TW200824790A

TW200824790A - Bound phosphorus-modified zeolite catalyst, method of preparing and method of using thereof

Info

Publication number: TW200824790A
Application number: TW095146508A
Authority: TW
Inventors: Ashim Kumar Ghosh; Pamela Harvey; Neeta Kulkarni
Original assignee: Saudi Basic Ind Corp
Priority date: 2006-12-12
Filing date: 2006-12-12
Publication date: 2008-06-16

Abstract

Disclosed is a bound phosphorus-modified zeolite catalyst. Zeolite is treated with a phosphorus compound to form the phosphorus-treated zeolite. Binder material is treated with a mineral acid prior to being bound with the phosphorus-modified zeolite. The binder material includes inorganic oxide materials, such as alumina, clay, aluminum phosphate and silica-alumina, in particular, a binder of alumina or clay or their combinations. The mineral acid includes hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid. The phosphorus-treated zeolite is combined with the acid-treated inorganic oxide binder material to form a zeolite-binder mixture. Water is added to form an extrudable paste which maybe shaped and is heated to a temperature of about 400 DEG C or higher to form a bound phosphorus-modified zeolite catalyst. For aromatic alkylation, the bound phosphorus-modified zeolite catalyst is contacted with an aromatic alkylation feed of an aromatic compound and an alkylating agent under reaction conditions suitable for aromatic alkylation.

Description

200824790 九、發明說明：【發明所屬之技術領域】本發明大體上係關於该芳族化合物之烷化反應及此反應所使用之觸媒及其製備。【先前技術】 1940年之前，幾乎包括二甲苯之所有芳族溶劑係皆由煤製造。此後，二曱苯開始由石油製備。大部分混合二曱笨一般係經由精煉廠催化重組富含芳族蒸氣之石油而製造。其亦可自諸如該碳氫化合物裂解期間製造烯烴之副產物、輕油裂解之副產物等汽油裂解所獲得。二曱苯亦可自甲苯之歧化反應或烧化反應所獲得。甲苯歧化反應（TDP) 係為一種甲苯催化反應以製造二甲苯及苯。如下所示，曱苯曱基化（TM)係為一種甲醇與甲苯之催化反應以製造二甲苯：200824790 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention generally relates to the alkylation reaction of the aromatic compound and the catalyst used in the reaction and its preparation. [Prior Art] Prior to 1940, all aromatic solvent systems including almost xylene were made of coal. Thereafter, the diphenylbenzene was initially prepared from petroleum. Most of the mixed bismuth is generally produced by refining the oil rich in aromatic vapors through a refinery. It can also be obtained from gasoline cracking such as the manufacture of by-products of olefins during the cracking of hydrocarbons, by-products of light oil cracking. Diphenylbenzene can also be obtained from the disproportionation reaction or the burning reaction of toluene. The toluene disproportionation reaction (TDP) is a toluene-catalyzed reaction to produce xylene and benzene. As shown below, hydrazinylation (TM) is a catalytic reaction of methanol with toluene to produce xylene:

所有這些方法一般都會製造出〆異構物之混合物。該間_二甲苯(m-二甲笨）、鄰-二甲苯(〇-;甲苯)及對-二甲苯 (p-二甲苯）等該二曱苯異構物係為重要之化學中間產物。〇-二甲苯係被氧化以製造酞酸酐，酞酸酐尤其係用於製造 200824790 酞酸酯增塑劑。二曱苯係被氧化以製造異酞酸，其係使用於未飽和聚赌樹脂(UPR)。然而，三種異構物中以p-二甲苯最有市場需求。該p-二曱苯最大用途係在於將其氧化以製造對酞酸。對酞酸轉而用於製造諸如聚乙烯對酞酸醋 (PET)及聚丁醯對酞酸酯（PBT)等聚合物。PET為世界上該最大體積聚合物之一種。對於p-二甲苯本身需求大於m-All of these methods generally produce a mixture of oxime isomers. The diterpenoid isomers such as m-xylene (m-dimethyl phenyl), o-xylene (〇-; toluene) and p-xylene (p-xylene) are important chemical intermediates. The hydrazine-xylene system is oxidized to produce phthalic anhydride, which is especially useful in the manufacture of the 200824790 phthalate plasticizer. The diterpene benzene is oxidized to produce isononanoic acid, which is used in unsaturated polygambling resins (UPR). However, p-xylene is the most commercially available in the three isomers. The greatest use of this p-diphenylene is to oxidize it to produce phthalic acid. The tannic acid is instead used to make polymers such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). PET is one of the largest volume polymers in the world. For p-xylene itself, the demand is greater than m-

及〇-二甲苯之數倍。商業上製造p-二甲苯係以結晶及吸附法自混合的二甲苯純化。〇_、m-、及p-二甲苯於5〇〇°c之熱力平衡組成物各約為25、50及25%。催化法諸如TDP及TM於混合的二, 苯(MX)中約可提供25%之p-二甲苯。然而，假若ι 觸媒具有形狀選擇特性其係可提供明顯大於25%之ρχ。一般而言，一形狀選擇觸媒可提供ΜΧ中大於85%之ρχ。沸石為經鋁取代之si〇4四面體單元相互連接所組鐵之^曰』體’⑽結晶架構中形成相異環狀及框架構造。該漭石之物縣構係為富有多孔性㈣有大量㈣及外部 t積*“銘^取代產生—電荷不平衡，其係必須經由補充抗衡離子對抗，例如質子。禅列及電子效應’沸石可為形狀選擇性觸某二產物、反應物或轉變狀態不能於孔洞中姐由轉為分子直徑之大小或形^ 擇反應可發生”^。_t ㈣ a 係可被改質以進行所欲產物之敎$觸之衣備其經改質之沸石觸媒已二成。，、糸已$用於方族之烷化，特別是甲 200824790 苯之甲基化以成為二曱苯，尤其是P-二曱苯。And several times the 〇-xylene. Commercially produced p-xylene is purified from the mixed xylene by crystallization and adsorption. The thermodynamic equilibrium compositions of 〇_, m-, and p-xylene at 5 ° C are each about 25, 50, and 25%. Catalytic processes such as TDP and TM provide about 25% p-xylene in the mixed di-benzene (MX). However, if the i-catalyst has a shape-selective property, it can provide a significant greater than 25% ρχ. In general, a shape-selective catalyst provides greater than 85% of the χ in the crucible. The zeolite is a ring-shaped and frame-like structure formed by the aluminum-substituted si〇4 tetrahedral unit interconnected with the iron group (10). The meteorite county structure is porous (4) with a large number (four) and external t product * "Ming ^ substitution generated - charge imbalance, its system must be countered by complementary counter ions, such as protons. Zen column and electronic effect 'zeolite The shape can be selectively touched to a certain two products, the reactants or the transition state cannot be changed in the pores to the size of the molecular diameter or the shape reaction can occur. _t (iv) a can be modified to carry out the desired product. The modified zeolite catalyst is already 20%. , 糸 has been used for the alkylation of the family, especially A 200824790 methylation of benzene to become diphenyl, especially P-diphenyl.

美國專利案第6,504,072號係揭示一種磷改質之沸石，其係使用於該甲苯選擇性甲基化以成為P-二甲苯。該經P-改質之沸石觸媒係可含有活性及非活性物質，例如黏土、二氧化矽及/或金屬氧化物，例如以礬土作為一黏著劑。其係並無揭示該黏著劑之改質或處理，且亦無揭示該黏著劑於對-二曱苯選擇性上改質或處理之效果。其他先前技術係揭示其他方法中所使用於沸石觸媒之該黏著劑材料改質或處理。美國專利案第5,907,073號係揭示一種芳族烷化之方法，其使用具有一 ZSM-12結晶結構共生經改質沸石召之分子篩子觸媒。在合成期間，NH4-/3及LaNHU-β係以經礬土處理之硝酸研磨、擠壓及煅燒，將NH4-/3及LaNH4-/5 分別轉換成Η-万觸媒及LaH_/5觸媒。完成之觸媒係用於將苯乙基化以形成乙苯。其係未揭示該黏著劑之改質或處理可具有一選擇性效果。美國專利案第5,380,690號係揭示一種用於輕鏈烯烴製造之觸媒，其係為一種黏土、無機氧化物及沸石之混合 200824790 物弗石之製備係經由混合該無機氧化物之前驅物（例如銘=膠、_水銘石（pseud()_b()hemite)、二氧切溶膠或/、此5物）及二氧化矽_礬土溶膠或含黏土之凝膠，以去陽離：水膠溶而製成一漿體，進一步均勻混合，使用例如氫氯酸、硝酸、磷酸或硫酸之無機酸調整並保持該漿體pH 值為2-4，靜態熟化後，添加一預計量之沸石，均質化、喷務乾燥、清洗以分離鈉離子並乾燥之。其係未揭示該調整並保持含該黏著劑前驅物之該漿體pH值係具有一選擇性之效果。美國專利案第6,047,544號係揭示一種其上有含纪慰, 鉑或铑之層狀引擎排放氣體淨化觸媒，其在單體基質上翁一沸石碳氫化合物吸附劑層狀物。合成期間，將經？心滲透之礬土粉末、經Pd-滲透之氧化鈽粉末、硝酸酸化馨生溶膠及水倒入一磁性球狀研磨機中，搗碎混合物以便獲皭一漿體。該硝酸酸化礬土溶膠係經由添加10重量％硝酸至-10重量％比密特緣土（ bemite alumina )中所獲得。其係未揭示該礬土之改質或處理可具有一選擇性之效果。美國專利案第6,399,530號係揭示一種氫化裂解觸媒，其係具有以瑞酸膠化一小孔狀釁土之一黏著劑，且具有240-280 m2/g之一特定表面積及0.4-0.5 ml/g之一孔洞體積。其係未揭示該礬土黏著劑之改質或處理可具有一選擇性之效果。美國專利案第6,566,293號係揭示一種用於製造輕鏈稀烴之一烯烴選擇性觸媒，其係為一種具有一黏著劑磷改 200824790 質之一沸石。贫樊分化合之姑著劑通常係於與其他觸媒組成物成溶之該氯’其並無揭示與—無機酸膠要。 '"者4或該礬土黏著劑膠溶可具有選擇性之效【發明内容】。'弗石觸媒為係-種經-磷化合物處理之一沸石以形成一經磷處理涨 ^U.S. Patent No. 6,504,072 discloses a phosphorus-modified zeolite which is selectively methylated to form P-xylene. The P-modified zeolite catalyst may contain active and inactive materials such as clay, cerium oxide and/or metal oxides, for example, alumina as an adhesive. It does not reveal the modification or treatment of the adhesive, nor does it reveal the effect of modifying or treating the adhesive on p-biphenyl. Other prior art techniques have been used to modify or treat the adhesive material used in zeolite catalysts in other processes. U.S. Patent No. 5,907,073 discloses an aromatic alkylation process using a molecular sieve catalyst having a ZSM-12 crystalline structure symbiotically modified zeolite. During the synthesis, NH4-/3 and LaNHU-β were milled, extruded and calcined by alumina treatment, and NH4-/3 and LaNH4-/5 were converted into Η-wan catalyst and LaH_/5 contact, respectively. Media. The completed catalyst is used to ethylate phenethyl to form ethylbenzene. It does not reveal that the modification or treatment of the adhesive can have a selective effect. U.S. Patent No. 5,380,690 discloses a catalyst for the manufacture of light chain olefins which is a mixture of clay, inorganic oxide and zeolite. 200824790 The preparation of feldspar is via mixing of the inorganic oxide precursors (for example Ming = glue, _ water Ming stone (pseud () _b () hemite), dioxosol or /, these 5) and cerium oxide _ 矾溶胶 or clay-containing gel to de-cation: water Glue to make a slurry, further uniformly mix, adjust and maintain the pH of the slurry with a mineral acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid. After static aging, add a predetermined amount of zeolite. Homogenization, spray drying, washing to separate sodium ions and drying. It does not reveal that the adjustment and maintaining the pH of the slurry containing the adhesive precursor has a selective effect. U.S. Patent No. 6,047,544 discloses a layered engine exhaust gas purifying catalyst having a concentrating, platinum or rhodium containing a zeolitic hydrocarbon adsorbent layer on a monomer substrate. During the synthesis, will it pass? The heart-permeable alumina powder, the Pd-permeated cerium oxide powder, the nitric acid-forming saponin and the water are poured into a magnetic spherical mill, and the mixture is mashed to obtain a slurry. The nitric acid-calcified alumina sol is obtained by adding 10% by weight of nitric acid to -10% by weight of bemite alumina. It does not reveal that the modification or treatment of the alumina can have a selective effect. U.S. Patent No. 6,399,530 discloses a hydrocracking catalyst which is an adhesive which gels a small pore of alumina, and has a specific surface area of 240-280 m2/g and 0.4-0.5 ml. /g One of the hole volumes. It does not reveal that the modification or treatment of the alumina adhesive can have an optional effect. U.S. Patent No. 6,566,293 discloses an olefin selective catalyst for the manufacture of light chain dilute hydrocarbons, which is a zeolite having an adhesive phosphorus reformation 200824790. The poorly differentiated acant is usually based on the chlorine that is dissolved in the other catalyst composition, which does not reveal the inorganic acid. '" 4 or the alumina adhesive can be selectively effective [invention]. 'Furstone catalyst is a type of zeolite-species-phosphorus compound to treat a zeolite to form a phosphorus treatment.

黏著劑材料。製造心無機酸處理之—無機氧化物已經由一無機酸處理之彿石-黏著劑混合物，。μ觸媒係可經由化合一經磷處理彿石與一無機氧化物黏著劑材料以形成一石_黏著航並於約4G(rC或更高之溫度加熱該海石觸掸係"形成一結合沸石觸媒。該結合磷改質沸成…ί❹於〜燒化芳族之製程，例如甲苯甲基化成為二甲笨，苴孫认^ 一# α ^ 適於芳族烷化之反應條件下，經由將一方族化合物及1化劑與該結合沸石觸雜觸。Adhesive material. Manufacture of heart mineral acid treatment - inorganic oxides Fossil-adhesive mixture which has been treated with a mineral acid. The μ catalyst system can form a stone by a combination of phosphorus-treated fossil and an inorganic oxide adhesive material, and heats the sea stone contact system at a temperature of about 4G (rC or higher) to form a combined zeolite. Catalyst. The combination of phosphorus modification and boiling into... ❹ ❹ 〜烧烧芳芳芳 , , , , , , , , , , , , , , , , , 芳芳芳芳芳芳芳芳芳芳芳芳芳芳芳芳芳芳芳The heterogeneous compound and the compounding agent are contacted with the bound zeolite.

【實施方式】 H甲苯曱基化已知發生於沸石或沸石型觸媒上，特別疋ZSM-5·型彿石觸媒。一般而言，鄰⑻、間（m)·及對(p)_ 甲笨之一熱力學平衡混合物係由甲苯甲基化所形成。 0_、m-及p-二甲苯之該熱力學平衡組成物在反應溫度約為 50〇°C係分別約為25、50及25莫耳❶/❻。然而，如此之曱苯甲基化係可發生於寬廣的溫度範圍。一高純度級(99+%)p-二曱苯係理想地用於其氧化成對 10 200824790 酞酸之製程’因此，增加超解衡之p_二曱苯濃度是被期待的。“，如此-濃度之製造成本可能很高。p_二甲笨係可藉由吸附作用及兴構化作用之循環自混合的二甲笨分離，而因為於該平衡混合物中之低異構濃度，其係必須經過多次重複。假若該？·二甲苯濃度係高於平衡，則高純度級P-二曱苯係可更谷易的被獲得。假若觸媒含有形狀選擇特性係可獲得一 P-二曱苯之量明顯高於平衡。如此之形狀選擇特性可經由該改質沸石而被結合於沸石觸媒。沸石係為一種結晶含水鋁矽酸鹽，其係亦可含有其他金屬，例如鈉、鈣、鋇及鉀，且其係具有離子交換特撤 (Encarta ⑧ World English Dictionary [North America[Embodiment] H-methylglycolylation is known to occur on zeolite or zeolite type catalysts, particularly 疋ZSM-5· type budstone catalyst. In general, a thermodynamic equilibrium mixture of o (8), m (m), and p (p)_ is a toluene methylation. The thermodynamic equilibrium composition of 0-, m-, and p-xylene is about 25, 50, and 25 moles/❻ at a reaction temperature of about 50 ° C, respectively. However, such a benzylation system can occur over a wide temperature range. A high purity grade (99+%) p-diphenylene is ideally used in its oxidation to 10 200824790 tannic acid process. Therefore, increasing the super-equilibrated concentration of p-diphenylbenzene is expected. "The production cost of such a concentration may be very high. The p_dimethyl system can be separated from the mixed dimethyl ester by adsorption and destructuring, because of the low isomeric concentration in the equilibrium mixture. The system must be repeated many times. If the concentration of xylene is higher than the equilibrium, the high-purity P-diphenylene can be obtained more easily. If the catalyst contains shape-selecting properties, a The amount of P-diphenylbenzene is significantly higher than the equilibrium. Such shape-selective properties can be bonded to the zeolite catalyst via the modified zeolite. The zeolite is a crystalline aqueous aluminosilicate which can also contain other metals. For example, sodium, calcium, barium, and potassium, and they have ion exchange withdrawals (Encarta 8 World English Dictionary [North America]

