CN104910071A - Caprolactam preparation method - Google Patents
Caprolactam preparation method Download PDFInfo
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- CN104910071A CN104910071A CN201510231582.9A CN201510231582A CN104910071A CN 104910071 A CN104910071 A CN 104910071A CN 201510231582 A CN201510231582 A CN 201510231582A CN 104910071 A CN104910071 A CN 104910071A
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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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- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
- C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
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Abstract
The invention discloses a caprolactam preparation method. The method is characterized in that caprolactam is prepared from cyclohexanone through oximation and rearrangement, and the method comprises the following steps: carrying out a catalytic reaction on cyclohexanone, hydrogen peroxide and ammonia to generate cyclohexanone oxime, extracting and separating by using a solvent A, adding a solvent B to the above obtained oil phase, carrying out a Beckmann rearrangement reaction under the action of oleum, carrying out slaking flash evaporation separation on the obtained product, hydrolyzing, extracting by using water, and carrying out original process refining to prepare finished caprolactam. The method shortens the caprolactam production process flow, reduces the consumption of raw materials and energy, generates less ammonium sulfate than original technologies, and improves the quality of the caprolactam product.
Description
Technical field
The present invention relates to a kind of method preparing organic compound, particularly a kind of method preparing hexanolactam, belongs to Organic Chemicals production technical field.
Background technology
Hexanolactam is the important industrial chemicals of synthon and engineering plastics.The hexanolactam of about 90% is prepared by Beckmann rearrangement reaction by cyclohexanone-oxime in the world.Traditional B eckmann rearrangement reaction process is: adopt oleum to make cyclohexanone-oxime form hexanolactam sulfuric ester, for the high yield obtaining hexanolactam needs to add excessive oleum, then use ammonia neutralization mixture, obtain hexanolactam and ammonium sulfate.In typical industry rearrangement process, the transformation efficiency of cyclohexanone-oxime is almost 100%, is 99% to the selectivity of hexanolactam, produces 1.3 ~ 1.8kg ammonium sulfate/kg cyclohexanone-oxime.This traditional technology uses oleum to be catalysts and solvents, and consume sulfuric acid and the ammonia of high value, the ammonium sulfate of a large amount of low value of by-product, adds production cost.Therefore, developing low by-product or meet green chemistry direction without the Beckmann rearrangement novel process of ammonium sulfate by-product, is the target that preparing process of caprolactam improves.ZL200610089036.7 discloses the method for preparing aminocaprolactam by catalysis of nicotinic acid in a kind of ionic liquid, and the method substitutes with ionic liquid or the solvent action of Some substitute nicotinic acid, and nicotinic acid only plays a part or mainly plays catalyzer.The method can reduce the usage quantity of nicotinic acid, reduces sulphur ammonium by product, easily realizes recycling of ionic liquid and be connected with now methodical.But the method complex process, require higher to processing condition such as temperature, and ionic liquid used is expensive, preparation cost is higher, is unsuitable for industrial application.ZL200610089037.1 discloses a kind of preparation method of hexanolactam, diacetyl oxide is adopted to be the Beckmann rearrangement that catalyzer carries out cyclohexanone-oxime in ionic liquid homogeneous system, then organic solvent extraction ionic liquid is used, hexanolactam and catalyzer are transferred in organic solvent completely, then realizes being separated of hexanolactam and catalyzer by solvent extraction.The transformation efficiency of the method rearrangement reaction cyclohexanone-oxime is high, and treating process is without ammonia neutralization, without by-product sulphur ammonium.But the method ionic liquid used and diacetyl oxide expensive, production cost is higher, and the selectivity of hexanolactam is lower, is difficult to reach industrial requirements.Comprehensively above-mentioned, although the transformation efficiency of partial monopoly cyclohexanone oxime and the selectivity of hexanolactam higher, and the output of by product ammonium sulfate is lower, and due to reasons such as economy, quality and techniques, its industrial applications is restricted.
Summary of the invention
the object of the invention is for the deficiencies in the prior art, simple, the low producing ammonium sulfate byproduct of a kind of technique, the method preparing hexanolactam that caprolactam product quality is higher are provided.
