、氧卤化物等,也可以与载体和催化剂中的其它组分以物理或化学的结合方式存在。成品催化剂中,IVA族金属优选以氧化态的形式存在。以金属元素计,本发明催化剂中IVA族金属含量优选0.1~2.0质量%。
本发明催化剂含有的镧系金属为Ce和Eu的混合物。Ce和Eu在催化剂中可以以氧化物、氢氧化物、卤化物、氧卤化物、铝酸盐,或与催化剂的一种或几种其它组分以化学结合的形态存在。Ce和Eu各自在催化剂中的含量以金属元素计,优选0.05~2.0质量%,更优选0.1~1.0质量%。本发明催化剂中铕/铂原子比为0.2~3.0∶1,优选0.2~1.0∶1,更优选0.5~1.0∶1,铈/铂原子比为0.2~5.0∶1,优选0.5~3.0∶1。还原后催化剂中60%以上的Ce以+3价的形式存在。
本发明催化剂中用于调节酸量的组分为卤素,优选氯。卤素在催化剂中的含量优选0.2~4.0质量%。
所述的催化剂载体选自耐高温无机氧化物,通常为一种多孔具有吸附性的物质,其比表面积为30-500米2/克。多孔载体的组成应是均匀的,并且在使用的条件下是难熔的。术语“组成均匀”的意思是指载体不分层,没有固有组分的浓度梯度。如果载体是两种或两种以上难熔材料的混合物,那么在整个载体上这些材料的相对量是恒定的或分布均匀的。本发明所述的耐高温无机氧化物包括:
(1)难熔无机氧化物,如氧化铝、氧化镁、氧化铬、氧化硼、氧化钛、氧化钍、氧化锌、氧化锆,或者以下两种氧化物的混合物:氧化硅-氧化铝、氧化硅-氧化镁、氧化铬-氧化铝、氧化铝-氧化硼、二氧化硅-氧化锆;
(2)各种陶瓷、各种矾土、和各种铝土矿;
(3)二氧化硅、碳化硅、合成或天然存在的各种硅酸盐和粘土,这些硅酸盐和粘土可以用或不用酸处理;
本发明优选的无机氧化物载体为Al2O3,更为优选的是烷氧基铝水解制得的高纯氧化铝。其结晶形态可为γ-Al2O3、η-Al2O3或θ-Al2O2,优选γ-Al2O3或η-Al2O3,更优选的结晶形态为γ-Al2O3。Al2O3粉末可制成任何形状,如球形、片形、颗粒形,条形、三叶草形。
上述球形载体可通过油氨柱法或热油柱法成型。条形或三叶草形载体可采用常规的挤出成型法制备。
所述耐高温无机氧化物载体具有的表观堆密度为0.4~1.0克/毫升,平均孔径为20-300、孔体积为0.2~1.0毫升/克、比表面积为100~500米2/克。
本发明所述催化剂的制备方法包括将IVA族金属、Eu和Ce分别引入无机氧化物载体,再引入VIII族金属,优选铂,每引入一种金属组元均需干燥、焙烧。
在催化剂制备中首先应引入的元素应为IVA族金属、Eu和Ce。它们的引入顺序可以是任意的,可先将IVA族金属引入载体,再引入Eu和Ce,也可以是相反。Eu和Ce可同时引入,也可分步引入。但每次进行引入金属组元的操作后,最好进行焙烧,以确保引入组元与载体牢固结合。
IVA族金属组分可采用任何方式引入催化剂中并达到组分均匀分布。可采用与多孔载体共沉淀、离子交换或以浸渍的方式进行引入。其中浸渍法是用IVA族金属的可溶性化合物溶液浸渍载体,使该溶液充满或分散在全部多孔载体材料中,适宜的IVA族金属可溶性化合物为其氧化物、氯化物、硝酸盐或醇盐,如溴化亚锡、氯化亚锡、四氯化锡、四氯化锡五水合物;二氧化锗、锗的四乙醇盐、四氯化锗;硝酸铅、乙酸铅或氯酸铅。优选四氯化锡、四氯化锗或氯酸铅,因上述氯化物可在引入金属组分的同时引入一部分卤素。另外,IVA族金属组分还可在载体制备的过程中引入。
催化剂中的铈和铕元素可通过本领域技术人员已知的任何方式引入,如与多孔载体的共沉淀、共胶凝、共挤压或胶凝过的载体材料进行离子交换等,其中优选的方法是在载体制备过程中加入相应的铈和铕的水合氧化物或氧卤化物形态共胶凝或共沉淀,然后再将固体干燥、焙烧。适宜的形成可溶性溶胶或可分散性溶胶的镧化合物为三氯化镧或镧的氧化物。
引入铈和铕的另一个优选方法是用铈和铕的可溶性化合物溶液浸渍多孔载体。用于配制浸渍溶液适宜的溶剂包括醇、醚、酸,优选的适宜酸类溶剂有HCl、HNO3等无机酸,草酸、丙二酸、柠檬酸等有机酸。用于浸渍载体的可溶性化合物为铈和铕的金属盐、化合物或配合物,如硝酸盐、氯化物、氟化物、有机烷基化物、氢氧化物、氧化物,优选硝酸铈、硝酸铕、氯化铈、氯化铕、氧化铈或氧化铕。在过程中可将Eu和Ce同时引入载体,也可分别引入载体。其引入步骤可在引入VIII族金属之前或之后,也可与之同时引入,优选在VIII族金属之后引入。