Edition] © & (P) 2〇01 Microsoft Corporation)。沸石之實例技術上已知有ZSM-5、ZSM_ 11、ZSM-5/ZSM-11中間產梅、 ZSM-12、ZSM-2卜 ZSM-22、ZSM-23、ZSM-35、ZSM-3終 ZSM-48、ZSM_50、MCM-22、沸石L、沸石石及絲光彿石。 ZSM-5沸石係為一種含二維孔洞結構與1〇-員氧環相父之多孔物質。具有此10-員氧環孔洞結構之沸石通常被分類為一中孔洞（medium-pore)沸石。本文中所使用該 “ZSM-5-型”一詞意指與ZSM-5沸石相等結構之沸石。此外，該等“ZSM-5”及“ZSM-5-型，，詞於本文中係為包含彼此而可更替使用，且不應被解釋為一限定之意義。 ZSM-5滞石觸媒及其製備係敘述於美國專利案第 3,702,886號，其係併於本文參考。在本發明中，該Ζ8]ν^5 沸石觸媒係可包括具有一二氧化矽/蓉土之莫耳比率為2〇〇 11 200824790 或更高，更明確而言，在改質前約為250至約為5〇〇。該起始之ZSM-5可為一種NH/或形式並可含微量之其他陽離子。具有含磷化合物之改質ZSM_5_型沸石觸媒係已顯示用以提供觸媒形狀選擇特性，當使用於甲苯甲基化時相較於未經改質之觸媒係可產生比熱力學平衡值明顯較大量之 p-—曱苯。此改質係已顯示可提供對於p-二甲苯選擇性大於 80%。該ZSM-5係可經由含磷化合物處理而改質，其係包括 (但不限於）膦酸、三價膦酸、填及麟酸、此類酸之鹽類及酯類及磷鹵化物。特別是，磷酸(H3P〇4)及磷酸氫銨 ((NH4)2HP〇4)係可使用作為該含磷化合物，以提供用於具有形狀選擇特性甲苯甲基化之一觸媒，提供增加之二甲苯選擇性。此類改質觸媒係可含有磷(P)之量自約〇·〇][至約〇·15 g P/g沸石，更特別的係自約〇.〇2至約0.13 g p/g 沸石，且更特別的係自約為0.07 gP/g沸石至約0.12 gp/g 沸石，且最特別的係自約為0.09 g P/g沸石至約0·11 g p/g 沸石。在鱗處理後，可將該經填處理之沸石乾燥。該磷改質ZSM-5之製造係可經由形成含一 ZSM-5-型沸石及一磷化合物水溶液之一漿體，並自該漿體移除水分以形成一磷改質ZSM_5沸石。敘述於公開（2005，10,27公開）之美國專利申請案第20050239635號（STC-03-0006) (其併於本文作為參考）中所製備該磷改質觸媒並不被蒸氣灌流且具有一孔洞體積係為0.2 ml/g或以下。 12 200824790 該磷改質ZSM-5之製造係可經由溶解礬土於含磷之酸性溶液，及以敘述於美國專利案第6,943，131號 (2005,9，13核准，其併於本文作為參考）之溶有馨土之溶液處理該潍石。該磷改質ZSM-5係可具有特定31p MAS NMR尖峰係表示存在者游離磷酸根，鱗酸根結合於外部結構鋁，或具有敘述於 U.S.S.N. 11/136,877 (STC_04_0023) 申請，其併於本文作為參考）之特定磷酸根種類。本發明所使用ZSM-5以外之沸石係為中孔洞沸石，其係具有10及/或I2員環通道系統，例如ZSM_4(沸石川‘Edition] © & (P) 2〇01 Microsoft Corporation). Examples of zeolites are known in the art as ZSM-5, ZSM_11, ZSM-5/ZSM-11 intermediate plum, ZSM-12, ZSM-2, ZSM-22, ZSM-23, ZSM-35, ZSM-3. ZSM-48, ZSM_50, MCM-22, zeolite L, zeolite stone and mercerized Buddha stone. The ZSM-5 zeolite is a porous material containing a two-dimensional pore structure and a parent of an oxygen ring. Zeolites having this 10-membered oxygen ring pore structure are generally classified as a medium-pore zeolite. The term "ZSM-5-type" as used herein means a zeolite of the same structure as the ZSM-5 zeolite. In addition, the words "ZSM-5" and "ZSM-5-" are used interchangeably herein and should not be construed as limiting. ZSM-5 talc catalyst and The preparation is described in U.S. Patent No. 3,702,886, the disclosure of which is incorporated herein by reference in its entirety in the the the the the the the the the the the the 〇〇11 200824790 or higher, more specifically, about 250 to about 5 在 before upgrading. The starting ZSM-5 can be an NH/ or a form and can contain traces of other cations. The modified ZSM_5_type zeolite catalyst system containing phosphorus compounds has been shown to provide catalyst shape selection characteristics. When used in toluene methylation, the thermodynamic equilibrium value is significantly higher than that of the unmodified catalyst system. Larger amount of p--nonylbenzene. This modification has been shown to provide greater than 80% selectivity for p-xylene. The ZSM-5 system can be modified via treatment with phosphorus-containing compounds, including but not limited to Phosphonic acid, trivalent phosphonic acid, filled with linonic acid, salts of such acids and esters and phosphorus halides. In particular, Acid (H3P〇4) and ammonium hydrogen phosphate ((NH4)2HP〇4) can be used as the phosphorus-containing compound to provide a catalyst for toluene methylation having shape-selective properties, providing an increased xylene choice. Such modified catalysts may contain phosphorus (P) in an amount from about 〇·〇] [to about g·15 g P/g of zeolite, more particularly from about 〇.〇2 to about 0.13 gp/ g zeolite, and more particularly from about 0.07 gP/g zeolite to about 0.12 gp/g zeolite, and most particularly from about 0.09 g P/g zeolite to about 0.11 gp/g zeolite. After the treatment, the treated zeolite may be dried. The phosphorus modified ZSM-5 may be produced by forming a slurry containing a solution of a ZSM-5-type zeolite and a phosphorus compound aqueous solution, and moving from the slurry. The phosphorus is prepared to form a phosphorus-modified ZSM_5 zeolite. The phosphorus is prepared in US Patent Application No. 20050239635 (STC-03-0006), which is incorporated herein by reference. The modified catalyst is not perfused by steam and has a pore volume of 0.2 ml/g or less. 12 200824790 The phosphorus modified ZSM-5 can be produced by dissolving bauxite. The acidic solution, and the vermiculite solution is treated with a solution of scented clay in the form of a scented clay described in U.S. Patent No. 6,943,131, the disclosure of which is incorporated herein by reference. The system may have a specific 31p MAS NMR spike indicating the presence of the free phosphate, the sulphate binding to the outer structure of the aluminum, or the specific phosphate species described in USSN 11/136,877 (STC_04_0023), which is incorporated herein by reference. The zeolite other than ZSM-5 used in the present invention is a medium pore zeolite having a 10 and/or I2 member ring channel system, such as ZSM_4 (Zechuanchuan ‘

所述之一結合沸石觸媒One of the combined zeolite catalysts

一無機酸或一無黏著劑係特別該黏著劑材料係包括、璘酸鋁及二氧化矽_ 13 200824790 备使用於相魅時，特別是曱苯甲基化機黏著劑材料結合碟改質之1石觸媒將提供.有該無苯選擇性，而該無_著_料在化合姉著甲碗改質之沸石之前’係已由—無機酸（例如氫氯酸、卿該魏或械）所處理。此外，與已由—錢 -夂、機黏著劑材料結合之—鱗改質沸石觸媒，將製造^:An inorganic acid or a non-adhesive agent, in particular, the adhesive material includes, aluminum silicate and cerium oxide _ 13 200824790 when used in the enchantment, especially the styrene methylation machine adhesive material combined with the dish modification 1 stone catalyst will be provided. There is no benzene selectivity, and the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ) processed. In addition, the squama-modified zeolite catalyst, which has been combined with the -cohol-based, machine-adhesive material, will be manufactured^:

，於C9+含量之f苯甲基化產物。再者，與已由—益機酉ί 處理之-無機黏著劑材料結合之—鱗改料石觸媒量測碎裂強度將更能抵抗觸媒耗損。〃 9 藉由添加-足置該無機酸而將該無機黏著劑材料以，之無機酸處理，⑽成該無機鱗騎料無液態無機酸一混合物，其中係無過量之液體。, the benzylation product of f at the C9+ content. Furthermore, the combination of the inorganic binder material and the inorganic binder material that has been treated with the inorganic binder will measure the fragmentation strength and will be more resistant to catalyst wear.无机 9 The inorganic binder material is treated with a mineral acid by adding-footing the inorganic acid, and (10) forming a mixture of the inorganic scale-free material without a liquid inorganic acid, wherein no excess liquid is present.

在开y成該热機黏著劑材料與該無機酸之該混合物後，將該鱗改料石混人該混合物中，並添加水已形成一糊狀物，其係可被擠壓⑽成—成型__物。將該觸媒前驅物於4GG°C或更高溫度烺燒以形成—結合沸石觸媒，更溫度間。如此加熱係可進行特別是於500。(2至700QC之一 0.5小時或更久以形成該結合觸媒。該結合觸媒可含有結合觸媒總重約1%至約99%之黏著劑，更特別是形成基於結合觸媒總重約10%至約50%之黏著劑。在使用該觸媒於任何反應前，該結合p_改質沸石觸媒係可於300QC或以下一之溫度被溫和地蒸氣灌流。該蒸氣灌流係可於該反應器之中或之外進行。於溫和溫度蒸氣灌 SlL觸媒之應用敛述於同時待審之美國專利申請案序號第 14 200824790 11/122,919 (STCMM-Oim) (2〇〇5,5,5 中請）號，名稱為 Hydrothermal Treatment of Phosphorus-Modified Zeolite Catalysts”，其併於本文參考。該結合P-改質ZSM-5觸媒係可於烷化反應條件下，與一芳族碳氫化合物及一烷化劑之一適當進料接觸，以進行芳族烷化。對於使用一甲苯/甲醇進料之曱苯曱基化該觸媒具有特定應用。一氣體共進料係亦可被使用。該共進料氣 _ 體係可包括氫氣或一惰性氣體。本文中所使用之“烷化進料 3係思}日包含该方族化合物及該烧化劑。本文中所使用之“甲基化進料”一詞係意指包含甲苯與甲醇之該進料I 除了任何共進料氣體之外，可為蒸氣形式之水亦可連同烷化進料導入反應器中作為共進料。在開始烷化反應期間’用於甲基化反應之水或蒸氣可與或不與氳氣或惰性氣體作為共進料而隨烷化進料導入該反應器中，或其係可淼最初開始後隨即導入。在此二種情況中，在與共進料氣體 _ (如有任何添加）與烷化進料混合前，係可添加液態水並以蒸氣灌流。該水共進料之應用係敘述於美國專利申請案第 US2005/0070749 A1 號（STC-03-0008；)) ( 2005,3,31 公開），且名稱為“Toluene Methylation Process，，及 U.S.S.N· 11/127,357 (STC-04-0016) (2005,5，12 中請），作為一部份連績申睛案名稱為 n Toluene Methylation Process with Increased Methanol Selectivity”，其二者併於本文參考。用於甲苯曱基化或其他芳族烷化之該反應器壓力係可變化，但一般之範圍約為10至约1000 psig。反應器溫度 15 200824790 係可雙化，但一般之範圍約為4〇〇至約7〇〇QC。在將進料導入該反應器上，該觸媒床溫度可調整至一經選擇反應溫度以產生一所欲之轉換。該溫度係可以約1QC/min至約 10°C/mm之速率逐漸增加，以提供所欲之該最終反應器溫度。如使用於該實施例中，反應器溫度係意指該反應器觸媒床入口所測得之該溫度。本發明所主張之該觸媒係可使用於具有一起始程序之一曱笨甲基化製程，其中在處於相對較低的每小時液體空間速度（liquid hourly space velocity ; LHSV)之該反應器啟動前’以相對較高之LHSV，將該曱苯/甲醇進料與氫氣共進料導入反應器中一個半至約20小時，如U.S.S.N. 10/632,254 (STC-03-0004) ( 2003,8，1 中請）中所述，其係併於本文參考。該反應可於一各種不同反應器中進行，該反應器通常被用於進行芳族烧化反應。單獨或串聯及/或並聯之複數個反應器係適於進行該芳族烷化。當使用串聯複數個反應器時，可將曱醇及/或甲苯添加至進入該第二及後續反應器中之該產物流。對於使用於甲苯曱基化，本文中所述之該P-改質 ZSM-5沸石觸媒具有特定應用，以自曱苯及甲醇一進料製備一二甲苯產物。當使用於曱苯甲基化時，該觸媒係提供增加P-二甲苯選擇性。具體而言，當使用於曱苯曱基化時，該觸媒係可提供大於85%、90%或95%之對二甲苯選擇性。此外，在某些情況中，可達到大於總二甲苯選擇性之 16 200824790 95%。此外，在如未結合P/ZSM-5觸媒及該無機黏著劑材料未以一無機酸處理之結合P/ZSM-5之適當反應條件下，本文所述之該結合P/ZSM-5觸媒，在相同時期經過係可提供曱苯曱基化穩固之觸媒活性及選擇性。甲苯曱基化以外，用於本發明之製程可係包括芳族烷化及烷基轉移作用、曱苯歧化反應、曱醇轉化汽油 Φ t0 gasoline; MTG)之製程及n-鏈烷烴(Q及更高）環化作用。本發明係已大致敘述，提供下列實施例係作為本發明之特定具體實施例，並以證明其實施及優點。其係必須瞭解，該實施例係以說明之方式提供，並無預期以任何方式限制說明及下述之申請專利範圍。下列實施例僅供說明，並不限制本發明。如本文中所使用，催化活性就甲苯進料之莫耳數雨吕’可以表示轉換的曱苯之莫耳％，且可以下列方程式定 • 義：莫耳％甲苯轉換= [(Ti-To)/Ti] X 100 (i) 其中，丁i係為甲苯進料之莫耳數，且τ〇係為未反應甲笨之莫耳數。如本文中所使用，對於混合二甲苯之選擇性係可表示為：莫耳％混合二甲苯選擇性=[Xtx/(Ti_To)；j X 1〇〇⑺ 其中’ Xtx係為該產物中混合(0-、m•或p_)二曱苯之莫耳數。 17 200824790 如本文中所使用，對於P-二曱苯之選擇性係可表示為：莫耳〇/〇1)-二甲苯選擇性二(Xp/Xtx) χ 1〇〇 (3) 其中，Xp為該P-二甲苯之莫耳數。如本文中所使用，曱醇轉換係可表示為：莫耳％甲醇轉換二[(Mi-Mo)/Mi] X 1〇〇 (4) 其中，Mi係為該甲醇進料之莫耳數，且Mc)為該未反應曱醇之莫耳數。After the mixture of the heat engine adhesive material and the inorganic acid is opened, the scale material is mixed with the mixture, and water is added to form a paste, which can be extruded (10) into - Forming __ objects. The catalyst precursor is calcined at 4 GG ° C or higher to form a combined zeolite catalyst, more between temperatures. Such a heating system can be carried out in particular at 500. (1 to 700 QC for 0.5 hour or more to form the bonding catalyst. The bonding catalyst may contain from about 1% to about 99% of the total weight of the bonding agent, more particularly based on the total weight of the combined catalyst) From about 10% to about 50% of the adhesive. The combined p-modified zeolite catalyst can be gently vapor-perfused at a temperature of 300 QC or below prior to any reaction using the catalyst. The vapor perfusion system can be In the middle or outside of the reactor, the application of the SlL catalyst at a mild temperature is described in the co-pending U.S. Patent Application Serial No. 14 200824790 11/122,919 (STCMM-Oim) (2〇〇5, 5,5, please note), entitled Hydrothermal Treatment of Phosphorus-Modified Zeolite Catalysts, which is incorporated herein by reference. The combined P-modified ZSM-5 catalyst system can be used under alkylation conditions with an aromatic One of the hydrocarbons and one of the alkylating agents is contacted appropriately for aromatic alkylation. The catalyst is useful for the use of a toluene/methanol feed. The gas cofeed system can also be used. Used. The co-feed gas _ system may include hydrogen or an inert gas As used herein, "alkylation feed 3 system" includes the compound and the burn-in agent. The term "methylation feed" as used herein means the inclusion of toluene and methanol. In addition to any co-feed gas, water in the form of a vapor may also be introduced into the reactor as a co-feed together with the alkylation feed. During the start of the alkylation reaction, the water or vapour used for the methylation reaction may Or with helium or inert gas as a co-feed into the reactor with the alkylation feed, or its system can be introduced immediately after the initial start. In both cases, in the co-feed gas _ (if Prior to mixing with the alkylation feed, liquid water can be added and perfused with steam. The application of the water co-feed is described in US Patent Application No. US2005/0070749 A1 (STC-03-0008;)) 2005, 3, 31 public), and the name is "Toluene Methylation Process,, and USSN 11/127, 357 (STC-04-0016) (2005, 5, 12), as part of the name of the succession n Toluene Methylation Process with Increased Methanol Selectiv "ity", both of which are incorporated herein by reference. The reactor pressure system for toluene oximation or other aromatic alkylation can vary, but will generally range from about 10 to about 1000 psig. The reactor temperature 15 200824790 can be doubled, but generally ranges from about 4 〇〇 to about 7 〇〇 QC. Upon introduction of the feed to the reactor, the temperature of the catalyst bed can be adjusted to a selected reaction temperature to produce a desired conversion. The temperature can be gradually increased at a rate of from about 1 QC/min to about 10 ° C/mm to provide the desired final reactor temperature. As used in this embodiment, the reactor temperature means the temperature measured at the inlet of the reactor bed. The catalyst system claimed in the present invention can be used in a methylation process having a starting procedure in which the reactor is started at a relatively low liquid hourly space velocity (LSSV). The former 'toluene/methanol feed and hydrogen co-feed are introduced into the reactor for one and a half to about 20 hours at a relatively high LHSV, as in USSN 10/632,254 (STC-03-0004) (2003, 8, 1) It is described in the middle of this article, and it is referred to in this article. The reaction can be carried out in a variety of different reactors which are typically used to carry out aromatic burning reactions. A plurality of reactors, either alone or in series and/or in parallel, are suitable for carrying out the aromatic alkylation. When a plurality of reactors are used in series, decyl alcohol and/or toluene may be added to the product stream entering the second and subsequent reactors. For use in toluene thiolation, the P-modified ZSM-5 zeolite catalyst described herein has particular application for the preparation of a mono-xylene product from a feed of benzene and methanol. When used in benzylation, the catalyst provides increased P-xylene selectivity. In particular, the catalyst system provides greater than 85%, 90% or 95% para-xylene selectivity when used in the indomethacination. In addition, in some cases, greater than the total xylene selectivity of 16 200824790 95% can be achieved. In addition, the combined P/ZSM-5 contact described herein can be carried out under suitable reaction conditions such as unbonded P/ZSM-5 catalyst and the inorganic binder material which is not treated with a mineral acid in combination with P/ZSM-5. The medium, during the same period, can provide the catalyst activity and selectivity of benzoylation. In addition to toluene oximation, the processes used in the present invention may include aromatic alkylation and transalkylation, benzene benzene disproportionation, sterol conversion gasoline Φ t0 gasoline; MTG) processes and n-paraffins (Q and Higher) cyclization. The present invention has been generally described, and the following examples are presented as specific embodiments of the invention, It is to be understood that the examples are provided by way of illustration and are not intended to limit the description and the scope of the claims. The following examples are for illustrative purposes only and are not limiting of the invention. As used herein, the catalytic activity of the molar amount of the toluene feed can represent the mole % of the converted toluene and can be determined by the following equation: More % toluene conversion = [(Ti-To) /Ti] X 100 (i) wherein, butyl is the molar number of the toluene feed, and τ is the unreacted mole. As used herein, the selectivity for mixed xylenes can be expressed as: molar % mixed xylene selectivity = [Xtx / (Ti_To); j X 1 〇〇 (7) where 'Xtx is the product in the mixture ( 0-, m• or p_) Molar number of diterpene. 17 200824790 As used herein, the selectivity for P-diphenylene can be expressed as: moir/〇1)-xylene selectivity II (Xp/Xtx) χ 1〇〇(3) where Xp Is the molar number of the P-xylene. As used herein, a sterol conversion system can be expressed as: More % methanol conversion bis [(Mi-Mo) / Mi] X 1 〇〇 (4) wherein Mi is the molar number of the methanol feed, And Mc) is the molar number of the unreacted sterol.

