阅读说明：本技术 一种制备1,2-丁二胺的方法、装置和催化剂 (Method, device and catalyst for preparing 1, 2-butanediamine ) 是由 王利国 徐爽 李会泉 曹妍 贺鹏 陈家强 郑征 王雪 于 2020-06-23 设计创作，主要内容包括：本发明提供一种制备1,2-丁二胺的方法及其装置和催化剂,所述方法采用1,2-环氧丁烷和氨源进行催化胺化反应,在较温和的反应条件下实现1,2-丁二胺的生产,收率高,操作简单,原料低毒,无污染,采用固定床反应器易于大规模连续生产,有良好工业应用前景；所述催化剂为负载型多相催化剂,催化性能高,其中1,2-丁二胺的选择性高。(The invention provides a method for preparing 1, 2-butanediamine and apparatus and catalyst thereof, said method adopts 1, 2-epoxybutane and ammonia source to carry on the catalytic amination reaction, realize the production of 1, 2-butanediamine under the milder reaction condition, the yield is high, easy to operate, the raw materials are low-toxic, pollution-free, adopt the fixed bed reactor to be apt to produce continuously on a large scale, there are good industrial application prospects; the catalyst is a supported heterogeneous catalyst, and has high catalytic performance, wherein the selectivity of the 1, 2-butanediamine is high.)

1. A process for preparing 1, 2-butanediamine, the process comprising: and (2) carrying out catalytic amination reaction on the ammonia source and the 1, 2-butylene oxide under the action of a catalyst to obtain the 1, 2-butylene diamine.

2. The method according to claim 1, wherein the catalyst comprises a carrier and an active component and an auxiliary agent supported on the carrier;

preferably, the active component comprises Ni and/or Co, preferably Ni and Co;

preferably, the auxiliary agent comprises a metal or an oxide of the metal;

preferably, the metal simple substance is selected from any one or a combination of at least two of Cu, Zn, Fe, Nb, Mo, Ta, W, La, Ce or Nd;

preferably, the carrier comprises SiO₂、Al₂O₃、ZrO₂Any one or the combination of at least two of kaolin, bentonite, montmorillonite, ZSM-5, X-type zeolite, Y-type zeolite, B-type zeolite or mordenite, and the combination of at least two is preferred;

preferably, the mass of the active component accounts for 5-40% of the total mass of the catalyst;

preferably, the mass of the auxiliary agent accounts for 0.5-10% of the total mass of the catalyst;

preferably, the particle size of the catalyst is 0.1-15 mm.

3. The method according to claim 1 or 2, wherein the ammonia source comprises ammonia water or liquid ammonia, preferably liquid ammonia;

preferably, the molar ratio of the liquid ammonia to the 1, 2-butylene oxide is (1-30): 1, preferably (2-20): 1;

preferably, the pressure of the catalytic amination reaction is 0.1-20 MPa, preferably 0.1-15 MPa;

preferably, the temperature of the catalytic amination reaction is 50-270 ℃, and preferably 70-250 ℃;

preferably, the weight hourly space velocity of the 1, 2-epoxybutane is 0.1-6 h^-1Preferably 0.3 to 3 hours^-1。

4. A method according to any one of claims 1 to 3, characterized in that the method comprises: carrying out catalytic amination reaction on an ammonia source and 1, 2-butylene oxide under the action of protective gas and a catalyst to obtain 1, 2-butylene diamine;

preferably, the protective gas is hydrogen;

preferably, the protective gas accounts for 1-15% of the mole fraction of the reaction materials, and preferably 1-10%;

preferably, the reaction mass comprises a protective gas, 1, 2-butylene oxide and a source of ammonia.

5. A method according to any one of claims 1 to 4, characterized in that the method comprises the steps of:

(1) preheating and mixing an ammonia source and 1, 2-butylene oxide in protective gas to obtain a preheated reaction raw material;

(2) and (2) carrying out catalytic amination on the preheated reaction raw materials in the step (1) under the action of a catalyst to obtain reaction products, and carrying out gas-liquid separation on the reaction products after condensation to obtain the 1, 2-butanediamine.

6. The method according to claim 5, wherein the temperature of the preheating in the step (1) is 65-300 ℃;

preferably, the preheating is carried out in a preheater;

preferably, the catalytic amination reaction in step (2) is carried out in a fixed bed reactor;

preferably, the catalyst is subjected to catalytic amination reaction after hydrogenation activation;

preferably, the temperature of the hydrogenation activation is 400-500 ℃;

preferably, the volume space velocity of hydrogen in the hydrogenation activation process is 200-500 h^-1；

Preferably, the treatment time of the hydrogenation activation is 2-5 h;

preferably, the condensation temperature is-20 to 10 ℃.

7. A method according to any one of claims 1 to 6, characterized in that the method comprises the steps of:

(1) after the catalyst is subjected to hydrogenation activation at 400-500 ℃ for 2-5 h, the volume space velocity of hydrogen in the hydrogenation activation process is 200-500 h^-1；

Preheating liquid ammonia and 1, 2-butylene oxide in protective gas to 65-300 ℃ for preheating and mixing to obtain a preheated reaction raw material;

wherein the molar ratio of the liquid ammonia to the 1, 2-butylene oxide is (1-30): 1, and the protective gas accounts for 1-15% of the molar fraction of the reaction materials;

(2) carrying out catalytic amination reaction on the preheated reaction raw material under the action of a catalyst at 50-270 ℃ and 0.1-20 MPa to obtain a reaction product, and carrying out gas-liquid separation on the reaction product after condensation to obtain 1, 2-butanediamine;

wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 0.1-6 h^-1。

8. An apparatus for preparing 1, 2-butanediamine, wherein said apparatus is used for carrying out the process for preparing 1, 2-butanediamine according to any one of claims 1 to 7;

the device comprises a reaction unit, wherein the inlet end of the reaction unit is respectively and independently connected with a raw material conveying pipeline and a gas conveying pipeline;

preferably, the reaction unit comprises a preheater and a reactor which are connected in sequence, and the inlet end of the preheater is respectively and independently connected with the raw material conveying pipeline and the gas conveying pipeline;

preferably, the reactor is a fixed bed reactor;

preferably, the system further comprises a collection unit connected to the reaction unit;

preferably, the collection unit comprises a condenser and a gas-liquid separator connected in series;

preferably, the condenser is connected to the reactor of the reaction unit.

