WO2011072469A1 - 一种用于合成吡啶碱的共结晶沸石催化剂及其制备方法和应用 - Google Patents

一种用于合成吡啶碱的共结晶沸石催化剂及其制备方法和应用 Download PDF

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WO2011072469A1
WO2011072469A1 PCT/CN2010/000527 CN2010000527W WO2011072469A1 WO 2011072469 A1 WO2011072469 A1 WO 2011072469A1 CN 2010000527 W CN2010000527 W CN 2010000527W WO 2011072469 A1 WO2011072469 A1 WO 2011072469A1
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catalyst
weight
pyridine
crystallized zeolite
synthesizing
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徐龙伢
刘盛林
谢素娟
辛文杰
朱向学
陈福存
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中国科学院大连化学物理研究所
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/08—Preparation by ring-closure
    • C07D213/09—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles
    • C07D213/10—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles from acetaldehyde or cyclic polymers thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing

Definitions

  • the invention relates to the field of chemical industry, in particular to a co-crystallized zeolite catalyst for synthesizing pyridine base and a preparation method thereof.
  • Pyridine is a six-membered heterocyclic compound formed by substituting a carbon atom on a benzene ring with a nitrogen atom.
  • Pyridine and alkylpyridine are commonly referred to as pyridine bases, and mainly include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, and 2-methyl-5-ethylpyridine.
  • pyridine series raw materials are important organic raw materials for the production of high value-added fine chemical products. They are widely used in medicine, pesticides, dyes, perfumes, feed additives, food additives, rubber additives and synthetic materials.
  • Chichbabin proposed an industrial method for the mass production of pyridine base using aldehydes and ammonia as raw materials. Through continuous improvement of the catalyst, the yield has increased from 40%-50% in the 1950s to around 80%. With the development of the oil and gas industry, taking into account the cost of raw materials, there have been methods for the catalytic synthesis of pyridine bases using ketones, alcohols, olefins, alkynes, etc., but the process is not mature and the yield is low. At present, 95% of the world's pyridine base is still obtained by catalytic synthesis using aldehyde and ammonia as raw materials.
  • the catalyst was first prepared for pyridine base synthesis mostly amorphous aluminosilicate catalyst and a through-modified amorphous aluminosilicate catalysts, as described in US Patent No. US2507618; US3946020 and US3932431 reported the Si0 2 -Al 2 0 3 and halogen compounds and modified ⁇ 0 4 3 ⁇ Si0 2 -Al 2 0 3 compound, but the total yield of pyridine bases which is generally not high ( ⁇ 50%).
  • the powder, Si0 2 is a molecular sieve made of a binder as a catalyst for the synthesis of pyridine base.
  • the pyridine yield of the catalyst was 47%, the molar ratio of aldehyde/formaldehyde was 1.4, the ammonia/aldehyde molar ratio was 1.5, and the reaction pressure was normal pressure.
  • the methylpyridine (including 2-methylpyridine, 3-methyl) The yield of the pyridine and 4-methylpyridine was 14%, and the total yield of pyridine and methylpyridine was 61%.
  • U.S. Patent No. 5,218,122 (1993), entitled “Synthesis of a Pyridine Base and Its Catalyst”, discloses a crystalline zeolite modified with tungsten, zinc or tin as a catalyst for the synthesis of pyridine base in a molar ratio of formaldehyde to acetaldehyde of 1, ammonia.
  • the gas/aldehyde molar ratio is 1.2, and the reaction temperature of 450 ° C under the reaction conditions, the pyridine yield of the tungsten modified catalyst is 32%, the yield of 3-methylpyridine is 16%, the yield of 2-methylpyridine It is 1%.
  • the zinc or tin modified catalyst had a pyridine yield of 34%, a yield of 13% of 3-methylpyridine, and a yield of 2-% of 2-methylpyridine.
  • the catalyst modified with zinc and tin at the same time had a pyridine yield of 34%, a yield of 16% of 3-methylpyridine, and a yield of 2-% of 2-methylpyridine.
