WO2003076372A1 - Transalkylation du benzene et d'hydrocarbures aromatiques c9+ - Google Patents

Transalkylation du benzene et d'hydrocarbures aromatiques c9+ Download PDF

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Publication number
WO2003076372A1
WO2003076372A1 PCT/CN2003/000146 CN0300146W WO03076372A1 WO 2003076372 A1 WO2003076372 A1 WO 2003076372A1 CN 0300146 W CN0300146 W CN 0300146W WO 03076372 A1 WO03076372 A1 WO 03076372A1
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Prior art keywords
zeolite
benzene
carbon
aromatic hydrocarbons
catalyst
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PCT/CN2003/000146
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English (en)
French (fr)
Inventor
Dejin Kong
Yu Xing
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China Petroleum & Chemical Corporation
Shanghai Research Institute Of Petrochemical Technology, Sinopec
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Priority claimed from CNB021110050A external-priority patent/CN1199918C/zh
Priority claimed from CNB021110042A external-priority patent/CN1193967C/zh
Application filed by China Petroleum & Chemical Corporation, Shanghai Research Institute Of Petrochemical Technology, Sinopec filed Critical China Petroleum & Chemical Corporation
Priority to AU2003211667A priority Critical patent/AU2003211667A1/en
Publication of WO2003076372A1 publication Critical patent/WO2003076372A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
    • C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
    • C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon

Definitions

  • the present invention relates to a method for the transalkylation of benzene with carbon nine and above.
  • toluene (Tol) and carbon octaaromatics (C 8 A) are generated by the transalkylation reaction of benzene (Ben) and carbon nine and above aromatics (C 9 + A), and the toluene selective disproportionation unit and C 8 A isomerization unit, used to increase the production of p-xylene.
  • Paraxylene is one of the main basic organic raw materials in the petrochemical industry, and has a wide range of uses in many chemical production fields such as chemical fiber, synthetic resins, pesticides, medicine, and plastics.
  • the typical production method of p-xylene (pX) is from thermodynamically balanced ethylbenzene containing xylene, i.e., octaaromatic hydrocarbons, produced by catalytic reforming of naphtha by multi-stage cryogenic crystallization separation or molecular bed sieve simulated moving bed adsorption separation
  • the cylinder is called adsorption separation) technology, which separates para-xylene from a mixture of isomers with a boiling point close to it.
  • C 8 A isomerization (referred to as isomerization) technology is often adopted to isomerize it into para-xylene.
  • isomerization For the treatment of ortho- and meta-xylene, C 8 A isomerization (referred to as isomerization) technology is often adopted to isomerize it into para-xylene.
  • C 9 + A toluene disproportionation or the disproportionation of toluene with carbon nine and above aromatics
  • transalkylation to generate benzene and C 8 A
  • Yue benzene industrialized selective disproportionation process - MSTDP mesoporous ZSM- 5 type zeolite catalyst treated feedstock processing toluene, p-xylene to obtain a high concentration (85 to 90% by weight, in addition to outside specified The same below) of C 8 A and nitrated benzene.
  • Industrial applications has not been reported PX-plus process, the process criteria is Yue benzene conversion rate of 30% under the conditions of two benzene Yue pX selectivity 90%, molar ratio of benzene to 7 pX 1.3.
  • high para-selectivity is accompanied by rigorous selection of raw materials.
  • This type of process can only use toluene as the raw material, and C 9 + A is useless in this process, at least it cannot be directly used.
  • this process also produces a large amount of benzene by-product, resulting in a low yield of p-dioxobenzene, which is a fatal shortcoming of the selective disproportionation process.
  • Tatoray typical process reactor feed aromatic hydrocarbon is toluene and nine carbon (C 9 A) as the starting material, C ie + hydrocarbon content (aromatics of C10 and above) must be strictly controlled.
  • Documents based on the Tatoray process include USP4341914, Chinese Patent 98110859.8, USP2795629, USP3551510. Chinese Patent 97106719.8, etc.
  • people have conducted further research and optimization of the Tatoray process, focusing on the development of its core technology, a catalyst, and improving the overall performance indicators of the catalyst, such as increasing weight space velocity, Extend the catalyst operating cycle and increase the average molecular weight of the aromatics reaction feed.
  • the increase of the average molecular weight is conducive to the increase of C 8 A, but when the content of heavy aromatics is too high, in order to maintain a certain conversion rate, that is, to maintain the catalyst activity, the side reactions, especially the hydrodealkylation reaction, will inevitably be intensified, and the reaction There are too many benzene products in the product, which causes the product C 8 A / Ben to be low, the aromatics loss is large, and the same raw materials are processed, and the C 8 A is small and the Ben amount is high.
  • the toluene disproportionation unit is indispensable because it can provide the role of C 8 A.
  • An increase in the amount of Ben and a decrease in the amount of C 8 A are obviously not conducive to the entire aromatics complex.
  • Hydrodealkylation process can obtain benzene, toluene, xylene from C 9 + A, but side reactions such as condensation of aromatics to form polycyclic or fused ring compounds are prone to occur.
  • Japanese patent JP10158201 describes a process whose purpose is to produce polyalkylbenzenes by transalkylation of benzene or toluene with polyalkylaromatic compounds.
  • the catalyst used in this patent is a hydrogen-type DGA zeolite that has not been metal-modified, and there is no report on the metal modification and catalyst stability of this zeolite.
  • the method for the transalkylation of nine or more aromatic hydrocarbons does not involve the problem that carbon ten or more heavy aromatics can be converted into useful toluene and carbon eight aromatic hydrocarbons.
