CN1311059C - 重芳烃加工 - Google Patents
重芳烃加工 Download PDFInfo
- Publication number
- CN1311059C CN1311059C CNB2003801032033A CN200380103203A CN1311059C CN 1311059 C CN1311059 C CN 1311059C CN B2003801032033 A CNB2003801032033 A CN B2003801032033A CN 200380103203 A CN200380103203 A CN 200380103203A CN 1311059 C CN1311059 C CN 1311059C
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- zsm
- catalyst composition
- aromatic hydrocarbons
- benzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000000203 mixture Substances 0.000 claims abstract description 87
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- 239000002808 molecular sieve Substances 0.000 claims abstract description 66
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- 238000000034 method Methods 0.000 claims abstract description 45
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 31
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- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
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- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
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- 239000011574 phosphorus Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
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- 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
在一种将C9+芳烃转化为轻质芳族产物的方法中,在烷基转移反应条件下,使包含C9+芳烃的原料与催化剂组合物接触,所述催化剂组合物包含:(i)第一分子筛,选自于ZSM-12、丝光沸石和多孔结晶无机氧化物材料,该材料具有包括d-间隔最大值在12.4±0.25、6.9±0.15、3.57±0.07和3.42±0.07处的X射线衍射图案;和(ii)第二分子筛,具有约束指数为3-12。至少第一分子筛具有与其结合的氢化组分,且第一和第二分子筛都含在同一催化剂床中。在烷基转移反应条件下,C9+芳烃转变成含有二甲苯的反应产物。
Description
技术领域
本发明涉及将重芳烃特别是C9+芳烃转化为轻质芳族产物特别是苯、甲苯和二甲苯(BTX)。
技术背景
苯和二甲苯的来源是催化重整产物,催化重整产物是通过使石脑油和氢的混合物,与在适当的酸性载体诸如卤素处理的氧化铝载体上的强氢化/脱氢催化剂诸如铂接触而制得。通常,从重整产物中分离出C6-C8级分,并用对芳烃或脂族烃有选择性的溶剂萃取,制得含脂族烃较少的芳族化合物的混合物。这种芳族化合物的混合物通常含有BTX以及乙苯。