  • Japanese patents Publication Nos. CN1330068 A and 1172915C
  • U.S. Patent No. 6,281,362 which are entitled “Methods for Preparing Pyridine Bases”
  • Japanese Patent No. 6,281,362 use crystals containing titanium and/or cobalt and silicon as constituent elements of zeolite.
  • the zeolite is used as a catalyst in which the atomic ratio of silicon to titanium and/or cobalt is from about 5 to about 1,000.
  • titanium and/or cobalt are synthesized in the molecular sieve structure, Entering the skeleton of the molecular sieve, the total yield of the pyridine base using the zeolite as a catalyst is less than 50%.
  • lead, tungsten, zinc, ruthenium, osmium and indium are modified into the zeolite framework, the total yield of pyridine base is increased, and the highest can reach 72.5%.
  • Lu Guanzhong et al. disclosed in Chinese patents CN1263741C and CN1565736A that the ZSM-5 catalyst was modified with a mixture of lead and cobalt in a continuous flow fixed bed at a space velocity of 1000 h, a formaldehyde/acetaldehyde molar ratio of 1/2, ammonia.
  • Xiao Guomin et al. disclosed in Chinese patent CN1631536A that the ZSM-5 catalyst was modified with lead, cobalt and palladium in a continuous flow fixed bed with a space velocity of 1000 h and a formaldehyde/acetaldehyde/ammonia molar ratio of 1/2/4.
  • Catalysts with a reaction temperature of 450 ° C, lead (2w%:), cobalt (10 w%) and palladium (0.01 w%) modified ZSM-5 (Si0 2 /Al 2 0 3 molar ratio 150) catalyst
  • the yield of pyridine was 55%, the total yield was 72%, and the regeneration period was 24 hours.
  • Chinese patent CN200710021347.4 discloses a catalyst for producing pyridine base and a preparation method thereof.
  • the catalyst is supported on a ZSM-5 molecular sieve support; the composition comprises a ZSM-5 molecular sieve support having a mass percentage of 90-99.9% and 10-0.1% ruthenium supported thereon.
  • the catalyst of the invention increases the selectivity of pyridine base, reduces high-boiling by-products, and can make pyridine and The total yield of the pyridine is up to 88%.
  • the present invention is a continuation of the first two inventions of the inventors (CN200910010393.3 and 200910010394.8), and the ratio of pyridine/3-methylpyridine is significantly higher than the values of the first two inventions while maintaining the similar yield of pyridine base (see comparison). Examples and examples).
  • the present invention is more advantageous for situations where high pyridine yields need to be produced.
  • An object of the present invention is to provide a co-crystallized zeolite catalyst for synthesizing pyridine base and a process for the preparation thereof.
  • the present invention provides a co-crystallized zeolite catalyst for synthesizing pyridine base, the catalyst comprising 25-45 wt% rare earth-ZSM5/ZSM11 co-crystallized zeolite, 0.5-3.0 wt% 1 0 2 (preferably Ti0 2 1.0-2.0%), The rest are tri-aluminum and kaolin.
  • the present invention provides a synthetic pyridine base co-crystallized zeolite catalyst, wherein the trialumina is derived from an aluminum sol in an amount of 10 to 40% by weight; and the kaolin content is 20 to 50% by weight.
  • the invention also provides a preparation method of a co-crystallized zeolite catalyst for synthesizing pyridine base, which is 25-45 wt% - rare earth-ZSM5/ZSM11, 0.5-3.0 wt% 110 2 , 10-40 wt% alumina, 20-50
  • the weight% kaolin and water are uniformly mixed, the solid/water weight ratio in the mixture is 0.2-0.5, spray-molded and dried to prepare a catalyst; wherein the inlet temperature in the spray condition is 480-650 ° C, and the exhaust gas temperature is 150-250 °C, spray pressure is 0.5-10Mpa, drying temperature is 500-650 ° C, time is 1-5 hours.
  • the catalyst provided by the invention is applied to the synthesis of pyridine base from formaldehyde acetaldehyde ammonia.
  • the invention has the advantages of being industrially operable, relatively simple in process, high in yield of pyridine base and the like.