如本文中所使用，對於甲苯甲基化之甲醇選擇性係可表不為· 莫耳％曱醇選擇性=[Xtx/(Mi-Mo)] X 1〇〇 (5) 其中，Xtx係為該混合(〇-、m-或p-)二甲苯之莫耳數， Mi係為該甲醇進料之莫耳數，且Mo係為該未反應曱醇之莫耳數。實施例1(比較性) 觸媒A · 觸媒A之合成。製造不含P-改質之一 ZSM-5 (P/ZSM-5) 黏著劑。該起始沸石粉末係為一種具有Si〇2/Al2〇3莫耳比率280之一 NH4-ZSM-5粉末。於2-L燒杯中製備含450.0 g NH4_ZSM-5沸石及900 ml水之漿體。將燒杯置於一加熱板上，並使用一機械攪袢器（架空）以250_300 rPm攪拌該沸石漿體。將該漿體溫度缓慢上升至約80_85°C，此時緩慢添加墻酸。將一重205.2 g之磷酸(Aldrich，85 wt%水溶液）添加至該燒杯中。該漿體溫度進一步增加至95-100°C之 18 200824790 間，且持續加熱直至所有液體蒸發。在下列溫度程序，將該經磷酸改質沸石在一對流爐於空氣中煅燒·· 90°C至 120°C 3小時，於340°C至360°C 3小時，及於520°C至 530°C於空氣中13小時。然後將該經煅燒沸石壓碎，並使用20及40網目之篩網區分大小而用於催化反應，或經由 80網目篩網篩選而用於與適當黏著劑結合。經由XRF法分析該P/ZSM-5之Si、Al及P，及經由N2吸附而分析BET 表面積及總孔洞體積。如表1所示，該P/ZSM-5沸石含 36.42 wt%之 Si、0.27 wt%之 A1 及 9.38 wt%之 P，且其具有BET表面積為154 m2/g及總孔洞體積為0.12 ml/g。在 5-55°範圍間，使用CuKal輻射於掃描率每分鐘2°之 P/ZSM-5之X射線繞射模型紀錄於Phillips (X，Pertv型）繞射儀，且獲得如表2中之結果。 '多 1 ' …—————————— ^ A素分析wt% j N2吸附As used herein, the methanol selective system for toluene methylation can be expressed as · Molar % sterol selectivity = [Xtx / (Mi-Mo)] X 1 〇〇 (5) where Xtx is The molar number of the mixed (〇-, m- or p-) xylene, Mi is the molar number of the methanol feed, and Mo is the molar number of the unreacted sterol. Example 1 (Comparative) Catalyst A · Synthesis of Catalyst A. Produces one of the P-modified ZSM-5 (P/ZSM-5) adhesives. The starting zeolite powder was a powder of NH4-ZSM-5 having a Si〇2/Al2〇3 molar ratio of 280. A slurry containing 450.0 g of NH4_ZSM-5 zeolite and 900 ml of water was prepared in a 2-L beaker. The beaker was placed on a hot plate and the zeolite slurry was agitated at 250-300 rPm using a mechanical stirrer (overhead). The slurry temperature was slowly raised to about 80-85 ° C, at which time the wall acid was slowly added. A weight of 205.2 g of phosphoric acid (Aldrich, 85 wt% aqueous solution) was added to the beaker. The slurry temperature is further increased to between 95 and 100 ° C for 18 2008 24790 and heating is continued until all liquid evaporates. The phosphoric acid modified zeolite is calcined in air in a pair of flow furnaces at the following temperature program: 90 ° C to 120 ° C for 3 hours, at 340 ° C to 360 ° C for 3 hours, and at 520 ° C to 530 °C in air for 13 hours. The calcined zeolite is then crushed and sized for use in a catalytic reaction using a 20 and 40 mesh screen or by a 80 mesh screen for binding to a suitable adhesive. The Si, Al and P of the P/ZSM-5 were analyzed by the XRF method, and the BET surface area and the total pore volume were analyzed by N2 adsorption. As shown in Table 1, the P/ZSM-5 zeolite contained 36.42 wt% of Si, 0.27 wt% of A1, and 9.38 wt% of P, and had a BET surface area of 154 m2/g and a total pore volume of 0.12 ml/ g. An X-ray diffraction model of P/ZSM-5 with CuKal radiation at a scan rate of 2° per minute was recorded on a Phillips (X, Pertv type) diffractometer in the range of 5-55° and obtained as shown in Table 2. result. '多1' ...—————————— ^ A factor analysis wt% j N2 adsorption

Si......... A1 P ^ i SA，m2/| PV, ml/g 36.42 0.27 9.38 154 0.12 粉末XRD強度* :=:=:: d-間萼[A] 強度 d-間距[A] 魅 11.11 100 5.56 7 10.02 57 4.01 10 9.73 17 3,93 13 8.04 11 3.85 51 6.69 8 3.74 19 6.54 9 3.71 29 19 200824790 6.34 11 3.64 10 5.97 16 2.52 25 5.70 8 2.98 9 *所顯示之強度以任意單位計數，因此最大強度尖峰為100。觸媒A係使用於曱苯甲基化反應。該反應係於固定床，連續流動型反應器中進行。將一 5.4 ml觸媒填料(觸媒大小：20-40網目）裝填於一 SS-316管狀(OD 0.5英吋，ID 0.33英吋)反應器。在氬氣流下（50 cc/min)，經由緩慢上升該觸媒床之溫度（約5QC/min)至200°C，將觸媒乾燥至少1 小時。然後導入具一 H2(459 cc/min)載體氣體之水蒸汽(2.2 mmole/min)，將觸媒於200°C蒸氣灌流隔夜。一預混合之曱苯及曱醇進料（莫耳比率約4.5)於200°C添加至該反應器中。每小時之液體空間速度(LHSV)(基於甲基化進料)保持於約2 hr·1，且飼入共進料Η?氣體並保持，以提供H2/甲基化進料莫耳比例約7-8。此外，將水添加至反應器作為進料，並在導入反應器之前被蒸發。該H2〇/甲基化進料莫耳比率約為0.8，且反應器壓力約為20 psig。該觸媒床又口溫度漸進增加以增加甲苯之轉換。分析反應器之氣流以计异轉換及選擇性。分析產物流。觸媒A上之甲苯甲矣化反應的轉換及選擇性顯示於表3。土 198J3 22T( ^r〇A ο —————_ — 530·3 529.6 531.0 533 表3 蒸氣灌流時間，h 觸媒床入口溫度，。c 24.10 52.60 119.60 452.3 487.7 495.7 液態產物分拚、wt% 200824790 水甲醇二曱醚苯甲苯乙苯 P-二甲苯 m-二甲苯〇-二曱苯乙基曱基苯三甲苯 C10+ 轉換/選擇性，莫耳％曱苯轉換混合二甲苯選擇性 P-二甲苯選擇性甲醇選擇性 19.31 0.86 0 0 75.92 0 2.95 0.35 0.38 0 0.22 0 3.09 94.92 80.02 28.98 20.07 0.75 0 0 7239 0 5.51 0.49 0.46 0.06 0.28 0 5.86 95.51 85.42 42.64 20.02 0.66 0 0 71.11 0 6.79 0.56 0.48 0.06 0.32 0 7.63 96.06 86.74 50.22 19.76 0.58 0 0 69.70 0 8.51 0.62 0.49 0 0.34 0 9.40 97.07 88.46 56.90 19.01 0.53 0 0 69.60 0 9.27 0.68 0.52 0 0.39 0 10.24 96.91 88.52 60.12 19.66 0.56 0 0 69.09 0 9.08 0.67 0.51 0 037 0 10.17 96.60 88.53 60.15 19.94 0.57 0 0 68.88 0 9.08 0.67 0.50 0 037 0 10.16 97：〇6 88.62 60.52 實施例2 (比較性）Si......... A1 P ^ i SA,m2/| PV, ml/g 36.42 0.27 9.38 154 0.12 Powder XRD strength* :=:=:: d-interval [A] Intensity d-spacing [A] Charm 11.11 100 5.56 7 10.02 57 4.01 10 9.73 17 3,93 13 8.04 11 3.85 51 6.69 8 3.74 19 6.54 9 3.71 29 19 200824790 6.34 11 3.64 10 5.97 16 2.52 25 5.70 8 2.98 9 *The strength shown is Any unit counts, so the maximum intensity spike is 100. Catalyst A is used in the benzylidene reaction. The reaction is carried out in a fixed bed, continuous flow reactor. A 5.4 ml catalyst filler (catalyst size: 20-40 mesh) was loaded into a SS-316 tubular (OD 0.5 inch, ID 0.33 inch) reactor. The catalyst was dried for at least 1 hour under a stream of argon (50 cc/min) by slowly raising the temperature of the catalyst bed (about 5 QC/min) to 200 °C. Water vapor (2.2 mmole/min) with a H2 (459 cc/min) carrier gas was then introduced and the catalyst was perfused at 200 ° C overnight. A premixed terpene and decyl alcohol feed (molar ratio of about 4.5) was added to the reactor at 200 °C. The hourly liquid space velocity (LHSV) (based on the methylation feed) is maintained at approximately 2 hr·1 and is fed to the co-feed Η gas and maintained to provide a H2/methylation feed molar ratio of approximately 7 -8. In addition, water is added to the reactor as a feed and is evaporated prior to introduction into the reactor. The H2〇/methylation feed molar ratio was about 0.8 and the reactor pressure was about 20 psig. The catalyst bed is gradually increased in temperature to increase the conversion of toluene. The gas flow from the reactor was analyzed to account for the conversion and selectivity. Analyze the product stream. The conversion and selectivity of the toluene methylation reaction on Catalyst A are shown in Table 3. Soil 198J3 22T( ^r〇A ο —————_ — 530·3 529.6 531.0 533 Table 3 Steam perfusion time, h Catalyst bed inlet temperature, .c 24.10 52.60 119.60 452.3 487.7 495.7 Liquid product splitting, wt% 200824790 water methanol diterpene ether benzene toluene ethylbenzene P-xylene m-xylene oxime-diphenyl phenylethyl decyl benzene trimethylbenzene C10+ conversion / selectivity, mol% benzene conversion mixed xylene selectivity P-two Selective methanol selectivity for toluene 19.31 0.86 0 0 75.92 0 2.95 0.35 0.38 0 0.22 0 3.09 94.92 80.02 28.98 20.07 0.75 0 0 7239 0 5.51 0.49 0.46 0.06 0.28 0 5.86 95.51 85.42 42.64 20.02 0.66 0 0 71.11 0 6.79 0.56 0.48 0.06 0.32 0 7.63 96.06 86.74 50.22 19.76 0.58 0 0 69.70 0 8.51 0.62 0.49 0 0.34 0 9.40 97.07 88.46 56.90 19.01 0.53 0 0 69.60 0 9.27 0.68 0.52 0 0.39 0 10.24 96.91 88.52 60.12 19.66 0.56 0 0 69.09 0 9.08 0.67 0.51 0 037 0 10.17 96.60 88.53 60.15 19.94 0.57 0 0 68.88 0 9.08 0.67 0.50 0 037 0 10.16 97:〇6 88.62 60.52 Example 2 (comparative)

觸媒B ZSM-5(如前觸媒a所述觸媒B之合成。將9_改質之、、 ^ 称八尸；r现與2〇 wt〇/〇礬土黏著劑結合。將17 5 g之蓉土(擬薄水㈣型’獲自 Alcoa，HiQ-40 級)盥 7〇〇之^ 、、久厂、/υ·υ g之p/Zsm_5沸石彩末(80網目）混合，並無酸用於該礬土。將水噴霧於該礬』及沸石混合物以形成一可擠壓糊狀物，將其擠壓以製超 1/16-英对圓柱型壓出物。將該結合觸媒在—對流爐於空泰中，使用觸媒A中所述之該相同溫度輪廓，以51〇。匸至 530°C間之一最大溫度（i〇h)煅燒。將該觸媒B壓碎，並偵用20及40網目之篩網區分大小而用於催化測試。使用觸 21 200824790 媒A之該相同測試條件，將觸媒B測試甲苯甲基化，且結果總結於表4。表4 蒸氣灌流時間，h 23.77 47.27 71.27 143.77 191.52 215.27 245.77 觸媒床入口溫度，°C 452.9 475.5 486.0 496.1 499.9 508.7 507.6 液態產物分析，wt% 水 19.59 20.57 20.62 20.79 20.52 20.68 20.74 甲醇 0.21 0.14 0.13 0.14 0.17 0.16 0.17 二甲醚 0 0 0 0 0 0 0 苯 0 0 0 0 0 0 0 曱苯 68.72 66.49 65.78 65.26 65.64 65.33 65.19 乙苯 0 0 0 0 0 0 0 P-二甲苯 9.23 10.67 11.32 11.70 11.56 11.70 11.73 m-二甲苯 0.85 0.89 0.92 0.92 0.89 0.90 0.89 〇-二曱苯 0.62 0.57 0.56 0.54 0.54 0.55 0.55 乙基曱基苯 0.16 0.13 0.12 0.11 0.11 0.10 0.10 三甲苯 0.56 0.54 0.55 0.55 0.57 0.58 0.62 C10+ 0.07 0 0 0 0 0 0Catalyst B ZSM-5 (such as the synthesis of the catalyst B of the former catalyst a. The 9_ modified, ^ called eight corpses; r is now combined with 2〇wt〇 / alumina adhesive. Will 17 5 g of Rong soil (pseudo-thin water (four) type 'obtained from Alcoa, HiQ-40 grade) 盥7〇〇^,, Jiuchang, /υ·υ g, p/Zsm_5 zeolite color (80 mesh) mixed, No acid is used in the alumina. Water is sprayed onto the mixture and the zeolite mixture to form an extrudable paste which is extruded to produce a super 1/16-inch pair of cylindrical extrudates. In combination with the catalyst in a convection oven, the same temperature profile as described in Catalyst A is used to calcine at a maximum temperature (i〇h) between 51 〇 and 530 ° C. B crushed, and used 20 and 40 mesh screens to distinguish the size for the catalytic test. Using the same test conditions of the touch 21 200824790 media A, the catalyst B was tested for methylation of toluene, and the results are summarized in Table 4. Table 4 Steam perfusion time, h 23.77 47.27 71.27 143.77 191.52 215.27 245.77 Catalyst bed inlet temperature, °C 452.9 475.5 486.0 496.1 499.9 508.7 507.6 Liquid product analysis, wt% water 19.59 20.57 20 .62 20.79 20.52 20.68 20.74 Methanol 0.21 0.14 0.13 0.14 0.17 0.16 0.17 Dimethyl ether 0 0 0 0 0 0 0 Benzene 0 0 0 0 0 0 0 Benzene 68.72 66.49 65.78 65.26 65.64 65.33 65.19 Ethylbenzene 0 0 0 0 0 0 0 P-xylene 9.23 10.67 11.32 11.70 11.56 11.70 11.73 m-xylene 0.85 0.89 0.92 0.92 0.89 0.90 0.89 〇-diphenylbenzene 0.62 0.57 0.56 0.54 0.54 0.55 0.55 ethyl decyl benzene 0.16 0.13 0.12 0.11 0.11 0.10 0.10 trimethylbenzene 0.56 0.54 0.55 0.55 0.57 0.58 0.62 C10+ 0.07 0 0 0 0 0 0

轉換/選擇性，莫耳％甲苯轉換 11.24 12.86 13.48 13.98 13.74 13.83 13.97 混合二甲苯選擇性 94.06 95.48 95.73 96.02 95.81 95.80 95.56 P-二曱苯選擇性 86.29 87.98 88.44 88.91 88.99 88.96 89.09 甲醇選擇性 51.28 58.08 60.63 62.77 62.74 63.22 64.07Conversion/selectivity, mol% Toluene conversion 11.24 12.86 13.48 13.98 13.74 13.83 13.97 Mixed xylene selectivity 94.06 95.48 95.73 96.02 95.81 95.80 95.56 P-diphenylbenzene selectivity 86.29 87.98 88.44 88.91 88.99 88.96 89.09 Methanol selectivity 51.28 58.08 60.63 62.77 62.74 63.22 64.07

實施例3Example 3

觸媒C 觸媒C之合成。將預煅燒之P-改質ZSM-5(如前述觸媒A所述)與20 wt%馨土黏著劑結合。17·5 g馨土(擬薄水 22 200824790 鋁石型，獲自 Alcoa，HiQ_40 級)與 7·8 g ΗΝ〇3(19·9 wt% 水溶液）混合，然後與70.1 g之P/ZSM-5沸石粉末（80網目）混合。將水喷灑於該沸石-礬土混合物上以形成一可擠壓糊狀物，將其擠壓以製造1/16-英吋圓柱型壓出物。將該結合觸媒在一對流爐於空氣中，使用觸媒A中所述之該相同溫度輪廓，以510°C至530°C間之一最大溫度（10 h)鍛燒。將該觸媒C壓碎，並使用20及40網目之篩網區分大小而用於催化測試。使用觸媒A之該相同測試條件，將觸媒C 測試曱苯甲基化，且結果總結於表5。表5Catalyst C Catalyst C synthesis. The pre-calcined P-modified ZSM-5 (as described for Catalyst A previously described) was combined with a 20 wt% clay binder. 17·5 g Xin soil (pseudo-thin water 22 200824790 aluminum stone type, obtained from Alcoa, HiQ_40 grade) mixed with 7·8 g ΗΝ〇3 (19·9 wt% aqueous solution), and then with 70.1 g of P/ZSM- 5 zeolite powder (80 mesh) mixed. Water was sprayed onto the zeolite-alumina mixture to form an extrudable paste which was extruded to produce a 1/16-inch cylindrical extrudate. The combined catalyst was calcined in a pair of flow furnaces in air using the same temperature profile as described in Catalyst A at a maximum temperature (10 h) between 510 ° C and 530 ° C. The catalyst C was crushed and used for catalysis testing using 20 and 40 mesh screens. Catalyst C was tested for benzylation using the same test conditions for Catalyst A, and the results are summarized in Table 5. table 5

