CN103896803A - Inorganic process liquid flowing from steam stripping HPO* extraction area and utilization of condensation heat - Google Patents
Inorganic process liquid flowing from steam stripping HPO* extraction area and utilization of condensation heat Download PDFInfo
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- CN103896803A CN103896803A CN201210587647.XA CN201210587647A CN103896803A CN 103896803 A CN103896803 A CN 103896803A CN 201210587647 A CN201210587647 A CN 201210587647A CN 103896803 A CN103896803 A CN 103896803A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
- C01B21/1409—Preparation
- C01B21/1418—Preparation by catalytic reduction of nitrogen oxides or nitrates with hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/14—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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Abstract
The present invention relates to steam strippings
The utilization of the inorganic process liquid and condensation heat of extraction section outflow, and a kind of continuation method for preparing cyclohexanone oxime is provided, the method includes being directly input to water stripping zone from extraction section by the aqueous phase of the extraction containing organic solvent; Evaporation at least 15% weight is present in the water in the aqueous phase of extraction; Moisture vapor streamer is input in heat exchanger and is transferred to heat in process on liquid from moisture vapor streamer, thus the liquid in heating progress and concentration at least partly streamer containing steam.
Description
Technical field
The present invention relates to prepare the method for cyclohexanone-oxime, described method contains uses organic solvent extraction cyclohexanone-oxime in extraction section, carry stripped containing water to associating stripping zone, wherein produced water vapor, organic solvent, pimelinketone and removed at least 15% weight extraction contain water.The streamer that contains water vapor that condensation produces at least in part and will the concentrated energy discharging for heating in-process liquid.
The present invention relates to a kind of cyclohexanone-oxime that adopts and carry out Beckmann rearrangement to prepare the continuation method of hexanolactam.Method of the present invention is not limited to arbitrary special lactan.The preferred ε-caprolactam of described lactan.The production method of described hexanolactam comprise according to so-called (improvement) Raschig technology, based on nitric oxide production hydrogenation technology, based on ammonia oxidation technology and
technology is prepared the method for intermediate.
Background technology
But implementing the method need to have the source of cyclohexanone-oxime.Preparing cyclohexanone-oxime has number of ways, is included under the existence of toluene buffering hydroxylammonium phosphate solution and pimelinketone are reacted to (so-called
technology), or under the existence of hydrogen peroxide, cyclohexanone-oxime (so-called oxidative ammonolysis technology) is prepared in the reaction of pimelinketone and ammoniacal liquor.
The important use of hydroxyl ammonium salt is to prepare oxime from ketone or aldehyde, particularly prepares cyclohexanone-oxime by pimelinketone.With regard to the preparation of this oxime, circulation method is known, and wherein moisture acidic buffer reaction medium synthesizes district and the maintenance circulation of the synthetic district of oxime by hydroxyl ammonium salt.Buffering salt, for example basic salt and/or ammonium salt acidic buffer that reaction medium is derived by for example phosphoric acid and/or sulfuric acid and these acid.In the synthetic district of hydroxyl ammonium salt, nitrate ion or oxynitrides in the moisture inorganic liquid of circulation are transformed into azanol with hydrogen.
Input fresh hydrogen is synthesized district to hydroxyl ammonium salt, and from system, regularly purifies a certain amount of gas to maintain constant hydrogen partial pressure.Purge gas comprises rare gas element composition in fresh hydrogen and the gaseous by-product nitrogen (N of generation
2) and nitrous oxide (N
2o).
Azanol reacts with free buffering acid and forms corresponding hydroxyl ammonium salt, and by the synthetic district of this hydroxyl ammonium salt input oxime, it generates corresponding oxime with reactive ketone there, discharges sour simultaneously subsequently.Isolate oxime from reaction medium after, reaction medium is recycled to the synthetic district of hydroxyl ammonium salt and adds fresh nitrate ion or oxynitrides in reaction medium.
By phosphoric acid and the synthetic hydroxyl ammonium salt of nitrate solution in the situation that, above-mentioned chemical reaction is expressed as follows:
Reaction 1) prepare hydroxylammonium in hydroxyl ammonium salt synthesis stage;
2H
3PO
4+NO
3 -+3H
2→NH
3OH
++2H
2PO
4 -+2H
2O
Reaction 2) prepare oxime in the synthetic district of oxime:
Reaction 3) isolate the oxime of formation after, with HNO
3form supplement new nitrate ion:
H
3PO
4+H
2PO
4-+HNO
3+3H
2O→2H
3PO
4+NO
3 -+3H
2O
First reaction is heterogeneous catalysis.Preferably, catalyzer exists as the disperse phase in liquid reaction mixture using the form of homodisperse solid.
