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Numero di pubblicazioneCN101417236 B
Tipo di pubblicazioneConcessione
Numero domandaCN 200710176274
Data di pubblicazione28 mar 2012
Data di registrazione24 ott 2007
Data di priorità24 ott 2007
Pubblicato anche comeCN101417236A
Numero di pubblicazione200710176274.6, CN 101417236 B, CN 101417236B, CN 200710176274, CN-B-101417236, CN101417236 B, CN101417236B, CN200710176274, CN200710176274.6
Inventori于政锡, 刘中民, 张新志, 杨立新, 王莹利, 袁翠峪, 许磊
Candidato中国科学院大连化学物理研究所
Esporta citazioneBiBTeX, EndNote, RefMan
Link esterni:  SIPO, Espacenet
Fluid bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin
CN 101417236 B
Estratto
The invention provides a catalyst used for preparing para-xylene and low-carbon olefin fluidized bed by selective methylation of toluene with methanol, which is obtained by the modification of zeolite molecular sieve by metal, nonmetal or/and rare earth metal, mixing, spraying, drying and forming of amorphous adhesive containing silicon or aluminium and the zeolite molecular sieve, and decoration of surface acidity and porous structure by siloxane-based compounds, wherein, the content of the alkaline earth metal is 0.1-8wt percent of the total weight of the catalyst, the content of the nonmetal is 0.1-8wt percent of the total weight of the catalyst, the content of the rare earth metal is 0.1-5wt percent of the total weight of the catalyst, and the loading of the Si decorated by the siloxane-based compound is 0.1-10wt percent of the total weight of the catalyst; the catalyst is used for the reaction of preparing para-xylene and low-carbon olefin fluidized bed by selective methylation of toluene with methanol; in the products, the selectivity of the para-xylene in the xylene isomers is more than 99 percent and the selectivity of the ethane and propylene in the composition C1-C5 is more than 90 percent.
Rivendicazioni(1)  tradotto da: Cinese
1. 一种甲苯甲醇烷基化制对二甲苯和低碳烯烃流化床催化剂在甲苯甲醇烷基化高选择性制取对二甲苯和低碳烯烃流化床反应中的应用,其特征在于:所述催化剂通过沸石分子筛由碱土金属、非金属和稀土金属改性,然后与含硅或铝的无定形粘结剂混合喷雾干燥成型,再经硅氧烷基化合物修饰表面酸性和孔结构得到;其中:碱土金属含量为催化剂总重量的0. I-Swt% ;非金属含量为催化剂总重量的0. I-Swt% ;稀土金属含量为催化剂总重量的0. l-5wt% ;硅氧烷基化合物修饰后Si的担载量为催化剂总重量的I-IOwt% ;沸石分子筛为具有结晶骨架结构的硅铝酸盐或硅磷铝酸盐,结构类型为MFI、MEL或AEL ;硅铝酸盐为ZSM-5或/和ZSM-Il沸石分子筛; 硅磷铝酸盐为SAP0-11分子筛; 硅氧烷基化合物如下式所示: An alkylation of toluene with methanol to light olefins paraxylene and fluid bed catalyst in toluene alkylation with methanol of high selectivity of p-xylene and the preparation of light olefins in a fluidized bed reactor application, characterized in that : the catalyst by zeolites by alkaline earth metals, non-metallic and rare earth modified, and then mixed with spray-dried molded aluminum silicon or amorphous binder, and then by a silicone-based compounds modified surface acidity and pore structure has been ; wherein: the alkaline earth metal content of the total catalyst weight 0. I-Swt%; non-metal content of the total catalyst weight 0. I-Swt%; rare earth metal content is 0. l-5wt% of the total catalyst weight; silicone alkyl-modified compound after the loading amount of Si to the total weight of the catalyst I-IOwt%; zeolite is a crystalline aluminosilicate or silica aluminophosphate, the skeleton structure is a structure type MFI, MEL or AEL; silicoaluminophosphate salt for ZSM-5 and / or ZSM-Il Zeolites; silicon aluminophosphate molecular sieves for SAP0-11; silicone-based compounds of the formula shown below:
Figure CN101417236BC00021
其中RpI^R3和R4是1-10个碳原子的烷基;应用时其反应温度为400-500°C。 Wherein RpI ^ R3 and R4 is an alkyl group of 1-10 carbon atoms; the application of the reaction temperature is 400-500 ° C.
Descrizione  tradotto da: Cinese

一种甲苯甲醇烷基化制对二甲苯和低碳烯烃流化床催化剂 One kind of alkylation of toluene with methanol paraxylene and olefins fluidized catalyst

技术领域 Art

[0001] 本发明涉及一种甲苯甲醇烷基化高选择性制对二甲苯和低碳烯烃流化床催化剂。 [0001] The present invention relates to the alkylation of toluene with methanol paraxylene and high selectivity to light olefins prepared fluid bed catalyst. 其特征在于,甲苯甲醇在该催化剂上可以同时进行烷基化反应和甲醇裂解反应高选择性生成对二甲苯和乙烯、丙烯。 Characterized in that the alkylation of toluene with methanol can be carried out the cleavage reaction and the reaction of methanol and paraxylene and high selectivity to ethylene and propylene at the same time on the catalyst.