蒸氣灌流時間，h 23.25 54.25 119.58 143.25 167.25 191.48 215:75 觸媒床入口溫度，QC 451.3 483.1 495.1 506.1 516.8 516.9 519.1 液態產物分析，wt% 水 21.46 20.53 20.76 20.85 20.98 20.85 ... 20:99 甲醇 0.48 0.25 0.25 0.26 0.21 0.22 0.25 二甲醚 0 0 0 0 0 0 0 苯 0 0 0 0 0 0 0 曱苯 67.32 66.60 66.44 66.09 65.40 65.51 65.27 乙苯 0 0 0 0 0 0 0 p-二甲苯 8.64 10.77 10.86 11.15 11.67 11,68 11.80 m-二甲苯 0.71 0.69 0.65 0.64 0.68 0.68 0.66 〇-二甲苯 0.57 0.49 0.44 0.42 0.43 0.43 0.42 乙基曱基苯 0.19 0.14 0.12 0.11 0.11 0.10 0.10 三甲苯 0.55 0.54 0.49 0.49 0.52 0.51 0.50 C10+ 0.08 0 0 0 0 0 0 轉換/選擇性，莫耳％曱苯轉換 10.78 12.51 12.57 12.87 13.11 13.33 13.38 混合二甲苯選擇性 93.47 95.44 95.90 96.04 96.08 96.11 96.22 23 200824790 p-二甲苯選擇性 87.14 90.14 90.89 91.34 91.32 91.27 91.58 甲醇選擇性 52.19 59.57 59.89 61.44 62.04 62.67 63.97 實施例4Vapor perfusion time, h 23.25 54.25 119.58 143.25 167.25 191.48 215:75 Catalyst bed inlet temperature, QC 451.3 483.1 495.1 506.1 516.8 516.9 519.1 Analysis of liquid product, wt% water 21.46 20.53 20.76 20.85 20.98 20.85 ... 20:99 Methanol 0.48 0.25 0.25 0.26 0.21 0.22 0.25 Dimethyl ether 0 0 0 0 0 0 0 Benzene 0 0 0 0 0 0 0 Benzene 67.32 66.60 66.44 66.09 65.40 65.51 65.27 Ethylbenzene 0 0 0 0 0 0 0 p-xylene 8.64 10.77 10.86 11.15 11.67 11,68 11.80 m-xylene 0.71 0.69 0.65 0.64 0.68 0.68 0.66 〇-xylene 0.57 0.49 0.44 0.42 0.43 0.43 0.42 ethyl decyl benzene 0.19 0.14 0.12 0.11 0.11 0.10 0.10 trimethylbenzene 0.55 0.54 0.49 0.49 0.52 0.51 0.50 C10+ 0.08 0 0 0 0 0 0 conversion / selectivity, molar % benzene conversion 10.78 12.51 12.57 12.87 13.11 13.33 13.38 mixed xylene selectivity 93.47 95.44 95.90 96.04 96.08 96.11 96.22 23 200824790 p-xylene selectivity 87.14 90.14 90.89 91.34 91.32 91.27 91.58 Methanol selectivity 52.19 59.57 59.89 61.44 62.04 62.67 63.97 Example 4

觸媒D 觸媒D之合成。將預煅燒之P-改質ZSM-5(如前述觸媒A所述)與20 wt%礬土黏著劑結合。17.5 g礬土(擬薄水鋁石型，獲自 Alcoa，HiQ_40 級）與 7.8 g ΗΝ03(40·0 wt% 水溶液）混合，然後與70.1 g之P/ZSM-5沸石粉末(80網目）混合。將水喷灑於該沸石-礬土混合物上以形成一可擠壓糊狀物，將其擠壓以製造1/16-英吋圓柱型壓出物。將該結合觸媒在一對流爐於空氣中，使用觸媒A中所述之該相同溫度輪廓，以510°C至530°C間之一最大溫度（10 h)煅燒。將該觸媒D壓碎，並使用20及40網目之篩網區分大小而用於催化測試。使用觸媒A之該相同測試條件，將觸媒D 測試甲苯曱基化，且結果總結於表6。蒸氣灌流時間，h 22.88 53.63 77.63 143.63 168.05 215.88 245.63 觸媒床入口溫度，°C 451.4 482.5 504.0 515.2 532.1 531.5 530.5 液態產物分析，wt% 水 20.87 19.11 20.10 20.63 20.15 20.44 20.24 甲醇 0.25 0.31 0.28 0.30 0.29 0.29 0.31 二曱醚 0 0 0 0 0 0 0 苯 0 0 0 0 0 0 0 甲苯 69.46 69.22 67.81 67.48 67.40 67.29 67.47 乙苯 0 0 0 0 0 0 0 24 200824790 P-二甲苯 8.31 10.16 10.63 10.47 11.04 10.85 10.86 m-二甲苯 0.37 0.42 0.42 0.42 0.43 0.43 0.43 〇-二曱苯 0.29 0.31 0.30 0.28 0.28 0.28 0.28 乙基甲基苯 0.15 0.12 0.10 0.08 0.07 0.08 0.07 三甲苯 030 0.35 0.35 0.33 0.34 0.34 0.34 C10+ 0 0 0 0 0 0 0 轉換/選擇性，莫耳％曱苯轉換 9.17 11.08 11.64 11.41 11.72 11.63 11.63 混合二甲苯選擇性 95.89 96.52 96.77 96.95 97.14 97.03 97.09 p-二甲苯選擇性 92.63 93.27 93.66 93.76 93.95 93.88 93.89 曱醇選擇性 45.11 55.24 57.50 57.28 59.15 58.50 59.18 實施例5Synthesis of Catalyst D Catalyst D. The pre-calcined P-modified ZSM-5 (as described for Catalyst A previously described) was combined with a 20 wt% alumina adhesive. 17.5 g bauxite (pseudo-boehmite type, obtained from Alcoa, HiQ_40 grade) mixed with 7.8 g ΗΝ03 (40. 0 wt% aqueous solution) and then mixed with 70.1 g of P/ZSM-5 zeolite powder (80 mesh) . Water was sprayed onto the zeolite-alumina mixture to form an extrudable paste which was extruded to produce a 1/16-inch cylindrical extrudate. The combined catalyst was calcined in a pair of flow furnaces in air using the same temperature profile as described in Catalyst A at a maximum temperature (10 h) between 510 ° C and 530 ° C. The catalyst D was crushed and used to catalyze the test using a 20 and 40 mesh screen size. Catalyst D was tested for toluene thiolation using this same test condition for Catalyst A, and the results are summarized in Table 6. Vapor perfusion time, h 22.88 53.63 77.63 143.63 168.05 215.88 245.63 Catalyst bed inlet temperature, °C 451.4 482.5 504.0 515.2 532.1 531.5 530.5 Liquid product analysis, wt% water 20.87 19.11 20.10 20.63 20.15 20.44 20.24 Methanol 0.25 0.31 0.28 0.30 0.29 0.29 0.31 II曱 ether 0 0 0 0 0 0 0 benzene 0 0 0 0 0 0 0 toluene 69.46 69.22 67.81 67.48 67.40 67.29 67.47 ethylbenzene 0 0 0 0 0 0 0 24 200824790 P-xylene 8.31 10.16 10.63 10.47 11.04 10.85 10.86 m- Toluene 0.37 0.42 0.42 0.42 0.43 0.43 0.43 〇-Diphenylbenzene 0.29 0.31 0.30 0.28 0.28 0.28 0.28 Ethylmethylbenzene 0.15 0.12 0.10 0.08 0.07 0.08 0.07 Trimethyl 030 0.35 0.35 0.33 0.34 0.34 0.34 C10+ 0 0 0 0 0 0 0 Conversion /selective, mol% benzene conversion 9.17 11.08 11.64 11.41 11.72 11.63 11.63 mixed xylene selectivity 95.89 96.52 96.77 96.95 97.14 97.03 97.09 p-xylene selectivity 92.63 93.27 93.66 93.76 93.95 93.88 93.89 sterol selectivity 45.11 55.24 57.50 57.28 59.15 58.50 59.18 Example 5

• ' ^ 觸媒E 觸媒E之合成。將預烺燒之？-改質28減-5(如前述觸媒A所述)與20 wt%礬土黏著劑結合。17.5 g礬土(擬薄水鋁石型，獲自 Alcoa，HiQ-40 級）與 7.8 g ΗΝ〇3(49·6 wt% ,：水溶液）混合，然後與70.0g之P/ZSM-5沸石粉末（80網目） φ 混合。將水喷灑於該沸石-礬土混合物上以形成一可擠壓糊狀物，將其擠壓以製造1/16-英吋圓柱型壓出物。將結合觸媒在一對流爐於空氣中，使用觸媒A中所述之該相同溫度輪廓，以510°C至530°C間之一最大溫度（10 h)煅燒。將該觸媒E壓碎，並使用20及40網目之篩網區分大小而用於催化測試。使用觸媒A之該相同測試條件，將觸媒E測試曱苯曱基化，且結果總結於表7。表7 蒸氣灌流時間，h 23.70 53.70 77.45 143.75 167.13 173.62 191.45 25 200824790 觸媒床入口溫度，QC 448.1 481.0 502.8 503.7 523.8 530.5 530.6 液態產物分析，wt% 水 20.73 19.54 19.90 20.64 20.42 20.70 20.74 甲醇 0.24 0.29 0.27 0.28 0.29 0.30 0.30 二曱醚 0 0 0 0 0 0 0 苯 0 0 0 0 0 0 0 曱苯 69.68 69.26 67.83 67.38 67.44 67.23 67.38 乙苯 0 0 0 0 0 0 0 p-二曱苯 8.38 9.84 10.92 10.65 10.80 10.72 10.56 m-二曱苯 032 0.38 0.41 0.39 0.42 0.42 0.40 〇-二甲苯 0.24 0.27 0.26 0.26 0.26 0.26 0.25 乙基曱基苯 0.16 0.12 0.10 0.10 0.08 0.07 0.07 三甲苯 0.25 0.30 0.30 0.29 0.30 0.30 0.29 C10+ 0 0 0 0 0 0 0 轉換/選擇性，莫耳％甲苯轉換 8.85 10.50 11.83 11.53 11.45 11.37 11.14 混合二甲苯選擇性 96.10 96.72 97.17 97.13 97.28 97.31 97.37 P-二甲苯選擇性 93.67 93.87 94.19 94.25 94.10 94.08 94.19 甲醇選擇性 43.34 52.29 58.23 58.46 58.09 57.73 57.06 實施例6• ' ^ Catalyst E Catalyst E synthesis. Will you pre-burn it? - Modification 28 minus -5 (as described for Catalyst A previously) combined with 20 wt% alumina binder. 17.5 g of bauxite (pseudo-boehmite type, obtained from Alcoa, HiQ-40 grade) mixed with 7.8 g ΗΝ〇3 (49·6 wt%, aqueous solution), and then with 70.0 g of P/ZSM-5 zeolite Powder (80 mesh) φ mixed. Water was sprayed onto the zeolite-alumina mixture to form an extrudable paste which was extruded to produce a 1/16-inch cylindrical extrudate. The combined catalyst was calcined in a pair of flow furnaces in air using the same temperature profile as described in Catalyst A at a maximum temperature (10 h) between 510 °C and 530 °C. The catalyst E was crushed and sieved using 20 and 40 mesh screens for catalysis testing. Catalyst E was tested for benzoquinone using the same test conditions for Catalyst A, and the results are summarized in Table 7. Table 7 Steam perfusion time, h 23.70 53.70 77.45 143.75 167.13 173.62 191.45 25 200824790 Catalyst bed inlet temperature, QC 448.1 481.0 502.8 503.7 523.8 530.5 530.6 Liquid product analysis, wt% water 20.73 19.54 19.90 20.64 20.42 20.70 20.74 Methanol 0.24 0.29 0.27 0.28 0.29 0.30 0.30 Dioxane 0 0 0 0 0 0 0 Benzene 0 0 0 0 0 0 0 Benzene 69.68 69.26 67.83 67.38 67.44 67.23 67.38 Ethylbenzene 0 0 0 0 0 0 0 p-Diphenylbenzene 8.38 9.84 10.92 10.65 10.80 10.72 10.56 M-diphenylbenzene 032 0.38 0.41 0.39 0.42 0.42 0.40 〇-xylene 0.24 0.27 0.26 0.26 0.26 0.26 0.25 ethyl decyl benzene 0.16 0.12 0.10 0.10 0.08 0.07 0.07 trimethyl 0.25 0.30 0.30 0.29 0.30 0.30 0.29 C10+ 0 0 0 0 0 0 0 conversion / selectivity, mol % toluene conversion 8.85 10.50 11.83 11.53 11.45 11.37 11.14 mixed xylene selectivity 96.10 96.72 97.17 97.13 97.28 97.31 97.37 P-xylene selectivity 93.67 93.87 94.19 94.25 94.10 94.08 94.19 methanol selectivity 43.34 52.29 58.23 58.46 58.09 57.73 57.06 Example 6

觸媒F 觸媒F之合成。將預煅燒之P-改質ZSM_5(如前述觸媒A所述)與20 wt%礬土黏著劑結合。17·5 g礬土(擬薄水鋁石型，獲自 Alcoa，HiQ-40 級）與 7.8 g ΗΝ03(70·0 wt% 水溶液）混合，然後與70.1 g之P/ZSM-5沸石粉末（80網目）混合。將水喷灑於該沸石-礬土混合物上以形成一可擠壓糊狀物，將其擠壓以製造1/16-英吋圓柱型壓出物。將該結合觸媒在一對流爐於空氣中，使用觸媒A中所述之該相同溫 26 200824790 度輪廓，以510°C至530°C間之一最大溫度（10 h)煅燒。將該觸媒F壓碎，並使用20及40網目之篩網區分大小而用於催化測試。使用觸媒A之該相同测試條件，將觸媒F 測試曱苯曱基化，且結果總結於表8。The synthesis of the catalyst F catalyst F. The pre-calcined P-modified ZSM_5 (as described for the aforementioned Catalyst A) was combined with a 20 wt% alumina adhesive. 17·5 g bauxite (pseudo-boehmite type, obtained from Alcoa, HiQ-40 grade) mixed with 7.8 g ΗΝ03 (70. 0 wt% aqueous solution), and then with 70.1 g of P/ZSM-5 zeolite powder ( 80 mesh) Mix. Water was sprayed onto the zeolite-alumina mixture to form an extrudable paste which was extruded to produce a 1/16-inch cylindrical extrudate. The combined catalyst was calcined in a pair of flow furnaces in air using the same temperature 26 200824790 degree profile as described in Catalyst A, at a maximum temperature (10 h) between 510 ° C and 530 ° C. The catalyst F was crushed and used for catalysis testing using 20 and 40 mesh screens. Catalyst F was tested for hydrazinolation using the same test conditions for Catalyst A, and the results are summarized in Table 8.

表8 蒸氣灌流時間，h 23.05 46.80 71.30 143.30 167.32 191.30 215.05 觸媒床入口溫度，QC 454.2 475.6 495.0 505.7 517.5 516.4 516.1 液態產物分析，wt% 水 20.50 20.37 20.17 20.29 20.20 20.17 20.23 曱醇 0.41 0·48 0.47 0.54 0.56 0.57 0.57 二曱醚 0 0 0 0 0 0 0 苯 0 0 0 0 0 0 0 甲苯 70.88 69.90 69.60 69.88 70.17 70.14 70.08 乙苯 0 0 0 0 0 0 0 P-二曱苯 7.50 8.55 9.02 8.59 8.38 8.41 8.41 m-二甲苯 0.21 0.22 0.24 0.24 0.24 0.24 0.24 〇-二甲苯 0.17 0.17 0.18 0.18 0.18 0.18 0.18 乙基曱基苯 0.14 0.12 0.10 0.08 0.07 0.07 0.07 三甲苯 0.18 0.19 0.21 0.21 0.20 0.21 0.21 C10+ 0 0 0 0 0 0 0 轉換/選擇性，莫耳％曱苯轉換 7.66 8.78 9.53 8.54 8.14 8.69 8.58 混合二甲苯選擇性 96.53 97.08 9732 97.23 97.33 97.43 97.36 p-二甲苯選擇性 95.19 95.60 95.53 95.32 95.23 95.19 95.16 甲醇選擇性 41.74 48.33 52.36 50.76 48.74 51.77 50.73 實施例7 觸媒G。將一 NH4-ZSM-5沸石（Si02/Al203莫耳比率 280)經由一濕浸潰法以H3P04處理，然後於550°C之一最 27 200824790 大溫度加熱。該P-處理之ZSM-5沸石粉末的分析顯示於表 9及表10。該P/ZSM-5顯示與觸媒A相似之性質。觸媒G 係使用該P/ZSM_5沸石粉末及20%礬土黏著劑製造，該礬土黏著劑已如下製備：將25.0 g之礬土（擬薄水鋁石型，獲自 Alcoa，Hi/Q_40 級）與 10.7 g ΗΝ03(70·0 wt%水溶液）混合，然後與100.0 g之P-處理之沸石粉末（80網目）混合。將水喷灑於該沸石-礬土混合物上以形成一可擠壓糊狀物，將其擠壓以製造1/16-英吋圓柱型壓出物。將經擠壓之如觸媒A所述緞燒。使用實施例1中之該相同測試條件，將觸媒G測試甲苯甲基化，且結果總結於表11。表10 粉末XRD強度1Table 8 Steam perfusion time, h 23.05 46.80 71.30 143.30 167.32 191.30 215.05 Catalyst bed inlet temperature, QC 454.2 475.6 495.0 505.7 517.5 516.4 516.1 Liquid product analysis, wt% water 20.50 20.37 20.17 20.29 20.20 20.17 20.23 sterol 0.41 0·48 0.47 0.54 0.56 0.57 0.57 Dioxane 0 0 0 0 0 0 0 Benzene 0 0 0 0 0 0 0 Toluene 70.88 69.90 69.60 69.88 70.17 70.14 70.08 Ethylbenzene 0 0 0 0 0 0 0 P-Diphenylbenzene 7.50 8.55 9.02 8.59 8.38 8.41 8.41 M-xylene 0.21 0.22 0.24 0.24 0.24 0.24 0.24 〇-xylene 0.17 0.17 0.18 0.18 0.18 0.18 0.18 ethyl decyl benzene 0.14 0.12 0.10 0.08 0.07 0.07 0.07 trimethylbenzene 0.18 0.19 0.21 0.21 0.20 0.21 0.21 C10+ 0 0 0 0 0 0 0 conversion / selectivity, molar % benzene conversion 7.66 8.78 9.53 8.54 8.14 8.69 8.58 mixed xylene selectivity 96.53 97.08 9732 97.23 97.33 97.43 97.36 p-xylene selectivity 95.19 95.60 95.53 95.32 95.23 95.19 95.16 methanol selectivity 41.74 48.33 52.36 50.76 48.74 51.77 50.73 Example 7 Catalyst G. An NH4-ZSM-5 zeolite (SiO2/Al203 molar ratio 280) was treated with H3P04 by a wet dipping method and then heated at a maximum temperature of 550 ° C at most 27 200824790. The analysis of the P-treated ZSM-5 zeolite powder is shown in Tables 9 and 10. This P/ZSM-5 shows properties similar to Catalyst A. Catalyst G was made using the P/ZSM_5 zeolite powder and 20% alumina adhesive. The alumina adhesive was prepared as follows: 25.0 g of alumina (pseudo-boehmite type, obtained from Alcoa, Hi/Q_40) Grade) was mixed with 10.7 g ΗΝ03 (70. 0 wt% aqueous solution) and then mixed with 100.0 g of P-treated zeolite powder (80 mesh). Water was sprayed onto the zeolite-alumina mixture to form an extrudable paste which was extruded to produce a 1/16-inch cylindrical extrudate. The extruded satin such as the catalyst A is burned. Catalyst G was tested for methylation of toluene using the same test conditions as in Example 1, and the results are summarized in Table 11. Table 10 Powder XRD Strength 1

d-間距[A] 強度強度 11.08 9.99 100 54 9.89 46 9.70 17 8.01 6 6.54 7 6.33 9 5.98 16 5.70 6 d-間距[A] 425 4.00 7 3.84 57 3.80 27 3.71 28 3.64 11 3.53 18 2.98 10 2.78 6 表9 原素分析wt% 一 X 一_一_·— N2吸附 Si A1 P SA，m2/g PV，ml/g 35.38 0.30 9.72 188 0.15 5.55 8 28 1 所顯示之強度以任意單位計數，因此最大強度之尖峰為100。 200824790 表11D-spacing [A] Strength intensity 11.08 9.99 100 54 9.89 46 9.70 17 8.01 6 6.54 7 6.33 9 5.98 16 5.70 6 d-pitch [A] 425 4.00 7 3.84 57 3.80 27 3.71 28 3.64 11 3.53 18 2.98 10 2.78 6 9 Element analysis wt% X X____- N2 adsorption Si A1 P SA, m2/g PV, ml/g 35.38 0.30 9.72 188 0.15 5.55 8 28 1 The intensity shown is counted in arbitrary units, so the maximum intensity The peak is 100. 200824790 Table 11

