CN105085282A - Preparation method for alkyl alcohol amine - Google Patents
Preparation method for alkyl alcohol amine Download PDFInfo
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Abstract
The invention discloses a preparation method for alkyl alcohol amine. The preparation method comprises the following steps: (1) feeding alkyl amine and a reaction promoter alkanolamine into a reaction kettle for stirring and mixing; (2) adding epoxy alkane for synthesis, wherein the feeding molar ratio of epoxy alkane for synthesis to alkyl amine is higher than the theoretical reaction molar ratio; (3) after the feeding is finished, carrying out heating and pressurization; (4) carrying out heat preservation conversion rate to obtain a crude product; (5) conducting continuous distillation on the crude product to separate out alkyl alcohol amine. During the preparation, alkanolamine is primary alkanolamine or secondary alkanolamine. Compared with the prior art, the preparation method provided by the invention adopts the technical scheme that alkanolamine is taken as the reaction promoter instead of water as a catalyst, so that the conversion rate of alkyl amine can reach 99.0% in general, the highest conversion rate can reach 99.9%, and the highest recovery rate of alkyl alcohol amine can reach 99.8%. Therefore, the preparation method provided by the invention has the advantages of being high in raw material conversion rate and recovery rate.
Description
Technical field
The present invention relates to a kind of preparation method of alkyl alcoholamine.
Background technology
Existing alkyl alcoholamine production technology, most employing batch tank reaction or continuous prodution, the common feature of these techniques mostly adopts water as synthesis reaction catalyst, and for suppressing the generation of polyethers by product, and adopt excessive alkylamine, as adopted the water of 2.5 ~ 50% as catalyzer in patent CN103261130A, the molar ratio of oxyethane and dialkylamine is 1: 1.1 ~ 10, because the reaction mol ratio of oxyethane and dialkylamine is 1: 1, in the publication, the consumption of alkylamine is excessive, the molar ratio of epoxy alkane and alkylamine is its theoretical 0.10 ~ 0.91 times of reacting mol ratio, and for example also mention the generation that excessive alkylamine significantly can suppress by product in patent US2337004A, but excessive due to amine, after completion of the reaction, a large amount of alkylamines is had to remain, this inevitable requirement adds de-amine equipment to reclaim excessive alkylamine in Production Flow Chart, make to have suffered Production Flow Chart to extend, simultaneously adding due to water, also need dewatering unit, the existence of water also causes the hydrolysising loss of epoxy alkane and reduces the utilization ratio of epoxy alkane in addition, for some special alkyl alcoholamines as N, N-dimethylisopro panolamine etc. can form azeotrope with water, this will inevitably moisturize further from difficulty, while also can increase the flow process of production.Although also there is patent to mention the method for anhydrous continuous synthesis alkyl alcoholamine product as patent CN102557960A etc., these methods still need the recovery process of excess amine.
But excessive due to amine, after completion of the reaction, have a large amount of alkylamines to remain, inevitable requirement adds de-amine equipment to reclaim excessive alkylamine in Production Flow Chart, makes to have suffered Production Flow Chart and extends; Simultaneously adding due to water, also need dewatering unit, the existence of water also causes the hydrolysising loss of epoxy alkane and reduces the utilization ratio of epoxy alkane in addition; For some special alkyl alcoholamines as N, N-dimethylisopro panolamine etc. can form azeotrope with water, this will inevitably moisturize further from difficulty, while also can increase the flow process of production.Although also there is patent to mention the method for anhydrous continuous synthesis alkyl alcoholamine product as patent CN102557960A etc., these methods still need the recovery process of excess amine.
Summary of the invention
First object of the present invention is the defect overcoming above-mentioned technique, there is provided technical process short, without the need to carrying out the preparation method of the alkyl alcoholamine of amine recovery, in this preparation method, adding without the need to water, the hydrolysising loss causing epoxy alkane due to the existence of water can be avoided, some special alkyl alcoholamines and water also can be avoided to form azeotrope, and increase product separation difficulty; Next is to simplify the recovery process for the rectifying kettle material after purification in prior art.