背景技术 BACKGROUND

[0002] 对二甲苯和乙烯是合成聚酯(PET)的两种基本原料。 [0002] Synthesis of p-xylene and ethylene are polyester (PET) of two basic raw materials. 目前,对二甲苯生产主要采用甲苯、C9芳烃及混合二甲苯为原料,通过歧化、异构化、吸附分离或深冷分离而制取。 Currently, the main use for the production of toluene, xylene, C9 aromatic hydrocarbon and mixed xylene as raw material by disproportionation, isomerization, adsorption separation or cryogenic separation system. 由于其产物中的对二甲苯含量受热力学控制,对二甲苯在C8混合芳烃中只占20%左右,工艺过程中物料循环处理量大,设备庞大,操作费用高。 Because of its products in the thermodynamically controlled by the content of paraxylene, mixed xylene only in the C8 aromatics about 20%, the process of material recycling processing capacity, a large equipment, high operating costs. 特别是二甲苯三个异构体的沸点相差很小,采用通常的蒸馏技术不能得到高纯度对二甲苯,而必须采用昂贵的吸附分离工艺。 Especially the three isomers of xylene boiling point difference is small, the use of the usual distillation technology to obtain high purity paraxylene can not, and must use expensive adsorptive separation processes. 乙烯是以原油炼制而得的轻质油(石脑油和轻柴油)和液化石油气(LPG)以及天然气加工制得的乙烷和丙烷为原料进行生产,主要依赖于石油资源。 Ethylene is derived from crude oil refining light oil (naphtha and light diesel oil) and liquefied petroleum gas (LPG) and natural gas processing obtained ethane and propane as raw materials for production, mainly dependent on oil resources. 随着全球聚酯需求量的迅速增长,所需的两种基本原料对二甲苯和乙烯的需求量也逐年递增。 With the rapid growth of global demand for polyester, two basic raw materials required for paraxylene and ethylene demand is also increasing year by year.