蒸氣灌流時間，h 23.42 47.08 77.42 144.08 173.42 214.88 245.75 觸媒床入口溫度，°C 463.4 463.8 487.0 501.0 511.0 511.8 509.20 液態產物分析，wt% 水 20.82 20.88 21.64 21.13 20.87 20.79 20.70 甲醇 0.04 0.08 0.06 0.05 0.06 0.06 0.06 二甲醚 0 0 0 0 0 0 0 苯 0 0 0 0 0 0 0 甲苯 66.97 67.20 65.19 64.61 64.51 64.68 64.60 乙苯 0 0 0 0 0 0 0 P-二甲苯 11.49 11.14 12.39 12.84 13.80 13.71 13.86 m-二曱苯 0.24 0.24 0.27 0.29 0.30 0.30 0.31 〇-二甲苯 0.14 0.14 0.15 0.15 0.16 0.16 0.16 乙基甲基苯 0.17 0.16 0.15 0.14 0.13 0.13 0.13 三甲苯 0.14 0.15 0.16 0.16 0.17 0.17 0.18 G10+ 0 0 0 0 0 0 0Vapor perfusion time, h 23.42 47.08 77.42 144.08 173.42 214.88 245.75 Catalyst bed inlet temperature, °C 463.4 463.8 487.0 501.0 511.0 511.8 509.20 Liquid product analysis, wt% water 20.82 20.88 21.64 21.13 20.87 20.79 20.70 Methanol 0.04 0.08 0.06 0.05 0.06 0.06 0.06 II Methyl ether 0 0 0 0 0 0 0 benzene 0 0 0 0 0 0 0 Toluene 66.97 67.20 65.19 64.61 64.51 64.68 64.60 Ethylbenzene 0 0 0 0 0 0 0 P-xylene 11.49 11.14 12.39 12.84 13.80 13.71 13.86 m-diphenylbenzene 0.24 0.24 0.27 0.29 0.30 0.30 0.31 〇-xylene 0.14 0.14 0.15 0.15 0.16 0.16 0.16 0.16 0.16 0.16 0.16 0.15 0.14 0.13 0.13 0.13 Trimethyl 0.14 0.15 0.16 0.16 0.17 0.17 0.18 G10+ 0 0 0 0 0 0 0

轉換/選擇性，莫耳％甲苯轉換 12.17 11.36 13.26 14.30 14.86 14.64 14.80 混合二甲苯選擇性 97.84 97.64 98.04 94.74 98.25 98.24 98.20 P-二甲苯選擇性 96.83 96.74 96.76 96.69 96.79 96.79 96.74 甲醇選擇性 54.01 51.43 59.13 62.95 66.06 65.70 65.39 實施例8-9 使用作為基質之黏土Conversion/selectivity, mol% Toluene conversion 12.17 11.36 13.26 14.30 14.86 14.64 14.80 Mixed xylene selectivity 97.84 97.64 98.04 94.74 98.25 98.24 98.20 P-xylene selectivity 96.83 96.74 96.76 96.69 96.79 96.79 96.74 Methanol selectivity 54.01 51.43 59.13 62.95 66.06 65.70 65.39 Examples 8-9 Using clay as a matrix

觸媒H-I 使用該P-改質ZSM-5粉末(如觸媒A所述），使用10% 礬土及10%高嶺土黏土做為黏著劑基質而形成二種觸媒。觸媒Η : 8·75 g馨土（擬薄水銘石型，獲自Alcoa， 29 200824790Catalyst H-I uses the P-modified ZSM-5 powder (as described for Catalyst A) and uses 10% alumina and 10% kaolin clay as the binder matrix to form two catalysts. Catalyst Η : 8·75 g Xinyu (small thin water Mingshi type, obtained from Alcoa, 29 200824790

HlQe40 級）與 8.75 g 高嶺土黏土(Aldrich)混合，且與 7·8 g ΗΝ〇3(19·9 wt%水溶液）混合，然後與70.1 g之P/ZSM-5沸石粉末（80網目）混合。將水喷灑於該沸石-礬土混合物上以形成一可擠壓糊狀物，將其擠壓以製造1/16-英吋圓柱型壓出物。將結合觸媒在一對流爐於空氣中，使用觸媒A中所述之該相同溫度輪廓，以51(rc至53{rc間之一最大溫度 (1〇 h)煅燒。將該觸媒η壓碎，並使用2〇及4〇網目之篩網區分大小而用於催化測試。使用該相同測試條件，將觸媒π測試甲苯甲基化，且結果總結於表12。着觸媒1。8.75 g礬土（擬薄水鋁石型，獲自Alcoa，HiQ_40 級）與 8·75 g 高嶺土黏土(Aldrich)與 7·8 ㊁ hn〇3 (40.0 wt% 水溶液）混合，然後與7(U g之P/ZSM_5沸石粉末(8〇網目）混合。將水喷灑於該沸石_礬土混合物上以形成一可擠壓糊狀物，將其擠壓以製造i/W-英吋圓柱型壓出物。將該結合觸媒在一對流爐於空氣中，使用觸媒A中所述之該相同溫度輪廓，以51(TC至53(TC間之最大溫度（1〇 h)烺燒。將 φ 該觸媒I壓碎，並使用20及40網目之篩網區分大小而用於催化測試。使用實施例1之該相同測試條件，將觸媒I 測試曱苯曱基化，且結果總結於表13。表12 觸媒床入口溫度，。C 452.6 475.7 506.2 518.1 521-5 523.8 523.9 參態產物分析，wt% 30 200824790HlQe 40 grade) was mixed with 8.75 g of kaolin clay (Aldrich) and mixed with 7·8 g of ΗΝ〇3 (19.9% by weight aqueous solution) and then mixed with 70.1 g of P/ZSM-5 zeolite powder (80 mesh). Water was sprayed onto the zeolite-alumina mixture to form an extrudable paste which was extruded to produce a 1/16-inch cylindrical extrudate. Combining the catalyst in a pair of flow furnaces in the air, using the same temperature profile as described in Catalyst A, calcining at 51 (rc to 53{rc maximum temperature (1 〇h). The catalyst η It was crushed and sieved using a 2 〇 and 4 〇 mesh screen for catalysis. Using the same test conditions, the catalyst π was tested for methylation of toluene, and the results are summarized in Table 12. Catalyst 1. 8.75 g bauxite (pseudo-boehmite type, obtained from Alcoa, HiQ_40 grade) mixed with 8.75 g kaolin clay (Aldrich) and 7·8 hn〇3 (40.0 wt% aqueous solution), then with 7 (U g P/ZSM_5 zeolite powder (8 mesh) mixed. Water was sprayed onto the zeolite_alumina mixture to form an extrudable paste, which was extruded to make an i/W-inch cylinder. The binder is used in a pair of flow furnaces in air, using the same temperature profile as described in Catalyst A, at 51 (TC to 53 (maximum temperature between TCs (1 〇h)). The catalyst I was crushed and used for catalysis testing using a 20 and 40 mesh screen. The catalyst I test was performed using the same test conditions of Example 1. Yue group of benzene, and the results are summarized in Table 13. Table 12 catalyst bed inlet temperature, .C 452.6 475.7 506.2 518.1 521-5 523.8 523.9 reference state product analysis, wt% 30 200824790

水 19.34 19.26 19.94 19.48 19.07 18.93 18.92 甲醇 0.31 0.29 0.24 0.22 0.25 0.27 0.27 二甲醚 0 0 0 0 0 0 0 苯 0 0 0 0 0 0 0 甲苯 71,33 69.61 67.30 67.38 67.64 67.68 67.62 乙苯 0 0 0 0 0 0 0 P-二甲苯 8.13 9.92 11.62 12.00 12.13 12.21 12.27 m-二甲苯 0.29 0.32 0.35 0.36 0.36 0.36 0.36 〇-二甲苯 0.23 0.22 0.21 0.21 0.21 0.21 0.22 乙基甲基苯 0.15 0.12 0.10 0.10 0.09 0.09 0.09 三甲苯 0.22 0.24 0.25 0.25 0.25 0.25 0.26 C10+ 0 0 0 0 0 0 0 轉換/選擇性，莫耳％甲苯轉換 8.73 10.60 12.63 12.86 12.88 12.89 12.90 混合二甲苯選擇性 96.51 97.18 97.66 97.75 97.78 97.80 97.79 ./ · P-二曱苯選擇性 94.04 94.76 95.37 95.43 95.54 95.52 95.48 ο甲酉1選曼色 42.93 51.87 60.22 60.41 63.03 62.30 63.05 表13 蒸氣灌流時間，h 29.23 53.40 77.40 149.40 191.23 215.15 245.40Water 19.34 19.26 19.94 19.48 19.07 18.93 18.92 Methanol 0.31 0.29 0.24 0.22 0.25 0.27 0.27 Dimethyl ether 0 0 0 0 0 0 0 Benzene 0 0 0 0 0 0 0 Toluene 71,33 69.61 67.30 67.38 67.64 67.68 67.62 Ethylbenzene 0 0 0 0 0 0 0 P-xylene 8.13 9.92 11.62 12.00 12.13 12.21 12.27 m-xylene 0.29 0.32 0.35 0.36 0.36 0.36 0.36 〇-xylene 0.23 0.22 0.21 0.21 0.21 0.21 0.22 0.25% ethyl methyl benzene 0.15 0.12 0.10 0.10 0.09 0.09 0.09 trimethylbenzene 0.22 0.24 0.25 0.25 0.25 0.25 0.26 C10+ 0 0 0 0 0 0 0 Conversion / Selectivity, Molar % Toluene Conversion 8.73 10.60 12.63 12.86 12.88 12.89 12.90 Mixed Xylene Selectivity 96.51 97.18 97.66 97.75 97.78 97.80 97.79 ./ · P-II Benzene selectivity 94.04 94.76 95.37 95.43 95.54 95.52 95.48 ο甲酉1选曼色42.93 51.87 60.22 60.41 63.03 62.30 63.05 Table 13 Vapor perfusion time, h 29.23 53.40 77.40 149.40 191.23 215.15 245.40

觸媒床入口溫度，。C 464.5 483.9 505.3 517.2 530.9 531.7 531.2 液態產物分析，wt% 水 21.06 19.90 20.70 19.67 19.42 19.94 19.14 甲醇 0.27 0.30 032 0.38 0.35 0.36 0.38 二甲醚 0 0 0 0 0 0 0 苯 0 0 0 0 0 0 0 甲苯 68.73 68.98 68.01 69.33 69.66 69.30 70.33 乙苯 0 0 0 0 0 0 0 P-二甲苯 9.14 9.97 10.12 9.81 9.80 9.65 9.34 m-二曱苯 0.27 0.30 0.30 0.31 0.30 0.28 0.29 〇-二甲苯 0.19 0.20 0.20 0.20 0.19 0.19 0.19 乙基曱基笨 0.13 0.11 0.10 0.07 0.06 0.06 0.06 三甲苯 0.21 0.24 0.24 0.23 0.22 0.22 0.22 31 200824790 C10+ 0 0 0 0 0 0 0 轉換/選擇性，莫耳％甲苯轉換 9.72 10.58 10.56 10.06 9.82 9.67 9.30 混合二甲苯選擇性 97.11 97.27 97.41 97.58 97.71 97.69 97.67 p-二甲苯選擇性 95.19 95.24 95.26 95.14 95.22 95.35 95.12 甲醇選擇性 48.49 * 52.69 53.99 蝴·顆雛 54.01 52.76 52.57 51.01 實施例10-12 以礬土消化法製造之觸媒Catalyst bed inlet temperature,. C 464.5 483.9 505.3 517.2 530.9 531.7 531.2 Analysis of liquid product, wt% Water 21.06 19.90 20.70 19.67 19.42 19.94 19.14 Methanol 0.27 0.30 032 0.38 0.35 0.36 0.38 Dimethyl ether 0 0 0 0 0 0 0 Benzene 0 0 0 0 0 0 0 Toluene 68.73 68.98 68.01 69.33 69.66 69.30 70.33 Ethylbenzene 0 0 0 0 0 0 0 P-xylene 9.14 9.97 10.12 9.81 9.80 9.65 9.34 m-diphenylbenzene 0.27 0.30 0.30 0.31 0.30 0.28 0.29 〇-xylene 0.19 0.20 0.20 0.20 0.19 0.19 0.19 B基曱基笨 0.13 0.11 0.10 0.07 0.06 0.06 0.06 Trimethylbenzene 0.21 0.24 0.24 0.23 0.22 0.22 0.22 0.2200824790 C10+ 0 0 0 0 0 0 0 Conversion / Selectivity, Molar % Toluene Conversion 9.72 10.58 10.56 10.06 9.82 9.67 9.30 Mixed xylene Selectivity 97.11 97.27 97.41 97.58 97.71 97.69 97.67 p-xylene selectivity 95.19 95.24 95.26 95.14 95.22 95.35 95.12 Methanol selectivity 48.49 * 52.69 53.99 Butterfly · stalk 54.01 52.76 52.57 51.01 Example 10-12 Touch made by bauxite digestion Media

觸媒J_L 一 P-改質ZSM-5經由下列敘述於美國專利案第 6,943,131 號(Ghosh et al·，2005)之方法製造。將 5.0 g 礬土 (擬薄水鋁石型，獲自Alcoa，HiQ_40級)於溫度70-80oC 溶於100 ml之水與67.04 g H3P04 (85 wt%水溶液）中。將該礬土溶液於溫度90-100QC添加至含250.0 g NH4ZSM-5 (Si02/Al203莫耳比率280)及500 ml水之一沸石漿體。攪拌該沸石漿體並蒸發至乾燥，且將該經改質ZSM-5使用先前段落中觸媒A所述之該溫度輪廓煅燒。如下所述，三種觸媒經由使用該P-改質ZSM-5所製造。實施例1〇(比較性）觸媒J :將該P-改質ZSM-5(如前述)與20 wt%礬土黏著劑結合。17.5 g礬土(擬薄水鋁石型，獲自Alcoa，HiQ-40 級)與70.1 g之P/ZSM-5沸石粉末(8〇網目）混合，並無酸使用於該礬土。將水噴灑於該沸石及礬土混合物上以形成 32 200824790 一可擠壓糊狀物，將其擠壓以製造1/16-英对圓柱型壓出物。將該結合觸媒在一對流爐於空氣中，使用觸媒A中所述之該相同溫度輪廓，以510〇C至530°C間之一最大溫度 (10 h)煅燒。將該觸媒j壓碎，並使用20及40網目之篩網區分大小而用於催化測試。使用實施例1之該相同.測試條件’將觸媒J測試甲苯甲基化，且結果總結於表14。 • 實施例11 觸媒K。將預煅燒P-改質ZSM_5(如前述)與20 wt%礬土黏者劑結合。16.34 g濛土（擬薄水銘石型，獲自Alcoa， HiQ_40級）與7.27 g HN〇3 (40·0 wt%水溶液）混合，然後與65.4 g之P/ZSM-5沸石粉末（80網目）混合。將水喷灑於該沸石-馨土混合物上以形成一可擠壓糊狀物，將其擠壓以. 製造1/16-英吋圓柱型壓出物。將該結合觸媒在一對流爐各空氣中，使用觸媒A中所述之該相同溫度輪廓，以510°C _ 至530°C間之一最大溫度（10 h)煅燒。將該觸媒κ壓碎，並使用20及40網目之篩網區分大小而用於催化測試。使用實施例1之該相同測試條件，將觸媒Κ測試甲苯甲基化，且結果總結於表15。實施例12 觸媒 L。將 37·8 g 馨土與 16.7 g HN〇3 (70.0 wt%水溶液)混合’然後與151·1 g該改質ZSM-5沸石粉末(80網目）混合。將水喷灑於該沸石-礬土混合物上以形成一可擠壓糊 33 200824790 狀物，將其擠壓以製造1/16-英吋圓柱型壓出物。將該結合觸媒在一對流爐於空氣中，使用觸媒A中所述之該相同溫度輪廓，以510°C至530°C間之一最大溫度（10 h)缎燒。將該觸媒L壓碎，並使用20及40網目之篩網區分大小而用於催化測試。使用實施例1之該相同測試條件，將觸媒 L測試甲苯甲基化，且結果總結於表16。表14 .....................................................................................................................................................................Catalyst J_L-P-modified ZSM-5 was produced by the method described in U.S. Patent No. 6,943,131 (Ghosh et al., 2005). 5.0 g of alumina (pseudo-boehmite type, obtained from Alcoa, HiQ_40 grade) was dissolved in 100 ml of water and 67.04 g of H3P04 (85 wt% aqueous solution) at a temperature of 70-80 °C. The alumina solution was added to a zeolite slurry containing 250.0 g of NH4ZSM-5 (Si02/Al203 molar ratio 280) and 500 ml of water at a temperature of 90-100 QC. The zeolite slurry was stirred and evaporated to dryness, and the modified ZSM-5 was calcined using the temperature profile described in Catalyst A in the previous paragraph. As described below, the three catalysts were produced by using the P-modified ZSM-5. Example 1 (Comparative) Catalyst J: The P-modified ZSM-5 (as described above) was combined with 20 wt% alumina adhesive. 17.5 g of bauxite (pseudo-boehmite type, obtained from Alcoa, HiQ-40 grade) was mixed with 70.1 g of P/ZSM-5 zeolite powder (8 〇 mesh), and no acid was used for the alumina. Water was sprayed onto the zeolite and alumina mixture to form 32 200824790 an extrudable paste which was extruded to produce a 1/16-inch pair of cylindrical extrudates. The combined catalyst was calcined in a pair of flow furnaces in air using the same temperature profile as described in Catalyst A at a maximum temperature (10 h) between 510 ° C and 530 ° C. The catalyst j was crushed and used for catalysis testing using a 20 and 40 mesh screen size. Catalyst J was tested for toluene methylation using the same. Test Conditions of Example 1 and the results are summarized in Table 14. • Example 11 Catalyst K. The precalcined P-modified ZSM_5 (as described above) was combined with a 20 wt% alumina binder. 16.34 g of monastite (pseudo-thin water type, obtained from Alcoa, HiQ_40 grade) mixed with 7.27 g of HN〇3 (40. 0 wt% aqueous solution) and then mixed with 65.4 g of P/ZSM-5 zeolite powder (80 mesh) . Water was sprayed onto the zeolite-sandwich mixture to form an extrudable paste which was extruded to produce a 1/16-inch cylindrical extrudate. The combined catalyst was calcined in each of a pair of flow furnaces using the same temperature profile as described in Catalyst A at a maximum temperature (10 h) between 510 ° C _ and 530 ° C. The catalyst κ was crushed and used for catalysis testing using 20 and 40 mesh screens to size. The catalyst was tested for toluene methylation using the same test conditions as in Example 1, and the results are summarized in Table 15. Example 12 Catalyst L. 37. 8 g of cassava was mixed with 16.7 g of HN 〇 3 (70.0 wt% aqueous solution) and then mixed with 151.1 g of the modified ZSM-5 zeolite powder (80 mesh). Water was sprayed onto the zeolite-alumina mixture to form an extrudable paste 33 200824790 which was extruded to make a 1/16-inch cylindrical extrudate. The bonding catalyst was satin-sintered in a pair of flow furnaces in air using the same temperature profile as described in Catalyst A at a maximum temperature (10 h) between 510 ° C and 530 ° C. The catalyst L was crushed and used for catalysis testing using a mesh of 20 and 40 mesh screens. Catalyst L was tested for methylation of toluene using the same test conditions as in Example 1, and the results are summarized in Table 16. Table 14 ................................................ .................................................. .................................................. .................

