CN104628576A - Method for preparing ethylene amine - Google Patents
Method for preparing ethylene amine Download PDFInfo
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- CN104628576A CN104628576A CN201410648337.3A CN201410648337A CN104628576A CN 104628576 A CN104628576 A CN 104628576A CN 201410648337 A CN201410648337 A CN 201410648337A CN 104628576 A CN104628576 A CN 104628576A
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- Prior art keywords
- ethyleneamines
- ammonia
- neutralization reaction
- sodium
- particle
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/03—Monoamines
- C07C211/05—Mono-, di- or tri-ethylamine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/04—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing ethylene amine and particularly provides a method for preparing ethylene amine, wherein the production efficiency is improved and the energy consumption is reduced.
Description
Technical field
The present invention relates to the method preparing ethyleneamines.
Background technology
Quadrol is chemical formula is C
2h
4(NH
2)
2organic compound, it is colourless liquid, and smell is similar to ammonia.Quadrol is by industrial manner ammonia solution (ammonolysis) ethylene dichloride (ethylenedichloride, EDC) preparation [C
2h
4cl
2+ 4NH
3→ C
2h
4(NH
2)
2+ 2NH
4cl].
Described EDC operation can obtain the multiple ethyleneamines such as quadrol (EDA), diethylenetriamine (DETA), Triethylenetetramine (TETA) (TETA), tetren (TEPA) simultaneously, and has the advantage of the composition that can regulate ethyleneamines as required.
But, because described EDC operation uses excess of ammonia, generate the ammonium chloride (NH as by product
4cl), therefore in and need while ammonium chloride to carry out reclaiming the technique [NH of ammonia
4cl+NaOH → NaCl+NH
3+ H
2o].
And described EDC operation, is separated by techniques such as evaporation or recrystallize the salt generated in described N-process; After removing moisture simultaneously; Finally obtain ethyleneamines, then obtain quadrol by purification ethyleneamines, this is general ordinary method.
Described a series of EDC operation, substantially carry out in aqueous phase (aqueous phase), especially in order to the salt generated in described neutralization reaction can be enable all to dissolve, a large amount of water (addition is make the salt of generation at least can dissolve with state of saturation and exist) is added further.
But, as described above, owing to adding a large amount of water in neutralization reaction, in the subsequent technique of described neutralization reaction, need to consume a large amount of energy for removing salt and moisture by methods such as evaporation, recrystallize, distillations, the problem that therefore process cost increase causes production efficiency to decline occurs.
Summary of the invention
The object of this invention is to provide a kind of reduction energy expenditure, thus the method preparing ethyleneamines of enhancing productivity.
The method preparing ethyleneamines provided by the invention, comprises the following steps:
Ammonia solution ethylene dichloride obtains the resultant comprising ethyleneamines and ammonium chloride;
The aqueous sodium hydroxide solution of 30 to 80 % by weight (W/V) is added, by the neutralization reaction precipitated sodium chloride particle of described ammonium chloride in described resultant;
The sodium-chlor particle of separating out is reclaimed by solid-liquid separation; And
The liquid that purification is reclaimed by described solid-liquid separation, thus reclaim ethyleneamines.
According to the present invention, the reaction that described ammonia solution is the ammonia soln of 20 to 80% by ethylene dichloride and concentration is carried out.
According to the present invention, described ammonia solution can 50 to 180 DEG C temperature and 80 to 180 bar pressure condition under carry out.
According to the present invention, described ethyleneamines can for being selected from quadrol (ethylenediamine), diethylenetriamine (diethylenetriamine), Triethylenetetramine (TETA) (triethylenetetramine), tetren (tetraethylenepentamine), penten (pentaethylenehexamine), six ethylidene seven amine (hexaethyleneheptamine), piperazine (piperazine), and 1-(2-aminoethyl) piperazine) at least one compound in (1-(2-aminoethyl) piperazine).
According to the present invention, the number average value particle diameter of being separated out the sodium-chlor particle obtained by described neutralization reaction can be 50 to 350 microns.