The preparation method of alkyl alcoholamine of the present invention, comprises the steps:
(1) alkylamine and reaction promotor alkanolamine to be put in reactor and to be uniformly mixed;
(2) then add synthesis epoxy alkane, the molar ratio of synthesis epoxy alkane and alkylamine is greater than its theory and reacts mol ratio;
(3) heat up after charging and pressurize;
(4) be incubated, generate thick product;
(5) thick product is isolated alkyl alcoholamine by continuous rectification;
Described alkanolamine is primary alkanol amine or sec alkanol amine.
Compared with existing preparation method, the present invention is without the need to adding water as catalyzer, but using alkanolamine as reaction promotor, having under alkanolamine existent condition, alkylamine shows higher reactive behavior and selectivity, preferential and the alkylamine of epoxy alkane generates alkyl alcoholamine, and only when the transformation efficiency of alkylamine reaches more than 90%, part primary alkanol amine or sec alkanol amine and epoxy alkane is just had to react, in the present invention, the transformation efficiency of alkylamine generally can reach 99.0%, peak rate of conversion can reach 99.9%, the rate of recovery of alkyl alcoholamine is also the highest can reach 99.8%, therefore the present invention is provided with feed stock conversion and the high advantage of the rate of recovery.Due in this preparation method, the epoxy alkane added is excessive, and alkylamine raw material can be made to transform completely, and epoxy alkane excessive in reaction system can absorb with alkanolamine complete reaction and generate two alkanolamines or trialkanolamine; Therefore without the need to the alkylamine recovery process in traditional technology, technical process is shortened.Simultaneously due to adding without the need to water, avoid the hydrolysising loss of epoxy alkane, more avoid some special alkyl alcoholamines with water forms azeotrope, make product of the present invention be easy to separation.
This preparation method also has another advantage, and the thick product colourity of synthesizing exactly is more shallow, and within 10APHA, meanwhile, the chromaticity stability of the product after purification is higher.
As further improvement, this preparation method also comprises the operation that the rectifying kettle material after by continuous rectification carries out aftertreatment, described postprocessing working procedures is: the rectifying kettle material after continuous still battery being completed sends into reactor, then adds the reaction of recovery epoxy alkane and prepares trialkanolamine product.Recovery epoxy alkane is propylene oxide, oxyethane, butylene oxide ring or R-GLYCIDOL; The molar ratio of the alkanolamine in recovery epoxy alkane and rectifying kettle material is its theoretical 0.95 ~ 0.98 times of reacting mol ratio.
In further improving, rectifying kettle material after purification is sent in reactor as raw material by the present invention, and add epoxy alkane, prepare corresponding commercial grade trialkanolamine product, owing to reclaiming without the need to carrying out purification to rectifying kettle material again, but directly it can be used as raw material to produce, simplifying recovery process, and therefore take full advantage of starting material, and produce without waste.
As preferably, alkanolamine has the structure of formula (I):
In formula I, R
1represent hydrogen, C
2~ C
5hydroxyalkyl; R
2represent C
2~ C
5hydroxyalkyl.
Alkanolamine is preferably at least one in Monoethanolamine MEA BASF, diethanolamine, α-amino isopropyl alcohol or diisopropanolamine (DIPA) further.
Alkylamine has the structure of formula (II):
In formula II, R
3represent hydrogen, methyl, ethyl, propyl group, sec.-propyl or butyl; R
4represent methyl, ethyl, propyl group, sec.-propyl or butyl.
Prepare the purity of alkyl alcoholamine alkylamine used more preferably greater than 99 % by weight, in alkylamine, the content of water is less than 0.5 % by weight.
Synthesis epoxy alkane be preferably in oxyethane, propylene oxide, butylene oxide ring or R-GLYCIDOL any one.Synthesis epoxy alkane at least divides 2 times and adds, and each add-on of synthesis epoxy alkane is 10 ~ 50 % by weight of its total add-on, and the interval time at every turn added is 7 ~ 10min, and feeding temperature is 50 ~ 80 DEG C.