the object of the invention is to realize in the following way, a kind of method preparing hexanolactam, comprises the following steps:
(1) at catalysis oximation reaction unit, under HTS existent condition, with pimelinketone, hydrogen peroxide and ammonia for raw material, cyclohexanone-oxime solution is obtained by catalysis oximation reaction;
Wherein, the oximation reaction device adopted is microreactor or multi-stage type tubular reactor or slurry hearth reactor; The HTS adopted is that TS-1 molecular sieve changes the former powder after wetting ability or shaping TS-1 catalyzer, and its particle size range is 0.1 ~ 30.0 μm; The mol ratio of hydrogen peroxide and pimelinketone is 0.5 ~ 6.0, preferably 1.0 ~ 1.2, and the mol ratio of ammonia and pimelinketone is 0.5 ~ 8.0, preferably 1.0 ~ 1.5; The massfraction of hydrogen peroxide is 15% ~ 70%; Oximation reaction temperature is 30 ~ 120 DEG C, preferably 60 ~ 95 DEG C; Pressure is 0.10 ~ 0.60MPa(gauge pressure), preferably 0.20 ~ 0.40MPa (gauge pressure); The recycle ratio 10 ~ 100 of oximation reaction, preferably 20 ~ 50, in circulation fluid, the massfraction of catalyzer is 0.5% ~ 5%, preferably 1.5% ~ 3.0%;
(2) at extracting and separating unit, in the cyclohexanone-oxime solution that step (1) obtains, add solvent orange 2 A carry out extracting and separating, obtain the solution A of organic phase cyclohexanone-oxime and the aqueous solution of inorganic phase catalyzer, the aqueous solution of catalyzer after filtering catalyzer is back to step (1) catalysis oximation reaction unit and recycles, the qualified discharge after treatment of the waste water after filtration;
Wherein, solvent orange 2 A is paraffinic hydrocarbons or naphthenic hydrocarbon, or their mixture, the naphthenic hydrocarbon of preferred carbonatoms 4 ~ 8;
(3) at preparation unit, in the solution A of the organic phase cyclohexanone-oxime obtained to step (2), add solvent B, be mixed with by the homogeneous phase solution C containing cyclohexanone-oxime of A, B two kinds of solvent compositions;
Wherein, solvent B is cycloalkane-carboxylic acid or alkylphenol, or their mixture, the alkylphenol of preferred carbonatoms 7 ~ 12; In homogeneous phase solution C, the massfraction of cyclohexanone-oxime is 5% ~ 80%, preferably 10% ~ 50%, more preferably 15% ~ 35%; The volume ratio of solvent orange 2 A and B is 0.4 ~ 5.0, preferably 0.6 ~ 3.0, more preferably 0.8 ~ 2.0;
(4) at rearrangement reaction unit, in the homogeneous phase solution C that step (3) obtains, add oleum carry out Beckmann rearrangement reaction, obtain rearrangement reaction thing;
Wherein, rearrangement reactor adopts the tubular reactor of microreactor or multi-stage type tubular reactor or high-shear mixer or the reactor of band premixer; Oleum is (with the SO in oleum
3conversion is for sulphur acid meter) be 0.5 ~ 3.0 with the mol ratio of cyclohexanone-oxime, preferably 0.6 ~ 1.1; Free SO in oleum used
3massfraction be 5% ~ 65%, preferably 5% ~ 25%; Rearrangement reaction temperature is 40 ~ 140 DEG C, preferably 60 ~ 120 DEG C; Rearrangement reaction pressure is-20KPa ~ 500KPa (gauge pressure), preferred 10KPa ~ 300KPa (gauge pressure); The recycle ratio of rearrangement reaction process is 1 ~ 100, preferably 5 ~ 20;
(5) at slaking flash evaporation unit, rearrangement reaction thing is stopped certain hour and carries out slaking, out by solvent orange 2 A flash separation and be back to the recycle of step (2) extracting and separating unit, and the solution obtained containing solvent B and hexanolactam sulfuric ester simultaneously;
Wherein, the rearrangement reaction thing curing time is 1 ~ 120 minute, preferably 3 ~ 80 minutes;
(6) in hydrolysis unit, in the solution that step (5) obtains containing solvent B and hexanolactam sulfuric ester, add water be hydrolyzed, obtain mutually light and heavy phase, be gently the B solution containing hexanolactam mutually, heavy phase is the dilution heat of sulfuric acid containing a small amount of hexanolactam;
Wherein, water used is the process water that secondary de-salted water or caprolactam refining unit are discharged, and hydrolysis temperature is 10 ~ 80 DEG C, preferably 30 ~ 40 DEG C; The hydrolysis residence time is 20 ~ 80 minutes, preferably 30 ~ 40 minutes; After hydrolysis, the massfraction of heavy phase dilute sulphuric acid is 5% ~ 60%, preferably 30% ~ 40%;
(7) in water extraction cells, step (6) is obtained light mutually in add water and extract, obtain the aqueous solution and the solvent B of hexanolactam, the aqueous solution of hexanolactam obtains hexanolactam finished product after sending subsequent cell refining, and solvent B is back to the recycle of step (3) preparation unit;
(8) add ammonia in heavy phase step (6) obtained or ammoniacal liquor carries out neutralization reaction and Crystallization Separation obtains ammonium sulfate and caprolactam water solution, caprolactam water solution prepares hexanolactam finished product after sending subsequent cell refining.
Method of the present invention, the transformation efficiency of cyclohexanone-oxime reaches 100%, be 99.5% ~ 99.9% to the selectivity of hexanolactam, prepared hexanolactam quality of finished product good, its light absorption value at 290 nm wavelength is lower than 0.02, and basicity is lower than 0.05mmol/kg, and potassium permanganate oxidation PM value was higher than 30000 seconds, other indices are better than GB premium grads index, can meet the specification of quality of down-stream enterprise's high-speed spinning very well.
The present invention obtains following beneficial effect:
(1) utilize extraction and separation technology, part instead of the operations such as the neutralization of original technique, crystallization, separation, achieves the straight-through technology of catalysis oximation reaction to rearrangement reaction, shortens existing preparing process of caprolactam flow process.
(2) require lower to the reaction conditions such as temperature, pressure, reduce energy consumption.
(3) in the method, solvent orange 2 A, solvent B, TS-1 are molecular sieve modified, catalyzer and water all recycle, and reduce production cost.
(4) hexanolactam by-product sulphur ammonium is few, and compared with existing industrial production by-product 1.3 ~ 1.8kg sulphur ammonium/kg cyclohexanone-oxime, present method can reduce sulphur ammonium by-product 20% to 50%.
Accompanying drawing explanation
What Fig. 1 provided is process flow diagram of the present invention.
Embodiment
Following examples are for illustration of the present invention.But just the invention will be further described for these embodiments, and should not be interpreted as limitation of the scope of the invention.
Embodiment 1
(1) at catalysis oximation reaction unit, pimelinketone, hydrogen peroxide, ammonia and shaping TS-1 catalyzer, add continuously from each corresponding charging mouth of pipe of microreactor by opening for feed order from top to bottom, carry out continuous catalysis oximation reaction and obtain cyclohexanone-oxime solution;
Wherein, shaping TS-1 catalyst particle size used is 0.1 μm; The mol ratio of hydrogen peroxide and pimelinketone is 1.0; The mol ratio of ammonia and pimelinketone is 1.0; The massfraction of hydrogen peroxide is 15%; Catalysis oximation reaction temperature is 70 DEG C; Pressure is 200KPa (gauge pressure); The internal circulating load of circulation fluid is 600m3/h; In circulation fluid, the massfraction of catalyzer is 3.0%.
