CN106316768A - 高选择性制备二甲苯的方法 - Google Patents

高选择性制备二甲苯的方法 Download PDF

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CN106316768A
CN106316768A CN201510344799.0A CN201510344799A CN106316768A CN 106316768 A CN106316768 A CN 106316768A CN 201510344799 A CN201510344799 A CN 201510344799A CN 106316768 A CN106316768 A CN 106316768A
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catalyst
dimethylbenzene
optionally substituted
zsm
zro
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CN106316768B (zh
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宋奇
郑均林
孔德金
祁晓岚
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to PCT/CN2016/000314 priority patent/WO2016201954A1/zh
Priority to US15/737,976 priority patent/US10435348B2/en
Priority to EP16810695.3A priority patent/EP3312285B1/en
Priority to ES16810695T priority patent/ES2880284T3/es
Priority to DK16810695.3T priority patent/DK3312285T3/da
Priority to KR1020187001727A priority patent/KR102454224B1/ko
Priority to BR112017027358-6A priority patent/BR112017027358B1/pt
Priority to JP2017565938A priority patent/JP6976863B2/ja
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Abstract

本发明涉及一种高选择性制备二甲苯的方法。该方法包括以下步骤：a)内酯类化合物与脱酯二聚催化剂接触，得到含碳八烯烃的物流；b)所述含碳八烯烃的物流与芳构化催化剂接触，得到含二甲苯的物流；所述内酯类化合物具有结构式(I)：式(I)中，R1为任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基、任选取代的C2-20直链或支链炔基、任选取代的C3-20环烷基或者任选取代的C6-20芳基；R2为氢、任选取代的C1-20直链或支链烷基、羧基、呋喃基。该方法可用于非化石资源制芳烃领域。

Description

高选择性制备二甲苯的方法
技术领域
本发明涉及一种高选择性制备二甲苯的方法，特别是涉及一种内酯类化合物芳构化高选择性制备二甲苯的方法。
背景技术
