CN110022977A - 制备用于通过烷基转移合成苯的钼-铂基催化剂的方法 - Google Patents
制备用于通过烷基转移合成苯的钼-铂基催化剂的方法 Download PDFInfo
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- CN110022977A CN110022977A CN201780074786.3A CN201780074786A CN110022977A CN 110022977 A CN110022977 A CN 110022977A CN 201780074786 A CN201780074786 A CN 201780074786A CN 110022977 A CN110022977 A CN 110022977A
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Classifications
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Abstract
制备催化剂组合物的方法,包括(a)制备载体,其包含(i)丝光沸石,基于载体的总重量,其量为20‑80wt%,(ii)ZSM‑5型沸石,基于载体的总重量,其量为10‑70wt%;和(iii)无机粘合剂,基于载体的总重量,其量为10‑50wt%;(b)作为金属基于催化剂组合物的总重量,将量为1‑10wt%的钼加入所述载体中,并使如此处理的载体经受100至至多300℃的温度;和(c)在步骤(b)中获得的含钼载体中加入作为金属基于催化剂组合物总重量的量为0.005‑1wt%的铂,并使如此处理的载体经受200至至多600℃的温度;以及使用所述方法制备的催化剂转化含烷基芳烃的原料的方法。使用制备的催化剂组合物用于烷基芳烃转化的方法。
Description
技术领域
本发明涉及制备催化剂组合物的方法以及使用所述催化剂组合物转化含有烷基芳烃的原料的方法。
背景技术
重整油是通过催化转化在70℃到190℃范围内沸腾的直馏烃(例如直馏石脑油)而获得的芳香族产物。用于产生重整油的催化剂通常是氧化铝载铂催化剂。重整油原料自身是通过石油原油的分馏或蒸馏获得,其的组合物视原油的来源而变化,但通常芳族含量较低。在转化成重整油时,芳香烃含量显著增加且所得烃混合物用作有价值的化学中间体来源以及用作汽油组分非常理想。主要组分是一组芳香烃,其通常称作BTX:苯、甲苯和二甲苯,包括乙苯。可以存在其他组分,例如它们的氢化同系物,例如环己烷。
在BTX组中,最有价值的组分是苯和二甲苯,且因此BTX经常经受以下处理以增加那些两个芳族的比例:将甲苯加氢脱烷基化成苯且将甲苯歧化成苯和二甲苯。在二甲苯中,对二甲苯是最有用的商品,并且已开发二甲苯异构化或烷基转移方法以增加对二甲苯的比例。
汽油生产者可利用的另一种方法是将乙苯加氢脱烷基化成苯。
通常,汽油生产者将BTX从重整油流中分离,且接着使BTX流经受二甲苯异构化,以使得对二甲苯组分最大化。二甲苯异构化是一种催化工艺。此过程中所使用的一些催化剂具有不仅使二甲苯异构化且同时使乙苯组分脱烷烃化的能力。正常情况下,接着分离出对二甲苯,留下苯、甲苯(除非已经应用了甲苯转化工艺)、剩余的混合二甲苯(包括乙苯),以及含有至少9个碳原子的芳香烃化合物。此BTX流可通过脱烷基化转化以选择性地消除乙苯且增加苯的产量,同时使二甲苯达到平衡浓度,或可通过通过烷基转移转化以增加苯和二甲苯的产量。后一种方法是本发明的目标。在BTX处理的后一阶段的烷基转移反应中,主要关注的是确保不仅催化剂的高活性而且还要获得高纯度的苯。
如果烃的转化方法,更具体地说烷基芳烃的烷基转移方法,将产生高纯度的苯,将是有利的。
发明内容
一个目的是提供一种制备催化剂组合物的方法,该催化剂组合物可用于转化烃,更具体地说,烷基芳烃的烷基转移,优选产生高纯度的苯。