[0003] 近年来,国内外许多专利公开了对二甲苯和乙烯生产的新途径,其中甲苯甲基化可以生产高选择性的对二甲苯,甲醇制低碳烯烃是非石油路线生产乙烯和丙烯。 [0003] In recent years, many domestic and foreign patent discloses a new way of paraxylene and ethylene production, wherein the toluene methylation can be produced with high selectivity for p-xylene, methanol to olefins are non-petroleum routes to produce ethylene and propylene. USP 3,965,207公开了使用ZSM-5分子筛做催化剂,反应温度500_750°C,在600°C对二甲苯的最高选择性约为90%;USP3,965,208使用VA元素改性ZSM-5分子筛做催化剂,抑制了间二甲苯的生成,主要生成对二甲苯和邻二甲苯,在600°C对二甲苯的最高选择性约为90%;USP 4,250,345使用磷和镁双元素改性的ZSM-5分子筛为催化剂,在450°C对二甲苯的最佳选择性约为98%;USP 4,670,616使用硼硅酸盐分子筛和氧化硅或氧化铝制备成催化剂,对二甲苯选择性式50-60% ;USP4, 276,438,4, 278,827使用特殊结构的分子筛(SiO2Al2O3彡12) 并用铜、银、金或锗、锡、铅等改性,可获得高选择性的对二烷基苯;USP 4,444,989使用结晶型的纯硅分子筛,并使砷磷、镁、硼和碲的化合物进行改性,提高了对二甲苯的选择性; USP 4,491,678使用结晶型硼硅酸盐与IIA和IIIA元素以及硅和磷为共同组分可以大大提高对二甲苯的选择性并能提高催化剂的寿命。 USP 3,965,207 discloses the use of ZSM-5 zeolite as catalyst, the reaction temperature 500_750 ° C, the highest selectivity of p-xylene at 600 ° C is about 90%; USP3,965,208 VA elements using modified ZSM- 5 zeolite catalyst and suppresses the generation of m-xylene, p-xylene and produce mainly ortho-xylene, the highest selectivity of p-xylene at 600 ° C of about 90%; USP 4,250,345 the use of phosphorus and magnesium bis elements modified ZSM-5 zeolite catalyst at 450 ° C optimum selectivity of p-xylene is about 98%; USP 4,670,616 borosilicate molecular sieves or alumina and silica to prepare a catalyst, para-xylene selectivity of formula 50-60%; USP4, 276,438,4, 278,827 the use of special structure zeolite (SiO2Al2O3 San 12) and treated with copper, silver, gold, germanium, tin, lead modification, obtained high selectivity to dialkylbenzene; USP 4,444,989 the use of pure crystalline silica molecular sieve, phosphorus and arsenic, magnesium, boron and tellurium compound is modified to improve the selectivity of p-xylene; USP 4,491,678 the use of crystalline borosilicate and IIA and IIIA elements and the common component of silicon and phosphorus can be greatly improved selectivity for p-xylene and can improve the life of the catalyst. USP 5,034,362使用SiO2Al2O3彡12的ZSM-5和ZSM-Il为催化剂,并在高于650°C的条件下进行焙烧,可以提高对二烷基苯的选择性。 USP 5,034,362 to use 12 SiO2Al2O3 San ZSM-5 and ZSM-Il as a catalyst, and firing at temperatures higher than 650 ° C conditions, can increase the selectivity to the dialkyl benzenes. USP 5,563,310使用含IVB元素的酸性分子筛并用VIB的金属进行改性催化剂,可以提高甲苯甲醇烷基化反应的对二烷基苯的选择性;USP6,504,072使用中孔分子筛优选ZSM-5,并在高于950°C的水蒸气下处理,然后以磷氧化物进行改性,提出了催化剂微孔的扩散效应对对二甲苯选择性的影响;USP 6,613,708使用有机金属化合物对催化剂进行改性,可以大大提高对二烷基苯的选择性。 USP 5,563,310 IVB element-containing acidic zeolite catalyst modification and VIB metal, can increase the selectivity of the alkylation reaction of toluene with methanol to dialkylbenzene; USP6,504,072 using mesoporous molecular sieve is preferably ZSM-5, and under the steam above 950 ° C treatment, and phosphorus oxide modified, proposed catalyst pore diffusion effect influence on the p-xylene selectivity; USP 6,613,708 Use organometallic compound catalyst modification, can greatly improve the selectivity of dialkylbenzene. 另一方面,国内外许多专利公开了利用甲醇或二甲醚等非石油路线制取乙烯和丙烯的技术。 On the other hand, many domestic and foreign patents disclose the use of methanol or dimethyl ether and other non-oil route preparation of ethylene and propylene technologies. 1976年Mobil Oil公司进行了甲醇在ZSM-5分子筛催化剂上转化为碳氢化合物的反应。 1976 Mobil Oil companies methanol on ZSM-5 zeolite catalysts for hydrocarbon conversion reactions. USP4,035,430中公开了甲醇在ZSM-5分子筛催化剂上转化汽油的过程;USP4,542, 252中公开了甲醇在ZSM-5分子筛催化剂上制取低碳烯烃的技术;USP 3,911,041,USP 4,049,573,USP 4,100,219,JP 60-126233,JP 61-97231,JP 62-70324 and EP 6501中公开了使用磷、镁、硅或碱金属元素改性的ZSM-5分子筛催化剂由甲醇制取低碳烯烃的反应;USP 5,367,100中公开了大连化学物理研究所使用磷和镧改性的ZSM-5分子筛催化剂由甲醇或二甲醚制取低碳烯烃的反应,其乙烯、丙烯和丁烯的总选择性可达到85%左右。 USP4,035,430 discloses the conversion of methanol gasoline on ZSM-5 zeolite catalyst process; USP4,542, 252 discloses a methanol on ZSM-5 zeolite catalyst technology to olefins; USP 3,911, 041, USP 4,049,573, USP 4,100,219, JP 60-126233, JP 61-97231, JP 62-70324 and EP 6501 discloses the use of phosphorus, magnesium, silicon, or an alkali metal element-modified ZSM -5 molecular sieve catalyst preparation reaction from methanol to light olefins; USP 5,367,100 discloses a ZSM-5 zeolite catalysts Dalian Institute of Chemical Physics, phosphorus and lanthanum modified by methanol or dimethyl ether preparation of low-carbon reaction of the olefin, the total selectivity to ethylene, propylene and butene is about 85% can be achieved.

[0004] 上述专利分别公开了制备对二甲苯和低碳烯烃的新途径,由于两个反应过程均为酸催化反应,均要求择形催化作用,因此均使用了改性HZSM-5分子筛做为催化剂的活性组分,但是由于目的产物不同,两个过程的催化剂的特点又存在很大的差异。 [0004] The patent discloses the preparation of each new ways of xylene and light olefins, since the two reactions are acid-catalyzed reactions require shape-selective catalysis, and therefore use the modified HZSM-5 zeolite as the active component of the catalyst, the desired product, but because of the different characteristics of the two processes and catalyst there is a big difference. 如果采用新技术制备一种催化剂同时满足甲苯甲醇烷基化制对二甲苯和甲醇制烯烃的要求,就可以实现在一个反应过程中同时生产对二甲苯和乙烯。 If using a catalyst of new technology while meeting the alkylation of toluene with methanol and methanol to olefins paraxylene requirements can be achieved in a reaction process while the production of paraxylene and ethylene.

