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Fluid bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin

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CN101417236B
CN101417236B CN 200710176274 CN200710176274A CN101417236B CN 101417236 B CN101417236 B CN 101417236B CN 200710176274 CN200710176274 CN 200710176274 CN 200710176274 A CN200710176274 A CN 200710176274A CN 101417236 B CN101417236 B CN 101417236B
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catalyst
percent
weight
xylene
metal
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CN 200710176274
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CN101417236A (en )
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于政锡
刘中民
张新志
杨立新
王莹利
袁翠峪
许磊
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中国科学院大连化学物理研究所
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/40Ethylene production
    • Y02P30/42Ethylene production using bio-feedstock

Abstract

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.

Description

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 Methanol Toluene alkylation of p-xylene and light olefins bed catalyst

技术领域 FIELD

[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。 Wherein, toluene alkylation with methanol may be the cleavage reaction and methanol selectivity to para-xylene and a high ethylene, propylene simultaneously on the catalyst.

背景技术 Background technique

[0002] 对二甲苯和乙烯是合成聚酯(PET)的两种基本原料。 [0002] p-xylene and ethylene synthetic polyester (PET) 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, major paraxylene with toluene, C9 aromatics and mixed-xylene, disproportionation, isomerization, separation or cryogenic adsorption separation preparation. 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 thermodynamically controlled-xylene content in the product, only p-xylene in a mixed C8 aromatics is about 20%, of material in the process loop processing capacity, large equipment and 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。 In particular three isomers of xylene boiling point difference is small, usual distillation techniques can not be obtained with high purity paraxylene, we 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 obtained by refining of crude oil light oil (light naphtha and diesel oil) and liquefied petroleum gas (LPG) and natural gas processing prepared for production of ethane and propane as a raw material, mainly dependent on petroleum 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 demand for p-xylene and ethylene 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 to produce ethylene and para-xylene, wherein the toluene methylation can be produced with high selectivity for ethylene and propylene production xylene, methanol to olefins are non-oil line. 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 USP 3,965,207 discloses the use of ZSM-5 zeolite as catalyst, the reaction temperature 500_750 ° C, maximum selectivity to xylene at 600 ° C is about 90%; USP3,965,208 VA elements using a modified ZSM- 5 zeolite as catalyst, suppressing the formation of meta-xylene, mainly generated, the highest selectivity for paraxylene and ortho-xylene at 600 ° C is about 90%; USP 4,250,345 phosphorus and magnesium bis elements modified zeolite ZSM-5 catalyst, optimal selectivity to xylene at 450 ° C is about 98%; USP 4,670,616 and borosilicate molecular sieve prepared as a silica or alumina catalyst, para-xylene selectivity of formula 50-60%; USP4, 276,438,4, 278,827 special structure using molecular sieves (SiO2Al2O3 San 12) and with copper, silver, gold or germanium, tin, lead modification, obtained a high selectivity of dimethyl benzene; USP 4,444,989 pure silicalite crystal form, and arsenic, phosphorus, magnesium, boron and tellurium compound is modified to improve the selectivity for para-xylene; the USP 4,491,678 and crystalline borosilicate type IIA and IIIA elements silicon and phosphorus as well as a common component can greatly improve 对二甲苯的选择性并能提高催化剂的寿命。 Xylene selectivity and catalyst life can be improved. 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 using ZSM-5 and ZSM-Il SiO2Al2O3 San 12 as a catalyst, and calcined at above 650 ° C, can improve the selectivity to 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 using an acidic molecular sieve IVB element-containing reforming catalyst and VIB metal, can improve the selectivity to dialkylbenzene alkylation of toluene with methanol; USP6,504,072 pore molecular sieves are preferably used in ZSM-5, and above 950 ° C under a water vapor treatment, and then modifying phosphorus oxide, the catalyst made microporous diffusion effect influence on the selectivity of para-xylene; USP 6,613,708 using the organometallic compound catalyst modified, can greatly improve the selectivity of dialkyl benzenes. 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 patent discloses a technique using a methanol or dimethyl ether and other non-petroleum routes to make ethylene and propylene. 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。 Mobil Oil Company in 1976 were the conversion of methanol to hydrocarbons over ZSM-5 zeolite catalyst. 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 a process of methanol conversion to gasoline on ZSM-5 zeolite catalyst; USP4,542, 252 discloses a technique in methanol ZSM-5 molecular sieve catalyst producing light 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 use of ZSM phosphorus, magnesium, silicon, or an alkali metal element modified -5 molecular sieve catalyst taken by the reaction of methanol to light olefins; USP 5,367,100 discloses use of ZSM-5 zeolite catalyst modified with phosphorus and lanthanum Dalian Institute of chemical Physics lower taken from methanol or dimethyl ether olefins, total selectivity to ethylene, propylene and butylene can reach 85%.