Drop in the material in reactor, the molar ratio of alkanolamine and alkylamine is preferably 0.2 ~ 3.0: 1, and further preferably, the molar ratio of alkanolamine and alkylamine is 1.0 ~ 2.5: 1.The molar ratio of synthesis epoxy alkane and alkylamine is its theoretical 1.1 ~ 1.8 times of reacting mol ratio.
Drop in the material in reactor, in order to ensure the complete reaction of synthesis epoxy alkane, make the total amount of alkanolamine and alkylamine many compared with the amount of synthesis epoxy alkane, optimum range is: the total amount of synthesis stage alkanolamine and alkylamine and the molar ratio of synthesis epoxy alkane are its theoretical 1.1 ~ 5.0 times of reacting mol ratio.
When preparing alkyl alcoholamine, preferred reaction conditions is: temperature of reaction is 60 ~ 150 DEG C, and soaking time is 2 ~ 6 hours, and reaction pressure is 0.1 ~ 1.0MPa.
The present invention reduces the rectifying number of times used when purification alkyl alcoholamine significantly, adopts twice rectifying at most, and when employing twice rectifying, the material of second time rectifying is the tower bottoms of first time rectifying.
For ensureing the effect of rectifying, when the total process of continuous rectification is a rectifying, one time rectifying feeding temperature is preferably 90 ~ 110 DEG C; When the total process of continuous rectification is twice rectifying, one time rectifying feeding temperature is preferably 90 ~ 110 DEG C, and secondary rectifying feeding temperature is preferably 120 ~ 170 DEG C.
Embodiment
PO hereinafter represents propylene oxide, EO oxyethane; DEA represents diethanolamine, and DIPA represents diisopropanolamine (DIPA), and MIPA represents monoisopropanolamine.
Comparative example:
1, in reactor, add dimethylamine 90g, stir, point six input PO, every minor tick 8min, the common PO of entering measures 116g, controls temperature of reaction at 70 DEG C, reaction pressure 0.7MPa, discharging after stirring reaction 3h, sampling carries out gas chromatographic analysis, dimethylamine transformation efficiency 91.2%, N, N-dimethylisopro panolamine yield 82.5%, synthetic crude product colourity 306APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 65.5 DEG C, N, N-dimethylisopro panolamine product purity >=99.0% after refining, colourity 0APHA, normal temperature places colourity 103APHA after 30 days, places colourity 205APHA after seven days for 60 DEG C.
Embodiment 1:
1, in reactor, add DEA105g, dimethylamine 45g, after stirring, divide four average input PO, every minor tick 10min, the common PO of entering measures 63.8g, control temperature of reaction at 70 DEG C, reaction pressure 0.7MPa, discharging after insulation 3h, gas chromatographic analysis is carried out in sampling, dimethylamine transformation efficiency 95.2%, N, N-dimethylisopro panolamine yield 94.4%, synthetic crude product colourity 4APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 53 DEG C, N, N-dimethylisopro panolamine product purity >=99.5% after refining, colourity 0APHA, normal temperature places colourity 6APHA after 90 days, places colourity 50APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue DEA, again add PO and carry out building-up reactions, the molar ratio of PO and the DEA again added is 0.98: 1, react discharging after 3 hours, obtain the diethanolamine monoisopropanolamine product of purity 98.7 % by weight.
Embodiment 2:
1, in reactor, add DEA105g, dimethylamine 45g, after stirring, divide five average input PO, every minor tick 8min, the common PO of entering measures 92.8g, control temperature of reaction at 80 DEG C, reaction pressure 0.7MPa, discharging after insulation 2h, gas chromatographic analysis is carried out in sampling, dimethylamine transformation efficiency 99.2%, N, N-dimethylisopro panolamine yield 98.9%, synthetic crude product colourity 6APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 53 DEG C, N, N-dimethylisopro panolamine product purity >=99.5% after refining, colourity 0APHA, normal temperature places colourity 4APHA after 90 days, places colourity 57APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue DEA, again add PO and carry out building-up reactions, the molar ratio of PO and the DEA again added is 0.96: 1, react discharging after 3 hours, obtain the diethanolamine monoisopropanolamine product of purity 98.3 % by weight.