[0005] 另一方面,甲苯甲醇烷基化制对二甲苯和以ZSM-5分子筛为催化剂的甲醇制低碳烯烃反应均采用固定床反应,由于反应积炭造成催化剂失活,因此固定床反应必须频繁切换再生,操作复杂。 [0005] On the other hand, methanol alkylation of toluene to p-xylene and methanol to olefins reaction with ZSM-5 zeolite catalyst is a fixed bed reactor are used, since the deactivation of the catalyst caused by coke deposition reaction, thus fixed bed reactor must be regenerated frequently switched, complex operation.

发明内容 SUMMARY

[0006] 本发明的目的在于提供一种甲苯甲醇烷基化高选择性制对二甲苯和低碳烯烃流化床催化剂。 [0006] The object of the present invention is the alkylation of toluene with methanol to provide a system of paraxylene and high selectivity to light olefins fluid bed catalyst.

[0007] 为实现上述目的,本发明提供的甲苯甲醇烷基化制对二甲苯和低碳烯烃流化床催化剂,是将沸石分子筛原粉由金属、非金属或/和稀土金属改性,然后与含硅或铝的无定形粘结剂混合喷雾干燥成型,再经硅氧烷基化合物修饰表面酸性和孔结构得到;其中: [0007] To achieve the above object, the present invention provides a methanol toluene alkylation of xylenes and olefins to a fluid bed catalyst, zeolite molecular sieve powder is a metal, non-metal and / or rare earth metal-modified, and mixed with amorphous silicon or aluminum adhesive spray drying molding, and then modified silicone-based compounds obtained surface acidity and pore structure; wherein:

[0008] 碱土金属含量为催化剂总重量的0. l-8wt% ; [0008] an alkaline earth metal content of 0. l-8wt% of the total catalyst weight;

[0009] 非金属含量为催化剂总重量的0. I-Swt% ; [0009] The non-metal content of the total catalyst weight 0. I-Swt%;

[0010] 稀土金属含量为催化剂总重量的0. l-5wt% ; [0010] the content of the rare earth metal is 0. l-5wt% of the total catalyst weight;

[0011] 硅氧烷基化合物修饰后Si的担载量为催化剂总重量的I-IOwt %。 [0011] After the modified silicone compound in the supported amount of Si by weight of the total catalyst I-IOwt%.

[0012] 所述的催化剂,其中沸石分子筛为具有结晶骨架结构的硅铝酸盐或硅磷铝酸盐, 结构类型为MFI、MEL或AEL。 [0012] The catalyst, wherein the zeolite is an aluminosilicate zeolite or silicon aluminophosphate having a crystalline framework structure, the structure type MFI, MEL or AEL.

[0013] 所述的催化剂,其中硅铝酸盐为ZSM-5或/和ZSM-Il沸石分子筛,优选ZSM-5 ;硅磷铝酸盐为SAP0-11分子筛。 [0013] The catalyst, wherein the aluminosilicate is ZSM-5 and / or zeolite ZSM-Il, preferably ZSM-5; silica aluminophosphate molecular sieve as SAP0-11.

[0014] 所述的催化剂,其中金属为碱土金属Mg、Ca氧化物或其可溶性盐;非金属为磷氧化物或磷酸;稀土金属为镧的可溶性盐。 [0014] The catalyst, wherein the metal is an alkaline earth metals Mg, Ca oxide or a soluble salt thereof; a non-metallic phosphorus or phosphoric oxide; rare earth metal is lanthanum soluble salts thereof.

[0015] 所述的催化剂,其中硅氧烷基化合物如下式所示: [0015] The catalyst, wherein the silicone-based compounds shown in the following formula:

[0016] [0016]

Figure CN101417236BD00041

[0017] 其中HR3和R4是1-10个碳原子的烷基。 [0017] where HR3 and R4 are alkyl groups of 1-10 carbon atoms.

[0018] 所述的催化剂,其中含硅或铝的无定形粘结剂为高岭土、粘土、氧化铝、铝溶胶、氧化硅和硅溶胶的一种或几种的混合物。 [0018] The catalyst, the amorphous silicon or aluminum wherein the binder is kaolin, clay, alumina, alumina sol, silica sol, and mixtures of one or more.