催化剂中的VIII族金属为贵金属组分,可采用共沉淀、离子交换或浸渍等方式引入载体。优选的方法是采用水溶性可分解的VIII族金属化合物浸渍载体。可采用VIII族金属的水溶性化合物或配合物的非限制性例子有:氯铂酸、氯铱酸、氯钯酸、氯铂酸铵、溴铂酸、三氯化铂、四氯化铂水合物、二氯化二氯羰基铂、二硝基二氨基铂、四硝基铂酸钠(II)(Sodium tetranitroplatinate(II))、氯化钯、硝酸钯、硫酸钯、二氨基钯氢氧化物(diamminepalladium(II)hydroxide)、氯四氨钯(tetrammine pallaclium(II)chloride)、氯六氨钯、氯化羰基铑、三氯化铑水合物、硝酸铑、六氯铑酸钠(Sodiumhexachlororhodate(III))、六硝基铑酸钠(Sodium hexanitrorhodate(III))、三溴化铱、二氯化铱、四氯化铱、六硝基铱酸钠(Sodiumhexanitroridate(III))、氯铱酸钾或氯铱酸钠、草酸铑钾。优选Pt、Ir、Rh或Pd的含氯化合物,如氯铂酸、氯铱酸、氯钯酸或三氯化铑的水合物。在载铂过程中为有利于卤素组分的引入和使各金属组分在整个载体材料上均匀分布,可在浸渍液中加入HCl或类似的酸,如HF酸。此外,在载体中浸渍VIII族金属之后最好进行焙烧,以减少VIII族金属在其它的浸渍过程中被洗脱的危险。较好的方法是引入其它金属组元之后再引入VIII族金属,这样可减少VIII族金属在其它浸渍过程中的损失。通常,VIII族金属在催化剂中均匀地分散、也可以是从催化剂颗粒表面到中心呈浓度逐渐衰减的形式分散。
上述引入金属组元的各步操作,在引入金属元素后都要进行干燥、焙烧。干燥温度为25~300℃,焙烧温度为370℃~700℃,优选550~650℃。所述的焙烧通常在含氧气氛中进行,优选的焙烧气体为空气。确定焙烧时间的基准是使催化剂中绝大部分金属组分转化成相应的氧化物,该时间随氧化温度和氧含量的变化而改变。焙烧时间优选0.5~10小时。
本发明催化剂还可含有其它组分或这些组分的混合物,单独用作或一起用作催化剂改性剂,以提高催化剂的活性、选择性或稳定性。所述的改性剂包括Rh、In、Co、Ni、Fe、W、Mo、Cr、Bi、Sb、Zn、Cd或Cu。这些组分可以任何方式在载体材料制备后或制备期间添加到载体材料中,或在本发明催化剂其它组分引入之前、同时或之后加入到催化剂中,其含量为0.05~5.0质量%。
本发明催化剂还可含有碱金属或碱土金属,可以任何已知的方式引入催化剂,优选用碱金属或碱土金属的水溶性可分解化合物的水溶液浸渍载体的方法。所述的碱金属为Cs、Rb、K、Na或Li,所述的碱土金属为Ca、Sr、Ba或Mg,其含量为0.05~5.0质量%。
为保证催化剂具有适宜的酸性,在其制备中还包含卤素调节步骤。用于引入卤素的化合物优选Cl、HCl或能分解出氯的有机化合物,如二氯甲烷、三氯甲烷、四氯化碳。卤素调节的温度为370~700℃,时间为0.5~5.0小时或更长。在此过程中,应有适量的水,水与HCl的摩尔比为1.0~150∶1。卤素调节步骤可与催化剂焙烧同时进行,也可在焙烧之前或之后进行。成品催化剂中卤素的含量优选0.2~4.0质量%。
本发明催化剂在使用前要进行还原,以将VIII族金属组分还原成相应元素的金属态,并保证较均匀地分布在全部耐高温无机氧化物载体上。还原步骤需要在基本无水的环境中进行,还原气中的水含量要小于20ppm。优选的还原气为氢气,也可采用CO等其它的还原性气体对催化剂进行还原。还原温度为315~650℃,优选的还原时间为0.5~10.0小时。还原步骤可在催化剂装入反应器之前进行,也可在重整反应开始进行前就地进行。
本发明催化剂适用于石脑油的催化重整反应,以提高汽油辛烷值和芳烃收率。所述的石脑油富含环烷烃和链烷烃,选自按ASTM D-86方法测定,初馏点为40~80℃、终馏点为160~220℃的全沸程汽油,沸程为60~150℃的轻质汽油,或沸程为100~200℃的重石脑油。适用的重整原料为直馏汽油、部分重整石脑油或脱氢石脑油、热裂化或催化裂化的汽油馏份以及合成汽油。