  • the rare earth-ZSM5/ZSM11 co-crystallized zeolite is different from the mechanical mixture of rare earth, ZSM5 and ZSM11.
  • the co-crystallized zeolite is in the synthesis of co-crystallized ZSM5/ZSM11 zeolite (unlike ZSM and ZSM11)
  • the mechanical mixture) is simultaneously embedded in the framework of the co-crystallized ZSM5/ZSM11 zeolite.
  • the zeolite molecular sieve has good acid hydrothermal stability and anti-impurity ability (see Chinese Patent CN1137022A and Republic of China Patent No. O 8330 O 2). This has great industrial practical significance for catalytic processes involving hydrothermal treatments such as regeneration of catalysts.
  • a certain amount of 70% by weight 283 ⁇ 4 -5/30 S% MCM-22 composite molecular sieve, Ti0 2 , aluminum sol, silica sol, kaolin, deionized water is uniformly mixed, spray-molded, and dried to obtain catalyst VIII.
  • the inlet temperature in the spray condition was 480 ° C
  • the exhaust gas temperature was 170 ° C
  • the spray pressure was 2.0 MPa
  • the drying temperature was 520 ° C for 4 hours.
  • the catalyst 8 was obtained by molding and drying.
  • the inlet temperature in the spray condition was 48 (TC, the exhaust gas temperature was 170 ° C, the spray pressure was 2.0 Mpa, and the drying temperature was 520 ° C, 4 hours.
  • the obtained catalyst B of which 70% by weight 281 ⁇ 1-11
  • the weight content of /30 fi%ZSM-35 composite molecular sieve, MgO, Co 3 0 4 and alumina were 39%, 1.5%, 0.8% and 36%, respectively.
  • Example 1 A certain amount of rare earth -50% by weight ZSM5 / 50% by weight ⁇ 81 ⁇ 11 co-crystallized zeolite (rare earth content of rare earth -30% by weight 28 / 15 / 70 weight% 28] ⁇ 11 co-crystallized zeolite (3.2% by weight), Ti0 2 , aluminum sol, kaolin, deionized water, uniformly mixed, spray-formed, and dried to obtain a catalyst (: wherein the inlet temperature in the spray condition is 620 ° C, the exhaust gas temperature is 200 ° C, the spray pressure is 5 MPa, the drying temperature It is 620 ° C, 2 hours.
  • the obtained catalyst C wherein the rare earth - 50% by weight ZSM5 / 50% by weight ZSM11 co-crystallized zeolite, Ti0 2 and alumina have a weight content of 41%, 1.9% and 30%, respectively.
  • a certain amount of rare earth -30 wt% ZSM5/70 M% ZSM11 co-crystallized zeolite (rare earth content accounts for 1.2 wt% of rare earth -30 wt% ⁇ 8 ⁇ 15 ⁇ 0 wt% 28] ⁇ 11 co-crystallized zeolite), Ti0 2 , aluminum sol, kaolin, deionized water is uniformly mixed, spray-formed, and dried to obtain catalyst D.
  • the inlet temperature in the spray condition was 480 ° C
  • the exhaust gas temperature was 170 ° C
  • the spray pressure was 2.0 MPa
  • the drying temperature was 520 Torr for 4 hours.
  • the obtained catalyst D wherein the rare earth-30 wt% ZSM5/70 wt% 281 ⁇ 11 co-crystallized zeolite, ⁇ 2 2 and alumina have a weight content of 39%, 1.5% and Example 3, respectively.
  • a certain amount of rare earth -50% by weight ZSM5/50 S%ZSM11 co-crystallized zeolite (rare earth content of 5% by weight of ZSM5/50 3 ⁇ 4% ZSM11 co-crystallized zeolite: 5.2% by weight:), Ti0 2 , aluminum sol, kaolin
  • the deionized water is uniformly mixed, spray-formed, and dried to obtain a catalyst E.
  • the inlet temperature in the spray condition was 500 ° C
  • the exhaust gas temperature was 200 ° C
  • the spray pressure was 8 MPa
  • the drying temperature was 580 ° C for 2 hours.
