CN105837457A - Method for synthesizing bis(dimethylaminoethyl)ether under catalysis of metal catalyst - Google Patents

Abstract

The invention discloses a method for catalytically synthesizing bis(dimethylaminoethyl)ether by using a metal catalyst. The method firstly prepares a metal oxide, and then prepares a metal catalyst through the metal oxide. Utilizing the catalytic effect of the metal catalyst, dimethyl Amine and dimethylaminoethoxyethanol are used as raw materials to prepare BDMAEE. The main inorganic by-product is water. The organic by-products can be recycled and reused after distillation and purification, which not only has considerable economic benefits, but also solves the current problem of BDMAEE production. The process is easy to cause the problem of environmental pollution.

Description

Application of metal catalysts to catalyze the method for synthesizing two (dimethylaminoethyl) ethers

technical field

The invention belongs to the technical field of bis(dimethylaminoethyl) ether synthesis, and specifically relates to the catalytic action of active metal components, using dimethylaminoethoxyethanol and dimethylamine as raw materials to generate bis(dimethylaminoethyl) in one step. Aminoethyl) ether process.

Background technique

Bis(dimethylaminoethyl)ether (BDMAEE) is an important foaming catalyst for flexible polyurethane foam and one of the three major polyurethane catalysts. Its appearance is light yellow transparent liquid, which is infinitely soluble in water. BDMAEE has extremely high catalytic activity and selectivity for polyurethane foaming reaction. Because its pure product has too high activity, it is often mixed with some alcohol solvents and used as a solution. Mainly used in flexible polyurethane foam systems.

Dimethylaminoethoxyethanol (DMAEE) is a commonly used organic raw material and intermediate, and can also be used as a polyurethane curing agent. It is usually prepared by the reaction of dimethylamine and ethylene oxide in industry.

The current method of synthesizing BDMAEE is likely to cause pollution such as SO ₂ , HCl and other toxic and harmful gases, as well as trimethylamine organic waste brine, etc., which has great environmental hazards and high cost of pollution control, and cannot meet the needs of energy-saving and environmentally-friendly production. In view of this, it is crucial to develop a pollution-free synthesis method of BDMAEE.

Contents of the invention

The invention provides a kind of bis(dimethylaminoethyl)ether obtained through one-step reaction and pollution-free synthesis using dimethylaminoethoxyethanol and dimethylamine as raw materials under the catalysis of an active metal catalyst. method.

In order to realize the purpose of the present invention, the inventor provides the following technical solutions.

A method for catalytically synthesizing bis(dimethylaminoethyl)ether with a metal catalyst, the operation steps comprising:

A． Preparation of Metal Catalysts

(1) At 40-65°C, add Na ₂ CO ₃ aqueous solution to metal nitrate aqueous solution and mix evenly until the pH value of the mixed solution is 8, then filter, wash the filter cake three times with deionized water, and filter the cake After drying at 150°C for 24 hours, calcining at 400-600°C for 4 hours, and pulverizing into 300-mesh powder to obtain a mixture of metal oxides;

(2) Knead the four solid materials of metal oxide mixture, molecular sieve or SiO ₂ powder, pseudo-thin water alumina, and starch evenly, add 7% nitric acid aqueous solution to mix, extrude into strips, and dry at room temperature in turn for 0- 5 days, drying at 150°C for 24h, and calcining at 540°C for 4h to obtain a metal catalyst;

B． Synthesis of bis(dimethylaminoethyl) ether

(1) Grinding and sieving the metal catalyst prepared in step A, putting it into a trickle bed reactor, feeding H ₂ , and successively reducing at 200°C for 5 hours, 300°C for 5 hours, and 380°C for 5 hours;

(2) Then add dimethylamine and dimethylaminoethoxyethanol to the trickle bed reactor respectively, and feed H ₂ at the same time, and control the reaction temperature at 180-260°C to obtain bis(dimethylaminoethyl) ether.