本发明催化剂用于催化重整反应过程所采用的绝对压力为100KPa~7MPa,优选350~2500KPa;温度为315~600℃,优选425~565℃;氢气/烃摩尔比为1~20,优选2~10;液时空速(LHSV)为0.1~10小时-1,优选1~5小时-1。
在重整过程中要控制在基本无水的条件下进行。原料在进入转化区时含水量应小于50ppm,最好小于20ppm。重整原料中的水可通过常规的吸附剂,如分子筛进行干燥,也可以通过分馏装置进行适当的汽提操作来调节。也可将吸附干燥和汽提干燥结合,来排除原料中的水。进入烃转化区的氢气流的水含量最好是不大于10~20ppm。
本发明的催化剂还适合于其它烃转化反应,如烃原料的脱氢、加氢、氢化裂化、氢解、异构化、脱硫、环化、烷基化、裂化和加氢异构化反应。
本发明催化剂优选在无硫环境下使用。石脑油原料脱硫可采用任何常规方法进行,如采用吸附脱硫、催化脱硫等。吸附脱硫可采用分子筛、结晶硅铝酸盐、高表面积的SiO2-Al2O3、活性炭、高表面积的金属化合物,例如含Ni或Cu等具有高表面积的化合物。催化脱硫可采用常规的加氢精制、加氢处理、加氢脱硫等方法。
本发明催化剂由于用铈和铕同时对双金属催化剂进行改性,使得催化剂的选择性和活性稳定性得到提高,与单独用铈和铕改性的催化剂相比,在同样的反应条件和芳烃收率下,本发明催化剂具有较高的液收,并且积碳速率大幅下降。
下面通过实施例详细说明本发明,但本发明开不限于此。
实施例1
制备本发明的球形催化剂。
(1)制备含Sn的Al2O3载体。
按CN1150169A实施例1的方法将100克SB氢氧化铝粉(德国,Condea公司生产)和适量去离子水,使液/固重量比为2.0,搅拌浆化。加入7.5毫升体积比为1∶1的稀硝酸,30克尿素和预定量的氯化亚锡的盐酸溶液,使溶液中的含Sn量相对干基氧化铝为0.30质量%,搅拌1小时,加入30克煤油和3克脂肪醇聚氧乙烯醚搅拌1小时,在油氨柱内滴球成型。湿球在氨水中固化1小时,然后过滤,用去离子水冲洗2~3次,60℃干燥6小时,120℃干燥10小时,600℃焙烧4小时,得含Sn的载体a。
(2)引铕
取100克球形载体a,加入浓度为2.27质量%硝酸铕的硝酸溶液180毫升,浸渍时的液固比为1.8,浸渍24小时后过滤,所得固体在60℃干燥6小时,120℃干燥10小时,然后在含2~3%水蒸气的空气中600℃焙烧4小时,得到含Sn和Eu的载体。
(3)引铈
将上述含Sn和Eu的载体,用0.58重量%的硝酸铈溶液180毫升浸渍24小时,浸渍液固比为1.8,然后过滤。所得固体于60℃干燥6小时,120℃干燥10小时,然后在含2~3%水蒸气的空气中600℃焙烧4小时,得到含Sn、Eu和Ce的载体。
(4)引铂
将上步制得的载体用按预定量配制的氯铂酸、盐酸和三氯乙酸的混合液浸渍,混合液中的铂含量应使制得的催化剂达到所需的铂含量,盐酸和三氯乙酸的量相对干基氧化铝质量分为1.2%和5.0%,浸渍混合液与载体的液/固比为1.8,浸渍时间24小时。浸渍过滤后固体在510℃、水/HCl的摩尔比为60∶1的条件下于空气中活化处理6小时,在500℃用纯氢还原后制得催化剂F,F的组成见表1。催化剂中Pt、Sn、Eu和Ce的含量用X光荧光法测定,氯含量用电极法测定。
实施例2
按实施例1的方法制备催化剂G,不同的是第(3)引铈加入的硝酸铈溶液的浓度为1.42质量%,第(2)、(3)两步浸铕和浸铈后的固体650℃空气中焙烧6小时,氢气还原后得到的催化剂G的组成见表1。
实施例3
按实施例1的方法制备催化剂H,不同的是第(3)引铈加入的硝酸铈溶液的浓度为1.70质量%,第(4)步浸铂过滤后固体在560℃、水/HCl摩尔比为50∶1的条件下于空气中活化处理6小时,氢气还原后得到的催化剂H的组成见表1。
实施例4
按实施例1的方法制备催化剂I,不同的是先在含Sn载体中引入铈,然后再引入铕,浸铈步骤所用的硝酸铈溶液浓度为4.98质量%,氢气还原后得到的催化剂I的组成见表1。
实施例5
本实施例用共浸渍法在载体中同时引入铕和铈。