炼油厂也集中于通过C9+芳烃和甲苯在含贵金属的沸石催化剂上进行烷基转移反应来生产苯和二甲苯。在含有贵金属的催化剂上、在C9+芳烃和甲苯经过烷基转移作用形成高价值石油化学产品诸如苯和二甲苯的过程中,在头几个月的操作中通常会产生副产物饱和化合物。这些副产物饱和化合物能够与所需芳族产物在相同的温度范围内沸腾,使得很难以高纯度级分离所需的产品。例如,工业级的苯产品的纯度必须超过99.85%。然而,在烷基转移反应产物蒸馏之后,由于存在共沸物诸如甲基环戊烷、环己烷、2,3-二甲基戊烷、二甲基环戊烷和3-甲基己烷,最初苯的纯度一般仅为99.2%-99.5%。因此,为了进一步将苯产品的纯度提高到所需水平,通常需要一个附加的萃取步骤。
一个解决在重芳烃的烷基转移反应过程中产生苯共沸物问题的方法,公开于美国专利US 5,942,651中,该解决方法包括在烷基转移反应条件下,使包含C9+芳烃和甲苯的原料与第一催化剂组合物接触的步骤,所述催化剂组合物包含一种具有约束指数为0.5-3的沸石诸如ZSM-12和一种氢化组分。然后使来自于第一接触步骤的流出液与第二催化剂组合物接触,所述第二催化剂组合物包含具有约束指数为3-12的沸石诸如ZSM-5,且可处于与第一催化剂组合物分离的分离床或分离反应器中,以制得包含苯和二甲苯的烷基转移反应产物。通过从烷基转移反应产物中蒸馏苯,可以获得纯度至少为99.85%的苯产品,而无需附加的萃取步骤。按照美国专利US 5,942,651,第二催化剂组合物占第一和第二催化剂组合物总重量的至多20wt%。
美国专利US 5,905,051公开了一种将诸如C9+芳族化合物之类的烃蒸气转化为C6-C8芳烃诸如二甲苯的方法,该方法是通过使该蒸气与包含第一催化剂组合物和第二催化剂组合物的催化剂体系接触而实现,其中所述两种催化剂组合物存在于分别的阶段,并且没有物理混合或共混,且其中所述第一催化剂组合物是金属促进的、氧化铝或二氧化硅结合的沸石β,所述第二催化剂组合物是其中引入了活性助催化剂的ZSM-5,所述助催化剂选自于硅、磷、硫和其混合物。按照美国专利US5,905,051,分别催化阶段的使用提高了C9+芳族化合物和萘转化为二甲苯的转化率,并降低了产物中不希望的乙苯的量。
与美国专利US 5,905,051中的教导相反,目前已经发现,包含至少两种不同的特定分子筛的单一阶段催化剂体系,对于除去C9+芳族原料中含乙基芳族化合物来说,表现出提高的活性,而C9+原料转化为有用化合物诸如二甲苯的转化率总体上不会降低。
发明概述
因此,本发明涉及一种将C9+芳烃转化为轻质芳族产物的方法,包括在烷基转移反应条件下,使包含C9+芳烃的原料与催化剂组合物接触的步骤,所述催化剂组合物包含:
(i)第一分子筛,选自于ZSM-12、丝光沸石和多孔结晶无机氧化物材料,该材料具有包括d-间隔最大值在12.4±0.25、6.9±0.15、3.57±0.07和3.42±0.07处的X射线衍射图案;和
(ii)第二分子筛,具有约束指数为3-12,
其中至少第一分子筛具有与其结合的氢化组分,且其中第一和第二分子筛都含在同一催化剂床中,C9+芳烃在烷基转移反应条件下转化为含有二甲苯的反应产物。
在一个实施方案中,第一分子筛是ZSM-12,第二分子筛是ZSM-5。
合适地,催化剂组合物是颗粒,且第一和第二分子筛含在分别的催化剂颗粒中,该颗粒在所述催化剂床中物理混合。
或者,催化剂组合物是颗粒,且第一和第二分子筛每一种都含在相同催化剂颗粒中。
典型地,原料也含有苯或甲苯。
在另一方面,本发明涉及一种生产苯的方法,包括下面的步骤:
(a)在烷基转移反应条件下,使C9+芳烃和甲苯在催化剂组合物存在下反应,其中所述催化剂组合物包含:
(i)第一分子筛,选自于ZSM-12、丝光沸石和多孔结晶无机氧化物材料,该材料具有包括d-间隔最大值在12.4±0.25、6.9±0.15、3.57±0.07和3.42±0.07处的X射线衍射图案;和
(ii)第二分子筛,具有约束指数为3-12,
其中至少第一分子筛具有与其结合的氢化组分,且其中第一和第二分子筛都含在同一催化剂床中,以生产包含苯和二甲苯的产物流;和
(b)从该产物流中蒸馏苯以获得苯产物。
实施方案详述
本发明提供一种方法,转化包含C9+芳烃、任选还有附加甲苯或苯的原料,以生产含有苯、甲苯和二甲苯的产物。所述方法包括在烷基转移反应条件下,使原料与催化剂组合物接触,该催化剂组合物包含至少两种不同的、都含在同一催化剂床中的分子筛。
催化剂组合物
本发明方法中所用的催化剂组合物包含:
(i)第一分子筛,选自于ZSM-12、丝光沸石和多孔结晶无机氧化物材料,该材料具有包括d-间隔最大值在12.4±0.25、6.9±0.15、3.57±0.07和3.42±0.07处的X射线衍射图案;和
(ii)第二分子筛,具有约束指数为3-12。
对于第一分子筛,ZSM-12更特别地描述于美国专利US 3,832,449中。丝光沸石自然存在,但是也可以其合成形式之一来使用,诸如TEA-丝光沸石(即由包含四乙基铵定向剂的反应混合物制备的合成丝光沸石),这公开于美国专利US 3,766,093和3,894,104中。具有所定义X-射线衍射图案的合适多孔结晶无机氧化物材料的例子包括MCM-22、PSH-3、SSZ-25、MCM-36、MCM-49或MCM-56。MCM-22描述于美国专利US 4,954,325中,PSH-3描述于美国专利US 4,439,409中,SSZ-25描述于美国专利US 4,826,667中,MCM-36描述于美国专利US 5,250,277中,MCM-49描述于美国专利US 5,236,575中,MCM-56描述于美国专利US 5,362,697中。上述每一专利的全部内容都被引入本文供参考。
对于第二分子筛,具有约束指数为3-12的合适材料包括ZSM-5、ZSM-11、ZSM-22、ZSM-23、ZSM-35、ZSM-48、ZSM-57和ZSM-58。ZSM-5描述于美国专利US 3,702,886中。ZSM-11描述于美国专利US 3,709,979中。ZSM-22描述于美国专利US 5,336,478中。ZSM-23描述于美国专利US 4,076,842中。ZSM-35描述于美国专利US 4,016,245中。ZSM-48描述于美国专利US 4,375,573中。ZSM-57描述于美国专利US 4,873,067中。ZSM-58描述于美国专利US 4,698,217中。约束指数和其测定方法描述于美国专利US 4,016,218中。上述每一专利的全部内容都被引入本文供参考。
典型地,基于催化剂组合物中第一和第二分子筛的总重量,第二分子筛占5-95wt%,例如从大于20至80wt%。
在一个实施方案中,第一分子筛是ZSM-12,且第二分子筛是ZSM-5。
当第一分子筛是ZSM-12时,ZSM-12可具有包含下面摩尔关系的组成:
X2O3∶(n)YO2
其中X是三价元素,诸如铝、硼、铁、铟和/或镓,优选铝;Y是四价元素,诸如硅、锡和/或锗,优选硅;n小于75,诸如20-小于60。可进一步选择ZSM-12,使其平均晶体大小为小于0.1微米,诸如约0.05微米,和当在100℃的温度和2乇的1,3,5-三甲基苯压力下测试时,相对于1,3,5-三甲基苯来说,扩散参数D/r2至少是1000×10-6 sec-1,诸如至少2000×10-6 sec-1。
正如这里所用,特定的多孔结晶材料的扩散参数被定义为D/r2×106,其中D是扩散系数(cm2/sec),r是晶体半径(cm)。所需的扩散参数可来自于吸着测试,条件是假定平面片材模型描述扩散方法。因而对于一个给定的吸着物负载Q,数值Q/Q∞与(Dt/r2)1/2数学关联,其中Q∞是平衡吸着物负载,t是达到吸着物负载Q所需的时间(sec)。平面片材模型的图解法由J.Grank在“The Mathematics of Diffusion”中给出,Oxford University Press,Ely House,伦敦,1967年。
也可使得用作第一分子筛的ZSM-12具有α值为至少150,诸如至少300。α值试验是催化剂裂化活性的测试,且描述于美国专利US3,354,078和
Journal of Catalysis,Vol.4,p.527(1965);Vol.6,p.278(1966);和Vol.61,p.395(1980)中,每一描述都被引入本文供参考。这里所用的试验条件包括538℃的恒温和
Journal of Catalysis,Vol.61,p.395中详细描述的可变流速。
具有前面段落中所述的组成、晶体大小、扩散参数和α值的ZSM-12,可通过合成混合物的结晶来生产,所述混合物含有碱金属或碱土金属(M)阳离子源,通常是钠,三价元素(X)的氧化物,通常是氧化铝,四价元素(Y)的氧化物,通常是二氧化硅,甲基三乙基铵离子(R),通常是碘盐、羟基离子和水。合成混合物可具有如下以氧化物的摩尔比表示的组成:
组分 | 适用的 | 优选的 |
YO2/X2O3 | 20-100 | 40-80 |
H2O/YO2 | 10-100 | 15-40 |
OH-/YO2 | 0.1-0.6 | 0.15-0.4 |
R/YO2 | 0.1-0.6 | 0.15-0.4 |
M/YO2 | 0.1-0.6 | 0.15-0.4 |
合成混合物也可含有ZSM-12的成核种子,当这样的种子存在时,它们一般占混合物的0.05-5wt%。可或是在搅拌或是在静止条件、优选搅拌条件下,在160℃或更低,诸如140℃-160℃经过48-500小时,进行合成混合物的结晶,之后将所得ZSM-12晶体与母液分离并回收。
理想地是结合在催化剂组合物中的每一分子筛与另一材料,该材料耐受本发明烷基转移方法中所用的温度和其他条件。此类材料包括活性和非活性材料及合成或天然沸石,以及无机材料诸如粘土、硅石和/或金属氧化物诸如氧化铝。无机材料可以或是天然存在,或是呈胶状沉淀或包括二氧化硅和金属氧化物的混合物的凝胶形式。
采用与所述分子筛或每一分子筛合用的材料,即与其结合或在其合成过程中存在的材料,该材料本身是催化活性的,可以改变催化剂组合物的转化率和/或选择性。非活性材料适合用作稀释剂,以控制转化的量,使得能够以经济和按有序的方式获得烷基转移产物,而无需使用控制反应速率的其他方式。这些催化活性或非活性材料可引入到例如天然粘土,诸如膨润土和高岭土中,以提高工业操作条件下催化剂组合物的抗碎强度。理想的是提供一种具有良好抗碎强度的催化剂组合物,因为在工业用途中,要求阻止催化剂组合物破碎成粉末状材料。
作为催化剂组合物的粘合剂、能够与所述分子筛或每一分子筛复合的天然粘土包括蒙脱土和高岭土类,该类包括变膨润土,和公知为Dixie、McNamee、Georgia和Florida粘土等的高岭土,其中主要矿物成分是多水高岭土、高岭石、地开石、珍珠陶土或富硅高岭土。此类粘土可以以原生态如最初被开采的状态或初步进行煅烧、酸处理或化学改性后的状态使用。
除了前述的材料外,所述或每一分子筛能够与多孔的基体粘合剂材料复合,所述粘合剂材料诸如选自于下面的无机氧化物:二氧化硅、氧化铝、氧化锆、氧化钛、氧化钍、氧化铍、氧化镁和其组合如二氧化硅-氧化铝、二氧化硅-氧化镁、二氧化硅-氧化锆、二氧化硅-氧化钍、二氧化硅-氧化铍、二氧化硅-氧化钛以及三元组合物如二氧化硅-氧化铝-氧化钍、二氧化硅-氧化铝-氧化锆、二氧化硅-氧化铝-氧化镁和二氧化硅-氧化镁-氧化锆。也有利地是,提供至少一部分呈胶体形式的上述多孔基体粘合剂材料,以便促进催化剂组合物的挤出。
每一分子筛通常与粘合剂或基体材料混合,使得最终催化剂组合物含有粘合剂或基体材料的量是5wt%-90wt%,且典型地是10wt%-60wt%。
在本发明的方法中,在同一催化剂床中含有第一和第二分子筛。通常这通过下面实现:或是物理混合优选以结合形式的单一分子筛的单独颗粒,或是共挤出所述分子筛的混合物,典型地与粘合剂的混合物,使得最终催化剂组合物的每一颗粒都含有第一和第二分子筛。或者,第一和第二分子筛之一的颗粒可以形成为所述第一和第二分子筛中另一种的粘合剂,这描述于国际专利申请WO 97/45198中,其全部内容都被引入本文供参考。
催化剂组合物中的至少第一分子筛并优选每一分子筛与至少一种氢化组分诸如钨、钒、钼、铼、铬、锰、选自于元素周期表(CAS版,1979)第VIII族的金属,或其混合物结合。有用的VIII族金属的具体例子是铁、钌、锇、镍、钴、铑、铱和贵金属诸如铂或钯。优选地,氢化组分是钯、铂或铼。
根据氢化活性和催化功能度之间的平衡来选择氢化组分的量。当使用活性最高的金属如铂来代替不具有如此强氢化活性的钯时,氢化组分需要的量少些。通常,催化剂组合物含有低于10wt%、典型地为0.01wt%-2wt%的氢化组分。
氢化组分进入催化剂组合物中可以是通过共结晶,一定程度地交换存在于分子筛结构中的IIIA族元素例如铝,浸渍在组合物中,或与分子筛和粘合剂混合,而进入组合物。这种成分可以浸渍在分子筛之中或之上,例如,在铂的情况下,将分子筛用含有含铂金属离子的溶液处理。用铂浸渍催化剂的适合铂化合物包括氯铂酸、氯化亚铂和各种含铂胺配合物的化合物,如Pt(NH3)4CI2·H2O。
或者,氢化组分的化合物可以在分子筛与粘合剂复合时,或在分子筛和粘合剂通过挤出或造粒的方法成型为颗粒之后加入到分子筛中。
