CN110903475A - Co-production method of 2- (2-amino-propoxy) ethanol and polyether polyol - Google Patents
Co-production method of 2- (2-amino-propoxy) ethanol and polyether polyol Download PDFInfo
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- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
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Abstract
The invention discloses a co-production method of 2- (2-amino-propoxy) ethanol and polyether polyol, which comprises the following steps: (1) carrying out chain connection reaction on ethylene glycol and propylene oxide to obtain a mixed product A; (2) adsorbing and filtering the mixed product A, and then fractionating to obtain a tower top product B and a tower bottom product C; (3) performing hydroamination reaction on the tower top product B to obtain a crude product, and purifying to obtain 2- (2-amino-propoxy) ethanol; (4) and (3) reacting the tower bottom product C with propylene oxide and/or ethylene oxide, and refining to obtain the polyether polyol. The invention utilizes the same process route to simultaneously produce the 2- (2-amino-propoxy) ethanol and the polyether polyol, thereby successfully solving the problems of complex process, more byproducts and difficult utilization of the byproducts in the prior synthesis technology and the problems of high production input cost and long time consumption of a step-by-step preparation method of the 2- (2-amino-propoxy) ethanol and the polyether polyol.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a co-production method of 2- (2-amino-propoxy) ethanol and polyether polyol.
Background
2- (2-amino-propoxy) ethanol is an alcamines compound containing hydroxyl and amino structures, and the compound can be used as an acid gas absorbent, a surfactant, a wetting agent and the like and can also be used as a raw material of a polymer. The synthesis methods can be generally divided into the following categories: the synthesis method of amino acid (or its derivatives), epoxy compound, aziridine derivatives as raw materials, the synthesis method of reaction of aldehyde (or ketone) and imine (or nitro compound, etc.), the synthesis method of amino hydroxylation, etc., wherein the synthesis method of epoxy compound as raw material is one of the common methods, which is mainly carried out by nucleophilic reaction of epoxy compound and amine, for example, U.S. Pat. No. 2649483A discloses a synthesis method of diethanol monoisopropanolamine, which is obtained by reaction of diethanol amine and propylene oxide; chinese patent CN102557960A discloses a method for producing alkyl alcohol amine, which is mainly prepared from alkylene oxide and alkylamine. Although the method is commonly used, certain defects exist, such as more byproducts, long reaction time, large energy consumption of equipment, complex process, low yield and the like.
The polyether polyol is a main raw material of a polyurethane product, and is prepared by ring-opening polymerization at a certain temperature and pressure by taking potassium hydroxide as a catalyst, small molecular polyol as an initiator and epoxide as a monomer, for example, Chinese patent CN103554471A discloses a preparation method of the polyether polyol for a thermal insulation material, which takes any three of propylene glycol, glycerol, pentaerythritol, sorbitol, sucrose or xylitol as the initiator to react with propylene oxide. For example, CN102617848A discloses a method for preparing sorbitol polyether polyol, which uses crystalline sorbitol and propylene oxide as raw materials, and performs polymerization reaction under the action of catalyst and regulator.
At present, the 2- (2-amino-propoxy) ethanol and the polyether polyol are prepared by respectively selecting corresponding independent process routes, which causes the increase of investment cost and long process time consumption, and because the reaction raw materials of the two relate to epoxide, if a suitable raw material can be found to be matched with the epoxide to achieve the joint production of the 2- (2-amino-propoxy) ethanol and the polyether polyol, the investment of capital and time can be greatly reduced.
