WO2018232546A1 - 一种选择性生成对甲基乙苯的烷基化催化剂及其制备方法 - Google Patents

一种选择性生成对甲基乙苯的烷基化催化剂及其制备方法 Download PDF

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WO2018232546A1
WO2018232546A1 PCT/CN2017/000584 CN2017000584W WO2018232546A1 WO 2018232546 A1 WO2018232546 A1 WO 2018232546A1 CN 2017000584 W CN2017000584 W CN 2017000584W WO 2018232546 A1 WO2018232546 A1 WO 2018232546A1
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solution
group
oxide
zsm
methylethylbenzene
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谢素娟
陈福存
徐龙伢
王玉忠
李洪星
刘盛林
高扬
李忠玲
张爽
朱向学
李秀杰
崔倩
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Dalian Institute of Chemical Physics of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention belongs to the field of heterogeneous catalysis, and in particular relates to an alkylation catalyst for selectively producing p-methylethylbenzene and a preparation method thereof.
  • P-methylethylbenzene is a key raw material for the production of p-methylstyrene (PMS), which produces high-end specialty chemicals such as high-end resins, high-performance rubber, new plastics and specialty coatings. Its downstream products are in automobiles and energy. , chemical and materials and many other industries have a wide range of applications.
  • PMS polymer poly(p-methylstyrene) (PPMS) is a high-performance plastic product developed in recent years. The polymer has the same good molding processability as polystyrene (PS), in specific gravity, heat resistance, Flame retardancy, transparency and shrinkage are superior to PS.
  • p-methylethylbenzene can be copolymerized with other monomers (such as styrene) to improve the heat resistance and flame retardancy of the polymer, and is widely used in the manufacture of engineering plastics, alkyd resin coatings, etc.
  • monomers such as styrene
  • ethyl ethylbenzene has become increasingly prominent.
  • the alkylation reaction of toluene with ethylene can be used to prepare p-methylethylbenzene, but the methylethylbenzene obtained by the conventional Friedel-Crafts catalyst is composed of three isomers with thermodynamic equilibrium (the PET is about 30%, and the rest is between Methyl ethyl benzene MET and o-methyl ethylbenzene OET). Therefore, in order to improve PET selectivity (selectivity of PET in methyl ethylbenzene, the same below), the development of a shape-selective catalyst is crucial.
  • USP 5,698,756 discloses the use of a silicone polymer for multiple silicon deposition modification of ZSM-5 molecular sieves, followed by alkali metal ion exchange, resulting in a catalyst having high PET selectivity under hydrogen conditions.
  • CN201110217577.4 discloses a PET which is firstly modified with an alkaline earth metal compound and a copper-containing compound, and then added with a group IV A element compound and a binder, and dried and calcined to obtain a catalyst under hydrogen conditions. The selectivity is over 95%.
  • CN201410424434.4 discloses that a citric acid-modified hydrogen type EU-1 molecular sieve and alumina are formed, dried and then treated with steam at 450-600 ° C. The catalyst used was used for the alkylation of toluene with ethylene.
  • the PET selectivity under non-hydrogen conditions was much higher than the thermodynamic equilibrium, but less than 95%.
  • the present invention is directed to the deficiencies of the prior art for the highly selective formation of PET catalysts for the alkylation of toluene with ethylene (the hydrogenation conditions increase process complexity, reduce economics, and the PET selectivity for non-hydrogen reactions needs to be improved), With ZSM-5/ZSM-11 co-crystallized molecular sieve as the main body, comprehensive acid treatment, different element modification on the acidity and pore structure of molecular sieves, etc., through a lot of research work, a selective generation of a pair of nails was developed.
  • the alkylation catalyst of ethylbenzene and the preparation method thereof, the catalyst of the invention can produce p-methylethylbenzene (PET selectivity >95%, no o-methylethylbenzene) under high hydrogen selectivity.
  • the present invention relates to an alkylation catalyst for selectively producing p-methylethylbenzene and a process for the preparation thereof.
