CN108367279A - 催化剂组合物、其制备方法和使用这类组合物的方法 - Google Patents
催化剂组合物、其制备方法和使用这类组合物的方法 Download PDFInfo
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- CN108367279A CN108367279A CN201680072819.6A CN201680072819A CN108367279A CN 108367279 A CN108367279 A CN 108367279A CN 201680072819 A CN201680072819 A CN 201680072819A CN 108367279 A CN108367279 A CN 108367279A
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Classifications
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- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
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- B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
- C07C4/12—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene
- C07C4/14—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene splitting taking place at an aromatic-aliphatic bond
- C07C4/18—Catalytic processes
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Abstract
一种催化剂组合物,包含载体和一种或多种第10族金属组分,其中所述载体包含(i)20到90重量%的丝光沸石,其具有10到60范围内的二氧化硅与氧化铝摩尔比;(ii)10到70重量%的ZSM‑5型沸石,其具有5到50范围内的二氧化硅与氧化铝摩尔比和5到50nm范围内的平均粒度;以及(iii)10到50重量%的结合剂;一种用于制备催化剂的方法,和一种使用所述催化剂转化含有芳香族烃的原料的方法。
Description
技术领域
本发明涉及催化剂组合物、用于制备催化剂的方法以及使用催化剂转化含有芳香族烃的原料的方法。
背景技术
各种苯和对二甲苯是工业上重要的起始物质。苯例如广泛用作进料以制备环己烷,环己烷又可用于制备尼龙,而对二甲苯用于制备例如聚酯纤维。
对二甲苯可以从二甲苯混合物获得,二甲苯混合物额外含有异构体间二甲苯和邻二甲苯。在二甲苯异构体中,最需要的是对二甲苯,而不太需要邻二甲苯和间二甲苯。因此,工业上重要的是将邻二甲苯和间二甲苯转化成对二甲苯。
二甲苯混合物通常是通过使石脑油经历重整过程,接着进行芳香族化合物提取而获得。二甲苯混合物还可以含有裂解的二甲苯,其已经通过使石脑油经历热分解处理,接着进行芳香族化合物提取而获得。除二甲苯异构体以外,这类二甲苯混合物还含有高浓度的乙基苯和非芳香族烃,如环状脂肪族化合物。
许多研究和开发工作涉及用于将这类二甲苯混合物转化成含有大量苯的混合物和大量对二甲苯的方法和催化剂。在这类转化过程中,进行乙基苯主要脱烷基化成苯,并且同时邻二甲苯和/或间二甲苯异构化成对二甲苯。
这类二甲苯混合物转化过程中出现的难点在于存在所谓的苯共沸物。苯共沸物是非芳香族烃杂质,如环己烷和甲基环戊烷,其极难以通过蒸馏与苯分离,因为其沸点与苯接近。因为作为起始物质的苯需要符合严格的纯度标准,需要借助于额外的提取步骤去除这些苯共沸物,这种额外的提取步骤是昂贵和耗时的。
另一个难点在于二甲苯和乙基苯的个别异构体的沸点接近,使得极难以通过蒸馏分离对二甲苯与乙基苯。
烷基芳烃转化催化剂已描述于WO0038834和WO2009016134中。
发明内容