Disclosure of Invention
The invention aims to achieve the desire of co-production of 2- (2-amino-propoxy) ethanol and polyether polyol, and specifically adopts the following technical scheme:
a co-production process of 2- (2-amino-propoxy) ethanol and polyether polyol comprising the steps of:
(1) heating ethylene glycol and propylene oxide to 60-160 ℃ under the action of an alkali catalyst to carry out a chain connecting reaction to obtain a mixed product A;
(2) removing the alkali catalyst in the mixed product A by adopting an adsorption method, filtering to obtain an alkali-removed mixture, and putting the alkali-removed mixture into a rectifying tower for fractionation to obtain a tower top product B and a tower bottom product C, wherein the distillation pressure is-0.1-0 MPa, and the tower top temperature is 60-200 ℃;
since the components of the dealkalized mixture have high boiling points and are easily oxidized, rectification under reduced pressure can be employed in the step (2). When the pressure in the kettle is reduced, the boiling points of the components are correspondingly reduced, so that better separation effect, energy consumption reduction and production efficiency improvement can be achieved. In the step (2), the preferable distillation pressure is-0.1 to-0.0995 MPa, and the corresponding tower top temperature is 60 to 80 ℃; the distillation pressure is-0.0995 to-0.095 MPa, and the corresponding tower top temperature is 80 to 110 ℃; the distillation pressure is-0.095 to-0.05 MPa, and the corresponding tower top temperature is 110 to 160 ℃; the distillation pressure is-0.05 to-0.02 MPa, and the corresponding tower top temperature is 160 to 180 ℃; the distillation pressure is-0.02-0 MPa, and the corresponding tower top temperature is 180-200 ℃.
(3) Carrying out hydroamination reaction on the tower top product B under the action of a catalyst D to obtain a crude product, wherein the reaction temperature is 80-300 ℃ and the reaction pressure is 0.5-20 MPa during the hydroamination reaction; purifying the crude product to obtain 2- (2-amino-propoxy) ethanol with a molecular formula of formula (1):
(4) and (3) reacting the tower bottom product C with propylene oxide and/or ethylene oxide under the action of an alkali metal catalyst, wherein the reaction temperature is 60-160 ℃, the reaction pressure is-0.1-1 MPa, so as to obtain crude polyether polyol, and refining the crude polyether polyol to obtain the polyether polyol.
The prior art purification techniques such as neutralization separation, adsorption, neutralization-adsorption, cation exchange resin, and extraction-adsorption can be used in this step.
The invention utilizes the same process route to simultaneously produce the 2- (2-amino-propoxy) ethanol and the polyether polyol, thereby successfully solving the problems of complex process, more byproducts, difficult utilization of the byproducts and large production input cost and long time consumption of a step-by-step preparation method of the 2- (2-amino-propoxy) ethanol and the polyether polyol in the prior synthesis technology.
According to the molecular structure and chemical characteristics of main products and byproducts of the polymerization reaction, the method analyzes the commonalities and differences, researches further utilized process paths, and finally designs a production process combining hydroxyl amination and polyether synthesis in a targeted manner. By utilizing the method, the co-production of the 2- (2-amino-propoxy) ethanol and the polyether polyol can be realized, the process flow is simplified, various intermediate products generated in the production process can be recycled, the intermediate products are used as raw materials for synthesizing the polyether polyol, the optimal selection and maximization of the raw material utilization rate are realized, the generation of waste and the resource waste are reduced, and the joint production of the 2- (2-amino-propoxy) ethanol and the polyether polyol becomes a cyclic, high-efficiency, energy-saving and environment-friendly co-production process.
Specifically, the feeding molar ratio of the ethylene glycol to the propylene oxide is 1 (0.05-2), and more preferably 1 (0.4-1.5).
In order to further improve the conversion rate of the 2- (2-amino-propoxy) ethanol, the molar ratio of the ethylene glycol to the propylene oxide is controlled to be 1 (0.05-2). If the amount is outside this range, 2- (2-amino-propoxy) ethanol is mainly present as a by-product, which is disadvantageous in terms of efficient use of raw materials. Meanwhile, in this range, the molar ratio of ethylene glycol to propylene oxide is 1:1, which is the optimum ratio, and in the range of 1 (0.05-0.4), small molecular byproducts are abundant, and in the range of 1 (1.5-2), large molecular byproducts are abundant, so 1 (0.4-1.5) is preferred.
Specifically, the overhead product B is ethylene glycol and 1- (2-hydroxy-ethoxy) isopropanol.
Specifically, the bottom product C is a low molecular weight diol. During the polymerization reaction, since the actual molar ratio of ethylene glycol to propylene oxide is different from the theoretical design value, various byproducts such as a diol having a molecular weight of 178, a diol having a molecular weight of 236, and a diol having a molecular weight of 294 are generated.
