CN103508955A - Method used for continuous conversion of epsilon-caprolactam from cyclohexanone-oxime - Google Patents

Method used for continuous conversion of epsilon-caprolactam from cyclohexanone-oxime Download PDF

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CN103508955A
CN103508955A CN201310261625.9A CN201310261625A CN103508955A CN 103508955 A CN103508955 A CN 103508955A CN 201310261625 A CN201310261625 A CN 201310261625A CN 103508955 A CN103508955 A CN 103508955A
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oxime
cyclohexanone
reaction mixture
rich
hexanolactam
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许渝化
约翰·托马斯·廷格
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Cap Iii Ltd Co
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D223/10—Oxygen atoms attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
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    • C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement

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Abstract

The invention discloses a method used for continuous production of epsilon-caprolactam from cyclohexanone-oxime by Beckmann rearrangement. The method comprises following steps: a mixture containing methylbenzene and cyclohexanone-oxime is delivered into a distillation section which is composed of at least one distillation column; and top steam that is rich in methylbenzene, and bottom steam that is rich in cyclohexanone-oxime are taken out from the distillation column, wherein the obtained bottom steam which is rich in cyclohexanone-oxime contains 1 to 500ppm of methylbenzene.

Description

Cyclohexanone-oxime is converted into the method for ε-caprolactam continuously
Technical field
The present invention relates to adopt cyclohexanone-oxime to carry out Beckmann rearrangement to prepare the continuation method of hexanolactam.
Background technology
The present invention relates to adopt cyclohexanone-oxime to carry out Beckmann rearrangement to prepare the continuation method of hexanolactam.
But, implement the source that the method need to have 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
Figure BDA00003418705500011
technology), or under the existence of hydrogen peroxide with pimelinketone and ammonia react, prepare cyclohexanone-oxime (so-called amidoximation technology).
The example of preparing the amidoximation technology of cyclohexanone-oxime employing can be referring to EP1700846.EP1700846 provides a kind of method of preparing cyclohexanone-oxime, the method comprises the following steps (1) to (6): (1) reactions steps: by pimelinketone, the reaction under titanium-silicate catalyst exists of hydrogen peroxide and ammonia, obtain containing cyclohexanone-oxime, water, the reaction soln of unreacted ammonia and unreacted pimelinketone, (2) first distilation steps: the reaction soln obtaining in step (1) is distilled, to distill out ammonia and acquisition contains cyclohexanone-oxime, the bottom product of water and pimelinketone, (3) extraction step: the bottom product obtaining in step (2) is mixed with organic solvent, subsequently mixture separation is become to organic layer and water layer, (4) washing step: will obtain organic layer and water mixing in step (3), subsequently mixture separation is become to organic layer and water layer, (5) after-fractionating step: distill obtaining organic layer in step (4), the bottom product that contains cyclohexanone-oxime and pimelinketone to distill out organic solvent and water and acquisition, (6) the 3rd distilation steps: the bottom product obtaining in step (5) is distilled, the bottom product that contains cyclohexanone-oxime to distill out pimelinketone and acquisition, the compound that adds the oxide compound, oxygen acid, oxysalt, esters of oxyacids and the oxygen acid acid amides that are selected from boron or phosphorus at least one in the organic layer that wherein will carry out step (5) to water and the middle acquisition of step (4) of the middle use of step (4).
US20110190539 discloses a kind of for example amidoximation method of cyclohexanone-oxime of oxime of preparing, in the method carbonyl compound in liquid phase with NH 3and H 2o 2under the existence of catalyzer, reaction is to form corresponding oxime, and wherein catalyzer comprises that the catalyst component of selecting from the metal oxide of period 5 and period 6 wherein especially preferentially selects niobium catalytic.
Water or the solvent mixture (for example water and the trimethyl carbinol) in the method for these two amidoximations, have been used.After reaction finishes, unreacted ammonia and the optionally moisture trimethyl carbinol (if present) are removed (general by distillation) from reaction mixture.
Utilize Toluene Extraction to reclaim cyclohexanone-oxime from the remaining water-based cyclohexanone-oxime that contains solvent, in later phases utilization distillation, remove toluene afterwards.
