WO2010094169A1 - Magnesium-cobalt based catalyst for synthesizing pyridine base from formaldehyde, acetaldehyde and ammonia and preparation method thereof - Google Patents

Magnesium-cobalt based catalyst for synthesizing pyridine base from formaldehyde, acetaldehyde and ammonia and preparation method thereof Download PDF

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WO2010094169A1
WO2010094169A1 PCT/CN2009/001484 CN2009001484W WO2010094169A1 WO 2010094169 A1 WO2010094169 A1 WO 2010094169A1 CN 2009001484 W CN2009001484 W CN 2009001484W WO 2010094169 A1 WO2010094169 A1 WO 2010094169A1
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zsm
catalyst
weight
magnesium
pyridine base
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PCT/CN2009/001484
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Chinese (zh)
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徐龙伢
刘盛林
杨寿海
陶峻
谢素娟
薛谊
王清遐
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中国科学院大连化学物理研究所
南京第一农药集团有限公司
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Publication of WO2010094169A1 publication Critical patent/WO2010094169A1/en

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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
    • 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
    • B01J37/04—Mixing
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25

Definitions

  • the invention relates to the field of chemical industry, in particular to a synthetic pyridine alkali magnesium cobalt-based fluidized bed catalyst 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-5ethylpyridine.
  • 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, alkenes, 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 The compound and the SiO 2 -Al 2 0 3 compound modified by halogen and P0 4 3_ , but the total yield of the pyridine base 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 under the reaction conditions of 450 Torr, the pyridine yield of the tungsten modified catalyst is 32%, the yield of 3-methylpyridine is 16%, and the yield of 2-methylpyridine 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%.
  • reaction space velocity SOOOh '1 ammonia / aldehyde molar ratio of 4.5, which is a yield of 55.5% pyridine, 3-methylpyridine in 25% yield, 2-methylpyridine 0.5%
  • the yield of 4-methylpyridine was 0, and the total yield was 81%.
  • 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. a reaction of 450 ° C under reaction conditions, lead (2w%), cobalt (10 w%) and palladium (0.01 w%) modified ZSM-5 (Si0 2 /Al 2 0 3 molar ratio of 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%.
  • An object of the present invention is to provide a magnesium-cobalt-based catalyst for the synthesis of pyridine base from formaldehyde acetaldehyde, and a preparation method thereof.
  • the invention provides a magnesium-cobalt-based catalyst for synthesizing pyridine base with formaldehyde acetaldehyde, wherein the weight percentage of each component in the catalyst is: ZSM-ll/ZSM-35 composite molecular sieve 30-45%, MgO 0.5-2.5% (preferably 1.0-2.0%), Co 3 0 4 0.5-5.0% (preferably 1.0-3.0%), the balance being the matrix component.
  • the invention provides a magnesium-cobalt-based catalyst for synthesizing pyridine base with formaldehyde acetaldehyde, wherein the weight ratio of ZSM-11 to ZSM-35 in the ZSM-ll/ZSM-35 composite molecular sieve is 0.05-20; the matrix contains alumina and Kaolin.
  • the present invention provides a magnesium-cobalt-based catalyst for the synthesis of pyridine base from formaldehyde acetaldehyde, which is derived from an aluminum sol and has a content of 15-35 wt%; and a kaolin content of 20-50 wt%.
  • the catalyst of the invention wherein the spraying conditions are an inlet temperature of 450-650 ° C, an exhaust gas temperature of 120-250 ° C, a spray pressure of 0.5-10 MPa, a drying temperature of 400-650 ° C, and a time of 2-4 hours.
  • the invention has the advantages of being industrially operable, relatively simple in process, high in yield of pyridine base and the like.
  • the spray conditions were an inlet temperature of 450 ° C, a tail temperature of 150 ° C, a spray pressure of 2.0 Mpa, and a drying temperature of 500 ° C for 2 hours.
  • a certain amount of 70 3 ⁇ 4% ZSM-ll/30 S% ZSM-35 composite molecular sieve, Mg(N0 3 ) 2 , aluminum sol, kaolin, deionized water were uniformly mixed, spray-molded, and dried to obtain catalyst B.