[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 above patent discloses the preparation of each new route xylene and lower olefins, since the two reactions are acid catalyzed reactions are required Shape Selective Catalysis, thus using both modified HZSM-5 zeolite as the active component of the catalyst, but the desired product because of the different characteristics of the catalyst and process two very different. 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 a catalyst prepared using new technologies while meeting the requirements alkylation of toluene with methanol and p-xylene of methanol to olefins, can be achieved while the production of ethylene and para-xylene in a reaction process.

[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, alkylation of toluene with methanol and p-xylene reacted to MTO catalyst zeolite ZSM-5 fixed bed reactors are used, carbon deposition due to the reaction caused by deactivation of the catalyst, so a fixed bed reactor It 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 to provide a highly selective alkylation of toluene with methanol prepared light olefins, and para-xylene 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 alkylation of toluene with methanol to light olefins and xylene fluid bed catalyst, zeolite molecular sieve raw powder is made of metal, non-metal and / or rare earth metal-modified, and mixing a binder with a silicon or amorphous aluminum-shaped spray drying, surface acidity and pore structure then obtained by modifying a siloxane compound; wherein:

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

[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 weight of the catalyst 0. I-Swt%;

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

[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 siloxane compound loading amount of Si to the total weight of the 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 aluminosilicate or silicon aluminophosphate having a framework structure of the crystal 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 ZSM-Il zeolitic molecular sieves, preferably ZSM-5; SAP0-11 as silicon aluminophosphate molecular sieves.

[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 alkaline earth metal is Mg, Ca oxide or a soluble salt thereof; nonmetal phosphorus oxide or a phosphate; rare earth metal is lanthanum soluble salt.

[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 siloxane compound 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] wherein HR3 and R4 are alkyl groups of 1 to 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, a mixture of one or more of kaolin, clay, alumina, alumina sol, silica sol, and wherein the aluminum or silicon-containing amorphous binder.

[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-shaped 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 catalysts of the invention is the alkylation of toluene with methanol for preparing high selectivity of p-xylene and lower olefins are: a fluidized bed reactor, the reaction temperature is 350-550 ° C, preferably temperature of 400-500 ° C.

具体实施方式 detailed description

[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 crystalline structure having a framework structure type of MFI, MEL, or AEL silicon aluminophosphate or aluminosilicate as the active component, with or amorphous silicon-containing binder mixture forming aluminum , then the modified catalyst is prepared an acidic outer surface, and a bore through the silicone agent, prepared 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 raw powder, prepared by calcining acidic zeolite molecular sieve.

[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 molecular sieve impregnated metal, non-metal or a rare earth metal, 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) After reforming catalyst mixed with a binder containing silicon or amorphous aluminum spray drying and pressing, to obtain the microspheres of the 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) the use of silicone-based reagent microspheres catalyst surface modification, modulation and outer surface acidity of the catalyst pore structure to give the 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] used in the present invention, the zeolite molecular sieve or silica alumina aluminum phosphate molecular sieves, silicoaluminophosphate molecular sieves can choose ZSM-5, ZSM-Il zeolite molecular sieve; Aluminophosphate Molecular Sieves silicon SAP0-11 optional molecular sieves.