  • the obtained catalyst E wherein the rare earth-50% ZSM5/50 heavy % ZSM11 co-crystallized zeolite, Ti0 2 and alumina have a weight content of 28%, 1.0% and twenty four%.
  • the obtained catalyst F wherein the rare earth-90 wt% ZSM5/10 wt% ⁇ 8] ⁇ 11 co-crystallized zeolite, Ti ⁇ 2 and alumina have a weight content of 37%, 0.7% and Example 5, respectively.
  • a certain amount of rare earth-90% by weight ZSM5/10 S% ZSM11 co-crystallized zeolite (rare earth content accounts for 2.5 wt% of rare earth-90 wt% ⁇ 81 ⁇ 5/10 wt% 281 ⁇ 11 co-crystallized zeolite:), Ti0 2 , aluminum sol, kaolin, deionized water is uniformly mixed, spray-formed, and dried to obtain catalyst G.
  • the inlet temperature in the spray condition was 500 ° C
  • the exhaust gas temperature was 210 ° C
  • the spray pressure was 5 MPa
  • the drying temperature was 550 ° C for 3 hours.
  • the obtained catalyst G, wherein the rare earth-90% by weight 28 ⁇ 15/10% by weight ZSM11 co-crystallized zeolite, Ti ⁇ 2 and alumina have a weight content of 39%, 2.5% and 23%, respectively.
  • the comparative examples and examples of the present invention are useful in the synthesis of pyridine base from formaldehyde acetaldehyde.
  • reaction tube fixed bed catalyst 800g under N2 atmosphere was heated to 500 ° C activation, N 2 atmosphere and then dropped to the reaction temperature, reaction was carried out under the conditions shown in Table 1, the raw material is formaldehyde, acetaldehyde Mix with ammonia gas, passing through the catalyst bed from bottom to top, at a certain airspeed and temperature
  • the gas phase condensation reaction produces a desired product of pyridine and methylpyridine, and the reaction is carried out for 40 minutes each time, followed by steam stripping, three times in succession, and quantification by gas chromatography, and the reaction results are averaged.
  • the catalysts prepared by the present invention (C, D, E, F and G) were prepared in accordance with the present invention under the conditions of similar pyridine base yields (about 66%) compared to Comparative Examples A and B.
  • the pyridine/3-methylpyridine ratio of the catalyst was significantly higher than that of the comparative example, and the numerical value of the comparative example was 3.38, while the present invention could reach 3.89.
  • the catalysts C, D, E, F and G provided by the present invention are similar in general, and the yield of pyridine and methylpyridine produced is more than 64%, and the ratio of pyridine/3-methylpyridine is more than 3.85.
  • Reaction conditions temperature 450 ⁇ ; acetaldehyde / formaldehyde / ammonia molar ratio 1 / 1/2; weight space velocity 0.3 h ' 1 ; fluidized bed, catalyst 800 g.

