WO2023071891A1 - 一种由苯胺选择性连续生产2-甲基吡啶和二苯胺的方法 - Google Patents

一种由苯胺选择性连续生产2-甲基吡啶和二苯胺的方法 Download PDF

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WO2023071891A1
WO2023071891A1 PCT/CN2022/126220 CN2022126220W WO2023071891A1 WO 2023071891 A1 WO2023071891 A1 WO 2023071891A1 CN 2022126220 W CN2022126220 W CN 2022126220W WO 2023071891 A1 WO2023071891 A1 WO 2023071891A1
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catalyst
aniline
metal component
temperature
picoline
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PCT/CN2022/126220
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English (en)
French (fr)
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李浩萌
赵响宇
王丽博
祁文博
王振宇
李澜鹏
艾抚宾
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中国石油化工股份有限公司
中石化（大连）石油化工研究院有限公司
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Priority to KR1020247018270A priority Critical patent/KR20240091273A/ko
Priority to EP22885769.4A priority patent/EP4421065A1/en
Priority to CN202280072779.0A priority patent/CN118139843A/zh
Publication of WO2023071891A1 publication Critical patent/WO2023071891A1/zh

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C07C211/55—Diphenylamines
    • 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
    • C07D213/12—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles from unsaturated compounds
    • 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
    • C07D213/16—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 containing only one pyridine ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention belongs to the field of fine chemicals, and in particular relates to a method for synthesizing 2-picoline from aniline and a method for selectively and continuously producing 2-picoline and diphenylamine from aniline.
  • 2-picoline molecular formula C 6 H 7 N, also known as ⁇ -picoline, ⁇ -picoline
  • 2-picoline is a kind of pyridine base, which is a colorless oily liquid at room temperature with a strong unpleasant smell.
  • the freezing point is -38.9°C and the boiling point is 129.5°C.
  • 2-picoline is an important chemical intermediate and an important raw material for fine chemicals. It can be used to produce long-acting sulfonamides, pesticide intermediates, and feed intermediates. It can also be used to synthesize special resin vinylpyridine and 2-vinylpyridine intermediates. .
  • the domestic consumption of 2-picoline is increasing at a rate of about 25% every year, so the domestic market of 2-picoline has great potential.
  • the production of pyridine base in the industrial field mainly includes coal tar separation method and chemical synthesis method.
  • the coal tar separation method not only has the disadvantages of serious pollution, few types of products, high cost, poor quality, and high energy consumption, but also the output of the product is low, which is difficult to improve.
  • the chemical synthesis method usually adopts the method of ammonium aldehyde condensation to synthesize pyridine base by reacting aldehyde, ketone and ammonia as raw materials.
  • the products of the ammonium aldehyde condensation method include 3-picoline, 2-picoline, 4-picoline, etc., which have problems such as subsequent product separation difficulties.
  • CN105384683A discloses a method for separating diphenylamine by-products 2-picoline and 4-picoline from aniline synthesis.
  • the steps are: use aniline as a raw material, flow through a fixed-bed reactor equipped with a molecular sieve catalyst, control the temperature and pressure of the reactor, and convert it into diphenylamine, ammonia, 2-picoline and 4-picoline through condensation reaction , water, acridine, 4-aminobiphenyl and other by-products, the mixture reaction solution is subjected to multi-stage rectification to obtain a low boiling point mixed fraction, the low boiling point mixed fraction is dehydrated, and the dehydrated mixture is then dried, and the dried mixed solution Carry out rectification, according to different boiling point, rectification obtains 2-picoline and 4-picoline.
  • the essence of the method is the separation method of by-products 2-picoline and 4-picoline in the synthesis of diphenylamine from traditional aniline. Therefore, because 2-picoline is a reaction process by-product in this method, its productive rate is relatively low, can't realize its large-scale production.
  • CA1190928A discloses a method for the production of ⁇ -picoline from aniline, the aniline starting material is passed through an acidic zeolite catalyst at 200-650°C in the presence of an inert gas such as nitrogen and helium to prepare a product containing ⁇ -picoline ,
  • the reaction pressure is from normal pressure to 25000kPa, usually at 200kPa, and the space velocity of aniline is preferably 0.2-5WHSV.
  • the acidic zeolite is preferably in the hydrogen form, including beta-zeolite, with a silicon-to-aluminum ratio of 10-100, up to 150.
  • embodiment 1 uses pure HZSM-5 under the condition of 510 °C, pressure 2860kPa, ammonia gas being 1.5mol% of aniline, nitrogen space velocity being 100GHSV, aniline transformation rate is 13.1%, the selectivity of ⁇ -picolin was 51.6%.
  • the zeolite-catalysed isomerization of aniline to a-picoline[J].Applied catalysis A: General 172(1998) 285-294" discloses a method for preparing ⁇ -picoline by aniline rearrangement reaction, which uses The molecular sieve is preferably Ga-MFI molecular sieve (better than ZSM-5) as a catalyst, and it is carried out under the conditions of 673K, a total pressure of 75bar, and an ammonia partial pressure of 5-60bar, preferably 20-25bar. Wherein the selectivity of ⁇ -picoline can reach more than 85%, but the conversion rate is only 3.7%.