[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 a metal, a rare earth metal or non-metal oxides, soluble salts modified acidic zeolite molecular sieve, the reaction aimed at improving the performance of the MTO catalyst.

[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 prepared by the present invention characterized in that the silicone-based compound of the following 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 are alkyl groups of 1 to 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 preparation of the present invention [0031] This applies to the methanol from the reaction of toluene and xylene lower olefins, the reaction temperature in the range of 350-550 ° C, the preferred temperature range is 400-500 ° C.

[0032] 本发明的流化床催化剂的磨损指数小于2。 [0032] Attrition Index of a fluidized bed catalyst of the present invention is 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 and xylene light olefins (ethylene and propylene) may be reacted with methanol (molar ratio) to change the ratio of p-xylene and the yield of light olefins by adjusting the toluene / . 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 %。 The product selectivity to p-xylene in the 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] The present invention is described in detail below 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) at 550 ° C calcined template removal, exchanged four times in a water bath at 80 ° C with ammonium nitrate solution, after exchanging at 550 ° C in calcined for 3 hours to obtain HZSM-5 zeolite molecular sieve.

[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 metal salt of zeolite HZSM-5 zeolite was modified steps are:

[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 zeolite molecular sieve 10kg, (MgCl2 · 6H20) was immersed overnight, after drying, was calcined for 3 hours at 550 ° C, to obtain Mg-HZSM-5 zeolite molecular sieve 9% Mg;

[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 molecular sieve containing silicon or aluminum and a binder are mixed by spray drying and pressing: 40% Mg-HZSM-5 (dry basis) +20% Al2O3 (pseudoboehmite boehmite) +40% Al2O3 (alumina sol) + amount of biological glue, beating, rubber mill, defoamed shaped spray drying, the catalyst particle size distribution of 20~100 μ m, in a muffle furnace at 550 ° C was calcined for 3 hours. the catalyst Attrition index of 1.4, to obtain microspheroidal Mg-HZSM-5 catalyst stream; [0040] (3) use of the silicone agent tetraethyl silicate Mg-HZSM-5 catalyst in the fluidized bed in step 2 to give surface modification: after 5kg Mg-HZSM-5 catalyst into the fluidized 5kg tetraethylorthosilicate immersed overnight, the liquid was decanted, after drying 120 ° C, calcined at 550 ° C for 3 hours to obtain the modified 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 molecular sieve 10kg, 9% Ca (CaCl2) overnight impregnated, dried and calcined at 550 ° C 3 hours to obtain a Ca-HZSM-5 zeolite molecular sieve;

[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 molecular sieve binder mixture obtained in step 1 with a silicon or aluminum shaped spray drying: 40% Ca-HZSM-5 (dry basis) + 20% Al2O3 (pseudoboehmite boehmite) + 40% kaolin + amount of biological glue, beating, rubber mill, defoamed shaped spray drying, the catalyst particle size distribution of 20~100 μ m, in a muffle furnace at 550 ° C was calcined for 3 hours. the catalyst was an Attrition 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) Use of the silicone agent tetraethyl silicate Ca-ZSM-5 catalyst stream in step 2 was subjected to 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。 Step respectively: the card 8 Ca-HZSM-5 catalyst microsphere discharge A ^ g tetraethylorthosilicate immersed overnight, the liquid was decanted and, after drying 120 ° C, washed with the solvent, calcined at 550 ° C for 3 hours to obtain the modified Ca-HZSM-5 catalyst stream, number 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 zeolite molecular sieve 20kg, 3% P (H3PO4) was immersed overnight, after drying, was calcined for 3 hours at 550 ° C, to give P-HZSM-5 zeolite molecular sieve;