本发明的目标是制备具有改良的纯度的苯。改良的纯度可以使所得产物含有较少的具有在苯的沸点范围内的沸点的化合物。如果以高产量获得苯,那么就更加有利。另一个目标可以是以高产量获得对二甲苯。此外,优选的是芳香族烃转化过程中仅损失有限量的芳香族化合物。
本发明涉及催化剂组合物,其包含载体和一种或多种负载于载体上的金属组分,其中所述载体包含(i)以载体总重量计,20到90重量%(wt%)范围内的量的丝光沸石,所述丝光沸石具有10到60范围内的二氧化硅与氧化铝摩尔比;(ii)以载体的总重量计,10到70重量%的量的ZSM-5型沸石,所述ZSM-5型沸石具有5到50范围内的二氧化硅与氧化铝摩尔比和5到50nm范围内的数值平均粒度;以及(iii)以载体的总重量计,10到50重量%范围内的量的无机结合剂;并且其中所述一种或多种金属组分包含第10族金属。
丝光沸石和ZSM-5各自如在《沸石框架类型图集(Atlas of Zeolite FrameworkTypes)》,第六修改版2007中定义。
整体或总体SAR可以通过多种化学分析技术中的任一种测定。这类技术包括X射线荧光、原子吸收和电感耦合等离子-原子发射光谱(ICP-AES)。所有将提供基本上相同整体比率值。用于本发明中的二氧化硅与氧化铝摩尔比是通过X射线荧光测定。
在含有芳香族烃的原料的转化,更具体地说烷基转移过程中使用本发明的催化剂可以产生高纯度的苯。
具体实施方式
本发明的催化剂组合物包含载体,以载体的总重量计,其包含20到90重量%的量的丝光沸石。优选地,以载体的总重量计,丝光沸石以30到70重量%范围内,更优选40到60重量%范围内的量存在。
丝光沸石具有10到60范围内的二氧化硅与氧化铝摩尔比。丝光沸石优选具有15到40范围内,更优选15到25范围内的二氧化硅与氧化铝摩尔比。
优选地,丝光沸石含有小于400ppm的过渡金属,更优选小于300ppm的过渡金属。过渡金属是IUPAC周期表中所谓的d区中的金属。这些金属是这一周期表中第3到12族的元素。具体地说,丝光沸石含有小于250ppm的铁,更优选小于100ppm的铁。适合的丝光沸石已描述于EP1447131,更具体地说,EP1447131的实例9中。
本发明的催化剂组合物包含载体,以载体物质化合物的总重量计,载体包含10到70重量%的量的ZSM-5型沸石。优选地,以载体的总重量计,ZSM-5型沸石以15到60重量%范围内,更优选20到40重量%范围内的量存在。
ZSM-5型沸石具有10到50范围内,优选20到40范围内并且更优选23到35范围内的二氧化硅与氧化铝摩尔比。
ZSM-5型沸石具有5到50nm范围内的数值平均粒度。通过计算已通过透射电子显微镜(TEM)测量的样品的数值平均粒度来测定平均粒度。优选地,ZSM-5型沸石具有10到45nm范围内,更优选20到40nm范围内的数值平均粒度。已发现,根据本发明使用的ZSM-5型沸石的小型平均粒子可以改良苯纯度和针对对二甲苯的选择性。
根据本发明使用的适合的ZSM-5型沸石可根据例如US 3,702,886和US 4,511,547中所描述来制备。ZSM-5型沸石的适合的实例包括CBV 3014E、CBV 3020E和CBV 8014,可以从Zeolyst International商购。
以载体的总重量计,本发明的催化剂还含有5到50重量%范围内的量的无机结合剂。优选地,以全部载体计,无机结合剂以10到40重量%范围内,更优选15到30重量%范围内的量存在。
适合地,无机结合剂选自由以下组成的组:γ-氧化铝、二氧化硅、二氧化硅-氧化铝、膨润土、高岭土、二氧化钛、氧化锆、氧化铈、氧化镓、克立莫(climotilolite)、蒙脱石和其任何混合物。优选的无机结合剂包括γ氧化铝、二氧化硅和二氧化硅-氧化铝的非晶形无机氧化物。更优选的无机结合剂包括γ氧化铝和二氧化硅。
在成形形式时,例如呈挤压物形式,载体通常具有200到600m2/g,优选250到500m2/g,更优选350到450m2/g范围内的表面积;和0.2到1.2ml/g,优选0.4到1.0ml/g,更优选0.5到0.8ml/g范围内的孔隙体积(通过汞浸入)。
本发明的催化剂组合物可以任何具体形式成形。适合的形状包括三叶形和圆柱形,优选地,本发明的催化剂组合物呈三叶形形状。
本发明的催化剂包含来自第10族金属的一种或多种金属组分,以催化剂的总重量计,优选以0.005到10重量%范围内的量。
