CN105837457B - The method that applied metal catalyst synthesizes bis- (dimethylaminoethyl) ethers - Google Patents

The method that applied metal catalyst synthesizes bis- (dimethylaminoethyl) ethers Download PDF

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CN105837457B
CN105837457B CN201610193326.XA CN201610193326A CN105837457B CN 105837457 B CN105837457 B CN 105837457B CN 201610193326 A CN201610193326 A CN 201610193326A CN 105837457 B CN105837457 B CN 105837457B
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dimethylaminoethyl
ethers
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bis
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CN105837457A (en
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路万里
马利国
孙艳荣
褚彭涛
郑本荣
范振发
吴晓亮
张峰敏
王涛
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Huamao Weiye Green Technology Co.,Ltd.
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Hebei Huamao Weiye Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8986Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166Y-type faujasite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80Mixtures of different zeolites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10After treatment, characterised by the effect to be obtained
    • B01J2229/20After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30After treatment, characterised by the means used
    • B01J2229/40Special temperature treatment, i.e. other than just for template removal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively

Abstract

The invention discloses the methods that applied metal catalyst synthesizes bis- (dimethylaminoethyl) ethers, metal oxide is first prepared in this method, then metallic catalyst is prepared by metal oxide, utilize the catalytic action of metallic catalyst, using dimethylamine and dimethylamino ethoxy ethyl alcohol as raw material, BDMAEE is prepared, host inorganic by-product is water, the organic by-products of generation can be recycled after distilation and recycle, not only economic benefits, while also solving the problem of current BDMAEE production technology easily causes environmental pollution.

Description

The method that applied metal catalyst synthesizes bis- (dimethylaminoethyl) ethers
Technical field
The invention belongs to bis- (dimethylaminoethyl) ether synthesis technical fields, and in particular to utilize urging for active metal component Change effect, using dimethylamino ethoxy ethyl alcohol and dimethylamine as raw material, single step reaction generates the mistake of bis- (dimethylaminoethyl) ethers Journey.
Background technique
Bis- (dimethylaminoethyl) ethers (BDMAEE) are a kind of kickers of important polyurethane flexible foam, are three One of big catalysts for polyurethanes, appearance is light yellow transparent liquid, can infinitely be dissolved in water.BDMAEE reacts polyurethane foam There are high catalytic activity and selectivity, since its sterling activity is too high, therefore is usually mixed with some alcohols solvents, wiring solution-forming After use.It is mainly used for flexible polyurethane foam system.
Dimethylamino ethoxy ethyl alcohol (DMAEE) is common Organic Ingredients and intermediate, it can also be used to urethane cures Agent industrially generallys use dimethylamine and is prepared with reacting ethylene oxide.
Synthesis BDMAEE method easily brings SO at present2, the toxic, pernicious gas such as HCl and trimethylamine organic effluent brine etc. Pollution, environmental hazard is big, and pollution treatment is at high cost, is not able to satisfy the needs of energy conservation and environmental protection production.In consideration of it, developing a kind of free of contamination BDMAEE synthetic method becomes most important.
Summary of the invention
The present invention provides one kind using dimethylamino ethoxy ethyl alcohol and dimethylamine as raw material, in active metal catalyst It is free of contamination to synthesize the method for obtaining bis- (dimethylaminoethyl) ethers through single step reaction under catalytic action.
In order to achieve the object of the present invention, following technical scheme is inventor provided.