By using a rectification method, 1- (2-hydroxyl-ethoxy) isopropanol is taken as a tower top product to be separated from a polymerization reaction product, so that the production process flow can be simplified, the purification treatment is convenient, and the conversion rate of 2- (2-amino-propoxy) ethanol is improved. Meanwhile, the tower bottom product C is mainly dihydric alcohol with low molecular weight and can be directly used as a raw material for polyether synthesis, so that no impurity or byproduct is generated in the polyether synthesis process, and the method is simple, efficient and environment-friendly.
The alkali metal catalyst is at least one of potassium alkoxide, sodium alkoxide and alkali metal hydroxide. In a specific use, any one or a mixture of two or more of the above alkali metal catalysts may be used.
In the reaction system, the catalyst can realize catalytic action under the condition of small dosage, the reaction efficiency and the conversion rate of a target product are improved, the generation of byproducts is reduced, and the catalyst can be conveniently moved out of the reaction system after the reaction is finished, so that the product purity is improved, and the production process is simplified.
Specifically, in order to ensure smooth reaction, the catalyst D is a supported catalyst, and includes a carrier material and a catalytic material, the carrier material has a porous structure and is aluminum oxide and/or titanium dioxide, and an active component of the catalytic material is a mixture of at least two of metal nickel, palladium, cobalt, chromium, molybdenum, and copper. Wherein the mass ratio of the carrier material to the active component is 20: 80-30: 70. The preparation method of the catalyst D comprises the following steps: preparing metal salt into a metal salt solution with the mass concentration of 68-73%, then adding a carrier, preheating and stirring at 70-75 ℃ for 20min, and dropwise adding Na with the mass concentration of 35-45% into the solution2CO3The temperature of the solution is 65-75 ℃ after the dropwise addition is finishedAging for 2 hours under the condition; carrying out suction filtration, vacuum drying and calcination, grinding the obtained product to 40-50 meshes, and carrying out vacuum drying on the product with the volume ratio of 30% H2/70％N2Reducing for 2h at 160-170 ℃ under the condition of mixed gas.
The catalyst and the preparation method have the advantages of high conversion rate, high primary amine selectivity and low reaction cost, meet the requirements of the production process, can ensure that the reaction conditions are mild and controllable, and reduce the risk in the operation process.
In the present application, the adsorption method in step (2) is a direct adsorption method, and the adsorption method comprises the following specific steps: based on the mass of the mixed product A, adding 1-6 wt% of pure water into the mixed product A, adding 0.1-5 wt% of adsorbent, stirring, carrying out vacuum dehydration, and filtering to obtain a filtrate which is an alkali-removed mixture;
and (3) at least one of magnesium silicate, aluminum silicate, bentonite and montmorillonite serving as an adsorbent in the step (2).
The adsorbent and the adsorption method can be well suitable for material treatment, the adsorption effect is improved, the filtration time is shortened, the impurity part in a system can be efficiently removed, the generation of byproducts in the adsorption process is reduced, and the process flow is simplified.
Overall, the combined advantages of the present application are:
(1) by adopting a co-production method, two products of 2- (2-amino-propoxy) ethanol and polyether polyol can be obtained simultaneously in one process, the process is simple, no waste is generated, and the production efficiency is improved;
(2) the tower bottom product is used as the initial raw material for polyether synthesis, so that the cyclic utilization of products in each process is realized, the waste of raw materials and environmental pollution are avoided, and the method has the characteristics of environmental friendliness, energy conservation and environmental protection;
(3) the conversion rate of the 2- (2-amino-propoxy) ethanol is more than or equal to 98 percent and the selectivity is more than or equal to 96 percent by the restriction of the mol ratio, the selection of the catalyst and the reaction conditions.
The specific implementation mode is as follows:
in order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the following examples, catalyst D was made by itself, and the remaining components were all commercially available.