  • the technical problem to be solved by the present invention is to overcome the disadvantages of the method for preparing 2-picoline by aniline rearrangement reaction in the prior art or the low conversion rate of aniline, or the low selectivity of 2-picoline, and provide a method that can be used in the existing aniline A method for selectively producing aniline and 2-picoline based on a diphenylamine production device.
  • the method of the present invention can conveniently and effectively realize the switching of aniline and 2-picoline products by controlling the temperature, the reaction conditions are mild, the yield of 2-picoline is high, the reaction selectivity is good, and it has good industrial application prospects .
  • the inventors of the present invention found that: the isomeric rearrangement of aniline to generate 2-picoline and the reaction of aniline condensation to prepare diphenylamine are affected by two factors: catalyst and reaction temperature.
  • Adopt the beta zeolite catalyst of at least one active metal component of loading W, Mo, Ni and Co in the present invention because the change of catalytic active center, the reaction route of aniline can be between 2-picoline and diphenylamine switch between.
  • lower reaction temperature is more conducive to the synthesis of 2-picoline. Based on this finding, the present invention proposes a method for producing 2-picoline and a method for selectively and continuously producing aniline and 2-picoline.
  • the first aspect of the present invention provides a method for selective and continuous production of 2-picoline and diphenylamine from aniline, the method comprising aniline and a catalyst at a temperature of 100-400°C in an atmosphere containing hydrogen Contact reaction, it is characterized in that, described catalyst is the beta zeolite of loading metal component, and described metal component comprises the active metal component of at least one in W, Mo, Ni and Co, and control described contact
  • the reaction temperature is 100°C-240°C to obtain a product mainly composed of 2-picoline; the temperature of the contact reaction is controlled to 260°C-400°C to obtain a product mainly composed of diphenylamine.
  • the second aspect of the present invention provides a method for synthesizing 2-picoline from aniline, which is characterized in that the method comprises contacting aniline with a catalyst under a hydrogen-containing atmosphere under isomerization rearrangement reaction conditions, and the The catalyst is zeolite beta loaded with metal components, the metal components include at least one active metal component selected from W, Mo, Ni and Co, and the temperature of the contact reaction is 100°C-240°C .
  • Synthesizing pyridine base compounds in the prior art usually all feeds a large amount of ammonia gas.
  • the presence of ammonia gas will occupy the acidic sites of the catalyst, resulting in a decrease in the activity of the catalyst.
  • high temperature and high pressure also limit the industrial application of this method.
  • the method provided by the present invention does not need to feed a large amount of ammonia gas, but only needs to feed a small amount of hydrogen gas, and the reaction conditions are mild, and the reaction raw material is only one kind of aniline, and high-purity 2-picoline can be obtained through subsequent distillation operations and high-purity diphenylamine.
  • Fig. 1 is the variation relationship diagram of the product distribution with temperature of the method for selective continuous production of 2-picoline and diphenylamine provided by the present invention.
  • the method for synthesizing 2-picoline from aniline provided by the present invention comprises the steps of contacting aniline with a catalyst under a hydrogen-containing atmosphere under isomerization rearrangement reaction conditions, and the catalyst is a catalyst loaded with a metal component.
  • Beta zeolite the metal component includes at least one active metal component selected from W, Mo, Ni and Co, and the temperature of the contact reaction is 100°C-240°C.
  • the present invention uses the beta zeolite carrying at least one active metal component selected from W, Mo, Ni and Co, under a hydrogen-containing atmosphere, and controls the reaction temperature to be lower than that of the usual aniline synthesis diphenylamine reaction.
  • the desired temperature unexpectedly increased the selectivity of 2-picoline while obtaining higher conversion of aniline.
  • the selective production of diphenylamine and 2-picoline can be realized by adjusting the reaction temperature under the same set of equipment and the same catalyst.
  • the content of the active metal component is 0.5-5 wt%, preferably 0.5-3 wt%, in terms of metal elements.
  • the metal component also includes at least one promoter metal component selected from Li, Na, K, Mg, Ca, based on the total amount of the catalyst, in terms of oxidation state, the promoter
  • the content of the metal component is 0-6.5 wt%, preferably 0.5-5.5 wt%.
  • the acid distribution on the surface of the catalyst and the pore structure of the catalyst can be improved by adding the promoter metal component, and the conversion rate of aniline and the selectivity of the target product can be further improved.
  • the inventors of the present invention have found that the above-mentioned metal components can be obtained by using zeolite beta to support the above-mentioned metal components only in an atmosphere containing hydrogen.
  • Other molecular sieves such as ZSM-5 cannot achieve the above effects.
  • the silicon-aluminum molar ratio of the zeolite beta is 25-300, preferably 60-220.
  • the specific surface area of the catalyst is 400-700m 2 /g, preferably 450-650m 2 /g; the pore volume is 0.25-0.6mL/g, preferably 0.4-0.55mL/g; the average pore diameter is 1.5-5nm , preferably 2-4nm; the particle size is preferably less than 9nm.
  • the catalyst may also contain an alumina binder, so that a shaped body of the catalyst is obtained.
  • the catalyst contains 50-85wt% of zeolite; in terms of metal elements, the active metal component is 0.5-5wt%; The components are 0-6.5wt%; the alumina binder is 10-45wt%.
  • the catalyst contains 50-85wt% of zeolite; 0.5-3wt% of active metal component in terms of metal element; 0.5-5.5wt% of auxiliary metal component in terms of oxidation state; 15-34.5wt% of alumina binder.