  • Toluene is produced in parallel to produce a small amount of octaaromatic hydrocarbons, so that toluene can be supplied to the selective disproportionation unit, and octaaromatic hydrocarbons can be supplied to the aromatic isomerization unit.
  • octaaromatic hydrocarbons can be supplied to the aromatic isomerization unit.
  • pX para-xylene
  • the benzene, carbon nine and above aromatics transalkylation method provided by the present invention has the characteristics of being applicable to a wide range of process conditions, high catalyst activity, good stability, and high selectivity of target products.
  • the technical scheme adopted by the present invention is as follows: A method for the transalkylation of benzene with carbon nine and above aromatic hydrocarbons, using benzene and carbon nine and above aromatic hydrocarbons as the raw materials for the transalkylation reaction to generate toluene and Carbaocene, the reaction conditions are:
  • the catalyst used is based on parts by weight, 10-90 parts of hydrogen-containing zeolite.
  • the molar ratio of Si0 2 / Al 2 0 3 is 3 to 500, 0.01 to 20 parts of metal or / and oxide of molybdenum is supported on the zeolite, and 10 to 90 parts of alumina is the binder in the catalyst.
  • the molar ratio of Si0 2 / Al 2 0 3 of the hydrogen-type zeolite is preferably 15 to 100, and more preferably 15 to 50.
  • a preferred zeolite scheme is selected from at least one of ZSM-5 zeolite, Y zeolite, mordenite, P zeolite, MCM-22 zeolite, MCM-49 zeolite or MCM-56 zeolite, and a more preferred scheme is selected from mordenite or / and P Zeolite.
  • the constraint index of zeolite is 0.1 to 15.
  • the amount of the metal or / and oxide of molybdenum in parts by weight is preferably in the range of 0.1 to 10.0, and more preferably in the range of 0.1 to 4,0 parts.
  • At least one metal or / and oxide selected from the group consisting of iron, cobalt, nickel, chromium, tungsten, bismuth, lanthanum, zirconium, or silver is supported on the zeolite in parts by weight, and the amount thereof ranges from 0.01 to 20 parts.
  • the preferred range is 0.1-5 parts.
  • a preferred embodiment of the metal or oxide supported on the zeolite is at least one selected from the group consisting of cobalt, chromium or bismuth.
  • Hydrogen-type zeolite can be directly synthesized, or it can be natural or dealuminated.
  • the constraint index and its measuring method are described in detail in US Pat. No. 4,016,218.
  • the preferred solution of carbon nine or more aromatics in the raw material is at least one selected from the group consisting of trimethylbenzene, methyl ethylbenzene, cumene, indane, carbon ten or more heavy aromatics, and the preferred solution of carbon eight aromatics is xylene, Ethylbenzene or a mixture thereof.
  • the catalyst used in the present invention is metal-modified on a hydrogen-type zeolite, the catalyst's ability to resist the moisture content of the raw material is greatly increased, and it can maintain high activity and stability, that is, a raw material containing 500 ppm of water can be used, that is, Used under relatively severe reaction conditions, for industrial installations, the drying and dehydration operations of the raw materials Ben and C 9 + A can be eliminated.
  • the hydrogen-type zeolite may be a dealuminated zeolite obtained by acid treatment of a low-silicon-alumina ratio zeolite, or may be a natural-type zeolite or a sodium-type high-silica zeolite obtained by direct crystallization through inorganic ammonium ion exchange, drying, and roasting Zeolite should have a sodium content of less than 0.2 weight. /.
  • High silica zeolites synthesized by direct crystallization are the most suitable.
  • the excellent performance of the catalyst of the present invention is the result of the combined action of the catalytic action of the hydrogen-type high-silica zeolite and the catalytic action of the metal and / or metal oxide supported on the zeolite.
  • the preparation method of the Ben and C 9 + A transalkylation catalyst used in the present invention is prepared by a general solution impregnation support method, and then the catalyst is obtained by drying and baking. It has the characteristics of mature technology, simple equipment, convenient operation, and easy industrialization.
  • the present invention is used for the transalkylation method of benzene, carbon nine and above aromatic hydrocarbons, the selectivity of toluene plus carbon eight aromatic hydrocarbons is up to 94.1%, and the conversion rate of benzene plus carbon nine and above aromatic hydrocarbons is highest
  • Sodium mordenite, sodium P zeolite, and sodium ZSM-5 zeolite were prepared according to ZL89106793.0, USP3308069, and USP4441991, respectively.
  • the three sodium-type zeolites were ion-exchanged with ammonium chloride or ammonium nitrate aqueous solution at 90-98TC for 1 to 8 hours.
  • the mother liquor was filtered, the ion-exchange was repeated several times, and then washed and dried to obtain ammonium-type zeolite.
  • the Si0 2 / Al 2 0 3 of the three ammonium zeolites are 25, 25, and 500, respectively.
  • the three ammonium zeolites were mixed with quasi-boehmite ( ⁇ - ⁇ 1 2 0 3 ⁇ H 2 0), diluted with nitric acid, ammonium molybdate and water, kneaded uniformly, squeezed, 110 dried, pelletized, 550
  • the catalysts Al, A2, A3 were obtained by calcination, and the molybdenum content of the three catalysts was 4.0% by weight.
  • Catalyst A4 was prepared by ion exchange, kneading, molding, and baking, and the metal molybdenum content of the catalyst A4 was 4.0% by weight.
  • Sodium MCM-22 zeolite, sodium MCM-49 zeolite and sodium MCM-56 zeolite were prepared according to USP4956514, USP5264643 and USP5453554, respectively.
  • the three sodium zeolites were ion-exchanged with ammonium chloride or ammonium nitrate aqueous solution at 90-98 C for 1 to 8 hours.