量是以催化剂的总重量计的金属量。如本文中所使用的对第10族的参考涉及周期表的当前IUPAC版。优选的催化活性金属是镍、钯和/或铂。最优选金属是铂。也有可能是两种或更多种催化活性金属的组合,优选是包含铂的金属组合。催化活性金属也可以化合物的形式提供,任选地需要在使用前活化。
优选地,以催化剂的总重量计,本发明的催化剂包含0.005到10重量%范围内,更优选0.01到5重量%范围内,更优选0.01到1重量%的量的第10族金属,优选是铂。
本发明的催化剂组合物可以适合地具有这类形状,使得填充有催化剂粒子的反应器的平均空隙分数是至少10体积%,优选在20%到70%范围内,更优选在35体积%到55体积%的范围内。
本发明的催化剂组合物可以使用用于组合载体的标准技术制备并且包括成形;与金属组分复合;和任何随后适用的方法步骤,如干燥、煅烧和还原。
本发明还涉及用于制备根据本发明的催化剂的方法,包含以下步骤:
(a)以任何可能的顺序混合丝光沸石、ZSM-5型沸石、无机结合剂以及第10族金属,优选铂;和
(b)煅烧如在步骤(a)中获得的混合物。
用于这一过程的每种丝光沸石和ZSM-5沸石优选是如上文关于催化剂组合物所描述。
在具体实施例中,催化剂组合物是通过制备载体并且接着并入一种或多种金属组分而获得。载体可以通过使载体成形,任选地干燥成形的载剂,并且接着煅烧来制备。干燥温度可以适合地在50到200℃范围内。干燥时间可以适合地在0.5到24小时范围内。煅烧温度可以适合地在200到800℃范围内,优选在300到600℃范围内。对于煅烧材料,可以适合地应用在0.5到5小时范围内的相对较短时间。煅烧可以适合地在400到700℃范围内,优选在450到600℃范围内的温度下进行。
在步骤(b)中,煅烧可以适合地在超过450℃,优选超过500℃的温度下进行。
适合地借助于第10族金属盐溶液将第10族金属并入载体中。金属盐溶液适合地具有在1到12范围内的pH值。可以适合地使用的金属盐包括氯铂酸和铵稳定化的金属盐。如果存在,那么可以适合地以含水溶性有机或无机盐的溶液形式添加其它金属。适合的盐的实例是硝酸盐、硫酸盐、氢氧化物和铵(胺)络合物。
金属可以依序或同时浸渍。优选同时添加金属。适合地,在组合型双金属盐溶液中使用络合剂或螯合剂以防止不合需要的金属沉淀。适合的络合剂的实例包括EDTA(乙二胺四乙酸)和其衍生物;HEDTA(N-(2-羟基乙基)乙二胺-N,N',N'-三乙酸)、EGTA(乙二醇-双(2-氨基乙醚)-N,N,N',N'-四乙酸)、DTPA(二乙醚三二胺五乙酸)和NTA(氮基三乙酸)。
在使用催化剂组合物之前,优选的是催化剂组合物上的金属呈金属(并且不是氧化)形式。相应地,催化剂组合物优选经历还原条件,其例如是在还原气氛(如在任选地由惰性气体(如氮气或二氧化碳)稀释的氢气中)中,在150到600℃范围内的温度下加热0.5到5小时范围内的时间段。
本发明还涉及用于使用根据本发明的催化剂进行的含有芳香族烃的原料的转化(更具体地说,烷基转移)的方法。适合地,芳香族烃包含苯、甲苯和/或含有至少9个碳原子的芳香族化合物。
含有芳香族烃的原料适合地包括用于制造对二甲苯的材料,如通过重整石脑油并且随后进行提取和/或分馏而获得的C8芳香族烃混合物;通过重整石脑油,但不进行用于提取环烷和链烷烃的过程以含有碳数为约9的环烷和链烷烃而获得的C8芳香族烃混合物;和经由裂解的汽油的提取和/或分馏而获得的C8芳香族烃混合物,所述裂解的汽油是作为石脑油热分解的副产物产生。
含有待烷基转移的芳香族烃的原料适合地包含C7到C9烃,并且具体地说,邻二甲苯、间二甲苯、对二甲苯、甲苯和除乙基苯以外的苯中的一种或多种。通常,原料中乙基苯的量在0.1到50重量%范围内并且总二甲苯含量通常是至少20重量%,皆以原料的总量计。通常,二甲苯不会处于热力学平衡,并且对二甲苯的量将低于其它二甲苯异构体的量。
原料宜在氢气存在下与催化剂组合物接触。这可以在固定床系统、移动床系统或流体化床系统中进行。这类系统可以连续或分批方式操作。优选在固定床系统中进行连续操作。催化剂可以用于一个反应器中或用于串联或在摆动系统中操作的几个独立的反应器中,以确保在催化剂更换期间连续操作。
本发明的烷基转移过程优选在200到600℃范围内,优选在250到500℃范围内并且更优选在300到400℃范围内的温度下进行。
所述过程是在5到50bara范围内的压力下,优选在10到40bara范围内的压力下并且更优选在25到35bara范围内的压力下进行。
在过程中施用的重量空间速度宜在0.2到30hr-1,优选2到20hr-1范围内,并且更优选在3到6hr-1范围内。