Preparation of catalyst D:
170g of nickel nitrate Ni (NO) was weighed out separately3)219g of cobalt nitrate Co (NO)3)21g of chromium nitrate Cr (NO)3)20.9g of molybdenum nitrate Mo (NO)3)2Putting the mixture into 90g of deionized water, and adding 15.4g of carrier Al according to the mass ratio of the carrier material to the active component of 20:802O3Heating and stirring to 70 deg.C, and adding Na with mass fraction of 35% dropwise after 20min2CO3Aging the solution at 65 ℃ for 2h after the dropwise addition is finished; performing suction filtration, respectively and fully washing with deionized water and absolute ethyl alcohol for 2 times, then performing vacuum drying at 100 ℃ for 2 hours, and then calcining at 500 ℃ for 2 hours; grinding the obtained catalyst to 40 meshes after calcining and sintering, and adding 30% H2/70％N2Reducing the mixed gas at 160 ℃ for 2h to obtain a black solid powder catalyst D which is named as a No. 1 catalyst.
170g of nickel nitrate Ni (NO) was weighed out separately3)220g of cobalt nitrate Co (NO)3)230g of chromium nitrate Cr (NO)3)230g of Pd (NO) palladium nitrate3)2Putting the mixture into 100g of deionized water, and adding 15.9g of carrier Al according to the mass ratio of the carrier material to the active component of 25:752O3And 12g of TiO2Heating and stirring to 75 deg.C, and adding Na with mass fraction of 40% after 20min2CO3Aging the solution at 70 ℃ for 2h after the dropwise addition is finished; performing suction filtration, respectively washing with deionized water and absolute ethyl alcohol for 2 times, then performing vacuum drying at 100 ℃ for 2h, and then calcining at 500 ℃ for 2 h; after calcination, the catalyst was ground to 50 mesh and then to 30% H2/70％N2Reducing the mixed gas at 165 ℃ for 2h to obtain a black solid powder catalyst D which is named as a No. 2 catalyst.
132g of nickel acetate Ni (CH) are weighed out separately3COO)256.7g of cobalt acetate Co (CH)3COO)219g of copper acetate Cu (CH)3COO)218.9g of molybdenum acetate Mo (CH)3COO)2Putting the mixture into 85g of deionized water, and adding 33.3g of carrier TiO according to the mass ratio of the carrier material to the active component of 30:702Heating and stirring to 75 deg.C, and adding Na with mass fraction of 45% after 20min2CO3Aging the solution at 75 ℃ for 2h after the dropwise addition is finished; performing suction filtration, respectively washing with deionized water and absolute ethyl alcohol for 2 times, then performing vacuum drying at 100 ℃ for 2h, and then calcining at 320 ℃ for 3.5 h; after calcination, the catalyst was ground to 40 mesh and then treated with 30% H2/70％N2Reducing the mixed gas at 170 ℃ for 2h to obtain black solid powder catalyst D which is named as 3# catalyst.
Example 1:
745g of ethylene glycol and 6.4g of potassium hydroxide are added into a 3L reaction kettle according to the feeding molar ratio of the ethylene glycol to the propylene oxide of 1: and 2, introducing 1394g of propylene oxide, and heating to 60 ℃ to perform a chain connecting reaction for 1h to obtain a mixed product A.
Then 21g of pure water is added into the mixed product A, 1.8g of magnesium silicate and 0.3g of aluminum silicate are added as adsorbents, the mixture is stirred for 1 hour, vacuum dehydration and filtration are carried out, then the mixture enters a rectifying tower, the distillation pressure is set to be 0MPa, the tower top temperature is set to be 200 ℃, components in the mixed product A are separated, and 1348g of tower top product B and 578g of tower bottom product C are obtained.
1348g of overhead product B and 149.7g of No. 1 catalyst were placed in a 5L autoclave, and N reaction was carried out on the resulting mixture, respectively2And H2Each of which was replaced twice, 1909g of liquid NH was introduced into the autoclave3Then filling H into the high-pressure reaction kettle2Heating to 80 deg.c, controlling the pressure inside the high pressure reactor to 20MPa, and hydroammoniation reaction for 3 hr. And (3) discharging the pressure in the kettle, filtering the obtained material, and distilling the material under reduced pressure for 1h at 80 ℃ under the vacuum degree of absolute pressure of 5kPa to obtain a compound No. 1. The conversion was 98% and the primary amine selectivity was 96%.