  • An alkylation catalyst for selectively producing p-methylethylbenzene having a composition by weight: 50% to 80% of a ZSM-5/ZSM-11 co-crystal molecular sieve, and 14% to 41% of a binder , IV A or V A group element oxide 2% to 10%, II A or III A group element oxide 2% to 14%.
  • the ZSM-5/ZSM-11 co-crystal molecular sieve comprises 50% to 90 wt.% of ZSM-5 molecular sieve, and is treated with dilute hydrochloric acid or dilute nitric acid solution; the binder is alumina or silica;
  • the Group A element oxide is silicon oxide, the Group V A element oxide is phosphorus oxide; the Group II A element oxide is magnesium oxide or calcium oxide, and the Group III A element oxide is boron oxide or aluminum oxide. .
  • a method for preparing an alkylation catalyst for selectively producing p-methylethylbenzene comprises the following steps:
  • ZSM-5/ZSM-11 is combined with dilute hydrochloric acid or dilute nitric acid solution with a concentration of 0.1-0.3M.
  • the crystal molecular sieve is subjected to two acid treatments at a solid-liquid ratio of 1:5 to 10 g/ml, and each treatment condition is: temperature 60 to 90 ° C for 1 to 3 hours; the acid-treated solid product is washed until the washing liquid is neutral, Drying at 100 to 120 ° C for 8 to 20 hours to obtain a solid powder a;
  • the molded product b is impregnated with a solution containing a silicon compound of a Group IV A element or a solution containing a phosphorus compound of a Group V A element, and dried at 100 to 120 ° C for 4 to 10 hours, and calcined at 500 to 530 ° C for 3 to 6 hours. Molding c containing modified silica or phosphorus oxide.
  • the molded product c is impregnated with a solution containing a Group II A elemental magnesium or a calcium compound or a solution containing a Group III A element boron or an aluminum compound, and dried at 100 to 120 ° C for 4 to 10 hours and at 500 to 530 ° C for firing. ⁇ 6h, the final catalyst was obtained.
  • the solution of the Group IV A element silicon compound in the step (3) is a cyclohexane solution containing tetraethyl orthosilicate, and the solution of the Group V A element phosphorus compound is dilute phosphoric acid, ammonium hydrogen phosphate solution and ammonium dihydrogen phosphate solution.
  • Any one of the magnesium compound of the Group IIA element in the step (4) is at least one of a magnesium nitrate solution, a magnesium chloride solution and a magnesium acetate solution, and the solution of the Group IIA element calcium compound is a calcium acetate solution.
  • a calcium chloride solution, a solution of a Group III A element boron compound is a boric acid solution, and a solution of the aluminum compound is an aluminum nitrate solution.
  • An application for selectively producing an alkylation catalyst for p-methylethylbenzene which is used for the highly selective preparation of p-toluene with alkylation of toluene with ethylene.
  • the main body of the catalyst is a ZSM-5/ZSM-11 co-crystal molecular sieve treated with an appropriate acid, and the acid treatment can modulate the acid distribution of the molecular sieve.
  • the ZSM-5/ZSM-11 co-crystallized molecular sieve can utilize the synergistic advantages of ZSM-5 and ZSM-11 molecular sieves, and combine the modification of the acidity and texture properties of the molecular sieve moldings with different modifying elements to prepare the catalyst. It has excellent reactivity and high PET selectivity in the alkylation process of toluene and ethylene, which can overcome the shortcomings of the prior art and has important application value.
  • a molded product c1 containing modified silica is obtained; c1 is impregnated with a magnesium nitrate solution, dried at 110 ° C for 7 h, and calcined at 500 ° C for 6 h to obtain a finished catalyst Cat-1 containing modified silica and magnesia, the composition of which is shown in Table 1.
  • the catalysts obtained in Examples 1 to 6 were used in the alkylation process of toluene and ethylene.
  • the evaluation of the reactivity of the catalyst was carried out on a conventional fixed bed reactor, and the amount of the catalyst was 5 g. Under nitrogen atmosphere, the catalyst was pretreated at 450 °C for 1 h, then cooled to the reaction temperature; the material was poured in and out, and the toluene was quickly injected into the reaction system with a plunger pump. After the outlet of the reaction device was discharged toluene, ethylene was introduced (controlled by mass flow meter). The required amount) is subjected to an alkylation reaction.