芳烃是石油化工工业的重要基础原料，在总数约800万种的有机化合物中，芳烃化合物约占30％，并广泛应用于聚酯、化纤、橡胶、医药以及精细化工等诸多领域，国内消费量可观，对国民经济发展具有重要影响，同时是社会发展的重要基本有机化工原料。苯甲苯二甲苯是芳烃中应用广泛的三种芳烃大宗化学品。其中，对二甲苯的需求量和使用面最为广泛。其最主要用途是用于制造对苯二甲酸，通过对苯二甲酸(PTA)或对苯二甲酸二乙酯(DMT)中间体，用于生产聚酷纤维如聚对苯二甲酸乙二醇酯(PET)、树脂和薄膜。目前国内外芳烃的生产主要依赖于不可再生的化石资源，如可通过在催化剂上将石油经过加氢、重整、芳烃转化和分离等工艺过程获得。但是，化石资源储量有限和不可再生性，使得以石油为主要炼制原料生产芳烃的成本愈见高涨。另外，化石资源的不断开发利用产生大量温室气体排放，所引起的一系列环境问题日趋严重，因此，发展从可再生资源路线生产二甲苯技术有重要意义和应用价值。
从生物质出发制备可再生的芳烃，尤其是二甲苯是目前的研究热点之一。现有文献也报道了将生物质转化为混合芳烃的工作，比如生物质经合成气再芳构化；快速热解制芳烃；生物质糖平台经催化转化制芳烃等路线(Katherine Bourzac.From biomass to chemicals in one step.MITTechnology Review，2010-03-29.；US20090227823，US20110257416A1)。但高选择性地生产二甲苯仍然面临较大问题。因此，充分利用生物质资源，高选择性地大规模制备二甲苯的技术有待进一步发展。
发明内容
本发明旨在提供一种高选择性制备二甲苯的方法。
为实现上述发明目的，本发明采取的技术方案如下：一种高选择性制备二甲苯的方法，包括以下步骤：
a)内酯类化合物与脱酯二聚催化剂接触，得到含碳八烯烃的物流；
b)所述含碳八烯烃的物流与芳构化催化剂接触，得到含二甲苯的物流。
上述技术方案中，优选地，所述内酯类化合物具有结构式(I)：
式(I)中，R1为任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基、任选取代的C2-20直链或支链炔基、任选取代的C3-20环烷基或者任选取代的C6-20芳基；R2为氢、任选取代的C1-20直链或支链烷基、羧基、呋喃基。
上述技术方案中，优选地，式(I)中，R1为任选取代的C2-10直链或支链烷基、任选取代的C2-10直链或支链烯基；R2为任选取代的C2-10直链或支链羧基；所述碳八烯烃选自2,4,4-三甲基戊烯、2,5-二甲基己二烯、3,4-二甲基-2-己烯、3-甲基-2-庚烯、5-甲基-3-庚烯、3-甲基-3庚烯或辛烯中的至少一种。
上述技术方案中，优选地，所述步骤a)脱酯二聚反应温度160～400℃，重量空速0.1～15小时-1。
上述技术方案中，优选地，所述脱酯二聚催化剂至少包含装填在上层的催化剂A和装填在下层的催化剂B；所述催化剂A和催化剂B包含分子筛、固体强酸、铋的氧化物、复合锆氧化物、Al2O3、Al2O3-SiO2或SiO2、Amberlyst系列树脂、全氟化磺酸系列聚合物Nafion；催化剂A和催化剂B不同，其重量比为10/1～1/10。其中，所述分子筛选自ZSM-5、ZSM-11、ZSM-23、ZSM-38、Y、beta、MCM-22或MCM-41中至少的一种。ZSM型分子筛的硅铝摩尔比SiO2/Al2O3＝10～500，优选15～200；Y分子筛的硅铝摩尔比SiO2/Al2O3＝2～70，优选3～50；beta分子筛的硅铝摩尔比SiO2/Al2O3＝10～150，优选15～65；MCM型分子筛的硅铝摩尔比SiO2/Al2O3＝20～250，优选40～150。