取实施例1制得的含Sn载体a 100克,用1.70质量%的硝酸铈和0.62质量%的硝酸铕溶液180毫升同时浸渍载体,过滤所得固体于60℃干燥6小时,120℃干燥10小时后,然后在含2~3%水蒸气的空气中600℃焙烧4小时,再按实施例1(4)步方法载铂制得催化剂J,其组成见表1。
实施例6
按实施例1的方法制备催化剂K,不同的是第(2)、(3)两步所用的浸渍液分别为180毫升3.78质量%的氯化铕溶液和1.29质量%的氯化铈溶液,氢气还原后得到的催化剂K的组成见表1。
对比例1
制备含Pt、Sn、Eu的球形催化剂A。
按实施例1的方法制备催化剂,不同的是不在载体中引入铈,且引入铕的浸渍液为0.62质量%的硝酸铕溶液180毫升,制得催化剂A的组成见表1。
对比例2
按对比例1的方法制备催化剂,不同的是引入铕的浸渍液为1.36质量%的硝酸铕溶液180毫升,制得催化剂B的组成见表1。
对比例3
按对比例1的方法制备催化剂,不同的是引入铕的浸渍液为2.31质量%的硝酸铕溶液180毫升,制得催化剂C的组成见表1。
对比例4
制备含Pt、Sn、Ce的球形催化剂。
按实施例1的方法制备催化剂,不同的是不在载体中引入铕,且引入铈的浸渍液为1.70质量%的硝酸铈溶液180毫升,制得的催化剂E组成见表1。
实施例7
本实施例证明本发明催化剂中稀土元素的价态。
使用含3mol%H2的He,采取程序升温,以8℃/分的速率从室温升温到800℃,测定本发明催化剂F、G、H、I、J以及参比剂A、B的氢吸收谱图,对600℃以下的还原峰进行积分,计算氢吸收量,其结果如表2所示。
由表2可知,催化剂F、G、H、I、J与不含铈的催化剂A和B相比,氢吸收量均有所增加,氢吸收的增加量说明本发明催化剂中85%以上的Ce的价态为+3。
实施例8
本实施例对本发明催化剂的选择性进行评价。
在微反装置中,装入2克催化剂,以86~151℃的直馏石脑油为原料,原料油的性质见表3。评价条件为:0.70MPa、进料体积空速2小时-1、氢油体积比800∶1。反应过程中调节温度为490℃、500℃、510℃、520℃,以改变芳烃产率,评价结果见图1。
由图1可知,在芳烃产率相同的情况下,本发明催化剂F-I与对比剂B相比,具有较高的C5 +收率,说明与单独含铕的对比催化剂B相比,本发明催化剂的选择性有较大的提高。
实施例9
在微反装置上评价本发明催化剂J、对比剂A和C,评价条件及原料油均同实施例8,评价结果见图2和图3。
由图2可知,在Eu含量相同时,本发明催化剂J与单含Eu的催化剂A相比,达到相同芳产时,催化剂J的C5 +收率比A高2m%以上。与Eu含量增加的对比催化剂C相比,催化剂J的C5 +液收略高于催化剂C。
但图3的数据表明,达到相同芳产时,催化剂C所需要的温度要比J高5~8℃,表明催化剂C的活性远低于本发明催化剂J。
实施例10
在微反装置上评价本发明催化剂J和对比剂E,评价条件及原料油均同实施例8,结果见图4和图5。
由图4可知,本发明催化剂与单独含铈的对比催化剂E相比,在芳烃产率相同的情况下,催化剂J的C5 +收率比E高2m%以上。说明选择性较对比剂高。图5表明达到相同芳产时,催化剂E与J的反应温度基本相同,说明其催化活性相当。
实施例11
用RIPP107-90法(参见杨翠定等编著的《石油化工分析方法》(RIPP试验方法)对催化剂积炭速率进行评定,所用评定仪器为美国LECO公司CS-344型红外碳硫测定仪,其结果见表4。表4中相对积碳速率由下式计算:
测定催化剂积碳速率使用的参比剂是按照实施例1(1)、(4)两步骤制备的Pt-Sn催化剂,其中Pt含量为0.34质量%,Sn含量为0.30质量%。
由表4可知,本发明催化剂与单独含铕的催化剂A、B、C和单独含铈的催化剂E相比,积炭速率有所下降,且随催化剂中Ce和Eu含量的增加,催化剂积炭速率呈下降趋势。另外,在催化剂中稀土含量相当的情况下,本发明催化剂J的相对积炭速率较对比剂C为低。
实施例12
本实施例考察催化剂铈含量对选择性的影响。
按实施例8的方法对催化剂F、G、H、I和对比催化剂B进行评价,结果见图6。
由图6可知,催化剂中Ce/Pt原子比小于1.3时,芳烃产率没有大的下降,相反,当反应温度大于500℃时,芳烃产率还有所增加。但催化剂中Ce/Pt原子比大于2.2时,芳烃产率将下降。