蒸氣灌流時間，h 23.50 47.48 77.83 167.52 191.52 215.45 239.43 觸媒床入口溫度，QC 456.2 478.0 488.5 489.1 489.3 489.3 489.2 液態產物分析，Wt% 水 20.06 20.10 19.97 20.07 19.82 19.94 19.74 甲醇 0.02 0 0 0 0 0 0 二曱醚 0 0 0 0 0 0 0 苯 0 0 0 0 0 0 0 甲苯 68.09 66.78 66.20 65.76 65.79 65.63 65.74 乙苯 0 0 0 0 0 0 0 P-二甲苯 9.01 10.23 10.80 11.05 11.23 11.31 11.39 m-二甲苯 1.23 1.47 1.59 1.63 1.63 1.63 1.63 〇-二曱苯 0.75 0.71 0.74 0.77 0.77 0.77 0.77 乙基甲基苯 0.19 0.16 0.15 0.14 0.13 0.13 0.13 三甲苯 0.59 0.55 0.56 0.58 0.59 0.59 0.60 C10+ 0.06 0 0 0 0 0 0 轉換/選擇性，莫耳％甲苯轉換 11.94 13.29 13.97 14.47 14.66 14.68 14.82 混合二甲苯選擇性 94.01 95.40 95.68 95.68 95.74 95.74 95.75 p-二甲苯選擇性 82.03 82.44 82.24 82.17 82.48 82.51 82.60 甲醇選擇性 51.13 57.39 60.57 62.64 63.36 63.65 64.04Vapor perfusion time, h 23.50 47.48 77.83 167.52 191.52 215.45 239.43 Catalyst bed inlet temperature, QC 456.2 478.0 488.5 489.1 489.3 489.3 489.2 Liquid product analysis, Wt% water 20.06 20.10 19.97 20.07 19.82 19.94 19.74 Methanol 0.02 0 0 0 0 0 0 Ether 0 0 0 0 0 0 0 Benzene 0 0 0 0 0 0 0 Toluene 68.09 66.78 66.20 65.76 65.79 65.63 65.74 Ethylbenzene 0 0 0 0 0 0 0 P-xylene 9.01 10.23 10.80 11.05 11.23 11.31 11.39 m-xylene 1.23 1.47 1.59 1.63 1.63 1.63 1.63 〇-diphenylbenzene 0.75 0.71 0.74 0.77 0.77 0.77 0.77 ethylmethylbenzene 0.19 0.16 0.15 0.14 0.13 0.13 0.13 0.13 0.15 0.55 0.55 0.56 0.58 0.59 0.59 0.60 C10+ 0.06 0 0 0 0 0 0 Conversion / Selectivity , mole % toluene conversion 11.94 13.29 13.97 14.47 14.66 14.68 14.82 mixed xylene selectivity 94.01 95.40 95.68 95.68 95.74 95.74 95.75 p-xylene selectivity 82.03 82.44 82.24 82.17 82.48 82.51 82.60 methanol selectivity 51.13 57.39 60.57 62.64 63.36 63.65 64.04

表15 34 200824790Table 15 34 200824790

蒸氣灌流時間，h 23.10 47.10 77.90 143.65 167.55 191.90 觸媒床入口溫度，°C 452.1 464.8 478.8 481.0 481.6 481.6 液態產物分析，wt% 水 19.69 19.54 20.06 19.54 19.76 20.31 曱醇 0.03 0 0 0 0.01 0.01 二甲醚 0 0 0 0 0 0 苯 0 0 0 0 0 0 曱苯 68.23 67.50 66.03 6637 66.16 65.44 乙苯 0 0 0 0 0 0 P-二曱苯 9.84 10.61 11.53 11.69 11.70 11.88 Π1-二《甲苯 0.96 1.11 1.16 1.17 1.15 1.14 〇-二甲苯 0.56 0.57 0.57 0.58 0.57 0.57 乙基曱基苯 0.18 0.18 0.15 0.15 0.15 0.14 三甲苯 0.52 0.49 0.50 0.51 0.51 0.51 C10+ 0 0 0 0 0 0 轉換/選擇性，莫耳％曱苯轉換 12.09 13.04 14.15 14.31 14.32 14.69 混合二甲苯選擇性 95.07 95.59 96.04 96.07 96.09 96.17—' P-二甲苯選擇性 86.64 86.34 86.96 87.00 87.21 87.44 ^ 曱醇選擇性 52.80 56.57 61.59 61.76 61.93 63.38Vapor perfusion time, h 23.10 47.10 77.90 143.65 167.55 191.90 Catalyst bed inlet temperature, °C 452.1 464.8 478.8 481.0 481.6 481.6 Liquid product analysis, wt% water 19.69 19.54 20.06 19.54 19.76 20.31 sterol 0.03 0 0 0 0.01 0.01 dimethyl ether 0 0 0 0 0 0 Benzene 0 0 0 0 0 0 Benzene 68.23 67.50 66.03 6637 66.16 65.44 Ethylbenzene 0 0 0 0 0 0 P-Diphenylbenzene 9.84 10.61 11.53 11.69 11.70 11.88 Π1-二Toluene 0.96 1.11 1.16 1.17 1.15 1.14 〇-xylene 0.56 0.57 0.57 0.58 0.57 0.57 ethyl decyl benzene 0.18 0.18 0.15 0.15 0.15 0.14 trimethylbenzene 0.52 0.49 0.50 0.51 0.51 0.51 C10+ 0 0 0 0 0 0 conversion / selectivity, mol % benzene conversion 12.09 13.04 14.15 14.31 14.32 14.69 Mixed xylene selectivity 95.07 95.59 96.04 96.07 96.09 96.17—' P-xylene selectivity 86.64 86.34 86.96 87.00 87.21 87.44 ^ Sterol selectivity 52.80 56.57 61.59 61.76 61.93 63.38

表16 蒸氣灌流時間，h 24.85 47.53 120.12 143.85 167.53 191.53 222.35 觸媒床入口溫度，°C 446.2 473.6 494.6 505.0 505.4 505.6 505.0 產物分析，wt% 水 19.97 19.74 20.11 19.80 19.85 20,03 20.11 甲醇 0.17 0.13 0.12 0.11 0.12 0.12 0.12 二甲醚 0 0 0 0 0 0 0 苯 0 0 0 0 0 0 0 甲苯 70.41 68.17 66.63 66.36 66.23 65.82 65.53 .乙苯 0 0 0 0 0 0 0 p-二甲苯 8.49 11.00 12.15 12.71 12.78 12.99 13.18 m-二曱苯 0.32 0.36 0.39 0.40 0.41 0.41 0.43 〇-二曱苯 0.24 0.23 0.23 0.23 0.23 0.23 0.24 35 200824790 觸媒 A 黏著劑 No黏著劑 gHN03/g黏著劑a PX選擇性（莫耳％) 88.53 B 20%A12〇3 0 88.91 C 20%A12〇3 0.089 91.58 D 20%A12〇3 0.178 93.84 E 20%A12〇3 0.220 94.15 F 20%A12〇3 0.311 95.19 G 20%A12〇3 0.311 96.76 Η io%ai2o3 (+10% 高領土） 0.089 95.16 I 10%A12〇3 (+10% 高領土） 0.178 95.22 Jb 20%A12〇3 0 82.41 Kb 20%A12〇3 0.178 87.20 Lb 20%A12〇3 0.311 95.28 ........................ a :黏著劑或黏著劑加高嶺土； b :經由A1消化法製造之PZSM-5Table 16 Steam perfusion time, h 24.85 47.53 120.12 143.85 167.53 191.53 222.35 Catalyst bed inlet temperature, °C 446.2 473.6 494.6 505.0 505.4 505.6 505.0 Product analysis, wt% Water 19.97 19.74 20.11 19.80 19.85 20,03 20.11 Methanol 0.17 0.13 0.12 0.11 0.12 0.12 0.12 dimethyl ether 0 0 0 0 0 0 0 benzene 0 0 0 0 0 0 0 toluene 70.41 68.17 66.63 66.36 66.23 65.82 65.53 . ethylbenzene 0 0 0 0 0 0 0 p-xylene 8.49 11.00 12.15 12.71 12.78 12.99 13.18 m - Diphenylbenzene 0.32 0.36 0.39 0.40 0.41 0.41 0.43 〇-Diphenylbenzene 0.24 0.23 0.23 0.23 0.23 0.23 0.23 0.24 35 200824790 Catalyst A Adhesive No Adhesive gHN03/g Adhesive a PX Selective (Molar%) 88.53 B 20 %A12〇3 0 88.91 C 20%A12〇3 0.089 91.58 D 20%A12〇3 0.178 93.84 E 20%A12〇3 0.220 94.15 F 20%A12〇3 0.311 95.19 G 20%A12〇3 0.311 96.76 Η io%ai2o3 (+10% high territory) 0.089 95.16 I 10%A12〇3 (+10% high territory) 0.178 95.22 Jb 20%A12〇3 0 82.41 Kb 20%A12〇3 0.178 87.20 Lb 20%A12〇3 0.311 95.28 .. ...................... a : Adhesive or adhesive plus kaolin b: the process for producing the A1 digestion PZSM-5

乙基曱基苯 0.17 0.14 0,12 0.11 0.11 __ 0,11 三甲苯 0.24 0.25 0.26 0.27 0.27 0.27 C10+ 0 0 0 0 0 0 轉換/選擇性，莫耳％甲苯轉換 9.42 12.10 13.41 14.08 14.06 14.32 混合二甲苯選擇性 96.36 97.27 97.55 97.67 97.68 97.67 P-二甲苯選擇性 93.84 94.97 95.18 95.27 95.28 95.27 甲醇選擇性 …：> ^ … 44.34 56.00 61.54 64.33 64.82 65.73 表17 在各種P-ZSM-5 觸媒上之PX選擇性 0.12 0.28 14.62 97.64 95.20 64.99 實施例13-16 (比較性）Ethylmercaptobenzene 0.17 0.14 0,12 0.11 0.11 __ 0,11 Trimethylbenzene 0.24 0.25 0.26 0.27 0.27 0.27 C10+ 0 0 0 0 0 0 Conversion / Selectivity, Molar % Toluene Conversion 9.42 12.10 13.41 14.08 14.06 14.32 Mixed Xylene Selectivity 96.36 97.27 97.55 97.67 97.68 97.67 P-xylene selectivity 93.84 94.97 95.18 95.27 95.28 95.27 Methanol selectivity...:> ^ ... 44.34 56.00 61.54 64.33 64.82 65.73 Table 17 PX selection on various P-ZSM-5 catalysts Sex 0.12 0.28 14.62 97.64 95.20 64.99 Example 13-16 (comparative)

m ^ M-N 觸媒M-N之合成。將佛石H-ZSM_5(Si02/Al203莫耳比率280)粉末與礬土結合，以製造二種觸媒，一種無混合 36 200824790 礬土與硝酸，而另一種混合礬土與硝酸。該沸石不以磷改質。實施例13 觸媒Μ :將25.0g礬土 (擬薄水鋁石型，獲自Alcoa， HiQ-40級）與100.1 g之該HZSM-5沸石粉末（80網目）混合。將水喷灑於該沸石與礬土混合物上，將其擠壓以製造 1/16-英对圓柱型壓出物。實施例14 觸媒N:將20.2 g之礬土 (擬薄水鋁石型，獲自Alcoa， HiQ-40級）與8.97 g HN〇3 (70.0 wt%水溶液）混合，然後與 80.6 g之該HZSM-5沸石粉末（80網目）混合。將水喷灑於該沸石-礬土混合物上以形成一可擠壓糊狀物，將其擠壓以製造1/16-英吋圓柱型壓出物。二種經擠壓之觸媒在一對流爐於空氣中，使用觸媒A 中所述之該相同溫度輪廓，以510°C至530°€間之一最大溫度（10 h)煅燒。將該觸媒壓碎，並使用20及40網目之篩網區分大小而用於催化測試。使用實施例1之該相同測試條件，將觸媒Μ及N測試曱苯曱基化，且結果分別總結於表18及19。奏18..................................................................................................................................................................................................................................................................................................................................................— 產氣樓流時間，h 23.32 47.33 77.87 143.28 173.88 198.08 245.57 觸媒床入口溫度，。C 453.7 464.4 463.7 474.9 472.5 473.2 472.5 37 200824790 液態產物分析，Wt% 水 20.28 19.86 20.11 20.18 20.00 19.68 20.03 甲醇 0 0 0 0 0 0 0 二甲醚 0 0 0 0 0 0 0 苯 0 0.16 0.12 0.13 0.10 0.09 0.08 甲苯 66.⑻ 66.03 65.83 65.75 66.01 66.47 66.21 乙苯 0 0 0 0 0 0 0 P-二甲苯 3.07 3.23 3.34 3.42 3.56 3.58 3.68 m-二甲苯 6.47 6.59 6.43 6.43 6.22 6.11 5.99 〇-二甲苯 2.68 2.74 2.71 2.72 2.64 2.61 2.56 乙基甲基苯 0.74 0.55 0.47 0.36 0.36 0.33 0.33 三甲苯 0.66 0.74 0.86 0.91 0.97 0.98 0.99 C10+ 0.11 0.11 0.13 0.12 0.14 0.14 0.14 轉換/選擇性，莫耳％甲苯轉換 13.70 14.05 14.08 14.26 13.86 13.74 13.68 混合二甲苯選擇性 90.02 89.53 89.36 89.87 90.07 89.67 90.18 P-二甲苯選擇性 25.13 25.70 26.74 27.20 28.64 29.14 30.10 曱醇選擇性 55.25 56.46 56.88 :故從::::;::::::::從欲功從:::::::::從欲》*%% 57.81 56.57 ；;::::從％:*%奴；:::％從欲:：：:欲雄《?5::狗^*:*: 55.94 55.88m ^ M-N Catalyst M-N synthesis. Fossil H-ZSM_5 (Si02/Al203 Mo ratio 280) powder was combined with alumina to make two catalysts, one without mixing 36 200824790 alumina and nitric acid, and the other mixing alumina with nitric acid. The zeolite is not modified with phosphorus. Example 13 Catalyst: 25.0 g of alumina (pseudo-boehmite type, obtained from Alcoa, HiQ-40 grade) was mixed with 100.1 g of this HZSM-5 zeolite powder (80 mesh). Water was sprayed onto the mixture of zeolite and alumina, which was extruded to produce a 1/16-inch pair of cylindrical extrudates. Example 14 Catalyst N: 20.2 g of alumina (pseudo-boehmite type, obtained from Alcoa, HiQ-40 grade) was mixed with 8.97 g of HN〇3 (70.0 wt% aqueous solution), and then with 80.6 g of this HZSM-5 zeolite powder (80 mesh) was mixed. Water was sprayed onto the zeolite-alumina mixture to form an extrudable paste which was extruded to produce a 1/16-inch cylindrical extrudate. The two extruded catalysts are calcined in a pair of flow furnaces in air using the same temperature profile as described in Catalyst A at a maximum temperature (10 h) between 510 ° C and 530 ° €. The catalyst was crushed and used for catalysis testing using a 20 and 40 mesh screen size. Catalyst and N were tested for hydrazinolation using the same test conditions of Example 1, and the results are summarized in Tables 18 and 19, respectively. Playing 18................................................ .................................................. .................................................. .................................................. .................................................. .................................................. ........................................ Gas production time, h 23.32 47.33 77.87 143.28 173.88 198.08 245.57 Catalyst bed inlet temperature, . C 453.7 464.4 463.7 474.9 472.5 473.2 472.5 37 200824790 Liquid product analysis, Wt% water 20.28 19.86 20.11 20.18 20.00 19.68 20.03 Methanol 0 0 0 0 0 0 0 Dimethyl ether 0 0 0 0 0 0 0 Benzene 0 0.16 0.12 0.13 0.10 0.09 0.08 Toluene 66.(8) 66.03 65.83 65.75 66.01 66.47 66.21 Ethylbenzene 0 0 0 0 0 0 0 P-xylene 3.07 3.23 3.34 3.42 3.56 3.58 3.68 m-xylene 6.47 6.59 6.43 6.43 6.22 6.11 5.99 〇-xylene 2.68 2.74 2.71 2.72 2.64 2.61 2.56 Ethylmethylbenzene 0.74 0.55 0.47 0.36 0.36 0.33 0.33 Trimethylbenzene 0.66 0.74 0.86 0.91 0.97 0.98 0.99 C10+ 0.11 0.11 0.13 0.12 0.14 0.14 0.14 Conversion / Selectivity, Molar % Toluene Conversion 13.70 14.05 14.08 14.26 13.86 13.74 13.68 Mix 2 Toluene selectivity 90.02 89.53 89.36 89.87 90.07 89.67 90.18 P-xylene selectivity 25.13 25.70 26.74 27.20 28.64 29.14 30.10 sterol selectivity 55.25 56.46 56.88: from::::;:::::::: :::::::::From Desire*%% 57.81 56.57 ;;::::From %:*% slaves::::% from desires::::要雄"?5::狗^* :*: 55.94 55.88