所述固体强酸选自SO4 2－/ZrO2、S2O8 2 －/ZrO2、SO4 2－/TiO2、SO4 2－/ZrO2-Fe3O4、Pt/SO4 2－/TiO2、SO4 2－/TiO2-ZrO2、SO4 2－/TiO2-Al2O3、SO4 2-/TiO2-WO3、SO4 2－/ZrO2-Fe2O3-Cr2O3、SbF5/SiO2-Al2O3、SO4 2－/ZrO2-WO3、SO4 2-/TiO2-MoO3、PF3/Al2O3-B2O3、AsF3/Al2O3-B2O3、SbF3/Al2O3-B2O3、BiF3/Al2O3-B2O3、TaF3/Al2O3-B2O3、VF3/Al2O3-B2O3、NbF3/Al2O3-B2O3、SO4 2－/ZrO2-Fe2O3-MnO2或AlCl3-CuCl2中的至少一种。所述复合锆氧化物为XaOb/ZrO2；其中，X选自钨、钼、铈、镧、锰中的至少一种，a和b为化学计量数；所述复合锆氧化物中，以重量份数计，XaOb的用量为0.1～40份，ZrO2的用量为99.9～60份。
上述技术方案中，优选地，所述的步骤b)反应温度420～800℃，重量空速为0.3～10小时-1；所述芳构化催化剂含有分子筛；所述分子筛选自ZSM-5、ZSM-11、ZSM-23、ZSM-38、Y、beta、MCM-22或MCM-41中至少的一种。ZSM型分子筛的硅铝摩尔比SiO2/Al2O3＝10～500，优选15～200；Y分子筛的硅铝摩尔比SiO2/Al2O3＝2～70，优选3～50；beta分子筛的硅铝摩尔比SiO2/Al2O3＝10～150，优选15～65；MCM型分子筛的硅铝摩尔比SiO2/Al2O3＝20～250，优选40～150。
上述技术方案中，优选地，所述原料来自生物质材料。
上述技术方案中，优选地，所述原料来自木糖醇、葡萄糖、纤维二糖、半纤维素或木质素中的至少一种。
上述技术方案中，优选地，所述原料来自甘蔗渣、葡萄糖、木材、玉米秸或稻草秸中的至少一种。
上述技术方案中，优选地，所述含对二甲苯的物流经分离后，得到纯度为70～99.9重量％的对二甲苯产品。
作为本发明的一个实施方式，所述内酯类化合物来自生物质材料。例如戊内酯，可由纤维素经过水解脱氧后获得，可参见文献“Directconversion of cellulose to levulinic acid and gamma-valerolactone using solidacid catalysts，Catal.Sci.Technol.,2013,3,927-931；Production of levulinicacid and gamma-valerolactone(GVL)from cellulose using GVL as a solventin biphasic systems，Energy Environ.Sci.,2012,5,8199-8203”。
本发明中，固体强酸催化剂的制备方法是为本领域所熟知的，可以采用沉淀-浸渍法。具体可参见文献《固体酸与精细化工》和“SO4 2-/MxOy型固体超强酸催化剂的研究进展，应用化工，2014,vol43,1879-1883”。
本发明中所述的复合锆氧化物XaOb/ZrO2；其中，X选自钨、钼、铈、镧或锰中的至少一种，a和b为化学计量数，这与所选金属的化合价有关。当所选金属确定时，各下标即具有确定的数值。其制备可采用本领域所熟知的浸渍法或沉淀法。浸渍法是将钨、钼、铈、镧或锰以盐溶液形式浸渍到氧化锆上，浸渍12～48小时后倒掉多余液体，100～200℃干燥处理，将水分蒸发出来留下活性组分，再经过培烧、活化工序处理后即得高度分散的载体催化别。沉淀法可通过将钨、钼、铈、镧或锰的金属盐水溶液、锆的金属水溶液和沉淀剂氨水同时加入，生成固体沉淀。生成的沉淀经洗涤、过滤、干燥、在400～600℃下焙烧经后可得到催化剂。