  • the spray conditions were an inlet temperature of 450 ° C, an exhaust gas temperature of 150 ° C, a spray pressure of 2.0 Mpa, and a drying temperature of 500 ° C for 2 hours.
  • the obtained catalyst B, wherein the ZSM-11 molecular sieve, MgO and alumina were 40% by weight, 1% and 22% by weight, respectively.
  • the spray conditions were an inlet temperature of 450 ° C, an exhaust gas temperature of 150 ° C, a spray pressure of 2.0 Mpa, and a drying temperature of 500 ° C for 2 hours.
  • the spray conditions were an inlet temperature of 450 ° C, an exhaust gas temperature of 150 ° C, a spray pressure of 2.0 Mpa, and a drying temperature of 500 ° C for 2 hours.
  • the obtained catalyst D wherein 70% by weight of ⁇ 81 ⁇ -11/30 weight %281 ⁇ -35 composite molecular sieve, MgO, Co 3 4 4 and alumina have a weight content of 39%, 1%, 3% and 22, respectively %.
  • the spray conditions were an inlet temperature of 500 Torr, an exhaust gas temperature of 200 ° C, a spray pressure of 8 Mpa, and a drying temperature of 580 ° C for 2 hours.
  • the obtained catalyst E, wherein 50% ZSM-ll/50 weight% 28] ⁇ -35 composite molecular sieve, MgO, Co 3 4 and alumina were respectively 35%, 0.7%, 4.5% and 19% by weight.
  • the spraying conditions were an inlet temperature of 650 Torr, an exhaust gas temperature of 200, a spray pressure of 0.8 Mpa, and a drying temperature of 450 ° C for 4 hours.
  • Catalyst F was obtained, wherein 10% by weight of 281 ⁇ -11/90% by weight of 281 ⁇ -35 composite molecular sieve, MgO, Co 3 0 4 and alumina were respectively 33%, 1%, 2% and 30% by weight.
  • the spray conditions were an inlet temperature of 620 ° C, an exhaust gas temperature of 200 ° C, a spray pressure of 5 Mpa, and a drying temperature of 620 ° C for 2 hours.
  • the obtained catalyst G, wherein 90 M% of ZSM-11/10 S% ZSM-35 composite molecular sieve, MgO, Co 3 4 and alumina had a weight content of 41%, 2%, 3% and 25%, respectively.
  • the spraying conditions were an inlet temperature of 500 ° C, an exhaust gas temperature of 200 ° C, a spray pressure of 5 Mpa, and a drying temperature of 500 ° C for 3 hours.
  • the obtained catalyst H, wherein 70 S% ZSM-ll/30 S% ZSM-35 composite molecular sieve, MgO, Co 3 4 and alumina were respectively 39%, 2%, 4% and 32% by weight.
  • a certain amount of 70 S% ZSM-ll/30 S% ZSM-35 composite molecular sieve, Mg(N0 3 ) 2 , Co(N0 3 ) 2 -6H 2 0, aluminum sol, kaolin, deionized water, evenly sprayed Molding, drying, and steam treatment were carried out to prepare a catalyst I.
  • the spray conditions were an inlet temperature of 500 ° C, an exhaust gas temperature of 200 ° C, a spray pressure of 5 Mpa, and a drying temperature of 500 ° C for 3 hours.
  • Reaction conditions temperature 450 ° C; acetaldehyde / formaldehyde / ammonia molar ratio 1 / 1/2; weight space velocity 0.3 h ; fluidized bed, catalyst 800 g.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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Abstract

A magnesium-cobalt based catalyst for synthesizing pyridine base from formaldehyde, acetaldehyde and ammonia consists of ZSM-11/ZSM-35 composite molecular sieve, MgO, Co3O4 and matrix, wherein the matrix comprises alumina and kaolin. The preparation method comprises the following steps: uniformly-mixing           ZSM-11/ZSM-35 composite molecular sieve, MgO, Co3O4, alumina and kaolin, spraying molding and drying to obtain the catalyst. The catalyst can be used in the industry with high pyridine base yield and can be prepared in a simple process.

