CN116874410B - Preparation method of N-alkyl carbazole - Google Patents

Preparation method of N-alkyl carbazole Download PDF

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CN116874410B
CN116874410B CN202311154300.0A CN202311154300A CN116874410B CN 116874410 B CN116874410 B CN 116874410B CN 202311154300 A CN202311154300 A CN 202311154300A CN 116874410 B CN116874410 B CN 116874410B
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carbazole
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CN116874410A (en
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Beijing Haiwang Hydrogen Energy Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese

Abstract

The invention relates to the technical field of preparation of N-alkyl carbazole, and discloses a preparation method of N-alkyl carbazole, which comprises the following steps: contacting carbazole with an alkylating agent in the presence of a catalyst under alkylation reaction conditions; wherein the alkylating agent is an alkylamine; the catalyst comprises a carrier, and an active metal component and an optional auxiliary component which are supported on the carrier, wherein the active metal component is selected from at least one of metal elements of VIII group and IB group, and the auxiliary component is selected from at least one of alkali metal, alkaline earth metal, IVB group metal, VIIB group metal and rare earth metal. In the preparation method provided by the invention, the alkylamine can be used as an alkylating reagent and a solvent at the same time, so that the use of an organic solvent is avoided. The process has the characteristics of high product selectivity and easy recovery of byproducts, and accords with the economy of green atoms.

Description

Preparation method of N-alkyl carbazole
Technical Field
The invention relates to the technical field of preparation of N-alkyl carbazole, in particular to a preparation method of N-alkyl carbazole.
Background
With the development of the hydrogen energy industry, the storage and transportation of hydrogen is also increasingly important, wherein the storage of hydrogen by organic liquid is the technical route with the most scale and commercialization prospect. N-alkyl carbazole is considered as a potential organic liquid hydrogen storage carrier that can achieve large scale hydrogen storage and release. Taking N-ethylcarbazole as an example, the theoretical hydrogen storage amount is 5.8wt%, and the hydrogen storage density is higher, and meanwhile, the hydrogen storage density is lower compared with liquid hydrogen storage systems such as toluene/cyclohexane, dibenzyl toluene/octadecyl H-dibenzyl toluene, naphthalene/decahydro H-naphthalene and the like due to the existence of N atoms on an aromatic ring.
Taking N-ethylcarbazole as an example, the current representative routes are mainly: the chloroethane method, the diethyl sulfate method, the diethyl carbonate method and the ethyl p-toluenesulfonate method, wherein the chloroethane method is established as an industrialized device in the existing part of the 90 th century.
(1) Haloalkane process
At present, carbazole is used as a raw material in the halothane method, sodium hydroxide or potassium hydroxide is added into a proper solvent, and the mixture reacts with carbazole to generate carbazole sodium salt or carbazole potassium salt, and then reacts with an alkylating agent to obtain a corresponding product. Alkyl phaseThe alkylation activity sequence of the same halogen ethane is as follows: RI > RBr > RCl > RF (R-is C) 2 H 5 - ) Because of the relatively high price of ethyl iodide, ethyl bromide and ethyl chloride are the main materials in the actual production process.
Patent CN1184202C uses benzyl triethyl ammonium chloride, polyethylene glycol, a surfactant and ethanol as phase transfer catalysts, and uses bromoethane as an alkylating agent in the presence of benzene and NaOH aqueous solution to catalyze carbazole to prepare N-ethylcarbazole, wherein the highest yield of the N-ethylcarbazole is 98%. The literature [ Nishi Hisao, kohno Hisao, kano Toshihiro, A Convenient Preparation of Some N-Alkylcarbazoles and N-Alkylacridones, bulletin of the Chemical Society of Japan, 1981, 54:1897-1898 ] catalyzes the reaction of bromoethane and carbazole using benzyltriethylammonium chloride (BTEAC) as a phase transfer catalyst with an N-ethylcarbazole yield of 86.2%. CN102115457A adds carbazole into aqueous solution containing phase transfer catalyst and deionized reagent to react to generate carbazole salt, then introduces bromoethane to generate N-ethylcarbazole, and the product yield can reach 98.7%.
Document [ Zhong Zengpei, zhou Jian energy use of KF/Al 2 O 3 Method for catalytic synthesis of N-ethylcarbazole [ J ]]Chemical notification, 1998 (01): 33-34.]Reported as KF/Al 2 O 3 The method for preparing the N-ethylcarbazole by using DMF as a solvent is used as a catalyst, and the experimental yield is 92.3-96.9%. Thereafter, documents [ Zhang Xiaohui, wang Jiehua, zhou Xiangdi, li Junhai, han Taibai ] KF/Al 2 O 3 Catalysis on N-ethylation of carbazole [ J]Bao Steel technology, 2001 (03): 61-63.]A catalyst KF/Al with an alkaline catalyst has also been reported 2 O 3 The method for synthesizing N-ethylcarbazole by catalyzing carbazole and haloethane does not need to add alkali liquor in the reaction process, namely halogen salt is not generated, and the method is environment-friendly, but the experimental yield is lower and is only 33.17%.