本发明方法中所述的分子筛催化剂的制备方法如下：将分子筛、粘结剂、助挤剂、扩孔剂混捏，挤条成型，成型后100～200℃干燥1～24小时，再于400～700℃下焙烧1～10小时。其中，所述助挤剂为田菁粉、聚乙二醇或羧甲基纤维素钠中的至少一种，所述扩孔剂为柠檬酸、草酸或乙二胺四乙酸中的至少一种，加入的助挤剂和扩孔剂的总量不超过混合物重量的10％。成型时加入酸进行捏合，加入的酸包括无机酸或乙酸中的至少一种，无机酸包括硝酸、硫酸或磷酸中的至少一种，所加入的酸溶液的量为混合物重量的50～90％。
本发明方法对提高生物质芳构化产物中的二甲苯的选择性有较好的作用，解决了以往生物质制芳烃过程中二甲苯选择性低的问题。采用本发明方法，原料转化率最高可达到99％；二甲苯目标产物的选择性最高可达到94％，取得了较好的技术效果。
下面通过实施例对本发明作进一步阐述。
具体实施方式
【实施例1】
脱酯二聚催化剂ZSM-5：称取35克硅铝比为25的ZSM-5与35克拟薄水铝石进行混合，加入田菁粉2.7克，混合均匀。之后加入硝酸质量百分含量为5.5％的48克硝酸水溶液，混捏成型，挤条。得到催化剂前体在120℃下干燥8小时，经过500℃焙烧2小时，得到分子筛催化剂。
芳构化催化剂的制备：称取35克硅铝比为25的氢型的ZSM-5与35克γ-氧化铝助剂进行混合，加入田菁粉2.7克，混合均匀。之后加入硝酸质量百分含量为5.5％的48克硝酸水溶液，混捏成型，挤条。得到催化剂前体在120℃下干燥8小时，经过500℃焙烧2小时，得到分子筛催化剂HZSM-5。
当归内酯进入脱酯二聚反应器R1，催化剂床层上层采用Al2O3-SiO2催化剂，催化剂下层采用上述制备的ZSM-5为催化剂，两种催化剂装填高度相同。在300℃，重量空速为1.5h-1条件下进行脱酯二聚，转化率为87％，碳八烯烃选择性79％，经过分离后，碳八烯烃进入芳构化反应器R2，在450℃，HZSM-5，空速为2h-1的作用下芳构化，得到含有二甲苯产物的物料，二甲苯在产物中的分布为79％。未反应完全的烯烃可重新返回二聚体反应器继续反应。得到的烯烃进一步进行分离后可以得到苯甲苯等轻芳烃，同时得到高纯度的对二甲苯。另外，还有部分作为重组分从塔釜得到。从塔顶出来的氢气可作为低聚体的加氢为汽柴油的原料，而塔釜重组分可以作为柴油的原料或者燃烧供热。
【实施例2】
称取1000克稻草秸，置于压力釜中并加入5000克水，再加入水质量7％的5mol/L的硫酸溶液，升温到210℃下反应30分钟，之后冷却，将冷却后的反应液过滤，得到滤饼和过滤液，过滤液为纤维素的水解液，反应结束后，采用质谱对反应结果进行鉴定主要产物为乙酰丙酸，其产生量为382克。得到的乙酰丙酸在固定床中在2％金属负载量的RuSn/C上加氢得到γ-戊内酯，转化率为99％，产物收率为98％。
脱酯二聚催化剂ZSM-5-A制备：称取35克硅铝比为50的氢型ZSM-5与35克拟薄水铝石进行混合，加入田菁粉2.7克，混合均匀。之后加入硝酸质量百分含量为5.5％的48克硝酸水溶液，混捏成型，挤条。得到催化剂前体在120℃下干燥8小时，经过500℃焙烧2小时，得到分子筛催化剂。脱酯二聚催化剂ZSM-5-B制备：称取65克硅铝比为150的氢型ZSM-5与35克拟薄水铝石进行混合，加入田菁粉3.5克，混合均匀。之后加入硝酸质量百分含量为5.5％的108克硝酸水溶液，混捏成型，挤条。得到催化剂前体在120℃下干燥8小时，经过500℃焙烧2小时，得到分子筛催化剂。