Figure BDA00003418705500021
method comprises that azanol forms section, by nitrate reduction becomes azanol with hydrogen under the existence at catalyzer with in phosphoric acid inorganic process solution moisture in this section.Also available nitrate ion supplement inorganic process solution and in inorganic process solution partly soluble by product ammonia be converted into nitrogen.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.
Then in oximate section, at azanol, form under section water-based azanol forming and the existence of pimelinketone at solvent toluene and carry out oximation reaction to form cyclohexanone-oxime.
The organic phase producing contains toluene and cyclohexanone-oxime.The concentration of cyclohexanone-oxime be 25% weight or more than, preferably at least 35% weight or more than.Discharge the organic phase and the water cleaning before being incorporated into distilling period that produce, in distilling period, reclaim toluene and obtained cyclohexanone-oxime.
Subsequently, utilize as above or amine oximation process is prepared cyclohexanone-oxime, the cyclohexanone-oxime of generation carries out Beckmann rearrangement to make hexanolactam.This Beckmann rearrangement passes through by cyclohexanone-oxime with containing hexanolactam, sulfuric acid and SO 3mixture mix (add and mix) and carry out.In such process, sulfuric acid and SO 3cyclohexanone-oxime to be converted into the catalyzer of hexanolactam.This conversion is moment generation almost, very fast.
Then, in purification section, remove the organic impurity in the inorganic phase producing, this inorganic phase carries out obtaining after oximation reaction.Adopt toluene extraction, vaporizing extract process and/or carbon absorption to carry out purifying.
WO2004/103964 discloses a kind of cyclohexanone-oxime that adopts and has carried out Beckmann rearrangement to prepare the continuation method of hexanolactam, the method comprise a) by (i) oleum and (ii) cyclohexanone-oxime import one and contain hexanolactam, sulfuric acid and SO 3the first reaction mixture in, b) by (iii) part the first reaction mixture and (iv) cyclohexanone-oxime send into one and contain hexanolactam, sulfuric acid and SO 3the second reaction mixture in, c) take out part the second reaction mixture, wherein the method further comprises the steps to obtain the cyclohexanone-oxime that this can send into reaction mixture: 1) prepare one and contain the organic medium 2 that cyclohexanone-oxime is dissolved in organic solvent) via distillation, from this organic medium, isolate cyclohexanone-oxime.This organic solvent is toluene or benzene.
WO2004/113287 discloses a kind of by through cyclohexanone-oxime and reaction mixture incompatible method of preparing cyclohexanone-oxime of premix in a mixing tank of comprising hexanolactam and sulfuric acid, described mixing tank comprises a (i) reaction tubes that can pass through for reaction mixture, (ii) be placed in tube wall passage around, this passage has opening on tube wall, described method comprises, reaction mixture is passed through to reaction tubes, and cyclohexanone-oxime is transported in reaction mixture by one or more described passages, wherein Re > 5000.
CN101709053 discloses a kind of process of preparing hexanolactam, comprises following steps, after pimelinketone and hexanaphthene are mixed, carries out amidoximation, obtains the cyclohexane solution of cyclohexanone-oxime; The cyclohexane solution of cyclohexanone-oxime is reacted with oleum, generate hexanolactam sulfuric ester solution, hexanolactam sulfuric ester solution is carried out to slaking, hexanolactam sulfuric ester solution after slaking carries out being isolated to hexanolactam crude product after neutralization reaction with ammoniacal liquor again, is extracting respectively and water makes finished product after stripping.What in this patent, carry out is amidoximation, and raw materials used be the mixture of pimelinketone and hexanaphthene.
US7423178 discloses a kind of method that processing comprises the organic solution of cyclohexanone-oxime, pimelinketone and organic solvent, described method comprises that distillation organic solution comprises the first product of organic solvent to obtain (i), (ii) comprise the second product of pimelinketone and the third product that (iii) comprises cyclohexanone-oxime; And the second product is fed in cyclohexanone-oxime synthesis stage, in this synthesis stage, hydroxylammonium reacts with pimelinketone and forms cyclohexanone-oxime.
In the method for prior art, before Beckmann rearrangement occurs, all toluene being separated from cyclohexanone-oxime is extremely important (conventionally adopting the method for distillation), otherwise will be to the hexanolactam producing and the mass formation certain influence of nylon-6.But this is also consuming time a, effort and uneconomic method.