[0019] 所述的催化剂,其中催化剂为喷雾成型的微球形催化剂。 [0019] The catalyst, wherein the catalyst is spray-forming micro-spherical catalyst. [0020] 本发明的催化剂用于在甲苯甲醇烷基化高选择性制取对二甲苯和低碳烯烃反应中:于流化床反应器中,其反应温度为350-550°C,较佳的温度为400-500°C。 [0020] The catalyst of the present invention is used for the alkylation of toluene with methanol in the preparation of high selectivity of p-xylene and the reaction of light olefins: in a fluidized bed reactor, the reaction temperature is 350-550 ° C, preferably temperature of 400-500 ° C.

具体实施方式 Specific embodiments

[0021] 本发明的催化剂是以具有结晶骨架结构的结构类型为MFI、MEL或AEL硅铝酸盐或硅磷铝酸盐为活性组分,与含硅或铝的无定形粘结剂混合成型,再通过硅氧烷试剂对其外表面酸性及孔道进行修饰制备成催化剂,其制备过程如下: [0021] The catalyst of the present invention is a structure type having a crystal framework structure of MFI, MEL, or AEL aluminosilicates or silica aluminophosphate as the active component, the molding mixture of the binder and the amorphous silicon or aluminum, , then the modified catalyst is prepared by an acidic outer surface, the silicone agents and the pore, and its preparation process is as follows:

[0022] 1)将沸石分子筛原粉经交换、焙烧制备成酸性沸石分子筛。 [0022] 1) The exchange of zeolite molecular sieve powder, baking preparation acidic zeolites.

[0023] 2)将酸性沸石分子筛浸渍金属、非金属或稀土金属,得到改性催化剂。 [0023] 2) an acidic zeolite impregnated metal, non-metal, or rare earth metals, to obtain a modified catalyst.

[0024] 3)将改性催化剂与含硅或铝的无定形粘结剂混合后喷雾干燥成型,得到微球催化剂。 [0024] 3) amorphous binder are mixed with a reforming catalyst containing silicon or aluminum formed after spray drying to obtain microspheres catalyst.

[0025] 4)使用硅氧烷基试剂对微球催化剂进行表面修饰,调变催化剂外表面酸性和孔结构,得到流化催化剂。 [0025] 4) Use a silicone-based reagents for microsphere catalyst surface modification, modulation outer surface of the catalyst acidity and pore structure to obtain a fluidized catalyst.

[0026] 本发明所用的沸石分子筛为硅铝分子筛或硅磷铝分子筛,硅铝分子筛可选用ZSM-5,ZSM-Il沸石分子筛;硅磷铝系列分子筛可选用SAP0-11分子筛。 [0026] As used herein aluminosilicate zeolite molecular sieve sieve sieve or silicon aluminum phosphate, silica zeolite can be used ZSM-5, ZSM-Il Zeolites; aluminum silicon phosphorus series zeolite molecular sieve can be used SAP0-11.

[0027] 本发明的催化剂,经过金属、非金属或稀土金属的氧化物、可溶性盐对酸性沸石分子筛进行改性,目的在于提高催化剂甲醇制低碳烯烃的反应性能。 [0027] The catalyst of the present invention, after the metal and non-metal or a rare earth oxide, a soluble salt of an acidic zeolite modified, aimed at improving the performance of the catalyst the reaction of methanol to light olefins.

[0028] 本发明制备的催化剂特征在于硅氧烷基化合物如下通式所示: [0028] The catalyst of the present invention is characterized in that the preparation of siloxane-based compound of the general formula:

[0029] [0029]

Figure CN101417236BD00051

[0030] 其中R1、&、R3和R4是1-10个碳原子的烷基。 [0030] wherein R1, &, R3 and R4 is an alkyl group of 1-10 carbon atoms.

[0031] 本发明制备的催化剂应用于甲苯甲醇反应制取对二甲苯和低碳烯烃反应,其反应温度范围为350-550°C,较佳的温度范围为400-500°C。 The catalyst prepared by the method [0031] The reaction of toluene with methanol is applied to the preparation of p-xylene and the reaction of olefins, the reaction temperature is in the range of 350-550 ° C, the preferred temperature range of 400-500 ° C.

[0032] 本发明的流化床催化剂的磨损指数小于2。 [0032] The fluid bed catalyst of the present invention, the wear index of less than 2.

[0033] 本发明的催化剂应用于甲苯甲醇反应制取对二甲苯和低碳烯烃(乙烯和丙烯)反应,可以通过调节甲苯/甲醇(摩尔比)比例改变对二甲苯及低碳烯烃的产率。 [0033] The catalyst of the present invention is applied to the methanol from the reaction of toluene to xylene and lower olefins (ethylene and propylene) reaction, by adjusting the toluene / methanol (molar ratio) to change the ratio of p-xylene and the yield of light olefins . 产物中对二甲苯在二甲苯异构体中的选择性大于99 %,乙烯和丙烯在C1-C5组分中选择性大于90 %。 Product selectivity for p-xylene in xylene isomers is greater than 99%, of ethylene and propylene selectivity of C1-C5 component is greater than 90%.

