阅读说明：本技术 一种聚醚胺的制备方法 (Preparation method of polyether amine ) 是由 刘野 赵亮 王岩 于庆志 党雷 于 2019-04-17 设计创作，主要内容包括：本发明公开一种聚醚胺的制备方法,采用管式反应器,液氨和聚醚作为进料I自反应器顶部进入反应器,液氨作为进料II由反应器底部进入反应器,所述反应器内由上至下设置若干交错排列的催化剂床层,所述催化剂床层包括床板和分布在床板上的催化剂,所述床板一端与反应器壁密闭连接,另一端沿水平方向延伸向对侧的反应器壁延伸并与之保持一定距离,所述床板末端设置挡板,床板上设有若干开孔,进料I由上至下穿过催化剂床层,发生反应,进料II由下至上与进料I逆向接触,进一步与进料I中未反应的聚醚反应。该反应器和进料方式使该反应过程同时具有滴流床和催化精馏的优点,提高了反应转化率。(The invention discloses a preparation method of polyether amine, which adopts a tubular reactor, wherein liquid ammonia and polyether are used as a feed I and enter the reactor from the top of the reactor, the liquid ammonia is used as a feed II and enters the reactor from the bottom of the reactor, a plurality of catalyst bed layers which are staggered are arranged in the reactor from top to bottom, each catalyst bed layer comprises a bed plate and a catalyst distributed on the bed plate, one end of the bed plate is hermetically connected with the wall of the reactor, the other end of the bed plate extends to the opposite reactor wall along the horizontal direction and keeps a certain distance with the reactor wall, a baffle is arranged at the tail end of the bed plate, a plurality of openings are arranged on the bed plate, the feed I penetrates through the catalyst bed layers from top to bottom to perform reaction, and the feed II reversely contacts with the feed I from bottom to top and. The reactor and the feeding mode enable the reaction process to have the advantages of a trickle bed and catalytic rectification at the same time, and the reaction conversion rate is improved.)

1. The preparation method of the polyetheramine is characterized in that a tubular reactor is adopted, a plurality of catalyst bed layers which are arranged in a staggered mode are arranged in the reactor from top to bottom, each catalyst bed layer comprises a bed plate and a catalyst distributed on the bed plate, one end of each bed plate is connected with the wall of the reactor in a sealing mode, the other end of each bed plate extends to the wall of the reactor on the opposite side along the horizontal direction and keeps a certain distance with the wall of the reactor, a vertical baffle is arranged at the tail end of each bed plate, and two bed plates which are adjacent up and down are connected to the wall of the reactor; the bed plate is provided with a plurality of openings, liquid ammonia and polyether are used as a feeding material I and enter the reactor from the top of the reactor, the liquid ammonia is used as a feeding material II and enters the reactor from the bottom of the reactor, the feeding material I penetrates through the catalyst bed layer from top to bottom to react, and the feeding material II is in reverse contact with the feeding material I from bottom to top and further reacts with the unreacted polyether in the feeding material I.

2. The process of claim 1, wherein feed I is introduced into the reactor as a spray.

3. The method of claim 1, wherein the length of the bed plate in the reactor is 2/3-3/4 of the diameter of the reactor.

4. The method of claim 1, wherein the reaction conditions in the reactor are as follows: the reaction temperature is 160-200 ℃, and preferably 180-190 ℃; the reaction pressure is 3-8 MPa, preferably 5-7 MPa.

5. The process according to claim 1, wherein the molar ratio of liquid ammonia to polyether in feed I is 100: 1-200: 1, preferably 140: 1-160: 1.

6. the preparation method according to claim 1, wherein the polyether volume space velocity in the feed I is 0.2-1 h-1, preferably 0.3-0.5 h-1.

7. The method according to claim 1, wherein the polyether is polypropylene glycol.

8. The preparation method according to claim 1, wherein the volume space velocity of the feed II is 10-30 h-1, preferably 15-20 h-1.

9. The method of claim 1, wherein the catalyst is a solid super acidic resin catalyst.

10. The method according to claim 10, wherein the solid super acidic resin catalyst is prepared by the following steps:

(1) ZrOCl₂And TiCl₄Dissolving in ethanol to obtain ZrOCl₂And TiCl₄Titrating with ammonia water under stirring to remove white precipitate, filtering, washing to remove chloride ion, drying to obtain white solid powder, extruding, drying, and roastingObtaining white solid particles for later use;

(2) and (2) dipping the white solid particles obtained in the step (1) by using a silver nitrate sulfuric acid solution, drying and roasting to obtain particles I, dipping the particles I by using a cobalt nitrate sulfuric acid solution and/or a molybdenum nitrate sulfuric acid solution, drying and roasting to obtain particles II, dipping the particles II by using a nickel nitrate sulfuric acid solution and/or a tungsten nitrate sulfuric acid solution, drying and roasting to obtain the metal-doped solid super acidic catalyst.