According to the present invention, as in the neutralization reaction of the ammonium chloride of by product generation in the building-up process of ethyleneamines, the aqueous sodium hydroxide solution of the high density using water-content to reduce, thus effectively can either remove salt, energy expenditure required in successive projects can be reduced again, therefore, it is possible to more effectively prepare ethyleneamines.
Accompanying drawing explanation
Fig. 1 is the partial schematic diagram of conventional EDC operation.
Fig. 2 is the partial schematic diagram of the synthetic method of the quadrol that one embodiment of the invention relates to.
Embodiment
Below describe the preparation method of the quadrol that specific embodiments of the invention relate in detail.
Before this, it should be noted that, in the whole text in specification sheets as without explicitly pointing out, dialect is to mention specific embodiment, being not intended to limit the present invention.
In addition, the odd number used in this specification sheets, as without the content clearly represented in contrast, also comprises plural number.
And, " comprising " of using in specification sheets, refer to specific particular characteristics, field, integer, step, action, key element and/or composition, instead of get rid of existence or other particular characteristics additional, field, integer, step, action, key element, composition and/or group.
In the whole text in specification sheets, " ethyleneamines " refers to the general designation of quadrol and its derivative, such as, can comprise quadrol, diethylenetriamine, Triethylenetetramine (TETA), tetren, penten, six heptan vinyl-amine, piperazine and 1-(2-aminoethyl) piperazine) etc.
In addition, as described in the background art, quadrol is by industrial manner ammonia solution ethylene dichloride (so-called " EDC operation ") preparation [C
2h
4cl
2+ 4NH
3→ C
2h
4(NH
2)
2+ 2NH
4cl].But use excess of ammonia in described EDC operation, and generate ammonium chloride (NH
4cl) by product, therefore and while ammonium chloride, needs the operation [NH carrying out reclaiming ammonia
4cl+NaOH → NaCl+NH
3+ H
2o].
Further, in described EDC operation, be separated by methods such as evaporation, recrystallize the sodium-chlor generated in described N-process; After removing moisture simultaneously; Finally obtain ethyleneamines, then obtain quadrol by purification ethyleneamines, this is general ordinary method.
Described a series of EDC operation, in order to easily reclaim ammonia, substantially carry out in aqueous phase (aqueous phase), especially in order to the salt generated in described neutralization reaction can be enable all to dissolve, a large amount of water (addition is make the salt of generation at least can dissolve with state of saturation and exist) is added further.
That is, in stoichiometry, in order to enable the sodium-chlor generated in described neutralization reaction process be dissolved with state of saturation, need to regulate water-content in ammonification solution resultant to reach about 70 % by weight.In order to accomplish this point, while adding the sodium hydroxide of equivalent in described neutralization reaction, need to add a large amount of water further.Such as, this neutralization reaction adds the aqueous sodium hydroxide solution of about 20 % by weight (W/V) of the sodium hydroxide containing equivalent.After reclaiming sodium-chlor by evaporation or recrystallize etc., the water of above-mentioned further interpolation needs to be reclaimed by methods such as distillations again.This moisture recovery process needs to consume a large amount of energy, thus reduces production efficiency.
But, result of study display of the present invention, if reduce the content of the water added in ammonium chloride neutralization reaction in described EDC operation (namely, use the aqueous sodium hydroxide solution of high density), before carrying out the operation of recovery ammonia, separate out (pre-eduction) sodium-chlor particle in advance in neutralization reaction, then carry out solid-liquid separation, then can reduce the energy consumed in follow-up moisture recovery process.
So, one embodiment of the invention provides a kind of method preparing ethyleneamines, comprises the following steps:
Ammonia solution ethylene dichloride obtains the resultant comprising ethyleneamines and ammonium chloride;
The aqueous sodium hydroxide solution of 30 to 80 % by weight (W/V) is added, by the neutralization reaction precipitated sodium chloride particle of described ammonium chloride in described resultant;
The sodium-chlor particle of separating out is reclaimed by solid-liquid separation; And
The liquid that purification is reclaimed by described solid-liquid separation, thus reclaim ethyleneamines.
Substantially, the preparation method that described embodiment relates to prepares the method for quadrol by ammonia solution (so-called " EDC operation ") ethylene dichloride (ethylenedichloride, EDC).