Description

一种用于合成吡啶碱的共结晶沸石催化剂
及其制备方法和应用
技术领域
本发明涉及化工领域， 具体涉及一种合成吡啶碱的共结晶沸石催化剂 及其制备方法。
背景技术
吡啶是苯环上一个碳原子被氮原子取代后所形成的六元杂环化合物。 吡啶及烷基吡啶通称为吡啶碱， 主要包括吡啶、 2-甲基吡啶、 3-甲基吡啶、 4-甲基吡啶和 2-甲基 -5-乙基吡啶等。 吡啶系列原料作为化学工业品， 是生 产高附加值精细化工产品的重要有机原料， 广泛应用于医药、农药、染料、 香料、 饲料添加剂、 食品添加剂、 橡胶助剂及合成材料等领域。
1924年 Chichbabin提出了以醛和氨为原料， 大批量生产吡啶碱的工业 方法，经过对催化剂的不断改进，产率已由 50年代的 40%-50%提高到 80% 左右。 随着石油天然气工业的发展， 考虑到原料成本， 又出现了以酮、醇、 烯烃、炔烃等为原料催化合成吡啶碱的方法， 但工艺尚不成熟而产率较低。 目前， 世界上 95%的吡啶碱仍然是以醛和氨作为原料， 经催化合成而得。
最早用于合成法制备吡啶碱的催化剂多为无定形硅铝酸盐催化剂及经 过改性的无定形硅铝酸盐催化剂， 如美国专利 US2507618; US3946020和 US3932431 等报道的 Si02-Al203化合物及经卤素和 Ρ04 3·改性的 Si02-Al203化合物， 但其吡啶碱的总产率一般不高（<50%)。
题为 "用具有 ZSM-5结构的晶型分子筛合成吡啶及烷基吡啶"的美国 专利 US4861894 ( 1989)披露了以 Si02/Al203摩尔比为 225的高硅 ZSM-5 沸石为原粉， Si02为粘结剂制成的分子筛作为吡啶碱合成的催化剂。 在乙 醛 /甲醛摩尔比为 1.4、 氨气 /醛摩尔比为 1.5、 反应压力为常压的反应条 件下， 催化剂的吡啶产率为 47%, 甲基吡啶 （包括 2-甲基吡啶， 3-甲基吡 啶和 4-甲基吡啶） 的产率为 14%， 吡啶和甲基吡啶的总产率为 61%。
题为 "吡啶碱的合成及其催化剂"的美国专利 US5218122 ( 1993 )披 露了以钨、 锌或锡改性的晶型沸石作为吡啶碱合成的催化剂， 在甲醛 /乙 醛摩尔比为 1、 氨气 /醛摩尔比为 1.2, 反应温度 450°C的反应条件下， 钨 改性催化剂的吡啶收率为 32%, 3-甲基吡啶的收率为 16%， 2-甲基吡啶的 收率为 1%。 在同样的反应条件下， 锌或锡改性的催化剂， 其吡啶收率为 34%, 3-甲基吡啶的收率为 14%, 2-甲基吡啶的收率为 1%。 同时用锌和锡 改性的催化剂， 其吡啶收率为 34%， 3-甲基吡啶的收率为 16%， 2-甲基吡 啶的收率为 1%。
题为 "吡啶及 3-甲基吡啶的合成"的美国专利 US5395940 ( 1995)披 露了以特定的晶型沸石如 MCM-22或 MCM-49作为吡啶及 3-甲基吡啶合成 的催化剂。 在乙醛 /甲醛 /氨气摩尔比为 1.4/1/3.6、 反应温度 427°C的反应条 件下， 吡啶的收率为 9.3%， 3-甲基吡啶的收率为 4.1%，. 2-甲基吡啶的收率 为 0.6%， 4-甲基吡啶的收率为 0.9%。虽然上述方法合成的吡啶及 3-甲基吡 啶中 2-甲基吡啶和 4-甲基吡啶的含量均很少， 但吡啶及 3-甲基吡啶的总收 率太低， 无任何工业应用的可能。
最近， 日本广荣化学株式会社的题为 "制备吡啶碱类的方法"的中国 专利（公开号 CN1330068 A和 1172915C)及美国专利 US 6281362采用含 钛和 /或钴和硅作为沸石组成元素的晶型沸石作为催化剂， 其中硅与钛和 / 或钴的原子比率为约 5至约 1000。但由于钛和 /或钴是合成于分子筛结构中， 进入分子筛的骨架， 用该沸石作催化剂的吡啶碱总收率低于 50%。 同样使 铅、 钨、 锌、 佗、 镧及铟等进入沸石骨架改性后， 吡啶碱的总收率有所提 高， 其中最高的可以达到 72.5%。