As everyone knows, toluene is not to stablize especially, in Beckmann rearrangement step it can with sulfuric acid and SO 3reaction.Described in US4242275, this reaction can form toluene-4-sulfonic acid, Toluene-2,4-diisocyanate-sulfonic acid and sulfone.The existence of impurity can affect hexanolactam and the nylon-6 quality of generation.
Summary of the invention
Therefore, the invention provides a kind of cyclohexanone-oxime that adopts and carry out the continuation method that Beckmann rearrangement is prepared hexanolactam, the method comprises the following steps that obtain cyclohexanone-oxime:
1), under the existence of toluene, buffering hydroxylammonium phosphate solution and pimelinketone are reacted; Or
2) under the existence of hydrogen peroxide, pimelinketone and ammonia are reacted, then with toluene, extract; The cyclohexanone-oxime wherein obtaining carries out processing treatment by following steps:
A) to the distilling period that comprises at least one distillation tower, add the mixture that contains toluene and cyclohexanone-oxime;
B) from first distillation tower, take out and be rich in the overhead vapor of toluene and from last distillation tower, take out the bottom steam that is rich in cyclohexanone-oxime;
C) by (i) sulfuric acid and SO 3and (ii) from b) bottom steam that is rich in cyclohexanone-oxime that obtains sends into one containing hexanolactam, sulfuric acid and SO 3the first reaction mixture,
D) take out part the first reaction mixture;
E) will part from d) taking-up the first reaction mixture join neutralizing zone;
F) utilize NH 3neutralization part is from d) the first reaction mixture acquisition neutralization reaction mixture of taking out;
G) neutralization reaction mixture is divided into and is rich in ammonium sulfate steam and is rich in hexanolactam steam; B wherein) toluene that the bottom steam that is rich in cyclohexanone-oxime obtaining in contains 1-500ppm.
Advantage of the present invention is, has low-level toluene but can not affect Beckmann rearrangement after distillation, can not affect the quality of hexanolactam and the nylon-6 of generation.
Low-level toluene is 500ppm or lower.
Step a) in, in mixture, the ratio of cyclohexanone-oxime and toluene is preferably 1:1-1:4.If passed through
Figure BDA00003418705500041
method obtains cyclohexanone-oxime, and in mixture, the ratio of cyclohexanone-oxime and toluene is preferably 1:1-1:2.
Utilize the combination of any applicable tower or tower to carry out step b) distillation.Distilling period comprises one or more distillation tower.Preferably, distilling period comprises two or three distillation towers, most preferably is two distillation towers.If distillation tower is more than one, so preferably distillation tower is connected.If distillation tower is more than one, can takes out the overhead vapor be rich in toluene from the first distillation tower so and from last distillation tower, take out the bottom steam that is rich in cyclohexanone-oxime simultaneously.If only there is a distillation tower, can take out the overhead vapor that is rich in toluene and the bottom steam that is rich in cyclohexanone-oxime from identical distillation tower so.
Step b) overhead vapor that is rich in toluene obtaining in preferably contains at least 95wt% toluene, and more preferably 99wt% toluene is at least especially 99.9wt% toluene at least.
Step b) bottom steam that is rich in cyclohexanone-oxime obtaining in preferably contains at least 95wt% cyclohexanone-oxime, and more preferably 99wt% cyclohexanone-oxime at least, most preferably is at least 99.8wt% cyclohexanone-oxime.
Step b) bottom steam that is rich in cyclohexanone-oxime obtaining in preferably contains the toluene lower than 400ppm (0.04wt%), more preferably less than 300ppm toluene, most preferably is the toluene lower than 200ppm.
Distillation actual temperature depend on employing pressure and in order to obtain clean as far as possible steam and to avoid to a great extent the generation of by product to choose suitable temperature and pressure condition by those skilled in the art.Such distillation is further described at US7423178.
This advantage can bearing the method for low-level toluene is, do not require point-device distillation, this means and can use the short distillation tower with small diameter and less backflow.More efficient like this, more economical (low input and less energy-consumption).Further advantage is, if the inventive method adopts current distillation tower, will have the capacity of turnout and Geng Gao faster.At step b) in the bottom steam that is rich in cyclohexanone-oxime that obtains, can bear low-level toluene is the very economical instrument without bottleneck for improving distillation tower treatment capacity.