The metal nitrate in step A is selected from Ni(NO ₃ ) ₂ ·6H ₂ O, Cu(NO ₃ ) ₂ ·6H ₂ O, Pt(NO ₃ ) ₂ , RuNO(NO ₃ ) ₃ , Pd(NO ₃ ) ₂ · 2H ₂ O, Co(NO ₃ ) ₂ · 6H ₂ O, Cr(NO ₃ ) ₃ · 9H ₂ O, Ga(NO ₃ ) ₃ , Ge(NO ₃ ) ₄ , In(NO ₃ ) ₃ , Mn (NO ₃ ) ₂ , Zn(NO ₃ ) ₂ ·6H ₂ O, La(NO ₃ ) ₃ ·6H ₂ O, Ce(NO ₃ ) ₃ ·6H ₂ O, Er(NO ₃ ) ₃ ·5H ₂ O, Any multiple of Hg(NO ₃ ) ₂ .

The concentration of the metal nitrate aqueous solution described in step A is 10-25%.

The concentration of the Na ₂ CO ₃ aqueous solution in step A is 15%-25%, preferably 20%.

The SiO described in the operation ( ₂ ) of step A The particle size of the powder is 200 mesh.

The weight of the mixture of metal oxides in the operation (2) of step A accounts for 10-65% of the total weight of the solid material, preferably 30-55%; the weight of molecular sieve or _SiO2 powder accounts for 1-20% of the total weight of the solid material %, preferably 3-15%; the weight of pseudo-thin water alumina accounts for 20-60% of the total weight of solid materials, preferably 30-50%; the weight of starch accounts for 15% of the weight of pseudo-thin water alumina.

The molecular sieve described in operation (2) of step A is one or more of HZSM-5 and USY.

The adding weight of nitric acid aqueous solution described in the operation (2) of step A is 30% of solid material gross weight.

The metal catalyst described in step B is crushed and sieved to a mesh size of 20-30 mesh.

The reduction pressure in the operation (1) of step B is 5 atm.

The molar ratio of dimethylamine and dimethylaminoethoxyethanol described in step B is 1:1.

The amount of dimethylaminoethoxyethanol added per minute in step B is 1/200 of the volume of the metal catalyst in the trickle bed reactor.

In operation (2) of step B, the pressure of introducing H ₂ is 10-15 atm.

The present invention comprehensively utilizes the catalysis of molecular sieves and active metals, and prepares BDMAEE through the reaction of dimethylamine and dimethylaminoethoxyethanol. The main inorganic by-product is water, and the generated organic by-products can be recovered after distillation and purification. Reuse does not produce other polluting inorganic products, and solves the problem that the current BDMAEE production process produces HCl, sulfur dioxide waste gas and high-salt waste water, which will cause environmental pollution.

It can be seen that the present invention realizes the green and clean production of BDMAEE, and has the advantages of high yield and low production cost. Compared with the prior art, the method provided by the invention has obvious economical and environmental protection effects.

detailed description

The content of the present invention will be described in further detail below in conjunction with specific embodiments.

Example 1

Weigh 160 grams of Ni(NO ₃ ) ₂ ·6H ₂ O , 200 grams of Cu(NO ₃ ) ₂ ·6H ₂ O, 80 grams of Cr(NO ₃ ) ₃ ·9H ₂ O, and add 1.5 liters of water to prepare a nitrate solution. Prepare a 20% Na ₂ CO ₃ aqueous solution.

At 50°C, add Na ₂ CO ₃ aqueous solution dropwise to metal nitrate aqueous solution under strong stirring until pH = 8; then filter, wash the filter cake with deionized water three times, and dry at 150°C for 24 hours , calcined at 480° C. for 4 hours, and pulverized to 300 mesh with a universal mill to obtain a mixture of metal oxides.

Weigh 110 grams of metal oxide mixture powder, 10 grams of dry base USY molecular sieve, 150 grams of pseudo-thin water alumina, 22.5 grams of starch, knead evenly, add 87.8g of 7% nitric acid aqueous solution, mix evenly, and use a single-screw extruder Extruded rods (cylindrical rods, 3 mm in diameter), dried at room temperature for 1 day, dried at 150°C for 24 hours, and calcined at 540°C for 4 hours to obtain metal catalysts.