  • the mother liquor was filtered, the ion exchange was repeated several times, then washed, and dried at 110TC to obtain ammonium zeolites.
  • the Si0 2 / Al 2 0 3 of the three ammonium zeolites are 30, 138, and 18, respectively.
  • a molybdenum-added alumina-deficient mordenite catalyst is prepared.
  • the above operation was repeated several times to obtain aluminum-deficient mordenite with Si0 2 / Al 2 0 3 of 20.4 and 26.7, respectively.
  • alumina deficient mordenite The three types of alumina deficient mordenite are mixed with commercially available pseudoboehmite at 50/50 (weight ratio), diluted with nitric acid, ammonium molybdate, and water, kneaded and evenly squeezed, squeezed, dried, and pelletized, 550
  • the catalysts Cl, C2, and C3 were obtained by calcination, and the contents of the three catalysts were all 4.0% by weight. [Examples 17 to 19]
  • ammonium-type mordenite in the examples (1 to 3), and mix it with a commercially available pseudo-boehmite (0- ⁇ 1 2 0 3 ⁇ H 2 0) in different proportions, add dilute nitric acid and water, and knead them. Squeezed, dried at 110 1C, pelletized, and roasted at 400TC to obtain a cylindrical object. This cylindrical object was immersed in an aqueous solution of ammonium molybdate overnight, then dried at 110TC, and then calcined at 540 "to obtain catalysts El, E2, E3, and E4 containing 0.05%, 1.0, 3.0, 8.0, and 16.0% by weight of metal molybdenum, respectively. , E5.
  • an HM zeolite catalyst Fl with a metal molybdenum content of 0.0% by weight was obtained.
  • Example (1-22) and Comparative Example 1-2 the transalkylation activity of the catalyst was evaluated on a pressurized fluidized fixed-bed reaction evaluation device.
  • the airspeed WHSV is 2.5 hours- 1 , and the results are shown in Table 1. The results show that the hydrogen-type zeolite-supported molybdenum catalyst prepared by the present invention has good transalkylation reaction activity.
  • ammonium mordenite in the examples (1 to 3) was mixed with pseudoboehmite at a weight ratio of 70/30, dilute nitric acid and water were added, kneaded and evenly squeezed, squeezed, dried, pelletized, and impregnated.
  • Molybdenum An ammonium acid aqueous solution and a cobalt nitrate aqueous solution were flooded at 110TC and calcined at 5501C to obtain a catalyst G1 having a metal molybdenum and a metal cobalt content of 4.0% by weight and 0.6% by weight, respectively.
  • Catalysts G2 to G8 containing molybdenum and at least one metal or a compound selected from the group consisting of cobalt, nickel, chromium, tungsten, bismuth, lanthanum, zirconium, and silver are prepared in a similar manner.
  • the catalysts G1 to G8 obtained in Examples (24 to 28) were used, and the activity evaluation device and conditions of Example 23 were used to investigate the transalkylation activity of the catalyst.
  • the results are shown in Table 2.
  • the results show that the catalyst containing molybdenum and at least one metal selected from the group consisting of iron, cobalt, nickel, chromium, tungsten, bismuth, lanthanum, zirconium, and silver, or a compound thereof has good transalkylation reaction activity.
  • the catalyst G3 obtained in Examples (24 to 28) was used, and the activity evaluation device and conditions of Example 23 were used.
  • the reaction transalkylation activity of the catalyst was selected using reaction raw materials of different compositions. The results are shown in Table 3. The results show that the catalyst prepared by the present invention has good transalkylation reaction activity, selectivity, and adaptability to raw materials of different compositions under the conditions of having different raw materials of reaction.
  • the catalyst G3 obtained in Examples (24 to 28) was used, and the activity evaluation device of Example 23 was used, and different process conditions were used to investigate the catalyst transalkylation activity.
  • the results are shown in Table 4. The results show that the catalyst prepared by the present invention has good transalkylation reaction activity, selectivity, and adaptability to different process conditions over a wide range of process conditions.
  • the catalysts Al, B1 and Comparative Examples Fl and F2 prepared in Examples (1 to 13) were used to further evaluate the transalkylation reaction activity of the catalysts in order to investigate their stability.
  • the reaction conditions were basically the same as those in Example 23, but The initial reaction temperature of catalysts A1 and B1 was 380 V, and the initial reaction temperature of catalysts F1 and F2 was 4101C.
  • the conversion rates of the catalysts Al and B1 are controlled at about 61 to 63% by weight, and a method of gradually increasing the reaction temperature is adopted to maintain the conversion rate at about 61 to 63% by weight. Controlling the catalyst Fl, F2 conversion rate of about 48 to 51 wt%, reaction temperature is increased stepwise approach taken to maintain the conversion rate of 48--51 About weight%.
  • the test results are shown in Table 5. It can be seen that the catalyst A1 of the present invention reacts for 1000 hours, the reaction temperature is always stable at 380 TC, and the average conversion rate is 62.2 weight. /. , Average (Tol + C 8 A) selectivity 93.0 weight. /. ; Comparative catalyst F1 was reacted for 500 hours, maintaining an average conversion of 48.0% by weight and an average (Tol + C 8 A) selectivity of 84.5% by weight. /. The reaction temperature increased from 4101C to 445 ° F at the end.
  • the catalyst B1 of the present invention reacted for 1000 hours, the reaction temperature was increased from 380 to 392 at the end, the average conversion rate was 63.2% by weight, and the average (Tol + C 8 A) selectivity was 90.4% by weight; compared to the catalyst F2, the reaction was performed for 500 hours to maintain average conversion
  • the yield was 50.3% by weight, the average (Tol + C 8 A) selectivity was 82.9% by weight, and the reaction temperature was increased from 410 to 4381C at the end.