芳构化催化剂制备：称取80克硅铝比为500的ZSM-5与20克拟薄水铝石进行混合，加入田菁粉3.9克，混合均匀。之后加入硝酸质量百分含量为5.5％的68.6克硝酸水溶液，混捏成型，挤条。得到催化剂前体在120℃下干燥8小时，经过500℃焙烧2小时，得到分子筛催化剂。
γ-戊内酯进入脱酯二聚反应器R1，催化剂床层上层采用ZSM-5-A催化剂，催化剂下层采用ZSM-5-B为催化剂，两种催化剂装填高度相同。在280℃，重量空速为1.5h-1条件下进行脱酯二聚，转化率为93％，碳八烯烃选择性86％，经过分离后，碳八烯烃进入芳构化反应器R2，在450℃，HZSM-5，空速为2h-1的作用下芳构化，得到含有二甲苯产物的物料，二甲苯在产物中的分布为83％。未反应完全的烯烃可重新返回二聚体反应器继续反应。得到的烯烃进一步进行分离后可以得到苯甲苯等轻芳烃，同时得到高纯度的对二甲苯。另外，还有部分作为重组分从塔釜得到。从塔顶出来的氢气可作为低聚体的加氢为汽柴油的原料，而塔釜重组分可以作为柴油的原料或者燃烧供热。
【实施例3】
脱脂二聚催化剂A：称取50克硅铝比为30的beta与50克拟薄水铝石进行混合，加入田菁粉3.9克，混合均匀。之后加入硝酸质量百分含量为5.5％的68.6克硝酸水溶液，混捏成型，挤条。得到催化剂前体在120℃下干燥8小时，经过500℃焙烧2小时，得到分子筛催化剂。脱酯二聚催化剂B：称取35克硅铝比为100的ZSM-5与35克γ-氧化铝助剂进行混合，加入田菁粉2.7克，混合均匀。之后加入硝酸质量百分含量为5.5％的48克硝酸水溶液，混捏成型，挤条。得到催化剂前体在120℃下干燥8小时，经过500℃焙烧2小时，得到分子筛催化剂
芳构化HZSM-5催化剂：称取35克硅铝比为150的ZSM-5与35克拟薄水铝石进行混合，加入田菁粉2.7克，混合均匀。之后加入硝酸质量百分含量为5.5％的48克硝酸水溶液，混捏成型，挤条。得到催化剂前体在120℃下干燥8小时，经过500℃焙烧2小时，得到分子筛催化剂。
δ-戊内酯进入脱酯二聚反应器R1，催化剂床层上层采用beta催化剂，催化剂下层采用ZSM-5为催化剂，两种催化剂装填高度相同。在280℃，重量空速为1.5h-1条件下进行脱酯二聚，转化率为99％，碳八烯烃选择性93％，经过分离后，碳八烯烃进入芳构化反应器R2，在450℃，HZSM-5，空速为2h-1的作用下芳构化，得到含有二甲苯产物的物料，二甲苯在产物中的分布为86％。未反应完全的烯烃可重新返回二聚体反应器继续反应。得到的烯烃进一步进行分离后可以得到苯甲苯等轻芳烃，同时得到高纯度的对二甲苯。另外，还有部分作为重组分从塔釜得到。从塔顶出来的氢气可作为低聚体的加氢为汽柴油的原料，而塔釜重组分可以作为柴油的原料或者燃烧供热。
【实施例4】
脱脂二聚催化剂B：称取35克硅铝比为150的ZSM-5与35克拟薄水铝石进行混合，加入田菁粉2.7克，混合均匀。之后加入硝酸质量百分含量为5.5％的48克硝酸水溶液，混捏成型，挤条。得到催化剂前体在120℃下干燥8小时，经过500℃焙烧2小时，得到分子筛催化剂。
芳构化HY催化剂：称取35克硅铝比为6的HY分子筛与35克γ-氧化铝助剂进行混合，加入羧甲基纤维素钠2.7克，混合均匀。之后加入硝酸质量百分含量为5.5％的48克硝酸水溶液，混捏成型，挤条。得到催化剂前体在120℃下干燥8小时，经过500℃焙烧2小时，得到分子筛催化剂C10。