The yield of N-ethylcarbazole synthesized by the haloalkane method is over 90 percent, but the alkali liquor and the organic solvent or both are added in the preparation method, so that the production cost is increased, and a large amount of harmful substances such as waste salt and wastewater are generated in the process of the mode, thereby causing harm to the environment.
(2) Diethyl sulfate process
The advantages of using diethyl sulfate as alkylating agent are that diethyl sulfate has strong alkylating capacity, and under proper condition, it can react with amino group only without affecting carbon or hydroxyl group on benzene ring, and the by-product potassium sulfate can be used as potash fertilizer. DE2132961A1 discloses a process for preparing N-ethylcarbazole with diethyl sulfate as alkylating agent, the yield of N-ethylcarbazole being 99%. The synthesis of N-ethylcarbazole [ Wu Jianzhong, zhang Weimin ] Jiangsu chemical, 1991 (03): 28-29 ] reports a process for preparing N-ethylcarbazole by the diethyl sulfate method. And adding carbazole into a mixed solution of chlorobenzene solvent and sodium hydroxide aqueous solution to react with diethyl sulfate, wherein the optimal yield of N-ethylcarbazole is 95%. However, the technology needs to add benzene, chlorobenzene, dichlorobenzene and other toxic organic solvents, and has the defects of high toxicity, long reaction time and the like of an alkylating reagent, so that the application of diethyl sulfate is not as wide as that of a haloalkane method.
(3) Diethyl carbonate process
The raw materials of the process are carbazole and diethyl carbonate. A certain amount of carbazole and alkali are mixed, and the mixture is added dropwise after the temperature of diethyl carbonate and the like reaches the reaction temperature. During the reaction, excessive diethyl carbonate is added, the reaction temperature is 220-280 ℃, and the total reaction requirement is 20-24 h. Patent EP0635490A1 discloses a method for preparing N-ethylcarbazole with 96% purity by catalyzing carbazole reaction at 130-320 ℃ by using diethyl carbonate as an alkylating agent and potassium carbonate, sodium hydroxide or potassium ethoxide as a proton removing agent.
In the process, the post-treatment of the solution is simple, and the product yield is high. However, the reaction time of the process is relatively long, the energy consumption is high, and a large amount of CO exists in the reaction product 2 。
(4) Ethyl p-toluenesulfonate process
Because the method has high raw material price and produces a byproduct of potassium p-toluenesulfonate, the method is rarely adopted.
In summary, most of the preparation methods of N-alkyl carbazole disclosed in the prior art have environmental protection problems, and some of the preparation methods have problems of relatively complex preparation methods, low product selectivity, low purity or high preparation cost, so that large-scale continuous production cannot be realized. Therefore, development of an inexpensive, environment-friendly and commercial-scale synthetic route for a high-quality hydrogen storage carrier N-alkyl carbazole has been urgent.
Disclosure of Invention
The invention aims to solve the problems of high raw material cost, poor environmental friendliness, complex preparation method and the like in the preparation of N-alkyl carbazole in the prior art, and provides a preparation method of N-alkyl carbazole, which has the advantages of simple flow, high product selectivity, continuous operation and no pollution waste such as halide which is difficult to treat in the traditional process in the process.
In order to achieve the above object, the present invention provides a method for preparing N-alkyl carbazole, the method comprising: contacting carbazole with an alkylating agent in the presence of a catalyst under alkylation reaction conditions;
wherein the alkylating agent is an alkylamine;
the catalyst comprises a carrier, and an active metal component and an optional auxiliary component which are supported on the carrier, wherein the active metal component is selected from at least one of metal elements of VIII group and IB group, and the auxiliary component is selected from at least one of alkali metal, alkaline earth metal, IVB group metal, VIIB group metal and rare earth metal.
Preferably, the active metal component is selected from at least one of Ni, fe, co, and Cu;
wherein the content of the active metal component in terms of elements is 10-60wt% based on the total amount of the catalyst, the content of the auxiliary component in terms of oxides is 0-10wt% and the content of the carrier is 30-90wt%.
Preferably, the active metal component is selected from at least one of Ir, pt and Pd;
wherein the content of the active metal component in terms of elements is 0.1-5wt% based on the total amount of the catalyst, the content of the auxiliary component in terms of oxides is 0-10wt% and the content of the carrier is 85-99.9wt%.
According to the preparation method of the N-alkyl carbazole, the alkylamine is used as an alkylating reagent in the alkylation reaction of the carbazole for the first time, a heterogeneous catalysis process is adopted, and the supported catalyst containing active metal components of VIII group and IB group metal elements is used for efficiently catalyzing the transalkylation process between the alkylamine and the carbazole, so that the preparation method has technical universality and can produce various N-alkyl carbazole. In the preparation method provided by the invention, the alkylamine can be used as an alkylating reagent and a solvent at the same time, other organic solvents are not needed to be additionally used, the generation of organic waste liquid is greatly reduced, the environmental pollution and the operation difficulty are reduced, the reaction byproduct is ammonia gas, the recycling is easy, and the process does not produce pollution wastes such as halide which are difficult to treat in the traditional process. The process can realize continuous production of alkylation process, and the catalyst is easy to separate and regenerate. The preparation method has high selectivity of target products, and accords with the economy of green genes.