9. A catalyst for preparing 1, 2-butanediamine is characterized by comprising a carrier, and an active component and an auxiliary agent which are loaded on the carrier;

the active component comprises Ni and/or Co;

the auxiliary agent comprises a metal simple substance or an oxide of the metal simple substance;

the metal simple substance is selected from any one or the combination of at least two of Cu, Zn, Fe, Nb, Mo, Ta, W, La, Ce or Nd.

10. The catalyst of claim 9, wherein the support comprises SiO₂、Al₂O₃、ZrO₂Any one or the combination of at least two of kaolin, bentonite, montmorillonite, ZSM-5, X-type zeolite, Y-type zeolite, B-type zeolite or mordenite, and the combination of at least two is preferred;

preferably, the active components are preferably Ni and Co;

preferably, the mass of the active component accounts for 5-40% of the total mass of the catalyst;

preferably, the mass of the auxiliary agent accounts for 0.5-10% of the total mass of the catalyst;

preferably, the particle size of the catalyst is 0.1-15 mm.

Technical Field

The invention relates to the technical field of butanediamine, relates to the technical field of preparation of 1, 2-butanediamine, and particularly relates to a method, a device and a catalyst for preparing 1, 2-butanediamine.

Background

The organic fatty amine and the derivatives thereof are important chemical raw materials, are widely applied to a plurality of fields such as daily chemicals, petrochemical industry and the like, and occupy a very important position in national economy. The derivative can be used as raw materials of rubber and coating, chelating agents, mineral dressing agents and the like, and the demand is large.

Industrial production of lower aliphatic amines is carried out by synthetic methods, and there have been developed an amine (ammonia) decomposition method using a halogenated hydrocarbon as a raw material, a reductive amine (ammonification) method, a hydroamination method using an organic nitrile as a raw material, a direct amine (ammonification) method using an olefin as a raw material, a reduction method using a nitroaromatic compound as a raw material, and the like, and these methods have been applied to some products.

However, the butanediamine is mainly 1, 4-butanediamine at present, and the synthesis method is mainly a biological method.

CN105925629A discloses a method for synthesizing butanediamine through microbial transformation, which comprises the steps of secreting and expressing ornithine decarboxylase into a periplasmic cavity of escherichia coli by constructing an escherichia coli recombinant strain, then adding a certain concentration of substrate ornithine into fermentation liquor, and converting the ornithine into butanediamine through the ornithine decarboxylase in the periplasmic cavity, so that the problem of transportation of the butanediamine to the outside of cells is solved; however, the butane diamine synthesized by microbial transformation is 1, 4-butane diamine, and the 1, 2-butane diamine is difficult to prepare.

CN101735067A discloses a method for synthesizing 1, 4-butanediamine, which adopts 40% methylamine water solution as aminolysis reagent to prepare 1, 4-butanediamine, and compared with a biological method, the method has the advantages of simple and safe operation, higher reaction yield and low production cost, but the method cannot be migrated to the preparation process of 1, 2-butanediamine.

CN101006183A discloses a biochemical synthesis method of 1, 4-butanediamine, which is also used for preparing 1, 4-butanediamine by using a microorganism, and 1, 2-butanediamine is difficult to prepare.

In summary, the preparation of butanediamine focuses on the preparation of 1, 4-butanediamine, and reports on the synthesis of 1, 2-butanediamine are few, but bifunctional compounds in which 1, 2-butanediamine has an ortho-diamine structure are relatively active in nature and easy to react, and have better reactivity than 1, 4-butanediamine in molecular structure in some cases.

Therefore, it is necessary to develop a process for preparing 1, 2-butanediamine to make up for the gap in the existing synthesis of 1, 2-butanediamine.

Disclosure of Invention

In view of the problems in the prior art, the invention provides a method for preparing 1, 2-butanediamine, a device and a catalyst thereof, wherein the method adopts 1, 2-epoxybutane and an ammonia source to carry out catalytic amination reaction, realizes the production of the 1, 2-butanediamine under mild reaction conditions, has simple operation, adopts a fixed bed reactor to easily carry out large-scale continuous production, and has good industrial application prospect; the catalyst is a supported heterogeneous catalyst, and has high catalytic performance, wherein the selectivity of the 1, 2-butanediamine is high.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a process for the preparation of 1, 2-butanediamine, said process comprising: and (2) carrying out catalytic amination reaction on the ammonia source and the 1, 2-butylene oxide under the action of a catalyst to obtain the 1, 2-butylene diamine.

The invention provides a method for preparing 1, 2-butanediamine by catalytic amination reaction of an ammonia source and 1, 2-butylene oxide, which makes up for the defects that the prior preparation of butanediamine focuses on the preparation of 1, 4-butanediamine and is little related to the preparation of 1, 2-butanediamine, has mild reaction conditions and high selectivity and yield of 1, 2-butanediamine.

The present invention is not particularly limited in terms of the source of the 1, 2-butylene oxide, and a source of 1, 2-butylene oxide known to those skilled in the art can be used without any limitation to the number of sheets.

Preferably, the 1, 2-butylene oxide is derived from propylene oxide byproduct recovery.