11. The method according to claim 10, wherein ZrOCl of step (1)₂And TiCl₄The mass concentration of the ethanol solution is 20-40% and 20-30% respectively.

12. The method according to claim 10, wherein the nitrate sulfuric acid solution in the step (2) is prepared by: dissolving nitrate in dilute sulfuric acid to obtain a nitrate sulfuric acid solution; the concentration of the dilute sulfuric acid is 0.3-0.6 mol/L, the concentration of the silver nitrate sulfuric acid solution is 2-4 mol/L, the concentration of the cobalt nitrate sulfuric acid solution and the concentration of the molybdenum nitrate sulfuric acid solution are 5-10 mol/L, and the concentration of the nickel nitrate sulfuric acid solution and the concentration of the tungsten nitrate sulfuric acid solution are 3-6 mol/L.

13. The preparation method according to claim 10, wherein the impregnation process in the step (2) is performed under reduced pressure and ultrasonic vibration, and the reduced pressure is 15000 to 20000 Pa; the ultrasonic condition is that the vibration frequency is 50-60 kHz.

Technical Field

The invention relates to a preparation method of polyether amine, in particular to a method for preparing polyether amine by taking polyether and liquid ammonia as raw materials.

Background

The polyether amine is also called amine terminated polyether, and is a polyoxyalkylene compound with a polyether skeleton as a molecular main chain and a terminated end by an amino group. These amine-terminated polyethers mostly use polyethers (polyethylene glycol, polyoxypropylene ether, etc.) as reaction raw materials, and the terminal hydroxyl groups of polyether polyols are converted into corresponding amine groups or amino groups (the terminal groups are usually primary amino groups, secondary amino groups or polyamine groups containing active hydrogen) by different treatment methods. Due to the reactivity of the terminal amino group or the amine group at the tail end of the polyether framework, the polyether framework can react with various reactive groups, such as epoxy groups, isocyanate groups and the like; in addition, due to the existence of ether bond in polyether chain, the polyether is easy to be dissolved in various organic matters, thus greatly widening the application range of the amino-terminated polyether in the industrial field. The amino-terminated polyether has excellent performance, and is widely applied to the fields of synthetic raw materials of polyurethane (polyurea), curing agents of epoxy resin, new-generation gasoline detergents and the like.

The synthesis method of the amino-terminated polyether mainly comprises a catalytic amination method, a leaving group method, a hydrolysis method and an amino phenoxy method. The amino-terminated polyether synthesized by the leaving group method has the hidden troubles that raw materials are not easy to purchase and the environment is easy to pollute, particularly, the post-treatment of the product needs a large amount of acid generated by the alkali neutralization reaction, a large amount of inorganic salt is generated in the production process, and the separation is difficult. In the hydrolysis process, although the viscosity of the product can be controlled by optimizing the synthesis and hydrolysis conditions of the prepolymer, a small amount of chain extension reaction occurs in the reaction process, and a carbamic acid group exists in the synthesis process, so that the viscosity of the product is higher than that of the original polyether polyol. The amino-terminated polyether prepared by the amino phenoxy method has simple process route, but in the reaction process of polyether polyol and a compound with an unsaturated group, side reactions are more, so the requirements on reaction conditions are strict, and the actual operation is difficult.

The synthesis of the amine-terminated polyether by the catalytic amination starts with the terminal hydroxyl group of polyether polyol, and replaces the terminal hydroxyl group with an amino group by ammonolysis reaction in the presence of a catalyst. Compared with the process route, the direct synthesis of the amino-terminated polyether by the catalytic amination method has the advantages of simple and convenient steps, cleanness, environmental protection, high product purity, less side reaction and the like. Is the main technical method for synthesizing the polyether amine at present.