The method that applied metal catalyst synthesizes bis- (dimethylaminoethyl) ethers, operating procedure include:
A. metallic catalyst is prepared
(1) under the conditions of 40~65 DEG C, by Na2CO3Aqueous solution is added in metal nitrate saline solution and is uniformly mixed, directly PH value to mixed liquor is 8, is then filtered, and filter cake makes to be washed with deionized three times, filter cake at 150 DEG C after dry 24 hours, It is roasted 4 hours at 400-600 DEG C, is ground into 300 mesh powders, obtains the mixture of metal oxide;
(2) by the mixture of metal oxide, molecular sieve or SiO2Powder intends four kinds of thin water aluminium oxide, starch solids Material, which is mediated, to be uniformly added 7% aqueous solution of nitric acid and mixes, and item is squeezed into, successively at drying at room temperature 0-5 days, 150 DEG C of dryings for 24 hours, 540 DEG C of roasting 4h, obtain metallic catalyst;
B. bis- (dimethylaminoethyl) ethers are synthesized
(1) the step A metallic catalyst being prepared is pulverized and sieved, is put into trickle bed reactor, is passed through H2, according to Secondary to restore at 200 DEG C 5 hours, 300 DEG C restore 5 hours, and 380 DEG C restore 5 hours;
(2) dimethylamine and dimethylaminoethoxyethanol is then added into trickle bed reactor respectively, while being passed through H2, Control reaction temperature be 180-260 DEG C to get arrive bis- (dimethylaminoethyl) ethers.
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 appoint It anticipates a variety of.
The concentration of metal nitrate saline solution described in step A is 10-25%.
Na described in step A2CO3The concentration of aqueous solution be 15%-25%, preferably 20%.
SiO described in the operation (2) of step A2200 mesh of granularity of powder.
The weight of the mixture of metal oxide described in the operation (2) of step A accounts for the 10- of solid material total weight 65%, preferably 30-55%;Molecular sieve or SiO2The weight of powder accounts for the 1-20% of solid material total weight, preferably 3-15%;Intend thin water The weight of aluminium oxide accounts for the 20-60% of solid material gross weight, preferably 30-50%;The weight of starch, which accounts for, intends thin water alumina weight 15%。
Molecular sieve described in the operation (2) of step A is one of HZSM-5, USY or a variety of.
The addition weight of aqueous solution of nitric acid described in the operation (2) of step A is the 30% of solid material gross weight.
The mesh number that metallic catalyst described in step B pulverizes and sieves is 20-30 mesh.
The pressure of reduction described in the operation (1) of step B is 5atm.
The molar ratio of dimethylamine described in step B and dimethylaminoethoxyethanol is 1:1.
The additional amount per minute of dimethylaminoethoxyethanol described in step B is metallic catalyst body in trickle bed reactor Long-pending 21 percent.
H is passed through described in the operation (2) of step B2Pressure be 10-15atm.
The invention comprehensively utilizes the catalytic action of molecular sieve and active metal, pass through dimethylamine and dimethylamino ethoxy BDMAEE is prepared in ethanol synthesis, and host inorganic by-product is water, and the organic by-products of generation can be recycled after distilation It recycles, does not generate the mineral products of other pollutions, solve current BDMAEE production technology and generate HCl, form waste gas of sulfur dioxide And high-salt wastewater, the problem of will cause environmental pollution.
It can be seen that the present invention realizes the green clean manufacturing of BDMAEE, and has yield high, production cost is low Advantage.Compared with prior art, method economy provided by the present invention and obvious with environment protecting.
Specific embodiment
Content of the present invention is described in further detail combined with specific embodiments below.
Embodiment 1
Weigh 160 grams of Ni (NO3)2·6H2O, 200 grams of Cu (NO3)2·6H2O, 80 grams of Cr (NO3)3·9H2O adds 1.5 liters Water is configured to nitrate solution.The Na that compound concentration is 20%2CO3Aqueous solution.
Under the conditions of 50 DEG C, under strong agitation by Na2CO3Aqueous solution is added drop-wise in metal nitrate saline solution, until pH= 8;Then it filters, filter cake is washed with deionized 3 times, after 150 DEG C 24 hours dry, roasts 4 hours at 480 DEG C, use is omnipotent Milling is broken to 300 mesh, obtains the mixture of metal oxide.
The mix powder of 110 grams of metal oxides is weighed, 10 grams of butt USY molecular sieves, 150 grams are intended thin water aluminium oxide, 22.5 grams of starch are mediated uniformly, 7% aqueous solution of nitric acid 87.8g are added, are uniformly mixed, with single-screw extruder extruded moulding (circle Column type item, diameter 3mm), at drying at room temperature 1 day, is dried at 150 DEG C for 24 hours, metal catalytic is made after roasting 4 hours at 540 DEG C Agent.