Grind the metal catalyst through a 30-mesh sieve, take 20ml of the sieved catalyst and put it into a tubular trickle bed reactor with a diameter of 60mm, pass in H ₂ , reduce at 200°C for 5 hours, at 300°C for 5 hours, and at 380°C For 5 hours, the _H2 pressure was controlled at 5 atm. Then feed dimethylamine and dimethylaminoethoxyethanol at a molar ratio of 1:1, control the addition rate of dimethylaminoethoxyethanol to 0.1ml/min, _H2 pressure to 15atm, _H2 flow rate to 200ml/min , the reaction temperature is 215°C.

The reaction product was detected by gas chromatography normalization method, and the crude reaction product (except water) contained 48.3% BDMAEE, 13% methylmorpholine, 4.5% dimethylamine, 19.5% dimethylaminoethoxyethanol, 2.7% dimethylamine Ethanolamine, 0.8% tetramethylethylenediamine, 11.2% other impurities.

Example 2

Weigh 145 grams of Cu(NO ₃ ) ₂ ·6H ₂ O, 45 grams of Co(NO ₃ ) ₂ ·6H ₂ O, 10 grams of Zn(NO ₃ ) ₃ ·6H ₂ O, and add 1 liter of water to prepare a nitrate solution. Prepare a 15% Na ₂ CO ₃ aqueous solution.

At 40°C, add the Na ₂ CO ₃ aqueous solution dropwise to the metal nitrate aqueous solution under strong stirring until pH = 8; then filter, wash the filter cake with deionized water three times, and dry it at 150°C for 24 hours , calcined at 530° C. for 4 hours, and pulverized to 300 mesh with a universal mill to obtain a mixture of metal oxides.

Weigh 50 grams of this metal oxide mixture powder, 10 grams of dry base USY molecular sieve, 10 grams of HZSM-5 molecular sieve (silicon-aluminum ratio is 200), 30 grams of pseudo-thin water alumina, 4.5 grams of starch, knead evenly, add 31.4g of 7% nitric acid aqueous solution, mixed evenly, extruded with a single-screw extruder (cylindrical strip, diameter 4mm), dried at room temperature for 2 days, dried at 150°C for 24h, and calcined at 540°C for 4 hours to obtain metal catalyst.

Crush the catalyst through a 20-mesh sieve, take 20ml of the sieved catalyst and put it into a tubular trickle bed reactor with a diameter of 60mm, pass in H ₂ , reduce at 200°C for 5 hours, at 300°C for 5 hours, and at 380°C for 5 hours Hours, the _H2 pressure is controlled at 5 atm. Then feed dimethylamine and dimethylaminoethoxyethanol at a molar ratio of 1:1, control the addition rate of dimethylaminoethoxyethanol to 0.1ml/min, _H2 pressure to 10atm, and _H2 flow rate to 150ml/min , The reaction temperature is 260°C.

The reaction product was detected by gas chromatography normalization method, and the crude reaction product (except water) contained 48.2% BDMAEE, 12% methylmorpholine, 5% dimethylamine, 19.5% dimethylaminoethoxyethanol, 1.7% dimethyl Ethanolamine, 0.4% tetramethylethylenediamine, 13.2% other impurities.

Example 3

Weigh 200 g of Cu(NO ₃ ) ₂ ·6H ₂ O, 2.6 g of Pt(NO ₃ ) ₂ , 3.5 g of Ce(NO ₃ ) ₃ ·6H ₂ O, 22 ml of 50% Mn(NO ₃ ) ₂ aqueous solution, 1.2 Add _{1 liter of} water to prepare nitrate solution. Prepare a 25% Na ₂ CO ₃ aqueous solution.

At 65°C, add Na ₂ CO ₃ aqueous solution dropwise to metal nitrate aqueous solution under strong stirring until pH = 8; then filter, wash the filter cake with deionized water three times, and dry at 150°C for 24 hours , calcined at 450° C. for 4 hours, and pulverized to 300 mesh with a universal mill to obtain a mixture of metal oxides.

Take by weighing 55 grams of this metal oxide mixture powder, 19 grams of dry base 200 mesh SiO ₂ powder, 26 grams of pseudo-thin hydrated alumina, 3.9 grams of starch, knead evenly, add 7% nitric acid aqueous solution 31.2g, mix well, use Single-screw extruder extruded (cylindrical rod, diameter 5mm), dried at room temperature for 3 days, dried at 150°C for 24 hours, and calcined at 540°C for 4 hours to prepare the metal catalyst.