Drawings
FIG. 1 is a GC-MS diagram of the product obtained in example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a preparation method of N-alkyl carbazole, which comprises the following steps: contacting carbazole with an alkylating agent in the presence of a catalyst under alkylation reaction conditions;
wherein the alkylating agent is an alkylamine;
the catalyst comprises a carrier, and an active metal component and an optional auxiliary component which are supported on the carrier, wherein the active metal component is selected from at least one of metal elements of VIII group and IB group, and the auxiliary component is selected from at least one of alkali metal, alkaline earth metal, IVB group metal, VIIB group metal and rare earth metal.
Alkylating agents employed in prior art processes for the preparation of N-alkyl carbazole are typically relatively expensive haloalkanes, lipids or sulfonates, etc., and the process uses a large amount of strong base solution and thus the production process generates a large amount of waste salt wastewater. In addition, a large amount of an organic solvent or the like is often required to be added to the conventional production method. Thus, conventional alkylation processes not only increase production costs, but also present an environmental hazard.
Because amino is not a good leaving group and is difficult to leave, alkylamines and derivatives thereof are rarely used as alkylating agents in organic synthesis, generally can only be matched with high-activity electrophiles, and have the problems of needing excessive strong acid as a catalyst, high reaction temperature, multiple byproducts and the like.
The inventors of the present invention creatively propose to use alkylamine as a carbazole alkylating agent to efficiently catalyze a transalkylation process between alkylamine and carbazole by a supported catalyst containing active metal components of group VIII and group IB metal elements. The preparation method has high selectivity of target products, and accords with the economy of green genes. In addition, the invention is beneficial to realizing continuous production and catalyst recycling by utilizing a heterogeneous catalysis process. In addition, the process greatly reduces the generation of organic waste liquid and reduces environmental pollution and operation difficulty.
According to the invention, the structural formula of the alkylating agent is expressed as follows: r is R n NH 3-n Wherein n is an integer from 1 to 3 and R is C 1 -C 5 Straight or branched alkyl of (a).
According to some preferred embodiments of the invention, R is selected from at least one of methyl, ethyl, propyl, butyl and pentyl and isomers thereof. When R is in the above preferred ranges, the corresponding alkylating agent is, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, or the corresponding dialkylamine, trialkylamine, etc., and may include various isomers. Preferably, the alkylamine is an n-alkylamine, such as methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine or at least one of the corresponding dialkylamines, trialkylamines. For example, the corresponding dialkylamine to ethylamine is diethylamine and the trialkylamine is triethylamine.
The reaction process of the preparation method provided by the invention is shown as a formula (1), and the N-alkyl carbazole containing the corresponding alkyl is generated by catalyzing the alkyl transfer process between the alkylamine and the carbazole through a catalyst.
(1)
According to some preferred embodiments of the invention, the molar ratio of alkylating agent to carbazole is from 2 to 25:1, preferably 3-22:1, for example, may be 3: 1. 4: 1. 5:1. 6: 1. 7: 1.8: 1. 9: 1. 10: 1. 11: 1. 12: 1. 13: 1. 14: 1. 15: 1. 16: 1. 17: 1. 18:1. 19: 1. 20:1. 21: 1. 22:1 or a range therebetween. More preferably, the molar ratio of alkylating agent to carbazole is from 6 to 20:1. the adoption of the preferable molar ratio of the alkylating reagent to the carbazole is beneficial to improving the conversion rate of the carbazole.
According to the invention, preferably, no additional organic solvent is required to be introduced in the reaction process, and the alkylamine can simultaneously play roles of an alkylating reagent and a solvent, so that no additional solvent is required, the generation of organic waste liquid is further reduced, the environmental pollution is further reduced, and the post-treatment difficulty is reduced.
The preparation method adopts a heterogeneous catalysis process, and the supported catalyst of the active metal component containing VIII group and IB group metal elements is used for efficiently catalyzing the alkyl transfer process between alkylamine and carbazole.
According to the invention, the catalyst comprises a carrier and an active metal component supported on the carrier, and preferably, the catalyst further comprises an auxiliary component. The auxiliary component is at least one selected from alkali metals, alkaline earth metals, IVB group metals, VIIB group metals and rare earth metals. In the catalyst, the promoter component is present as an oxide. The synergistic effect of the auxiliary component and the active metal component is beneficial to improving the activity of the catalyst, preventing the active center metal from sintering and prolonging the service life of the catalyst.
According to the invention, the auxiliary component is selected from at least one of alkali metals, alkaline earth metals, group IVB metals, group VIIB metals and rare earth metals. Preferably, the adjunct component is selected from at least one of Li, na, K, rb, cs, mg, ca, ba, sr, ti, zr, re, mn, ce and La, preferably at least one of Zr, mn, ce, mg, K and Cs.