在用氢化组分处理后,分子筛通常要进行干燥,方法是在温度65℃-160℃(150-320)、典型地是110℃-143℃(230-290),和压力100-200kPa(0-15psig)下加热至少1分钟、通常不长于24小时。其后,将分子筛在干气流如空气或氮气中,和温度260℃-650℃(500-1200)下煅烧1-20小时。进行煅烧的压力典型地为100-300kPa(0-30psig)。
使用之前,催化剂组合物可以进行蒸汽处理,使催化剂组合物的芳烃氢化活性降到最低。在蒸汽加工时,催化剂组合物通常与5-100%的蒸汽在温度至少260℃至650℃(500-1200)、压力100-2590kPa(0-360psig)下接触至少1小时、特别是1-20小时。
另外,在催化剂组合物与烃原料接触之前,可将氢化组分硫化。这可通过使催化剂与硫源诸如硫化氢在约320℃-480℃(600-900)的温度范围内接触而方便地实现。硫源可通过载气诸如氢或氮与催化剂接触。
原料
本发明方法中所用的芳族原料包含一种或多种含有至少9个碳原子的芳族化合物。典型的原料中出现的具体C9+芳族化合物包括1,3,5-三甲基苯、杜烯(1,2,4,5-四甲基苯)、连三甲基苯(1,2,3-三甲基苯)、假枯烯(1,2,4-三甲基苯)、1,2-甲基乙基苯、1,3-甲基乙基苯、1,4-甲基乙基苯、丙基取代的苯、丁基取代的苯和二甲基乙苯。C9+芳烃适合的来源是任何富产芳烃的炼油厂工艺来的任何C9+馏份。这种芳烃馏份含有大比例的C9+芳烃,例如至少80wt%的C9+芳烃,其中优选至少80wt%,更优选90wt%以上的烃类是C9-C12烃。典型的可用炼油厂馏份包括催化重整产物、FCC石脑油或TCC石脑油。
本发明方法的原料也可包括苯或甲苯。因而,在一个实际实施方案中,加入到烷基转移反应器的原料包含C9+芳烃和甲苯。原料也可包括循环的/未反应的甲苯和通过烷基转移反应本身的流出产物蒸馏得到的C9+芳烃。典型地,甲苯占整个原料的40wt%-90wt%、例如50wt%-70wt%,而C9+芳烃成分占加入烷基转移反应区的整个原料的10wt%-60wt%、例如30wt%-50wt%。
烃转化工艺
该工艺可以在任何适当的反应器中进行,所述反应器包括径向流反应器、固定床反应器、连续下流式反应器或流化床反应器。烷基转移反应条件典型地包括:温度为约343℃-约510℃(650-950),诸如约400℃-约454℃(750-850);压力为约380-约4240kPa(50-600psig),诸如约1480-约3550kPa(200-500psig);氢和烃的摩尔比为约1-约5,诸如约1-约3,WHSV为约0.2-约20,诸如1-约5。烷基转移反应条件足以使重芳烃原料转变成含大部分是C6-C8的芳族化合物如苯、甲苯和二甲苯,特别是苯和二甲苯的产物。
参考下面的实施例更具体地描述本发明。
实施例1(比较例)
制备双床催化剂组合物,其中第一床含有铼浸渍的ZSM-12催化剂(65wt%的ZSM-12/35wt%的氧化铝和0.5wt%的铼),其在催化剂制备的最终阶段中在480℃(900)下蒸5.5小时,第二床含有ZSM-5催化剂(65wt%的ZSM-5/35wt%的氧化铝)。第一床中所用的ZSM-12具有二氧化硅/氧化铝摩尔比为约200、α值为30、晶体大小为约0.1微米,和对于1,3,5-三甲基苯来说,在100℃的温度和2乇的1,3,5-三甲基苯压力下,D/r2为1900×10-6 sec-1。第二床中所用的ZSM-5具有晶体大小为0.02-0.05微米,二氧化硅/氧化铝摩尔比为约60。第一床与第二床的重量比是9∶1。
实施例2
通过共挤出40wt%的实施例1中所用的ZSM-12、40wt%的实施例1中所用的ZSM-5和20wt%的氧化铝的混合物,制备单床催化剂组合物。通过在氮气中预煅烧,用硝酸铵溶液交换,然后在540℃(1000)的空气中煅烧6小时,将挤出物转变成H型。然后用铼浸渍所得催化剂颗粒,达到整个催化剂组合物上含有0.5wt%的铼,并在524℃(975)的空气中煅烧1小时。然后在900下将该材料蒸5.5小时,之后催化剂具有α值为67。
实施例3
以与实施例2相同的方式制备单床催化剂组合物,只是所用的ZSM-5具有晶体大小为0.2-0.5微米,且二氧化硅/氧化铝摩尔比为约25。
实施例4