Embodiment 3:
1, in reactor, add DEA105g, dimethylamine 45g, after stirring, divide five average input PO, every minor tick 7min, the common PO of entering measures 104.4g, control temperature of reaction at 60 DEG C, reaction pressure 0.7MPa, discharging after insulation 3h, gas chromatographic analysis is carried out in sampling, dimethylamine transformation efficiency 98.7%, N, N-dimethylisopro panolamine yield 98.1%, synthetic crude product colourity 8APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 53 DEG C, N, N-dimethylisopro panolamine product purity >=99.5% after refining, colourity 0APHA, normal temperature places colourity 10APHA after 90 days, places colourity 70APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue DEA, again add PO and carry out building-up reactions, the molar ratio of PO and the DEA again added is 0.98: 1, react discharging after 3 hours, obtain the diethanolamine monoisopropanolamine product of purity 97.2 % by weight.
Embodiment 4:
1, in reactor, add DEA105g, dimethylamine 67.5g, after stirring, divide seven average input PO, every minor tick 8min, the common PO of entering measures 95.7g, control temperature of reaction at 100 DEG C, reaction pressure 0.1MPa, discharging after insulation 4h, gas chromatographic analysis is carried out in sampling, dimethylamine transformation efficiency 99.4%, N, N-dimethylisopro panolamine yield 98.8%, synthetic crude product colourity 7APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 53 DEG C, N, N-dimethylisopro panolamine product purity >=99.5% after refining, colourity 0APHA, normal temperature places colourity 5APHA after 90 days, places colourity 30APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue DEA, again add PO and carry out building-up reactions, the molar ratio of PO and the DEA again added is 0.98: 1, react discharging after 3 hours, obtain the diethanolamine monoisopropanolamine product of 98.9% purity.
Embodiment 5:
1, in reactor, add DEA105g, dimethylamine 67.5g, after stirring, divide seven average input PO, every minor tick 9min, the common PO of entering measures 139.2g, control temperature of reaction at 90 DEG C, reaction pressure 0.7MPa, discharging after insulation 3h, gas chromatographic analysis is carried out in sampling, dimethylamine transformation efficiency 99.8%, N, N-dimethylisopro panolamine yield 99.5%, synthetic crude product colourity 4APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 53 DEG C, N, N-dimethylisopro panolamine product purity >=99.5% after refining, colourity 0APHA, normal temperature places colourity 2APHA after 90 days, places colourity 20APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue DEA, again add PO and carry out building-up reactions, the molar ratio of PO and the DEA again added is 0.97: 1, react discharging after 3 hours, obtain the diethanolamine monoisopropanolamine product of 98.1% purity.
Embodiment 6:
1, in reactor, add DEA105g, dimethylamine 67.5g, after stirring, divide five average input PO, every minor tick 9min, the common PO of entering measures 156.6g, control temperature of reaction at 120 DEG C, reaction pressure 0.3MPa, discharging after insulation 5h, gas chromatographic analysis is carried out in sampling, dimethylamine transformation efficiency 99.9%, N, N-dimethylisopro panolamine yield 95.8%, synthetic crude product colourity 10APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 53 DEG C, N, N-dimethylisopro panolamine product purity >=99.5% after refining, colourity 0APHA, normal temperature places colourity 12APHA after 90 days, places colourity 80APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue DEA, again add PO and carry out building-up reactions, the molar ratio of PO and the DEA again added is 0.98: 1, react discharging after 3 hours, obtain the diethanolamine monoisopropanolamine product of 97.3% purity.
Embodiment 7:
1, in reactor, add DIPA133g, dimethylamine 45g, after stirring, divide quadratic average to drop into PO, every minor tick 10min, the common PO of entering measures 63.8g, control temperature of reaction at 110 DEG C, reaction pressure 0.7MPa, discharging after insulation 3h, gas chromatographic analysis is carried out in sampling, dimethylamine transformation efficiency 95.3%, N, N-dimethylisopro panolamine yield 94.7%, synthetic crude product colourity 4APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 53 DEG C, N, N-dimethylisopro panolamine product purity >=99.5% after refining, colourity 0APHA, normal temperature places colourity 10APHA after 90 days, places colourity 30APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue DIPA, again add EO and carry out building-up reactions, the molar ratio of EO and the DIPA again added is 0.98: 1, react discharging after 3 hours, obtain the hydroxyethyl diisopropanol amine product of 98.7% purity.