Description

用于甲醛乙醛氨合成吡啶碱的镁钴基催化剂及其制备方法 技术领域  Magnesium-cobalt-based catalyst for formaldehyde acetaldehyde ammonia synthesis of pyridine base and preparation method thereof
本发明涉及化工领域， 具体涉及一种合成吡啶碱镁钴基流化床催化剂 及其制备方法。  The invention relates to the field of chemical industry, in particular to a synthetic pyridine alkali magnesium cobalt-based fluidized bed catalyst and a preparation method thereof.
背景技术 Background technique
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。  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-5ethylpyridine. As a chemical industrial product, 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.
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。  1924 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, alkenes, 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.
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 P04 3_改性的 Si02-Al203化合物， 但其吡啶碱的总产率一般不高（<50%)。 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 The compound and the SiO 2 -Al 2 0 3 compound modified by halogen and P0 4 3_ , but the total yield of the pyridine base is generally not high (<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%。 U.S. Patent No. 4,861,894 (1989), entitled "Synthesis of Pyridine and Alkyl Pyridine with a Crystalline Molecular Sieve of ZSM-5 Structure", discloses a high silicon ZSM-5 zeolite having a SiO 2 /Al 2 0 3 molar ratio of 225. The powder, Si0 2 is a molecular sieve made of a binder as a catalyst for the synthesis of pyridine base. In B 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%.
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 450Ό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%。  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 under the reaction conditions of 450 Torr, the pyridine yield of the tungsten modified catalyst is 32%, the yield of 3-methylpyridine is 16%, and the yield of 2-methylpyridine is 1. %. Under the same reaction conditions, 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.
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 427Ό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 ¾ 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。  U.S. Patent No. 5,395,940 (1995), entitled "Synthesis of Pyridine and 3-Methylpyridine", discloses the use of specific crystalline zeolites such as MCM-22 or MCM-49 as catalysts for the synthesis of pyridine and 3-methylpyridine. Under the reaction conditions of a acetaldehyde/formaldehyde/ammonia molar ratio of 1.4/1/3.6 and a reaction temperature of 427 Torr, the yield of pyridine was 9.3%, and the yield of 3-methylpyridine was 4.1%, 2-methylpyridine. The yield was 3⁄4 0.6%, and the yield of 4-methylpyridine was 0.9%. Although the content of 2-methylpyridine and 4-methylpyridine in pyridine and 3-methylpyridine synthesized by the above method is small, the total yield of pyridine and 3-methylpyridine is too low, and there is no industrial application. may.
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%。 Recently, Japanese patents (Publication Nos. CN1330068 A and 1172915C) and "U.S. Patent No. 6,281,362", which are entitled "Methods for Preparing Pyridine Bases", and 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. But since 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%. Similarly, when 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%.
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'1, 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 SOOOh'1,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%。 Chinese patent CN1263741C, etc. LU Guanzhong and CN1565736A disclose a mixture of lead and cobalt be modified ZSM-5 catalyst in a continuous flow fixed bed, a space velocity: 1000 h '1, formaldehyde / acetaldehyde molar ratio of 1/2, Catalyst with a molar ratio of ammonia/aldehyde of 4.5 and a reaction temperature of 450 Torr, lead (2.5 w%) and cobalt (1.5 w%) modified ZSM-5 (Si0 2 /Al 2 0 3 molar ratio 150) catalyst The reaction was continued for 4 hours, the yield of pyridine was 68%, the yield of 3-methylpyridine was 4.5%, and the yield of 2-methylpyridine was 4%. Other conditions are the same, except that the reaction space velocity SOOOh '1, ammonia / aldehyde molar ratio of 4.5, which is a yield of 55.5% pyridine, 3-methylpyridine in 25% yield, 2-methylpyridine 0.5% The yield of 4-methylpyridine was 0, and the total yield was 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。 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. a reaction of 450 ° C under reaction conditions, lead (2w%), cobalt (10 w%) and palladium (0.01 w%) modified ZSM-5 (Si0 2 /Al 2 0 3 molar ratio of 150) catalyst, The yield of pyridine was 55%, the total yield was 72%, and the regeneration period was 24 hours. Other conditions are the same, lead (12.5w%), cobalt (2w%) and palladium (0.2w%) modified ZSM-5 (Si0 2 /Al 2 0 3 molar ratio of 150) catalyst, pyridine yield of 70% The total yield was 87% and the regeneration cycle was 48 hours.
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%。 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%.