丙位己内酯进入脱酯二聚反应器R1，催化剂床层上层采用SO4 2-/TiO2-WO3催化剂，催化剂下层采用上述制备的ZSM-5为催化剂，两种催化剂装填高度相同。在250℃，重量空速为1.5h-1条件下进行脱酯二聚，转化率为99％，碳八烯烃选择性89％，经过分离后，碳八烯烃进入芳构化反应器R2，在450℃，HY分子筛，空速为2h-1的作用下芳构化，得到含有二甲苯产物的物料，二甲苯在产物中的分布为88％。未反应完全的烯烃可重新返回二聚体反应器继续反应。得到的烯烃进一步进行分离后可以得到苯甲苯等轻芳烃，同时得到高纯度的对二甲苯。另外，还有部分作为重组分从塔釜得到。从塔顶出来的氢气可作为低聚体的加氢为汽柴油的原料，而塔釜重组分可以作为柴油的原料或者燃烧供热。
【实施例5】
脱酯二聚催化剂B：称取60克硅铝比为8的Y分子筛与40克γ-氧化铝助剂进行混合，加入田菁粉3.9克，混合均匀。之后加入硝酸质量百分含量为5.5％的68.6克磷酸水溶液，混捏成型，挤条。得到催化剂前体在120℃下干燥8小时，经过500℃焙烧2小时，得到分子筛催化剂。
芳构化MCM-22催化剂：称取70克硅铝比为8的Y与30克拟薄水铝石进行混合，加入田菁粉3.9克，混合均匀。之后加入硝酸质量百分含量为5.5％的68.6克硝酸水溶液，混捏成型，挤条。得到催化剂前体在120℃下干燥8小时，经过500℃焙烧2小时，得到分子筛催化剂。
丙位庚内酯进入脱酯二聚反应器R1，催化剂床层上层采用Amberlyst催化剂，催化剂下层采用上述制备的Y为催化剂，两种催化剂装填高度相同。在180℃，重量空速为1.5h-1条件下进行脱酯二聚，转化率为96％，碳八烯烃选择性81％，经过分离后，碳八烯烃进入芳构化反应器R2，在450℃，MCM-22分子筛，空速为2h-1的作用下芳构化，得到含有二甲苯产物的物料，二甲苯在产物中的分布为94％。未反应完全的烯烃可重新返回二聚体反应器继续反应。得到的烯烃进一步进行分离后可以得到苯甲苯等轻芳烃，同时得到高纯度的对二甲苯。另外，还有部分作为重组分从塔釜得到。从塔顶出来的氢气可作为低聚体的加氢为汽柴油的原料，而塔釜重组分可以作为柴油的原料或者燃烧供热。
【实施例6】
脱酯二聚催化剂B：称取35克硅铝比为150的ZSM-5与45克拟薄水铝石进行混合，加入田菁粉3.2克，混合均匀。之后加入硝酸质量百分含量为5.5％的48克硝酸水溶液，混捏成型，挤条。得到催化剂前体在120℃下干燥8小时，经过500℃焙烧2小时，得到分子筛催化剂。
芳构化催化剂：称取35克硅铝比为150的ZSM-5与35克拟薄水铝石进行混合，加入田菁粉2.7克，混合均匀。之后加入硝酸质量百分含量为5.5％的48克硝酸水溶液，混捏成型，挤条。得到催化剂前体在120℃下干燥8小时，经过500℃焙烧2小时，得到分子筛催化剂。
γ-戊内酯进入脱酯二聚反应器R1，催化剂床层上层采用Amberlyst催化剂，催化剂下层采用上述制备的ZSM-5为催化剂，两种催化剂装填高度相同。在180℃，重量空速为1.5h-1条件下进行脱酯二聚，转化率为96％，碳八烯烃选择性91％，经过分离后，碳八烯烃进入芳构化反应器R2，在450℃，ZSM-5分子筛，空速为2h-1的作用下芳构化，得到含有二甲苯产物的物料，二甲苯在产物中的分布为86％。未反应完全的烯烃可重新返回二聚体反应器继续反应。得到的烯烃进一步进行分离后可以得到苯甲苯等轻芳烃，同时得到高纯度的对二甲苯。另外，还有部分作为重组分从塔釜得到。从塔顶出来的氢气可作为低聚体的加氢为汽柴油的原料，而塔釜重组分可以作为柴油的原料或者燃烧供热。

Claims (10)

1.一种高选择性制备二甲苯的方法，包括以下步骤：
a)内酯类化合物与脱酯二聚催化剂接触，得到含碳八烯烃的物流；
b)所述含碳八烯烃的物流与芳构化催化剂接触，得到含二甲苯的物流。