[0034] 下面通过实施例详述本发明。 [0034] Hereinafter, the present invention is described in detail by way of examples.

[0035] 实施例1 (制备Mg-HZSM-5流化催化剂) [0035] Example 1 (Preparation of Mg-HZSM-5 catalyst flow)

[0036] 将ZSM-5沸石分子筛原粉(Si02/Al203 = 61)在550°C下焙烧去除模板剂,在80°C 水浴中用硝酸铵溶液进行交换4次,交换后在550°C下焙烧3小时,得到HZSM-5沸石分子筛。 [0036] The ZSM-5 zeolite molecular sieve powder (Si02 / Al203 = 61) was calcined at 550 ° C to remove the template agent, a water bath at 80 ° C with ammonium nitrate solution was exchanged four times at 550 ° C after the exchange of at calcined for 3 hours to obtain HZSM-5 zeolite.

[0037] 使用金属盐对HZSM-5沸石分子筛进行改性,步骤分别为: [0037] The use of salt on HZSM-5 zeolites modified, the steps are as follows:

[0038] (l)HZSM-5 沸石分子筛10kg,9% Mg(MgCl2 · 6H20)浸渍过夜,烘干后,在550°C下焙烧3小时,得到Mg-HZSM-5沸石分子筛; [0038] (l) HZSM-5 zeolites 10kg, 9% Mg (MgCl2 · 6H20) dipping overnight, after drying, calcination 3 hours at 550 ° C, the obtained Mg-HZSM-5 zeolites;

[0039] (2)将步骤1得到的Mg-HZSM-5沸石分子筛与含硅或铝粘结剂混合进行喷雾干燥成型:40 % Mg-HZSM-5 (干基)+20 % Al2O3 (拟薄水铝石)+40 % Al2O3 (铝溶胶)+适量生物胶,打浆、胶磨、去泡,喷雾干燥成型,催化剂粒径分布20〜100 μ m,在马福炉中550°C焙烧3小时,催化剂磨损指数为1. 4,得到微球形的Mg-HZSM-5流化催化剂; [0040] (3)使用硅氧烷试剂硅酸四乙酯对步骤2得到的Mg-HZSM-5流化床催化剂进行表面修饰:5kg Mg-HZSM-5流化催化剂放入5kg硅酸四乙酯中浸渍过夜,倾出液体后,在120°C 烘干后,在550°C焙烧3小时,得到修饰后Mg-HZSM-5流化催化剂,编号为TMFC-Ol。 [0039] (2) obtained in the step 1 Mg-HZSM-5 zeolite containing silicon or aluminum with a binder formed by spray drying: 40% Mg-HZSM-5 (dry basis) +20% Al2O3 (pseudoboehmite boehmite) +40% Al2O3 (alumina sol) + appropriate amount of biological glue, beating, plastic mill, to bubble, spray drying and forming the catalyst particle size distribution 20~100 μ m, in a muffle furnace at 550 ° C calcined three hours, the catalyst Attrition Index of 1.4, a slightly spherical Mg-HZSM-5 catalyst stream; [0040] (3) the use of silicone reagents tetraethylorthosilicate obtained in step 2 Mg-HZSM-5 fluid bed catalysts surface modification: after 5kg Mg-HZSM-5 catalyst into the fluidized tetraethylorthosilicate 5kg immersed overnight, the liquid was decanted, 120 ° C, after drying, calcination at 550 ° C for 3 hours, after modification Mg -HZSM-5 fluidized catalyst, numbered TMFC-Ol. [0041 ] 实施例2 (制备Ca-HZSM-5流化催化剂) [0041] Example 2 (Preparation of Ca-HZSM-5 catalyst flow)

[0042] (l)HZSM-5沸石分子筛10kg,9% Ca(CaCl2)浸渍过夜,烘干后,在550°C下焙烧3 小时,得到Ca-HZSM-5沸石分子筛; [0042] (l) HZSM-5 zeolite 10kg, 9% Ca (CaCl2) was immersed overnight, after drying, calcination at 550 ° C for 3 hours to obtain a Ca-HZSM-5 zeolite;