At this, described ammonia solution refers to the solvolysis reaction in ammonia liquor.That is, according to an embodiment, described ammonia solution is undertaken by the reaction of ethylene dichloride and ammonia soln, and described ammonia solution can obtain the resultant [C comprising ethyleneamines and ammonium chloride
2h
4cl
2+ 4NH
3→ C
2h
4(NH
2)
2+ 2NH
4cl].
At this, as ethylene dichloride (EDC) and the ammonia (NH of reactant
3) mol ratio can regulate according to the composition of ethyleneamines resultant, preferably, can excess of ammonia be added.According to an embodiment, ethylene dichloride (EDC) and ammonia that mol ratio is 1:5 to 1:15,1:5 to 1:12,1:5 to 1:10,1:5 to 1:8,1:7 to 1:15,1:8 to 1:15 or 1:10 to 1:15 in described reactant, can be comprised.That is, consider from the angle of the turnover ratio guaranteeing described ammonia solution, described mol ratio is that more than 1:5 is more favourable.Just, when considering the problems such as the amount of the ammonia of recirculation and handling easiness, described mol ratio is that below 1:15 is more favourable.
In addition, according to an embodiment, the concentration of described ammonia soln is preferably 20 to 80%, 30 to 80%, 40 to 80%, 50 to 80%, 20 to 65%, 20 to 60%, 20 to 50%.At this, described percentage concentration refers to the weight (such as 20 to 80g) of unit weight (such as 100g) than ammonia of solution.That is, consider from the angle of the turnover ratio guaranteeing described ammonia solution, more favourable when described ammonia soln concentration is more than 20%; And consider the amount and handling easiness etc. of the water circulated in whole technique, described ammonia soln concentration is less than 80% more favourable.
Especially, under condition noted earlier, when carrying out described ammonolysis reaction, the ethyleneamines that quadrol content is 25 to 50 % by weight can be prepared.
In addition, according to an embodiment, described ammonia solution can 50 to 180 DEG C temperature and 80 to 180 bar pressure under carry out.That is, described ammonia solution is as non-catalytic reaction, in order to ensure the turnover ratio of ammonia solution, compares favourable under the pressure in the temperature more than 50 DEG C and 80 Palestine and Israels.Just, when considering minimum side reactions and handling easiness, described ammonia solution compares favourable below 180 DEG C under temperature and 180 Palestine and Israel's overdraft.
And according to an embodiment, described ammonia solution can use tubular reactor etc. by can successional technique carry out, and now, can carry out a series of reaction by dynamic pressure.
The resultant containing ethyleneamines and ammonium chloride is generated by described ammonia solution.Now, described ethyleneamines can for being selected from quadrol, diethylenetriamine, Triethylenetetramine (TETA), tetren, penten, six ethylidene seven amine, piperazine and 1-(2-aminoethyl) piperazine) at least one compound.That is, described resultant can comprise multiple ethyleneamines, can comprise ammonium chloride as by product.In addition, described ethyleneamines, in the ending of whole technique, by purifying technique, carries out Separation and Recovery to each compound.
In addition, the method preparing ethyleneamines that a described embodiment relates to comprises the aqueous sodium hydroxide solution adding 30 to 80 % by weight (W/V) in described resultant, by the step of the neutralization reaction precipitated sodium chloride particle of described ammonium chloride.
Described step is as the ammonium chloride by comprising in the described resultant of neutralization to reclaim the technique of ammonia, and the ammonia of recovery can be reused in described ammonolysis reaction.Further, ammonium chloride is converted to ammonia, sodium-chlor and water [NH by using sodium hydroxide by described neutralization reaction
4cl+NaOH → NaCl+NH
3+ H
2o].
At this, existing method (so-called " CL technique (all soluble process) ") as shown in Figure 1, dissolve with state of saturation to enable the sodium-chlor generated in described neutralization reaction, and the water adding aequum further (such as, the aqueous sodium hydroxide solution comprising about 20 % by weight (W/V) of the sodium hydroxide of equivalent is added) in this neutralization reaction, the resultant of distillation neutralization reaction is to reclaim ammonia, reclaim sodium-chlor by evaporation or recrystallize etc. afterwards, this is general ordinary method.But described existing method, when again reclaiming a large amount of moisture added in neutralization reaction, needs the energy of at substantial.