发明内容 Summary of the invention
本发明的目的是提供一种用于甲醛乙醛氨合成吡啶碱的镁钴基催化剂 及其制备方法。  SUMMARY OF THE INVENTION An object of the present invention is to provide a magnesium-cobalt-based catalyst for the synthesis of pyridine base from formaldehyde acetaldehyde, and a preparation method thereof.
本发明提供了一种用于甲醛乙醛氨合成吡啶碱的镁钴基催化剂， 该催 化剂中各组分占整个催化剂的重量百分比为： ZSM-ll/ZSM-35复合分子筛 30-45%, MgO 0.5-2.5% (优选 1.0-2.0%)， Co3040.5-5.0% (优选 1.0-3.0%), 其余为基质组分。 The invention provides a magnesium-cobalt-based catalyst for synthesizing pyridine base with formaldehyde acetaldehyde, wherein the weight percentage of each component in the catalyst is: ZSM-ll/ZSM-35 composite molecular sieve 30-45%, MgO 0.5-2.5% (preferably 1.0-2.0%), Co 3 0 4 0.5-5.0% (preferably 1.0-3.0%), the balance being the matrix component.
本发明提供的用于甲醛乙醛氨合成吡啶碱的镁钴基催化剂， 所述 ZSM-ll/ ZSM-35复合分子筛中 ZSM-11与 ZSM-35重量比为 0.05-20;基质 含有氧化铝和高岭土。  The invention provides a magnesium-cobalt-based catalyst for synthesizing pyridine base with formaldehyde acetaldehyde, wherein the weight ratio of ZSM-11 to ZSM-35 in the ZSM-ll/ZSM-35 composite molecular sieve is 0.05-20; the matrix contains alumina and Kaolin.
本发明提供的用于甲醛乙醛氨合成吡啶碱的镁钴基催化剂， 所述氧化 铝来源于铝溶胶， 其含量为 15-35重％; 高岭土含量为 20-50重％。  The present invention provides a magnesium-cobalt-based catalyst for the synthesis of pyridine base from formaldehyde acetaldehyde, which is derived from an aluminum sol and has a content of 15-35 wt%; and a kaolin content of 20-50 wt%.
本发明提供了用于甲醛乙醛氨合成吡啶碱钛基的催化剂的制备方法， 具体步骤为：将 30-45重％∑81^-11/ 281^-35复合分子筛， 0.5-2.5重％ MgO， 0.5-5.0 S%Co304, 15-35重％氧化铝， 20-50重％高岭土混合均匀后 （混合 物中固体 /水 = 0.2-0.5， 重 /重）喷雾成型和干燥， 制得本发明催化剂； 其中 喷雾条件为入口温度 450-650°C，尾气温度 120-250°C，喷雾压力 0.5-10Mpa， 干燥温度 400-650°C， 时间 2-4小时。 The invention provides a preparation method of a catalyst for synthesizing a pyridyl titanium base of formaldehyde acetaldehyde, wherein the specific steps are: 30-45 wt% ∑81^-11/281^-35 composite molecular sieve, 0.5-2.5 wt% MgO , 0.5-5.0 S%Co 3 0 4 , 15-35 wt% alumina, 20-50% by weight of kaolin mixed uniformly (solid/water = 0.2-0.5 in the mixture, heavy/heavy) spray-formed and dried, obtained The catalyst of the invention; wherein the spraying conditions are an inlet temperature of 450-650 ° C, an exhaust gas temperature of 120-250 ° C, a spray pressure of 0.5-10 MPa, a drying temperature of 400-650 ° C, and a time of 2-4 hours.
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。 本发明最佳具体实施方式  The invention has the advantages of being industrially operable, relatively simple in process, high in yield of pyridine base and the like. BEST MODE FOR CARRYING OUT THE INVENTION
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。 The following examples will further illustrate the present invention, but do not limit the present invention. Bright.