According to the invention, in the catalyst, the auxiliary component is present in the form of an oxide.
According to some preferred embodiments of the present invention, the active metal component is selected from at least one of group VIII and IB non-noble metal elements, preferably at least one of Ni, fe, co and Cu, further preferably at least one of Fe, co and Cu.
Preferably, the content of the active metal component is 15 to 60wt%, preferably 15 to 50wt%, more preferably 18 to 40wt% in terms of elements, based on the total amount of the catalyst; the content of the auxiliary component in terms of oxide is 0 to 10wt%, preferably 0.2 to 8wt%, more preferably 1 to 5wt%; the carrier is present in an amount of 30 to 85wt%, preferably 42 to 84.8wt%, more preferably 55 to 81wt%.
According to other preferred embodiments of the present invention, the active metal component is selected from at least one of group VIII and group IB noble metal elements, preferably at least one of Ru, rh, ir, pt, ag, au and Pd, further preferably at least one of Ir, pt and Pd.
Preferably, the content of the active metal component in elemental form is 0.1 to 5wt%, preferably 0.3 to 3wt%, more preferably 0.5 to 2wt%, based on the total amount of the catalyst; the content of the auxiliary component in terms of oxide is 0 to 10wt%, preferably 0.2 to 8wt%, more preferably 0.3 to 5wt%; the carrier is present in an amount of 95 to 99.9wt%, preferably 89 to 99.3wt%, more preferably 93 to 99.2wt%.
In the present invention, the composition of the catalyst was tested by the ICP-OES method.
The invention has a wide selection range for the carrier in the catalyst, and the conventional catalyst carrier in the field can be applied to the invention. For example, the support may be at least one of activated carbon, an oxide support, and a molecular sieve.
According to some preferred embodiments of the invention, the oxide support is selected from one-component oxide supports and/or two-component oxide supports; the one-component oxide support is selected from Al 2 O 3 、CeO 2 、La 2 O 3 、MgO、SiO 2 、ZrO 2 、TiO 2 And ZnO; more preferably Al 2 O 3 、ZrO 2 And SiO 2 At least one of them. The two-component oxide support is selected from ZrO 2 -Al 2 O 3 、MgO-ZrO 2 、ZrO 2 -SiO 2 、ZnO-ZrO 2 、CeO 2 -ZrO 2 、SiO 2 -Al 2 O 3 At least one of them is preferably ZrO 2 -Al 2 O 3 、SiO 2 -Al 2 O 3 And ZrO(s) 2 -SiO 2 At least one of them. Preferably, the mass ratio of the two oxide components in the two-component oxide carrier is 1-10:1-10.
The source of the oxide support is not particularly limited, and a commercially available molded support may be used, for example, the alumina support may be spherical alumina, and the specific surface area is preferably 100 to 150m 2 And/g. Or may be an oxide support prepared by means known in the art.
According to a particularly preferred embodiment of the invention, the catalyst comprises a support, and an active metal component selected from at least one of Ir, pt and Pd and optionally an auxiliary component selected from at least one of Mg, K and Cs supported on the support, the support being alumina. The content of the active metal component in terms of elements is 0.5-2wt% based on the total amount of the catalyst; the content of the auxiliary agent component calculated by oxide is 0.3-5wt%; the content of the carrier is 93-99.2wt%. The adoption of the preferable catalyst composition is beneficial to further improving the conversion rate of carbazole and the selectivity of N-alkyl carbazole.
The source of the catalyst is not particularly limited, and may be prepared by a method conventional in the art, such as impregnation, precipitation, sol-gel, etc., as is well known to those skilled in the art. The specific preparation conditions and operation of the catalyst are not particularly limited, and may be carried out using catalyst preparation conditions known in the art.
According to some preferred embodiments of the invention, before the reaction, a step of activating the catalyst is further included, so that at least part of the active metal component is present in elemental form.
Preferably, the activation treatment is carried out under a hydrogen-containing atmosphere at a temperature of 200-600 ℃, preferably 300-500 ℃, for a time of 0.5-6 hours, preferably 2-5 hours.
The hydrogen-containing atmosphere may be hydrogen or a mixture of hydrogen and an inert gas, preferably nitrogen. Preferably, the hydrogen-containing atmosphere has a hydrogen content of 10 to 100% by volume.
The production method of the present invention may be carried out by any means conventional in the art, and the present invention is not particularly limited thereto, and for example, a fixed bed reactor or a tank reactor may be used.
According to some preferred embodiments of the invention, the preparation process is a continuous reaction, which can be carried out in a fixed bed reactor, the total liquid hourly space velocity of the feedstock being from 0.1 to 1.8h -1 Preferably 0.2-1.2h -1 Further preferably 0.3 to 0.9h -1 The volumetric liquid hourly space velocity of the feedstock is the total number of cubes per hour per cubic catalyst of carbazole and alkylating agent treated.