(2) at extracting and separating unit, in the cyclohexanone-oxime solution that step (1) obtains, add solvent orange 2 A carry out extracting and separating, obtain the solution A of organic phase cyclohexanone-oxime and the aqueous solution of inorganic phase catalyzer, the aqueous solution of catalyzer after filtering catalyzer is back to step (1) catalysis oximation reaction unit and recycles, the qualified discharge after treatment of the waste water after filtration;
Wherein, solvent for use A is hexanaphthene.
(3) at preparation unit, in the solution A of the organic phase cyclohexanone-oxime obtained to step (2), add solvent B, be mixed with by the homogeneous phase solution C containing cyclohexanone-oxime of A, B two kinds of solvent compositions;
Wherein, solvent B is p-methyl phenol; In homogeneous phase solution C, the content of cyclohexanone-oxime is 15%(wt%); The volume ratio of solvent orange 2 A and B is 0.8.
(4) add in the homogeneous phase solution C obtained to step (3) in the microreactor of rearrangement reaction unit containing free SO
3oleum, carry out Beckmann rearrangement reaction, obtain rearrangement reaction thing;
Wherein, oleum is (with the SO in oleum
3conversion is for sulphur acid meter) be 0.6 with the mol ratio of cyclohexanone-oxime; Free SO in oleum
3concentration is 5%(wt%); Rearrangement reaction temperature is 60 DEG C, and pressure is 100KPa (gauge pressure); Recycle ratio is 5.
(5) at slaking flash evaporation unit, rearrangement reaction thing is stopped certain hour and carries out slaking, out by solvent orange 2 A flash separation and be back to the recycle of step (2) extracting and separating unit, and the solution obtained containing solvent B and hexanolactam sulfuric ester simultaneously;
Wherein, the rearrangement reaction thing curing time is 5 minutes.
(6) in hydrolysis unit, in the solution that step (5) obtains containing solvent B and hexanolactam sulfuric ester, add water be hydrolyzed, obtain mutually light and heavy phase, be gently the B solution containing hexanolactam mutually, heavy phase is the dilution heat of sulfuric acid containing a small amount of hexanolactam;
Wherein, water used is the process water that caprolactam refining unit is discharged; Hydrolysis temperature is 30 DEG C, and the residence time is 30 minutes; After hydrolysis, heavy phase dilute sulphuric acid concentration is 30%(wt%).
(7) in water extraction cells, step (6) is obtained light mutually in add water and extract, obtain the aqueous solution and the solvent B of hexanolactam, the aqueous solution of hexanolactam obtains hexanolactam finished product after sending subsequent cell refining, and solvent B is back to the recycle of step (3) preparation unit;
(8) add ammonia in heavy phase step (6) obtained or ammoniacal liquor carries out neutralization reaction and Crystallization Separation obtains ammonium sulfate and caprolactam water solution, caprolactam water solution prepares hexanolactam finished product after sending subsequent cell refining.
In the present embodiment, rearrangement process, the transformation efficiency of cyclohexanone-oxime is up to 99.93%, be 99.2% to the selectivity of hexanolactam, rearrangement solution colourity 45 breathes out gloomy value, titration value 0.32,290nm light absorption value 0.028, cyclohexanone-oxime content 2ppm(wt%), produce 0.8kg ammonium sulfate/kg cyclohexanone-oxime.
Embodiment 2
(1) at catalysis oximation reaction unit, pimelinketone, hydrogen peroxide, ammonia and TS-1 molecular sieve change the former powder after wetting ability, add continuously from each corresponding charging mouth of pipe of microreactor by opening for feed order from top to bottom, carry out continuous catalysis oximation reaction and obtain cyclohexanone-oxime solution;
Wherein, the former powder footpath after TS-1 molecular sieve change wetting ability used is 1.0 μm; The mol ratio of hydrogen peroxide and pimelinketone is 1.1; The mol ratio of ammonia and pimelinketone is 1.2; The concentration 20%(wt% of hydrogen peroxide); Catalysis oximation reaction temperature is 80 DEG C; Pressure is 250KPa (gauge pressure); The internal circulating load of circulation fluid is 700m3/h; In circulation fluid, catalyst concn is 2.7%(wt%).
(2) at extracting and separating unit, in the cyclohexanone-oxime solution that step (1) obtains, add solvent orange 2 A carry out extracting and separating, obtain the solution A of organic phase cyclohexanone-oxime and the aqueous solution of inorganic phase catalyzer, the aqueous solution of catalyzer after filtering catalyzer is back to step (1) catalysis oximation reaction unit and recycles, the qualified discharge after treatment of the waste water after filtration;
Wherein, solvent for use A is suberane.
(3) at preparation unit, in the solution A of the organic phase cyclohexanone-oxime obtained to step (2), add solvent B, be mixed with by the homogeneous phase solution C containing cyclohexanone-oxime of A, B two kinds of solvent compositions;
Wherein, solvent for use B is m-methyl phenol; In described homogeneous phase solution C, the content of cyclohexanone-oxime is 20%(wt%); The ratio (vol) of solvent orange 2 A and B is 1.0.
(4) add in the homogeneous phase solution C obtained to step (3) in the microreactor of rearrangement reaction unit containing free SO
3oleum, carry out Beckmann rearrangement reaction, obtain rearrangement reaction thing;
Wherein, oleum is (with the SO in oleum
3conversion is for sulphur acid meter) be 0.7 with the mol ratio of cyclohexanone-oxime; Free SO in oleum
3concentration is 10%(wt%); Rearrangement reaction temperature is 70 DEG C, and pressure is 100KPa (gauge pressure); Recycle ratio is 10.