表19 _§^里碑時間，h 23.23 47.48 71.23 142.98 173.23 197.23 244.55 ―翌赛疼入口溫度，。C 449.9 441.2 440.1 442.5 453,7 460.3 469.2 ............. 液fe、產物分析，wt% 水 20.60 21.23 21.00 21.26 20.91 19.52 19.65 甲醇 0 0 0 0 0 0 0 二甲鱗 0 0 0 0 0 0 0 苯 0.23 0.12 0.10 0.08 0.09 0.10 0.10 甲苯 64.02 64.68 65.05 65.08 65.22 66.02 65.80 乙苯 0 0 0 0 0 0 0 P-二甲苯 3.38 3.17 3.22 3.41 3.46 3.65 3.69 m-二曱苯 7.22 6.49 6.37 6.07 6.20 6.50 6.59 〇-二甲苯 3.03 2.70 2.65 2.55 2.61 2.72 2.75Table 19 _§^Libei time, h 23.23 47.48 71.23 142.98 173.23 197.23 244.55 ―翌赛痛 inlet temperature,. C 449.9 441.2 440.1 442.5 453,7 460.3 469.2 ............. Liquid fe, product analysis, wt% water 20.60 21.23 21.00 21.26 20.91 19.52 19.65 Methanol 0 0 0 0 0 0 0 Dimethyl scale 0 0 0 0 0 0 0 benzene 0.23 0.12 0.10 0.08 0.09 0.10 0.10 toluene 64.02 64.68 65.05 65.08 65.22 66.02 65.80 ethylbenzene 0 0 0 0 0 0 0 P-xylene 3.38 3.17 3.22 3.41 3.46 3.65 3.69 m-diphenylbenzene 7.22 6.49 6.37 6.07 6.20 6.50 6.59 〇-xylene 3.03 2.70 2.65 2.55 2.61 2.72 2.75

38 200824790 乙基甲基苯 0.71 0.76 0.73 0.58 0.50 0.43 0.39 三曱苯 0.71 0.73 0.76 0.85 0.90 0.93 0.92 C10+ 0.11 0.11 0.11 0.12 0.12 0.13 0.11 轉換/選擇性，莫耳％甲苯轉換 15.36 14.25 14.05 13.29 13.40 14.31 14.01 混合二甲苯選擇性 88.47 88.26 88.67 88.42 89.41 89.72 90.67 p-二曱苯選擇性 24.81 25.66 26.30 28.36 28.20 28.35 28.32 甲醇選擇性觸媒O-P 60.32 55.75 55.58 52.29 53.87 57.24 56.56 觸媒0及P之合成。將彿石NH4-ZSM-5 (Si02/Al203 莫耳比率700)粉末與礬土結合以製造二種觸媒，一種無混合蓉土與硝酸，而另一種混合礬土。該沸石不以磷改質。實施例15 觸媒0 :將17·5 g礬土(擬薄水鋁石型，獲自Alcoa， HiQ40級）與70.0 g之NH4ZSM-5沸石粉末（80網目）混合。 _ 將水喷灑於該沸石與礬土混合物上，並擠壓以製造1/16-英吋圓柱型壓出物。實施例16 觸媒P :將17·5 g之馨土(擬薄水銘石型，獲自Alcoa， HiQ_40級）與7.79 g ΗΝ03(70·0 wt%水溶液）混合，然後與 70.1 g之該NH4ZSM-5沸石粉末（80網目）混合。將水喷灑於該沸石-馨土混合物上以形成一可擠壓糊狀物，將其擠壓以製造1/16-英吋圓柱型壓出物。 39 200824790 二種經擠壓之觸媒在一對流爐於空氣中，使用觸媒A 中所述之該相同溫度輪廓，以510QC至530QC間之一最大溫度（10 h)煅燒。將該觸媒壓碎，並使用20及40網目之篩網區分大小而用於催化測試。使用實施例1之該相同測試條件，將觸媒0及P測試甲苯甲基化，且結果分別總結於表20及21。表2038 200824790 Ethylmethylbenzene 0.71 0.76 0.73 0.58 0.50 0.43 0.39 Triterpenes Benzene 0.71 0.73 0.76 0.85 0.90 0.93 0.92 C10+ 0.11 0.11 0.11 0.12 0.12 0.13 0.11 Conversion / Selectivity, Molar % Toluene Conversion 15.36 14.25 14.05 13.29 13.40 14.31 14.01 Mix Xylene selectivity 88.47 88.26 88.67 88.42 89.41 89.72 90.67 p-diphenylbenzene selectivity 24.81 25.66 26.30 28.36 28.20 28.35 28.32 methanol selective catalyst OP 60.32 55.75 55.58 52.29 53.87 57.24 56.56 Synthesis of catalysts 0 and P. The Fossil NH4-ZSM-5 (Si02/Al203 Moire Ratio 700) powder was combined with alumina to produce two catalysts, one without mixing and nitric acid, and the other with alumina. The zeolite is not modified with phosphorus. Example 15 Catalyst 0: 17·5 g of alumina (pseudo-boehmite type, obtained from Alcoa, HiQ 40 grade) was mixed with 70.0 g of NH4ZSM-5 zeolite powder (80 mesh). Water was sprayed onto the mixture of zeolite and alumina and extruded to produce a 1/16-inch cylindrical extrudate. Example 16 Catalyst P: 17 5 g of cinnabar (pseudo-thin water type, obtained from Alcoa, HiQ_40 grade) was mixed with 7.79 g of ΗΝ03 (70. 0 wt% aqueous solution), and then with 70.1 g of the NH4ZSM- 5 zeolite powder (80 mesh) was mixed. Water was sprayed onto the zeolite-sandwich mixture to form an extrudable paste which was extruded to produce a 1/16-inch cylindrical extrudate. 39 200824790 Two extruded catalysts are calcined in a pair of flow furnaces in air using the same temperature profile as described in Catalyst A, at a maximum temperature (10 h) between 510 QC and 530 QC. The catalyst was crushed and used for catalysis testing using a 20 and 40 mesh screen size. Catalysts 0 and P were tested for methylation of toluene using the same test conditions of Example 1, and the results are summarized in Tables 20 and 21, respectively. Table 20

寧氣灌爽時間23.58 — 53.58 119.58 143.58 173.58 197.83 221.58 觸媒床入口溫度，°c 446.9 479.10 483.9 495.1 497.6 494.4 494.4 產物分析，wt% 水 21.15 20.35 21.01 20.60 19.62 20.37 20.33 甲醇 0 0 0 0 0 0 0 二甲醚 0 0 0 0 0 0 0 苯 0 0.05 0.05 0.05 0.05 0 0.05 曱苯 66.11 65.62 65.08 64.97 65.72 64.94 65.09 乙苯 0 0 0 0 0 0 0 P-二曱苯 5.62 5.80 6.15 6.51 7.06 7.43 7.47 m-二曱苯 4.16 4.80 4.57 4.72 4.56 4.32 4.23 〇-二甲苯 1.77 2.12 2.02 2.04 1.96 1.88 1.82 乙基曱基苯 0.32 0.11 0.08 0.07 0.07 0.07 0.07 三甲苯 0.77 0.94 0.93 0.91 0.91 0.90 0.86 C10+ 0.10 0.11 0.10 0.09 0.09 0.08 0.07 轉換/選擇性，莫耳％曱苯轉換 12.62 13.78 13.85 14.28 14.47 14.56 14.42 混合二甲苯選擇性 91.98 91.95 92.74 93.07 93.37 93.87 93.63 p-二曱苯選擇性 48.68 45.55 48.23 49.05 52.12 54.50 55.25 甲醇選擇性 51.59 56.85 57.64 59.64 60.84 61.57 60.82Ningqi filling time 23.58 — 53.58 119.58 143.58 173.58 197.83 221.58 Catalyst bed inlet temperature, °c 446.9 479.10 483.9 495.1 497.6 494.4 494.4 Product analysis, wt% water 21.15 20.35 21.01 20.60 19.62 20.37 20.33 Methanol 0 0 0 0 0 0 2 Methyl ether 0 0 0 0 0 0 0 benzene 0 0.05 0.05 0.05 0.05 0 0.05 Benzene 66.11 65.62 65.08 64.97 65.72 64.94 65.09 Ethylbenzene 0 0 0 0 0 0 0 P-diphenylbenzene 5.62 5.80 6.15 6.51 7.06 7.43 7.47 m- Benzene 4.16 4.80 4.57 4.72 4.56 4.32 4.23 〇-xylene 1.77 2.12 2.02 2.04 1.96 1.88 1.82 Ethyl decyl benzene 0.32 0.11 0.08 0.07 0.07 0.07 0.07 Trimethylbenzene 0.77 0.94 0.93 0.91 0.91 0.90 0.86 C10+ 0.10 0.11 0.10 0.09 0.09 0.08 0.07 Conversion /selective, mole % benzene conversion 12.62 13.78 13.85 14.28 14.47 14.56 14.42 Mixed xylene selectivity 91.98 91.95 92.74 93.07 93.37 93.87 93.63 p-diphenylbenzene selectivity 48.68 45.55 48.23 49.05 52.12 54.50 55.25 methanol selectivity 51.59 56.85 57.64 59.64 60.84 61.57 60.82

40 200824790 表2140 200824790 Table 21

蒸氣灌流時間，h 24.38 52.88 119.88 143.22 173.88 198.02 221.88 觸媒床入口溫度，QC 449.2 495.7 502.7 503.3 495.7 496.7 500.7 產物分析，wt% 水 20.20 18.40 20.24 20.17 21.11 17.95 20.86 甲醇 0 0 0 0 0 0 0 二曱醚 0 0 0 0 0 0 0 苯 0 0.06 0.06 0 0 0 0 甲苯 66.44 66.31 64.95 64.71 64.74 65.98 64.28 乙苯 0 0 0 0 0 0 0 P-二甲苯 5.31 6.13 6.25 7.03 7.35 7.93 7.45 m-二甲苯 4.84 5.43 5.01 4.73 4.41 4.59 4.19 〇-二曱苯 1.99 2.34 2.21 2.14 2.08 2.17 1.97 乙基曱基苯 0.31 0.18 0.14 0.08 0.08 0.09 0.08 三甲苯 0.81 1.03 1.03 1.04 1.09 1.17 1.07 C10+ 0.10 0.12 0.11 0.11 0.12 0.13 0:11 轉換/選擇性，莫耳％曱苯轉換 13.02 14.71 14.57 14.99 14.16 15.51 14.76 混合二甲苯選擇性 92.24 91.95 92.08 93.06 98.19 92.60 •_sC. 92.69 p-二甲苯選擇性 43.70 44.13 46.39 50.59 53.09 54.00 54.75 甲醇選擇性 53.55 60.41 60.08 62.45 62.82 63.98 61.08 如上述資料所顯示，於用於甲苯曱基化製程之觸媒中，該化合一磷改質ZSM-5與已由硝酸處理之礬土或黏土黏著劑材料產生對於P-二曱苯改良選擇性之結果。不含黏著劑（實施例1)之該比較實施例、無以無機酸處理之該黏著劑（實施例2及10)、無磷改質之該沸石（實施例13-16)比具有已由硝酸處理礬土或黏土黏著劑材料一磷改質ZSM-5 之一觸媒（實施例3-9、11及12)，顯示對於p-二曱苯較低 41 200824790 的選擇性。第1圖係顯示一結合P-改質ZSM-5以（實施例 2，觸媒B)及不以（實施例6，觸媒F)無機酸處理之該黏著劑於p-二甲苯選擇性上之差異。第2圖係顯示一結合 ZSM-5無磷改質且不以（實施例13，觸媒M)及以（實施例 14,觸媒N)無機酸處理之該黏著劑在p-二甲苯選擇性上缺乏效果。使用一平板法之該碎裂強度量測觸媒B(實施例2比較性不以酸處理該黏著劑）、觸媒C、觸媒D及觸媒F(實施例3、4及6以酸處理該黏著劑）之經煅燒1/16-英吋壓出物。該平均碎裂強度係顯示於表22。奏 22 ~--—————------------------------------ _ 于巧，—強度（lb/mm) B 2.10Vapor perfusion time, h 24.38 52.88 119.88 143.22 173.88 198.02 221.88 Catalyst bed inlet temperature, QC 449.2 495.7 502.7 503.3 495.7 496.7 500.7 Product analysis, wt% Water 20.20 18.40 20.24 20.17 21.11 17.95 20.86 Methanol 0 0 0 0 0 0 0 Dioxane 0 0 0 0 0 0 0 Benzene 0 0.06 0.06 0 0 0 0 Toluene 66.44 66.31 64.95 64.71 64.74 65.98 64.28 Ethylbenzene 0 0 0 0 0 0 0 P-xylene 5.31 6.13 6.25 7.03 7.35 7.93 7.45 m-xylene 4.84 5.43 5.01 4.73 4.41 4.59 4.19 〇-diphenylbenzene 1.99 2.34 2.21 2.14 2.08 2.17 1.97 ethyl mercaptobenzene 0.31 0.18 0.14 0.08 0.08 0.09 0.08 trimethylbenzene 0.81 1.03 1.03 1.04 1.09 1.17 1.07 C10+ 0.10 0.12 0.11 0.11 0.12 0.13 0:11 Conversion / selection Sex, mol% benzene conversion 13.02 14.71 14.57 14.99 14.16 15.51 14.76 Mixed xylene selectivity 92.24 91.95 92.08 93.06 98.19 92.60 •_sC. 92.69 p-xylene selectivity 43.70 44.13 46.39 50.59 53.09 54.00 54.75 methanol selectivity 53.55 60.41 60.08 62.45 62.82 63.98 61.08 As shown in the above information, in the catalyst used in the toluene thiolation process, this The result of improved selectivity for P-diphenylbenzene by the combination of a single phosphorus-modified ZSM-5 and an alumina or clay adhesive material that has been treated with nitric acid. The comparative example without the adhesive (Example 1), the adhesive without the inorganic acid treatment (Examples 2 and 10), and the phosphate-free modified zeolite (Examples 13-16) have Nitric acid treated alumina or clay adhesive material-phosphorus modified ZSM-5 one of the catalysts (Examples 3-9, 11 and 12) showed selectivity for p-diphenylene lower 41 200824790. Figure 1 shows the adhesion of the adhesive to P-xylene in combination with P-modified ZSM-5 (Example 2, Catalyst B) and not treated with (Inventive 6, Catalyst F) mineral acid. The difference. Figure 2 shows a combination of ZSM-5 phosphate-free modification and not treated with (Inventive 13, Catalyst M) and (Example 14, Catalyst N) mineral acid in p-xylene Sexually lacking in effect. The fragmentation strength of the catalyst B was measured using a plate method (Comparative Example 2 does not treat the adhesive with acid), Catalyst C, Catalyst D, and Catalyst F (Examples 3, 4, and 6 are acid The 1/16-inch indentate of the adhesive) was calcined. The average fragmentation strength is shown in Table 22. Playing 22 ~----------------------------------- _ Yu Qiao,-strength (lb/mm ) B 2.10

C 336 D 3.41C 336 D 3.41

F ⑽'一⑽…一.............:…_^一认 3 6 δ 如上述資料所顯示，該化合一磷改質之ZSM-5與已由硝酉夂處理礬土或黏土黏著劑材料產生改良之碎裂強度。一有不、、、工由硝酸處理礬土黏著劑材料之一磷改質ZSM-5 (觸媒B)之比較實施例，顯示碎裂強度低於具有已由硝酸 =恭土黏著劑材料之p_ZSMj觸媒(觸媒cd及巧。 :乂门碎衣強度係表不此觸媒在製程狀態巾，應具有更少的觸餘理性損耗及更長_媒壽命。、貝^基於上述之教示，本發明可能有多數修正及變 42 200824790 化。因此，必須理解，在附隨之申請專利範圍的範圍内，本發明可實施於本文中未具體說明者。【圖式簡單說明】當考量有關附隨之圖示時，本發明更完整理解及其許多相關及所產生之優點將經由參考下列詳細說明而可更容易理解，該圖示中相異圖中類似數字代表相同結構或元件 •，其中·· 第一圖係為關於實施例2觸媒B及實施例6觸媒F之曱苯曱基化反應，P-二曱苯選擇性隨時間經過之函數圖示第二圖係為關於實施例13觸媒Μ及實施例14觸媒N 之曱苯曱基化反應，ρ-二曱苯選擇性隨時間經過之函數圖示0 【主要元件符號說明】無0 43F (10) '一(10)...一.............:..._^一认3 6 δ As shown in the above data, the compound-phosphorus-modified ZSM-5 has been夂 Treatment of bauxite or clay adhesive materials produces improved fracture strength. A comparative example of phosphorus-modified ZSM-5 (catalyst B), which is one of the clay binder materials treated with nitric acid, shows that the fracture strength is lower than that of the material having been made of nitric acid = sinter adhesive p_ZSMj catalyst (catalyst cd and clever.: The strength of the smashing machine is not the catalyst in the process state, it should have less residual rational loss and longer _ media life. The present invention is susceptible to numerous modifications and changes. Therefore, it is to be understood that the invention may be practiced otherwise than as specifically described herein within the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in the The first figure is the benzoylation reaction of the catalyst B of Example 2 and the catalyst F of Example 6, and the second graph of the P-diphenyl benzene selectivity over time is shown. Example 13 Catalyst and Example 14 Catalyst N Yue Yue phenyl hydroformylation reaction, ρ- two Yue benzene selectivity with time of a function diagram showing principal elements [0] None REFERENCE SIGNS 043