在各单独实验中使用实施例1-3的催化剂组合物,在约425℃的温度、2445kPa(340psig)的压力、氢与烃摩尔比为1.02和WHSV为6的条件下,进行下面混合物的烷基转移反应:61wt%的甲苯、0.12wt%的乙苯、3.5wt%的二甲苯、0.36wt%的枯烯、1.15wt%的正丙基苯、13.55wt%的乙基甲苯、19.36wt%的三甲基苯、0.35wt%的二乙苯、0.42wt%的二甲基乙苯和0.21wt%的1,2-二氢化茚。结果总结于下面的表1中。
由表1中可以看出,实施例2-4的共挤出单床催化剂,对于含乙基C9+芳烃来说,比实施例1的双床催化剂表现出约两倍的转化活性。而且,含乙基芳烃的转化率从实施例1的双床催化剂的约41wt%升高到实施例2和3的共挤出单床催化剂的80-86wt%。
表1
实施例1 | 实施例2 | 实施例3 | |
温度(℃)连续开工日Wt%,H/C基础C1C2C3C4C5苯甲苯乙苯二甲苯乙基甲苯三甲基苯二乙基苯二甲基乙基苯四甲基苯茚满萘甲基萘其他乙基转化率(wt%)丙基转化率(wt%)甲苯转化率(wt%)A9+转化率(wt%) | 4271.50.130.470.430.120.0110.4335.922.3131.314.3010.700.101.680.740.080.110.320.8441.43100.0041.1246.94 | 4282.50.050.970.260.070.0110.0742.720.6230.651.2811.660.000.460.510.000.060.170.4583.95100.0029.9759.46 | 4251.50.150.950.270.040.019.5044.110.6729.001.6411.870.000.550.550.040.070.200.3980.59100.0027.7057.10 |
实施例5
由包含下面成分的混合物合成小晶体、高活性的ZSM-12:11280g的水、1210g的甲基三乙基氯化铵(MTEACl)、1950g的Ultrasil PM、229g的铝酸钠溶液(45%)和364g的50%氢氧化钠溶液。所述混合物具有下面的摩尔组成:
SiO2/Al2O3=50
H2O/SiO2=22
OH-/SiO2=0.2
Na+/SiO2=0.2
MTEACl/SiO2=0.26
在以150RPM搅拌的5加仑高压釜中,在320(160℃)下使混合物反应144小时。过滤产物,用去离子(DI)水洗涤,在250(120℃)下干燥。这样合成的材料的XRD图案显示ZSM-12拓扑结构的典型纯位相。这样合成的材料的SEM显示,所述材料包含小晶体的附聚物(平均晶体大小为约0.05微米)。
通过在室温下用硝酸铵溶液的两次离子交换,将这样合成的晶体转变成氢形式,然后在250(120℃)下干燥,在1000(540℃)煅烧6小时。所得ZSM-12晶体具有SiO2/Al2O3摩尔比是44.98,α值为500,和对于1,3,5-三甲基苯来说,在100℃的温度和2乇的1,3,5-三甲基苯压力下,D/r2为大于5000×10-6 sec-1。
将含有40wt%的上面制得的ZSM-12、40wt%的ZSM-5和20wt%的氧化铝的混合物挤出成颗粒,尺寸为1.3mm(1/20英寸)长并具有四叶形(quadrulobe)横截面。在120℃(250)下干燥粒料,然后在480℃(900)氮气中煅烧3小时。然后用硝酸铵交换该材料,在120℃(250)下干燥,在540℃(1000)空气中煅烧6小时。接着通过来自于四胺硝酸钯水溶液的初期润湿浸渍,向催化剂中加入0.1%的Pd。在120℃(250)下干燥浸渍的材料,在350℃(660)空气中煅烧6小时,制得最终催化剂。
使用3g所得催化剂组合物,在约480℃的温度、2170kPa(300psig)的压力、氢与烃摩尔比为2和WHSV为2.7的条件下,对具有表2中给出组成的甲苯/C9+芳烃混合物的混合物进行烷基转移反应。连续开工4.4天后的结果总结于下面的表2中。
表2
Wt%,H/C基础 | 原料 | 产物 |
C5-非芳烃苯甲苯乙苯二甲苯C9C10C11+总量甲苯转化率(%)A9转化率(%)A10转化率(%)乙基转化率(%)丙基转化率(%) | 61.270.030.2629.828.310.3099.99 | 8.240.0412.7939.580.1128.808.450.861.1299.9935.3971.6489.4696.5297.19 |