  • the above ethylene raw materials were added with 1.5 wt.% of methane as an internal standard, and the gas phase and liquid phase components were analyzed by an Agilent Technologies 7890B gas chromatograph using an FID detector and a PONA column.
  • the reaction conditions were: a pressure of 0.5 MPa, a temperature of 380 ° C, a toluene/ethylene (molar ratio) of 7, and an ethylene weight space velocity of 0.5 h -1 .
  • the results of the reaction for 7 h are shown in Table 1.
  • the catalysts Cat-1, Cat-2, Cat-3, Cat-4, Cat-5 and Cat-6 of the present invention have high reactivity and high p-methylethylbenzene under hydrogen-free conditions. Selectivity is significantly superior to the prior art.
  • Ethylene conversion 100% ⁇ (ethylene / methane - discharged ethylene / methane) / (ethylene / methane fed)
  • PET selectivity 100% ⁇ (the amount of PET produced / the amount of methyl ethylbenzene produced)
  • Table 1 shows the catalyst composition obtained in Examples 1 to 6 and the alkylation reaction between toluene and ethylene

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

一种选择性生成对甲基乙苯的烷基化催化剂及其制备方法。该催化剂按重量百分比的组成为：ZSM-5/ZSM-11共结晶分子筛50％～80％，粘结剂14％～41％，IV A或V A族元素氧化物2％～10％，II A或III A族元素氧化物2％～14％。催化剂的制备通过先对ZSM-5/ZSM-11共结晶分子筛进行酸处理，再将酸处理产物与粘结剂混捏、挤条成型，然后依次采用含IV A族或V A族元素化合物的溶液、含II A族或III A族元素化合物的溶液进行改性处理来实现。该催化剂在非临氢条件具有活性好、选择性高的特点，具有应用价值。

Description

一种选择性生成对甲基乙苯的烷基化催化剂及其制备方法 技术领域
本发明属于多相催化领域，具体涉及一种选择性生成对甲基乙苯的烷基化催化剂及其制备方法。
背景技术
对甲基乙苯(PET)是生产对甲基苯乙烯(PMS)、进而生产高端树脂、高性能橡胶、新型塑料及特种涂料等诸多高端专用化学品的关键原料，其下游产品在汽车、能源、化工和材料等诸多行业具有广泛应用。PMS的聚合体聚对甲基苯乙烯(PPMS)是国外近几年开发的高性能塑料品种，该聚合物与聚苯乙烯(PS)具有同样良好的成型加工性，在比重、耐热性、阻燃性、透明度和收缩率等方面则优于PS。同时，对甲基乙苯可与其它单体(如苯乙烯)共聚，提高聚合物的耐热性和阻燃性，大量用于工程塑料、醇酸树脂涂料等方面的制造，因而合成对甲基乙苯的重要性日益凸显。