CN1546550A discloses a method for preparing polyetheramine, wherein a Raney nickel catalyst is adopted in the method, the reaction is carried out in a high-pressure kettle, the reaction temperature is 180-280 ℃, and the reaction pressure is 11-21 MPa. CN101982482 discloses a method for preparing polyetheramine, which adopts amorphous alloy as a catalyst, and the reaction is carried out in a high-pressure kettle at the reaction temperature of 200 ℃ and the reaction pressure of 3.0-7.0 MPa. These methods have problems that the reaction is not continuous and the reaction conditions are severe. CN201310442410.7 discloses a device and a method for continuously synthesizing polyetheramine, wherein the device is provided with 1-3 fixed bed reactors, the reaction temperature is 150-300 ℃, and the reaction pressure is 1-20 MPa. CN104119239A discloses a process method for continuously producing small molecular weight polyetheramine, which adopts 2-6 fixed bed reactors connected in series, wherein different catalysts are filled in the reactors to improve the reaction conversion rate. CN105542146A discloses a continuous production process of polyetheramine, which adopts a tubular reactor, and obtains the polyetheramine product by twice rectification after the reaction is finished, wherein the catalyst is a metal-loaded catalyst, and the carrier is gamma-Al₂O₃. Although the method is a continuous reaction, the process flow is complex, the reaction conditions are harsh, and the gamma-Al is adopted₂O₃The carrier catalyst is easy to have Al ion migration under the action of liquid ammonia, which causes the reduction of the service life of the catalyst.

Disclosure of Invention

The invention provides a preparation method of polyether amine, aiming at the problems of complex flow, harsh reaction conditions, low raw material conversion rate and low product selectivity in the method for preparing polyether amine by taking polyether and liquid ammonia as raw materials in the prior art. The method takes polyether and liquid ammonia as raw materials, and the polyether and the liquid ammonia are fed into a reactor through an upper part and a lower part at the same time, and are matched with a metal-doped solid super acidic catalyst, so that the conversion rate of the reaction can be effectively improved, the process is simple, no pollution is caused, the condition is mild, and the reactor can be stably operated for a long period.

In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:

the preparation method of the polyether amine adopts a tubular reactor, a plurality of catalyst bed layers which are arranged in a staggered mode are arranged in the reactor from top to bottom, each catalyst bed layer comprises a bed plate and catalysts distributed on the bed plate, one end of each bed plate is connected with the wall of the reactor in a sealing mode, the other end of each bed plate extends to the wall of the reactor on the opposite side along the horizontal direction and keeps a certain distance from the wall of the reactor, a vertical baffle is arranged at the tail end of each bed plate, and two bed plates which are adjacent up and down are connected to the wall of the reactor on different sides; the bed plate is provided with a plurality of openings, liquid ammonia and polyether are used as a feeding material I and enter the reactor from the top of the reactor, the liquid ammonia is used as a feeding material II and enters the reactor from the bottom of the reactor, the feeding material I penetrates through the catalyst bed layer from top to bottom to react, and the feeding material II is in reverse contact with the feeding material I from bottom to top and further reacts with the unreacted polyether in the feeding material I.

In the above preparation method, further, the feed I is fed into the reactor in the form of a spray.

In the preparation method, further, an upper feed port is arranged at the top of the reactor, and an atomizing nozzle is arranged at the upper feed port.

In the preparation method, the length of the bed plate in the reactor is 2/3-3/4 of the diameter of the reactor.

In the preparation method, the diameter of the hole on the bed plate is 0.5-2 mm.

In the preparation method, further, the height of the baffle is 30-80 mm.

In the above preparation method, further, the reaction conditions in the reactor are: the reaction temperature is 160-200 ℃, and preferably 180-190 ℃; the reaction pressure is 3-8 MPa, preferably 5-7 MPa.

In the above preparation method, further, the molar ratio of liquid ammonia to polyether in the feed I is 100: 1-200: 1, preferably 140: 1-160: 1, the volume space velocity of polyether is 0.2-1 h^-1Preferably 0.3 to 0.5h^-1。

In the above preparation method, further, the polyether is polypropylene glycol, and the polypropylene glycol has an average molecular weight of 200.

In the preparation method, further, the volume space velocity of the feeding material II is 10-30 h^-1Preferably 15 to 20 hours^-1。

In the preparation method, further, the catalyst is selected from common catalysts for preparing polyether amine by reacting liquid ammonia with polyether in the prior art, and in the technical scheme of the invention, a solid super acidic catalyst is preferred.

In the preparation method, the catalyst can be in any shape, most preferably in a strip-shaped clover shape, and the length of the catalyst is 2-4 mm.