  • the catalyst is strip-shaped or spherical particles.
  • its cross-section can be cylindrical, clover or four-leaf clover, and the cross-sectional width of the strip-shaped particles is 0.5-3.0mm, preferably 1.0-2.0mm;
  • the particle diameter is 0.5-5.0 mm, preferably 1.0-3.0 mm.
  • the catalyst of the present invention can be prepared by the following method: (1) contact the H ⁇ zeolite with the nitrate aqueous solution of the promoter metal component by means of equal volume impregnation; (2) filter the mixture obtained in step (1) , washing and drying; (3) after the modified H ⁇ zeolite obtained in step (2), alumina binder and processing aids (such as extrusion aid and peptizing agent) are fully mixed and kneaded, shaped, followed by drying and roasting (4) In the nitrate aqueous solution of the support and the active metal component obtained in step (3), add NaBH 4 Reflux reduction, filtration, vacuum drying to obtain the catalyst.
  • alumina binder and processing aids such as extrusion aid and peptizing agent
  • the contact temperature in step (1) is 80-100°C, and the time is 3-6h; step (2) is dried at 60-120°C for 6-12h; step (3) is dried at 60-120°C for 6-12h ; Calcination at 450-550°C for 4-16h; step (4) at 80-100°C, reflux reduction for 6-8h, and then vacuum drying at 80-100°C for 6-12h.
  • the contact reaction is carried out without feeding ammonia gas.
  • the hydrogen-containing atmosphere refers to a hydrogen concentration of 10-100% by volume.
  • the temperature of the contact reaction is 100-240°C, specifically 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 199°C, 200°C, 210°C, 220°C, 230°C, 240°C, and any value in the range formed by any two of these point values.
  • the preferred reaction temperature is 130-180°C, specifically 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, and any value in the range formed by any two of these point values.
  • the method of the present invention can be carried out continuously or batchwise, preferably continuously.
  • Batch-type operation usually refers to tank-type operation.
  • the raw material aniline and catalyst are added into the reaction tank, and the reaction is carried out under suitable conditions to obtain the target product.
  • Continuous operation generally means that the raw material aniline is reacted through a fixed-bed reactor containing a catalyst.
  • the inventors of the present invention found that the optimum reaction temperature and pressure are slightly different between continuous and batch.
  • the temperature of the contact reaction is preferably 130-180°C
  • the pressure is preferably 2-4MPa
  • the reaction time is preferably 4-8h; preferably, the amount of the catalyst accounts for 1-4wt% of the amount of raw aniline.
  • the temperature of the contact reaction is preferably 160-240°C
  • the pressure is preferably 1.5-3 MPa
  • the liquid hourly mass space velocity of aniline is preferably 0.5-3h -1 , more preferably 1-1.5h -1 .
  • the continuous operation is preferably to react the raw material aniline through the catalyst bed layer of the fixed-bed reactor containing the catalyst by adopting the lower feeding mode.
  • the inventors of the present invention have also found that: the reaction of aniline isomerization rearrangement to generate 2-picoline and the reaction of aniline condensation to prepare diphenylamine are affected by catalyst and reaction temperature.
  • the reaction route of aniline can be switched between 2-picoline and diphenylamine.
  • lower reaction temperature is more conducive to the synthesis of 2-picoline, and higher temperature is beneficial to the formation of phenylenediamine.
  • the present invention also provides a method for selectively and continuously producing 2-picoline and diphenylamine from aniline, the method comprising, under a hydrogen-containing atmosphere, mixing aniline and a catalyst at a temperature of 100-400° C.
  • the contact reaction is carried out under, it is characterized in that, described catalyst is the zeolite of loading metal component, and described metal component comprises the active metal component selected from at least one in W, Mo, Ni and Co, controls described
  • the temperature of the contact reaction is 100-240° C. to obtain a product mainly composed of 2-picoline; the temperature of the contact reaction is controlled to be 260-400° C. to obtain a product mainly composed of diphenylamine.
  • the temperature of the contact reaction is 160-240°C
  • the pressure is 1.5-3MPa
  • the liquid hourly mass space velocity of the aniline is preferably 0.5-3h -1
  • the temperature of the contact reaction is 280-360°C
  • the pressure is 1.5-3MPa
  • the liquid hourly mass space velocity of the aniline is preferably 0.3-1.5h -1 .
  • the product mainly composed of 2-picoline means that the selectivity of 2-picoline is not lower than 40%
  • the product mainly composed of diphenylamine means that the selectivity of diphenylamine is not lower than 40%.
  • the conditions for synthesizing diphenylamine from aniline in the present invention include: the temperature of the contact reaction is preferably 280-360°C; the pressure is preferably 1.5-3MPa; the liquid hourly mass space velocity of aniline is 0.3-1.5h -1 , preferably 0.5-1h - 1 .