(5) at slaking flash evaporation unit, rearrangement reaction thing is stopped certain hour and carries out slaking, out by solvent orange 2 A flash separation and be back to the recycle of step (2) extracting and separating unit, and the solution obtained containing solvent B and hexanolactam sulfuric ester simultaneously;
Wherein, the rearrangement reaction thing curing time is 10 minutes.
(6) in hydrolysis unit, in the solution that step (5) obtains containing solvent B and hexanolactam sulfuric ester, add water be hydrolyzed, obtain mutually light and heavy phase, be gently the B solution containing hexanolactam mutually, heavy phase is the dilution heat of sulfuric acid containing a small amount of hexanolactam;
Wherein, water used is the process water that caprolactam refining unit is discharged; Hydrolysis temperature is 35 DEG C, and the residence time is 35 minutes; After hydrolysis, heavy phase dilute sulphuric acid concentration is 35%(wt%).
(7) in water extraction cells, step (6) is obtained light mutually in add water and extract, obtain the aqueous solution and the solvent B of hexanolactam, the aqueous solution of hexanolactam obtains hexanolactam finished product after sending subsequent cell refining, and solvent B is back to the recycle of step (3) preparation unit;
(8) add ammonia in heavy phase step (6) obtained or ammoniacal liquor carries out neutralization reaction and Crystallization Separation obtains ammonium sulfate and caprolactam water solution, caprolactam water solution prepares hexanolactam finished product after sending subsequent cell refining.
In the present embodiment, rearrangement process, the transformation efficiency of rearrangement process cyclohexanone-oxime is up to 99.89%, be 99.4% to the selectivity of hexanolactam, rearrangement solution colourity 47 breathes out gloomy value, titration value 0.36,290nm light absorption value 0.031, cyclohexanone-oxime content 2ppm(wt%), produce 0.9kg ammonium sulfate/kg cyclohexanone-oxime.
Embodiment 3
(1) at catalysis oximation reaction unit, pimelinketone, hydrogen peroxide, ammonia and shaping TS-1 catalyzer, add continuously from each corresponding charging mouth of pipe of microreactor by opening for feed order from top to bottom, carry out continuous catalysis oximation reaction and obtain cyclohexanone-oxime solution;
Wherein, shaping TS-1 catalyst particle size used is 5.0 μm; The mol ratio of hydrogen peroxide and pimelinketone is 1.2; The mol ratio of ammonia and pimelinketone is 1.3; The concentration 25%(wt% of hydrogen peroxide); Catalysis oximation reaction temperature is 85 DEG C; Pressure is 300KPa (gauge pressure); The internal circulating load of circulation fluid is 800m3/h; In circulation fluid, catalyst concn is 2.5%(wt%).
(2) at extracting and separating unit, in the cyclohexanone-oxime solution that step (1) obtains, add solvent orange 2 A carry out extracting and separating, obtain the solution A of organic phase cyclohexanone-oxime and the aqueous solution of inorganic phase catalyzer, the aqueous solution of catalyzer after filtering catalyzer is back to step (1) catalysis oximation reaction unit and recycles, the qualified discharge after treatment of the waste water after filtration;
Wherein, described solvent orange 2 A is suberane.
(3) at preparation unit, in the solution A of the organic phase cyclohexanone-oxime obtained to step (2), add solvent B, be mixed with by the homogeneous phase solution C containing cyclohexanone-oxime of A, B two kinds of solvent compositions;
Wherein, solvent for use B is 2,4-dimethyl benzene phenolic group phenol; In described homogeneous phase solution C, the content of cyclohexanone-oxime is 25%(wt%); The ratio (vol) of solvent orange 2 A and B is 1.2.
(4) add in the homogeneous phase solution C obtained to step (3) in the microreactor of rearrangement reaction unit containing free SO
3oleum, carry out Beckmann rearrangement reaction, obtain rearrangement reaction thing;
Wherein, oleum is (with the SO in oleum
3conversion is for sulphur acid meter) be 0.8 with the mol ratio of cyclohexanone-oxime; Free SO in oleum
3concentration is 15%(wt%); Rearrangement reaction temperature is 80 DEG C, and pressure is 100KPa (gauge pressure); Recycle ratio is 15.
(5) at slaking flash evaporation unit, rearrangement reaction thing is stopped certain hour and carries out slaking, out by solvent orange 2 A flash separation and be back to the recycle of step (2) extracting and separating unit, and the solution obtained containing solvent B and hexanolactam sulfuric ester simultaneously;
Wherein, the rearrangement reaction thing curing time is 20 minutes.
(6) in hydrolysis unit, in the solution that step (5) obtains containing solvent B and hexanolactam sulfuric ester, add water be hydrolyzed, obtain mutually light and heavy phase, be gently the B solution containing hexanolactam mutually, heavy phase is the dilution heat of sulfuric acid containing a small amount of hexanolactam;
Wherein, water used is secondary de-salted water; Hydrolysis temperature is 40 DEG C, and the residence time is 40 minutes; After hydrolysis, heavy phase dilute sulphuric acid concentration is 40%(wt%).
(7) in water extraction cells, step (6) is obtained light mutually in add water and extract, obtain the aqueous solution and the solvent B of hexanolactam, the aqueous solution of hexanolactam obtains hexanolactam finished product after sending subsequent cell refining, and solvent B is back to the recycle of step (3) preparation unit;
(8) add ammonia in heavy phase step (6) obtained or ammoniacal liquor carries out neutralization reaction and Crystallization Separation obtains ammonium sulfate and caprolactam water solution, caprolactam water solution prepares hexanolactam finished product after sending subsequent cell refining.
In the present embodiment, rearrangement process, the transformation efficiency of cyclohexanone-oxime is almost 99.98%, be 99.6% to the selectivity of hexanolactam, rearrangement solution colourity 41 breathes out gloomy value, titration value 0.34,290nm light absorption value 0.026, cyclohexanone-oxime content 2ppm(wt%), produce 1.0kg ammonium sulfate/kg cyclohexanone-oxime.