According to other preferred embodiments of the invention, the preparation process is a batch reaction, which can be carried out in a tank reactor, the catalyst being used in an amount of 1 to 15% by weight, preferably 3 to 10% by weight, based on the mass of carbazole, for a reaction time of 6 to 24 hours, preferably 8 to 12 hours.
When the preparation is carried out by using a kettle reactor, in order to reduce the activation temperature in the reaction kettle and improve the activation effect, the catalyst after the activation treatment is preferably passivated in an oxygen-containing atmosphere for 2-12 hours before the catalyst is filled, so that a passivation layer is formed on the surface of the catalyst. Then the catalyst is filled in an autoclave and reduced for 0.5 to 4 hours at 200 to 300 ℃ in a hydrogen atmosphere. The hydrogen-containing atmosphere is the same as defined above, and the oxygen-containing atmosphere may be a mixed gas of oxygen and nitrogen, wherein the oxygen content is 1-5vol%.
According to some preferred embodiments of the invention, the alkylation reaction temperature is 160-350 ℃, preferably 180-300 ℃, more preferably 200-280 ℃.
According to some preferred embodiments of the present invention, the reaction pressure of the alkylation reaction is 2 to 12MPa, preferably 3 to 7MPa, more preferably 3.5 to 6.5MPa, still more preferably 4 to 6MPa.
In the present invention, the reaction temperature, pressure, etc. of the alkylation reaction in the fixed bed reactor and the tank reactor may be the same or different, and preferably, the alkylation reaction conditions in both the fixed bed reactor and the tank reactor satisfy the above-mentioned preferred ranges.
The present invention will be described in detail by examples.
Unless otherwise indicated, all starting materials used were from commercial sources.
The analysis of the product composition was performed using a gas chromatograph-mass spectrometer (GC-MS).
The following preparation examples are presented to illustrate the preparation of the catalysts of the present invention.
Preparation example 1 impregnation method for preparing catalyst
1.09 g palladium nitrate solution (Pd mass fraction 18.36%) and 4.27 g magnesium nitrate hexahydrate were dissolved in 16.91 g water. Then the metal mixed solution is dripped into 20g of Al 2 O 3 Carrier (spherical, specific surface area 120 m) 2 In/g), stirring was carried out for 30 min, and then allowed to stand at room temperature for 12. 12h. The resulting catalyst was dried at 120℃for 12h and then calcined at 550℃for 4h. Tabletting the obtained catalyst powder, and sieving to obtain30-40 mesh. The resulting catalyst was designated as catalyst Hywin-2023-1#.
The content of palladium is 0.91wt%, the content of magnesium oxide is 3.11wt%, and Al is based on the total mass of the catalyst 2 O 3 The content of carrier was 95.98wt%.
Preparation example 2 precipitation method for preparing catalyst
20g of nickel nitrate hexahydrate and 5.2. 5.2 g of manganese nitrate aqueous solution (concentration 50. 50 wt%) were dissolved in 100 mL of water and kept at a constant temperature of 60℃and then co-current with 1mol/L aqueous ammonia solution, the pH was controlled to 7.0, and stirred for 30 minutes. 40wt% ammonium silica sol (available from Qingdao sea-yang chemical Co., ltd.) of 40 g was then added with stirring, followed by heating to 70℃and aging with stirring 2h, and washing by filtration 3 times. The resulting filtrate was dried at 120℃for 2 hours, followed by calcination at 450℃for 4 hours. The obtained catalyst powder is pressed into tablets and then sieved to 30-40 meshes. The resulting catalyst was designated as catalyst Hywin-2023-2#.
Based on the total mass of the catalyst, the content of nickel is 18.24wt%, the content of manganese oxide is 4.75wt%, and SiO 2 The content of (2) was 77.01% by weight.
PREPARATION EXAMPLE 3 Sol-gel Process
Firstly, weighing 10.73 g zirconium nitrate pentahydrate and 13.25 g cobalt nitrate hexahydrate, placing in a beaker, adding 50 mL deionized water, uniformly mixing, adding 16.75 g citric acid, fully mixing, placing in a 500 mL rotary evaporation bottle, performing rotary evaporation at 80 ℃, drying 12h in a 110 ℃ drying oven after the solution is gelatinous, roasting 4h in a muffle furnace at 500 ℃ after the drying is finished, and obtaining Co-ZrO 2 。
Dissolving 0.094g of potassium hydroxide in 3.29 g of g water, and adding the Co-ZrO obtained in the above step 2 The catalyst was subjected to an equal volume impregnation and then dried in rotary vacuum at 90℃for 3 hours, followed by calcination at 500℃for 4h. The obtained catalyst powder is pressed into tablets and then sieved to 30-40 meshes. The resulting catalyst was designated as catalyst Hywin-2023-3#.
Based on the total mass of the catalyst, the content of Co is 38.41wt%, the content of auxiliary agent potassium oxide is 1.05wt%, and ZrO 2 The content of (2) was 60.54% by weight.