Adding 578g of tower bottom product C and 2g of potassium hydroxide into a 2L reaction kettle, replacing with nitrogen until the oxygen content is lower than 100ppm, heating to 60 ℃ under stirring, then adding 580g of propylene oxide, controlling the reaction temperature to be 60-70 ℃, controlling the reaction pressure to be 0.5-1 MPa, and reducing the pressure in the kettle to normal pressure after reacting for 1 h. Then 12g of pure water is added into the reaction kettle, 1.2g of magnesium silicate is added as an adsorbent, after stirring for 1h, vacuum dehydration is carried out, when the water content reaches below 0.05 percent, the dehydration is stopped, and filtration is carried out, thus obtaining the No. 1 polyether polyol with the number average molecular weight of 1158.
Example 2:
745g of ethylene glycol, 2.4g of sodium ethylene glycol and 3g of sodium hydroxide are added into a 3L reaction kettle, and the molar ratio of the fed ethylene glycol to the fed propylene oxide is 1: 1.5 introducing 1045g of propylene oxide, heating to 80 ℃ and carrying out a chain connection reaction for 1h to obtain a mixed product A.
Then, 36g of pure water is added into the mixed product A, 17.9g of magnesium silicate is added, after stirring for 1 hour, vacuum dehydration and filtration are carried out, and then the mixture enters a rectifying tower, the distillation pressure is set to be-0.02 MPa, the tower top temperature is set to be 180 ℃, components in the mixed product A are separated, and 1209g of tower top product B and 403g of tower bottom product C are obtained.
1209g of overhead product B and 80.6g of No. 2 catalyst were placed in a 5L autoclave, and N was carried out separately2And H2Replacing twice, introducing 1712g of liquid NH into the high-pressure reaction kettle3Then filling H into the high-pressure reaction kettle2Heating to 140 ℃, controlling the pressure in the high-pressure reaction kettle to be 15MPa, and carrying out the hydroamination reaction for 3 hours under the condition. Cooling to 100 ℃, discharging the pressure in the kettle, performing suction filtration on the obtained material, and performing reduced pressure distillation for 1h at 100 ℃ under the vacuum degree of 5kPa absolute pressure to obtain a 2# compound. The conversion was 98.7% and the primary amine selectivity was 97%.
Adding 403g of tower bottom product C and 2g of potassium hydroxide into a 2L reaction kettle, replacing with nitrogen until the oxygen content is lower than 100ppm, heating to 80 ℃ under stirring, then adding 440g of ethylene oxide, controlling the reaction temperature to be 80-90 ℃ and the reaction pressure to be 0.5-0.8 MPa, and reducing the pressure in the kettle to normal pressure after reacting for 1 h. Then 17g of pure water is added into the reaction kettle, 8.4g of magnesium silicate is added as an adsorbent, the mixture is stirred for 1 hour, then vacuum dehydration is carried out, when the water content reaches below 0.05 percent, the dehydration is stopped, and the mixture is filtered to obtain the 2# polyether polyol with the number average molecular weight of 843.
Example 3:
745g of ethylene glycol and 4.3g of sodium hydroxide are added to a 2L reactor in a molar ratio of ethylene glycol to propylene oxide of 1: 697g of propylene oxide is introduced into 1, and the temperature is raised to 100 ℃ to carry out chain connection reaction for 1h, so that a mixed product A is obtained.
Then 43g of pure water is added into the mixed product A, 18.8g of magnesium silicate and 10g of bentonite are added as adsorbents, the mixture is stirred for 1 hour, vacuum dehydration and filtration are carried out, then the mixture enters a rectifying tower, the distillation pressure is set to be-0.05 MPa, the tower top temperature is set to be 160 ℃, and the components in the mixed product A are separated, so that 1103g of tower top product B and 195g of tower bottom product C are obtained.