Metallic catalyst be crushed into 30 meshes, the catalyst after taking 20ml to be sieved is put into the tubulose drip that diameter is 60mm In bed reactor, it is passed through H2, 200 DEG C restore 5 hours, and 300 DEG C restore 5 hours, and 380 DEG C restore 5 hours, H2Pressure control exists 5atm.Then 1:1 is passed through dimethylamine and dimethylaminoethoxyethanol in molar ratio, and control dimethylaminoethoxyethanol is added Speed is 0.1ml/min, H2Pressure is 15atm, H2Flow velocity is 200ml/min, and reaction temperature is 215 DEG C.
Reaction product is detected using gas-chromatography normalization method, and reacting coarse product (in addition to water) contains 48.3%BDMAEE, 13% first Base morpholine, 4.5% dimethylamine, 19.5% dimethylaminoethoxyethanol, 2.7% dimethylethanolamine, 0.8% tetramethylethylenediamine, 11.2% other impurity.
Embodiment 2
Weigh 145 grams of Cu (NO3)2·6H2O, 45 grams of Co (NO3)2·6H2O, 10 grams of Zn (NO3)3·6H2O adds 1 liter of water to match Nitrate solution is made.The Na that compound concentration is 15%2CO3Aqueous solution.
Under the conditions of 40 DEG C, under strong agitation by Na2CO3Aqueous solution is added drop-wise in metal nitrate saline solution, until pH= 8;Then it filters, filter cake is washed with deionized 3 times, after 150 DEG C 24 hours dry, roasts 4 hours at 530 DEG C, use is omnipotent Milling is broken to 300 mesh, obtains the mixture of metal oxide.
Weigh the mix powder of 50 grams of this metal oxides, 10 grams of butt USY molecular sieves, 10 grams of HZSM-5 molecular sieves (silica alumina ratio 200), 30 grams are intended thin water aluminium oxide, and 4.5 grams of starch are mediated uniformly, and 7% aqueous solution of nitric acid 31.4g, mixing is added Uniformly, with single-screw extruder extruded moulding (cylinder profile bar, diameter 4mm), at drying at room temperature 2 days, 150 DEG C it is dry for 24 hours, 540 DEG C roasting 4 hours after be made metallic catalyst.
Catalyst be crushed into 20 meshes, it is anti-that the catalyst after taking 20ml to be sieved is put into the tubulose trickle bed that diameter is 60mm It answers in device, is passed through H2, 200 DEG C restore 5 hours, and 300 DEG C restore 5 hours, and 380 DEG C restore 5 hours, H2Pressure is controlled in 5atm.So 1:1 is passed through dimethylamine and dimethylaminoethoxyethanol in molar ratio afterwards, and control dimethylaminoethoxyethanol is added speed and is 0.1ml/min, H2Pressure is 10atm, H2Flow velocity is 150ml/min, 260 DEG C of reaction temperature.
Reaction product is detected using gas-chromatography normalization method, and reacting coarse product (in addition to water) contains 48.2%BDMAEE, 12% first Base morpholine, 5% dimethylamine, 19.5% dimethylaminoethoxyethanol, 1.7% dimethylethanolamine, 0.4% tetramethylethylenediamine, 13.2% other impurity.
Embodiment 3
Weigh 200 grams of Cu (NO3)2·6H2O, 2.6 grams of Pt (NO3)2, 3.5 grams of Ce (NO3)3·6H2O, 22 milliliters of 50%Mn (NO3)2Aqueous solution, 1.2 grams of La (NO3)3·6H2O adds 1 liter of water to be configured to nitrate solution.The Na that compound concentration is 25%2CO3Water Solution.
Under the conditions of 65 DEG C, under strong agitation by Na2CO3Aqueous solution is added drop-wise in metal nitrate saline solution, until pH= 8;Then it filters, filter cake is washed with deionized 3 times, after 150 DEG C 24 hours dry, roasts 4 hours at 450 DEG C, use is omnipotent Milling is broken to 300 mesh, obtains the mixture of metal oxide.