Preparation example 4
Zirconium nitrate pentahydrate 5.0. 5.0 g was dissolved in 100. 100 mL water, and then 40wt% ammonium type silica sol (40% of Qingdao sea-yang chemical Co., ltd.) of 20. 20g was added and stirred uniformly. Then the temperature was raised to 70℃and then the mixture was allowed to flow in parallel with 1mol/L aqueous ammonia solution, the pH was controlled to 7.5, and the mixture was stirred for 30 minutes. 13.25 g ferric nitrate hexahydrate and 1.80 g cerium nitrate hexahydrate are dissolved in 100 mL water, then the mixed solution is dripped under stirring, then ammonia water is added to the pH=7.5, aging is 2h, and filtering and washing are carried out for 3 times. The resulting filtrate was dried at 120℃for 6 hours, followed by calcination at 500℃for 4 hours. The obtained catalyst powder is pressed into tablets and then sieved to 30-40 meshes. The resulting catalyst was designated as catalyst Hywin-2023-4#.
Based on the total mass of the catalyst, the content of Fe is 19.14wt%, the content of the auxiliary agent cerium oxide is 4.56wt%, and ZrO 2 /SiO 2 The content of the carrier was 76.3wt%, zrO in the carrier 2 /SiO 2 The mass ratio of (2) is 1.8:8.
preparation example 5
The procedure of preparation 1 was followed except that magnesium nitrate hexahydrate was not added. The resulting catalyst was designated Hywin-2023-5#.
The content of palladium is 0.95wt% based on the total mass of the catalyst, al 2 O 3 The content of the carrier was 99.05% wt%.
The following examples illustrate the preparation of N-alkyl carbazole in the present invention
Example 1
Selecting triethylamine as an alkylating reagent, and carrying out N-alkylation reaction with carbazole to prepare N-ethylcarbazole, wherein the molar ratio of the triethylamine to the carbazole is 7:1.
10mL of Hywin-2022-1# catalyst was charged into a fixed bed reactor, activated with a mixture of hydrogen and nitrogen (hydrogen content: 10 vol%) at 450℃for 2h before use, and then the prepared raw material was fed from the upper part of the reactor by a metering pump, with a liquid hourly space velocity of 0.7 h -1 The reaction temperature was set at 280℃and the reaction pressure was set at 6MPa.
After reaction 2h, a sample was taken out of the gas-liquid separator after condensing to 60 ℃ from the bottom of the fixed bed, and after dissolving with N-methylpyrrolidone (NMP), gas chromatography-combined analysis was performed, and the GC-MS diagram is shown in fig. 1, indicating that the target product N-ethylcarbazole was obtained. According to the analysis of the area normalization method, the carbazole conversion rate is 65.15 mol% and the N-ethyl carbazole selectivity is 99.51mol% calculated by carbazole.
Example 2
N-propylamine is selected as an alkylating reagent, and N-alkylation reaction is carried out on the N-propylamine and carbazole to prepare N-propylcarbazole, wherein the molar ratio of N-propylamine to carbazole is 20:1.
10mL of Hywin-2022-2# catalyst was charged into a fixed bed reactor, activated with a mixture of hydrogen and nitrogen (hydrogen content: 20 vol%) at 500℃for 3 hours before use, and then the prepared raw material was fed from the upper portion of the reactor by a metering pump, and the liquid hourly space velocity was 0.5. 0.5 h -1 The reaction temperature was set at 250℃and the reaction pressure was set at 5 MPa.
After 2 hours of reaction, the sample was taken out from the gas-liquid separator after condensing to 60 ℃ from the bottom of the fixed bed, and was dissolved with N-methylpyrrolidone (NMP) and analyzed by gas chromatography. According to the analysis of the area normalization method, the carbazole conversion rate is 61.37mol% and the N-ethyl carbazole selectivity is 98.41mol% calculated by carbazole.
Example 3
N-butylamine is selected as an alkylating reagent, and N-alkylation reaction is carried out on the N-butylamine and carbazole to prepare N-butylcarbazole, wherein the molar ratio of N-butylamine to carbazole is 25:1.
10mL of Hywin-2022-3# catalyst was charged into a fixed bed reactor, activated with a mixture of hydrogen and nitrogen (hydrogen content: 30 vol%) at 300℃for 4 hours before use, and then the prepared raw material was fed from the upper portion of the reactor by a metering pump, and the liquid hourly space velocity was 0.7. 0.7 h -1 The reaction temperature was set at 220℃and the reaction pressure was set at 4 MPa.
After 2 hours of reaction, the sample was taken out from the gas-liquid separator after condensing to 60 ℃ from the bottom of the fixed bed, and was dissolved with N-methylpyrrolidone (NMP) and analyzed by gas chromatography. According to the analysis of the area normalization method, the carbazole conversion rate is 52.41 mol% and the N-butylcarbazole selectivity is 99.10 mol% calculated by carbazole.