  • the catalyst stability test results show that the catalyst of the invention has high activity, high selectivity and good stability.
  • mordenites with Si0 2 / Al 2 0 3 of 10, 20 and 40 were prepared according to ZL89106793.0. After ammonium exchange and drying, the mordenite was exchanged with commercially available pseudo-boehmite ( ⁇ - ⁇ 1 2 0 3 ⁇ H 2 0) Mix at 50/50 (weight ratio), add dilute nitric acid and water, knead evenly, squeeze the sliver, dry at 1 10 1C, pelletize, and roast at 400 TC to obtain a cylindrical object.
  • pseudo-boehmite ⁇ - ⁇ 1 2 0 3 ⁇ H 2 0
  • This cylindrical object was immersed in an aqueous solution of ammonium molybdate overnight, then dried at 1 101C, and then calcined at 540 to obtain 4.0% by weight of catalysts W1, W2, and W3 containing molybdenum metal.
  • the catalysts W1 to W3 obtained in Examples (33 to 35) were used to examine the transalkylation activity of the catalyst using the activity evaluation device and conditions of Example 23. The results are shown in Table 1. The results show that the molybdenum-containing mordenite catalysts of different silicon-aluminum ratios prepared by the present invention have good transalkylation reaction activity.

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Description

苯与碳九及其以上芳烃烷基转移方法 技术领域
本发明涉及苯与碳九及其以上芳烃烷基转移方法。 具体地说， 是 通过苯 (Ben)和碳九及其以上芳烃 (C9+A)的烷基转移反应生成甲苯 (Tol) 和碳八芳烃 (C8A)， 供给甲苯选择性歧化单元和 C8A 异构化单元， 用 于增产对二曱苯。
背景技术
对二甲苯是石化工业主要的基本有机原料之一， 在化纤、 合成树 脂、 农药、 医药、 塑料等众多化工生产领域有着广泛的用途。 典型的 对二曱苯 (pX)生产方法是从石脑油催化重整生成的热力学平衡的含乙 苯的二甲苯即碳八芳烃中通过多级深冷结晶分离或分子筛模拟移动床 吸附分离（筒称吸附分离）技术， 将对二甲苯从沸点与之相近的异构体 混合物中分离出来。而对于邻位和间位的二甲苯的处理，往往采取 C8A 异构化（简称异构化)技术， 使之异构化为对二甲苯。 为了增产对二甲 苯， 利用甲苯歧化或甲苯与碳九及其以上芳烃 (C9+A)歧化与烷基转移 反应生成苯和 C8A， 从而增产 C8A 是有效的增产对二甲苯的工艺路 线。
迄今为止， 世界上比较典型的、 也比较成熟的与曱苯歧化相关的 工艺有六十年代末工业化的 Tatoray传统曱苯歧化工艺、 八十年代末 推出的 MTDP及近年来推出的 S-TDT工艺和 TransPlus工艺。 甲苯 选择性歧化是生产对二曱苯的一个新途径。 由于甲苯在经改性的 ZSM-5催化剂上进行选择性歧化生成苯和高对二曱苯浓度的 C8A， 因 此只需经筒单的一步冷冻分离就能分离出大部分的高纯度的对二曱 苯。 近年来， 随着催化剂性能的不断提高， 该工艺取得了长足的进展。 其典型工艺有八十年代后期已工业化的 MSTDP 甲苯选择性歧化工艺 和近年来推出的 pX-Plus工艺。
已工业化的曱苯选择性歧化工艺 - MSTDP , 以经过处理的 ZSM- 5 型中孔分子筛为催化剂处理甲苯原料， 可得到高对二甲苯浓度 (85 ~ 90% , 重量百分比， 除注明外以下相同）的 C8A 和硝化级的苯。 尚未 见工业应用报道的 PX-plus工艺， 其主要工艺指标为曱苯转化率 30% 条件下， 二曱苯中 pX的选择性达到 90%， 苯与 pX的摩尔比为 1.37。 然而， 在这类甲苯选择性歧化的工艺中， 在具有高对位选择性的 同时伴随着对原料选择的苛刻性。此类工艺只能以甲苯为原料，而 C9+A 在此工艺中是没有用途的， 至少不能被直接利用。 除此以外， 该工艺 还副产大量的苯， 造成对二曱苯收率偏低， 这是选择性歧化工艺致命 的缺点。