在一个方面,本发明涉及一种制备催化剂组合物的方法,其包括(a)制备载体,所述载体包含(i)基于载体的总重量,量在20-90重量%(wt%)的范围内的丝光沸石,(ii)基于载体的总重量,其量为10-70wt%的ZSM-5型沸石;和(iii)基于载体的总重量,其量为10-50wt%的无机粘合剂;(b)在载体中加入钼,作为金属基于催化剂的总重量,其量在1-10wt%的范围,并使如此处理的载体经受100至最高300℃的温度,以及(c)在步骤(b)中获得的含钼载体中加入基于催化剂总重量为0.005-1wt%的铂,并使如此处理的载体经受200至至多600℃的温度。
在进一步的方面,本发明涉及使用如上所述的方法制备的催化剂转化包含烷基芳烃的原料的方法。
具体实施方式
一个目的是提供一种制备催化剂组合物的方法,该催化剂组合物可用于转化烷基芳烃,更具体地说,烷基芳烃的烷基转移,优选产生高纯度的苯。进一步的目的是提供具有减少的气体产量的这种方法。现在已经发现,当使用通过特定方法制备的催化剂组合物时,可以实现该目的。
丝光沸石型沸石和ZSM-5型沸石在本领域中是众所周知的。对于本申请,这些沸石如在“Atlas of Zeolite Framework Types”,Baerlocher等人编辑,第六修订版(Elsevier2007)中定义和描述。
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。
丝光沸石优选地具有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10到40范围内,更优选10到30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元素周期表第3至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的实施例9中。
丝光沸石优选具有20到500nm范围内的数均粒度。优选地,丝光沸石具有30到300nm范围内,更优选50到200nm范围内的数均粒度。
本文所述的沸石的平均粒度通过计算通过使用X射线衍射(线加宽)和Scherrer方程测量的样品的数均粒径来确定。该技术在用于确定微晶粒度的本领域中是众所周知的(参见,例如,“Catalysis:An Integrated Approach to Homogeneous,Heterogeneous andIndustrial Catalysis”,J.A.Moulijn,P.W.N.M.van Leeuwen,R.A.van Santen(Eds.),Elsevier,1993,pp.365-367,WO 2009/158244 A2)。
具体地,平行于在丝光沸石的12环通道的方向上的平均晶粒长度是通过应用Scherrer公式至X射线衍射数据测定的,其中在分析之前,通过在氮气中将NH4交换的形式加热至540℃2小时,然后在空气中加热5小时,将丝光沸石转化为氢形式。具体地,对于CuKα辐射,在23.8°2θ处测量(002)衍射峰的半峰全宽(FWHM),然后从Scherrer方程可以计算平行于12环通道方向的平均微晶长度L0002。假设峰的形状是部分高斯的并且部分Cauchy的。
本发明的催化剂组合物包含载体,以载体的总重量计,载体包含10到70重量%的量的ZSM-5型沸石。按载体总重量计,ZSM-5型沸石的存在量优选在15到60wt%范围内,更优选在20到40wt%范围内。
ZSM-5型沸石优选具有10到50范围内、优选15到40范围内、更优选15到35范围内且更优选18到30范围内的二氧化硅与氧化铝摩尔比。