比较例 1 Comparative example 1
将一定量的 70重％281^-11/30 S%ZSM-35复合分子筛，铝溶胶（氧化 铝占铝溶胶 23.0重％， 以下相同， 不再叙述)， 高岭土， 去离子水混合均匀 后喷雾成型，干燥制得催化剂 A。其中喷雾条件为入口温度 450°C，尾气温 度 150°C， 喷雾压力 2.0 Mpa， 干燥温度 500°C， 2小时。 制得的催化剂 A， 其中 ZSM-11分子筛和氧化铝的重量含量分别为 40%和 22%。  A certain amount of 70% by weight of 281^-11/30 S% ZSM-35 composite molecular sieve, aluminum sol (alumina accounted for 23.0% by weight of aluminum sol, the same below, no longer described), kaolin, deionized water mixed evenly after spraying Molding and drying to obtain Catalyst A. The spray conditions were an inlet temperature of 450 ° C, a tail temperature of 150 ° C, a spray pressure of 2.0 Mpa, and a drying temperature of 500 ° C for 2 hours. The catalyst A obtained, wherein the ZSM-11 molecular sieve and alumina were 40% by weight and 22% by weight, respectively.
比较例 2 Comparative example 2
将一定量的 70 ¾%ZSM-ll/30 S%ZSM-35复合分子筛， Mg(N03)2， 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 B。 其 中喷雾条件为入口温度 450°C， 尾气温度 150°C， 喷雾压力 2.0 Mpa， 干燥 温度 500°C， 2小时。制得的催化剂 B， 其中 ZSM-11分子筛， MgO和氧化 铝的重量含量分别为 40%, 1%和 22%。 A certain amount of 70 3⁄4% ZSM-ll/30 S% ZSM-35 composite molecular sieve, Mg(N0 3 ) 2 , aluminum sol, kaolin, deionized water were uniformly mixed, spray-molded, and dried to obtain catalyst B. The spray conditions were an inlet temperature of 450 ° C, an exhaust gas temperature of 150 ° C, a spray pressure of 2.0 Mpa, and a drying temperature of 500 ° C for 2 hours. The obtained catalyst B, wherein the ZSM-11 molecular sieve, MgO and alumina were 40% by weight, 1% and 22% by weight, respectively.
比较例 3 Comparative example 3
将一定量的 70 重％28\1-11/30 重％ZSM-35 复合分子筛， A certain amount of 70%%28\1-11/30 weight %ZSM-35 composite molecular sieve,
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<：。其中喷雾条件为入口温度 450°C， 尾气温度 150°C， 喷雾压力 2.0 Mpa,干燥温度 500°C， 2小时。制得的催化剂 C，其中 70 S%ZSM-ll/30 重％∑81^-35 复合分子筛， Co304和氧化铝的重量含量分别为 40%, 3%和 22%。 Co(N0 3 ) 2 -6H 2 0, aluminum sol, kaolin, deionized water, uniformly mixed, spray-formed, and dried to obtain a catalyst <:. The spray conditions were an inlet temperature of 450 ° C, an exhaust gas temperature of 150 ° C, a spray pressure of 2.0 Mpa, and a drying temperature of 500 ° C for 2 hours. The obtained catalyst C, wherein 70 S% ZSM-ll/30 wt% ∑81^-35 composite molecular sieve, Co 3 0 4 and alumina had a weight content of 40%, 3% and 22%, respectively.
实施例 1 Example 1
将一定量的 70重％∑81^-11/30 S%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 D。其中喷雾条件为入口温度 450°C , 尾气温度 150°C， 喷雾压力 2.0 Mpa,干燥温度 500°C， 2小时。制得的催化剂 D，其中 70重％∑81^-11/30 重％281^-35复合分子筛， MgO, Co304和氧化铝的重量含量分别为 39%， 1%, 3%和 22%。 A certain amount of 70% by weight ∑81^-11/30 S%ZSM-35 composite molecular sieve, Mg(N0 3 ) 2 , Co(N0 3 ) 2 -6H 2 0, aluminum sol, kaolin, deionized water, uniformly mixed, spray-formed, and dried to obtain catalyst D. The spray conditions were an inlet temperature of 450 ° C, an exhaust gas temperature of 150 ° C, a spray pressure of 2.0 Mpa, and a drying temperature of 500 ° C for 2 hours. The obtained catalyst D, wherein 70% by weight of ∑81^-11/30 weight %281^-35 composite molecular sieve, MgO, Co 3 4 4 and alumina have a weight content of 39%, 1%, 3% and 22, respectively %.