Embodiment 8:
1, in reactor, add DIPA133g, dimethylamine 45g, after stirring, divide five average input PO, every minor tick 9min, the common PO of entering measures 92.8g, control temperature of reaction at 140 DEG C, reaction pressure 0.5MPa, discharging after insulation 3h, gas chromatographic analysis is carried out in sampling, dimethylamine transformation efficiency 99.7%, N, N-dimethylisopro panolamine yield 99.5%, synthetic crude product colourity 15APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 53 DEG C, N, N-dimethylisopro panolamine product purity >=99.5% after refining, colourity 0APHA, normal temperature places colourity 5APHA after 90 days, places colourity 57APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue DIPA, again add EO and carry out building-up reactions, the molar ratio of EO and the DIPA again added is 0.95: 1, react discharging after 3 hours, obtain the hydroxyethyl diisopropanol amine product of 98.2% purity.
Embodiment 9:
1, in reactor, add DIPA133g, dimethylamine 45g, after stirring, divide five average input PO, every minor tick 8min, the common PO of entering measures 104.4g, control temperature of reaction at 70 DEG C, reaction pressure 0.7MPa, discharging after insulation 3h, gas chromatographic analysis is carried out in sampling, dimethylamine transformation efficiency 99.9%, N, N-dimethylisopro panolamine yield 99.6%, synthetic crude product colourity 25APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 53 DEG C, N, N-dimethylisopro panolamine product purity >=99.5% after refining, colourity 0APHA, normal temperature places colourity 12APHA after 90 days, places colourity 83APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue DIPA, again add EO and carry out building-up reactions, the molar ratio of EO and the DIPA again added is 0.98: 1, react discharging after 3 hours, obtain the hydroxyethyl diisopropanol amine product of 97.2% purity.
Embodiment 10:
1, in reactor, add DIPA133g, dimethylamine 67.5g, after stirring, divide seven average input PO, every minor tick 7min, the common PO of entering measures 95.7g, control temperature of reaction at 150 DEG C, reaction pressure 0.4MPa, discharging after insulation 6h, gas chromatographic analysis is carried out in sampling, dimethylamine transformation efficiency 96.2%, N, N-dimethylisopro panolamine yield 95.4%, synthetic crude product colourity 7APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 53 DEG C, N, N-dimethylisopro panolamine product purity >=99.5% after refining, colourity 0APHA, normal temperature places colourity 6APHA after 90 days, places colourity 33APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue DIPA, again add EO and carry out building-up reactions, the molar ratio of EO and the DIPA again added is 0.98: 1, react discharging after 3 hours, obtain the hydroxyethyl diisopropanol amine product of 99.1% purity.
Embodiment 11:
1, in reactor, add DIPA133g, dimethylamine 67.5g, after stirring, divide seven average input PO, each amount dropping into PO is not less than 10%, every minor tick 8min, the common PO of entering measures 139.2g, controls temperature of reaction at 70 DEG C, reaction pressure 0.7MPa, discharging after insulation 3h, sampling carries out gas chromatographic analysis, dimethylamine transformation efficiency 99.9%, N, N-dimethylisopro panolamine yield 99.5%, synthetic crude product colourity 11APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 53 DEG C, N, N-dimethylisopro panolamine product purity >=99.5% after refining, colourity 0APHA, normal temperature places colourity 10APHA after 90 days, places colourity 20APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue DIPA, again add EO and carry out building-up reactions, the molar ratio of EO and the DIPA again added is 0.98: 1, react discharging after 3 hours, obtain the hydroxyethyl diisopropanol amine product of 98.5% purity.