ZSM-5型沸石优选具有20到500nm范围内的数均粒度。优选地,ZSM-5型沸石具有30到300nm范围内,更优选50到200nm范围内的数均粒度。据观察,根据本发明使用的ZSM-5型沸石的低的数均粒度能够提高苯纯度。如上所述通过使用X射线衍射(谱线加宽)和Scherrer方程确定平均粒度。根据本发明使用的适合的ZSM-5型沸石可以根据例如US3702886和US4511547中所述来制备。ZSM-5型沸石的适合实例包括可以从ZeolystInternational购得的CBV 3014E、CBV 3020E和CBV 8014。
按载体总重量计,催化剂组合物含有含量在10到50wt%范围内的无机粘合剂。优选地,按总载体计,无机粘合剂的存在量在10到40wt%范围内,更优选在15到30wt%范围内。
无机粘合剂宜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、斜发沸石、蒙脱石和其任何混合物。优选的无机粘合剂是氧化铝,更具体地说,γ氧化铝。
呈成形形式(例如挤出物)的载体通常具有属于200到600m2/g、优选250到500m2/g、更优选350到450m2/g范围内的BET表面积。BET表面积宜根据ASTM D3663-03(2015)测量。另外,根据压汞法,挤出物优选具有0.2到1.2ml/g、优选0.4到1.0ml/g、更优选0.5到0.8ml/g范围内的孔体积。孔体积根据ASTM D4222-03测量。
本发明的催化剂组合物可以成形为任何特定形式。适合的形状包括三叶形和圆柱形,本发明的催化剂组合物优选三叶形形状。
载体可以通过混合丝光沸石、ZSM-5型沸石和无机粘合剂,使混合物成型并使成型混合物在200至800℃的温度下进行煅烧来制备。可在煅烧之前干燥成型混合物。干燥温度宜在50℃到200℃的范围内。干燥时间宜在0.5到24小时范围内。煅烧温度宜在200℃到800℃范围内,优选在300℃到600℃范围内。煅烧载体材料时,宜应用相对短的时间,例如0.5到5小时范围内。煅烧宜在400到700℃范围内,优选450到600℃范围内的温度下进行。
本催化剂组合物包括钼,作为金属按催化剂组合物总重量计,其量在1-10wt%的范围内,更优选地按催化剂组合物总重量计在2-9wt%的范围内、更优选在2-8wt%、更优选2-6wt%的金属。
本发明催化剂还包含铂,作为金属基于催化剂组合物的总重量,其量为0.005-1wt%的范围,更优选0.01-0.5wt%、更特别是0.01-0.2wt%的范围。最优选地,本催化剂还包含铂,作为金属基于催化剂组合物总重量,其量为0.01-0.1wt%或0.01-0.05wt%的范围。
金属的量作为独立于实际存在的化合物的金属来计算。
根据本发明的催化剂组合物可合适地具有这类形状,使得填充有催化剂粒子的反应器的平均空隙分数为至少10体积%,优选地在20体积%到70体积%的范围内,更优选地在35体积%到55体积%的范围内。
钼和铂适合在单独的金属盐溶液的帮助下加入载体中。优选地,通过孔体积浸渍掺入每种钼和铂。
钼可以在包含七钼酸盐的溶液的帮助下掺入。
铂可以在包含一种或多种选自氯铂酸和铵稳定的铂盐的化合物的溶液的帮助下掺入。
在载体中加入钼后,对含钼载体进行热处理。步骤(b)的热处理为100至至多300℃,优选100至至多250℃,更优选至多200℃,最优选至多170℃。
特别优选步骤(b)中得到的含钼载体的温度在步骤(c)中至多170℃,直到在步骤(c)中将铂加入含钼载体中。然后对如此处理的载体进行热处理。
步骤(c)的热处理为200至至多600℃,优选至少300℃,更优选至少350℃,更优选至少400℃,以及优选至多570℃,更优选至多550℃,最优选至多520℃。
各步骤(b)和(c)的热处理可适当地施加0.5至5小时,更具体地1至4小时,更优选1至3小时的范围。
使用催化剂组合物作为催化剂之前,优选的是使催化剂组合物上的金属呈金属化(而非氧化)形式。因此,催化剂组合物优选经历还原条件,例如在还原气氛(例如在氢气中,任选地用惰性气体(例如氮气或二氧化碳)稀释)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。