表1
实施例号 | 催化剂编号 | Pt,m% | Sn,m% | Eu,m% | Ce,m% | Cl,m% |
1 | F | 0.33 | 0.30 | 0.33 | 0.18 | 1.15 |
2 | G | 0.33 | 0.30 | 0.33 | 0.39 | 1.12 |
3 | H | 0.33 | 0.30 | 0.33 | 0.49 | 0.97 |
4 | I | 0.33 | 0.30 | 0.33 | 1.17 | 1.20 |
5 | J | 0.33 | 0.30 | 0.15 | 0.48 | 1.15 |
6 | K | 0.34 | 0.30 | 0.49 | 0.48 | 1.16 |
对比例1 | A | 0.33 | 0.30 | 0.15 | - | 1.18 |
对比例2 | B | 0.33 | 0.30 | 0.33 | - | 1.15 |
对比例3 | C | 0.33 | 0.30 | 0.56 | - | 1.15 |
对比例4 | E | 0.33 | 0.30 | - | 0.48 | 1.25 |
表2
催化剂 | A | J | B | F | G | H | I |
耗氢量,μmol/g | 66.7 | 83.3 | 72.2 | 78.3 | 86.0 | 89.2 | 108.8 |
表3
表3
密度(20℃),千克/米3 | 727.4 |
ASTM D-86馏程,℃初馏点/50%/终馏点 | 86/109/151 |
组成,质量%直链烷烃/环烷烃/芳烃 | 55.70/41.38/2.92 |
芳烃潜含量,质量% | 41.59 |
表4
催化剂编号 | A | B | C | E | F | G | H | I | J | K |
相对积碳速率,% | 0.80 | 0.80 | 0.73 | 0.80 | 0.70 | 0.65 | 0.58 | 0.40 | 0.64 | 0.53 |
Claims (11)
1.一种多金属重整催化剂,包括质量百分数如下的各组分:
VIII族金属 0.01~2.0
IVA族金属 0.01~5.0
Eu 0.01~10.0
Ce 0.01~10.0
卤素 0.10~10.0
耐高温无机氧化物 63.00~99.86。
2.按照权利要求1所述的催化剂,其特征在于催化剂中各组分的质量百分数为:
VIII族金属 0.05~1.0
IVA族金属 0.10~2.0
Eu 0.05~2.0
Ce 0.05~2.0
卤素 0.20~4.0
耐高温无机氧化物 89.00~99.55。
3.按照权利要求1或2所述的催化剂,其特征在于催化剂中60%以上的Ce以+3价的形式存在。
4.按照权利要求3所述的催化剂,其特征在于所述的耐高温无机氧化物为氧化铝。
5.按照权利要求4所述的催化剂,其特征在于所述的氧化铝为烷氧基铝水解制得的高纯氧化铝。
6.按照权利要求3所述的催化剂,其特征在于所述的VIII族金属为铂、IVA族金属为锡、卤素为氯,催化剂中铕/铂原子比为0.2~3.0∶1,铈/铂原子比为0.2~5.0∶1。
7.按照权利要求6所述的催化剂,其特征在于所述催化剂中铕/铂原子比为0.5~1.0∶1,铈/铂原子比为0.5~3.0∶1。
8.一种权利要求1所述催化剂的制备方法,包括将IVA族金属、Eu和Ce分别引入无机氧化物载体,再引入VIII族金属,每引入一种金属组元均需干燥、焙烧。
9.按照权利要求8所述的制备方法,其特征在于所述VIII族金属是铂。
10.按照权利要求8所述的制备方法,其特征在于催化剂制备过程中采用共沉淀或共浸渍的方法将Eu和Ce同时引入载体。