Embodiment 12:
1, in reactor, add DIPA133g, dimethylamine 67.5g, after stirring, divide five average input PO, every minor tick 9min, the common PO of entering measures 156.6g, control temperature of reaction at 130 DEG C, reaction pressure 0.9MPa, discharging after insulation 3h, gas chromatographic analysis is carried out in sampling, dimethylamine transformation efficiency 99.9%, N, N-dimethylisopro panolamine yield 99.8%, synthetic crude product colourity 17APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 53 DEG C, N, N-dimethylisopro panolamine product purity >=99.5% after refining, colourity 0APHA, normal temperature places colourity 12APHA after 90 days, places colourity 96APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue DIPA, again add EO and carry out building-up reactions, the molar ratio of EO and the DIPA again added is 0.98: 1, react discharging after 3 hours, obtain the hydroxyethyl diisopropanol amine product of 97.7% purity.
Embodiment 13:
1, in reactor, add MIPA75g, diethylamine 73g, after stirring, divide four average input EO, every minor tick 10min, the common EO of entering measures 48.4g, control temperature of reaction at 70 DEG C, reaction pressure 0.8MPa, discharging after insulation 3h, gas chromatographic analysis is carried out in sampling, diethylamine transformation efficiency 94.2%, N, N-diethylethanolamine yield 92.7%, synthetic crude product colourity 8APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 65.5 DEG C, N, N-diethylethanolamine product purity >=99.5% after refining, colourity 0APHA, and normal temperature places colourity 8APHA after 90 days; Place colourity 20APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue MIPA and hydroxyethyl α-amino isopropyl alcohol, again add EO and carry out building-up reactions, the molar ratio of the total amount of EO and the MIPA again added and hydroxyethyl α-amino isopropyl alcohol is 0.98 times of theoretical reaction mol ratio, react discharging after 3 hours, obtain the di-alcohol monoisopropanolamine product of 98.9% purity; Hydroxyethyl α-amino isopropyl alcohol is wherein reacted by MIPA and EO and generated in reaction process.
Embodiment 14:
1, in reactor, add MIPA75g, diethylamine 73g, after stirring, divide four average input EO, every minor tick 10min, the common EO of entering measures 70.4g, control temperature of reaction at 80 DEG C, reaction pressure 0.8MPa, discharging after insulation 3h, gas chromatographic analysis is carried out in sampling, diethylamine transformation efficiency 97.2%, N, N-diethylethanolamine yield 96.5%, synthetic crude product colourity 10APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 65.5 DEG C, N, N-diethylethanolamine product purity >=99.5% after refining, colourity 0APHA, and normal temperature places colourity 8APHA after 90 days; Place colourity 23APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue MIPA and hydroxyethyl α-amino isopropyl alcohol, again add EO and carry out building-up reactions, the molar ratio of the total amount of EO and the MIPA again added and hydroxyethyl α-amino isopropyl alcohol is 0.98 times of theoretical reaction mol ratio, react discharging after 3 hours, obtain the di-alcohol monoisopropanolamine product of 98.3% purity; Hydroxyethyl α-amino isopropyl alcohol is wherein reacted by MIPA and EO and generated in reaction process.
Embodiment 15:
1, in reactor, add MIPA75g, diethylamine 73g, after stirring, divide four average input EO, every minor tick 9min, the common EO of entering measures 79.2g, control temperature of reaction at 70 DEG C, reaction pressure 0.8MPa, discharging after insulation 3h, gas chromatographic analysis is carried out in sampling, diethylamine transformation efficiency 99.4%, N, N-diethylethanolamine yield 98.8%, synthetic crude product colourity 15APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 65.5 DEG C, N, N-diethylethanolamine product purity >=99.5% after refining, colourity 0APHA, and normal temperature places colourity 10APHA after 90 days; Place colourity 35APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue MIPA and hydroxyethyl α-amino isopropyl alcohol, again add EO and carry out building-up reactions, the molar ratio of the total amount of EO and the MIPA again added and hydroxyethyl α-amino isopropyl alcohol is 0.98 times of theoretical reaction mol ratio, react discharging after 3 hours, obtain the di-alcohol monoisopropanolamine product of 98.1% purity; Hydroxyethyl α-amino isopropyl alcohol is wherein reacted by MIPA and EO and generated in reaction process.