In hydroxylammonium salt solution, the reaction mixture of the first step is the moisture inorganic process liquid (IPL) containing solid catalyst particle suspensoid.
From reaction process, inorganic process liquid can contain intermediate material, for example azanol or ammonia, and it also can be turned to for example hydroxylammonium or ammonium by proton.That is to say, according to the present invention, azanol and hydroxylammonium can be interpreted as azanol and/or hydroxylammonium, and ammonia and ammonium can be understood as ammonia and/or ammonium simultaneously.
Before, preferably from this moisture inorganic process liquid, isolate solid catalyst particle this moisture inorganic process liquid (IPL) being input to the synthetic district of oxime (reaction 2).After filtration, this moisture inorganic process liquid is hydroxylammonium salt solution filtrate.
Such process comprises DSM's
(reference example is as H.J.Damme, J.T.vanGoolen and A.H.de Rooij, Cyclohexanone oxime made without by-product (NH for process
4)
2sO
4, July 10,1972, Chemical Engineering; Pp 54/55 or Ullmann ' sEncyclopedia of Industrial Chemistry (2005) at page 6/7under chapterCaprolactam).
Although the preparation of hydroxylammonium is in decades known and also for many years studied, the existing still Shortcomings of the commercial run with persistence that improves known preparation method.
US3940442 discloses a kind of method of preparing cyclohexanone-oxime, wherein be rich in from solution and the pimelinketone of the azanol of hydroxylammonium synthesis zone and together join the synthetic district of this cyclohexanone-oxime, wherein azanol and the pimelinketone generation cyclohexanone-oxime that reacts to each other, from this solution, cyclohexanone-oxime is separated with unreacted pimelinketone, reclaim this solution to described hydroxylammonium synthesis zone.Then, to be recovered to from the synthetic district of cyclohexanone-oxime the solution stripping sufficiently long time of hydroxylammonium synthesis zone, so that the pimelinketone existing in solution after the cyclohexanone-oxime producing and the residual quantity of cyclohexanone-oxime significantly ease down to below 0.02% weight in the synthetic district of removal cyclohexanone-oxime.This solution is recovered to hydroxylammonium synthesis zone from the synthetic district of cyclohexanone-oxime, and the backward steam stripped solution of this recovery solution of stripping adds nitrate ion and can prevent that palladium catalyst is poisoning.
US7309801 discloses the method for preparing cyclohexanone-oxime, described method comprises that making to contain phosphatic aqueous medium enters the synthetic district of cyclohexanone-oxime from the synthetic district of hydroxylammonium, from this aqueous medium, extract after pimelinketone and cyclohexanone-oxime, aqueous medium is transported to stripping zone from the synthetic district of cyclohexanone-oxime, turn back to again the synthetic district of hydroxylammonium from stripping zone, and by water vapor stripping the aqueous medium in stripping zone; And draw off vapour stream from this stripping zone; Condensed steam stream obtains the aqueous fluids of condensation; And clean organic product with the aqueous fluids of this condensation.
US7408081 discloses a kind of method of preparing cyclohexanone-oxime, comprises the aqueous medium of phosphorous acid group is delivered to the synthetic district of cyclohexanone-oxime from the synthetic district of hydroxylammonium, delivers to He Cong stripping zone, stripping zone turn back to the synthetic district of hydroxylammonium from the synthetic district of cyclohexanone-oxime.In above-mentioned stripping zone, use steam stripped aqueous medium; Wherein carry out described stripping at pressure under higher than the condition of 0.11MPa.From stripping zone discharge produce vapour stream simultaneously by the thermal exchange of vapour stream to process liquid.Aqueous medium is contacted and carries out described extraction with any suitable solvent.
The known aqueous medium that contains phosphoric acid salt steam of method by US7408081 is leaving the organic solvent that contains significant quantity behind the synthetic district of cyclohexanone-oxime and with organic solvent from described aqueous medium extraction pimelinketone and cyclohexanone-oxime.This organic solvent not only exists and can also be entrained in homodisperse organic drop with the form of dissolving.Although clear having demonstrated entering before stripping zone, is removed from aqueous medium for the organic solvent of removing pimelinketone and cyclohexanone-oxime in US7408081, in US7408081 and undeclared how operation.