实施例 2 Example 2
将一定量的 50 ¾%ZSM-ll/50 S%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E。 其中喷雾条件为入口温度 500Ό , 尾气温度 200°C， 喷雾压力 8 Mpa,干燥温度 580°C， 2小时。制得的催化剂 E,其中 50 %ZSM-ll/50 重％28]^-35复合分子筛， MgO， Co304和氧化铝的重量含量分别为 35%， 0.7%, 4.5%和 19%。 A certain amount of 50 3⁄4% ZSM-ll/50 S% ZSM-35 composite molecular sieve, Mg(N0 3 ) 2 , Co(N0 3 ) 2 -6H 2 0, aluminum sol, kaolin, deionized water, evenly sprayed Molding and drying to obtain catalyst E. The spray conditions were an inlet temperature of 500 Torr, an exhaust gas temperature of 200 ° C, a spray pressure of 8 Mpa, and a drying temperature of 580 ° C for 2 hours. The obtained catalyst E, wherein 50% ZSM-ll/50 weight% 28]^-35 composite molecular sieve, MgO, Co 3 4 and alumina were respectively 35%, 0.7%, 4.5% and 19% by weight.
实施例 3 Example 3
将一定量的 10 fi%ZSM-ll/90重％∑81^-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， 水蒸汽处理， 制得催化剂 F。 其中喷雾条件为入口温度 650Ό , 尾气温度 200 , 喷雾压力 0.8 Mpa， 干燥温度 450°C， 4小时。 制得催化剂 F， 其中 10重％281^-11/90重％281^-35复合分子筛， MgO， Co304和氧化铝的重量 含量分别为 33%， 1%, 2%和 30%。 A certain amount of 10 fi% ZSM-ll/90 wt% ∑81^-35 composite molecular sieve, Mg(N0 3 ) 2 , Co(N0 3 ) 2-6H 2 0, aluminum sol, kaolin, deionized water, evenly mixed Post-spray molding, drying, and steam treatment to prepare catalyst F. The spraying conditions were an inlet temperature of 650 Torr, an exhaust gas temperature of 200, a spray pressure of 0.8 Mpa, and a drying temperature of 450 ° C for 4 hours. Catalyst F was obtained, wherein 10% by weight of 281^-11/90% by weight of 281^-35 composite molecular sieve, MgO, Co 3 0 4 and alumina were respectively 33%, 1%, 2% and 30% by weight.
实施例 4 Example 4
将一定量的 90重％∑81^-11/10重％28^1-35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， 水蒸汽处理， 制得催化剂 G。 其中喷雾条件为入口温度 620°C， 尾气温度 200°C， 喷雾压力 5 Mpa, 干燥温度 620°C , 2小时。 制得的催化剂 G， 其 中 90 M%ZSM-11/10 S%ZSM-35复合分子筛， MgO, Co304和氧化铝的重 量含量分别为 41%， 2%, 3%和 25%。 A certain amount of 90% by weight ∑81^-11/10 weight%28^1-35 composite molecular sieve, Mg(N0 3 ) 2 , Co(N03)2-6H 2 0, aluminum sol, kaolin, deionized water mixed Evenly sprayed, dried, Steam treatment to obtain catalyst G. The spray conditions were an inlet temperature of 620 ° C, an exhaust gas temperature of 200 ° C, a spray pressure of 5 Mpa, and a drying temperature of 620 ° C for 2 hours. The obtained catalyst G, wherein 90 M% of ZSM-11/10 S% ZSM-35 composite molecular sieve, MgO, Co 3 4 and alumina had a weight content of 41%, 2%, 3% and 25%, respectively.
实施例 5 Example 5
将一定量的 70 S%ZSM-ll/30重％∑81^-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， 水蒸汽处理， 制得催化剂 H。 其中喷雾条件为入口温度 500°C , 尾气温度 200°C， 喷雾压力 5 Mpa， 干燥温度 500°C， 3小时。 制得的催化剂 H， 其 中 70 S%ZSM-ll/30 S%ZSM-35复合分子筛， MgO, Co304和氧化铝的重 量含量分别为 39%， 2%, 4%和 32%。 A certain amount of 70 S% ZSM-ll/30 wt% ∑81^-35 composite molecular sieve, Mg(N0 3 ) 2 , Co(N0 3 ) 2 -6H 2 0, aluminum sol, kaolin, deionized water, evenly mixed Post-spray molding, drying, and steam treatment to prepare catalyst H. The spraying conditions were an inlet temperature of 500 ° C, an exhaust gas temperature of 200 ° C, a spray pressure of 5 Mpa, and a drying temperature of 500 ° C for 3 hours. The obtained catalyst H, wherein 70 S% ZSM-ll/30 S% ZSM-35 composite molecular sieve, MgO, Co 3 4 and alumina were respectively 39%, 2%, 4% and 32% by weight.