11.按照权利要求8所述的制备方法,其特征在于采用卤素调节法引入卤素,卤素调节的温度为370~700℃,水/HCl的摩尔比为1.0~150∶1。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8475650B2 (en) | 2007-10-31 | 2013-07-02 | China Petroleum & Chemical Corporation | Pre-passivation process for a continuous reforming apparatus, and passivation process for a continuous reforming apparatus during the initial reaction |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10208254A1 (de) * | 2002-02-26 | 2003-09-04 | Bayer Ag | Katalysator |
US20060102520A1 (en) * | 2004-11-12 | 2006-05-18 | Lapinski Mark P | Reforming process using high density catalyst |
US8309780B2 (en) * | 2007-12-21 | 2012-11-13 | Exxonmobil Research And Engineering Company | Process for making olefin oligomers and alkyl benzenes in the presence of mixed metal oxide catalysts |
CN101468313B (zh) * | 2007-12-28 | 2014-08-20 | 中国石油化工股份有限公司 | 一种重整催化剂的制备方法 |
FR2947465B1 (fr) * | 2009-07-01 | 2012-05-11 | Inst Francais Du Petrole | Catalyseur multi-metallique presentant une proximite de sites optimisee |
CN102049267B (zh) * | 2009-10-29 | 2013-01-30 | 中国石油化工股份有限公司 | 一种丙烷脱氢制丙烯的催化剂及制备与应用 |
US8758599B2 (en) | 2011-07-15 | 2014-06-24 | Uop Llc | Reforming catalyst and process |
US8912110B2 (en) * | 2012-03-29 | 2014-12-16 | Uop Llc | Catalyst for conversion of hydrocarbons |
CN103372454B (zh) * | 2012-04-27 | 2016-01-13 | 中国石油化工股份有限公司 | 一种多金属重整催化剂及其制备与应用 |
CN103962135B (zh) * | 2013-01-30 | 2017-04-12 | 中国石油天然气股份有限公司 | 一种多金属连续重整催化剂及其制备方法 |
CN103962161B (zh) * | 2013-01-30 | 2016-11-23 | 中国石油天然气股份有限公司 | 一种连续重整催化剂及其制备方法 |
CN104148066B (zh) * | 2013-05-15 | 2016-08-24 | 中国石油化工股份有限公司 | 一种多金属重整催化剂及其制备与应用 |
CN104275198B (zh) * | 2013-07-01 | 2016-04-27 | 中国石油化工股份有限公司 | 一种多金属重整催化剂的制备方法 |
CN104511292B (zh) * | 2013-09-27 | 2017-04-05 | 中国石油天然气股份有限公司 | 一种连续重整催化剂及其制备方法 |
CN105771981A (zh) * | 2014-12-24 | 2016-07-20 | 中国石油天然气股份有限公司 | 一种石脑油重整催化剂及其制备方法 |
FR3039082B1 (fr) | 2015-07-24 | 2017-07-21 | Ifp Energies Now | Catalyseur multi-metallique dope par du phosphore et un lanthanide |