Make variable cost higher in view of whole separating devices need the consumption of additional energy in very high input and whole process, the method for prior art is not still very economical.
And, an object of the present invention is, compare with the traditional method of implementing in identical production unit, when being provided, a kind of improved method can maintain certain hydroxylammonium productivity.With respect to the traditional method of implementing in identical production unit, the method by be one more environmental protection and more save method.
Contriver surprisingly finds, by removing the solvent in aqueous medium and removing pimelinketone in aqueous medium and cyclohexanone-oxime is combined in an independent stripping zone and can reduces the cost, because method of the present invention needs less equipment and less energy.Feature is that the present invention is without an independent liquid-liquid phase separation district or without an organic solvent stripping zone.
Summary of the invention
Therefore, the invention provides a kind of continuation method of preparing cyclohexanone-oxime, comprise the following steps:
I) prepare moisture hydroxylammonium solution in the synthetic district of hydroxylammonium with hydrogen catalytic reduction nitrate or oxynitride;
II) in the synthetic district of cyclohexanone-oxime by step I) hydroxylammonium react and prepares cyclohexanone-oxime with pimelinketone, thereby one of generation contains water and the first organic phase;
III) by Step II) produce contain water, salt, organic solvent, cyclohexanone-oxime and pimelinketone be input to extraction section containing water;
IV) produce stripped water and the Second Organic Phase of containing in extraction section with organic solvent extraction cyclohexanone-oxime and pimelinketone;
V) by least part of step IV) the defeated Step II of getting back to of Second Organic Phase that produces) the synthetic district of cyclohexanone-oxime;
V1) by step IV) produce be strippedly input to water stripping zone containing water;
VII) thus will be present in the water stripping zone stripped evaporation of the water containing water at least 5% weight produces a stripping containing water and a moisture vapor streamer;
VIII) by step VII) produce moisture vapor streamer be input in heat exchanger;
IX) in heat exchanger, the heat of moisture vapor streamer is transformed in in-process liquid, thereby heats in-process liquid;
X) by least part of step VII) stripping that obtains turns back to step I containing water) in;
Wherein
A) Step II) produce the first organic phase contain the cyclohexanone-oxime higher than 25% weight;
B) step IV) extraction that produces also contain organic solvent containing water; And
C) step IX) in during transfer of heat, be condensed to the moisture vapor streamer of small part.
Here " at least partly " refer to higher than 50% weight, more preferably status is higher than 75% weight, most preferably status is higher than 85% weight.
Therefore, method of the present invention is without independent liquid-liquid phase separation district.
Therefore, method of the present invention is at step IV) and step VI) between without organic solvent stripping zone.
The organic solvent of any suitable solubilized pimelinketone and cyclohexanone-oxime is all applicable to method of the present invention.Preferably, organic solvent can be selected from benzene,toluene,xylene, methylcyclopentane, hexanaphthene or its mixture.More preferably, organic solvent is toluene.
Organic solvent can be used for for example oximate district and extraction section.One or more extraction equipments can be contained in extraction section, for example, and (pulse) packing tower, rotating disc contactor and/or mixer-settler.Preferably, the Pulsed Packed Extraction Column that a counter-current operation is contained in extraction section in this tower, can reclaim pimelinketone and cyclohexanone-oxime from inorganic process liquid.
The inorganic process liquid (from the water that contains of step IV extraction) of leaving extraction section can contain a small amount of pimelinketone and cyclohexanone-oxime, contains saturated organic solvent and this inorganic process liquid and can contain the organic solvent drop of carrying secretly.
Preferably, the stripped weight fraction containing organic solvent in water that in the streamer of moisture vapor, the weight fraction of organic solvent is at least 5 times.
Preferably, in moisture vapor streamer, the weight fraction of pimelinketone is 0.1-2% weight.
Preferably, step IV) content containing organic solvent in water that obtains extraction is 100-2000ppm weight.This wondrous because it mean and have low-level organic solvent but do not impair method of the present invention.
Preferably, being input to pre-heating step IV before water stripping zone) in extraction containing water.At step I) re-use before this heat, use step VII) extraction that obtains carries out preheating containing the heat of water, or also can choice for use step IX) in the energy of moisture vapor streamer carry out preheating.