In an embodiment of the present invention, can be by step b) bottom steam that is rich in cyclohexanone-oxime that obtains joins in a lot of parallel Beckmann rearrangement systems of carrying out (step c)).Step c) in, by component i) and component i i) join and contain certain hexanolactam and sulfuric acid and SO 3mixture in.This is a continuous method, only has part material to be removed, and rest part is stayed in system.
Step c) sulfuric acid and the SO that in, use 3amount to be preferably mol ratio M be between 1.0-2.0.
Mol ratio M is defined as (n h2SO4+ n sO3)/n oxime, wherein
N h2SO4the H that=step c) adds 2sO 4amount mol/s (1mol H 2sO 4be equivalent to 98g),
N sO3the SO that=step c) adds 3amount mol/s (1mol SO 3be equivalent to 80g),
And n oximethe amount mol/s of the cyclohexanone-oxime that=step c) adds (1mol cyclohexanone-oxime is equivalent to 113g).
In one embodiment of the invention, Beckmann rearrangement carries out in one or more series block.In a preferred embodiment, Beckmann rearrangement is at one, and two, or carry out in three series block.In a preferred embodiment, Beckmann rearrangement carries out in two or three series block.
In a preferred embodiment of the invention, Beckmann rearrangement carries out two series block.In described embodiment, adopt following continuous method to obtain hexanolactam:
C) by (i) sulfuric acid and SO 3(ii) bottom steam that is rich in cyclohexanone-oxime part steps b) obtaining joins one containing hexanolactam and sulfuric acid and SO 3the first reaction mixture in,
D1) take out part the first reaction mixture;
D2) by part the first reaction mixture d1) and (ii) remaining part steps b) bottom steam that is rich in cyclohexanone-oxime that obtains joins containing hexanolactam and sulfuric acid and SO 3the second reaction mixture in,
D3) take out part the second reaction mixture, and proceed step e).
In preferred embodiment of the present invention, Beckmann rearrangement carries out in three series block.In described embodiment, adopt following continuous method to obtain hexanolactam:
C) by (i) sulfuric acid and SO 3(ii) bottom steam that is rich in cyclohexanone-oxime part steps b) obtaining joins one containing hexanolactam and sulfuric acid and SO 3the first reaction mixture in,
D1) take out part the first reaction mixture;
D2) by part the first reaction mixture d1) and (ii) another part step b) bottom steam that is rich in cyclohexanone-oxime that obtains joins containing hexanolactam and sulfuric acid and SO 3the second reaction mixture in,
D3) take out part the second reaction mixture;
D4) by part the second reaction mixture d3) and (ii) remaining part steps b) bottom steam that is rich in cyclohexanone-oxime that obtains joins containing hexanolactam and sulfuric acid and SO 3the 3rd reaction mixture in,
D5) take out part the 3rd reaction mixture, and proceed step e).
As mentioned above in the steps d of embodiment), d3) or d5) in, take out part reaction mixture and also add (step e)) in neutralizing zone.The ratio (mark) of the partial reaction mixture taking out is not critical the efficiency that still should select to optimize continuation method.Described mark is preferably steps d), d3) or d5) in the 0.25%-10% of overall accumulated amount of the reaction mixture that uses, more preferably 0.5-7.5%, most preferably is 1-5%.
Consider that it is a continuous method, its target be make into and out of continuation method material keep balance.
From d), d3) or d5) to reclaim hexanolactam in the reaction mixture that obtains be at step f) and in in ammonia with complete.By adding ammonia to neutralization procedure f by the water-soluble form with aqueous solution of ammonia or with the form of gas and/or liquid (under pressure)).Preferably, with the form of aqueous solution, add ammonia.Then utilize step g) in the separated ammonium sulfate producing that is separated from hexanolactam.
The ammonium sulfate that produces after neutralization is all dissolved in the water, or a part of as solid matter in a part of dissolved water, or in anhydrous situation all as solid matter.In the example being added as gas and/or liquid at ammonia, the ammonium sulfate of generation is probably as solid matter.In adding the example of water-soluble ammonia, the ammonium sulfate of generation is all dissolved in water, or an a part of water-soluble part is as solid matter.