甲苯与乙烯的烷基化反应可用于制备对甲基乙苯，但常规Friedel-Crafts催化剂得到的甲基乙苯是组成为热力学平衡的三个异构体(其中PET 30％左右，其余为间甲基乙苯MET和邻甲基乙苯OET)。因此，为提高PET选择性(PET在甲基乙苯中的选择性，以下同)，具有择形效应催化剂的开发至关重要。USP5698756披露了采用硅酮聚合物对ZSM-5分子筛进行多次硅沉积改性，再经碱金属离子交换，得到的催化剂在临氢条件下具有很高的PET选择性。CN201110217577.4披露了先对丝光沸石分别用碱土金属化合物、含铜化合物改性，再加入IV A族元素化合物及粘结剂挤条成型，经过干燥、焙烧得到的催化剂在临氢条件下的PET选择性可达95％以上。CN201410424434.4披露了将柠檬酸改性的氢型EU-1分子筛与氧化铝成型，干燥后再经450～600℃水蒸气处理得 到的催化剂用于甲苯与乙烯的烷基化过程，非临氢条件下的PET选择性虽然远高于热力学平衡，但低于95％。
虽然选择性生成对甲基乙苯的烷基化催化剂的研究取得了一些进展，仍不尽如人意。此外，有关分子筛催化剂的研究属实验性很强的学科领域，各种结论需基于实验数据，如果通过“由此及彼”和“举一反三”进行推理，很可能大相径庭。
发明内容
本发明针对用于甲苯与乙烯烷基化高选择性生成PET催化剂的现有技术的不足(临氢条件增加了过程复杂性、降低了经济性，非临氢反应的PET选择性有待提高)，以ZSM-5/ZSM-11共结晶分子筛为主体，综合酸处理、不同元素改性对分子筛酸性、孔结构的影响等多种因素，通过大量的研究工作，开发出一种选择性生成对甲基乙苯的烷基化催化剂及其制备方法，本发明催化剂在非临氢条件下，可高选择性生成对甲基乙苯(PET选择性＞95％，无邻甲基乙苯)。
本发明涉及一种选择性生成对甲基乙苯的烷基化催化剂及其制备方法。
一种选择性生成对甲基乙苯的烷基化催化剂，所述催化剂按重量百分比的组成为：ZSM-5/ZSM-11共结晶分子筛50％～80％，粘结剂14％～41％，IV A或V A族元素氧化物2％～10％，II A或III A族元素氧化物2％～14％。
所述ZSM-5/ZSM-11共结晶分子筛含50％～90wt.％的ZSM-5分子筛，并经过稀盐酸或稀硝酸溶液处理；所述粘结剂为氧化铝或氧化硅；所述IV A族元素氧化物为氧化硅，所述V A族元素氧化物为氧化磷；所述II A族元素氧化物为氧化镁或氧化钙，所述III A族元素氧化物为氧化硼或氧化铝。
一种选择性生成对甲基乙苯的烷基化催化剂的制备方法，包括如下步骤：
(1)采用浓度为0.1～0.3M的稀盐酸或稀硝酸溶液，对ZSM-5/ZSM-11共结 晶分子筛进行两次酸处理，固液比1∶5～10g/ml，每次处理条件为：温度60～90℃，时间1～3h；将酸处理固体产物洗涤至洗液呈中性，在100～120℃干燥8～20h，得到固体粉末a；
(2)将固体粉末a与粘结剂按照干基质量百分比为55～85％∶15～45％混合，再加入占干基总质量2～4％的田菁粉混合均匀，用与干基总质量比为0.4～0.8∶1的质量浓度为8～15％稀硝酸溶液对其进行混捏、挤条成型，然后在100～120℃干燥4～15h、530～550℃焙烧4～8h，得到成型物b；
(3)采用含IV A族元素硅化合物的溶液或含V A族元素磷化合物的溶液对成型物b进行浸渍，经过100～120℃干燥4～10h、500～530℃焙烧3～6h，得到含改性氧化硅或氧化磷的成型物c。