1103g of overhead product B and 61.3g of No. 1 catalyst were placed in a 5L autoclave. Respectively carry out N2And H2Replacing twice, introducing 1563g of liquid NH into the high-pressure reaction kettle3Then filling H into the high-pressure reaction kettle2Heating to 180 ℃, controlling the pressure in the high-pressure reaction kettle to be 10MPa, and maintaining the condition to carry out the hydroamination reaction for 3 hours. Cooling to 100 ℃, discharging the pressure in the kettle, performing suction filtration on the obtained material, and performing reduced pressure distillation for 1h at 100 ℃ under the vacuum degree of 5kPa absolute pressure to obtain a 3# compound. The conversion was 99% and the primary amine selectivity was 98%.
Adding 195g of tower bottom product C and 2g of potassium hydroxide into a 2L reaction kettle, replacing with nitrogen until the oxygen content is lower than 100ppm, heating to 100 ℃ under stirring, then adding 580g of propylene oxide, controlling the reaction temperature at 100-110 ℃ and the reaction pressure at 0.2-0.9 MPa, and reducing the pressure in the kettle to the normal pressure after reacting for 1 h. Then 23g of pure water and 15.5g of magnesium silicate are added into the reaction kettle, after stirring for 1h, vacuum dehydration is carried out, when the water content reaches below 0.05 percent, the dehydration is stopped, and filtration is carried out, thus obtaining the No. 3 polyether polyol with the number average molecular weight of 775.
Example 4:
745g of ethylene glycol and 3.9g of sodium ethylene glycol are added into a 2L reaction kettle according to the feeding molar ratio of 1: and introducing 558g of propylene oxide into the reactor, and heating the reactor to 120 ℃ to perform a chain connecting reaction for 1 hour to obtain a mixed product A.
Then, 52g of pure water was added to the mixed product A, 39.1g of magnesium silicate was added as an adsorbent, and after stirring for 1 hour, vacuum dehydration and filtration were carried out, and then the mixture was fed into a rectifying column, and distillation pressure was set at-0.095 MPa, and column top temperature was set at 110 ℃ to separate components in the mixed product A, thereby obtaining 938g of column top product B and 394g of column bottom product C.
938g of overhead product B, 83.4g of catalyst # 2 were placed in a 3L autoclave. Respectively carry out N2And H2Replacing twice, and introducing 1329g of liquid NH into the high-pressure reaction kettle3Then filling H into the high-pressure reaction kettle2And heating to 230 ℃, controlling the pressure in the high-pressure reaction kettle to be 5MPa, and maintaining the condition to carry out the hydroamination reaction for 3 hours. Cooling to 100 ℃, discharging the pressure in the kettle, performing suction filtration on the obtained material, and performing reduced pressure distillation for 1h at 100 ℃ under the vacuum degree of 5kPa absolute pressure to obtain a 4# compound. The conversion was 98.5% and the primary amine selectivity was 97.5%.
394g of tower bottom product C and 2g of potassium hydroxide are added into a 2L reaction kettle, nitrogen is used for replacement until the oxygen content is lower than 100ppm, the temperature is raised to 120 ℃ under stirring, then 580g of cyclopropyl is added, the reaction temperature is controlled to be 120-130 ℃, the reaction pressure is 0-0.6 MPa, and after 1h of reaction, the pressure in the kettle is reduced to the normal pressure. Then 39g of pure water was added into the reaction kettle, 29.2g of magnesium silicate was added as an adsorbent, and after stirring for 1 hour, vacuum dehydration was carried out, and when the water content reached 0.05% or less, dehydration was stopped, and filtration was carried out to obtain # 4 polyether polyol having a number average molecular weight of 974.
Example 5:
1118g of ethylene glycol, 1g of potassium ethylene glycol and 3.6g of potassium hydroxide were added to a 2L reactor in a molar ratio of ethylene glycol to propylene oxide of 1: 418g of propylene oxide is introduced into the reactor 0.4, and the temperature is raised to 140 ℃ to carry out chain connection reaction for 1h, so as to obtain a mixed product A.