Embodiment 4
(1) at catalysis oximation reaction unit, pimelinketone, hydrogen peroxide, ammonia and TS-1 molecular sieve change the former powder after wetting ability, add continuously from each corresponding charging mouth of pipe of multi-stage type tubular reactor by opening for feed order from top to bottom, carry out continuous catalysis oximation reaction and obtain cyclohexanone-oxime solution;
Wherein, the former powder footpath after TS-1 molecular sieve change wetting ability used is 10.0 μm; The mol ratio of hydrogen peroxide and pimelinketone is 1.0; The mol ratio of ammonia and pimelinketone is 1.4; The concentration 30%(wt% of hydrogen peroxide); Catalysis oximation reaction temperature is 85 DEG C; Pressure is 350KPa (gauge pressure); The internal circulating load of circulation fluid is 900m3/h; In circulation fluid, catalyst concn is 2.3%(wt%).
(2) at extracting and separating unit, in the cyclohexanone-oxime solution that step (1) obtains, add solvent orange 2 A carry out extracting and separating, obtain the solution A of organic phase cyclohexanone-oxime and the aqueous solution of inorganic phase catalyzer, the aqueous solution of catalyzer after filtering catalyzer is back to step (1) catalysis oximation reaction unit and recycles, the qualified discharge after treatment of the waste water after filtration;
Wherein, solvent for use A is cyclooctane.
(3) at preparation unit, in the solution A of the organic phase cyclohexanone-oxime obtained to step (2), add solvent B, be mixed with by the homogeneous phase solution C containing cyclohexanone-oxime of A, B two kinds of solvent compositions;
Wherein, solvent for use B is 2,3,5-TEP; In described homogeneous phase solution C, the content of cyclohexanone-oxime is 30%(wt%); The ratio (vol) of solvent orange 2 A and B is 1.4.
(4) add in the homogeneous phase solution C obtained to step (3) in the multi-stage type tubular reactor of rearrangement reaction unit containing free SO
3oleum, carry out Beckmann rearrangement reaction, obtain rearrangement reaction thing;
Wherein, oleum is (with the SO in oleum
3conversion is for sulphur acid meter) be 1.1 with the mol ratio of cyclohexanone-oxime; Free SO in oleum
3concentration is 20%(wt%); Rearrangement reaction temperature is 90 DEG C, and pressure is 100KPa (gauge pressure); Recycle ratio is 20.
(5) at slaking flash evaporation unit, rearrangement reaction thing is stopped certain hour and carries out slaking, out by solvent orange 2 A flash separation and be back to the recycle of step (2) extracting and separating unit, and the solution obtained containing solvent B and hexanolactam sulfuric ester simultaneously;
Wherein, the rearrangement reaction thing curing time is 30 minutes.
(6) in hydrolysis unit, in the solution that step (5) obtains containing solvent B and hexanolactam sulfuric ester, add water be hydrolyzed, obtain mutually light and heavy phase, be gently the B solution containing hexanolactam mutually, heavy phase is the dilution heat of sulfuric acid containing a small amount of hexanolactam;
Wherein, water used is secondary de-salted water; Hydrolysis temperature is 30 DEG C, and the residence time is 35 minutes; After hydrolysis, heavy phase dilute sulphuric acid concentration is 35%(wt%).
(7) in water extraction cells, step (6) is obtained light mutually in add water and extract, obtain the aqueous solution and the solvent B of hexanolactam, the aqueous solution of hexanolactam obtains hexanolactam finished product after sending subsequent cell refining, and solvent B is back to the recycle of step (3) preparation unit;
(8) add ammonia in heavy phase step (6) obtained or ammoniacal liquor carries out neutralization reaction and Crystallization Separation obtains ammonium sulfate and caprolactam water solution, caprolactam water solution prepares hexanolactam finished product after sending subsequent cell refining.
In the present embodiment, rearrangement process, the transformation efficiency of cyclohexanone-oxime is almost 99.97%, be 99.7% to the selectivity of hexanolactam, rearrangement solution colourity 41 breathes out gloomy value, titration value 0.23,290nm light absorption value 0.024, cyclohexanone-oxime content 3ppm(wt%), produce 1.3kg ammonium sulfate/kg cyclohexanone-oxime.
Embodiment 5
(1) at catalysis oximation reaction unit, pimelinketone, hydrogen peroxide, ammonia and shaping TS-1 catalyzer, add continuously from each corresponding charging mouth of pipe of multi-stage type tubular reactor by opening for feed order from top to bottom, carry out continuous catalysis oximation reaction and obtain cyclohexanone-oxime solution;
Wherein, shaping TS-1 catalyst particle size used is 15.0 μm; The mol ratio of hydrogen peroxide and pimelinketone is 1.1; The mol ratio of ammonia and pimelinketone is 1.5; The concentration 35%(wt% of hydrogen peroxide); Catalysis oximation reaction temperature is 90 DEG C; Pressure is 400KPa (gauge pressure); The internal circulating load of circulation fluid is 1000m3/h; In circulation fluid, catalyst concn is 2.0%(wt%).
(2) at extracting and separating unit, in the cyclohexanone-oxime solution that step (1) obtains, add solvent orange 2 A carry out extracting and separating, obtain the solution A of organic phase cyclohexanone-oxime and the aqueous solution of inorganic phase catalyzer, the aqueous solution of catalyzer after filtering catalyzer is back to step (1) catalysis oximation reaction unit and recycles, the qualified discharge after treatment of the waste water after filtration;
Wherein, solvent for use A is suberane.