(4)采用含II A族元素镁或钙化合物的溶液或含III A族元素硼或铝化合物的溶液对成型物c进行浸渍，经过100～120℃干燥4～10h、500～530℃焙烧3～6h，得到最终催化剂。
所述步骤(3)中IV A族元素硅化合物的溶液为含正硅酸乙酯的环己烷溶液，V A族元素磷化合物的溶液为稀磷酸、磷酸氢铵溶液和磷酸二氢铵溶液中的任意一种；所述步骤(4)中II A族元素镁化合物的溶液为硝酸镁溶液、氯化镁溶液和醋酸镁溶液中的至少一种，II A族元素钙化合物的溶液为醋酸钙溶液或氯化钙溶液，III A族元素硼化合物的溶液为硼酸溶液，铝化合物的溶液为硝酸铝溶液。
一种选择性生成对甲基乙苯的烷基化催化剂的应用，所述催化剂用于甲苯与乙烯烷基化高选择性制备对甲乙苯过程。
本发明所述上述技术方案中催化剂的主体是经过适当酸处理的ZSM-5/ZSM-11共结晶分子筛，酸处理可以调变分子筛的酸分布，采用 ZSM-5/ZSM-11共结晶分子筛则可以利用ZSM-5和ZSM-11分子筛的协同优势，同时结合不同改性元素对分子筛成型物的酸性和织构性质的修饰作用，可使制备的催化剂在甲苯与乙烯烷基化过程中具有出色的反应活性和很高的PET选择性，能够克服现有技术的不足，具有重要应用价值。
具体实施方式
下面通过实施例对本发明做进一步说明，但本发明并不局限于所列出的实施例。
实施例1
取150g含80％ZSM-5的ZSM-5/ZSM-11共结晶分子筛，采用0.3M的稀盐酸溶液对其进行两次酸处理，固液比1/5(g/ml)，酸处理温度为75℃，时间为2h，将酸处理固体产物洗涤至洗液呈中性，在120℃干燥8h，得到固体粉末a1；取100g固体粉末a1和41.4g氧化铝，二者的干基质量百分比为75％∶25％，加入3.5g田菁粉(占干基总质量3％)混合后，再加入70g质量浓度为10％的稀硝酸溶液(与干基总质量比为0.6∶1)进行混捏、挤条成型，然后在110℃干燥8h、540℃焙烧6h，得到成型物b1；采用正硅酸乙酯的环己烷溶液对b1进行浸渍，经过100℃干燥10h、530℃焙烧3h，得到含改性氧化硅的成型物c1；采用硝酸镁溶液对c1进行浸渍，经过110℃干燥7h、500℃焙烧6h，得到含改性氧化硅和氧化镁的成品催化剂Cat-1，其组成见表1。
实施例2
取150g含50％ZSM-5的ZSM-5/ZSM-11共结晶分子筛，采用0.1M的稀硝酸溶液对其进行两次酸处理，固液比1/10(g/ml)，酸处理温度为60℃，时间为3h，将酸处理固体产物洗涤至洗液呈中性，在100℃干燥20h，得到固体粉末a2；取100g固体粉末a2和39g硅溶胶，二者的干基质量百分比为85％∶15％， 加入4.2g田菁粉(占干基总质量4％)混合后，再加入42g质量浓度为15％的稀硝酸溶液(与干基总质量比为0.4∶1)进行混捏、挤条成型，然后在100℃干燥15h、530℃焙烧8h，得到成型物b2；采用稀磷酸溶液对b2进行浸渍，经过120℃干燥4h、500℃焙烧6h，得到含改性氧化磷的成型物c2；采用醋酸钙溶液对c2进行浸渍，经过100℃干燥10h、530℃焙烧3h，得到含改性氧化磷和氧化钙的成品催化剂Cat-2，其组成见表1。
实施例3
取150g含70％ZSM-5的ZSM-5/ZSM-11共结晶分子筛，采用0.2M的稀盐酸溶液对其进行两次酸处理，固液比1/7(g/ml)，酸处理温度为80℃，时间为2h，将酸处理固体产物洗涤至洗液呈中性，在110℃干燥12h，得到固体粉末a3；取100g固体粉末a3和29.4g氧化铝，二者的干基质量百分比为80％∶20％，加入3.2g田菁粉(占干基总质量3％)混合后，再加入85g质量浓度为8％的稀硝酸溶液(与干基总质量比为0.8∶1)进行混捏、挤条成型，然后在110℃干燥8h、540℃焙烧5h，得到成型物b3；采用磷酸氢铵溶液对b3进行浸渍，经过110℃干燥6h、520℃焙烧4h，得到含改性氧化磷的成型物c3；采用硼酸溶液对c3进行浸渍，经过120℃干燥4h、530℃焙烧3h，得到含改性氧化磷和氧化硼的成品催化剂Cat-3，其组成见表1。