本发明还涉及用于使用根据本发明制备的催化剂转化含有烷基芳烃的原料(更具体地说,烷基转移)的方法。
在一个优选的实施方案中,本发明提供了一种用于包含甲苯和含有至少9个碳原子的烷基芳烃的烷基芳烃原料的烷基转移的方法。
合适地,烷基芳烃原料包含总量至少90wt%的甲苯和含有至少9个碳原子的烷基芳烃。烷基芳烃原料最优选地包含35到75wt%的甲苯和25到65wt%的含有至少9个碳原子的烷基芳烃化合物。烷基芳烃优选由氢、碳和任选的氧组成。
原料宜在氢气存在下与催化剂接触。接触可在固定床系统、移动床系统或流体化床系统中进行。这种系统可以连续地或以分批方式操作。优选在固定床系统中进行连续操作。催化剂可在一个反应器中或串联的数个独立的反应器中使用或在摆动系统中操作,以确保在催化剂更换期间连续的操作。
本发明的烷基转移方法优选在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。
所述方法优选在1到30巴范围内的压力下、优选在2到20巴范围内的压力下且更优选在2到10巴范围内的压力下进行。
所述方法中应用的重量空速宜在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是在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,即二甲苯和苯。未反应的反应物(例如甲苯)宜进行再循环以供进一步反应。
本公开不限于如上所述的实施方案和所附权利要求。可以想到许多修改,并且可以组合各个实施方案的特征。
为便于更好地理解本发明,提供一些实施方案的某些方面的以下实施例。这些实施例决不应被理解为限制或限定本发明的范围。
实施例
实施例1
通过挤出包含基于干组分为50wt%的二氧化硅与氧化铝摩尔比为20和数均晶体尺寸为60至100nm的丝光沸石、30wt%的二氧化硅与氧化铝的摩尔比为23和数均晶体尺寸为100nm的ZSM-5沸石和20wt%的氧化铝(可从Sasol得到的Pural SB1)的混合物,制备载体。在约550℃下干燥且煅烧原始挤出物1小时。
该载体用于制备下文所述的所有催化剂。
通过孔隙体积浸渍将金属掺入载体中。
在七钼酸铵的水溶液的帮助下掺入钼。
在氯铂酸水溶液的帮助下掺入铂。
每种钼和铂的浓度使得提供铂含量为0.03wt%和/或4wt%钼的最终催化剂,各金属基于总催化剂。在每次浸渍完成后,催化剂在2小时内经受140或480℃的热处理,以足够低的升温速率以实现金属相的充分分散。表2中提供了关于每种对比催化剂A-F和催化剂1(根据本发明方法制备)的制备、浸渍顺序和浸渍后热处理温度的全部信息。
实施例2
对比催化剂A-F和根据本发明方法制备的催化剂1用于如表1所述的烷基芳烃原料的烷基转移反应。
表1
组分 | 含量(wt%) |
甲苯(C7) | 50.4 |
三甲基苯(C9) | 28.6 |
乙基甲苯(C9) | 11.0 |
丙基苯(C9) | 0.8 |
茚满(C9) | 1.4 |
乙基二甲苯(C10) | 7.0 |
四甲基苯(C10) | 0.5 |
C10+其余 | 0.3 |
使用气相色谱评估所得产物。测试在30巴的总压力和氢气:烃摩尔比为5下进行。在整个实验中保持这些条件。
测试之前,催化剂在氢气流中、在室温和大气压下干燥1小时,接着加热到400℃维持1小时,加压到30巴,在这些条件下再维持1小时,并且最后冷却到360℃。以2.5h-1的重时空速引入进料。
对于催化剂老化,将温度升至420℃并在该温度下保持24小时。随后,将反应器冷却至360℃并将重时空速增加至3.5h-1。在这些条件下,在320至380℃的温度范围内评价催化剂。
通过插值在不同温度下的转化率,确定达到甲苯和C9+芳烃至所需C8-芳烃(C8A)和苯的总转化率45%所需的温度。表2比较了该温度下的关键性能参数。