In contrast, preparation method's (so-called " separating out technique (pre-eduction process) in advance ") that one embodiment of the invention relates to, by formed can in described neutralization reaction the condition of precipitated sodium chloride, thus separate out in neutralization reaction the sodium-chlor particle that generates in advance and reclaim, then reclaim ammonia, water, ethyleneamines in subsequent technique.
In order to realize described method, compared with the conventional method, preparation method of the present invention uses a small amount of water in described neutralization reaction, such as, as shown in Figure 2, uses the aqueous sodium hydroxide solution of high density.That is, existing method, in order to enable the sodium-chlor resultant of neutralization reaction dissolve with state of saturation, adding water and making the water-content comprised in resultant of reaction reach about 70 % by weight.For this reason, the aqueous sodium hydroxide solution of about 20 % by weight (W/V) that comprise the sodium hydroxide of equivalent adds in neutralization reaction by existing method.In contrast, the neutralization reaction of described one embodiment of the invention, can use the sodium hydroxide containing equivalent and the lower high-concentration sodium hydroxide aqueous solution of water-content.
According to one embodiment of the invention, can use during described neutralization is anti-comprise can in and more than 30 % by weight (W/V), 30 to 80 % by weight (W/V) of sodium hydroxide of equivalent of ammonium chloride, 30 to 70 % by weight (W/V), 30 to 60 % by weight (W/V), 30 to 50 % by weight (W/V), 35 to 50 % by weight (W/V), 40 to 80 % by weight (W/V), 40 to 70 % by weight (W/V), 40 to 60 % by weight (W/V) or 40 to 50 % by weight (W/V) aqueous sodium hydroxide solution.That is, in order to separate out the sodium-chlor particle that described neutralization reaction generates, use the aqueous sodium hydroxide solution with 30 % by weight (W/V) above concentration more favourable.But when considering the amount and precipitation efficiency etc. of the water circulated in whole technique, the concentration of the aqueous sodium hydroxide solution of interpolation is that 80 % by weight (W/V) are more favourable below.
According to one embodiment of the invention, different according to the concentration of the aqueous sodium hydroxide solution used, the particle diameter of the sodium-chlor particle of separating out in described neutralization reaction is also thereupon different.That is, when using the aqueous sodium hydroxide solution of lower concentration (such as, 30 % by weight (W/V)), the sodium-chlor particle that number average value particle diameter is relatively large can be separated out.On the contrary, when using the aqueous sodium hydroxide solution of high energy degree (such as, 30 % by weight (W/V)), the sodium-chlor particle that number average value particle diameter is relatively little can be separated out.
Now, in order to easily reclaim sodium-chlor particle by solid-liquid separation in subsequent step, the number average value particle diameter of the sodium-chlor particle of precipitation be 50 to 350 microns, 100 to 350 microns, 100 to 300 microns or 100 to 250 microns more favourable.At this, the particle diameter of sodium-chlor particle can be measured by usual means such as dry laser diffraction analysis instrument.
Described neutralization reaction by adding sodium hydroxide in described ammonolysis reaction resultant, under the temperature condition of about 50 to 200 DEG C, can be carried out with the method that 50 to 500rpm stirs.
In addition, the method preparing ethyleneamines that a described embodiment relates to comprises the step being reclaimed the sodium-chlor particle of separating out by solid-liquid separating method.
That is, the preparation method that relates to of a described embodiment, before carrying out conventional recovery ammonia step, by foregoing step precipitated sodium chloride particle in advance, and reclaims described sodium-chlor particle by solid-liquid separation in advance.Therefore, not only can reduce the amount of the water circulated in whole technique, and effectively can remove salt, reduce the energy expenditure in subsequent handling simultaneously, thus effectively can prepare ethyleneamines.