[0043] (2)将步骤1得到的Ca-HZSM-5沸石分子筛与含硅或铝粘结剂混合进行喷雾干燥成型:40% Ca-HZSM-5 (干基)+20% Al2O3 (拟薄水铝石)+40%高岭土+适量生物胶,打浆、 胶磨、去泡,喷雾干燥成型,催化剂粒径分布20〜100 μ m,在马福炉中550°C焙烧3小时,催化剂磨损指数为1. 2,得到微球形Ca-HZSM-5流化催化剂; [0043] (2) The Ca-HZSM-5 zeolite containing silicon or a binder obtained in Step 1 was spray-dried with forming of aluminum: 40% Ca-HZSM-5 (dry basis) + 20% Al2O3 (pseudoboehmite boehmite) + 40% kaolin + right amount of biological glue, beating, plastic mill, to bubble, spray drying and forming the catalyst particle size distribution 20~100 μ m, in a muffle furnace at 550 ° C calcined three hours, the catalyst for an abrasion index 2, to obtain microspheroidal Ca-HZSM-5 catalyst stream;

[0044] (3)使用硅氧烷试剂硅酸四乙酯对步骤2得到的Ca-ZSM-5流化催化剂进行表面修饰。 [0044] (3) the use of silicone reagents tetraethylorthosilicate Ca-ZSM-5 catalyst stream obtained in step 2 for surface modification. 步骤分别为:将证8 Ca-HZSM-5微球催化剂放A^g硅酸四乙酯中浸渍过夜,倾出液体后,在120°C烘干后,使用溶剂洗涤,在550°C焙烧3小时,得到修饰后Ca-HZSM-5流化催化剂,编号为TMFC-02。 Steps are as follows: the card 8 Ca-HZSM-5 catalyst microspheres put A ^ g tetraethylorthosilicate immersed overnight, pour out the liquid after drying at 120 ° C after using cleaning solvent, at 550 ° C calcined 3 hours, obtained after modification Ca-HZSM-5 catalyst is fluidized, numbered TMFC-02.

[0045] 实施例3 (制备P-HZSM-5流化催化剂) [0045] Example 3 (Preparation of P-HZSM-5 catalyst flow)

[0046] (l)HZSM-5沸石分子筛20kg,3% P(H3PO4)浸渍过夜,烘干后,在550°C下焙烧3小时,得到P-HZSM-5沸石分子筛; [0046] (l) HZSM-5 zeolites 20kg, 3% P (H3PO4) dipping overnight, after drying, calcination 3 hours at 550 ° C, the obtained P-HZSM-5 zeolites;

[0047] (2)将^g P-HZSM-5沸石分子筛与含硅或铝粘结剂混合进行喷雾干燥成型,步骤分别为:40% P-HZSM-5(干基)+20 ^Al2O3 (拟薄水铝石)+40% SiO2 (硅溶胶)+适量生物胶,打浆、胶磨、去泡,喷雾干燥成型,催化剂粒径分布20〜100 μ m,在马福炉中550°C焙烧3小时,催化剂磨损指数为1. 8,得到微球形的P-HZSM-5流化催化剂; [0047] (2) ^ g P-HZSM-5 zeolite containing silicon or aluminum with a binder by spray drying and forming step were: 40% P-HZSM-5 (dry basis) +20 ^ Al2O3 ( Quasi-boehmite) + 40% SiO2 (silica) + the right amount of biological glue, beating, plastic mill, to bubble, spray drying and forming the catalyst particle size distribution 20~100 μ m, in a muffle furnace 550 ° C calcined three hours , catalyst attrition index of 1.8, to give a slightly spherical P-HZSM-5 catalyst stream;

[0048] (3)使用硅氧烷试剂硅酸四乙酯对步骤2得到的P-ZSM-5流化催化剂进行表面修饰,步骤分别为:将证8 P-HZSM-5微球催化剂放入5kg硅酸四乙酯中浸渍过夜,倾出液体后,在120°C烘干后,使用溶剂洗涤,在550°C焙烧3小时,得到修饰后P-HZSM-5流化催化剂,编号为TMFC-03。 [0048] (3) the use of silicone reagents tetraethylorthosilicate stream P-ZSM-5 catalyst in step 2 was subjected to surface modification steps were as follows: the card 8 P-HZSM-5 catalyst into the microspheres 5kg tetraethylorthosilicate immersed overnight, after the liquid was decanted, 120 ° C after drying, washing with a solvent, calcined at 550 ° C for 3 hours, after the modified P-HZSM-5 catalyst is fluidized, numbered TMFC -03.