CN107152356B (zh) * | 2017-06-09 | 2023-05-26 | 李秋生 | 前置式u型机动车燃油催化器 |
CN109201051B (zh) * | 2017-07-05 | 2021-08-06 | 中国石油化工股份有限公司 | 一种多金属连续重整催化剂的制备方法 |
FR3074063B1 (fr) | 2017-11-30 | 2019-11-01 | IFP Energies Nouvelles | Catalyseur multi-metallique dope par du phosphore et de l'ytterbium |
FR3074062B1 (fr) | 2017-11-30 | 2020-06-26 | IFP Energies Nouvelles | Catalyseur multi-metallique dope par du phosphore et de l'yttrium |
CN110064421B (zh) * | 2018-01-23 | 2021-11-30 | 中国石油天然气股份有限公司 | 一种重整催化剂及其制备方法 |
CN110064422B (zh) * | 2018-01-23 | 2022-01-04 | 中国石油天然气股份有限公司 | 一种多金属连续重整催化剂及其制备方法 |
CN110064392B (zh) * | 2018-01-23 | 2021-11-30 | 中国石油天然气股份有限公司 | 一种氧化态半再生重整催化剂及其制备方法 |
CN110064418B (zh) * | 2018-01-23 | 2021-11-02 | 中国石油天然气股份有限公司 | 一种氧化态重整催化剂及其制备方法 |
RU2767882C1 (ru) * | 2021-04-29 | 2022-03-22 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Катализатор риформинга бензиновых фракций и способ его получения |
CN115999540A (zh) * | 2021-10-21 | 2023-04-25 | 中国石油化工股份有限公司 | 一种丙烷脱氢制丙烯催化剂及其制备方法 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3852190A (en) * | 1972-10-27 | 1974-12-03 | Chevron Res | Reforming with platinum on alumina derived from a byproduct of a ziegler process |
US4003826A (en) | 1973-12-06 | 1977-01-18 | Uop Inc. | Hydrocarbon conversion with an acidic multimetallic catalytic composite |
US3915845A (en) | 1973-12-06 | 1975-10-28 | Universal Oil Prod Co | Hydrocarbon conversion with a multimetallic catalytic composite |
FR2280426A1 (fr) * | 1974-07-30 | 1976-02-27 | Raffinage Cie Francaise | Catalyseurs d'hydrotraitement d'hydrocarbures et application desdits catalyseurs |
US4148715A (en) * | 1978-03-13 | 1979-04-10 | Uop Inc. | Hydrocarbon conversion with an acidic multimetallic catalytic composite |