According to an embodiment, described solid-liquid separation process can be undertaken by conventional solid-liquid separation process.And described solid-liquid separation process according to the sodium-chlor particle diameter of separating out in abovementioned steps, can carry out with different conditions.In non-limiting manner, such as, described solid-liquid separation process can carry out 2 to 10 times repeatedly, can use such as required, the device of swirler (cyclone), whizzer (centrifuge) (pusher (pusher type), decant formula (dencanter type)).
In addition, the method preparing ethyleneamines that a described embodiment relates to comprises the liquid of purifying and being reclaimed by described solid-liquid separation, thus reclaims the step of ethyleneamines.
Reclaimed in the liquid after sodium-chlor particle containing ethyleneamines, ammonia, water etc. by described solid-liquid separation.Therefore, can the liquid that described solid-liquid separation reclaims be supplied in recovery ammonia tower, reclaim ammonia by distillation, extraction etc., and by carrying out distilling etc. operation to its remaining liq, reclaim the ethyleneamines removing moisture.Then, by the ethyleneamines reclaimed of purifying, can be separated and obtain quadrol, diethylenetriamine etc.
At this, reclaiming described ammonia, water etc. and purification ethyleneamines etc. can be undertaken by the customary means of the technical field of the invention, does not limit concrete equipment and process condition.
In order to help to understand the present invention, below the preferred embodiments of the present invention are described.But following embodiment just illustrates the present invention to exemplify, and the present invention is not limited to this.
comparative example
The ammonia soln of ethylene dichloride and 60% is added in tubulose EDC reactor with the mol ratio of about 1:8, and under the pressure of about 160 bar, the temperature of reactor rear end is maintained about 120 DEG C, carries out ammonolysis reaction with this understanding.Now, by the content of gc analysis chlorion, thus confirm the turnover ratio of ethylene dichloride.
In order to neutralize the ammonium chloride that described ammonia solution generates, in described resultant of reaction, add the aqueous sodium hydroxide solution comprising about 20 % by weight (W/V) of the sodium hydroxide of equivalent.Then, at the temperature of about 140 DEG C, stir with 150rpm speed, to carry out neutralization reaction.Along with the carrying out of described neutralization reaction, the sodium-chlor of generation can state of saturation dissolve, and now, the content of the water comprised in solution is confirmed as about 71 % by weight (W/V).
After described neutralization reaction terminates, described resultant of reaction is supplied to recovery ammonia tower, by distillation to reclaim ammonia.Then, by the evaporation technology to remaining liq, crystallization Isolating chlorinated sodium, water is recycled by distillation.The ethyleneamines having removed sodium-chlor and moisture, as the finished product, is separated in knockout tower.
embodiment 1
By ethylene dichloride and 60% ammonia soln add tubulose EDC reactor to the mol ratio of about 1:8 after, and under the pressure of about 160 bar, the temperature of reactor rear end is maintained about 120 DEG C, carries out ammonolysis reaction with this understanding.Now, by the content of gc analysis chlorion, thus confirm the turnover ratio of ethylene dichloride.
In order to neutralize the ammonium chloride that described ammonia solution generates, in described resultant of reaction, add the aqueous sodium hydroxide solution comprising about 30 % by weight (W/V) of the sodium hydroxide of equivalent.Then, at the temperature of about 140 DEG C, stir with 150rpm speed, to carry out neutralization reaction.Now, the content of the water comprised in solution is confirmed as about 63 % by weight (W/V), along with described neutralization reaction, observes with the naked eye the precipitation of solid particles (sodium-chlor particle).Through confirming, during with the sodium hydroxide adding identical amount in described neutralization reaction for basis conversion, the amount of the water added further in the neutralization reaction of described embodiment 1, compared with comparative example, approximately reduces 29%.
After described neutralization reaction terminates, reclaim sodium-chlor particle by centrifugation (under the condition of 700atm pressurization, carrying out twice, about 10 minutes at every turn).Analyze granularity by dry laser diffraction analysis instrument, the number average value particle diameter of the sodium-chlor particle of recovery is about 248 microns.