典型的 Tatoray工艺的反应器进料是以甲苯和碳九芳烃 (C9A)为反 应原料， Cie+烃 (碳十及其以上芳烃）的含量必须严格控制。 以 Tatoray 工艺 为基础的文献有 USP4341914、 中 国 专利 98110859.8、 USP2795629, USP3551510. 中国专利 97106719.8 等。 为了提高装置 的经济效益， 降低能耗和物耗， 人们对 Tatoray 工艺进行了进一步的 研究和优化， 主要致力于其核心技术一一催化剂的研制， 提高催化剂 的总体性能指标， 如提高重量空速、 延长催化剂操作周期和增加芳烃 反应原料的平均分子量。 平均分子量的提高有利于增加 C8A， 但当重 芳烃含量过高时， 为了维持一定的转化率， 即维持催化剂活性， 必然 导致副反应尤其是加氢脱烷基反应的加剧， 从而使反应产物中苯产品 偏多， 造成产物 C8A/Ben偏低， 芳烃损失较大， 处理同等原料， 得到 的 C8A偏少、 Ben量偏多。 而对于芳烃联合装置而言， 曱苯歧化装置 之所以不可缺少是因为它能提供 C8A的作用。 Ben量的提高、 C8A量 的减少明显不利于整个芳烃联合装置。 这些不足之处， 已经限制了此 类工艺的发展。
总结以上各工艺不难看出： 所有的这些专利， 都是针对某一特定 的曱苯歧化与烷基转移催化剂在某一或某些方面， 如对重芳烃的烷基 转移能力或反应产物的分离方案上作合理的改动而成， 却总未突破原 有 Tatoray 工艺思路的限制。 其共同的缺点是： 利用甲苯或甲苯和碳 九以上芳烃生产碳八芳烃来增产对二曱苯， 不可避免地要副产苯， 并 且不能有效地利用重质芳烃。
传统的芳烃烷基转移催化剂和工艺， 主要是以甲苯和 C A 为原 料来制取苯和二甲苯， 而生成的大量苯经常属于销路不畅的产品。
甲苯选择性歧化制取对二曱苯的催化剂和工艺， 因为不能利用 C9+A， 只能在有限范围内有较强的竟争力。
加氢脱烷基工艺可以从 C9+A 得到苯、 甲苯、 二甲苯， 但是容易 发生芳烃缩合生成多环或稠环化合物等副反应， 反应温度越高， 副反 应越大， 大分子缩合产物愈多， 催化剂结焦也愈多， 催化剂活性下降 得愈快。
各国在环境方面的立法日趋严格， 特别是汽油中芳香族化合物的 含量将不得不逐渐减少， 这样， 各国石油公司将不得不考虑抽出多余 的苯以符合环境法规。 随着各国石油公司大力进行乙烯装置扩能改造 工程， 作为副产物的苯也将越来越多。 虽然苯在石化行业中占有举足 轻重的作用， 是合成苯乙烯、 酚类和无水马来酸等的基本原料， 但今 后这些领域对苯的需求难以增长。 因此， 有必要为苯开辟一个新的市 场， 寻找新的应用领域。
目前涉及苯与 C9+A 之间烷基转移反应的文献很少。 日本专利 JP10158201 介绍了一种工艺， 其目的在于通过苯或甲苯同多烷基芳 香族化合物之间的烷基转移， 制造多烷基苯。 该专利使用的催化剂是 一种未经金属改性的氢型 DGA 沸石， 没有关于该种沸石金属改性及 催化剂稳定性的报道。
发明内容 九及其以上芳烃烷基转移方法或未涉及可将碳十及其以上重芳烃转化 成有用的甲苯与碳八芳烃的问题， 提供一种以苯与碳九及其以上芳烃 为反应原料， 生产甲苯并联产少量的碳八芳烃， 从而可以为选择性歧 化单元供应甲苯， 为芳烃异构化单元供应碳八芳烃， 通过芳烃烷基转 移、 甲苯选择性歧化和芳烃异构化单元的共同作用， 达到充分利用苯 与碳九及其以上芳烃为原料来增产对二甲苯 (pX)的目的。 另外本发明 提供的苯与碳九及其以上芳烃烷基转移方法， 具有适用较宽的工艺条 件、 催化剂的活性高、 稳定性好、 目标产物选择性高的特点。
为解决上述技术问题， 本发明采用的技术方案如下： 一种苯与碳 九及其以上芳烃烷基转移方法， 以苯和碳九及其以上芳烃为反应原料 进行烷基转移反应， 生成甲苯和碳八芳烃， 其反应条件为：
a) 在临氢条件下， 原料苯和碳九及其以上芳烃通过气固相固定床 反应器与催化剂接触， 苯与碳九及其以上芳烃的重量比为 10 ~ 90： 90 - 10, 反应温度为 300 ~ 600iC , 反应压力为 1.0 ~ 6.0MPa， 原料芳 烃重量空速 WHSV为 0.5 ~ 5.0小时 -1 , H2/烃摩尔比为 1 ~ 15；
b) 所用的催化剂以重量份数计， 含氢型沸石 10 - 90 份， 沸石的 Si02/Al203摩尔比为 3 - 500， 在沸石上负栽钼的金属或 /和氧化物 0.01 ~ 20份， 在催化剂中粘结剂氧化铝为 10 - 90份。
上述技术方案中氢型沸石的 Si02/Al203摩尔比优选范围为 15 ~ 100, 更优选范围为 15 ~ 50。 沸石优选方案选自 ZSM-5沸石、 Y沸石、 丝光沸石、 P沸石、 MCM-22 沸石、 MCM-49 沸石或 MCM-56 沸石 中的至少一种， 更优选方案为选自丝光沸石或 /和 P沸石。 沸石的约束 指数为 0.1 ~ 15。 以重量份数计钼的金属或 /和氧化物的量优选范围为 0.1 - 10.0 更优选范围为 0.1 ~ 4,0份。 以重量份数计沸石上还负载 了选自铁、 钴、 镍、 铬、 钨、 铋、 镧、 锆或银中的至少一种金属或 /和 氧化物， 其用量范围为 0.01 ~ 20 份， 优选范围为 0.1 - 5份。 沸石上 负载的金属或氧化物的优选方案为选自钴、 铬或铋中的至少一种。 氢 型沸石可以是直接合成的， 也可以是天然的或经脱铝处理的， 约束指 数及其测量方法在美国专利 US4016218中有详细叙述。 原料中的碳九 及其以上芳烃优选方案为选自三甲苯、 甲乙苯、 丙苯、 茚满、 碳十或 碳十以上重质芳烃中的至少一种， 碳八芳烃优选方案为二甲苯、 乙苯 或它们的混合物。