Add inorganic process liquid to water stripping zone, wherein steam is as steam stripping agent.One or more water strippers can be contained in stripping zone.Preferably, adopt single can be to the stripped water stripper that longer residence time is provided containing water.
Water stripper is equipped with a reboiler, and it utilizes the outside high pressure steam providing as energy source.Liquid in described high pressure steam heating reboiler in tower, is translated into the steam rising along stripper.This is called as steam stripped.Because heat is imported into the stripped containing water of part, at least 5% weight, is more preferably that 7-20% weight is evaporated as moisture vapor streamer, and this will strip organic solvent and the pimelinketone of (almost whole).Cyclohexanone-oxime has very high boiling point and can not be stripped.But the unstable meeting of cyclohexanone-oxime at this temperature is decomposed into pimelinketone (and hydroxyl ammonium salt).
Exterior source of energy can be introduced for evaporation at least 5% weight step VII by inner or outside reboiler) water.Exterior source of energy can be the moisture vapor streamer of a super-atmospheric pressure.
Reclaim at least partly the contained energy of moisture vapor streamer (additionally containing for example organic solvent of some organic compositions and pimelinketone).After leaving water stripper in heat exchanger condensed water steam at least in part.And, the also organic substance in recyclable water vapor in the methods of the invention recycling.Preferably, the organic solvent and the pimelinketone that are present in the condensation product that step c) obtains are re-used at least in part in the method for preparing cyclohexanone-oxime.
Utilize energy that heat exchanger can discharge the condensation of moisture vapor streamer for heating for example in-process liquid.
Heat exchanger can be the reboiler of a distillation tower, and for example, in this distillation tower, cyclohexanone-oxime separates from the organism containing pimelinketone and organic solvent; The heat exchanger of crystallizer, for example, in this crystallizer, thereby water evaporates the crystallization that realizes ammonia sulfate crystal from ammoniumsulphate soln; And organic streams enters extraction tower.
Embodiment comprises the energy of release for heating the reboiler of oxime distillation tower; Heat in the heat exchanger of exchange in ammonium sulphate crystallizer and carrying; Heat-shift heats the reboiler of ammoniumsulphate soln concentrator; Heating enters the organic stream of extraction tower; Or by thermal exchange outside system in liquid (for example water) thus be heated or produce streamer (low pressure).
In cyclohexanone-oxime cleaning area, described water vapor stream also can be used as the steam stripping agent of sewage stripper.
The present invention also provides the method for preparing hexanolactam that comprises method of the present invention.The hexanolactam that another one embodiment of the present invention also provides the method according to this invention to obtain.
Embodiment
The present invention further illustrates by following embodiment, but is not limited to this.
Fig. 1 represents the contrast embodiment being derived by art methods, comprises organic solvent stripper and liquid-liquid phase separation device.
Fig. 2 represents embodiment of the present invention, wherein without organic solvent stripper or liquid-liquid phase separation device.
Fig. 1
The derivative contrast embodiment of art methods as shown in Figure 1, the part that the method contains continuous purification and condensation inorganic process liquid (IPL).
That by line [1], oximate district is discharged contains water, salt, and the top that the aqueous stream (Fig. 1 does not show) of organic solvent, cyclohexanone-oxime and pimelinketone joins extraction tower [E] is incorporated into organic solvent by line [4] bottom of extraction tower [E] simultaneously.In extraction tower [E], utilize the recyclable cyclohexanone-oxime being present in containing (dissolving and/or carry secretly) in water of organic solvent extraction.Discharge by line [3] obtain stripped containing water.The first organic phase that contains organic solvent, cyclohexanone-oxime and pimelinketone obtaining is discharged by line [2] and preferably can again be utilized (Fig. 1 does not show) in the synthetic district of cyclohexanone-oxime.
By line [3], the moisture of extraction being obtained by extraction tower [E] bottom is incorporated in liquid-liquid phase separation device [P] mutually.The extraction obtaining contain some cyclohexanone-oximes and pimelinketone and at least 100 ppm organic solvents (dissolving and/or carry secretly) containing water.In separator [P], form containing water and organic phase.Organic phase is left liquid-liquid phase separation device [P] by line [5].Joining in organic solvent stripper [T] by line [7] containing water (thering is the organic phase of some dissolvings) of liquid liquid separator [P].By line [8], water vapor is incorporated into organic solvent stripper [T] thus bottom carry out the stripping in organic solvent stripper [T].The steam that organic solvent stripper [T] produces contains water and organic solvent.This steam is left from the top of organic solvent stripper [T] and is introduced directly in liquid liquid separator [P] concentrated by line [6].