Then, the liquid reclaimed is supplied to recovery ammonia tower and distills, thus reclaimed ammonia by described solid-liquid separation, remove moisture, to obtain ethyleneamines by distillation remaining liq afterwards.
embodiment 2
By ethylene dichloride and 60% ammonia soln add tubulose EDC reactor to the mol ratio of about 1:8 after, and under the pressure of about 160 bar, the temperature of reactor rear end is maintained about 120 DEG C, carries out ammonolysis reaction with this understanding.Now, by the content of gc analysis chlorion, thus confirm the turnover ratio of ethylene dichloride.
In order to neutralize the ammonium chloride that described ammonia solution generates, in described resultant of reaction, add the aqueous sodium hydroxide solution comprising about 40 % by weight (W/V) of the sodium hydroxide of equivalent.Then, at the temperature of about 140 DEG C, stir with 150rpm speed type, to carry out neutralization reaction.Now, the content of the water comprised in solution is confirmed as about 57 % by weight (W/V), along with described neutralization reaction, has observed with the naked eye solid particles (sodium-chlor particle) and has separated out.Through confirming, during with the sodium hydroxide adding identical amount in described neutralization reaction for basis conversion, the amount of the water added further in the neutralization reaction of described embodiment 2, compared with comparative example, approximately reduces 45%.
After described neutralization reaction terminates, reclaim sodium-chlor particle by centrifugation (under the condition of 700atm pressurization, carrying out twice, about 10 minutes at every turn).Analyze granularity by dry laser diffraction analysis instrument, the number average value particle diameter of the sodium-chlor particle of recovery is about 192 microns.
Then, the liquid reclaimed is supplied to recovery ammonia tower and distills, thus reclaimed ammonia by described solid-liquid separation, remove moisture, to obtain ethyleneamines by distillation remaining liq afterwards.
embodiment 3
After adding ethylene dichloride and 60% ammonia soln to tubulose EDC reactor with the mol ratio of about 1:8, and under the pressure of about 160 bar, the temperature of reactor rear end is maintained about 120 DEG C, carries out ammonolysis reaction with this understanding.Now, by the content of gc analysis chlorion, thus confirm the turnover ratio of ethylene dichloride.
In order to neutralize the ammonium chloride that described ammonia solution generates, in described resultant of reaction, add the aqueous sodium hydroxide solution comprising about 50 % by weight (W/V) of the sodium hydroxide of equivalent.Then, at the temperature of about 140 DEG C, stir with 150rpm speed, to carry out neutralization reaction.Now, the content of the water comprised in solution is confirmed as about 53 % by weight (W/V), along with described neutralization reaction, has observed with the naked eye solid particles (sodium-chlor particle) and has separated out.Through confirming, during with the sodium hydroxide adding identical amount in described neutralization reaction for basis conversion, the amount of the water added further in the neutralization reaction of described embodiment 3, compared with comparative example, approximately reduces 53%.
After above-mentioned neutralization reaction terminates, reclaim sodium-chlor particle by centrifugation (under the condition of 700atm pressurization, carrying out twice, about 10 minutes at every turn).Analyze granularity by dry laser diffraction analysis instrument, the number average value particle diameter of the sodium-chlor particle of recovery is about 104 microns.
Then, the liquid reclaimed is supplied to recovery ammonia tower and distills, thus reclaimed ammonia by described solid-liquid separation, remove moisture, to obtain ethyleneamines by distillation remaining liq afterwards.
experimental example
In order to quantitatively confirm energy saving effect, Aspen Plus is utilized to simulate in the method for embodiment 3 and the distillation tower of the follow-up recovery ammonia operation of carrying out of operation.Specifically, NH is designed
3distillation tower (Distillation Tower), and be suitable for physical property method (Property Method) ENRTL_RK.Its result, reduces by the situation of embodiment 3 of about 53%, with reboiler (Reboiler) for benchmark, has the energy-saving effect of about 27% relative to comparative example for the amount of the water added in neutralization reaction.
Known by described comparative example, embodiment and experimental example, compared with described comparative example, the amount of the underway water with additionally adding during reaction of described embodiment 1 to 3 can reduce about 53% at most.Obtained by same procedure, the method for embodiment 1 to 3, separate out in advance when carrying out neutralization reaction and reclaim sodium-chlor particle, afterwards subsequent handling is carried out to the liquid be separated, thus the energy expenditure in subsequent handling can be reduced.