EB/C8A表示C8芳族化合物(C8A)馏分中乙苯(EB)的百分比。苯纯度定义为苯与其共沸物(环己烷和甲基环戊烷)的混合物中苯的百分比。三甲苯(TMB)转化率是催化剂转化的所有三甲基苯的百分比。总的气体量定义为反应器流出物中C1-C5分子的重量百分比。
表2.催化剂综述和烷基转移性能
*基于总载体的wt%。
**基于总催化剂的wt%。
在表2中,对比催化剂A和B包含ZSM-5/丝光沸石载体以及钼作为唯一的掺杂剂。所述催化剂在不同温度下处理。两种体系均显示出高苯纯度,但两种体系的活性(由总转化率达到45%所需的温度表示)不足以进行有效的商业应用。
对比催化剂C基于铂作为ZSM-5/丝光沸石载体上的唯一掺杂剂。与对比催化剂A和B不同,对比催化剂C显示出令人满意的活性(由较低的所需温度表示,实现45%的总转化率)。但是,所述催化剂显示出不可接受的低苯纯度。
对比催化剂D-F和催化剂1都是包含ZSM-5/丝光沸石载体以及钼和铂掺杂剂的组合的催化剂。但是,所述催化剂通过不同方法制备。
令人惊讶的是,在本发明中,已经发现,取决于金属掺杂剂添加的顺序和用于中间和最终热处理的温度,在随后的催化测试中获得了惊人不同的结果。特别地,仅对于通过首先在ZSM-5/丝光沸石载体上浸渍钼、在140℃的低温下干燥、然后直接用铂浸渍制备的催化剂1,获得优异的高苯纯度,同时还保持着良好的活性。用于制备催化剂对比催化剂D-F的其他顺序导致类似于仅Pt催化剂(对比催化剂C)或仅Mo催化剂(对比催化剂B)的行为,在商业操作中都没有吸引力。
这从表2中清楚,根据本发明制备的催化剂出乎意料地允许获得甲苯和含有至少9个碳原子的芳族化合物的高转化率,同时获得高纯度的苯。另一个优点是可以用低总气体产量获得高纯度的苯。
在表2中测试的催化剂中,只有通过本发明方法制备的催化剂1能够在商业上可行的反应温度下提供高苯纯度、高苯产率和高产物选择性。对比催化剂A-F对工业过程中的效用而言具有太低的活性或选择性太低。
Claims (10)
1.制备催化剂组合物的方法,包括
(a)制备载体,其包含(i)丝光沸石,基于载体的总重量,其量为20-80wt%,(ii)ZSM-5型沸石,基于载体的总重量,其量为10-70wt%;和(iii)无机粘合剂,基于载体的总重量,其量为10-50wt%;
(b)作为金属基于催化剂组合物的总重量,将量为1-10wt%的钼加入所述载体中,并使如此处理的载体经受100至至多300℃的温度;和
(c)在步骤(b)中获得的含钼载体中加入作为金属基于催化剂组合物总重量的量为0.005-1wt%的铂,并使如此处理的载体经受200至至多600℃的温度。
2.根据权利要求1所述的方法,其中步骤(b)包括使含钼载体经受100至至多170℃的温度。
3.根据权利要求2所述的方法,其中在步骤(c)中含钼载体的温度至多170℃,直到铂已在步骤(c)中加入含钼载体中,并且然后使如此处理的载体经受200至最高600℃的温度。
4.根据权利要求1至3所述的方法,其中所述丝光沸石具有的二氧化硅与氧化铝的摩尔比在10到40的范围中。
5.根据权利要求1至4所述的方法,其中所述ZSM-5型沸石具有15到40范围内的二氧化硅与氧化铝摩尔比。
6.根据权利要求1至5所述的方法,其中所述ZSM-5型沸石具有20到500nm范围内的数均粒度,其通过X射线衍射测定。
7.根据权利要求1至6所述的方法,其中所述丝光沸石的数均粒度为20至500nm,其通过X射线衍射测定。
8.根据权利要求1至7所述的方法,其中所述载体通过混合丝光沸石、ZSM-5型沸石和无机粘合剂,使混合物成型并使成型混合物经受200至800℃的温度进行制备。
9.一种使用根据权利要求1到8中任一项所述的方法制备的催化剂使含有烷基芳烃的原料转化的方法。
10.根据权利要求9所述的方法,其中所述原料包含35到75wt%的甲苯和25到65wt%的含有至少9个碳原子的烷基芳烃化合物,所有的量基于原料的总量。
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