Moisture underflow (almost) organic solvent-free that organic solvent stripper [T] obtains, it is left and is introduced in the top of water stripper [W] by line [9].In this water stripper [W], by evaporation, the water of at least 5% weight is removed.In addition, remove pimelinketone while cyclohexanone-oxime by stripping and be broken down into pimelinketone.
Due to the part evaporation of (being present in liquid phase) water, can realize stripping to (approach does not show) bottom water stripper [W] by the water vapor that produces due to the dividing potential drop of water in water stripper [W] bottom and/or by introducing water vapor, organic solvent is thickened.
Utilize the water in extra power part evaporation (inner or outside) reboiler (not showing in figure), carry out logistics in water stripping stripper to produce this in-process steam.The steam that water stripper [W] produces contains water and pimelinketone, leaves from water stripper [W] top by line [10].After condensed steam stream, reclaim pimelinketone (Fig. 1 does not show).The aqueous stream of condensation is by line [11] leaving water stripper [W].
Fig. 2
The embodiment of the inventive method that contains continuous IPL purifying and concentrating part as shown in Figure 2.
The top that the aqueous stream that contains water, salt, organic solvent, cyclohexanone-oxime and pimelinketone (Fig. 2 does not show) of oximate district being discharged by line [1] joins extraction tower [E] is incorporated into organic solvent by line [4] bottom of extraction tower [E] simultaneously.In extraction tower [E], utilize the recyclable cyclohexanone-oxime being present in containing (dissolving and/or carry secretly) in water of organic solvent extraction.The first organic phase that contains organic solvent, cyclohexanone-oxime and pimelinketone obtaining is discharged by line [2] and preferably can again be utilized (Fig. 2 does not show) in the synthetic district of cyclohexanone-oxime.
The discharging and being incorporated in water stripper [W] containing water the extraction being obtained by extraction tower [E] bottom by line [3].The extraction obtaining contain some cyclohexanone-oximes and pimelinketone and 100ppm organic solvent (dissolving and/or carry secretly) at least containing water.In this water stripper [W], by evaporation, the water of at least 5% weight is removed.In addition, remove pimelinketone while cyclohexanone-oxime by stripping and be broken down into pimelinketone.
Due to the part evaporation of (being present in liquid phase) water, can, by realizing stripping due to water partial pressure generation water vapor or by introducing water vapor to water stripper [W] bottom (approach does not show) in water stripper [W] bottom, organic solvent be thickened.。
Utilize the steam in extra power part evaporation (inner or outside) reboiler (not showing in figure) to carry this in-process steam of logistics water generates in stripper.The steam that water stripper [W] produces contains water and pimelinketone, leaves from water stripper [W] top by line [10].After condensed steam stream, reclaim pimelinketone (Fig. 2 does not show).The aqueous stream of condensation is by line [11] leaving water stripper [W].
As shown in Figure 2, between extraction tower [E] and water stripper [W] without organic solvent stripper or liquid-liquid phase separation device.Simplify like this technique and reduced required investments and can not affect end product quality simultaneously.
Claims (14)
1. a continuation method of preparing cyclohexanone-oxime, comprises the following steps:
I) prepare moisture hydroxylammonium solution in the synthetic district of hydroxylammonium with hydrogen catalytic reduction nitrate or oxynitride;
II) in the synthetic district of cyclohexanone-oxime by step I) hydroxylammonium react and prepares cyclohexanone-oxime with pimelinketone, thereby one of generation contains water and the first organic phase;
III) by Step II) produce contain water, organic solvent, cyclohexanone-oxime and pimelinketone be input to extraction section containing water;
IV) produce stripped water and the Second Organic Phase of containing in extraction section with organic solvent extraction cyclohexanone-oxime and pimelinketone;
V) by least part of step IV) the defeated Step II of getting back to of Second Organic Phase that produces) the synthetic district of cyclohexanone-oxime;
VI) by step IV) produce be strippedly input to water stripping zone containing water;
VII) thus in water stripping zone, evaporate at least 5% weight and produce a stripping containing water and a moisture vapor streamer being present in the stripped water containing water;
VIII) by step VII) produce moisture vapor streamer be input in heat exchanger;
IX) in heat exchanger by the thermal exchange of moisture vapor streamer in in-process liquid, thereby heat in-process liquid;
X) by least part of step VII) stripping that obtains turns back to step I containing water) in; Wherein
A) Step II) produce the first organic phase contain the cyclohexanone-oxime higher than 25% weight;
B) step IV) extraction that produces also contain organic solvent containing water; And
C) step IX) in during transfer of heat, be condensed to the moisture vapor streamer of small part.