Because the existence of the density variation between lower mutual content and phase and phase has produced completely, be separated, so be rich in ammonium sulfate steam and be rich in hexanolactam steam, produce organic phase/aqueous phase separation.Hexanolactam steam is organic phase, utilizes methods known in the art to be further purified to obtain hexanolactam.Be rich in ammonium sulfate steam and be preferably water, the method for this water employing separation and/or purifying for example evaporative crystallization is processed with reclaim(ed) sulfuric acid ammonium.
In addition, further advantage is, the reaction mixture neutralization by obtaining after Beckmann rearrangement, obtains hexanolactam steam, this steam does not contain toluene or the residue/product based on toluene (in can sensing range), thereby can be converted into the nylon-6 of high-quality.
Fig. 1
Fig. 1 represents pimelinketone to be converted into continuously the preferred embodiment of ε-caprolactam.
In this embodiment, by line [1], pimelinketone is joined to cyclohexanone-oxime synthesis stage [A], in this section, pimelinketone is converted into cyclohexanone-oxime.In cyclohexanone-oxime synthesis stage [A], under the existence of toluene, adopt buffering hydroxylammonium phosphate solution to react with pimelinketone to prepare cyclohexanone-oxime (so-called
Figure BDA00003418705500071
or under the existence of hydrogen peroxide, adopt pimelinketone and ammonia react to prepare cyclohexanone-oxime (so-called amidoximation) technology).
By line [2], what from cyclohexanone-oxime synthesis stage [A], flow out imports to purification section [B] containing cyclohexanone-oxime fluid.Purification section [B] preferably includes the step of utilizing aqueous solution to clean cyclohexanone-oxime, in synthesis stage [A], adopt so-called amidoxime technology to prepare in the embodiment of cyclohexanone-oxime, before carrying out cleaning step, in section [B], add toluene to containing in cyclohexanone-oxime fluid.
By line [3], the cyclohexanone-oxime that contains toluene vapor is drained into distilling period [C] from purification section [B].Distilling period [C] comprises at least one distillation tower, and this distillation tower is separated into the bottom steam that is rich in cyclohexanone-oxime and the overhead vapor that is rich in toluene by feed liquid.The bottom steam that is rich in cyclohexanone-oxime usually contains certain toluene.Toluene amount in this bottom steam will contain toluene lower than 500ppm. by line [4], be rich in cyclohexanone-oxime bottom steam and discharge and import to Beckmann rearrangement section [D] from section [C].
In Beckmann rearrangement section [D], the cyclohexanone-oxime importing by line [4] may be divided into one or more strands of steam.In Beckmann rearrangement section [D], by line [5], import sulfuric acid and SO 3.Sulfuric acid and the SO of introduction segment [D] 3mol ratio M be preferably between 1.0-2.0.
By line [6], will contain hexanolactam, sulfuric acid and SO 3reaction mixture is discharged and is incorporated in neutralizing zone [E] from section [D].In neutralizing zone [E], use NH 3(as the composition of gas and/or liquefaction or be dissolved in the water) neutralization contains hexanolactam, sulfuric acid and SO 3reaction mixture, NH 3by line [7], import.
By line [8], discharge neutralization reaction mixture and be introduced in segregation section [F].Optionally, neutralizing zone [E] and segregation section [F] are combined into one section.
By line [9] and line [10], from segregation section [F], discharge two fluid streams respectively, be rich in ammoniumsulphate soln and be rich in caprolactam solution.By line [10], will be rich in caprolactam solution and import hexanolactam purification section [H], according to the known technology of those skilled in the art in purification section by hexanolactam purifying.Can be for the production of nylon-6 from hexanolactam purification section [H] discharge and this hexanolactam by the hexanolactam of the purifying producing by line [11].
The present invention further illustrates by following embodiment, but is not limited to this.
Embodiment:
Embodiment 1
The present embodiment exists
Figure BDA00003418705500081
in equipment, carry out, the water-based hydroxylammonium phosphate solution that utilizes hydrogen that water-based nitrate solution is reduced into azanol and generation in this equipment is added into cyclohexanone-oxime synthesis stage.
The formation of cyclohexanone-oxime and purification process are as shown in Figure 2.
Cyclohexanone-oxime synthesis stage is to be formed by two pulse packed towers (PPC ' s) [A1] and [A2].First PPC[A1] be to operate under temperature 50 C condition, second PPC[A2] be to operate under temperature 70 C condition.