The industrial production of the 1, 2-butylene oxide in the invention mainly comes from the recovery of a byproduct of propylene oxide, and the comprehensive utilization of the 1, 2-butylene oxide can improve the added value of products.

Preferably, the catalyst comprises a carrier and an active component and an auxiliary agent which are loaded on the carrier.

Preferably, the active component comprises Ni and/or Co, preferably Ni and Co.

Preferably, the auxiliary agent comprises an elemental metal or an oxide of the elemental metal.

Preferably, the metal element is selected from any one or a combination of at least two of Cu, Zn, Fe, Nb, Mo, Ta, W, La, Ce or Nd, wherein typical non-limiting combinations are Cu and Nb, Cu and La, La and Nb, Zn and Mo, and Mo and Ta.

Preferably, the carrier comprises SiO₂、Al₂O₃、ZrO₂Any one or combination of at least two of kaolin, bentonite, montmorillonite, ZSM-5, X-type zeolite, Y-type zeolite, B-type zeolite or mordenite, wherein a typical non-limiting combination is SiO₂And Al₂O₃Combination of (A) and (B), SiO₂And kaolin, Al₂O₃And kaolin, Al₂O₃And bentonite, kaolin and bentonite, ZSM-5 and Al₂O₃Combination of (b), ZSM-5 and ZrO₂Combination of (A) and (B), ZrO₂And Al₂O₃Preferably a combination of at least two thereof, more preferably ZSM-5 and Al₂O₃Combinations of (a) and (b).

Preferably, the mass of the active component is 5 to 40% of the total mass of the catalyst, for example, 5%, 10%, 15%, 20%, 25%, 30%, 35% or 40%, but not limited to the recited values, and other values not recited within the range of the values are also applicable.

Preferably, the mass of the promoter is 0.5-10% of the total mass of the catalyst, and may be, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the catalyst has a particle size of 0.1 to 15mm, and may be, for example, 0.1mm, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, 11mm, 12mm, 13mm, 14mm or 15mm, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.

The method for preparing the catalyst is not particularly limited, and any method for preparing a supported catalyst known to those skilled in the art may be used, and is not particularly limited.

Preferably, the catalyst is prepared by any one or a combination of at least two of ion exchange method, impregnation method, coprecipitation method or mixing method, wherein typical non-limiting combinations are the combination of ion exchange method and coprecipitation method, the combination of impregnation method and coprecipitation method, the combination of ion exchange method and impregnation method, and the combination of ion exchange method and mixing method.

Preferably, the ammonia source comprises ammonia water or liquid ammonia, preferably liquid ammonia.

Liquid ammonia is preferably adopted in the invention, so that the energy consumption of subsequent separation can be reduced. The method for synthesizing the novel diamine product 1, 2-butanediamine by taking the 1, 2-butylene oxide and the liquid ammonia as raw materials is a relatively green and environment-friendly path, has important significance for the industrial production of butanediamine and derivatives thereof, and has good application prospect.

The molar ratio of liquid ammonia to 1, 2-butylene oxide is preferably (1 to 30):1, and may be, for example, 1:1, 2:1, 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, 23:1, 24:1, 25:1, 26:1, 27:1, 28:1, 29:1 or 30:1, but is not limited to the recited values, and other values not recited in the range are also applicable, and preferably (2 to 20): 1.

Preferably, the pressure of the catalytic amination reaction is 0.1 to 20MPa, and may be, for example, 0.1MPa, 1MPa, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11MPa, 12MPa, 13MPa, 14MPa, 15MPa, 16MPa, 17MPa or 20MPa, but is not limited to the values listed, and other values not listed within the range of the values are also applicable, and preferably 0.1 to 15 MPa.

Preferably, the temperature of the catalytic amination reaction is 50 to 270 ℃, for example, 50 ℃, 70 ℃, 90 ℃, 110 ℃, 130 ℃, 150 ℃, 170 ℃, 190 ℃, 210 ℃, 230 ℃, 250 ℃ or 270 ℃, and is not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 70 to 250 ℃.

Preferably, the weight hourly space velocity of the 1, 2-epoxybutane is 0.1-6 h^-1For example, it may be 0.1h^-1、1h^-1、1.5h^-1、2h^-1、2.5h^-1、3h^-1、3.5h^-1、4h^-1、4.5h^-1、5h^-1、5.5h^-1Or 6h^-1However, the number is not limited to the recited number, and other non-recited numbers within the range are also applicable, and preferably 0.3 to 3 hours^-1。

Preferably, the method comprises: and (3) carrying out catalytic amination reaction on the ammonia source and the 1, 2-butylene oxide under the action of protective gas and a catalyst to obtain the 1, 2-butylene diamine.

Preferably, the protective gas is hydrogen.

Preferably, the protective gas is present in an amount of 1 to 15% by mole of the reaction mass, for example 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%, but is not limited to the recited values, and other values not recited within this range are equally applicable, preferably 1 to 10%.

Preferably, the reaction mass comprises a protective gas, 1, 2-butylene oxide and a source of ammonia.

As a preferred technical scheme of the invention, the method comprises the following steps:

(1) preheating and mixing an ammonia source and 1, 2-butylene oxide in protective gas to obtain a preheated reaction raw material;

(2) and (2) carrying out catalytic amination on the preheated reaction raw materials in the step (1) under the action of a catalyst to obtain reaction products, and carrying out gas-liquid separation on the reaction products after condensation to obtain the 1, 2-butanediamine.

Preferably, the temperature of the preheating in the step (1) is 65 to 300 ℃, and may be, for example, 65 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃ or 300 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the preheating is carried out in a preheater.

Preferably, the catalytic amination reaction in step (2) is carried out in a fixed bed reactor.

Preferably, the catalyst is subjected to hydrogenation activation and then to catalytic amination reaction.