2.根据权利要求1所述高选择性制备二甲苯的方法，其特征在于所述内酯类化合物具有结构式(I)：
式(I)中，R1为任选取代的C1-20直链或支链烷基、任选取代的C2-20直链或支链烯基、任选取代的C2-20直链或支链炔基、任选取代的C3-20环烷基或者任选取代的C6-20芳基；R2为氢、任选取代的C1-20直链或支链烷基、羧基、呋喃基。
3.根据权利要求2所述高选择性制备二甲苯的方法，其特征在于式(I)中，R1为任选取代的C2-10直链或支链烷基、任选取代的C2-10直链或支链烯基；R2为任选取代的C2-10直链或支链羧基；所述碳八烯烃选自2,4,4-三甲基戊烯、2,5-二甲基己二烯、3,4-二甲基-2-己烯、3-甲基-2-庚烯、5-甲基-3-庚烯、3-甲基-3庚烯或辛烯中的至少一种。
4.根据权利要求1所述高选择性制备二甲苯的方法，其特征在于所述步骤a)脱酯二聚反应温度160～400℃，重量空速0.1～15小时-1；
所述脱酯二聚催化剂至少包含装填在上层的催化剂A和装填在下层的催化剂B；所述催化剂A和催化剂B包含分子筛、固体强酸、铋的氧化物、复合锆氧化物、Al2O3、Al2O3-SiO2或SiO2、Amberlyst系列树脂、全氟化磺酸系列聚合物Nafion；催化剂A和催化剂B不同，其重量比为10/1～1/10。
5.根据权利要求4所述高选择性制备二甲苯的方法，其特征在于所述分子筛选自ZSM-5、ZSM-11、ZSM-23、ZSM-38、Y、beta、MCM-22或MCM-41中至少的一种；
所述固体强酸选自SO4 2－/ZrO2、S2O8 2－/ZrO2、SO4 2－/TiO2、SO4 2－/ZrO2-Fe3O4、Pt/SO4 2－/TiO2、SO4 2－/TiO2-ZrO2、SO4 2－/TiO2-Al2O3、SO4 2-/TiO2-WO3、SO4 2－/ZrO2-Fe2O3-Cr2O3、SbF5/SiO2-Al2O3、SO4 2－/ZrO2-WO3、SO4 2-/TiO2-MoO3、PF3/Al2O3-B2O3、AsF3/Al2O3-B2O3、SbF3/Al2O3-B2O3、BiF3/Al2O3-B2O3、TaF3/Al2O3-B2O3、VF3/Al2O3-B2O3、NbF3/Al2O3-B2O3、SO4 2－/ZrO2-Fe2O3-MnO2或AlCl3-CuCl2中的至少一种；
所述复合锆氧化物为XaOb/ZrO2；其中，X选自钨、钼、铈、镧、锰中的至少一种，a和b为化学计量数；所述复合锆氧化物中，以重量份数计，XaOb的用量为0.1～40份，ZrO2的用量为99.9～60份。
6.根据权利要求1所述高选择性制备二甲苯的方法，其特征在于所述的步骤b)反应温度420～800℃，重量空速为0.3～10小时-1；
所述芳构化催化剂含有分子筛；所述分子筛选自ZSM-5、ZSM-11、ZSM-23、ZSM-38、Y、beta、MCM-22或MCM-41中至少的一种。
7.根据权利要求1所述高选择性制备二甲苯的方法，其特征在于所述原料来自生物质材料。
8.根据权利要求1所述高选择性制备二甲苯的方法，其特征在于所述原料来自木糖醇、葡萄糖、纤维二糖、半纤维素或木质素中的至少一种。
9.根据权利要求1所述高选择性制备二甲苯的方法，其特征在于所述原料来自甘蔗渣、葡萄糖、木材、玉米秸或稻草秸中的至少一种。
10.根据权利要求1所述高选择性制备二甲苯的方法，其特征在于所述含对二甲苯的物流经分离后，得到纯度为70～99.9重量％的对二甲苯产品。
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