(3) at preparation unit, in the solution A of the organic phase cyclohexanone-oxime obtained to step (2), add solvent B, be mixed with by the homogeneous phase solution C containing cyclohexanone-oxime of A, B two kinds of solvent compositions;
Wherein, described solvent B is 4-ethylphenol; In described homogeneous phase solution C, the content of cyclohexanone-oxime is 35%(wt%); The ratio (vol) of solvent orange 2 A and B is 1.6.
(4) in the multi-stage type tubular reactor of rearrangement reaction unit, add in the homogeneous phase solution C that step (3) obtains containing free SO
3oleum, carry out Beckmann rearrangement reaction, obtain rearrangement reaction thing;
Wherein, oleum is (with the SO in oleum
3conversion is for sulphur acid meter) be 1.0 with the mol ratio of cyclohexanone-oxime; Free SO in oleum
3concentration is 25%(wt%); Rearrangement reaction temperature is 100 DEG C, and pressure is 100KPa (gauge pressure); Recycle ratio is 5.
(5) at slaking flash evaporation unit, rearrangement reaction thing is stopped certain hour and carries out slaking, out by solvent orange 2 A flash separation and be back to the recycle of step (2) extracting and separating unit, and the solution obtained containing solvent B and hexanolactam sulfuric ester simultaneously;
Wherein, the rearrangement reaction thing curing time is 40 minutes.
(6) in hydrolysis unit, in the solution that step (5) obtains containing solvent B and hexanolactam sulfuric ester, add water be hydrolyzed, obtain mutually light and heavy phase, be gently the B solution containing hexanolactam mutually, heavy phase is the dilution heat of sulfuric acid containing a small amount of hexanolactam;
Wherein, water used is the process water that caprolactam refining unit is discharged; Hydrolysis temperature is 35 DEG C, and the residence time is 30 minutes; After hydrolysis, heavy phase dilute sulphuric acid concentration is 40%(wt%).
(7) in water extraction cells, step (6) is obtained light mutually in add water and extract, obtain the aqueous solution and the solvent B of hexanolactam, the aqueous solution of hexanolactam obtains hexanolactam finished product after sending subsequent cell refining, and solvent B is back to the recycle of step (3) preparation unit;
(8) add ammonia in heavy phase step (6) obtained or ammoniacal liquor carries out neutralization reaction and Crystallization Separation obtains ammonium sulfate and caprolactam water solution, caprolactam water solution prepares hexanolactam finished product after sending subsequent cell refining.
In the present embodiment, rearrangement process, the transformation efficiency of cyclohexanone-oxime is up to 100%, be 99.3% to the selectivity of hexanolactam, rearrangement solution colourity 47 breathes out gloomy value, titration value 0.31,290nm light absorption value 0.029, cyclohexanone-oxime content 1ppm(wt%), produce 1.2kg ammonium sulfate/kg cyclohexanone-oxime.
Embodiment 6
(1) at catalysis oximation reaction unit, pimelinketone, hydrogen peroxide, ammonia and TS-1 molecular sieve change the former powder after wetting ability, add continuously from each corresponding charging mouth of pipe of multi-stage type tubular reactor by opening for feed order from top to bottom, carry out continuous catalysis oximation reaction and obtain cyclohexanone-oxime solution;
Wherein, the former powder footpath after TS-1 molecular sieve change wetting ability used is 20.0 μm; The mol ratio of hydrogen peroxide and pimelinketone is 1.2; The mol ratio of ammonia and pimelinketone is 1.0; The concentration 40%(wt% of hydrogen peroxide); Catalysis oximation reaction temperature is 95 DEG C; Pressure is 200KPa (gauge pressure); The internal circulating load of circulation fluid is 1100m3/h; In circulation fluid, catalyst concn is 1.8%(wt%).
(2) at extracting and separating unit, in the cyclohexanone-oxime solution that step (1) obtains, add solvent orange 2 A carry out extracting and separating, obtain the solution A of organic phase cyclohexanone-oxime and the aqueous solution of inorganic phase catalyzer, the aqueous solution of catalyzer after filtering catalyzer is back to step (1) catalysis oximation reaction unit and recycles, the qualified discharge after treatment of the waste water after filtration;
Wherein, solvent for use A is cyclooctane.
(3) at preparation unit, in the solution A of the organic phase cyclohexanone-oxime obtained to step (2), add solvent B, be mixed with by the homogeneous phase solution C containing cyclohexanone-oxime of A, B two kinds of solvent compositions;
Wherein, solvent for use B is 4-n-propyl phenol; In described homogeneous phase solution C, the content of cyclohexanone-oxime is 15%(wt%); The ratio (vol) of solvent orange 2 A and B is 1.8.
(4) add in the homogeneous phase solution C obtained to step (3) in the tubular reactor of the unit high-shear mixer of rearrangement reaction containing free SO
3oleum, carry out Beckmann rearrangement reaction, obtain rearrangement reaction thing;
Wherein, oleum is (with the SO in oleum
3conversion is for sulphur acid meter) be 0.9 with the mol ratio of cyclohexanone-oxime; Free SO in oleum
3concentration is 5%(wt%); Rearrangement reaction temperature is 110 DEG C, and pressure is 100KPa (gauge pressure); Recycle ratio is 10.
(5) at slaking flash evaporation unit, rearrangement reaction thing is stopped certain hour and carries out slaking, out by solvent orange 2 A flash separation and be back to the recycle of step (2) extracting and separating unit, and the solution obtained containing solvent B and hexanolactam sulfuric ester simultaneously;
Wherein, the rearrangement reaction thing curing time is 50 minutes.
(6) in hydrolysis unit, in the solution that step (5) obtains containing solvent B and hexanolactam sulfuric ester, add water be hydrolyzed, obtain mutually light and heavy phase, be gently the B solution containing hexanolactam mutually, heavy phase is the dilution heat of sulfuric acid containing a small amount of hexanolactam;
Wherein, water used is the process water that caprolactam refining unit is discharged; Hydrolysis temperature is 40 DEG C, and the residence time is 35 minutes; After hydrolysis, heavy phase dilute sulphuric acid concentration is 30%(wt%).