Preferably, the temperature of the hydrogenation activation is 400 to 500 ℃, for example, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃ or 500 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the volume space velocity of hydrogen in the hydrogenation activation process is 200-500 h^-1For example, it may be 200h^-1、250h^-1、300h^-1、350h^-1、400h^-1、450h^-1Or 500h^-1However, the numerical values recited are not intended to be limiting, and other numerical values not recited within the numerical range may be equally applicable.

Preferably, the treatment time of the hydrogenation activation is 2 to 5 hours, for example, 2.0 hours, 2.5 hours, 3.0 hours, 3.5 hours, 4.0 hours, 4.5 hours or 5.0 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the condensation temperature is-20 to 10 ℃, for example, -20 ℃, -10 ℃, 0 ℃, 10 ℃ or 20 ℃, but is not limited to the recited values, and other values not recited in the range of values are also applicable.

As a preferred technical scheme of the invention, the method comprises the following steps:

(1) after the catalyst is subjected to hydrogenation activation at 400-500 ℃ for 2-5 h, the volume space velocity of hydrogen in the hydrogenation activation process is 200-500 h^-1；

Preheating liquid ammonia and 1, 2-butylene oxide in protective gas to 65-300 ℃ for preheating and mixing to obtain a preheated reaction raw material;

wherein the molar ratio of the liquid ammonia to the 1, 2-butylene oxide is (1-30): 1, and the protective gas accounts for 1-15% of the molar fraction of the reaction materials;

(2) carrying out catalytic amination reaction on the preheated reaction raw material under the action of a catalyst at 50-270 ℃ and 0.1-20 MPa to obtain a reaction product, and carrying out gas-liquid separation on the reaction product after condensation to obtain 1, 2-butanediamine;

wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 0.1-6 h^-1。

In a second aspect, the present invention provides an apparatus for preparing 1, 2-butanediamine, said apparatus being adapted to carry out the method for preparing 1, 2-butanediamine according to the first aspect. The device comprises a reaction unit, wherein the inlet end of the reaction unit is respectively and independently connected with a raw material conveying pipeline and a gas conveying pipeline.

The device for preparing 1, 2-butanediamine can be used for continuous production and has a high industrial application prospect.

Preferably, the reaction unit comprises a preheater and a reactor which are connected in sequence, and the inlet end of the preheater is respectively and independently connected with the raw material conveying pipeline and the gas conveying pipeline.

Preferably, the reactor is a fixed bed reactor.

Preferably, the system further comprises a collection unit connected to the reaction unit.

Preferably, the collection unit comprises a condenser and a gas-liquid separator connected in series.

Preferably, the condenser is connected to the reactor of the reaction unit.

In a third aspect, the present invention provides a catalyst for preparing 1, 2-butanediamine, comprising a carrier, and an active component and an auxiliary agent supported on the carrier; the active component comprises Ni and/or Co; the auxiliary agent comprises a metal simple substance or an oxide of the metal simple substance; the metal simple substance is selected from any one or combination of at least two of Cu, Zn, Fe, Nb, Mo, Ta, W, La, Ce or Nd, wherein typical non-limiting combinations are Cu and Nb, Cu and La, La and Nb, Zn and Mo, and Mo and Ta.

The catalyst provided by the invention comprises a carrier, and an active component and an auxiliary agent which are loaded on the carrier, has high catalytic performance, can be obtained by adopting various preparation methods, and has good application prospect.

Preferably, the carrier comprises SiO₂、Al₂O₃、ZrO₂Any one or combination of at least two of kaolin, bentonite, montmorillonite, ZSM-5, X-type zeolite, Y-type zeolite, B-type zeolite or mordenite, wherein a typical non-limiting combination is SiO₂And Al₂O₃Combination of (A) and (B), SiO₂And kaolin, Al₂O₃And kaolin, Al₂O₃And bentonite, kaolin and bentonite, ZSM-5 and Al₂O₃Combination of (b), ZSM-5 and ZrO₂Combination of (A) and (B), ZrO₂And Al₂O₃Preferably a combination of at least two thereof, more preferably ZSM-5 and Al₂O₃Combinations of (a) and (b).

Compared with other catalysts, the catalyst of the invention preferably adopts at least two carriers to prepare the catalyst, and can further improve the catalytic effect of the catalyst relatively.

Preferably, the active components are preferably Ni and Co.

The active component of the invention is preferably the combination of Ni and Co, and the catalytic effect is better.

Preferably, the mass of the active component is 5 to 40% of the total mass of the catalyst, for example, 5%, 10%, 15%, 20%, 25%, 30%, 35% or 40%, but not limited to the recited values, and other values not recited within the range of the values are also applicable.

Preferably, the mass of the promoter is 0.5-10% of the total mass of the catalyst, and may be, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the catalyst has a particle size of 0.1 to 15mm, and may be, for example, 0.1mm, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, 11mm, 12mm, 13mm, 14mm or 15mm, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.

The method for preparing the catalyst is not particularly limited, and any method for preparing a supported catalyst known to those skilled in the art may be used, and is not particularly limited.

Preferably, the catalyst is prepared by any one or a combination of at least two of ion exchange method, impregnation method, coprecipitation method or mixing method, wherein typical non-limiting combinations are the combination of ion exchange method and coprecipitation method, the combination of impregnation method and coprecipitation method, the combination of ion exchange method and impregnation method, and the combination of ion exchange method and mixing method.