  • the conversion rate of aniline, the selectivity and yield of 2-picoline, the calculation method of the selectivity and yield of diphenylamine are as follows:
  • the conversion rate of aniline (the number of moles of aniline in the raw material before the reaction-the number of moles of aniline in the product)/the number of moles of aniline in the raw material before the reaction ⁇ 100%;
  • the yield of 2-picoline the number of moles of 2-picoline in the product/the number of moles that aniline in the raw material before the reaction is completely converted into 2-picoline in theory
  • the selectivity of 2-picoline (the number of moles of 2-picoline in the product)/(the number of moles of aniline in the raw material before the reaction-the number of moles of aniline in the product) ⁇ 100%;
  • the yield of diphenylamine the number of moles of diphenylamine in the product/the number of moles that aniline in the raw material before the reaction is completely converted into diphenylamine in theory;
  • the selectivity of diphenylamine 2 ⁇ (the number of moles of diphenylamine in the product)/(the number of moles of aniline in the raw material before the reaction-the number of moles of aniline in the product) ⁇ 100%.
  • the alumina binder used is commercially available ⁇ -alumina, and the used zeolite is commercially available H ⁇ zeolite.
  • the specific surface area of the H ⁇ zeolite is 620m 2 /g and the particle size is ⁇ 9nm.
  • the catalysts used in the examples and comparative examples are prepared by the saturated impregnation method of supporting metal components and active metal components.
  • alumina binder such as thin diaspore
  • processing aids such as extrusion aids and peptizers
  • step (1) wherein the contact temperature in step (1) is 90 DEG C, time is 4h; Step (2) is dried at 80 DEG C for 10 hours; Step (3) is dried at 80 DEG C for 10 hours; Roasting at 550 DEG C for 10 hours; Step (4) Reflux reduction at 100°C for 8h, followed by vacuum drying at 100°C for 10h.
  • a tank reactor was selected, and the reaction was carried out under a hydrogen atmosphere.
  • the amount of catalyst used was 1 g, and the amount of aniline added was 50 g.
  • the reaction conditions were shown in Table 2 below.
  • the conversion reaction of aniline was carried out according to the method of Example 1, except that zeolite beta (no metal component was supported) was used as a catalyst, and other reaction conditions were shown in Table 2 below.