(7) in water extraction cells, step (6) is obtained light mutually in add water and extract, obtain the aqueous solution and the solvent B of hexanolactam, the aqueous solution of hexanolactam obtains hexanolactam finished product after sending subsequent cell refining, and solvent B is back to the recycle of step (3) preparation unit;
(8) add ammonia in heavy phase step (6) obtained or ammoniacal liquor carries out neutralization reaction and Crystallization Separation obtains ammonium sulfate and caprolactam water solution, caprolactam water solution prepares hexanolactam finished product after sending subsequent cell refining.
In the present embodiment, rearrangement process, the transformation efficiency of cyclohexanone-oxime is up to 99.98%, be 99.3% to the selectivity of hexanolactam, rearrangement solution colourity 46 breathes out gloomy value, titration value 0.31,290nm light absorption value 0.027, cyclohexanone-oxime content 2ppm(wt%), produce 1.1kg ammonium sulfate/kg cyclohexanone-oxime.
Embodiment 7
(1) at catalysis oximation reaction unit, pimelinketone, hydrogen peroxide, ammonia and shaping TS-1 catalyzer, add continuously from each corresponding charging mouth of pipe of slurry hearth reactor by opening for feed order from top to bottom, carry out continuous catalysis oximation reaction and obtain cyclohexanone-oxime solution;
Wherein, shaping TS-1 catalyst particle size used is 25.0 μm; The mol ratio of hydrogen peroxide and pimelinketone is 1.0; The mol ratio of ammonia and pimelinketone is 1.1; The concentration 45%(wt% of hydrogen peroxide); Catalysis oximation reaction temperature is 60 DEG C; Pressure is 250KPa (gauge pressure); The internal circulating load of circulation fluid is 1200m3/h; In circulation fluid, catalyst concn is 1.5%(wt%).
(2) at extracting and separating unit, in the cyclohexanone-oxime solution that step (1) obtains, add solvent orange 2 A carry out extracting and separating, obtain the solution A of organic phase cyclohexanone-oxime and the aqueous solution of inorganic phase catalyzer, the aqueous solution of catalyzer after filtering catalyzer is back to step (1) catalysis oximation reaction unit and recycles, the qualified discharge after treatment of the waste water after filtration;
Wherein, solvent for use A is hexanaphthene.
(3) at preparation unit, in the solution A of the organic phase cyclohexanone-oxime obtained to step (2), add solvent B, be mixed with by the homogeneous phase solution C containing cyclohexanone-oxime of A, B two kinds of solvent compositions;
Wherein, solvent for use B is butylphenol; In described homogeneous phase solution C, the content of cyclohexanone-oxime is 20%(wt%); The ratio (vol) of solvent orange 2 A and B is 2.0.
(4) add in the homogeneous phase solution C obtained to step (3) in the tubular reactor of the high-shear mixer of rearrangement reaction unit containing free SO
3oleum, carry out Beckmann rearrangement reaction, obtain rearrangement reaction thing;
Wherein, oleum is (with the SO in oleum
3conversion is for sulphur acid meter) be 0.8 with the mol ratio of cyclohexanone-oxime; Free SO in oleum
3concentration is 10%(wt%); Rearrangement reaction temperature is 60 DEG C, and pressure is 100KPa (gauge pressure); Recycle ratio is 15.
(5) at slaking flash evaporation unit, rearrangement reaction thing is stopped certain hour and carries out slaking, out by solvent orange 2 A flash separation and be back to the recycle of step (2) extracting and separating unit, and the solution obtained containing solvent B and hexanolactam sulfuric ester simultaneously;
Wherein, the rearrangement reaction thing curing time is 60 minutes.
(6) in hydrolysis unit, in the solution that step (5) obtains containing solvent B and hexanolactam sulfuric ester, add water be hydrolyzed, obtain mutually light and heavy phase, be gently the B solution containing hexanolactam mutually, heavy phase is the dilution heat of sulfuric acid containing a small amount of hexanolactam;
Wherein, water used is secondary de-salted water; Hydrolysis temperature is 30 DEG C, and the residence time is 40 minutes; After hydrolysis, heavy phase dilute sulphuric acid concentration is 35%(wt%).
(7) in water extraction cells, step (6) is obtained light mutually in add water and extract, obtain the aqueous solution and the solvent B of hexanolactam, the aqueous solution of hexanolactam obtains hexanolactam finished product after sending subsequent cell refining, and solvent B is back to the recycle of step (3) preparation unit;
(8) add ammonia in heavy phase step (6) obtained or ammoniacal liquor carries out neutralization reaction and Crystallization Separation obtains ammonium sulfate and caprolactam water solution, caprolactam water solution prepares hexanolactam finished product after sending subsequent cell refining.
In the present embodiment, rearrangement process, the transformation efficiency of cyclohexanone-oxime is up to 99.92%, be 99.7% to the selectivity of hexanolactam, rearrangement solution colourity 40 breathes out gloomy value, titration value 0.34,290nm light absorption value 0.035, cyclohexanone-oxime content 2ppm(wt%), produce 1.0kg ammonium sulfate/kg cyclohexanone-oxime.
Embodiment 8
(1) at catalysis oximation reaction unit, pimelinketone, hydrogen peroxide, ammonia and TS-1 molecular sieve change the former powder after wetting ability, add continuously from each corresponding charging mouth of pipe of slurry hearth reactor by opening for feed order from top to bottom, carry out continuous catalysis oximation reaction and obtain cyclohexanone-oxime solution;
Wherein, the former powder footpath after TS-1 molecular sieve change wetting ability used is 30.0 μm; The mol ratio of hydrogen peroxide and pimelinketone is 1.1; The mol ratio of ammonia and pimelinketone is 1.2; The concentration 50%(wt% of hydrogen peroxide); Catalysis oximation reaction temperature is 70 DEG C; Pressure is 300KPa (gauge pressure); The internal circulating load of circulation fluid is 1300m3/h; In circulation fluid, catalyst concn is 2.0%(wt%).