2. method according to claim 1, the weight fraction containing organic solvent in water of the extraction that wherein in the streamer of moisture vapor, the weight fraction of organic solvent is at least 5 times.
3. method according to claim 1, wherein in moisture vapor streamer, the weight fraction of pimelinketone is 0.1-2% weight.
4. method, wherein step IV according to claim 1) content containing organic solvent in water that obtains extraction is 100-2000ppm weight.
According to before any one method of claim, wherein organic solvent can be selected from benzene,toluene,xylene, methylcyclopentane, hexanaphthene or its mixture.
6. method according to claim 1, wherein re-uses the organic solvent and the pimelinketone that are present in the condensation product that step c) obtains in the method for preparing cyclohexanone-oxime at least in part.
7. method according to claim 1, wherein heat exchanger comprises the reboiler in the extraction tower that distillation tower, ammonium sulphate crystallizer and carrying and/or organic stream enter.
8. method according to claim 1, wherein being input to pre-heating step IV before water stripping zone) in extraction containing water.
9. method according to claim 8, wherein at step I) re-use before this heat transfer step VII) extraction that obtains carries out preheating containing the heat of water.
10. method according to claim 8, wherein at step IX) in shift moisture vapor streamer energy carry out preheating.
11. methods according to claim 1, wherein evaporation at least 5% weight step VII) in water institute energy requirement can utilize exterior source of energy to pass through inside or outside reboiler is introduced.
12. according to method described in claim 11, and wherein exterior source of energy can be the moisture vapor streamer of a super-atmospheric pressure.
13. 1 kinds of methods that contain the hexanolactam that according to claim 1 prepared by method.
14. hexanolactams that method obtains according to claim 1.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210587647.XA CN103896803A (en) | 2012-12-28 | 2012-12-28 | Inorganic process liquid flowing from steam stripping HPO* extraction area and utilization of condensation heat |
| KR1020157020072A KR102218342B1 (en) | 2012-12-28 | 2013-12-18 | Steam stripping inorganic process liquid discharged from hpo® extraction section and utilizing heat of condensation |
| PCT/EP2013/077057 WO2014102106A1 (en) | 2012-12-28 | 2013-12-18 | Steam stripping inorganic process liquid discharged from hpo® extraction section and utilizing heat of condensation |
| CN201380068013.6A CN105143175A (en) | 2012-12-28 | 2013-12-18 | Steam stripping inorganic process liquid discharged from hpo extraction section and utilizing heat of condensation |
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|---|---|---|---|
| CN201210587647.XA CN103896803A (en) | 2012-12-28 | 2012-12-28 | Inorganic process liquid flowing from steam stripping HPO* extraction area and utilization of condensation heat |
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| CN201380068013.6A Pending CN105143175A (en) | 2012-12-28 | 2013-12-18 | Steam stripping inorganic process liquid discharged from hpo extraction section and utilizing heat of condensation |
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|---|---|
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| CN112912168B (en) * | 2018-10-17 | 2022-05-10 | Cap Iii 有限公司 | Improved process and plant for the production of oximes |
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| KR100763111B1 (en) * | 2000-06-05 | 2007-10-04 | 디에스엠 아이피 어셋츠 비.브이. | Process for the preparation of cyclohexanone oxime |
| EP1318141A1 (en) * | 2001-12-04 | 2003-06-11 | Dsm Nv | Process for treating an aqueous medium containing phosphate, cyclohexanone and cyclohexanone oxime |
| DE60126686T2 (en) * | 2001-12-04 | 2007-10-31 | Dsm Ip Assets B.V. | METHOD FOR THE TREATMENT OF A CYCLOHEXANONEOXY AND CYCLOHEXANONE-CONTAINING AQUEOUS MEDIA |
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| KR20150100871A (en) | 2015-09-02 |
| WO2014102106A1 (en) | 2014-07-03 |
| CN105143175A (en) | 2015-12-09 |
| KR102218342B1 (en) | 2021-02-22 |
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