卢冠忠等在中国专利 CN1263741C和 CN1565736A披露了以铅和钴的 混合物对 ZSM-5催化剂进行改性， 在连续流动固定床， 空速： 1000 h ， 甲 醛 /乙醛摩尔比为 1/2、 氨气 /醛摩尔比为 4.5， 反应温度 450Ό的反应条 件下， 铅（2.5w%) 和钴（1.5w%) 改性的 ZSM-5 (Si02/Al203摩尔比为 150)催化剂，连续反应 4小时，吡啶收率为 68%， 3-甲基吡啶的收率为 4.5%, 2-甲基吡啶的收率为 4%。其它条件相同， 只是反应空速 3000^,氨气 /醛 摩尔比为 4.5， 其吡啶收率为 55.5%， 3-甲基吡啶的收率 25%， 2-甲基吡啶 的收率 0.5%， 4-甲基吡啶的收率为 0， 总收率为 81%。
肖国民等在中国专利 CN1631536A披露了以铅，钴和钯对 ZSM-5催化 剂进行改性， 在连续流动固定床， 空速： 1000h ， 甲醛 /乙醛 /氨摩尔比为 1/2/4, 反应温度 450°C的反应条件下， 铅（2w%：)， 钴（10 w%)和钯（0.01 w%)改性的 ZSM-5 (Si02/Al203摩尔比为 150)催化剂，吡啶收率为 55%, 总收率为 72%，再生周期为 24小时。其它条件相同，铅（ 12.5w%),钴（2w%) 和钯（0.2w%)改性的 ZSM-5 (Si02/Al203摩尔比为 150)催化剂， 吡啶收 率为 70%, 总收率为 87%, 再生周期为 48小时。
中国专利 CN200710021347.4披露一种生产吡啶碱的催化剂及其制备 方法。 该催化剂为将铋负载在 ZSM-5分子筛载体上； 其组成包括质量百分 比为 90-99.9%的 ZSM-5分子筛载体和负载于其上的 10-0.1%的铋。 本发明 的催化剂增加了吡啶碱的选择性， 减少了高沸点副产物， 可以使吡啶及甲 基吡啶的总收率最高至 88%。
本发明是发明人前两个发明 （CN200910010393.3 和 200910010394.8) 的延续， 在保持吡啶碱收率相似的条件下， 吡啶 /3-甲基吡啶的比明显高于 前两个发明的数值 (见比较例和实施例）。对于需要生产高吡啶收率的情况， 本发明更有优势。
发明内容
本发明的目的是提供一种合成吡啶碱的共结晶沸石催化剂及其制备方 法。
本发明提供了一种合成吡啶碱的共结晶沸石催化剂， 该催化剂含有 25-45 重％稀土 -ZSM5/ZSM11 共结晶沸石， 0.5-3.0重％1 02 (优选 Ti02 1.0-2.0%), 其余为三氧化铝和高岭土。
本发明提供的合成吡啶碱的共结晶沸石催化剂， 所述三氧化铝来源于 铝溶胶， 其含量为 10-40重％; 高岭土含量为 20-50重％。
本发明还提供了合成吡啶碱的共结晶沸石催化剂的制备方法， 将 25-45 重％ -稀土 -ZSM5/ZSM11 , 0.5-3.0重％1102, 10-40重％三氧化铝， 20-50重％ 高岭土和水混合均匀，混合物中固体 /水重量比 = 0.2-0.5，喷雾成型和干燥， 制得催化剂；其中，喷雾条件中的入口温度为 480-650°C ,尾气温度为 150-250 °C， 喷雾压力为 0.5-10Mpa， 干燥温度为 500-650°C， 时间为 1-5小时。
本发明提供的催化剂应用于甲醛乙醛氨合成吡啶碱方面。