[0049] 实施例4 (制备P-La-HZSM-5流化催化剂) [0049] Example 4 (Preparation of P-La-HZSM-5 catalyst flow)

[0050] (1)取实施例3中步骤1制备的? [0050] (1) take the Example 3 prepared in Example 1 step? -瓜511-5沸石分子筛101^,3%1^(1^(而3)3*6!120) 浸渍过夜,烘干后,在550°C下焙烧3小时,得到P-La-HZSM-5沸石分子筛; - Zeolite melon 511-5 101 ^ 1 ^ 3% (1 ^ (and 3) 3 * 6 120!) Impregnated overnight, dried at 550 ° C and calcined for 3 hours to give P-La-HZSM- 5 zeolite molecular sieve;

[0051] (2)将P-La-HZSM-5分子筛与含硅或铝粘结剂混合进行喷雾干燥成型,步骤分别为:40 % P-La-HZSM-5 (干基)+20 % Al2O3 (拟薄水铝石)+40 % SiO2 (硅溶胶)+适量生物胶, 打浆、胶磨、去泡,喷雾干燥成型,催化剂粒径分布20〜100 μ m,在马福炉中550°C焙烧3小时,催化剂磨损指数为1. 7,得到P-La-HZSM-5流化催化剂; [0051] (2) The P-La-HZSM-5 zeolite with a binder containing silicon or aluminum forming the spray drying step were: 40% P-La-HZSM-5 (dry basis) +20% Al2O3 (to be boehmite) +40% SiO2 (silica) + appropriate amount of biological glue, beating, plastic mill, to bubble, spray drying and forming the catalyst particle size distribution 20~100 μ m, in a muffle furnace at 550 ° C firing 3 hours, catalyst attrition index of 1.7, to give P-La-HZSM-5 catalyst stream;

[0052] (3)使用硅氧烷试剂硅酸四乙酯对步骤2得到的P-La-ZSM-5流化催化剂进行表面修饰,步骤分别为:将证8 P-La-HZSM-5放入^g硅酸四乙酯中浸渍过夜,倾出液体后,在120°C烘干后,使用溶剂洗涤,在550°C焙烧3小时,得到修饰后P-La-HZSM-5流化催化剂,编号为TMFC-04。 [0052] (3) the use of silicone reagents tetraethylorthosilicate P-La-ZSM-5 catalyst stream obtained in step 2 was subjected to surface modification, the steps are as follows: the card 8 P-La-HZSM-5 release the ^ g tetraethylorthosilicate was immersed overnight, after the liquid was decanted, 120 ° C after drying, washing with a solvent, calcined at 550 ° C for 3 hours, after the modified P-La-HZSM-5 catalyst stream numbered TMFC-04. [0053] 实施例5 (反应评价) [0053] Example 5 (Reaction Evaluation)

[0054] 反应在中型循环流化床反应装置内进行。 [0054] The reaction medium in the circulating fluidized bed reactor apparatus. 反应条件如下:催化剂装填量为^(g,反应器藏量为1. ^(g,催化剂循环量为0. l_5Kg/hr,反应温度为450°C,再生气温度600°C,原料甲苯:甲醇(摩尔比)=2 : 1,甲苯甲醇重量空速为2小时-1。采用Varian 3800气相色谱,CP-WAX 52CB毛细管色谱柱在线分析产物分布(去除甲苯后归一化),如表1所示。 其中C1-C5组成分析采用Varian 3800气相色谱,CP-PoraPLOT Q-HT毛细管色谱柱,结果如表2所示。 The reaction conditions were as follows: Catalyst loading amount of ^ (g, a reactor volume of reservoir 1. ^ (g, catalyst circulation is 0. l_5Kg / hr, the reaction temperature was 450 ° C, the regeneration gas temperature 600 ° C, a raw material of toluene: methanol (molar ratio) = 2: 1, methanol, toluene and WHSV of 2 hr-1 using Varian 3800 gas chromatography, CP-WAX 52CB capillary column analysis of the product distribution line (after removal of the toluene normalization), as shown in Table 1. shown wherein the C1-C5 Composition analysis using Varian 3800 gas chromatograph, CP-PoraPLOT Q-HT capillary column and the results are shown in Table 2.

[0055] 表1 [0055] Table 1

[0056] [0056]

Figure CN101417236BD00071

[0057] *对二甲苯在二甲苯异构体中的选择性[0058] 表2 [0059] [0057] * p-xylene selectivity in xylene isomers [0058] Table 2 [0059]

Figure CN101417236BD00072
Figure CN101417236BD00081
Citazioni di brevetti
Brevetto citato Data di registrazione Data di pubblicazione Candidato Titolo
CN1110628A18 apr 199425 ott 1995大连理工大学Preparation of silicon/magnesium-mixed rear-earth modified catalyzer and its appliance
CN1721378A14 lug 200418 gen 2006中国科学院大连化学物理研究所Process for combined preparation of p-xylene and low carbon olefin by methylation of toluene
US536710029 apr 199322 nov 1994Dalian Institute Of Chemical PhysicsDehydration of methanol or dimethyl ether with zeolite catalyst
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Riferimento
1曹德安.甲苯甲醇烷基化制对二甲苯技术研究进展.化学反应工程与工艺.2007,23(4),359-364.
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