Further, the invention also provides a preparation method of the applicable solid super acidic catalyst, which comprises the following steps:

(1) ZrOCl₂And TiCl₄Dissolving in ethanol to obtain ZrOCl₂And TiCl₄Titrating with ammonia water under stirring until no white precipitate is generated, filtering, washing until no chloride ion is generated, drying to obtain white solid powder, extruding into strips, drying, and roasting to obtain white solid particles;

(2) and (2) dipping the white solid particles obtained in the step (1) by using a silver nitrate sulfuric acid solution, drying and roasting to obtain particles I, dipping the particles I by using a cobalt nitrate sulfuric acid solution and/or a molybdenum nitrate sulfuric acid solution, drying and roasting to obtain particles II, dipping the particles II by using a nickel nitrate sulfuric acid solution and/or a tungsten nitrate sulfuric acid solution, drying and roasting to obtain the metal-doped solid super acidic catalyst.

Further, ZrOCl in the step (1)₂And TiCl₄The mass concentration of the ethanol solution is 20-40% and 20-30% respectively.

Further, the drying temperature in the step (1) is 70-90 ℃, the drying time is 4-6 hours, the roasting temperature is 450-550 ℃, and the roasting time is 4-6 hours.

Further, the preparation process of the nitrate sulfuric acid solution in the step (2) is as follows: dissolving nitrate in dilute sulfuric acid to obtain a nitrate sulfuric acid solution; the concentration of the dilute sulfuric acid is 0.3-0.6 mol/L, the concentration of the silver nitrate sulfuric acid solution is 2-4 mol/L, the concentration of the cobalt nitrate sulfuric acid solution and the concentration of the molybdenum nitrate sulfuric acid solution are 5-10 mol/L, and the concentration of the nickel nitrate sulfuric acid solution and the concentration of the tungsten nitrate sulfuric acid solution are 3-6 mol/L.

Further, the impregnation process in the step (2) is carried out under the conditions of reduced pressure and ultrasonic vibration. The decompression condition is 15000-20000 Pa; the ultrasonic condition is that the vibration frequency is 50-60 kHz; the dipping temperature is 55-60 ℃, and the dipping time in each step is 4-6 h.

Further, the drying conditions in the step (2) are as follows: the drying temperature is 80-100 ℃, and the drying time is 6-8 hours; the roasting conditions are as follows: the roasting temperature is 450-550 ℃, and the roasting time is 4-6 hours.

Furthermore, the catalyst prepared by the method is preferably strip-shaped clover-shaped particles with the length of 2-4 mm.

Compared with the prior art, the invention has the following advantages:

(1) ammoniation reaction of liquid ammonia and polyether is carried out on a tubular reactor with a bed plate, feeding is carried out in an upper and lower simultaneous feeding mode, reaction materials fed in an upper mode contact with a catalyst on the bed plate and react, reactants flow to a next bed plate step by step through air holes in the catalyst bed plate and react, reaction materials fed in a lower mode enter the reactor under the condition of certain airspeed, are gasified rapidly under the reaction condition, rise step by step through the air holes in the bed plate and permeate in the reactor space through gaps among the catalyst bed plates, the concentration and the flow rate of lower feeding gas in the reactor are improved, the lower feeding gas and the reactants fed in the upper mode are mixed and then further react on the catalyst bed plate, and the reactor and the feeding mode enable the reaction process to have the advantages of a trickle bed and catalytic rectification simultaneously, and improve the reaction conversion rate.

(2) In the preparation process of the solid super acidic catalyst, ZrO is adopted₂-TiO₂The composite carrier and different metal solutions are respectively impregnated in a certain order under the conditions of reduced pressure, ultrasonic vibration and a certain impregnation temperature, and the impregnating solution is continuously boiled, so that the catalyst has uniform propertiesParticle size, SO₄ ^2-The coordination with the metal ions on the surface of the oxide is rapid and uniform, so that the catalyst has stronger acidity. ZrO (ZrO)₂-TiO₂The composite carrier forms new active site in the carrier interface, and the active metal and the carrier's defect site activate C-H bond together to raise the reaction activity. Ag⁺Is pre-doped to ZrO₂The crystal grains tend to exist in a monoclinic type (M), and the monoclinic type (M) is a relatively stable crystal phase structure, so that the catalyst has higher activity and better stability.

(3) The reaction material of upper feeding enters the reactor through the atomizing nozzle under a certain airspeed condition, and the material passing through the atomizing nozzle exists in a mixing state of mist small droplets under the reaction condition, so that the mixing and the distribution are more uniform, and the reaction efficiency on a catalyst bed layer is higher.