Example 4
N-pentylamine is selected as an alkylating reagent, and N-alkylation reaction is carried out on the N-pentylcarbazole and carbazole to prepare N-pentylcarbazole, wherein the molar ratio of N-pentylamine to carbazole is 18:1.
10mL of Hywin-2022-4# catalyst was charged into a fixed bed reactor, activated with a mixture of hydrogen and nitrogen (hydrogen content: 50 vol%) at 600℃for 5 hours before use, and then the prepared raw material was fed from the upper portion of the reactor by a metering pump, and the liquid hourly space velocity was 0.9h -1 The reaction temperature was set at 260℃and the reaction pressure was set at 5 MPa.
After 2 hours of reaction, the sample was taken out from the gas-liquid separator after condensing to 60 ℃ from the bottom of the fixed bed, and was dissolved with N-methylpyrrolidone (NMP) and analyzed by gas chromatography. According to the analysis of the area normalization method, the carbazole conversion rate is 63.41 mol% and the N-butylcarbazole selectivity is 99.34 mol% calculated by carbazole.
Example 5
Selecting diethylamine as an alkylating reagent, and carrying out N-alkylation reaction with carbazole to prepare N-ethylcarbazole, wherein the molar ratio of diethylamine to carbazole is 10:1, the catalyst accounts for 10% of the mass of carbazole.
The catalyst Hywin-2022-1# is added in H 2 /N 2 Reduction of 4h at 500 ℃ in a mixed gas stream followed by 1%O 2 /N 2 And passivation 5h. The obtained catalyst powder is pressed into tablets and then sieved to 30-40 meshes. Then 0.418g of catalyst is put into a 100 mL kettle reactor, activated for 2 hours in the hydrogen atmosphere at 250 ℃, then 4.175 g carbazole and 18.26 g diethylamine are added into the 100 mL kettle reactor, nitrogen is replaced for three times, the reaction temperature is set to 280 ℃, the reaction pressure is self-generated to 6.5MPa, and the reaction is carried out for 12 hours. After the reaction, the temperature is lowered, a sample is taken out, dissolved by N-methyl pyrrolidone (NMP) and subjected to gas chromatography. According to the analysis of the area normalization method, the carbazole conversion rate is 68.41mol% and the N-ethyl carbazole selectivity is 99.21mol% calculated by carbazole.
Example 6
The procedure of example 1 was followed except that catalyst Hywin-2022-5# was used instead of catalyst Hywin-2022-1#.
After 2 hours of reaction, the sample was taken out from the gas-liquid separator after condensing to 60 ℃ from the bottom of the fixed bed, and was dissolved with N-methylpyrrolidone (NMP) and analyzed by gas chromatography. According to the analysis of the area normalization method, the carbazole conversion rate is 38.12 mol% and the N-ethyl carbazole selectivity is 98.41mol% calculated by carbazole.
Example 7
The procedure of example 1 was followed except that the reaction temperature was 150 ℃.
After 2 hours of reaction, the sample was taken out from the gas-liquid separator after condensing to 60 ℃ from the bottom of the fixed bed, and was dissolved with N-methylpyrrolidone (NMP) and analyzed by gas chromatography. According to the analysis of the area normalization method, the carbazole conversion rate is 25.41 mol% and the N-ethyl carbazole selectivity is 97.15mol% calculated by carbazole.
Comparative example 1
Selecting bromoethane as an alkylating reagent, and carrying out N-alkylation reaction with carbazole to prepare N-ethylcarbazole, wherein the molar ratio of bromoethane to carbazole is 5:1, the catalyst accounts for 10% of the mass ratio of carbazole, and DMF is used as a solvent.
The catalyst Hywin-2022-2# is added in H 2 /N 2 Reduction of 4h at 500 ℃ in a mixed gas stream followed by 1%O 2 /N 2 And passivation 5h. The obtained catalyst powder is pressed into tablets and then sieved to 30-40 meshes. Then 0.418g of catalyst is put into a 100 mL kettle reactor, activated and treated for 2 hours in the hydrogen atmosphere at 250 ℃, then 4.175 g carbazole, 28mL DMF and 13.60 g bromoethane are added into the 100 mL kettle reactor for nitrogen replacement for three times, the reaction temperature is set at 80 ℃, the reaction pressure is self-generated to 3.01MPa, and the reaction is carried out for 12 hours. After the reaction, the temperature is lowered, a sample is taken out, dissolved by N-methyl pyrrolidone (NMP) and subjected to gas chromatography. According to the analysis of the area normalization method, the carbazole conversion rate is 2.54mol% and the N-ethyl carbazole selectivity is 52.12 mol% calculated by carbazole.