The solution of the aquosity azanol that is 1.3mol/kg by concentration by line [101] joins first PPC[A1] top.By line [109], the top product of second cyclohexanone-oxime distillation tower [C2] is joined to first PPC[A1] in.By line [102] to first PPC[A1] bottom add pimelinketone simultaneously by line [103] by organic medium from second PPC[A2] top flow out.Contain dissolve cyclohexanone-oxime aqueous solution from first PPC[A1] flow out and pass through line [108] join second PPC[A2] top.By line [104] from first PPC[A1] organic solution that flows out of top comprises cyclohexanone-oxime (35% weight), toluene (63% weight) and a certain amount of unreacted pimelinketone.By line [113], will use the aqueous solution of methylbenzene extraction from second PPC[A2] discharge.
For reclaiming different salt, first organic solution is joined in multistage cleaning section [B].By line [105], add for reclaiming the water of these salt.By line [106], the water-based containing reclaiming salt producing is discharged mutually.By line [107], the organic solution of the cleaning of acquisition is incorporated in first cyclohexanone-oxime distillation tower (packed column with a stripping stage and rectifying section) [C1].This cyclohexanone-oxime distilling period is comprised of first cyclohexanone-oxime distillation tower [C1] and second cyclohexanone-oxime distillation tower [C2].These two cyclohexanone-oxime distillation towers are the packed column with a stripping stage and a rectifying section.
In first cyclohexanone-oxime distillation tower [C1], this distillation tower operates under vacuum condition, can obtain the top product being comprised of almost pure toluene (purity=99.9% weight).The toluene leaving from first cyclohexanone-oxime distillation tower [C1] top has been recycled to second PPC[A2 by line [111]] at the bottom of tower.First cyclohexanone-oxime distillation tower [C1] bottoms adds second cyclohexanone-oxime distillation tower [C2] top that is similarly vacuum condition operation to by line [110].Main second cyclohexanone-oxime distillation tower [C2] top products being comprised of toluene, pimelinketone and cyclohexanone-oxime is added to first PPC[A1 by line [109]] in.
By line [112], the bottom steam that is rich in cyclohexanone-oxime is drawn to the bottom of second cyclohexanone-oxime distillation tower [C2].
The toluene level of the cyclohexanone-oxime producing is 43mg/kg (43ppm).
Embodiment 2
The cyclohexanone-oxime is here added into one, and with three grades of Beckmann rearrangement systems of continuous-mode operation, this system comprises first recycle system, second recycle system and third circulation system (referring to Fig. 3).First recycle system comprises mixing equipment [A1], collection tube [B1], and pump [C1] and water cooler [D1], the first reaction mixture keeps circulation by line [201] simultaneously.Mol ratio M maintains 1.65.This process is carried out with continuous pattern.
Second recycle system comprises mixing equipment [A2], collection tube [B2], and pump [C2] and water cooler [D2], the second reaction mixture keeps circulation by line [211] simultaneously.
Third circulation system comprises mixing equipment [A3], collection tube [B3], and pump [C3] and water cooler [D3], the 3rd reaction mixture keeps circulation by line [221] simultaneously.
The bottom steam that cyclohexanone-oxime is rich in first part joins the first reaction mixture by line [202].By line [203] by sulfuric acid and SO 3(oleum) joins in first reaction mixture.Part the first reaction mixture is taken out and has been added into the second reaction mixture from collection tube [B1] by line [204].
The bottom steam that second section is rich in cyclohexanone-oxime joins the second reaction mixture by line [212].Part the second reaction mixture is taken out and has been added into the 3rd reaction mixture from collection tube [B2] by line [214].
The remainder that is rich in the bottom steam of cyclohexanone-oxime joins the 3rd reaction mixture by line [222].Part the 3rd reaction mixture takes out from collection tube [B3] by line [224].
The temperature of pump [C1], [C2] and [C3] remains on respectively 102,86 and 86 ℃.The weight ratio that is rich in cyclohexanone-oxime bottom steam of adding by line [202], [212] and [222] is respectively about 70%, 19% and 11%.
By line [224], the reaction mixture obtaining in the back segment [B3] of Beckmann rearrangement is joined to neutralizing zone, there, in water with ammonia neutralization reaction mixture.Due to this neutralization reaction, formed a biphasic system, this system is comprised of the water-based lower floor of liquid containing ammonium sulfate and the organic upper strata being mainly comprised of hexanolactam.Adopt known method purifying caprolactam solution, the method comprises with benzene extraction, water strips and distillation.