Weigh the mix powder of 55 grams of this metal oxides, 19 grams of 200 mesh SiO of butt2Powder, 26 grams are intended thin water oxygen Change aluminium, 3.9 grams of starch are mediated uniformly, 7% aqueous solution of nitric acid 31.2g is added, are uniformly mixed, with single-screw extruder extruded moulding (cylinder profile bar, diameter 5mm) was dried for 24 hours at 150 DEG C at drying at room temperature 3 days, metal is made after roasting 4 hours at 540 DEG C and urges Agent.
Catalyst be crushed into 20 meshes, it is anti-that the catalyst after taking 20ml to be sieved is put into the tubulose trickle bed that diameter is 60mm It answers in device, is passed through H2, 200 DEG C restore 5 hours, and 300 DEG C restore 5 hours, and 380 DEG C restore 5 hours, H2Pressure is controlled in 5atm.So 1:1 is passed through dimethylamine and dimethylaminoethoxyethanol in molar ratio afterwards, and control dimethylaminoethoxyethanol is added speed and is 0.1ml/min, H2Pressure is 12atm, H2Flow velocity is 250ml/min, 180 DEG C of reaction temperature.
Reaction product using gas-chromatography normalization method detect, reacting coarse product (in addition to water) contain BDMAEE48.2%, 10.5% Methyl morpholine, 6% dimethylamine, dimethylamino ethoxy ethyl alcohol 22%, 2.2% dimethylethanolamine, 0.8% tetramethylethylenediamine, 10.3% other impurity.
Embodiment 4
Weigh 150 grams of Ni (NO3)2·6H2O, 50 grams of Co (NO3)2·6H2O, 2.1 grams of Ga (NO3)3, 1.8 grams of In (NO3)3、 1.2 grams of La (NO3)3·6H2O, 0.6 gram of Er (NO3)3·5H2O adds 1 liter of water preparing metal nitrate at solution.Compound concentration is 20% Na2CO3Aqueous solution.
Under the conditions of 55 DEG C, under strong agitation by Na2CO3Aqueous solution is added drop-wise in metal nitrate saline solution (per second 3 Drop), until pH=8;Then it filters, filter cake is washed with deionized 3 times, after 150 DEG C 24 hours dry, roasts 4 at 500 DEG C Hour, 300 mesh are broken to omnipotent milling, obtain the mixture of metal oxide.
Weigh the mix powder of 55 grams of this metal oxides, the SiO of 15 grams of 200 mesh of butt2Powder, 30 grams are intended thin water Aluminium oxide, 4.5 grams of starch, mediate uniformly, be added 7% aqueous solution of nitric acid 31.4g, be uniformly mixed, with single-screw extruder extrusion at Type (cylinder profile bar, diameter 4mm) was dried for 24 hours at 150 DEG C at drying at room temperature 4 days, metal is made after roasting 4 hours at 540 DEG C Catalyst.
Catalyst be crushed into 30 meshes, it is anti-that the catalyst after taking 20ml to be sieved is put into the tubulose trickle bed that diameter is 60mm It answers in device, is passed through H2, 200 DEG C restore 5 hours, and 300 DEG C restore 5 hours, and 380 DEG C restore 5 hours, H2Pressure is controlled in 5atm.So 1:1 is passed through dimethylamine and dimethylaminoethoxyethanol in molar ratio afterwards, and control dimethylaminoethoxyethanol is added speed and is 0.1ml/min, H2Pressure is 15atm, H2Flow velocity is 210ml/min, 230 DEG C of reaction temperature
Reaction product using gas-chromatography normalization method detect, reacting coarse product (in addition to water) contain 64.6%BDMAEE, 8.5% Methyl morpholine, 5% dimethylamine, 13.3% dimethylaminoethoxyethanol, 1.7% dimethylethanolamine, 0.4% tetramethylethylenediamine, 6.5% other impurity.