实施例4
取150g含90％ZSM-5的ZSM-5/ZSM-11共结晶分子筛，采用0.1M的稀盐酸溶液对其进行两次酸处理，固液比1/8(g/ml)，酸处理温度为90℃，时间为1h，将酸处理固体产物洗涤至洗液呈中性，在110℃干燥12h，得到固体粉末a4；取70g固体粉末a4和72g氧化铝，二者的干基质量百分比为55％∶45％，加入2.3g田菁粉(占干基总质量2％)混合后，再加入79g质量浓度为12％的稀硝酸溶液 (与干基总质量比为0.7∶1)进行混捏、挤条成型，然后在110℃干燥8h、540℃焙烧5h，得到成型物b4；采用磷酸二氢铵溶液对b4进行浸渍，经过110℃干燥6h、520℃焙烧4h，得到含改性氧化磷的成型物c4；采用硝酸铝溶液对c4进行浸渍，经过120℃干燥4h、530℃焙烧3h，得到含改性氧化磷和氧化铝的成品催化剂Cat-4，其组成见表1。
实施例5
取150g含70％ZSM-5的ZSM-5/ZSM-11共结晶分子筛，采用0.2M的稀盐酸溶液对其进行两次酸处理，固液比1/8(g/ml)，酸处理温度为70℃，时间为2.5h，将酸处理固体产物洗涤至洗液呈中性，在110℃干燥15h，得到固体粉末a5；取100g固体粉末a5和39g氧化铝，二者的干基质量百分比为75％∶25％，加入3.7g田菁粉(占干基总质量3.2％)混合后，再加入57.5g质量浓度为12％的稀硝酸溶液(与干基总质量比为0.5∶1)进行混捏、挤条成型，然后在120℃干燥4h、540℃焙烧6h，得到成型物b5；采用稀磷酸溶液对b5进行浸渍，经过120℃干燥4h、530℃焙烧3h，得到含改性氧化磷的成型物c5；采用氯化镁和醋酸镁溶液对c5进行浸渍，经过110℃干燥7h、530℃焙烧3h，得到含改性氧化磷和氧化镁的成品催化剂Cat-5，其组成见表1。
实施例6
取150g含60％ZSM-5的ZSM-5/ZSM-11共结晶分子筛，采用0.2M的稀硝酸溶液对其进行两次酸处理，固液比1/7(g/ml)，酸处理温度为80℃，时间为1.5h，将酸处理固体产物洗涤至洗液呈中性，在110℃干燥15h，得到固体粉末a6；取100g固体粉末a6和29g氧化铝，二者的干基质量百分比为80％∶20％，加入3.8g田菁粉(占干基总质量3.5％)混合后，再加入75.6g质量浓度为12％的稀硝酸溶液(与干基总质量比为0.7∶1)进行混捏、挤条成型，然后在110℃干燥12h、 540℃焙烧6h，得到成型物b6；采用磷酸二氢铵溶液对b6进行浸渍，经过120℃干燥4h、520℃焙烧4h，得到含改性氧化磷的成型物c6；采用氯化钙溶液对c6进行浸渍，经过110℃干燥7h、530℃焙烧3h，得到含改性氧化磷和氧化钙的成品催化剂Cat-6，其组成见表1。
实施例7
将实施例1～6所得催化剂用于甲苯与乙烯的烷基化过程。催化剂的反应性能评价在常规固定床反应装置上进行，催化剂用量5g。氮气气氛下催化剂在450℃预处理1h，然后降温至反应温度；物料上进下出，用柱塞泵向反应体系快速注入甲苯，待反应装置出口流出甲苯后，通入乙烯(用质量流量计控制所需量)进行烷基化反应。上述的乙烯原料中加入1.5wt.％的甲烷作为内标，气相和液相组分皆采用Agilent Technologies 7890B气相色谱仪进行分析，采用FID检测器，PONA色谱柱。反应条件为：压力0.5MPa，温度380℃，甲苯/乙烯(摩尔比)7，乙烯重量空速0.5h-1。反应7h的结果列于表1。从表1可见，本发明实施例催化剂Cat-1、Cat-2、Cat-3、Cat-4、Cat-5和Cat-6在不临氢条件下具有高反应活性及高对甲基乙苯选择性，比现有技术具有显著优越性。