The hexanolactam that the method produces has better quality and for all products, comprises high speed melt-spun nylon-6 fiber (product).

Claims (9)

1. adopt cyclohexanone-oxime to carry out Beckmann rearrangement to prepare a continuation method for hexanolactam, the method comprises the steps to obtain cyclohexanone-oxime:
1), under the existence of toluene, buffering hydroxylammonium phosphate solution and pimelinketone are reacted; Or
2) under the existence of hydrogen peroxide, pimelinketone and ammonia are reacted, then with adopting toluene extraction; The cyclohexanone-oxime wherein obtaining carries out processing treatment by following steps:
A) to the distilling period that comprises at least one distillation tower, add the mixture that contains toluene and cyclohexanone-oxime;
B) from first distillation tower, take out and be rich in the overhead vapor of toluene and from last distillation tower, take out the bottom steam that is rich in cyclohexanone-oxime;
C) by (i) sulfuric acid and SO 3and (ii) from b) bottom steam that is rich in cyclohexanone-oxime that obtains sends into one containing hexanolactam, sulfuric acid and SO 3the first reaction mixture,
D) take out part the first reaction mixture;
E) will part from d) taking-up the first reaction mixture join neutralizing zone;
F) utilize NH 3neutralization part is from d) the first reaction mixture of taking out to obtain the reaction mixture neutralizing;
G) reaction mixture of neutralization is separated into and is rich in ammonium sulfate steam and is rich in hexanolactam steam;
B wherein) toluene that the bottom steam that is rich in cyclohexanone-oxime obtaining in contains 1-500ppm.
2. according to the method for claim 1, also comprise a1) purification step.
3. according to the method for claim 2, purification step a1 wherein) comprise that use solution cleans cyclohexanone-oxime.
According to before any one method of claim, wherein ii), the bottom steam that is rich in cyclohexanone-oxime contains the cyclohexanone-oxime that is greater than 99wt%.
According to before any one method of claim, wherein step c) sulfuric acid and the SO that use 3amount be that mol ratio is preferably between 1.0-2.0.
According to before any one method of claim, the described method that contains the Beckmann rearrangement carrying out two series block comprises:
C) by (i) sulfuric acid and SO 3(ii) bottom steam that is rich in cyclohexanone-oxime part steps b) obtaining joins one containing hexanolactam and sulfuric acid and SO 3the first reaction mixture;
D1) take out part the first reaction mixture;
D2) by part the first reaction mixture d1) and (ii) remaining part steps b) bottom steam that is rich in cyclohexanone-oxime that obtains joins containing hexanolactam and sulfuric acid and SO 3the second reaction mixture in,
D3) take out part the second reaction mixture, and adopt step e) proceed.
According to before any one method of claim, the described method that contains the Beckmann rearrangement carrying out three series block comprises:
C) by (i) sulfuric acid and SO 3(ii) bottom steam that is rich in cyclohexanone-oxime part steps b) obtaining joins one containing hexanolactam and sulfuric acid and SO 3the first reaction mixture,
D1) take out part the first reaction mixture;
D2) by part the first reaction mixture d1) and (ii) another part step b) bottom steam that is rich in cyclohexanone-oxime that obtains joins containing hexanolactam and sulfuric acid and SO 3the second reaction mixture in,
D3) take out part the second reaction mixture;
D4) by part the second reaction mixture d3) and (ii) remaining part steps b) bottom steam that is rich in cyclohexanone-oxime that obtains joins containing hexanolactam and sulfuric acid and SO 3the 3rd reaction mixture in,
D5) take out part the 3rd reaction mixture, and adopt step e) proceed.
According to before any one method of claim, the method that wherein obtains cyclohexanone-oxime is 1) under the existence of toluene, buffering hydroxylammonium phosphate solution and pimelinketone are reacted (
Figure FDA00003418705400021
method).
9. the hexanolactam that before basis prepared by the method for any one claim.
CN201310261625.9A 2012-06-28 2013-06-27 Method used for continuous conversion of epsilon-caprolactam from cyclohexanone-oxime Pending CN103508955A (en)

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Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
周少东等: "催化合成肟的绿色新工艺", 《浙江大学学报（工学版）》 *

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