Embodiment 16:
1, in reactor, add MIPA75g, diethylamine 111g, after stirring, divide four average input EO, every minor tick 8min, the common EO of entering measures 72.6g, control temperature of reaction at 70 DEG C, reaction pressure 1.0MPa, discharging after insulation 3h, gas chromatographic analysis is carried out in sampling, diethylamine transformation efficiency 97.2%, N, N-diethylethanolamine yield 96.4%, synthetic crude product colourity 5APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 65.5 DEG C, N, N-diethylethanolamine product purity >=99.5% after refining, colourity 0APHA, and normal temperature places colourity 8APHA after 90 days; Place colourity 25APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue MIPA and hydroxyethyl α-amino isopropyl alcohol, again add EO and carry out building-up reactions, the molar ratio of the total amount of EO and the MIPA again added and hydroxyethyl α-amino isopropyl alcohol is 0.98 times of theoretical reaction mol ratio, react discharging after 3 hours, obtain the di-alcohol monoisopropanolamine product of 98.9% purity; Hydroxyethyl α-amino isopropyl alcohol is wherein reacted by MIPA and EO and generated in reaction process.
Embodiment 17:
1, in reactor, add MIPA75g, diethylamine 111g, after stirring, divide five average input EO, every minor tick 8min, the common EO of entering measures 105.6g, control temperature of reaction at 70 DEG C, reaction pressure 0.8MPa, discharging after insulation 3h, gas chromatographic analysis is carried out in sampling, diethylamine transformation efficiency 99.2%, N, N-diethylethanolamine yield 98.4%, synthetic crude product colourity 8APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 65.5 DEG C, N, N-diethylethanolamine product purity >=99.5% after refining, colourity 0APHA, and normal temperature places colourity 11APHA after 90 days; Place colourity 33APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue MIPA and hydroxyethyl α-amino isopropyl alcohol, again add EO and carry out building-up reactions, the molar ratio of the total amount of EO and the MIPA again added and hydroxyethyl α-amino isopropyl alcohol is 0.98 times of theoretical reaction mol ratio, react discharging after 3 hours, obtain the di-alcohol monoisopropanolamine product of 98.4% purity; Hydroxyethyl α-amino isopropyl alcohol is wherein reacted by MIPA and EO and generated in reaction process.
Embodiment 18:
1, in reactor, add MIPA75g, diethylamine 111g, after stirring, divide four average input EO, every minor tick 8min, the common EO of entering measures 118.8g, control temperature of reaction at 70 DEG C, reaction pressure 0.6MPa, discharging after insulation 3h, gas chromatographic analysis is carried out in sampling, diethylamine transformation efficiency 99.8%, N, N-diethylethanolamine yield 99.4%, synthetic crude product colourity 18APHA.
2, carry out continuous rectification to thick product, vacuum tightness is-0.099MPa, feeding temperature 100 DEG C, tower top cutting temperature 65.5 DEG C, N, N-diethylethanolamine product purity >=99.5% after refining, colourity 0APHA, and normal temperature places colourity 15APHA after 90 days; Place colourity 31APHA after seven days for 60 DEG C.
3, after rectifying kettle material passes into reactor, analyze the amount of residue MIPA and hydroxyethyl α-amino isopropyl alcohol, again add EO and carry out building-up reactions, the molar ratio of the total amount of EO and the MIPA again added and hydroxyethyl α-amino isopropyl alcohol is 0.98 times of theoretical reaction mol ratio, react discharging after 3 hours, obtain the di-alcohol monoisopropanolamine product of 98.0% purity; Hydroxyethyl α-amino isopropyl alcohol is wherein reacted by MIPA and EO and generated in reaction process.
Embodiment more specifically shows:
Compared with prior art, first advantage of the present invention is to improve the transformation efficiency of raw material and the rate of recovery of product, solve the problem of alkylamine low conversion rate in traditional alkyl alcoholamine preparation method, and eliminate recovery process and the dewatering process flow of alkylamine raw material, shorten Production Flow Chart, and because this reducing production energy consumption; Next is that the colourity of not only obtained thick product is more shallow, and the colourity of product after purifying also has higher stability.