实施例 6 Example 6
将一定量的 70 S%ZSM-ll/30 S%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， 水蒸汽处理，制得催化剂 I。其中喷雾条件为入口温度 500°C，尾气温度 200 °C， 喷雾压力 5 Mpa, 干燥温度 500°C， 3小时。 制得的催化剂 I, 其中 70 重％251^-11/30重％281^-35复合分子筛， MgO, Co304和氧化铝的重量含 量分别为 39°/。， 2.5%, 0.8%和 30%。 A certain amount of 70 S% ZSM-ll/30 S% ZSM-35 composite molecular sieve, Mg(N0 3 ) 2 , Co(N0 3 ) 2 -6H 2 0, aluminum sol, kaolin, deionized water, evenly sprayed Molding, drying, and steam treatment were carried out to prepare a catalyst I. The spray conditions were an inlet temperature of 500 ° C, an exhaust gas temperature of 200 ° C, a spray pressure of 5 Mpa, and a drying temperature of 500 ° C for 3 hours. The obtained catalyst I, wherein 70% by weight of 251^-11/30% by weight of 281^-35 composite molecular sieve, MgO, Co 3 4 and alumina had a weight content of 39 °/, respectively. , 2.5%, 0.8% and 30%.
实施例和比较例的应用 Application of examples and comparative examples
本发明的实施例和比较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 N2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。 The use of the examples and comparative examples of the present invention in the synthesis of pyridine base from formaldehyde acetaldehyde to ammonia. In the interior of the reaction tube fixed bed catalyst 800g was heated under N 2 atmosphere to 500 ° C activation, and then lowered to the reaction temperature in an atmosphere of N 2, the reaction was carried out under the conditions as shown in Table 1, the raw material is formaldehyde, The mixture of acetaldehyde and ammonia gas passes through the catalyst bed from bottom to top, and a gas phase condensation reaction occurs at a certain space velocity and temperature to form the desired product pyridine and methylpyridine, etc., each reaction for 40 minutes, and then steam stripping. , three times in a row, quantified by gas chromatography, and the reaction results were averaged.
由表 1的结果可见，单纯采用 ZSM-11/ZSM-35, ZSM-ll/ZSM-35+Mg, ZSM-ll/ZSM-35+Co作催化剂（表 1中催化剂 A， B, C), 吡啶碱总摩尔产 率均低于本发明的 ZSM-ll/ZSM-35+Mg+Co催化剂。 本发明提供的催化剂 D， E， F， G H和 I均有较好的吡啶碱产率。  From the results of Table 1, it can be seen that ZSM-11/ZSM-35, ZSM-ll/ZSM-35+Mg, ZSM-ll/ZSM-35+Co are used as catalysts (catalysts A, B, C in Table 1). The total molar yield of the pyridine base was lower than the ZSM-ll/ZSM-35+Mg+Co catalyst of the present invention. The catalysts D, E, F, G H and I provided by the present invention all have good pyridine base yields.
表 1 吡啶催化剂评价结果  Table 1 Evaluation results of pyridine catalyst
Figure imgf000010_0001
Figure imgf000010_0001
反应条件： 温度 450°C ; 乙醛 /甲醛 /氨摩尔比 1/1/2; 重量空速 0.3 h ; 流化床， 催化剂 800 g。 Reaction conditions: temperature 450 ° C; acetaldehyde / formaldehyde / ammonia molar ratio 1 / 1/2; weight space velocity 0.3 h ; fluidized bed, catalyst 800 g.