本发明具有可供工业操作， 工艺比较简单， 吡啶碱收率高等优点。 稀土 -ZSM5/ZSM11共结晶沸石不同于稀土、 ZSM5和 ZSM11的机械混合 物。该共结晶沸石是在合成共结晶 ZSM5/ZSM11沸石（不同于 ZSM和 ZSM11 的机械混合物）的同时将稀土镶嵌到了共结晶 ZSM5/ZSM11沸石骨架中形成 的。 该沸石分子筛具有良好的酸性水热稳定性和抗杂质污染能力 （见中国 专利 CN1137022A和中华民国专利第 O八三七 O二号）。这对于涉及到水热处 理（如催化剂的再生） 的催化过程而言具有极大的工业实用意义。
具体实施方式
下面的实施例将对本发明予以进一步的说明， 但并不因此而限制本发 明。
对比例 1
将一定量的 70重％28¾ -5/30 S%MCM-22复合分子筛， Ti02，铝溶胶， 硅溶胶， 高岭土， 去离子水混合均匀后喷雾成型， 干燥制得催化剂八。 其 中喷雾条件中的入口温度为 480°C，尾气温度为 170°C，喷雾压力为 2.0Mpa， 干燥温度为 520°C， 4小时。 制得的催化剂 A， 其中 70重％ ZSM-5/30重 %MCM-22复合分子筛， Ti02， 氧化铝以及氧化硅的重量含量分别为 39%, 1.5%, 30%和 1%。
对比例 2
将一定量的 70 ¾%ZSM-ll/30 fi%ZSM-35复合分子筛， Mg(N03)2, Co(N03)2-6H20, 铝溶胶， 高岭土， 去离子水混合均匀后喷雾成型， 干燥制 得催化剂8。 其中喷雾条件中的入口温度为 48(TC， 尾气温度为 170°C， 喷 雾压力为 2.0 Mpa， 干燥温度为 520°C， 4小时。 制得的催化剂 B， 其中 70 重％281^1-11/30 fi%ZSM-35复合分子筛， MgO， Co304和氧化铝的重量含 量分别为 39%， 1.5%, 0.8%和 36%。
实施例 1 将一定量的稀土 -50重％ ZSM5/50重％∑81^11共结晶沸石（稀土含量 占稀土 -30重％ 28\15/70重％28]^11共结晶沸石的 3.2重％), Ti02， 铝溶 胶， 高岭土， 去离子水混合均匀后喷雾成型， 干燥制得催化剂（：。 其中喷 雾条件中的入口温度为 620 °C , 尾气温度为 200°C， 喷雾压力为 5Mpa， 干 燥温度为 620°C， 2小时。 制得的催化剂 C， 其中稀土 -50重％ ZSM5/50重 %ZSM11 共结晶沸石， Ti02以及氧化铝的重量含量分别为 41%， 1.9%和 30% o
实施例 2
将一定量的稀土 -30重％ ZSM5/70 M%ZSM11共结晶沸石（稀土含量 占稀土 -30重％∑8\15〃0重％28]^11共结晶沸石的 1.2重％)， Ti02， 铝溶 胶， 高岭土， 去离子水混合均匀后喷雾成型， 干燥制得催化剂 D。 其中喷 雾条件中的入口温度为 480 °C， 尾气温度为 170°C， 喷雾压力为 2.0Mpa， 干燥温度为 520Ό， 4小时。 制得的催化剂 D, 其中稀土 -30重％ ZSM5/70 重％281^11共结晶沸石， Γι02以及氧化铝的重量含量分别为 39%， 1.5%和 实施例 3
将一定量的稀土 -50重％ ZSM5/50 S%ZSM11共结晶沸石（稀土含量 占稀土 -50重％ ZSM5/50 ¾%ZSM11共结晶沸石的 5.2重％：)， Ti02， 铝溶 胶， 高岭土， 去离子水混合均匀后喷雾成型， 干燥制得催化剂 E。 其中喷 雾条件中的入口温度为 500°C， 尾气温度为 200°C , 喷雾压力为 8Mpa，，干 燥温度为 580°C , 2小时。 制得的催化剂 E， 其中稀土 -50 % ZSM5/50重 %ZSM11 共结晶沸石， Ti02以及氧化铝的重量含量分别为 28%， 1.0%和 24%。
实施例 4