Compared with the prior art, the invention has at least the following beneficial effects:

(1) the method for preparing 1, 2-butanediamine provided by the invention can realize the catalytic amination of 1, 2-butylene oxide to produce 1, 2-butanediamine under mild reaction conditions, the conversion rate of the 1, 2-butylene oxide is more than 60 wt%, the selectivity of the 1, 2-butanediamine is more than 70 wt%, the conversion rate of the 1, 2-butylene oxide is more than 88 wt%, and the selectivity of the 1, 2-butanediamine is more than 90 wt% under better conditions, and the method is simple to operate, low in raw material toxicity and free of pollution;

(2) the method for preparing the 1, 2-butanediamine adopts the fixed bed reactor, so that the 1, 2-butanediamine can be continuously produced, and the production efficiency is improved;

(3) the catalyst for preparing 1, 2-butanediamine provided by the invention is a heterogeneous catalyst, is stable and efficient, and is easy to recover; the method has good industrial prospect when being applied to the preparation process of the 1, 2-butanediamine.

Drawings

FIG. 1 is a schematic diagram of an apparatus used in a method for preparing 1, 2-butanediamine according to example 1 of the present invention.

In the figure: 1-a reactor; 2-a preheater; 201-raw material conveying pipeline; 202-gas delivery line; 3-a condenser; 301-condensing medium inlet pipe; 302-condensing medium outlet pipe; 4-a gas-liquid separator; 401-product discharge pipe; 402-backpressure regulation component.

Detailed Description

The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.

The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.

Catalyst

Catalyst I

Catalyst I: 10% Ni-5% Co-1% La/(70% Al)₂O₃+14％ZrO₂)

The preparation method of the catalyst I specifically comprises the following steps:

(1) weighing 6.9g of nickel nitrate hexahydrate, 3.5g of cobalt nitrate hexahydrate and 0.43g of lanthanum nitrate hexahydrate, and dissolving in 21.5g of water to obtain an impregnation liquid;

(2) soaking the prepared solutionThe solution was divided into 5 parts by mass and one part was impregnated with 11.7g of carrier Al₂O₃And ZrO₂(40-60 mesh, Al)₂O₃In 5 parts of ZrO₂1 part); then drying the impregnated carrier particles at 110 ℃ for 12h, and then roasting at 500 ℃ for 3 h;

(3) repeating the dipping process of the step (2), and repeating the same treatment process for 4 times by using the rest four portions of dipping solution to finally obtain the product with the composition of 10% Ni-5% Co-1% La (70% Al)₂O₃+14％ZrO₂) The supported catalyst of (1).

Catalyst II

Catalyst II: 10% Ni-5% Co-1% Cu/(64% Al)₂O₃+20％ZSM-5)

The preparation method of the catalyst II comprises the following steps:

(1) weighing 6.9g of nickel nitrate hexahydrate and 3.5g of cobalt nitrate hexahydrate, and dissolving in 16.5g of water to obtain an impregnation liquid;

(2) dividing the prepared impregnation liquid into 5 parts by mass, and impregnating 8.9g of carrier Al with one part of the impregnation liquid₂O₃Coating the powder, drying the impregnated carrier at 110 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr;

(3) repeating the impregnation process in the step (2), and repeating the same treatment process for 4 times by using the remaining 4 parts of impregnation liquid, wherein the obtained solid is marked as A;

(4) weighing 0.53g of copper nitrate trihydrate and 2.8g of ZSM-5 powder, dispersing the copper nitrate trihydrate and the ZSM-5 powder in 10g of water, reacting in a 90 ℃ water bath for 6h under the condition of stirring, and then carrying out rotary evaporation and evaporation in a 80 ℃ water bath to dryness to obtain a solid, and drying the solid at 110 ℃ for 12h to obtain a solid B;

(5) mixing the solid A and the solid B uniformly, and then granulating and screening the catalyst with 40-60 meshes for later use to obtain the catalyst with the composition of 10% Ni-5% Co-1% Cu/(64% Al)₂O₃+ 20% ZSM-5) supported catalyst

Catalyst III

Catalyst III: 10% Ni-5% Co-1% Cu/(70% Al)₂O₃+ 14% Kaolin

The preparation method of the catalyst III specifically comprises the following steps:

(1) weighing 6.9g of nickel nitrate hexahydrate, 3.5g of cobalt nitrate hexahydrate and 0.53g of copper nitrate trihydrate, and dissolving the nickel nitrate hexahydrate, the cobalt nitrate hexahydrate and the copper nitrate trihydrate into 21.5g of water to obtain a salt solution; 11.7g of carrier Al₂O₃And kaolin (powder, Al)₂O₃5 parts of kaolin, 1 part of kaolin) in 60g of water to obtain a suspension of the carrier; dissolving 6g of sodium hydroxide in 100g of water to obtain a precipitant solution;

(2) then, dripping the precipitant solution and the salt solution into the suspension containing the carrier, and controlling the pH value of the solution to be 10; then filtering and washing the mixture, and drying the filter cake at 110 ℃ for 12h to obtain a catalyst precursor;

(3) crushing and screening a catalyst precursor into particles of 40-80 meshes, then uniformly mixing the particles with 0.5 wt% of graphite, tabletting and molding, and roasting at 500 ℃ for 3 hours to obtain the catalyst precursor with the composition of 10% Ni-5% Co-1% Cu/(70% Al)₂O₃+ 14% kaolin).

Catalyst IV

And catalyst IV: 10% Ni-5% Co-1% Mo/Al₂O₃

The preparation method of the catalyst IV specifically comprises the following steps:

weighing 12.7g of nickel oxide, 7.0g of cobaltous oxide, 1.95g of molybdenum oxide and 84.0g of carrier Al₂O₃And 0.5g of graphite, uniformly mixing, sequentially granulating (40-80 meshes), tabletting and molding, and roasting at 500 ℃ for 3 hours to obtain the material with the composition of 10% of Ni, 5% of Co and 1% of Mo/Al₂O₃The supported catalyst of (1).

Catalyst V

Catalyst V: 10% Ni-5% Co-1% La/(84% Al)₂O₃)

Preparation of catalyst V except for the step (2) in which ZrO was not added₂All adopt Al₂O₃Otherwise, the rest of the preparation method is the same as the preparation method of the catalyst I.