[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 molecular sieve containing silicon or aluminum and a binder are mixed spray drying molding step were: 40% P-HZSM-5 (dry basis) +20 ^ Al2O3 ( quasi boehmite) + 40% SiO2 (silica) + amount of biological glue, beating, rubber mill, defoamed shaped spray drying, the catalyst particle size distribution of 20~100 μ m, 550 ° C calcined in a muffle furnace for 3 hours , catalyst attrition index of 1.8, obtained microspheroidal 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 tetraethyl silicate silicone agent for P-ZSM-5 catalyst stream in step 2 was subjected to surface modification, the steps are: a card 8 P-HZSM-5 catalyst into the microspheres 5kg tetraethyl silicate was immersed overnight, the liquid was decanted, after drying 120 ° C, washed with the solvent, calcined at 550 ° C for 3 hours to obtain the modified P-HZSM-5 catalyst stream, 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) taking in Example 3 Step 1 Preparation of? -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; - ^ melon 511-5 101 Zeolite, 3% 1 ^ (^ 1 (and 3) 3 * 6120!) Was immersed overnight, dried, calcined at 550 ° C for 3 hours to give P-La-HZSM- 5 zeolite;

[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 silicon-aluminum mixed binder spray drying or molding step were: 40% P-La-HZSM-5 (dry basis) +20% Al2O3 (quasi boehmite) +40% SiO2 (silica) + amount of biological glue, beating, rubber mill, defoamed shaped spray drying, the catalyst particle size distribution of 20~100 μ m, in a muffle furnace at 550 ° C calcined 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) Use of the silicone agent tetraethyl silicate P-La-ZSM-5 catalyst stream in step 2 was subjected to surface modification, the steps are: a card 8 P-La-HZSM-5 discharge the ^ g tetraethylorthosilicate was immersed overnight, the liquid was decanted, after drying 120 ° C, washed with the solvent, calcined at 550 ° C for 3 hours to give P-La-HZSM-5 catalyst was fluidized modified numbered TMFC-04. [0053] 实施例5 (反应评价) [0053] Example 5 (Evaluation of Reaction)

[0054] 反应在中型循环流化床反应装置内进行。 [0054] The reaction medium-circulating fluidized bed reactor in the 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。 Reaction conditions were as follows: catalyst loading is ^ (g, reserves reactor 1. ^ (g, catalyst circulation is 0. l_5Kg / hr, the reaction temperature was 450 ° C, the regeneration gas temperature of 600 ° C, toluene feedstock: methanol (molar ratio) = 2: 1 toluene methanol WHSV of 2 hr-1 using Varian 3800 gas chromatograph, CP-WAX 52CB capillary column analysis online product distribution (after toluene was removed normalization), as shown in table 1. shown wherein the C1-C5 compositional analysis using Varian 3800 gas chromatograph, CP-PoraPLOT Q-HT capillary column, the results 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] * para-xylene selectivity in xylene isomers [0058] Table 2 [0059]

Figure CN101417236BD00072
Figure CN101417236BD00081

Claims (1)

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 and xylene fluid bed catalyst in the alkylation of toluene with methanol preparing high selectivity of p-xylene and light olefins in a fluidized bed reactor application, wherein : zeolite molecular sieve catalyst is prepared by the alkaline earth metals, rare earth metals and non-metal-modified, and then mixed with an aluminum containing silicon or amorphous binder spray drying the molding, and then the surface acidity and pore structure obtained by modifying a siloxane compound ; wherein: the total weight of the alkaline earth metal content of the catalyst is 0. I-Swt%; non-metal content of the total weight of the catalyst 0. I-Swt%; rare earth metal content of 0. l-5wt% of the total weight of the catalyst; silicone alkyl-modified compound after the loading amount of Si to the total weight of the catalyst I-IOwt%; the zeolite is MFI, MEL, or aluminosilicate having AEL or silicon aluminophosphate, crystalline framework structure type structures; aluminosilicates acid zeolite is ZSM-5 and / or zeolite ZSM-Il; silica aluminophosphate molecular sieve is SAP0-11; siloxane compound represented by the formula as follows:
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 are alkyl groups of 1 to 10 carbon atoms; the reaction temperature at the time the application is 400-500 ° C.
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