  • aniline is used to produce 2-picoline: use pure HZSM-5 at 510°C, pressure 2.9MPa, when the molar ratio of raw material aniline to ammonia is 1:8, and the mass space velocity is 1.0h -1 Next, the aniline is converted to 2-picoline.
  • the preparation method of 2-picoline provided by the present invention can obtain higher aniline conversion and 2-picoline selectivity at a lower reaction temperature.
  • the method for the selective continuous production of diphenylamine and 2-picoline provided by the present invention can be easily realized on a set of equipment by adjusting process parameters such as reaction temperature and pressure to obtain Different target products diphenylamine and 2-picoline.

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  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Pyridine Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

本发明属于精细化工领域，具体公开了一种苯胺合成2-甲基吡啶的方法和由苯胺选择性连续生产2-甲基吡啶和二苯胺的方法。该方法包括在含氢气的气氛下，将苯胺与催化剂在温度为100-400℃的条件下进行接触反应，其特征在于，所述催化剂为担载金属组分的β沸石，所述金属组分包括选自W、Mo、Ni和Co中的至少一种的活性金属组分，控制所述接触反应的温度为100-240℃，以获得以2-甲基吡啶为主的产物；控制所述接触反应的温度为260-400℃，以获得以二苯胺为主的产物。本发明的方法，通过控制温度就能够方便有效的实现苯胺和2-甲基吡啶产品的切换，反应条件温和，2-甲基吡啶收率高，反应选择性好，具有很好的工业应用前景。

Description

一种由苯胺选择性连续生产2-甲基吡啶和二苯胺的方法
相关申请的交叉引用
本申请要求2021年10月31日提交的中国专利申请202111278790.6的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明属于精细化工领域，具体涉及一种苯胺合成2-甲基吡啶的方法和由苯胺选择性连续生产2-甲基吡啶和二苯胺的方法。
背景技术
2-甲基吡啶，分子式C 6H 7N，又称α-甲基吡啶、α-皮考啉，是吡啶碱的一种，其在室温下是无色油状液体，具有强烈不愉快的气味，凝固点为-38.9℃，沸点为129.5℃，有强烈的毒性，与丙酮、乙醇、乙醚、水等溶剂互溶。2-甲基吡啶是重要的化学中间体，也是精细化工的重要原料，可用于生产长效磺胺、农药中间体、饲料中间体，还可用于合成特种树脂乙烯吡啶和2-乙烯基吡啶中间体。2-甲基吡啶的用量国内每年大约以25％的速度增加，因此2-甲基吡啶国内市场潜力很大。
工业领域生产吡啶碱主要包括煤焦油分离法和化学合成法。煤焦油分离法不仅存在污染严重、产品种类少、耗资大、质量差、能耗高等缺点，且产品的产量较低，很难提高。化学合成法通常采用铵醛缩合的方法，以醛、酮与氨为原料反应合成吡啶碱。但铵醛缩合法的产物包括3-甲基吡啶、2-甲基吡啶、4-甲基吡啶等，其存在后续产物分 离困难等问题。
CN105384683A公开了一种苯胺合成二苯胺副产物2-甲基吡啶、4-甲基吡啶的分离方法。其步骤为：以苯胺为原料，流经装有分子筛催化剂的固定床反应器，控制反应器的温度和压力，经缩合反应转化成二苯胺、氨以及2-甲基吡啶、4-甲基吡啶、水、吖啶、4-氨基联苯等副产物，将混合物反应液经多级精馏得到低沸点混合馏分，将低沸点混合馏分脱水，脱水后的混合物再进行干燥，干燥后的混合液进行精馏，根据不同沸点，精馏得到2-甲基吡啶和4-甲基吡啶。该方法的本质为传统苯胺合成二苯胺中副产物2-甲基吡啶和4-甲基吡啶的分离方法。因此，该方法中由于2-甲基吡啶为反应过程副产物，其产率较低，无法实现其大规模生产。
CA1190928A公开了一种由苯胺生产α-皮考林的方法，苯胺起始物质在惰性气体如氮气和氦气存在下于200-650℃下穿过酸性沸石催化剂制备含α-皮考林的产物，反应压力从常压至25000kPa，通常在200kPa，苯胺空速优选为0.2-5WHSV。所述酸性沸石优选为氢型，包括beta-沸石，其硅铝比为10-100，可高达150。其中实施例1使用纯的HZSM-5在510℃、压力2860kPa、氨气为苯胺的1.5mol％、氮气空速为100GHSV的条件下，苯胺转化率为13.1％，α-皮考林的选择性为51.6％。
“The zeolite-catalysed isomerization of aniline to a-picoline[J].Applied catalysis A：General 172(1998)285-294”公开了一种通过苯胺重排反应制备α-皮考林的方法，该方法采用分子筛优选Ga-MFI分子筛(优于ZSM-5)作为催化剂，在673K、总压力为75bar、氨气分压为5-60bar优选20-25bar的条件下进行。其中α-皮考林的选择性可以 达到85％以上，但转化率仅3.7％。