Drawings

FIG. 1 is a schematic view of a tubular reactor for producing polyether ammonia according to the present invention.

Wherein: wherein: 1-an upper feeding port; 2-lower feed inlet; 3-discharging port; 4-a catalyst; 5-a baffle plate; 6-bed board; 7-atomizing nozzle.

The working process of the reactor of the invention is as follows: the feeding I enters the reactor from the upper feeding port 1, after being atomized by the atomizing nozzle 7, a mist mixture is formed to contact with the catalyst 4 filled in a space formed by the bed plate 6 and the baffle plate 5, the reaction is carried out under certain reaction conditions, reactants flow to the next bed plate step by step through the air holes on the bed plate 6 and react, the feeding II enters the reactor from the lower feeding port 2, the gasification is carried out rapidly under the reaction conditions, the reactants ascend step by step through the open holes of the bed plate 6 and permeate the space of the reactor through the gaps among the catalyst bed plates, the reactants mixed with the feeding I further react on the catalyst bed plate, and the final reaction product is discharged from the discharging port 3.

Detailed Description

The technical scheme of the invention is specifically described as follows:

the preparation process of the solid super acidic catalyst comprises the following steps: firstly, respectively mixing 50-100 g ZrOCl₂And TiCl₄Dissolving in ethanol to obtain ZrOCl₂Mass concentration of 20-40 percent TiCl₄The method comprises the steps of titrating an ethanol solution with the mass concentration of 20-30% with 20-25% ammonia water until no white precipitate exists, washing the solution for several times with deionized water, washing the solution for 5-10 minutes each time at the washing temperature of 40-50 ℃ until no chloride ion exists, then drying the solution in a vacuum drying oven for 4-6 hours at the temperature of 80-90 ℃, extruding the solution to form strips, and roasting the strips for 8 hours at the temperature of 500 ℃ to obtain white solid particles for later use. Secondly, dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 2-4 mol/L, wherein the dipping temperature is 55-60 ℃, and the dipping time is 4-6 h; the decompression vacuum degree is 15000-20000 Pa; and (3) the ultrasonic vibration frequency is 50-60 kHz, then the solid particles are placed in a vacuum drying oven to be dried for 4-6 hours at the temperature of 80-90 ℃, and then the solid particles are roasted for 8 hours at the temperature of 500 ℃ to obtain particles I. And thirdly, repeating the impregnation process in the second step by using a cobalt nitrate sulfuric acid solution and/or a molybdenum nitrate sulfuric acid solution to obtain particles II. And fourthly, repeating the process of the second step by using a nickel nitrate sulfuric acid solution and/or a tungsten nitrate sulfuric acid solution to obtain the metal-doped solid super acidic catalyst.

The preparation method of the polyether amine comprises the following steps: reacting on a fixed bed continuous reactor with a catalyst bed plate, wherein liquid ammonia and polyether are used as a feed I and enter the reactor from the top of the reactor under reaction conditions, liquid ammonia is used as a feed II and enters the reactor from the bottom of the reactor, a plurality of catalyst bed layers which are staggered are arranged in the reactor from top to bottom, each catalyst bed layer comprises a bed plate and a catalyst distributed on the bed plate, one end of each bed plate is hermetically connected with the wall of the reactor, the other end of each bed plate horizontally extends to the wall of the opposite reactor and keeps a certain distance with the opposite reactor, a vertical baffle is arranged at the tail end of each bed plate, and two adjacent bed plates are connected to the walls of the reactors at different sides; the bed plate is provided with a plurality of openings, the feeding I penetrates through the catalyst bed layer from top to bottom to react, and the feeding II is in reverse contact with the feeding I from bottom to top and further reacts with unreacted polyether in the feeding I.

The following examples are provided to illustrate specific embodiments of the present invention. In the following examples and comparative examples,% represents mass unless otherwise specified. The model of an ultrasonic vibrator used in the preparation of the metal-doped solid super acidic catalyst is KQ-550B, and the model of an upper feeding atomization nozzle is JLN-G type high-pressure fine atomization nozzle, which is purchased from Jining Jun spray equipments, Inc. The inner diameter of the reactor is 25mm, the height of the reactor is 160cm, the length of the bed plate is 2/3-3/4 of the diameter of the reactor, and the edge of the bed plate is hermetically connected with the tube wall of the reactor. The aperture of the air holes is 0.5-2 mm, and the air holes are uniformly distributed on the bed plate; the height of the baffle at the tail end of the bed plate is 30-80 mm.