本发明制备催化剂的性能按如下方法判断：
乙烯转化率＝100％×(进料的乙烯/甲烷-出料的乙烯/甲烷)/(进料的乙烯/甲烷)
PET选择性＝100％×(PET生成量/甲基乙苯生成量)
表1实施例1～6所得催化剂组成及甲苯与乙烯烷基化反应结果
Figure PCTCN2017000584-appb-000001

Claims (8)

  1. 一种选择性生成对甲基乙苯的烷基化催化剂，其特征在于：该催化剂按重量百分比，具有以下组成：ZSM-5/ZSM-11共结晶分子筛50％～80％，粘结剂14％～41％，IV A或V A族元素氧化物2％～10％，II A或III A族元素氧化物2％～14％。
  2. 按照权利要求1所述一种选择性生成对甲基乙苯的烷基化催化剂，其特征在于：所述ZSM-5/ZSM-11共结晶分子筛含质量百分比50％～90％的ZSM-5分子筛，并经过稀盐酸或稀硝酸溶液处理。
  3. 按照权利要求1所述一种选择性生成对甲基乙苯的烷基化催化剂，其特征在于：所述粘结剂为氧化铝或氧化硅。
  4. 按照权利要求1所述一种选择性生成对甲基乙苯的烷基化催化剂，其特征在于：所述IV A族元素氧化物为氧化硅，所述V A族元素氧化物为氧化磷；所述II A族元素氧化物为氧化镁或氧化钙，所述III A族元素氧化物为氧化硼或氧化铝。
  5. 按照权利要求1～4任意权利要求所述一种选择性生成对甲基乙苯的烷基化催化剂的制备方法，其特征在于包括以下步骤：
    (1)采用浓度为0.1～0.3M的稀盐酸或稀硝酸溶液，对ZSM-5/ZSM-11共结晶分子筛进行两次酸处理，固液比1∶5～10g/ml，每次处理条件为：温度60～90℃，时间1～3h；将酸处理固体产物洗涤至洗液呈中性，在100～120℃干燥8～20h，得到固体粉末a；
    (2)将固体粉末a与粘结剂按照干基质量百分比为55～85％∶15～45％混合，再加入占干基总质量2～4％的田菁粉混合均匀，用与干基总质量比为0.4～0.8∶1的质量浓度为8～15％稀硝酸溶液对其进行混捏、挤条成型，然后在100～120℃干燥4～15h、530～550℃焙烧4～8h，得到成型物b；
    (3)采用含IV A族元素硅化合物的溶液或含V A族元素磷化合物的溶液对成型物b进行浸渍，经过100～120℃干燥4～10h、500～530℃焙烧3～6h，得到含改性氧化硅或氧化磷的成型物c；
    (4)采用含II A族元素镁或钙化合物的溶液或含III A族元素硼或铝化合物的溶液对成型物c进行浸渍，经过100～120℃干燥4～10h、500～530℃焙烧3～6h，得到最终催化剂。
  6. 按照权利要求5所述一种选择性生成对甲基乙苯的烷基化催化剂的制备方法，其特征在于：所述步骤(3)中IV A族元素硅化合物的溶液为含正硅酸乙酯的环己烷溶液；V A族元素磷化合物的溶液为稀磷酸、磷酸氢铵溶液和磷酸二氢铵溶液中的任意一种。
  7. 按照权利要求5所述一种选择性生成对甲基乙苯的烷基化催化剂的制备方法，其特征在于：所述步骤(4)中II A族元素镁化合物的溶液为硝酸镁溶液、氯化镁溶液和醋酸镁溶液中的至少一种，II A族元素钙化合物的溶液为醋酸钙溶液或氯化钙溶液；III A族元素硼化合物的溶液为硼酸溶液，铝化合物的溶液为硝酸铝溶液。
  8. 按照权利要求1～4任意权利要求所述一种选择性生成对甲基乙苯的烷基化催化剂的应用，其特征在于：该催化剂用于甲苯与乙烯烷基化高选择性制备对甲乙苯过程。
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