Crush the catalyst through a 20-mesh sieve, take 20ml of the sieved catalyst and put it into a tubular trickle bed reactor with a diameter of 60mm, pass in H ₂ , reduce at 200°C for 5 hours, at 300°C for 5 hours, and at 380°C for 5 hours Hours, the _H2 pressure is controlled at 5 atm. Then feed dimethylamine and dimethylaminoethoxyethanol at a molar ratio of 1:1, control the addition rate of dimethylaminoethoxyethanol to 0.1ml/min, _H2 pressure to 12atm, _H2 flow rate to 250ml/min , The reaction temperature is 180°C.

The reaction product was detected by gas chromatography normalization method, and the crude reaction product (except water) contained BDMAEE48.2%, 10.5% methylmorpholine, 6% dimethylamine, 22% dimethylaminoethoxyethanol, 2.2% Dimethylethanolamine, 0.8% tetramethylethylenediamine, 10.3% other impurities.

Example 4

Weigh 150 grams of Ni(NO ₃ ) ₂ ·6H ₂ O, 50 grams of Co(NO ₃ ) ₂ ·6H ₂ O, 2.1 grams of Ga(NO ₃ ) ₃ , 1.8 grams of In(NO ₃ ) ₃ , 1.2 grams of La( NO ₃ ) ₃ ·6H ₂ O, 0.6 g of Er(NO ₃ ) ₃ ·5H ₂ O and 1 liter of water were added to prepare a metal nitrate solution. Prepare a 20% Na ₂ CO ₃ aqueous solution.

At 55°C, under strong stirring, Na ₂ CO ₃ aqueous solution was added dropwise to the metal nitrate aqueous solution (3 drops per second) until pH = 8; then filtered, the filter cake was washed 3 times with deionized water, and the After drying at 150° C. for 24 hours, calcining at 500° C. for 4 hours, and pulverizing to 300 mesh with a universal mill, a mixture of metal oxides was obtained.

Take by weighing 55 grams of this metal oxide mixture powder, 15 grams of dry base 200 mesh SiO ₂ powder, 30 grams of pseudo-thin hydrated alumina, 4.5 grams of starch, knead evenly, add 7% nitric acid aqueous solution 31.4g, mix well, use Single-screw extruder extruded (cylindrical strip, diameter 4mm), dried at room temperature for 4 days, dried at 150°C for 24h, and calcined at 540°C for 4 hours to prepare the metal catalyst.

Crush the catalyst through a 30-mesh sieve, take 20ml of the sieved catalyst and put it into a tubular trickle bed reactor with a diameter of 60mm, pass in H ₂ , reduce for 5 hours at 200°C, 5 hours at 300°C, and 5 hours at 380°C Hours, the _H2 pressure is controlled at 5 atm. Then feed dimethylamine and dimethylaminoethoxyethanol at a molar ratio of 1:1, control the addition rate of dimethylaminoethoxyethanol to 0.1ml/min, _H2 pressure to 15atm, and _H2 flow rate to 210ml/min , reaction temperature 230℃

The reaction product was detected by gas chromatography normalization method. The crude reaction product (except water) contained 64.6% BDMAEE, 8.5% methylmorpholine, 5% dimethylamine, 13.3% dimethylaminoethoxyethanol, 1.7% dimethylamine Ethanolamine, 0.4% tetramethylethylenediamine, 6.5% other impurities.

Claims (10)

1. the method for double (dimethylaminoethyl) ether of applied metal catalyst synthesis, it is characterised in that operating procedure includes:

A. metallic catalyst is prepared

(1) under the conditions of 40～65 DEG C, it is the Na of 15-25% by concentration₂CO₃Aqueous solution joins in metal nitrate saline solution mixed Closing uniformly, until the pH value of mixed liquor is 8, then filter, filter cake makes to be washed with deionized three times, and filter cake is dried at 150 DEG C After 24 hours, 400-600 DEG C of roasting 4 hours, it is ground into the powder of 300 mesh, obtains the mixture of metal-oxide；