本发明使用的催化剂， 由于在氢型沸石上进行了金属改性， 使催 化剂的抗原料水分能力大大增加， 且能保持较高的活性与稳定性， 即 可以使用含水 500ppm 的原料， 也就是说在相当苛刻的反应条件下使 用， 对工业装置而言， 可免去原料 Ben和 C9+A的干燥脱水操作。
0.01 - 20 份以及非强制性加入的至少一种选自铁、 钴、 镍、 铬、 钨、 铋、 镧、 锆或银中的至少一种金属或 /和氧化物 0.01 - 20 份的氢型沸 石。 氢型沸石可以是低硅铝比沸石经酸处理得到的脱铝沸石， 也可以 是天然沸石或直接晶化得到的钠型高硅沸石经无机铵离子交换、 干 燥、 焙烧得到的氢型高硅沸石， 其钠含量应低于 0.2 重量。 /。， 而以直 接晶化合成的高硅沸石最为合适。 本发明的催化剂的优良性能是由氢 型高硅沸石催化作用与沸石上负载的金属和 /或金属氧化物的催化作用 所共同作用的结果。
本发明使用的 Ben 和 C9+A 烷基转移催化剂的制备方法通过一般 的溶液浸渍负载的方法制备， 然后经干燥、 焙烧得催化剂。 具有工艺 成熟、 设备简单、 操作方便、 易于实现工业化等特点。 本发明用于苯和碳九及其以上芳烃的烷基转移方法， 其甲苯加碳 八芳烃选择性最高达 94.1%， 苯加碳九及其以上芳烃转化率最高达
64% , 且具有稳定性好， 原料中允许含水量较高， 且碳十及其以上芳 烃含量较高， 可转化为有用的苯和碳八芳烃， 取得了较好的技术效果。
苯与碳九及其以上芳烃烷基转移反应数据按以下公式处理：
进反应器苯-反应器出口苯
苯转化率 X 100% (重量)
进反应器苯
进反应器 C9+A -反应器出口 C9 +A
C9 +A转化率 X 100% (重量)
进反应器 C9+A 进反应器苯和 C9+A -反应器出口苯和 C9 +A
总转化率 X 100% (重量) 进反应器苯和 C9+A 生成的 (曱苯 + C8A)
甲苯 + C8A选择性 100% (重量)
反应掉的 (苯 + C9+A) 下面通过实施例对本发明作进一步阐述。
具体实施方式
【实施例 1 ~ 31
分别按 ZL89106793.0, USP3308069和 USP4441991 制得钠型丝 光沸石、 钠型 P沸石和钠型 ZSM-5 沸石。 三种钠型沸石分别与氯化 铵或硝酸铵水溶液在 90 ~ 98TC离子交换 1 - 8 小时， 滤去母液， 重复 离子交换数次， 然后洗涤， 110 烘干得到铵型沸石。 三种铵型沸石 的 Si02/Al203分别为 25、 25和 500。 三种铵型沸石分别与拟薄水铝石 ( α -Α1203■ H20)混和， 加稀硝酸、 钼酸铵和水， 捏合均匀， 挤条， 110 烘干， 切粒， 550 焙烧得到催化剂 Al、 A2、 A3 , 三种催化剂金属 钼含量均为 4.0重量％。
【实施例 4】
取市售钠型 Y 沸石（Si02/Al203 = 4)， 按实施例（1 ~ 3)的方法进行 离子交换、 捏合、 成型、 焙烧， 制得催化剂 A4， 催化剂 A4的金属钼 含量为 4.0重量％。
【实施例 5 - 71
分别按 USP4956514 , USP5264643 和 USP5453554 制得钠型 MCM-22沸石、 钠型 MCM-49沸石和钠型 MCM-56沸石。 三种钠型 沸石分别与氯化铵或硝酸铵水溶液在 90 - 98 C离子交换 1 ~ 8 小时， 滤去母液， 重复离子交换数次， 然后洗涤， 110TC烘干得到铵型沸石。 三种铵型沸石的 Si02/Al203分别为 30、 138和 18。 三种铵型沸石分别 与拟薄水铝石（α -Α1203 · H20)混和， 加稀硝酸、 钼酸铵和水， 捏合均 匀， 挤条， 1101C烘干， 切粒， 5501C焙烧得到催化剂 A5、 A6、 A7, 三种催化剂金属钼含量均为 4.0重量％。
【实施例 8 ~ 13】
按 USP3308069制备 Si02/Al203分别为 25.7、 35.1、 40.2和 44.0 的四种 P沸石， 经铵交换、干燥后， 与市售拟薄水铝石（α -Α1203 · Η20) 按 50/50(重量比）混和， 加稀硝酸和水， 捏合均勾， 挤条， 110Ό烘干， 切粒， 400 焙烧得到圓柱形物。 此圆柱形物浸渍于钼酸铵水溶液中 过夜， 然后在 烘干， 再于 540 焙烧得到含金属钼 4.0重量％的 催化剂 Bl、 Β2、 Β3、 Β4。 按同样方法得到 Η β沸石与市售拟薄水铝 石重量比分别为 70/30、 30/70的催化剂 Β5和 Β6。
【实施例 14 ~ 16】