77g of pure water is added into the mixed product A, 50g of magnesium silicate and 11.4g of montmorillonite are added as adsorbents, the mixture is stirred for 1 hour, then the mixture is dehydrated in vacuum, filtered and then enters a rectifying tower, the distillation pressure is set to be-0.0995 MPa, the tower top temperature is set to be 80 ℃, and the components in the mixed product A are separated, so 1037g of tower top product B and 346g of tower bottom product C are obtained.
1037g of overhead product B, 80.6gThe 3# catalyst was placed in a 3L autoclave. Respectively carry out N2And H2The reaction solution was replaced twice, and 1468g of liquid NH was introduced into the autoclave3Then filling H into the high-pressure reaction kettle2Heating to 280 deg.c, controlling the pressure inside the high pressure reactor to 2MPa, and maintaining the conditions for hydroamination reaction for 3 hr. Cooling to 100 ℃, discharging the pressure in the kettle, performing suction filtration on the obtained material, and performing reduced pressure distillation for 1h at 100 ℃ under the vacuum degree of 5kPa absolute pressure to obtain a 5# compound. The conversion was 99.5% and the primary amine selectivity was 96.5%.
346g of tower bottom product C and 2g of potassium hydroxide are added into a 2L reaction kettle, nitrogen is used for replacing until the oxygen content is lower than 100ppm, the temperature is raised to 140 ℃ under stirring, then 580g of cyclopropyl is added, the reaction temperature is controlled to be 140-150 ℃, the reaction pressure is-0.05-0 MPa, and after 1 hour of reaction, the pressure in the kettle is reduced to normal pressure. Then 46g of pure water and 37g of magnesium silicate are added into the reaction kettle, the mixture is stirred for 1 hour, and then the mixture is dehydrated in vacuum, when the water content is less than 0.05 percent, the dehydration is stopped, and the mixture is filtered, so that the No. 5 polyether polyol with the number average molecular weight of 926 is obtained.
Example 6:
to a 2L reactor, 1490g ethylene glycol and 2.7g potassium hydroxide and 2g sodium hydroxide were added in a molar ratio of ethylene glycol to propylene oxide of 1: and introducing 70g of propylene oxide into 0.05, heating to 160 ℃, and carrying out a chain connection reaction for 1h to obtain a mixed product A.
Then 94g of pure water is added into the mixed product A, 47g of magnesium silicate and 31g of aluminum silicate are added as adsorbents, the mixture is stirred for 1 hour, then the mixture is dehydrated in vacuum, filtered and then enters a rectifying tower, the distillation pressure is set to be-0.1 MPa, the tower top temperature is set to be 60 ℃, and the components in the mixed product A are separated, so that 983g of tower top product B and 395g of tower bottom product C are obtained.
983g of overhead product B and 98.3g of No. 3 catalyst were placed in a 3L autoclave. Respectively carry out N2And H2Replacing twice, and introducing 1392g of liquid NH into the high-pressure reaction kettle3Then filling H into the high-pressure reaction kettle2Heating to 300 deg.c, controlling the pressure inside the high pressure reactor to 0.5MPa and maintaining the condition for hydroamination reaction for 3 hr.Cooling to 100 ℃, discharging the pressure in the kettle, performing suction filtration on the obtained material, and performing reduced pressure distillation for 1h at 100 ℃ under the vacuum degree of 5kPa absolute pressure to obtain a 6# compound. The conversion was 98% and the primary amine selectivity was 96%.
395g of tower bottom product C and 2g of potassium hydroxide are added into a 2L reaction kettle, nitrogen is used for replacing until the oxygen content is lower than 100ppm, the temperature is raised to 150 ℃ under stirring, then 580g of cyclopropyl is added, the reaction temperature is controlled to be 150-160 ℃, the reaction pressure is-0.1-0 MPa, and after 1h of reaction, the pressure in the kettle is reduced to normal pressure. Then 59g of pure water is added into the reaction kettle, 48.8g of magnesium silicate is added as an adsorbent, the mixture is stirred for 1 hour, then vacuum dehydration is carried out, when the water content reaches below 0.05 percent, the dehydration is stopped, and filtration is carried out, thus obtaining the 6# polyether polyol with the number average molecular weight of 975.