As can be seen from the above examples and comparative examples, the preparation method provided by the invention uses alkylamine as a carbazole alkylating agent, adopts a heterogeneous catalysis process, efficiently catalyzes a transalkylation process between alkylamine and carbazole by using a supported catalyst containing active metal components of VIII-group and IB-group metal elements, has technical versatility, and can produce various N-alkyl carbazole. And the selectivity of the product is higher, the selectivity of the product is about 99mol percent, and the product accords with the economy of green genes.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (9)

1. A method for preparing an N-alkyl carbazole, the method comprising: contacting carbazole with an alkylating agent in the presence of a catalyst under alkylation reaction conditions;
wherein the alkylating agent is an alkylamine; the structural general formula of the alkylating reagent is expressed as follows: r is R n NH 3-n Wherein n is an integer from 1 to 3 and R is C 1 -C 5 Straight or branched alkyl of (a);
the catalyst comprises a carrier, and an active metal component and an optional auxiliary component which are supported on the carrier, wherein the auxiliary component is selected from at least one of Ce, mg, zr, mn, K and Cs;
the active metal component is selected from at least one of Ni, fe, co and Cu, the content of the active metal component is 15-60wt% based on the total amount of the catalyst, the content of the auxiliary component is 0-10wt% based on oxide, and the content of the carrier is 30-85wt%; or alternatively, the first and second heat exchangers may be,
the active metal component is at least one of Ir, pt and Pd, the content of the active metal component is 0.1-5wt% based on the total amount of the catalyst, the content of the auxiliary component is 0-10wt% based on oxide, and the content of the carrier is 85-99.9wt%.
2. The production method according to claim 1, wherein R is at least one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl and isopentyl.
3. The process of claim 1, wherein the molar ratio of alkylating agent to carbazole is from 2 to 25:1.
4. the process according to claim 3, wherein the molar ratio of alkylating agent to carbazole is from 6 to 20:1.
5. the preparation method according to claim 1, wherein the carrier is at least one of activated carbon, an oxide carrier, and a molecular sieve.
6. The preparation method according to claim 5, wherein the oxide support is selected from a one-component oxide support and/or a two-component oxide support;
the one-component oxide support is selected from Al 2 O 3 、CeO 2 、La 2 O 3 、MgO、SiO 2 、ZrO 2 、TiO 2 And ZnO; the two-component oxide support is selected from ZrO 2 -Al 2 O 3 、MgO-ZrO 2 、ZnO-ZrO 2 、CeO 2 -ZrO 2 、ZrO 2 -SiO 2 And SiO 2 -Al 2 O 3 At least one of them.
7. The process of claim 1, wherein the process is carried out in a fixed bed reactor, the alkylation reaction conditions comprising: the reaction temperature is 160-350 ℃, the reaction pressure is 2-12MPa, and the total volume liquid hourly space velocity of the raw materials is 0.1-1.8h -1 。
8. The process of claim 1, wherein the process is carried out in a tank reactor, and the alkylation reaction conditions include: the reaction temperature is 160-350 ℃, and the reaction pressure is 2-12MPa; the catalyst is used in an amount of 1-10wt% based on the mass of carbazole, and the reaction time is 6-24h.
9. The production method according to claim 1, wherein the production method further comprises: before the contact, the catalyst is subjected to an activation treatment;
the activation treatment is carried out under the atmosphere containing hydrogen, the temperature of the activation treatment is 200-600 ℃, and the activation time is 0.5-6h.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3041349A (en) * 1959-11-09 1962-06-26 Martin Marietta Corp Synthesis of carbazoles
CN102115457A (en) * 2011-03-05 2011-07-06 太原理工大学 Preparation method of N-ethylcarbazole
CN107488140A (en) * 2017-10-10 2017-12-19 厦门大学 A kind of synthetic method of N ethyl carbazoles
CN108794381A (en) * 2018-05-08 2018-11-13 中国科学院青岛生物能源与过程研究所 A method of preparing N- vinyl carbazoles
CN111170997A (en) * 2019-12-31 2020-05-19 广州医科大学 Carbazole compound and preparation method and application thereof
CN114276334A (en) * 2022-01-11 2022-04-05 内蒙古民族大学 Carbazole alkylated aromatic heterocyclic derivative and preparation method thereof
CN116425638A (en) * 2023-06-13 2023-07-14 北京海望氢能科技有限公司 Preparation method of N-alkyl carbazole

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3041349A (en) * 1959-11-09 1962-06-26 Martin Marietta Corp Synthesis of carbazoles
CN102115457A (en) * 2011-03-05 2011-07-06 太原理工大学 Preparation method of N-ethylcarbazole
CN107488140A (en) * 2017-10-10 2017-12-19 厦门大学 A kind of synthetic method of N ethyl carbazoles
CN108794381A (en) * 2018-05-08 2018-11-13 中国科学院青岛生物能源与过程研究所 A method of preparing N- vinyl carbazoles
CN111170997A (en) * 2019-12-31 2020-05-19 广州医科大学 Carbazole compound and preparation method and application thereof
CN114276334A (en) * 2022-01-11 2022-04-05 内蒙古民族大学 Carbazole alkylated aromatic heterocyclic derivative and preparation method thereof
CN116425638A (en) * 2023-06-13 2023-07-14 北京海望氢能科技有限公司 Preparation method of N-alkyl carbazole

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