US5254518A (en) * | 1992-07-22 | 1993-10-19 | Exxon Research & Engineering Company | Group IVB oxide addition to noble metal on rare earth modified silica alumina as hydrocarbon conversion catalyst |
US5258567A (en) | 1992-08-26 | 1993-11-02 | Exxon Research And Engineering Company | Dehydrogenation of hydrocarbons |
US6059960A (en) * | 1995-06-05 | 2000-05-09 | Uop Llc | Catalytic reforming utilizing a selective bifunctional multimetallic reforming catalyst |
US5665223A (en) * | 1995-06-05 | 1997-09-09 | Uop | Selective bifunctional multimetallic reforming catalyst |
US6013173A (en) * | 1996-12-09 | 2000-01-11 | Uop Llc | Selective bifunctional multimetallic reforming catalyst |
US6495487B1 (en) * | 1996-12-09 | 2002-12-17 | Uop Llc | Selective bifunctional multimetallic reforming catalyst |
US6809061B2 (en) * | 1996-12-09 | 2004-10-26 | Uop Llc | Selective bifunctional multigradient multimetallic catalyst |
CN1075106C (zh) | 1997-09-08 | 2001-11-21 | 环球油品公司 | 有选择性的双功能多金属烃类转化催化剂组合物及其使用方法 |
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US8475650B2 (en) | 2007-10-31 | 2013-07-02 | China Petroleum & Chemical Corporation | Pre-passivation process for a continuous reforming apparatus, and passivation process for a continuous reforming apparatus during the initial reaction |
EP2910624A1 (en) | 2007-10-31 | 2015-08-26 | China Petroleum & Chemical Corporation | Passivation process for a continuous reforming apparatus during the initial reaction |
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CA2445321C (en) | 2008-07-15 |
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US6780814B2 (en) | 2004-08-24 |
EP1390140A1 (en) | 2004-02-25 |
KR100572922B1 (ko) | 2006-04-24 |
RU2259233C2 (ru) | 2005-08-27 |
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