Claims

权 利 要 求 Rights request
1、一种用于甲醛乙醛氨合成吡啶碱的镁钴基催化剂， 其特征在于： 该 催化剂含有 30-45 ¾%ZSM-11/ ZSM-35复合分子筛， 0.5-2.5 S%MgO, 0.5-5.0重％0>304， 其余为基质组分。 A magnesium-cobalt-based catalyst for the synthesis of pyridine base from formaldehyde acetaldehyde, characterized in that the catalyst comprises 30-45 3⁄4% ZSM-11/ZSM-35 composite molecular sieve, 0.5-2.5 S% MgO, 0.5- 5.0% by weight> 3 0 4 , and the rest are matrix components.
2、 按照权利要求 1所述用于甲醛乙醛氨合成吡啶碱的镁钴基催化剂， 其特征在于：所述 ZSM-11/ ZSM-35复合分子筛中 ZSM-11与 ZSM-35重量 比为 0.05-20。  2. A magnesium-cobalt-based catalyst for the synthesis of pyridine base from formaldehyde acetaldehyde to ammonia according to claim 1, wherein the weight ratio of ZSM-11 to ZSM-35 in the ZSM-11/ZSM-35 composite molecular sieve is 0.05. -20.
3、 按照权利要求 1所述用于甲醛乙醛氨合成吡啶碱的镁钴基催化剂， 其特征在于： 所述 MgO的含量为 1.0-2.0重％。  A magnesium-cobalt-based catalyst for the synthesis of pyridine base from formaldehyde acetaldehyde to ammonia according to claim 1, wherein the MgO content is 1.0 to 2.0% by weight.
4、 按照权利要求 1所述用于甲醛乙醛氨合成吡啶碱的镁钴基催化剂， 其特征在于： 所述 Co304的含量为 1.0-3.0重％。 A magnesium-cobalt-based catalyst for the synthesis of pyridine base from formaldehyde acetaldehyde to ammonia according to claim 1, wherein the content of Co 3 0 4 is from 1.0 to 3.0% by weight.
5、 按照权利要求 1所述用于甲醛乙醛氨合成吡啶碱的镁钴基催化剂， 其特征在于： 所述基质含有氧化铝， 高岭土。  5. A magnesium-cobalt based catalyst for the synthesis of pyridine base from formaldehyde acetaldehyde to ammonia according to claim 1, wherein: said matrix comprises alumina, kaolin.
6、 按照权利要求 5所述用于甲醛乙醛氨合成吡啶碱的镁钴基催化剂， 其特征在于： 所述氧化铝来源于铝溶胶， 其含量为 15-35重％。  6. A magnesium-cobalt-based catalyst for the synthesis of pyridine base from formaldehyde acetaldehyde to ammonia according to claim 5, wherein the alumina is derived from an aluminum sol in an amount of from 15 to 35 % by weight.
7、 按照权利要求 5所述用于甲醛乙醛氨合成吡啶碱的镁钴基催化剂， 其特征在于： 所述高岭土含量为 20-50重％。  A magnesium-cobalt-based catalyst for the synthesis of pyridine base from formaldehyde acetaldehyde to ammonia according to claim 5, wherein the kaolin content is 20 to 50% by weight.
8、 权利要求 1 所述催化剂的制备方法， 其特征在于： 将 30-45 重％ ZSM-11/ZSM-35复合分子筛， 0.5-2.5重％^¾0， 0.5-5.0重％Co304， 15-35 重％氧化铝， 20-50重％高岭土混合均匀后喷雾成型和干燥， 制得催化剂。 8. The method for preparing a catalyst according to claim 1, characterized in that: 30-45 wt% ZSM-11/ZSM-35 composite molecular sieve, 0.5-2.5 wt% ^3⁄40, 0.5-5.0 wt% Co 3 0 4 , 15-35% by weight of alumina, 20-50% by weight of kaolin is uniformly mixed, spray-molded and dried to obtain a catalyst.
9、按照权利要求 8所述催化剂的制备方法， 其特征在于： 所述喷雾条 件为入口温度 450-650°C， 尾气温度 120-250°C , 喷雾压力 0.5-10Mpa, 干 燥温度 400-650eC， 时间 2-4小时。 The method for preparing a catalyst according to claim 8, characterized in that: the spraying condition is an inlet temperature of 450-650 ° C, an exhaust gas temperature of 120-250 ° C, a spray pressure of 0.5-10 Mpa, and a dry Drying temperature 400-650 e C, time 2-4 hours.
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