Catalyst VI

Catalyst VI: 15% Ni-1% La/(70% Al)₂O₃+14％ZrO₂)

The preparation steps of the catalyst VI are the same as those of the preparation method of the catalyst I except that the cobalt nitrate hexahydrate is not added in the step (1) and the mass of the cobalt nitrate hexahydrate is correspondingly replaced by the mass of the nickel nitrate hexahydrate.

Catalyst VII

Catalyst VII: 20% Ni-12% Co-0.5% La/(60% Al)₂O₃+7.5％ZrO₂)

The preparation method of the catalyst VII specifically comprises the following steps:

(1) weighing 13.8g of nickel nitrate hexahydrate, 8.4g of cobalt nitrate hexahydrate and 0.22g of lanthanum nitrate hexahydrate, and dissolving in 18.0g of water to obtain an impregnation liquid;

(2) dividing the prepared impregnation liquid into 5 parts by mass, and impregnating 9.4g of carrier Al with one part of the impregnation liquid₂O₃And ZrO₂(40-60 mesh, Al)₂O₃8 portion of ZrO₂1 part); then drying the impregnated carrier particles at 110 ℃ for 12h, and then roasting at 500 ℃ for 3 h;

(3) repeating the dipping process of the step (2), repeating the same treatment process for 4 times by using the remaining four portions of dipping solution, and finally obtaining the product with the composition of 5% Ni-2% Co-0.5% La/(80% Al)₂O₃+12.5％ZrO₂) The supported catalyst of (1).

Catalyst VIII

Catalyst VIII: 2% Ni-5% Co-5% La/(80% Al)₂O₃+8％ZrO₂)

The preparation method of the catalyst VIII specifically comprises the following steps:

(1) weighing 1.4g of nickel nitrate hexahydrate, 3.5g of cobalt nitrate hexahydrate and 2.2g of lanthanum nitrate hexahydrate, and dissolving in 22.5g of water to obtain an impregnation liquid;

(2) dividing the prepared impregnation liquid into 5 parts by mass, and impregnating 12.3g of carrier Al with one part of the impregnation liquid₂O₃And ZrO₂(40-60 mesh, Al)₂O₃10 portions of ZrO₂1 part); then drying the impregnated carrier particles at 110 ℃ for 12h, and then roasting at 500 ℃ for 3 h;

(3) the dipping process of the step (2) is repeated, the same treatment process is repeated for 4 times by using the remaining four portions of dipping solution, and finally the material with the composition of 2 percent Ni-5 percent Co-5％La/(80％Al₂O₃+8％ZrO₂) The supported catalyst of (1).

The percentage content of the catalyst is mass percentage content.

Second, example

Example 1

The embodiment provides a method for preparing 1, 2-butanediamine, which specifically comprises the following steps:

(1) weighing 4.2g (about 5mL) of the catalyst I, and filling the catalyst I into a fixed bed reactor with the length of 1000mm and the inner diameter of 10.0 mm;

before the catalytic amination reaction is started, carrying out hydrogenation activation on the supported catalyst, wherein the treatment conditions of the hydrogenation activation are as follows: at normal pressure and 400 ℃ with volume space velocity of 300h^-1Reducing for 3 h;

conveying the raw materials with the molar ratio of liquid ammonia to 1, 2-butylene oxide of 10:1 to a preheater at 90 ℃ for preheating and mixing to obtain preheated reaction raw materials; wherein, hydrogen in the reaction system accounts for 3 percent of the mole fraction of the reaction materials;

(2) when the temperature in the reactor is reduced to 100 ℃, the pressure is increased to 5MPa, the preheated reaction raw materials enter the reactor to perform catalytic amination reaction under the action of a catalyst to obtain a reaction product, the reaction product enters a condenser to be condensed at the condensation temperature of-10 ℃, and then enters a gas-liquid separator to perform gas-liquid separation to obtain 1, 2-butanediamine;

wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 0.5h^-1。

The apparatus used in the method for preparing 1, 2-butanediamine provided in example 1 is shown in fig. 1, and the apparatus comprises a reaction unit, the reaction unit comprises a preheater 2 and a reactor 1 which are connected in sequence, the inlet end of the preheater 2 is independently connected with a raw material conveying pipeline 201 and a gas conveying pipeline 202, the raw material conveying pipeline 201 conveys liquid ammonia and 1, 2-butylene oxide into the preheater 2, and the gas conveying pipeline 202 conveys protective gas into the preheater 2.

The device still includes the collection unit who links to each other with the reaction unit, the collection unit includes condenser 3 and vapour and liquid separator 4 that connect gradually along the product discharge direction, reactor 1 is connected to condenser 3, be provided with condensing medium import pipe 301 and condensing medium outlet pipe 302 on the condenser 3, be provided with product discharging pipe 401 and backpressure regulating assembly 402 on the vapour and liquid separator 4.