Claims (8)

1. the method that applied metal catalyst synthesizes bis- (dimethylaminoethyl) ethers, which is characterized in that operating procedure includes:
A. metallic catalyst is prepared
(1) under the conditions of 40~65 DEG C, the Na for being 15-25% by concentration2CO3Aqueous solution is added in metal nitrate saline solution It is uniformly mixed, until the pH value of mixed liquor is 8;Then it filters, filter cake makes to be washed with deionized three times, and filter cake is dry at 150 DEG C After dry 24 hours, is roasted 4 hours at 400-600 DEG C, be ground into 300 mesh powders, obtain the mixture of metal oxide;It is described Metal nitrate is Ni (NO3)2 · 6H2O 、 Co(NO3)2 · 6H2O 、 Ga (NO3)3 、 In(NO3)3 、 La (NO3)3 · 6H2O 、 Er (NO3)3 · 5H2The mixture of O;
(2) by the mixture of metal oxide, the SiO of 200 mesh2Powder intends four kinds of thin water aluminium oxide, starch solid materials kneadings Uniformly, 7% aqueous solution of nitric acid is added to mix, is squeezed into item, successively at drying at room temperature 0-5 days, 150 DEG C of dryings for 24 hours, 540 DEG C 4h is roasted, metallic catalyst is obtained;
B. bis- (dimethylaminoethyl) ethers are synthesized
(1) the step A metallic catalyst being prepared is pulverized and sieved, is put into trickle bed reactor, is passed through H2, successively 200 DEG C reduction 5 hours, 300 DEG C restored 5 hours, and 380 DEG C restore 5 hours, and pressure when reduction is 5atm;
(2) dimethylamine and dimethylaminoethoxyethanol is then added into trickle bed reactor respectively, while being passed through H2, control Pressure is 10-15atm, control reaction temperature be 180-260 DEG C to get arrive bis- (dimethylaminoethyl) ethers.
2. the method that applied metal catalyst according to claim 1 synthesizes bis- (dimethylaminoethyl) ethers, special Sign is that the concentration of metal nitrate saline solution described in step A is 10-25%.
3. the method that applied metal catalyst according to claim 1 synthesizes bis- (dimethylaminoethyl) ethers, special Sign is that the weight of the mixture of metal oxide described in the operation (2) of step A accounts for the 10-65% of solid material total weight; SiO2The weight of powder accounts for the 1-20% of solid material total weight;The weight for intending thin water aluminium oxide accounts for the 20- of solid material gross weight 60%;The weight of starch, which accounts for, intends the 15% of thin water alumina weight.
4. the method that applied metal catalyst according to claim 1 synthesizes bis- (dimethylaminoethyl) ethers, special Sign is that the weight of the mixture of metal oxide described in the operation (2) of step A accounts for the 30-55% of solid material total weight; SiO2The weight of powder accounts for the 3-15% of solid material total weight;The weight for intending thin water aluminium oxide accounts for the 30- of solid material gross weight 50%;The weight of starch, which accounts for, intends the 15% of thin water alumina weight.
5. the method that applied metal catalyst according to claim 1 synthesizes bis- (dimethylaminoethyl) ethers, special Sign is that the addition weight of aqueous solution of nitric acid described in the operation (2) of step A is the 30% of solid material gross weight.
6. the method that applied metal catalyst according to claim 1 synthesizes bis- (dimethylaminoethyl) ethers, special Sign is that the mesh number that metallic catalyst described in step B pulverizes and sieves is 20-30 mesh.
7. the method that applied metal catalyst according to claim 1 synthesizes bis- (dimethylaminoethyl) ethers, special Sign is that the molar ratio of dimethylamine described in step B and dimethylaminoethoxyethanol is 1:1.
8. the method that applied metal catalyst according to claim 1 synthesizes bis- (dimethylaminoethyl) ethers, special Sign is that the additional amount per minute of dimethylaminoethoxyethanol described in step B is metallic catalyst body in trickle bed reactor Long-pending 21 percent.
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CN106316868B (en) * 2016-08-19 2019-01-29 浙江皇马科技股份有限公司 A kind of synthetic method of bis- (2- dimethylaminoethyl) ethers
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