本实施例是制备加钼的缺铝丝光沸石催化剂。 缺铝丝光沸石的制 备： 市售钠型丝光沸石（SiO2/Al2O3=10)， 用稀硝酸在 901C下回流， 使 丝光沸石脱铝， 过滤， 洗涤， HO 烘干得到 Si02/Al203 = 15.2 的缺 铝丝光沸石。 重复上述操作数次，分别得到 Si02/Al203为 20.4和 26.7 的缺铝丝光沸石。三种缺铝丝光沸石分别与市售拟薄水铝石按 50/50(重 量比）混和， 加稀硝酸、 钼酸铵和水， 捏合均勾， 挤条， ΙΙΟΌ烘干， 切粒， 550 焙烧得到催化剂 Cl、 C2、 C3 , 三种催化剂金属钼含量 均为 4.0重量％。 【实施例 17~ 19】
按照实施例（8 ~ 13)的方法用 Si02/Al203 = 25.7 的 β沸石与拟薄水 铝石捏合， 挤条成形， 浸渍钼酸铵水溶液， 得到金属钼含量分别为 0.05、 1.0、 3.0 、 8.0和 16.0重量％的催化剂 Dl、 D2、 D3、 D4、 D5。
【实施例 20~22】
用实施例（1 ~ 3)中的铵型丝光沸石， 与市售拟薄水铝石（0 - Α1203 · H20)按不同比例混和， 加稀硝酸和水， 捏合均勾， 挤条， 110 1C烘干， 切粒， 400TC焙烧得到圓柱形物。 此圓柱形物浸渍于钼酸铵 水溶液中过夜， 然后在 110TC烘干， 再于 540" 焙烧得到含金属钼分 别为 0.05、 1.0、 3.0 、 8.0和 16.0重量％的催化剂 El、 E2、 E3、 E4、 E5。
【比较例 1】
按照实施例（1~ 3)的方法， 得到金属钼含量为 0.0 重量％的 HM 沸石催化剂 Fl。
【比较例 2】
按照实施例（13 ~ 15)的方法， 得到金属钼含量为 0.0重量％的 Ηβ 沸石催化剂 F2。
【实施例 23】
用实施例（1-22)和对比例 1-2 制得的各种催化剂， 在加压流动 式固定床反应评价装置上考评催化剂烷基转移活性。 催化剂装填量 20 克， 反应温度 380Ό, 反应压力 3.0MPa (表）， 氢烃分摩尔比 5.3， 原 料 Ben/C9A/C1Q+A 重量比为 57/43/5, 含水量 500ppm， 重量空速 WHSV2.5 小时 -1， 结果如表 1。 结果表明本发明制得的氢型沸石负载 钼催化剂具有良好的烷基转移反应活性。
【实施例 24~ 28】
用实施例（1~ 3)中的铵型丝光沸石， 与拟薄水铝石按重量比 70/30 混合， 加稀硝酸和水， 捏合均勾， 挤条， 110 烘干， 切粒， 浸渍钼 酸铵水溶液和硝酸钴水溶液， 110TC洪干， 5501C焙烧得到金属钼和金 属钴含量分别为 4.0重量％和 0.6重量％的催化剂 Gl。 用类似的方法 制得含钼和至少一种选自钴、 镍、 铬、 钨、 铋、 镧、 锆、 银等金属或 其化合物的催化剂 G2 ~ G8。
【实施例 29】
用实施例（24 ~ 28)制得的催化剂 G1 ~ G8， 用实施例 23 的活性评 价装置和条件进行催化剂烷基转移活性考察， 结果如表 2。 结果表明 本发明制得的含钼以及至少一种选自铁、 钴、 镍、 铬、 钨、 铋、 镧、 锆、 银等金属或其化合物的催化剂， 具有良好的烷基转移反应活性。
【实施例 30】
用实施例 (24 ~ 28)制得的催化剂 G3， 用实施例 23 的活性评价装 置和条件， 选用不同组成的反应原料， 进行催化剂烷基转移活性考察， 结果如表 3。 结果表明， 在具有不同组成反应原料的条件下， 本发明 制得的催化剂， 具有良好的烷基转移反应活性、 选择性和对不同组成 原料的适应性。
【实施例 31】
用实施例 (24 ~ 28)制得的催化剂 G3， 用实施例 23 的活性评价装 置， 选用不同的工艺条件， 进行催化剂烷基转移活性考察， 结果如表 4。 结果表明， 在较宽的工艺条件范围， 本发明制得的催化剂具有良 好的烷基转移反应活性、 选择性和对不同工艺条件的适应性。
【实施例 32】
用实施例（1 ~ 13)制得的催化剂 Al、 B1 和对比例 Fl、 F2 进行催 化剂烷基转移反应活性的进一步评价， 目的是考察他们的稳定性， 反 应条件与实施例 23基本相同，但催化剂 A1、B1的起始反应温度是 380 V , 对比催化剂 Fl、 F2的起始反应温度是 4101C。 控制催化剂 Al、 B1 的转化率 61 ~ 63 重量％左右， 采取逐步提高反应温度的方法来维 持转化率在 61 - 63重量％左右。 控制催化剂 Fl、 F2的转化率 48 ~ 51 重量％左右， 采取逐步提高反应温度的方法来维持转化率在 48 - 51 重量％左右。 试验结果如表 5。 可以看出， 本发明催化剂 A1反应 1000 小时， 反应温度始终稳定在 380 TC , 平均转化率 62.2 重量。 /。， 平均 (Tol+C8A)选择性 93.0重量。 /。； 对比催化剂 F1反应 500小时， 维持平 均转化率 48.0重量％， 平均 (Tol+C8A)选择性 84.5重量。 /。， 反应温度 由 4101C提升至终了时的 445 Ό。 本发明催化剂 B1反应 1000小时， 反应温度由 380 提升至终了时的 392 ， 平均转化率 63.2 重量％， 平均 (Tol+C8A)选择性 90.4重量％； 对比催化剂 F2反应 500小时， 维 持平均转化率 50.3重量％， 平均 (Tol+C8A)选择性 82.9重量％, 反应 温度由 410 提升至终了时的 4381C。 催化剂稳定性试验结果表明本 发明催化剂具有高活性、 高选择性和良好的稳定性。
【实施例 33 - 35】