As can be seen from the above embodiments, when adopting primary alkanol amine as reaction promotor, have part primary alkanol amine and epoxy alkane generates sec alkanol amine, but this part sec alkanol amine in the reaction of aftertreatment, can continue to react with epoxy alkane to generate trialkanolamine; Also namely in the present invention, when adopting primary alkanol amine as reaction promotor, having part primary alkanol amine and being converted into sec alkanol amine, but this can regard that employing primary alkanol amine and sec alkanol amine are as reaction promotor as simultaneously.
Embodiment also shows simultaneously, owing to the rectifying kettle material after purification being sent in reactor as raw material, and adds epoxy alkane, prepare corresponding commercial grade trialkanolamine product, take full advantage of starting material, produce without waste, reach the effect of cleaner production.
Claims (10)
1. a preparation method for alkyl alcoholamine, is characterized in that, comprises the steps:
(1) alkylamine and reaction promotor alkanolamine to be put in reactor and to be uniformly mixed;
(2) then add synthesis epoxy alkane, the molar ratio of synthesis epoxy alkane and alkylamine is greater than its theory and reacts mol ratio;
(3) heat up after charging and pressurize;
(4) be incubated, generate thick product;
(5) thick product is isolated alkyl alcoholamine by continuous rectification;
Described alkanolamine is primary alkanol amine or sec alkanol amine.
2. preparation method according to claim 1, it is characterized in that, also comprise the operation that the rectifying kettle material after by continuous rectification carries out aftertreatment, described postprocessing working procedures is: the rectifying kettle material after continuous still battery being completed sends into reactor, adds the reaction of recovery epoxy alkane and prepares trialkanolamine product.
3. preparation method according to claim 2, is characterized in that, the recovery epoxy alkane described in postprocessing working procedures is propylene oxide, oxyethane, butylene oxide ring or R-GLYCIDOL; The molar ratio of the alkanolamine in recovery epoxy alkane and rectifying kettle material is its theoretical 0.95 ~ 0.98 times of reacting mol ratio.
4. the preparation method described in arbitrary claim according to claims 1 to 3, is characterized in that, alkanolamine has the structure of formula (I):
Wherein R
1represent hydrogen, C
2~ C
5hydroxyalkyl;
R
2represent C
2~ C
5hydroxyalkyl.
5. the preparation method described in arbitrary claim according to claims 1 to 3, is characterized in that, alkylamine has the structure of formula (II):
Wherein R3 represents hydrogen, methyl, ethyl, propyl group, sec.-propyl or butyl;
R4 represents methyl, ethyl, propyl group, sec.-propyl or butyl.
6. the preparation method described in arbitrary claim according to claims 1 to 3, is characterized in that, synthesis epoxy alkane is any one in oxyethane, propylene oxide, butylene oxide ring or R-GLYCIDOL.
7. the preparation method described in arbitrary claim according to claims 1 to 3, it is characterized in that, synthesis epoxy alkane at least divides 2 times and adds, the each add-on of synthesis epoxy alkane is 10 ~ 50 % by weight of its total add-on, the interval time at every turn added is 7 ~ 10min, and feeding temperature is 50 ~ 80 DEG C.
8. the preparation method described in arbitrary claim according to claims 1 to 3, is characterized in that,
The molar ratio of alkanolamine and alkylamine is 0.2 ~ 3.0: 1;
The molar ratio of synthesis epoxy alkane and alkylamine is its theoretical 1.1 ~ 1.8 times of reacting mol ratio.
9. the preparation method described in arbitrary claim according to claims 1 to 3, is characterized in that, temperature of reaction is 60 ~ 150 DEG C, and soaking time is 2 ~ 6 hours, and reaction pressure is 0.1 ~ 1.0MPa.
10. the preparation method described in arbitrary claim according to claims 1 to 3, is characterized in that, the total process of continuous rectification is a rectifying or twice rectifying; During twice rectifying, the material of second time rectifying is the tower bottoms of first time rectifying.
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