将一定量的稀土 -90重％ ZSM5/10 M%ZSM11共结晶沸石 （稀土含量 占稀土 -90重％ ZSM5/10 %ZSM11共结晶沸石的 4.2重％), Ti02， 铝溶 胶， 高岭土， 去离子水混合均匀后喷雾成型， 干燥制得催化剂 F。 其中喷 雾条件中的入口温度为 650'C , 尾气温度为 230°C， 喷雾压力为 0.8Mpa， 干燥温度为 630°C， 1.5小时。制得的催化剂 F， 其中稀土 -90重％ZSM5/10 重％∑8]^11共结晶沸石， Ti〇2以及氧化铝的重量含量分别为 37%, 0.7%和 实施例 5
将一定量的稀土 -90重％ ZSM5/10 S%ZSM11共结晶沸石（稀土含量 占稀土 -90重％∑81^5/10重％281^11共结晶沸石的 2.5重％：)， Ti02， 铝溶 胶， 高岭土， 去离子水混合均匀后喷雾成型， 干燥制得催化剂 G。 其中喷 雾条件中的入口温度为 500°C， 尾气温度为 210°C， 喷雾压力为 5Mpa， 干 燥温度为 550°C， 3小时。 制得的催化剂 G, 其中稀土 -90重％28^15/10重 %ZSM11 共结晶沸石， Ti〇2以及氧化铝的重量含量分别为 39%， 2.5%和 23%
对比例和实施例的应用
本发明的对比例和实施例在甲醛乙醛氨合成吡啶碱方面的应用。 在固 定流化床反应管内装 800g催化剂，在 2气氛下升温到 500°C活化，然后在 N2气氛下降到反应温度， 在如表 1所示的条件下进行反应， 原料为甲醛、 乙醛和氨气混合物， 自下而上通过催化剂床层， 在一定的空速和温度下发 生气相缩合反应， 生成目的产物吡啶和甲基吡啶等， 每次反应 40分钟， 然 后用水蒸汽汽提， 连续三次， 用气相色谱进行定量， 反应结果取平均值。
由表 1的结果可见， 本发明制备的催化剂（C， D, E， F和 G)与对比 例 A和 B相比， 在吡啶碱收率相似 (66%左右）的条件下， 本发明制备的催 化剂的吡啶 /3-甲基吡啶比明显高于对比例的数值， 对比例的数值最高为 3.38， 而本发明的却可以达到 3.89。
另外，本发明提供的催化剂 C， D, E， F和 G， 总体情况差不多，生 成的吡啶和甲基吡啶收率在 64%以上，吡啶 /3-甲基吡啶比大于 3.85。
表 1 吡啶催化剂评价结果
Figure imgf000009_0001
反应条件： 温度 450Ό ; 乙醛 /甲醛 /氨摩尔比 1/1/2; 重量空速 0.3 h'1; 流化床， 催化剂 800 g。

Claims

权 利 要 求
1、一种合成吡啶碱的共结晶沸石催化剂， 其特征在于： 该催化剂含有 25-45重％稀土 -ZSM5/ZSM11共结晶沸石， 0.5-3.0重％1 02，其余为三氧化 铝和高岭土。
2、按照权利要求 1所述合成吡啶碱的共结晶沸石催化剂，其特征在于： 所述 Ti02的含量为 1.0-2.0重％。
3、按照权利要求 1所述合成吡啶碱的共结晶沸石催化剂，其特征在于： 所述三氧化铝来源于铝溶胶， 其含量为 10-40重％。
4、 按照权利要求 1所述合成吡啶碱的共结晶沸石催化剂， 其特征在于: 所述高岭土含量为 20-50重％。
5、 权利要求 1所述合成吡啶碱的共结晶沸石催化剂的制备方法， 其特 征在于： 将 25-45重％ -稀土 -ZSM5/ZSM11 , 0.5-3.0fi%TiO2, 10-40重％三氧 化铝， 20-50重％高岭土和水混合均匀， 混合物中固体 /水重量比 = 0.2-0.5， 喷雾成型和干燥， 制得催化剂。 ，
6、 按照权利要求 5所述催化剂的制备方法， 其特征在于： 所述喷雾条 件中的入口温度为 480-650 °C， 尾气温度为 150-250 °C , 喷雾压力为 0.5-10Mpa, 干燥温度为 500-650°C， 时间为 1-5小时。
7、 权利要求 1所述催化剂应用于甲醛乙醛氨合成吡啶碱方面。
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