发明内容
本发明所要解决的技术问题是克服现有技术苯胺重排反应制备2-甲基吡啶的方法或者苯胺转化率低，或者2-甲基吡啶选择性低的缺点，提供一种能够在现有苯胺生产二苯胺装置的基础上选择性生产苯胺和2-甲基吡啶的方法。本发明的方法，通过控制温度就能够方便有效的实现苯胺和2-甲基吡啶产品的切换，反应条件温和，2-甲基吡啶收率高，反应选择性好，具有很好的工业应用前景。
本发明的发明人发现：苯胺异构重排生成2-甲基吡啶反应和苯胺缩合制备二苯胺反应受到催化剂和反应温度两个因素的双重影响。采用本发明中担载W、Mo、Ni和Co中的至少一种的活性金属组分的β沸石催化剂，由于催化活性中心的改变，苯胺的反应路线可以在2-甲基吡啶和二苯胺之间转换。同时，较低的反应温度更有利于2-甲基吡啶的合成。基于该发现，本发明提出了生产2-甲基吡啶的方法和选择性连续生产苯胺和2-甲基吡啶的方法。
本发明第一方面提供一种由苯胺选择性连续生产2-甲基吡啶和二苯胺的方法，该方法包括在含氢气的气氛下，将苯胺与催化剂在温度为100-400℃的条件下进行接触反应，其特征在于，所述催化剂为担载金属组分的β沸石，所述金属组分包括选自W、Mo、Ni和Co中的至少一种的活性金属组分，控制所述接触反应的温度为100℃-240℃，以获得以2-甲基吡啶为主的产物；控制所述接触反应的温度260℃-400℃，以获得以二苯胺为主的产物。
本发明第二方面提供一种苯胺合成2-甲基吡啶的方法，其特征在于，该方法包括在含氢气的气氛下，在异构重排反应条件下，将苯胺 与催化剂进行接触反应，所述催化剂为担载金属组分的β沸石，所述金属组分包括选自W、Mo、Ni和Co中的至少一种的活性金属组分，所述接触反应的温度为100℃-240℃。
采用本发明的方法生产2-甲基吡啶，不仅苯胺转化率高，而且目标产物2-甲基吡啶选择性高。推断其可能的原因：在含氢气的气氛下，由于选择了含有W、Mo、Ni和Co中的至少一种活性金属的β沸石催化剂，使得其反应机理发生了较大变化，热力学因素成为影响2-甲基吡啶选择性的因素之一，在较高的温度下，以两个苯胺分子缩合生成一个二苯胺分子的反应为主反应，通过降低温度转变为以苯胺分子异构重排生成2-甲基吡啶为主的反应。从而本发明的方法能够实现以苯胺为原料生产2-甲基吡啶的目的，以及在现有二苯胺工艺装置上选择性生产二苯胺和2-甲基吡啶。
现有技术中合成吡啶碱类化合物，通常都通入大量的氨气。氨气的存在会占据催化剂的酸性位点，导致催化剂的活性降低。同时，高温高压也限制了该方法的工业应用。而本发明提供的方法，不需要大量通入氨气，仅需通入少量氢气即可，且反应条件温和，反应原料只有苯胺一种，后续通过蒸馏操作便可获得高纯度2-甲基吡啶和高纯度二苯胺。
附图说明
图1为本发明提供的由苯胺选择性连续生产2-甲基吡啶和二苯胺的方法的产品分布随温度的变化关系图。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明提供的苯胺合成2-甲基吡啶的方法，该方法包括在含氢气的气氛下，异构重排反应条件下，将苯胺与催化剂进行接触反应，所述催化剂为担载金属组分的β沸石，所述金属组分包括选自W、Mo、Ni和Co中的至少一种的活性金属组分，所述接触反应的温度100℃-240℃。
本发明通过使用担载选自W、Mo、Ni和Co中的至少一种的活性金属组分的β沸石，在含氢气的气氛下，并且控制反应温度低于通常的苯胺合成二苯胺反应所需的温度，在获得较高的苯胺转化率的同时意外的提高了2-甲基吡啶的选择性。而且可以实现在同一套装置、相同的催化剂下通过调整反应温度选择性的生产二苯胺和2-甲基吡啶。
根据本发明的一种优选实施方式，以催化剂的总量为基准，以金属元素计，所述活性金属组分的含量为0.5-5wt％，优选0.5-3wt％。
优选地，所述金属组分还包括选自Li、Na、K、Mg、Ca中的至少一种的助剂金属组分，以催化剂的总量为基准，以氧化态计，所述助剂金属组分的含量为0-6.5wt％优选0.5-5.5wt％。
通过加入助剂金属组分，能够改善催化剂表面的酸分布以及催化剂孔道结构，进一步提高苯胺转化率和目标产物的选择性。
尽管机理还不明确，但本发明的发明人发现，只有在含氢气的气氛下，使用β沸石负载上述金属组分才能获得上述通过调整温度即可 获得以苯胺或2-甲基吡啶为主产物的效果，其他分子筛如ZSM-5均不能实现上述效果。
优选地，所述β沸石的硅铝摩尔比为25-300，优选60-220。
优选地，所述催化剂的比表面积为400-700m 2/g，优选450-650m 2/g；孔容为0.25-0.6mL/g，优选0.4-0.55mL/g；平均孔直径为1.5-5nm，优选2-4nm；粒径优选小于9nm。
该催化剂还可以含有氧化铝粘结剂，从而获得催化剂的成型体。
根据本发明的一种优选实施方式，以催化剂的总量为基准，所述催化剂含有沸石50-85wt％；以金属元素计，活性金属组分0.5-5wt％；以氧化态计，助剂金属组分0-6.5wt％；氧化铝粘结剂10-45wt％。优选地，沸石60-85wt％；以金属元素计，活性金属组分0.5-3wt％；以氧化态计，助剂金属组分0.5-5.5wt％；氧化铝粘结剂15-34.5wt％。
优选地，所述催化剂为条形或球形颗粒，为条形时其截面可以是圆柱形、三叶草或四叶草形状，条形颗粒的横截面宽度为0.5-3.0mm，优选1.0-2.0mm；为球形时，其颗粒直径为0.5-5.0mm，优选1.0-3.0mm。
上述催化剂可以采用本领域技术人员公知的方法制备得到，或者商购得到。例如，本发明催化剂可以采用如下的方法制备得到：(1)采用等体积浸渍的方式将Hβ沸石与助剂金属组分的硝酸盐水溶液接触；(2)将步骤(1)所得的混合物经过滤、洗涤和干燥；(3)将步骤(2)得到的改性后Hβ沸石、氧化铝粘结剂和加工助剂(如助挤剂与胶溶剂)充分混捏后，成型，随后进行干燥和焙烧；(4)向步骤(3)得到的载体与活性金属组分的硝酸盐水溶液中，加入NaBH 4回流还原，过滤、真空干燥制得催化剂。