Claims (5)
1. prepare a method for ethyleneamines, comprise the following steps:
Ammonia solution ethylene dichloride obtains the resultant comprising ethyleneamines and ammonium chloride;
The aqueous sodium hydroxide solution of 30 to 80 % by weight (W/V) is added, by the neutralization reaction precipitated sodium chloride particle of described ammonium chloride in described resultant;
The sodium-chlor particle of separating out is reclaimed by solid-liquid separation; And
The liquid that purification is reclaimed by described solid-liquid separation, thus reclaim ethyleneamines.
2. prepare the method for ethyleneamines as claimed in claim 1, it is characterized in that:
Described ammonia solution is that the reaction being the ammonia soln of 20 to 80% by ethylene dichloride and concentration is carried out.
3. prepare the method for ethyleneamines as claimed in claim 1, it is characterized in that:
Described ammonia solution be 50 to 180 DEG C temperature and 80 to 180 bar pressure condition under carry out.
4. prepare the method for ethyleneamines as claimed in claim 1, it is characterized in that:
Described ethyleneamines is for being selected from quadrol, diethylenetriamine, Triethylenetetramine (TETA), tetren, penten, six ethylidene seven amine, piperazine and 1-(2-aminoethyl) piperazine) at least one compound.
5. prepare the method for ethyleneamines as claimed in claim 1, it is characterized in that:
The number average value particle diameter of being separated out the sodium-chlor particle obtained by described neutralization reaction is 50 to 350 microns.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130138509A KR20150055924A (en) | 2013-11-14 | 2013-11-14 | Method for producing ethyleneamines |
| KR10-2013-0138509 | 2013-11-14 |
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| Publication Number | Publication Date |
|---|---|
| CN104628576A true CN104628576A (en) | 2015-05-20 |
Family
ID=53196517
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410648337.3A Pending CN104628576A (en) | 2013-11-14 | 2014-11-14 | Method for preparing ethylene amine |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2015093872A (en) |
| KR (1) | KR20150055924A (en) |
| CN (1) | CN104628576A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013172675A1 (en) * | 2012-05-18 | 2013-11-21 | Hanwha Chemical Corporation | Method for producing ethyleneamines |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2769841A (en) * | 1953-12-23 | 1956-11-06 | Dow Chemical Co | Production of ethylene polyamines |
| US3484488A (en) * | 1967-02-28 | 1969-12-16 | Jefferson Chem Co Inc | Controlled production of ethylene amines |
| CN102224129A (en) * | 2008-10-06 | 2011-10-19 | 联合碳化化学品及塑料技术公司 | Method of manufacturing ethyleneamines |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3183269A (en) * | 1959-09-25 | 1965-05-11 | Montedison Spa | Process for making ethylene diamine by treating ethylene dichloride with ammonia, and separation of vinyl chloride from ammonia |
| GB1510538A (en) * | 1974-06-22 | 1978-05-10 | Bayer Ag | Colourless triethylene tetramine and tetraethylene pentamine |
| DE102005048552A1 (en) * | 2005-10-11 | 2007-04-12 | Basf Ag | Process for the preparation of ethylene amines |
| WO2013172675A1 (en) * | 2012-05-18 | 2013-11-21 | Hanwha Chemical Corporation | Method for producing ethyleneamines |
-
2013
- 2013-11-14 KR KR1020130138509A patent/KR20150055924A/en not_active Application Discontinuation
-
2014
- 2014-11-13 JP JP2014230567A patent/JP2015093872A/en active Pending
- 2014-11-14 CN CN201410648337.3A patent/CN104628576A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2769841A (en) * | 1953-12-23 | 1956-11-06 | Dow Chemical Co | Production of ethylene polyamines |
| US3484488A (en) * | 1967-02-28 | 1969-12-16 | Jefferson Chem Co Inc | Controlled production of ethylene amines |
| CN102224129A (en) * | 2008-10-06 | 2011-10-19 | 联合碳化化学品及塑料技术公司 | Method of manufacturing ethyleneamines |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20150055924A (en) | 2015-05-22 |
| JP2015093872A (en) | 2015-05-18 |
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Application publication date: 20150520 |