表2中的结果显示,实施例5的催化剂是高活性的,特别是对于C9+芳烃的转化率来说,该芳烃包括含乙基的物料。然而,所测试的具体催化剂确实显示出随着生产进行而老化的迹象。
Claims (21)
1、一种将C9+芳烃转化为轻质芳族产物的方法,包括在烷基转移反应条件下,使包含C9+芳烃的原料与催化剂组合物接触的步骤,所述催化剂组合物包含:
(i)第一分子筛,选自于ZSM-12和多孔结晶无机氧化物材料,该材料具有包括d-间隔最大值在12.4±0.25、6.9±0.15、3.57±0.07和3.42±0.07处的X射线衍射图案;和
(ii)第二分子筛,具有约束指数为3-12,
其中至少第一分子筛具有与其结合的氢化组分,且其中第一和第二分子筛都含在同一催化剂床中,C9+芳烃在烷基转移反应条件下转化为含有二甲苯的反应产物。
2、权利要求1的方法,其中第一分子筛是ZSM-12。
3、权利要求2的方法,其中ZSM-12具有包含下面摩尔关系的组成:
X2O3:(n)YO2
其中X是三价元素,Y是四价元素,n小于60。
4、权利要求3的方法,其中n是从20至小于60。
5、权利要求4的方法,其中X是铝且Y是硅。
6、权利要求5的方法,其中ZSM-12具有平均晶体大小为小于0.1微米。
7、权利要求6的方法,其中当在100℃的温度和2乇的1,3,5-三甲基苯压力下测试时,相对于1,3,5-三甲基苯来说,ZSM-12具有扩散参数D/r2至少是1000×10-6sec-1。
8、权利要求7的方法,其中ZSM-12具有α值为至少150。
9、权利要求1的方法,其中第二分子筛是ZSM-5。
10、权利要求9的方法,其中基于第一和第二分子筛的总重量,第二分子筛占5wt%-95wt%。
11、权利要求10的方法,其中基于第一和第二分子筛的总重量,第二分子筛占大于20wt%至80wt%。
12、权利要求1的方法,其中所述氢化组分选自于钨、钒、钼、铼、铬、锰、元素周期表第VIII族的金属及其混合物。
13、权利要求12的方法,其中所述氢化组分是铱、铼、铂或钯。
14、权利要求13的方法,其中所述氢化组分是铼。
15、权利要求12的方法,其中在所述接触步骤之前,将所述氢化组分硫化。
16、权利要求1的方法,其中催化剂组合物是颗粒状的,且第一和第二分子筛含在分别的催化剂颗粒中,该颗粒在所述催化剂床中物理混合。
17、权利要求1的方法,其中催化剂组合物是颗粒状的,且第一和第二分子筛每一种都含在相同催化剂颗粒中。
18、任何上述权利要求的方法,其中所述原料也含有苯或甲苯。
19、权利要求1的方法,其中烷基转移反应条件包括:温度为约343℃-约510℃(650-950),压力为约380-约4240kPa(50-600psig),氢和烃的摩尔比为约1-约5,WHSV为约0.2-约20。
20、权利要求1的方法,其中烷基转移反应条件包括:温度约400℃-约454℃(750-850);压力约1480-约3550kPa(200-500psig);氢和烃的摩尔比为约1-约3,WHSV为约1-约5。
21、一种如权利要求1中所述将C9+芳烃转化为轻质芳族产物的方法,包括下面的步骤:
(a)在烷基转移反应条件下,使C9+芳烃和甲苯在催化剂组合物存在下反应,其中所述催化剂组合物包含:
(i)第一分子筛,选自于ZSM-12和多孔结晶无机氧化物材料,该材料具有包括d-间隔最大值在12.4±0.25、6.9±0.15、3.57±0.07和3.42±0.07处的X射线衍射图案;和
(ii)第二分子筛,具有约束指数为3-12,
其中至少第一分子筛具有与其结合的氢化组分,且其中第一和第二分子筛都含在同一催化剂床中,以生产包含苯和二甲苯的产物流;和
(b)从该产物流中蒸馏苯以获得苯产物。
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US10/294,428 US7148391B1 (en) | 2002-11-14 | 2002-11-14 | Heavy aromatics processing |
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US7485763B2 (en) | 2009-02-03 |
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