The 1-6# compounds prepared in the above examples were all 2- (2-amino-propoxy) ethanol.
Claims (10)
1. A co-production method of 2- (2-amino-propoxy) ethanol and polyether polyol is characterized by comprising the following steps:
(1) heating ethylene glycol and propylene oxide to 60-160 ℃ under the action of an alkali catalyst to carry out a chain connecting reaction to obtain a mixed product A;
(2) removing the alkali catalyst in the mixed product A by adopting an adsorption method, filtering to obtain an alkali-removed mixture, and putting the alkali-removed mixture into a rectifying tower for fractionation to obtain a tower top product B and a tower bottom product C, wherein the distillation pressure is-0.1-0 MPa, and the tower top temperature is 60-200 ℃;
(3) carrying out hydroamination reaction on the tower top product B under the action of a catalyst D to obtain a crude product, wherein the reaction temperature is 80-300 ℃ and the reaction pressure is 0.5-20 MPa during the hydroamination reaction; purifying the crude product to obtain 2- (2-amino-propoxy) ethanol with a molecular formula of formula (1):
(4) and (3) reacting the tower bottom product C with propylene oxide and/or ethylene oxide under the action of an alkali metal catalyst, wherein the reaction temperature is 60-160 ℃, the reaction pressure is-0.1-1 MPa, so as to obtain crude polyether polyol, and refining the crude polyether polyol to obtain the polyether polyol.
2. The co-production method as claimed in claim 1, wherein the feeding molar ratio of the ethylene glycol to the propylene oxide is 1 (0.05-2).
3. The co-production process of claim 1, wherein the overhead product B is ethylene glycol and 1- (2-hydroxy-ethoxy) isopropanol.
4. The co-production process of claim 1, wherein the bottoms product C is a low molecular weight diol.
5. The co-production process of claim 1, wherein the alkali metal catalyst is at least one of potassium alkoxide, sodium alkoxide, and alkali metal hydroxide.
6. The co-production process according to claim 1, wherein the catalyst D is a supported catalyst comprising a carrier material and a catalytic material, wherein the carrier material has a porous structure and is alumina and/or titania, and the active component of the catalytic material is a mixture of at least two of nickel, palladium, cobalt, chromium, molybdenum and copper.
7. The co-production method according to claim 6, wherein the mass ratio of the carrier material to the active component is 20:80 to 30: 70.
8. The co-production process according to any one of claims 1 to 6, wherein the catalyst D is prepared by: preparing metal salt into a metal salt solution with the mass concentration of 68-73%, then adding a carrier, preheating and stirring at 70-75 ℃ for 20min, and dropwise adding Na with the mass concentration of 35-45% into the solution2CO3Aging the solution for 2 hours at the temperature of 65-75 ℃ after the dropwise addition; carrying out suction filtration, vacuum drying and calcination, grinding the obtained product to 40-50 meshes, and carrying out vacuum drying on the product with the volume ratio of 30% H2/70％N2Reducing for 2h at 160-170 ℃ under the condition of mixed gas.
9. Cogeneration process according to claim 1,
the adsorption method in the step (2) is a direct adsorption method, and the adsorption method comprises the following specific steps: based on the mass of the mixed product A, adding 1-6 wt% of pure water into the mixed product A, adding 0.1-5 wt% of adsorbent, stirring, carrying out vacuum dehydration, and filtering to obtain a filtrate which is an alkali-removed mixture.
10. The co-production process of claim 9, wherein the adsorbent in step (2) is at least one of magnesium silicate, aluminum silicate, bentonite, and montmorillonite.
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| WO2021093292A1 (en) * | 2019-11-15 | 2021-05-20 | 红宝丽集团股份有限公司 | Co-production method for 2-(2-amino-propoxy)ethanol and polyether polyol |
| CN114031510A (en) * | 2021-11-25 | 2022-02-11 | 万华化学集团股份有限公司 | Preparation method of 2-aminopropanol |
| CN115894260A (en) * | 2022-12-15 | 2023-04-04 | 红宝丽集团股份有限公司 | Co-production method of amino-terminated polyether and diol compounds |
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