Claims

200824790 十、申請專利範圍： 1. 一種製備一沸石觸媒之方法，其係包含： a) 以磷化合物處理一沸石，以形成一磷處理沸石； b) 以一無機酸處理一無機氧化物黏著劑材料； c) 化合該磷處理沸石與該經處理無機氧化物黏著劑材料，以形成一沸石-黏著劑混合物；及 d) 於約400°C或以上溫度加熱該沸石-黏著劑混合物，以形成一結合沸石觸媒。 _ 2. 如申請專利範圍第1項之方法，其中該黏著劑材料係含礬土、黏土、磷酸鋁或二氧化矽-礬土中至少一種。 3. 如申請專利範圍第1項之方法，其中該黏著劑材料係為一含礬土材料。 4. 如申請專利範圍第1項之方法，其中該黏著劑材料之存在量為該結合沸石觸媒重量百分比之約1 %至約99%。 5. 如申請專利範圍第1項之方法，其中該黏著劑材料含礬土重量百分比之約1%至99%。 ⑩ 6. 如申請專利範圍第1項之方法，其中該無機酸係為氫氯酸、硝酸、磷酸或硫酸。 7. 如申請專利範圍第1項之方法，其中該無機酸係為硝酸。 8. 如申請專利範圍第1項之方法，其中該沸石係含10-氧環孔洞。 9. 如申請專利範圍第1項之方法，其中該沸石係為一 ZSM-5沸石。 10. 如申請專利範圍第1項之方法，其中該沸石-黏著劑混 44 200824790 合物係於400°C至約700°C之一溫度加熱。如申請專利範圍第1項之方法，其係進一步包含添加水至該沸石-黏著劑混合物，並將該沸石-黏著劑混合物成型。 12.如申請專利範圍第1項之方法，其係進一步包含於 300。€或以下之一溫度蒸氣灌流該結合沸石。 13·如申請專利範圍第1項之方法，其中談沸石係以一磷化合物處理而形成一磷處理沸石，其係具有每克沸石含 0.01至約0.15克磷之磷含量。 14·如申請專利範圍第13項之方法，其中該沸石係含10-. 氧環孔洞。 15·如申請專利範圍第13項之方法，其中該沸石係為一 ZSM-5 沸石。； 16.如申請專利範圍第13項之方法，其中該黏著劑材料之α - 译存在量為該結合沸石觸媒重量百分比之約1%至約 99% 〇 17·如申請專利範圍第13項之方法，其中該黏著劑材料含礬土或黏土或其之組合重量百分比之約1%至99%。 18. 如申請專利範圍第13項之方法，其係進一步包含添加水至該沸石-黏著劑混合物，並將該沸石-黏著劑混合物成型。 19. 如申請專利範圍第13項之方法，其中該磷處理沸石係具有每克沸石含0.07至約0.12克磷之磷含量。 20·如申請專利範圍第13項之方法，其係進一步包含於 45 200824790 300°C或以下之溫度蒸氣灌流該結合沸石。 21. 如申請專利範圍第13項之方法，其中該沸石-黏著劑混合物係於400QC至約700°C之一溫度加熱。 22. —種沸石觸媒，其係經由下列製備： a) 以一磷化合物處理一沸石，以形成一磷處理沸石； b) 以一無機酸處理一無機氧化物黏著劑材料； c) 化合該磷處理沸石與一礬土或黏土黏著劑材料，以形成一沸石-黏著劑混合物；及 d) 於約400°C或以上之一溫度加熱該沸石-黏著劑混合物，以形成一結合彿石觸媒。 23. 如申請專利範圍第22項之沸石觸媒，其中該磷處理沸石具有每克沸石含0.01至約0.15克磷之磷含量。 24. 如申請專利範圍第22項之沸石觸媒，其中該黏著劑材料係含礬土、黏土、磷酸鋁或二氧化矽-礬土中至少一種。 25. 如申請專利範圍第22項之沸石觸媒，其中該黏著劑材料係為一含馨土材料。 26. 如申請專利範圍第22項之沸石觸媒，其中該黏著劑材料之存在量為結合沸石觸媒重量百分比之約1%至約 99%。 27. 如申請專利範圍第22項之沸石觸媒，其中該黏著劑材料含礬土重量比之約1%至99%之。 28. 如申請專利範圍第22項之沸石觸媒，其中該沸石係含 10-氧環孔洞。 46 200824790 29. 如申請專利範圍第22項之沸石觸媒，其中該沸石係為一 ZSM-5 沸石。 30. 如申請專利範圍第22項之沸石觸媒，其係進一步包含在化合該磷處理沸石與該礬土或黏土黏著劑材料之前，於約300°C或以上之一溫度加熱該填處理濟石。 31·如申請專利範圍第22項之沸石觸媒，其中於400°C至約700°C之一溫度加熱該沸石-黏著劑混合物。 32·如申請專利範圍第22項之沸石觸媒，其係進一步包含添加水至該;弗石-黏者劑混合物’並將該彿石-黏著劑混合物成型。 33·如申請專利範圍第22項之沸石觸媒，其中於300°C或'' 以下之一溫度蒸氣灌流該結合沸石。 34·—種沸石觸媒，其係包含：與一無機氧化物黏著劑結合之一含礎滞石，該無機。氧化物黏著劑在與該含磷沸石結合之前，已經由一無機酸處理。 35·如申請專利範圍第34項之沸石觸媒，其中該無機酸係為氫氯酸、硝酸、磷酸或硫酸。 36·如申請專利範圍第35項之沸石觸媒，其中該無機酸係為頌酸。 37·如申請專利範圍第34項之沸石觸媒，其中該黏著劑材料係為礬土、黏土、磷酸鋁或二氧化矽-礬土中至少一種。 38·如申請專利範圍第34項之沸石觸媒，其中該黏著劑材 47 200824790 料係為蓉土。 39·如申請專利範圍園弟34項之沸石觸媒，盆中兮料之存在量為蛀石觸媒〃中該黏者劑材 99〇/〇〇、w弗石觸媒重量百分比之約1%至約 40.如申請專利範圍第％項料含礬土重量百八L 觸杀，、肀該黏者劑材里百分比之約1%至99%之。 41 ·如申請專利範囹 1 Λ " w 弟34項之沸石觸媒’其中該沸；?；在入 10-氧環孔洞。 τ必部石係含 42·如申請專利範囹圍弟34項之沸石觸媒，其中一 ZSM-5沸石。邊沸石係為 43 ·如申清專利範图楚石具有每克滞^ 弗石觸媒’其中該碟處理彿 44 -種f備一浐/ 〇.01至約〇.15克磷之磷含量。備⑥基芳族產物之方法，其係包含. a) 以：：化合物處理一含1〇_氧環一磷處理彿石；以形成 b) 以m機酸處理一無機氧化物黏著劑材料； c) 化合該磷處理滞石與—無機氧化物黏著劑材料形成一沸石-黏著劑混合物； d) 於、、、勺40〇〇C或以上之一溫度加熱該游石·黏著劑混合物’以形成一結合沸石觸媒；及 e) 在適於芳族燒化之反應條件下，將結合該彿石觸媒舁含芳族化合物與一烷化劑之芳族烷化進料接觸。 45.如申請專利範圍第44項之方法，其中該黏著劑材料係 48 200824790 含礬土、黏土、磷酸鋁及二氧化矽-礬土中至少一種。 46. 如申請專利範圍第44項之方法，其中該黏著劑材料係為一含礬土材料。 47. 如申請專利範圍第44項之方法，其中該黏著劑材料之存在量為結合沸石觸媒重量百分比之約1%至約99%。 48·如申請專利範圍第44項之方法，其中該黏著劑材料含礬土或黏土或其之組合重量百分比之約1%至約99%。 49·如申請專利範圍第44項之方法，其中該沸石係為一 ZSM-5沸石。 50.如申請專利範圍第44項之方法，其中於約300。€或以上之一溫度加熱該磷處理沸石。 51·如申請專利範圍第44項之方法，其中該沸石-黏著劑混合物於400QC至約700QC之一溫度加熱。 52·如申請專利範圍第44項之方法，其進一步包含添加冰至該沸石-黏著劑混合物，並將該沸石-黏著劑混合物成型〇 53·如申請專利範圍第44項之方法，其中該芳族化合物係為曱苯。 54·如申請專利範圍第44項之方法，其中該芳族化合物係為曱苯，且該烷化劑係為甲醇。 55·如申請專利範圍第44項之方法，其係進一步包含在與芳族烷化進料接觸前，於300°C或以下之一溫度蒸氣灌流該結合沸石。 56·如申請專利範圍第44項之方法，其中該沸石係以一磷 49 200824790 化合物處理而形成一磷處理沸石，其係具有每克沸石人 0.01至約0.15克磷之磷含量。 3 57·如申請專利範圍第56項之方法，其中該沸石係為 ZSM-5沸石。黏著劑材料係中至少一者。黏著劑材料係 58·如申請專利範圍第項之方法’其中該含馨土、黏土、鱗酸銘及一氧化妙-彖土 59·如申請專利範圍第57項之方法，其中該為含礬土材料。 60·如申請專利範圍第57項之方法，其中該黏著劑材料之存在量為結合ZSM-5沸石觸媒重量百分比之約1%至約 99%。 ° 61·如申請專利範圍第57項之方法，其中該黏著劑材料含礬土重量百分比之約1%至99%。 62.如申請專利範圍第57項之方法，其中於约3〇〇。匸或以上之一溫度加熱該鱗處理沸石。 63·如申請專利範圍第56項之方法，其中於4〇〇〇c至約 700 C之一溫度加熱該沸石_黏著劑混合物。 64·如申請專利範圍第54項之方法，其係進一步包含在與甲苯進料接觸前，於3〇〇〇c或以下之一溫度蒸氣灌流該結合ZSM-5沸石。 65·如申請專利範圍第44項之方法，其中該無機酸係為氯氯酸、硝酸、磷酸或硫酸。 66·如申請專利範圍第65項之方法，其中該無機酸係為硝酸0 50200824790 X. Patent Application Range: 1. A method for preparing a zeolite catalyst comprising: a) treating a zeolite with a phosphorus compound to form a phosphorus-treated zeolite; b) treating an inorganic oxide with an inorganic acid. a material; c) combining the phosphorus treated zeolite with the treated inorganic oxide adhesive material to form a zeolite-adhesive mixture; and d) heating the zeolite-adhesive mixture at a temperature of about 400 ° C or above to A combined zeolite catalyst is formed. 2. The method of claim 1, wherein the adhesive material comprises at least one of alumina, clay, aluminum phosphate or ceria-alumina. 3. The method of claim 1, wherein the adhesive material is a bauxite-containing material. 4. The method of claim 1, wherein the adhesive material is present in an amount from about 1% to about 99% by weight of the bound zeolite catalyst. 5. The method of claim 1, wherein the adhesive material comprises from about 1% to about 99% by weight of the earth. 10. The method of claim 1, wherein the inorganic acid is hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid. 7. The method of claim 1, wherein the inorganic acid is nitric acid. 8. The method of claim 1, wherein the zeolite comprises a 10-oxo ring hole. 9. The method of claim 1, wherein the zeolite is a ZSM-5 zeolite. 10. The method of claim 1, wherein the zeolite-adhesive mixture is heated at a temperature of from 400 ° C to about 700 ° C. The method of claim 1, further comprising adding water to the zeolite-adhesive mixture and shaping the zeolite-adhesive mixture. 12. The method of claim 1, further comprising 300. One or more of the following temperature vapor perfusion of the combined zeolite. 13. The method of claim 1, wherein the zeolite is treated with a phosphorus compound to form a phosphorus treated zeolite having a phosphorus content of from 0.01 to about 0.15 grams of phosphorus per gram of zeolite. 14. The method of claim 13, wherein the zeolite comprises 10-. oxygen ring pores. 15. The method of claim 13, wherein the zeolite is a ZSM-5 zeolite. 16. The method of claim 13, wherein the adhesive material has an alpha-translation amount of from about 1% to about 99% by weight of the bound zeolite catalyst. 〇17. The method wherein the adhesive material comprises from about 1% to about 99% by weight of alumina or clay or a combination thereof. 18. The method of claim 13, further comprising adding water to the zeolite-adhesive mixture and shaping the zeolite-adhesive mixture. 19. The method of claim 13, wherein the phosphorus-treated zeolite has a phosphorus content of from 0.07 to about 0.12 grams of phosphorus per gram of zeolite. 20. The method of claim 13, further comprising vapour permeating the bound zeolite at a temperature of 45 200824790 300 ° C or less. 21. The method of claim 13, wherein the zeolite-adhesive mixture is heated at a temperature of from 400 QC to about 700 °C. 22. A zeolite catalyst prepared by: a) treating a zeolite with a phosphorus compound to form a phosphorus treated zeolite; b) treating an inorganic oxide binder material with a mineral acid; c) combining the Phosphating the zeolite with an alumina or clay binder material to form a zeolite-adhesive mixture; and d) heating the zeolite-adhesive mixture at a temperature of about 400 ° C or above to form a combined fossil contact Media. 23. The zeolite catalyst of claim 22, wherein the phosphorus treated zeolite has a phosphorus content of from 0.01 to about 0.15 grams of phosphorus per gram of zeolite. 24. The zeolite catalyst of claim 22, wherein the adhesive material comprises at least one of alumina, clay, aluminum phosphate or cerium oxide-alumina. 25. The zeolite catalyst of claim 22, wherein the adhesive material is a mulch-containing material. 26. The zeolite catalyst of claim 22, wherein the binder material is present in an amount from about 1% to about 99% by weight of the bound zeolite catalyst. 27. The zeolite catalyst of claim 22, wherein the adhesive material comprises from about 1% to about 99% by weight of the alumina. 28. The zeolite catalyst of claim 22, wherein the zeolite comprises a 10-oxo ring. 46 200824790 29. The zeolite catalyst of claim 22, wherein the zeolite is a ZSM-5 zeolite. 30. The zeolite catalyst according to claim 22, further comprising heating the filling treatment at a temperature of about 300 ° C or above before combining the phosphorus-treated zeolite with the alumina or clay adhesive material. stone. 31. The zeolite catalyst of claim 22, wherein the zeolite-adhesive mixture is heated at a temperature of from 400 ° C to about 700 ° C. 32. The zeolite catalyst of claim 22, further comprising adding water to the; a vermiculite-adhesive mixture' and shaping the smectite-adhesive mixture. 33. The zeolite catalyst of claim 22, wherein the bound zeolite is perfused at a temperature of 300 ° C or below. 34. A zeolite catalyst comprising: one of a combination of an inorganic oxide binder and a base stone, the inorganic. The oxide adhesive has been treated with a mineral acid prior to combining with the phosphorus-containing zeolite. 35. The zeolite catalyst of claim 34, wherein the inorganic acid is hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid. 36. The zeolite catalyst of claim 35, wherein the inorganic acid is citric acid. 37. The zeolite catalyst of claim 34, wherein the adhesive material is at least one of alumina, clay, aluminum phosphate or cerium oxide-alumina. 38. The zeolite catalyst according to item 34 of the patent application, wherein the adhesive material 47 200824790 is a rare earth material. 39. If the zeolite catalyst of the patent application scope is 34, the amount of the potted material in the pot is 99 〇/〇〇 of the viscous agent, and the weight percentage of the w-stone catalyst is about 1 % to about 40. If the first item of the patent application scope contains the weight of the earth, it is about 1% to 99% of the percentage of the adhesive. 41 · If you apply for a patent 囹 1 Λ " w brother 34 of the zeolite catalyst 'which is boiling;?; in the 10-oxo ring hole. The τ Bianshi stone system contains 42. For example, the zeolite catalyst of the patent application Fan Wei is 34, one of which is ZSM-5 zeolite. The zeolite is 43. If the Shenqing patent Fantu Chushi has a gram of stagnation per gram of sulphate, the dish is treated with a 44-species 备/〇.01 to about 〇.15g phosphorus phosphorus content. . A method for preparing a 6-based aromatic product, which comprises: a) treating: a compound containing 1 〇 _ oxygen ring-phosphorus treatment of smectite; to form b) treating an inorganic oxide adhesive material with m-acid; c) combining the phosphorus-treated staghorn and the inorganic oxide adhesive material to form a zeolite-adhesive mixture; d) heating the tourmaline/adhesive mixture at a temperature of 40 〇〇C or above Forming a bound zeolite catalyst; and e) contacting the arsenic-containing aromatic compound with an aromatic alkylation feed of an alkylating agent under reaction conditions suitable for aromatic burning. 45. The method of claim 44, wherein the adhesive material is 48 200824790 comprising at least one of alumina, clay, aluminum phosphate, and cerium oxide-alumina. 46. The method of claim 44, wherein the adhesive material is a bauxite-containing material. 47. The method of claim 44, wherein the adhesive material is present in an amount from about 1% to about 99% by weight of the combined zeolite catalyst. 48. The method of claim 44, wherein the adhesive material comprises from about 1% to about 99% by weight of the alumina or clay or a combination thereof. 49. The method of claim 44, wherein the zeolite is a ZSM-5 zeolite. 50. The method of claim 44, wherein the method is about 300. The phosphorus treated zeolite is heated at a temperature of one or more of the above. 51. The method of claim 44, wherein the zeolite-adhesive mixture is heated at a temperature of from 400 QC to about 700 QC. 52. The method of claim 44, further comprising adding ice to the zeolite-adhesive mixture and forming the zeolite-adhesive mixture. The method of claim 44, wherein the aromatic The family compound is anthracene. 54. The method of claim 44, wherein the aromatic compound is toluene and the alkylating agent is methanol. 55. The method of claim 44, further comprising steam injecting the bound zeolite at a temperature of 300 ° C or below prior to contacting the aromatic alkylation feed. 56. The method of claim 44, wherein the zeolite is treated with a phosphorus 49 200824790 compound to form a phosphorus treated zeolite having a phosphorus content of from 0.01 to about 0.15 grams of phosphorus per gram of zeolite. The method of claim 56, wherein the zeolite is a ZSM-5 zeolite. At least one of the adhesive material systems. Adhesive material system 58. The method of claim 1, wherein the method comprises the method of scented clay, clay, scaly, and sulphuric acid-aluminum 59. Soil material. 60. The method of claim 57, wherein the adhesive material is present in an amount from about 1% to about 99% by weight of the ZSM-5 zeolite catalyst. The method of claim 57, wherein the adhesive material comprises from about 1% to about 99% by weight of the alumina. 62. The method of claim 57, wherein the method is about 3 〇〇. The scale treated zeolite is heated at or above one of the temperatures. 63. The method of claim 56, wherein the zeolite-adhesive mixture is heated at a temperature of from 4 ° C to about 700 ° C. 64. The method of claim 54, further comprising steam injecting the combined ZSM-5 zeolite at a temperature of 3 ° C or below prior to contacting the toluene feed. 65. The method of claim 44, wherein the inorganic acid is chlorous acid, nitric acid, phosphoric acid or sulfuric acid. 66. The method of claim 65, wherein the inorganic acid is nitric acid 0 50