Example 2

The embodiment provides a method for preparing 1, 2-butanediamine, which specifically comprises the following steps:

(1) weighing 4.2g (about 5mL) of the catalyst I, and filling the catalyst I into a fixed bed reactor with the length of 1000mm and the inner diameter of 10.0 mm;

before the catalytic amination reaction is started, carrying out hydrogenation activation on the supported catalyst, wherein the treatment conditions of the hydrogenation activation are as follows: at normal pressure and 400 ℃ with volume space velocity of 300h^-1Reducing for 3 h;

conveying the raw materials with the molar ratio of liquid ammonia to 1, 2-butylene oxide of 10:1 to a preheater at 90 ℃ for preheating and mixing to obtain preheated reaction raw materials; wherein, hydrogen in the reaction system accounts for 3 percent of the mole fraction of the reaction materials;

(2) when the temperature in the reactor is reduced to 100 ℃, the pressure is increased to 8MPa, the preheated reaction raw materials enter the reactor to perform catalytic amination reaction under the action of a catalyst to obtain a reaction product, the reaction product enters a condenser to be condensed at the condensation temperature of-10 ℃, and then enters a gas-liquid separator to perform gas-liquid separation to obtain 1, 2-butanediamine;

wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 0.5h^-1。

Example 3

The embodiment provides a method for preparing butanediamine, which specifically comprises the following steps:

(1) weighing 4.2g (about 5mL) of the catalyst I, and filling the catalyst I into a fixed bed reactor with the length of 1000mm and the inner diameter of 10.0 mm;

before the catalytic amination reaction is started, carrying out hydrogenation activation on the supported catalyst, wherein the treatment conditions of the hydrogenation activation are as follows: at normal pressure and 400 ℃ with volume space velocity of 300h^-1Reducing for 3 h;

conveying the raw materials with the molar ratio of liquid ammonia to 1, 2-butylene oxide of 10:1 to a preheater at 90 ℃ for preheating and mixing to obtain preheated reaction raw materials; wherein, hydrogen in the reaction system accounts for 3 percent of the mole fraction of the reaction materials;

(2) when the temperature in the reactor is reduced to 150 ℃, the pressure is increased to 8MPa, the preheated reaction raw materials enter the reactor to perform catalytic amination reaction under the action of a catalyst to obtain a reaction product, the reaction product enters a condenser to be condensed at the condensation temperature of-10 ℃, and then enters a gas-liquid separator to perform gas-liquid separation to obtain 1, 2-butanediamine;

wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 0.5h^-1。

Example 4

The embodiment provides a method for preparing 1, 2-butanediamine, which specifically comprises the following steps:

(1) weighing 4.2g (about 5mL) of the catalyst I, and filling the catalyst I into a fixed bed reactor with the length of 1000mm and the inner diameter of 10.0 mm;

before the catalytic amination reaction is started, carrying out hydrogenation activation on the supported catalyst, wherein the treatment conditions of the hydrogenation activation are as follows: at normal pressure and 400 ℃ with volume space velocity of 300h^-1Reducing for 3 h;

conveying the raw materials with the molar ratio of liquid ammonia to 1, 2-butylene oxide of 10:1 to a preheater at 90 ℃ for preheating and mixing to obtain preheated reaction raw materials; wherein, hydrogen in the reaction system accounts for 3 percent of the mole fraction of the reaction materials;

(2) when the temperature in the reactor is reduced to 100 ℃, the pressure is increased to 5MPa, the preheated reaction raw materials enter the reactor to perform catalytic amination reaction under the action of a catalyst to obtain a reaction product, the reaction product enters a condenser to be condensed at the condensation temperature of-10 ℃, and then enters a gas-liquid separator to perform gas-liquid separation to obtain 1, 2-butanediamine;

wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 1h^-1。

Example 5

The embodiment provides a method for preparing 1, 2-butanediamine, which specifically comprises the following steps:

(1) weighing 4.2g (about 5mL) of the catalyst I, and filling the catalyst I into a fixed bed reactor with the length of 1000mm and the inner diameter of 10.0 mm;

before the catalytic amination reaction is started, carrying out hydrogenation activation on the supported catalyst, wherein the treatment conditions of the hydrogenation activation are as follows: at normal pressure and 400 ℃ with volume space velocity of 300h^-1Reducing for 3 h;

conveying the raw materials with the molar ratio of the liquid ammonia to the 1, 2-butylene oxide of 15:1 to a preheater of 90 ℃ for preheating and mixing to obtain preheated reaction raw materials; wherein, hydrogen in the reaction system accounts for 3 percent of the mole fraction of the reaction materials;

(2) when the temperature in the reactor is reduced to 100 ℃, the pressure is increased to 5MPa, the preheated reaction raw materials enter the reactor to perform catalytic amination reaction under the action of a catalyst to obtain a reaction product, the reaction product enters a condenser to be condensed at the condensation temperature of-10 ℃, and then enters a gas-liquid separator to perform gas-liquid separation to obtain 1, 2-butanediamine;

wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 0.5h^-1。

Example 6

The embodiment provides a method for preparing 1, 2-butanediamine, which specifically comprises the following steps:

(1) weighing 4.2g (about 5mL) of the catalyst IV, and filling the catalyst IV into a fixed bed reactor with the length of 1000mm and the inner diameter of 10.0 mm;

before the catalytic amination reaction is started, carrying out hydrogenation activation on the supported catalyst, wherein the treatment conditions of the hydrogenation activation are as follows: at normal pressure and 400 ℃ with volume space velocity of 300h^-1Reducing for 3 h;

conveying the raw materials with the molar ratio of liquid ammonia to 1, 2-butylene oxide of 10:1 to a preheater at 90 ℃ for preheating and mixing to obtain preheated reaction raw materials; wherein, hydrogen in the reaction system accounts for 5 percent of the mole fraction of the reaction materials;

(2) when the temperature in the reactor is reduced to 100 ℃, the pressure is increased to 5MPa, the preheated reaction raw materials enter the reactor to perform catalytic amination reaction under the action of a catalyst to obtain a reaction product, the reaction product enters a condenser to be condensed at the condensation temperature of-20 ℃, and then enters a gas-liquid separator to perform gas-liquid separation to obtain 1, 2-butanediamine;

wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 0.5h^-1。

Example 7

The embodiment provides a method for preparing 1, 2-butanediamine, which specifically comprises the following steps:

(1) weighing 6.3g (about 8mL) of the catalyst II, and filling the catalyst II into a fixed bed reactor with the length of 1200mm and the inner diameter of 15.0 mm;

before the catalytic amination reaction is started, carrying out hydrogenation activation on the supported catalyst, wherein the treatment conditions of the hydrogenation activation are as follows: at normal pressure and 500 ℃ and volume space velocity of 500h^-1Reducing for 5 h;

conveying the raw materials with the molar ratio of liquid ammonia to 1, 2-butylene oxide of 30:1 to a preheater of 65 ℃ for preheating and mixing to obtain preheated reaction raw materials; wherein, hydrogen in the reaction system accounts for 10 percent of the mole fraction of the reaction materials;

(2) when the temperature in the reactor is reduced to 50 ℃, the pressure is increased to 10MPa, the preheated reaction raw materials enter the reactor to perform catalytic amination reaction under the action of a catalyst to obtain a reaction product, the reaction product enters a condenser to be condensed at the condensation temperature of-10 ℃, and then enters a gas-liquid separator to perform gas-liquid separation to obtain 1, 2-butanediamine;

wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 0.1h^-1。

Example 8

The embodiment provides a method for preparing 1, 2-butanediamine, which specifically comprises the following steps:

(1) weighing 6.3g (about 8mL) of catalyst III, and filling the catalyst III into a fixed bed reactor with the length of 1200mm and the inner diameter of 15.0 mm;

before the catalytic amination reaction is started, carrying out hydrogenation activation on the supported catalyst, wherein the treatment conditions of the hydrogenation activation are as follows: at 102.5kPa, at 450 ℃ and a volume space velocity of 200h^-1Reducing for 2 hours;

conveying the raw materials with the molar ratio of liquid ammonia to 1, 2-butylene oxide of 5:1 to a preheater at 270 ℃ for preheating and mixing to obtain preheated reaction raw materials; wherein, hydrogen in the reaction system accounts for 1 percent of the mole fraction of the reaction materials;

(2) when the temperature in the reactor is 270 ℃, boosting the pressure to 1MPa, feeding the preheated reaction raw materials into the reactor to perform catalytic amination reaction under the action of a catalyst to obtain a reaction product, feeding the reaction product into a condenser to perform condensation, wherein the condensation temperature is-10 ℃, and feeding the condensation product into a gas-liquid separator to perform gas-liquid separation to obtain 1, 2-butanediamine;

wherein the weight hourly space velocity of the 1, 2-epoxybutane in the catalytic amination reaction process is 6h^-1。

Example 9

This example provides a process for preparing 1, 2-butanediamine, which is identical to example 1, except that the liquid ammonia in step (1) is replaced with aqueous ammonia, and the molar ratio of ammonia to 1, 2-epoxybutane in the aqueous ammonia is maintained at 10: 1.

Examples 10 to 13

Examples 10-13 provide methods for preparing 1, 2-butanediamine, which are the same as in example 1 except that catalysts v through viii were used, respectively.

Third, test and results

The 1, 2-butanediamine obtained by gas-liquid separation in the above example was stabilized for 48 hours, and then sampled and tested, the mass content of 1, 2-butanediamine in the product was determined by gas chromatography, and the conversion of 1, 2-butylene oxide and the selectivity of 1, 2-butanediamine were calculated from the total sample amount, and the results are shown in table 1.

From table 1, the following points can be seen:

(1) it can be seen from the comprehensive examples 1 to 12 that, in the method for preparing 1, 2-butanediamine provided in examples 1 to 12, 1, 2-butylene oxide is used as a raw material to perform a catalytic amination reaction with an ammonia source, and the conversion rate of 1, 2-butylene oxide is above 60 wt%, the selectivity of 1, 2-butanediamine is above 70 wt%, under a better condition, the conversion rate of 1, 2-butylene oxide is above 88 wt%, and the selectivity of 1, 2-butanediamine is above 90 wt%, so that the reaction effect is good, and the method has a good industrial application prospect;

(2) by combining example 1 and example 9, it can be seen that, in example 1, liquid ammonia is used as a reaction raw material, compared with ammonia water as a reaction raw material in example 9, the conversion rate of 1, 2-butylene oxide is 90 wt%, the selectivity of 1, 2-butylene diamine is 95 wt% in example 1, and the conversion rate of 1, 2-butylene oxide is only 65 wt% and the selectivity of 1, 2-butylene diamine is 78 wt% in example 9, thereby indicating that liquid ammonia is preferably used in the present invention, which not only can reduce the emission of subsequent waste water, but also can improve the conversion rate and selectivity of the reaction;

(3) it can be seen from the combination of example 1 and examples 10 to 11 that in example 10, only Al is used₂O₃As a support, only Ni was used as an active component in example 11, compared to 70% Al in example 1₂O₃+14％ZrO₂The combination of the two is used as a carrier, and the combination of Ni and Co is used as an active component, the selectivity and the conversion rate in the embodiment 10 and the embodiment 11 are lower than those in the embodiment, thereby showing that the invention improves the catalytic amination reaction effect by preferably using the combination of Ni and Co as the active component and using the combination of at least two of the carriers, and finally improves the conversion rate of 1, 2-butylene oxide and the selectivity of 1, 2-butylene diamine.

In conclusion, the method for preparing 1, 2-butanediamine provided by the invention takes the 1, 2-butylene oxide and the ammonia source as reaction materials, can prepare the 1, 2-butanediamine under a mild condition, makes up the vacancy that the preparation of the butanediamine is basically 1, 4-butanediamine in the existing market, and has the advantages of high yield, simple operation, low toxicity of raw materials, no pollution, conversion rate of the 1, 2-butylene oxide of more than 60 wt%, selectivity of the 1, 2-butanediamine of more than 70 wt%, and good industrial application prospect; the catalyst provided by the invention has the advantages that the active component and the auxiliary agent are loaded on the carrier, so that the catalytic efficiency and the selectivity are improved, and the catalyst has a good application prospect.

The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.