其中步骤(1)中的接触温度为80-100℃，时间为3-6h；步骤(2)在60-120℃下干燥6-12h；步骤(3)在60-120℃下干燥6-12h；在450-550℃ 下焙烧4-16h；步骤(4)在80-100℃下，回流还原6-8h，之后在80-100℃下，真空干燥6-12h。
本发明通过使用上述催化剂，在含氢气的气氛而非传统的氨气气氛下即可在较低温度下获得较高的2-甲基吡啶收率。因此优选地，所述接触反应在不通入氨气的情况下进行。所述含氢气的气氛是指氢气的浓度为10-100体积％。
进一步，所述接触反应的温度为100-240℃，具体可以为100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃、199℃、200℃、210℃、220℃、230℃、240℃，以及这些点值中的任意两个所构成范围中的任意值。优选的反应温度为130-180℃，具体可以为130℃、140℃、150℃、160℃、170℃、180℃，以及这些点值中任意两个所构成范围中的任意值。
本发明的方法可以采用连续式进行也可以采用间歇式进行，优选连续式进行。间歇式操作通常是指釜式操作，将原料苯胺和催化剂加入反应釜中，在适宜条件下进行反应，可得到目标产物。连续式操作通常是指将原料苯胺通过含有催化剂的固定床反应器进行反应。
本发明的发明人发现，连续式和间歇式的最佳反应温度和压力稍有不同。采用间歇式进行时，接触反应的温度优选为130-180℃，压力优选为2-4MPa，反应时间优选为4-8h；优选催化剂用量优选占原料苯胺用量的1-4wt％。采用连续式时，接触反应的温度优选为160-240℃，压力优选为1.5-3MPa；苯胺的液时质量空速优选为0.5-3h -1，进一步优选为1-1.5h -1。
连续式的操作优选为采用下进料方式将原料苯胺通过含有催化剂的固定床反应器的催化剂床层进行反应。
本发明的发明人还发现：苯胺异构重排生成2-甲基吡啶的反应和 苯胺缩合制备二苯胺的反应受到催化剂及反应温度两个因素的双重影响。采用本发明中担载金属的β沸石催化剂，由于催化活性中心的改变，苯胺的反应路线可以在2-甲基吡啶和二苯胺之间转换。同时，较低的反应温度更有利于2-甲基吡啶的合成，较高的温度则有利于苯二胺的生成。
由此，本发明的还提供一种由苯胺选择性连续生产2-甲基吡啶和二苯胺的方法，该方法包括在含氢气的气氛下，将苯胺与催化剂在温度为100-400℃的条件下进行接触反应，其特征在于，所述催化剂为担载金属组分的沸石，所述金属组分包括选自W、Mo、Ni和Co中的至少一种的活性金属组分，控制所述接触反应的温度为100-240℃，以获得以2-甲基吡啶为主的产物；控制所述接触反应的温度为260-400℃，以获得以二苯胺为主的产物。
优选地，获得以2-甲基吡啶为主的产物时，所述接触反应的温度为160-240℃、压力为1.5-3MPa，优选所述苯胺的液时质量空速为0.5-3h -1；获得以二苯胺为主的产物时，所述接触反应的温度为280-360℃、压力为1.5-3MPa，优选所述苯胺的液时质量空速为0.3-1.5h -1。
本发明中，以2-甲基吡啶为主的产物是指2-甲基吡啶的选择性不低于40％，以二苯胺为主的产物是指二苯胺的选择性不低于40％。
催化剂已在上文中描述，在此不再赘述。
本发明的苯胺合成二苯胺的条件包括：接触反应的温度优选为280-360℃；优选压力为1.5-3MPa；苯胺的液时质量空速为0.3-1.5h -1，优选为0.5-1h -1。
实施例及比较例中，苯胺的转化率、2-甲基吡啶的选择性和收率、二苯胺的选择性和收率的计算方法如下：
苯胺的转化率＝(反应前原料中苯胺的摩尔数－产品中苯胺的摩尔数)/反应前原料中苯胺的摩尔数×100％；
2-甲基吡啶的收率＝产品中2-甲基吡啶的摩尔数/反应前原料中苯胺理论上全部转化为2-甲基吡啶的摩尔数；
2-甲基吡啶的选择性＝(产品中2-甲基吡啶的摩尔数)/(反应前原料中苯胺的摩尔数－产品中苯胺的摩尔数)×100％；
二苯胺的收率＝产品中二苯胺的摩尔数/反应前原料中苯胺理论上全部转化为二苯胺的摩尔数；
二苯胺的选择性＝2×(产品中二苯胺的摩尔数)/(反应前原料中苯胺的摩尔数－产品中苯胺的摩尔数)×100％。
苯胺、二苯胺、2-甲基吡啶的含量根据气相色谱测得。
所使用的氧化铝粘结剂为市售γ-氧化铝，所使用的沸石为市售Hβ沸石，Hβ沸石的比表面积为620m 2/g、粒径<9nm。
实施例和比较例中使用的催化剂采用饱和浸渍法负载助剂金属组分和活性金属组分的方法制得，具体方法如下：(1)采用等体积浸渍的方式将Hβ沸石与助剂金属组分的硝酸盐水溶液接触；(2)将步骤(1)所得的混合物经过滤、洗涤和干燥；(3)将步骤(2)得到的改性后Hβ沸石、氧化铝粘结剂(如拟薄水铝石)和加工助剂(如助挤剂与胶溶剂)充分混捏后，成型，随后进行干燥和焙烧；(4)向步骤(3)得到的载体与活性金属组分的硝酸盐水溶液中，加入NaBH 4回流还原，过滤、真空干燥制得球形催化剂，颗粒直径3mm。其中步骤(1)中的接触温度为90℃，时间为4h；步骤(2)在80℃下干燥10h；步骤(3)在80℃下干燥10h；在550℃下焙烧10h；步骤(4)在100℃下回流还原8h，之后在100℃下真空干燥10h。
催化剂的性质列于表1。
表1催化剂
Figure PCTCN2022126220-appb-000001
实施例1-8
选择釜式反应器，反应在氢气气氛下进行，催化剂用量为1g，苯胺加入量为50g，反应条件如下表2所示。
比较例1-2
按照实施例1的方法进行苯胺的转化反应，不同的是，反应条件如下表2所示。
比较例3
按照实施例1的方法进行苯胺的转化反应，不同的是，使用β沸石(未负载金属组分)作为催化剂，其他反应条件如下表2所示。
比较例4