(2) by the mixture of metal-oxide, molecular sieve or the SiO of 200 mesh₂Powder, intend thin water aluminium oxide, four kinds of solids of starch Material is mediated uniformly, adds the aqueous solution of nitric acid mixing of 7%, is squeezed into bar, and successively in drying at room temperature 0-5 days, 150 DEG C are dried 24h, 540 DEG C of roasting 4h, obtain metallic catalyst；

B. double (dimethylaminoethyl) ether of synthesis

(1) metallic catalyst that step A prepares is pulverized and sieved, put in trickle bed reactor, be passed through H₂, exist successively 200 DEG C are reduced 5 hours, and 300 DEG C are reduced 5 hours, and 380 DEG C are reduced 5 hours, and pressure during reduction is 5atm；

(2) in trickle bed reactor, add dimethylamine and dimethylaminoethoxyethanol the most respectively, be passed through H simultaneously₂, control Pressure is 10-15atm, controls reaction temperature and is 180-260 DEG C, i.e. obtains double (dimethylaminoethyl) ether.

The method of double (dimethylaminoethyl) ether of applied metal catalyst the most according to claim 1 synthesis, it is special Levying and be, metal nitrate described in step A is selected from Ni (NO₃)₂·6H₂O、Cu(NO₃)₂·6H₂O、Pt(NO₃)₂、RuNO(NO₃)₃、 Pd(NO₃)₂·2H₂O、Co(NO₃)₂·6H₂O、Cr(NO₃)₃·9H₂O、Ga(NO₃)₃、Ge(NO₃)₄、In(NO₃)₃、Mn(NO₃)₂、Zn (NO₃)₂·6H₂O、La(NO₃)₃·6H₂O、Ce(NO₃)₃·6H₂O、Er(NO₃)₃·5H₂O、Hg(NO₃)₂In the most multiple.

The method of double (dimethylaminoethyl) ether of applied metal catalyst the most according to claim 1 synthesis, it is special Levying and be, the concentration of metal nitrate saline solution described in step A is 10-25%.

The method of double (dimethylaminoethyl) ether of applied metal catalyst the most according to claim 1 synthesis, it is special Levying and be, described in the operation (2) of step A, the weight of the mixture of metal-oxide accounts for the 10-65% of solid material gross weight； Molecular sieve or SiO₂The weight of powder accounts for the 1-20% of solid material gross weight；Intending the weight of thin water aluminium oxide, to account for solid material total The 20-60% of weight；The weight of starch accounts for intends the 15% of thin water alumina weight.

The method of double (dimethylaminoethyl) ether of applied metal catalyst the most according to claim 1 synthesis, it is special Levying and be, described in the operation (2) of step A, the weight of the mixture of metal-oxide accounts for the 30-55% of solid material gross weight； Molecular sieve or SiO₂The weight of powder accounts for the 3-15% of solid material gross weight；Intending the weight of thin water aluminium oxide, to account for solid material total The 30-50% of weight；The weight of starch accounts for intends the 15% of thin water alumina weight.

The method of double (dimethylaminoethyl) ether of applied metal catalyst the most according to claim 1 synthesis, it is special Levying and be, described in the operation (2) of step A, molecular sieve is one or more in HZSM-5, USY.

The method of double (dimethylaminoethyl) ether of applied metal catalyst the most according to claim 1 synthesis, it is special Levy and be, described in the operation (2) of step A addition weight is solid material gross weight the 30% of aqueous solution of nitric acid.

The method of double (dimethylaminoethyl) ether of applied metal catalyst the most according to claim 1 synthesis, it is special Levying and be, the mesh number that metallic catalyst described in step B pulverizes and sieves is 20-30 mesh.

The method of double (dimethylaminoethyl) ether of applied metal catalyst the most according to claim 1 synthesis, it is special Levying and be, the mol ratio of dimethylamine described in step B and dimethylaminoethoxyethanol is 1:1.

The method of double (dimethylaminoethyl) ether of applied metal catalyst the most according to claim 1 synthesis, it is special Levying and be, the addition per minute of dimethylaminoethoxyethanol described in step B is metallic catalyst body in trickle bed reactor One of two long-pending percentages.