按 ZL89106793.0制备 Si02/Al203分别为 10、 20和 40 的四种丝 光沸石， 经铵交换、 干燥后， 与市售拟薄水铝石（α -Α1203 · H20)按 50/50(重量比）混和， 加稀硝酸和水， 捏合均匀， 挤条， 1 10 1C洪干， 切粒， 400 TC焙烧得到圓柱形物。 此圆柱形物浸渍于钼酸铵水溶液中 过夜， 然后在 1 101C烘干， 再于 540 焙烧得到含金属钼 4.0重量％的 催化剂 Wl、 W2、 W3。
【实施例 36】
用实施例 (33 - 35)制得的催化剂 Wl - W3， 用实施例 23的活性评 价装置和条件进行催化剂烷基转移活性考察， 结果如表 1。 结果表明 本发明制得的不同硅铝比的含钼丝光沸石催化剂， 具有良好的烷基转 移反应活性。
表 1催化剂活性评价结果
Figure imgf000011_0001
丝光' 石 2催化剂活性评价结果
Figure imgf000012_0002
表 3催化剂活性评价结果 (一)
原料中 总转化率 (Tol+QA)^ 生 Toi ^ /qA f生 催化剂
Figure imgf000012_0001
/(重量％) /(**%) (摩尔比） 编 号
(重量比）
G3 40/60/5 55.6 90.6 2.7
G3 45/55/5 60.7 93.0 3.1
G3 50/50/5 62.4 93.3 3.5
G3 55/45/5 63.2 93.9 3.7
G3 60/40/5 60.6 94.2 3.8 表 4催化剂活性评价结果 (二)
Figure imgf000013_0001
表 5催化剂稳定性试验
催化剂 反应时间 温度， 平均转化率 (Tol+C8A)平均 Tol选择^ C8A 编号 /小时 始→末 /(重量％) 选择^ (重量％) 选捧 f生 rc (摩尔比）
A1 1000 380→ 380 62.2 93.0 3.2
F1 500 410→445 48.0 84.5 1.2
B1 1000 380→ 392 63.2 90.4 3.0
F2 500 410— 438 50.3 82.9 0.8

Claims

权 利 要 求
1、 一种苯与碳九及其以上芳烃烷基转移方法， 以苯和碳九及其 以上芳烃为反应原料进行烷基转移反应， 生成曱苯和碳八芳烃， 其反 应条件为：
a) 在临氢条件下， 原料苯和碳九及其以上芳烃通过气固相固定床 反应器与催化剂接触， 苯与碳九及其以上芳烃的重量比为 10 ~ 90： 90 - 10, 反应温度为 300 ~ 6001：， 反应压力为 1.0 ~ 6.0MPa， 原料芳 烃重量空速 WHSV为 0.5 ~ 5.0小 B^-1 , H2/烃摩尔比为 1 - 15;
b) 所用的催化剂以重量份数计， 含氢型沸石 10 ~ 90 份， 沸石的 Si02/Al203摩尔比为 3 ~ 500， 在沸石上负栽钼的金属或 /和氧化物 0.01 - 20 在催化剂中粘结剂氧化铝为 10 ~ 90份。
2、 根据权利要求 1 所述苯与碳九及其以上芳烃烷基转移方法， 其特征在于原料中的碳九及其以上芳烃为选自三甲苯、 甲乙苯、 丙苯、 茚满、 碳十或碳十以上重质芳烃中的至少一种。
3、 根据权利要求 1 所述苯与碳九及其以上芳烃烷基转移方法， 其特征在于碳八芳烃为二甲苯、 乙苯或它们的混合物。
4、 根据权利要求 1 所述苯与碳九及其以上芳烃烷基转移方法， 其特征在于以重量份数计所用催化剂含有钼的金属或 /和氧化物的量为 0.1 - 10.0份。
5、 根据权利要求 4 所述用于苯与碳九及其以上芳烃烷基转移的 催化剂， 其特征在于以重量份数计钼的金属或 /和氧化物的量为 0.1 ~ 4.0份。
6、 根据权利要求 1 所述苯与碳九及其以上芳烃烷基转移方法， 其特征在于所用沸石的 Si02/Al203摩尔比为 15 ~ 100。
7、 根据权利要求 6 所述用于苯与碳九及其以上芳烃烷基转移的 催化剂， 其特征在于氢型沸石的 8102/ 1203摩尔比为 15 ~ 50。
8、 根据权利要求 1 所述苯与碳九及其以上芳烃烷基转移方法， 其特征在于所用沸石选自 ZSM-5沸石、 Y沸石、 丝光沸石、 β沸石、 MCM-22沸石、 MCM-49沸石或 MCM-56沸石中的至少一种。
9、 根据权利要求 1 所述苯与碳九及其以上芳烃烷基转移方法， 其特征在于所用沸石是丝光沸石或 /和 ρ沸石。
10、 根据权利要求 1 所述苯与碳九及其以上芳烃烷基转移方法， 其特征在于以重量份数计在沸石上还负载了选自铁、 钴、 镍、 铬、 钨、 铋、 镧、 锆或银中的至少一种金属或 /和氧化物， 其用量为 0.01 - 20 份。
11、 根据权利要求 10 所述苯与碳九及其以上芳烃烷基转移方法， 其特征在于以重量份数计在沸石上还负载了选自铁、 钴、 镍、 铬、 钨、 铋、 镧、 锆或银中的至少一种金属或 /和氧化物的用量为 0.1 - 5份。
PCT/CN2003/000146 2002-03-13 2003-02-25 Transalkylation du benzene et d'hydrocarbures aromatiques c9+ WO2003076372A1 (fr)

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