按照CA1190928A实施例1的方法苯胺生产2-甲基吡啶：使用纯的HZSM-5在510℃、压力2.9MPa、原料苯胺与氨的摩尔比为1:8 时，质量空速1.0h -1条件下，使苯胺转化为2-甲基吡啶。
表2
Figure PCTCN2022126220-appb-000002
实施例9-16
选择固定床反应器，原料苯胺以下进料方式，通过催化剂床层，氢气气氛下，先在适合于生成2-甲基吡啶的条件下反应48小时，然后以30℃/小时的升温速度切换为适合于生成二苯胺的条件继续反应48小时，测得产品分布如下表3所示。
表3
Figure PCTCN2022126220-appb-000003
Figure PCTCN2022126220-appb-000004
实施例17
按照实施例9的方法由原料苯胺生产二苯胺和2-甲基吡啶，以考察温度对产品分布的影响，每次取样后以30℃/小时的升温速度升温至下一温度，产品分布随温度变化关系图如图1所示。
从表2和图1的结果可以看出，本发明提供的2-甲基吡啶的制备方法，能够在较低的反应温度下获得较高的苯胺转化率和2-甲基吡啶选择性。
从表3和图1的结果可以看出，本发明提供的选择性连续生产二苯胺和2-甲基吡啶的方法，能够方便的实现在一套装置上通过调整反应温度和压力等工艺参数获得不同的目标产物二苯胺和2-甲基吡啶。

Claims (16)

  1. 一种由苯胺选择性连续生产2-甲基吡啶和二苯胺的方法，该方法包括在含氢气的气氛下，将苯胺与催化剂在温度为100-400℃的条件下进行接触反应，其特征在于，所述催化剂为担载金属组分的β沸石，所述金属组分包括选自W、Mo、Ni和Co中的至少一种的活性金属组分，控制所述接触反应的温度为100-240℃，以获得以2-甲基吡啶为主的产物；控制所述接触反应的温度为260-400℃，以获得以二苯胺为主的产物。
  2. 按照权利要求1所述的方法，其中，以所述催化剂的总量为基准，以金属元素计，所述活性金属组分的含量为0.5-5wt％优选0.5-3wt％。
  3. 按照权利要求1或2所述的方法，其中，所述金属组分还包括选自Li、Na、K、Mg、Ca中的至少一种的助剂金属组分，以所述催化剂的总量为基准，以氧化态计，所述助剂金属组分的含量为0-6.5wt％优选0.5-5.5wt％。
  4. 按照权利要求1-3中任意一项所述的方法，其中，该催化剂还含有氧化铝粘结剂，以所述催化剂的总量为基准，所述催化剂含有β沸石50-85wt％；以金属元素计，活性金属组分0.5-5wt％；以氧化态计，助剂金属组分0-6.5wt％；氧化铝粘结剂10-45wt％。
  5. 按照权利要求4所述的方法，其中，以所述催化剂的总量为基准，所述催化剂含有β沸石60-85wt％；以金属元素计，活性金属组分0.5-3wt％；以氧化态计，助剂金属组分0.5-5.5wt％；氧化铝粘结 剂15-34.5wt％。
  6. 按照权利要求1-5中任意一项所述的方法，其中，所述接触反应的压力为1.5-4MPa，所述接触反应在氢气气氛下进行。
  7. 按照权利要求1-6中任意一项所述的方法，其中，所述接触反应在不通入氨气的情况下进行。
  8. 按照权利要求1-7任意一项所述的方法，其中，
    获得以2-甲基吡啶为主的产物时，所述接触反应的温度为160-240℃、压力为1.5-3MPa，优选所述苯胺的液时质量空速为0.5-3h -1；或者，
    获得以二苯胺为主的产物时，所述接触反应的温度为280-360℃、压力为1.5-3MPa，优选所述苯胺的液时质量空速为0.3-1.5h -1。
  9. 按照权利要求8所述的方法，其中，所述原料苯胺通过含有所述催化剂的固定床反应器进行反应；
    优选地，所述原料苯胺采用下进料方式送入所述固定床反应器并通过催化剂床层。
  10. 一种苯胺合成2-甲基吡啶的方法，其特征在于，该方法包括在含氢气的气氛下，在异构重排反应条件下，将苯胺与催化剂进行接触反应，所述催化剂为担载金属组分的β沸石，所述金属组分包括选自W、Mo、Ni和Co中的至少一种的活性金属组分，所述接触反应的温度为100℃-240℃。
  11. 按照权利要求10所述的方法，其中，以所述催化剂的总量为基准，以金属元素计，所述活性金属的含量为0.5-5wt％优选0.5-3wt％。
  12. 按照权利要求10或11所述的方法，其中，所述金属组分还包括选自Li、Na、K、Mg、Ca中的至少一种的助剂金属组分，以所述催化剂的总量为基准，以氧化态计，所述助剂金属组分的含量为0-6.5wt％。
  13. 按照权利要求10-12中任意一项所述的方法，其中，该催化剂还含有氧化铝粘结剂，以所述催化剂的总量为基准，所述催化剂含有β沸石50-85wt％；以金属元素计，活性金属组分0.5-5wt％；以氧化态计，助剂金属0-6.5wt％；氧化铝粘结剂10-45wt％。
  14. 按照权利要求13所述的方法，其中，以所述催化剂的总量为基准，所述催化剂含有β沸石60-85wt％；以还原态计，活性金属组分0.5-3wt％；以氧化态计，助剂金属组分0.5-5.5wt％；氧化铝粘结剂15-34.5wt％。
  15. 按照权利要求10-14中任意一项所述的方法，其中，所述接触反应在不通入氨气的情况下进行。
  16. 按照权利要求10-15任意一项所述的方法，其中，所述接触反应间歇进行，所述接触反应的温度为130-180℃、压力为2-4MPa、反应时间为4h-8h，优选所述催化剂用量占原料苯胺用量的1-4wt％；或者，
    所述接触反应连续进行，接触反应的温度为160-240℃、压力为1.5-3MPa，优选所述苯胺的液时质量空速为0.5-3h -1；
    优选地，所述原料苯胺通过含有所述催化剂的固定床反应器进行反应，优选所述原料苯胺采用下进料方式进入所述固定床反应器并通过催化剂床层。
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