进料与氢气比率mol.mol-1在0.5到100范围内,优选在1到10范围内。
优选将回收反应流出物并且经历蒸馏处理以移出所需产物,即对二甲苯和苯。未反应的反应物(例如甲苯)可以适合地再循环以用于其它反应。
现将通过以下实例说明本发明。
实例1
包含23g丝光沸石(SAR是20)、15g ZSM-5(SAR是24并且平均粒度在35与50之间)和8g氧化铝结合剂的组合物与包含锡和铂的金属盐溶液一起混合和胶溶。所述量是以干燥组合物的总量计。挤压胶溶的混合物以获得具有1.5mm直径的颗粒。这些挤压物在120℃下干燥2小时,接着在样品的空气中,在550℃下煅烧2小时。所述组合物在下文中称为催化剂组合物A。
作为比较,如上文所描述制备催化剂组合物,但不同之处在于ZSM-5是可从Zeolyst International购得的SAR为23并且平均粒度在75到125nm范围内的ZSM-5。所述组合物在下文中称为催化剂组合物B。
实例2
进行催化活性测定,其使用其中组成如表1中所概述的进料。
表1
组分 | 含量(重量%) |
甲苯 | 50.5 |
三甲苯 | 28.6 |
乙基甲苯 | 11 |
丙基苯 | 0.8 |
茚满 | 1.4 |
乙基二甲苯 | 7 |
四甲基苯 | 0.5 |
剩下的包括含有至少10个碳原子的化合物+其余部分 | 0.3 |
一旦催化剂组合物转化成其还原状态就进行活性测定,所述转化可以通过使经干燥和煅烧的催化剂组合物A和B在400℃下暴露于常压氢气(>99%纯度)1小时来实现。所得催化剂分别称为催化剂A和催化剂B。
在本发明的情况下,在固定床反应器中使用3.0克进料/克催化剂/小时的重量每小时空间速度、4.5mol.mol-1的氢气与进料比率和30巴的总系统压力。改变温度以实现所需转化率45%。
性能特征显示于以下表2中。
苯的纯度提供为在产物中苯沸腾范围中沸腾的部分中苯的量。这一部分将含有以下:含有6个碳原子的化合物,如苯;含有5个碳的经甲基取代的环状化合物和含有6个碳原子环状化合物。
芳香族损失计算为:进料中的芳香族化合物重量%减去产物中的芳香族化合物重量%,再除以进料中的芳香族化合物重量%。当使用催化剂B时,这个量是关于芳香族化合物损失给出。
表2
催化剂A | 催化剂B(比较性) | |
共沸物的相对百分比 | 19 | 43 |
相对芳香族化合物损失(%) | 78.95 | 100 |
以上实验结果表明本发明的催化剂可以获得具有增加的苯纯度的产物。此外,有可能降低芳香族化合物的损失。
Claims (9)
1.一种催化剂组合物,其包含载体和负载于所述载体上的一种或多种金属组分,其中所述载体包含(i)以载体的总重量计,20到90重量%范围内的量的丝光沸石,所述丝光沸石具有10到60范围内的二氧化硅与氧化铝摩尔比;(ii)以载体的总重量计,10到70重量%的量的ZSM-5型沸石,所述ZSM-5型沸石具有5到50范围内的二氧化硅与氧化铝摩尔比和5到50nm范围内的平均粒度;和(iii)以载体的总重量计,10到50重量%范围内的量的无机结合剂;并且其中所述一种或多种金属组分包含第10族金属。
2.根据权利要求1所述的催化剂组合物,其中以载体的总重量计,所述丝光沸石以30到70重量%范围内的量存在。
3.根据权利要求1所述的催化剂组合物,其中以载体的总重量计,所述ZSM-5型沸石以15到60重量%范围内的量存在。
4.根据权利要求1所述的催化剂组合物,其中以载体材料的总重量计,所述无机结合剂以10到40重量%范围内的量存在。
5.根据权利要求1所述的催化剂组合物,其中所述ZSM-5型沸石具有10到45nm范围内的数值平均粒度。
6.根据权利要求1所述的催化剂组合物,其中所述丝光沸石含有小于200ppm的过渡金属。
7.一种制备根据权利要求1所述的催化剂的方法,包含以下步骤:
(a)以任何可能的顺序混合所述丝光沸石、ZSM-5型沸石、无机结合剂和第10族金属;和
(b)煅烧如在步骤(a)中获得的所述混合物。
8.一种转化含有芳香族烃的原料的方法,其使用根据权利要求1到6中任一项所述的组合物作为催化剂。
9.根据权利要求8所述的方法,其中所述原料包含0.1到50重量%范围内的量的乙基苯和至少20重量%的总二甲苯内含物,皆以原料的总量计。
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