(2) at extracting and separating unit, in the cyclohexanone-oxime solution that step (1) obtains, add solvent orange 2 A carry out extracting and separating, obtain the solution A of organic phase cyclohexanone-oxime and the aqueous solution of inorganic phase catalyzer, the aqueous solution of catalyzer after filtering catalyzer is back to step (1) catalysis oximation reaction unit and recycles, the qualified discharge after treatment of the waste water after filtration;
Wherein, solvent for use A is suberane.
(3) at preparation unit, in the solution A of the organic phase cyclohexanone-oxime obtained to step (2), add solvent B, be mixed with by the homogeneous phase solution C containing cyclohexanone-oxime of A, B two kinds of solvent compositions;
Wherein, described solvent B is 2-isopropyl-phenol; In described homogeneous phase solution C, the content of cyclohexanone-oxime is 25%(wt%); The ratio (vol) of solvent orange 2 A and B is 0.8.
(4) add in the homogeneous phase solution C obtained to step (3) in the tubular reactor of the high-shear mixer of rearrangement reaction unit containing free SO
3oleum, carry out Beckmann rearrangement reaction, obtain rearrangement reaction thing;
Wherein, oleum is (with the SO in oleum
3conversion is for sulphur acid meter) be 0.9 with the mol ratio of cyclohexanone-oxime; Free SO in oleum
3concentration is 15%(wt%); Rearrangement reaction temperature is 80 DEG C, and pressure is 100KPa (gauge pressure); Recycle ratio is 20.
(5) at slaking flash evaporation unit, rearrangement reaction thing is stopped certain hour and carries out slaking, out by solvent orange 2 A flash separation and be back to the recycle of step (2) extracting and separating unit, and the solution obtained containing solvent B and hexanolactam sulfuric ester simultaneously;
Wherein, the rearrangement reaction thing curing time is 70 minutes.
(6) in hydrolysis unit, in the solution that step (5) obtains containing solvent B and hexanolactam sulfuric ester, add water be hydrolyzed, obtain mutually light and heavy phase, be gently the B solution containing hexanolactam mutually, heavy phase is the dilution heat of sulfuric acid containing a small amount of hexanolactam;
Wherein, water used is secondary de-salted water; Hydrolysis temperature is 35 DEG C, and the residence time is 30 minutes; After hydrolysis, heavy phase dilute sulphuric acid concentration is 40%(wt%).
(7) in water extraction cells, step (6) is obtained light mutually in add water and extract, obtain the aqueous solution and the solvent B of hexanolactam, the aqueous solution of hexanolactam obtains hexanolactam finished product after sending subsequent cell refining, and solvent B is back to the recycle of step (3) preparation unit;
(8) add ammonia in heavy phase step (6) obtained or ammoniacal liquor carries out neutralization reaction and Crystallization Separation obtains ammonium sulfate and caprolactam water solution, caprolactam water solution prepares hexanolactam finished product after sending subsequent cell refining.
In the present embodiment, rearrangement process, the transformation efficiency of cyclohexanone-oxime is up to 99.98%, be 99.5% to the selectivity of hexanolactam, rearrangement solution colourity 37 breathes out gloomy value, titration value 0.27,290nm light absorption value 0.026, cyclohexanone-oxime content 2ppm(wt%), produce 1.1kg ammonium sulfate/kg cyclohexanone-oxime.
Embodiment 9
(1) at catalysis oximation reaction unit, pimelinketone, hydrogen peroxide, ammonia and shaping TS-1 catalyzer, add continuously from each corresponding charging mouth of pipe of slurry hearth reactor by opening for feed order from top to bottom, carry out continuous catalysis oximation reaction and obtain cyclohexanone-oxime solution;
Wherein, shaping TS-1 catalyst particle size used is 10.0 μm; The mol ratio of hydrogen peroxide and pimelinketone is 1.2; The mol ratio of ammonia and pimelinketone is 1.3; The concentration 55%(wt% of hydrogen peroxide); Catalysis oximation reaction temperature is 80 DEG C; Pressure is 350KPa (gauge pressure); The internal circulating load of circulation fluid is 1400m3/h; In circulation fluid, catalyst concn is 2.5%(wt%).
(2) at extracting and separating unit, in the cyclohexanone-oxime solution that step (1) obtains, add solvent orange 2 A carry out extracting and separating, obtain the solution A of organic phase cyclohexanone-oxime and the aqueous solution of inorganic phase catalyzer, the aqueous solution of catalyzer after filtering catalyzer is back to step (1) catalysis oximation reaction unit and recycles, the qualified discharge after treatment of the waste water after filtration;
Wherein, solvent for use A is cyclooctane.
(3) at preparation unit, in the solution A of the organic phase cyclohexanone-oxime obtained to step (2), add solvent B, be mixed with by the homogeneous phase solution C containing cyclohexanone-oxime of A, B two kinds of solvent compositions;
Wherein, solvent for use B is Pentaphen; In described homogeneous phase solution C, the content of cyclohexanone-oxime is 30%(wt%); The ratio (vol) of solvent orange 2 A and B is 1.0.
(4) add in the homogeneous phase solution C obtained to step (3) in the reactor of the band premixer of rearrangement reaction unit containing free SO
3oleum, carry out Beckmann rearrangement reaction, obtain rearrangement reaction thing;
(5) at slaking flash evaporation unit, rearrangement reaction thing is stopped certain hour and carries out slaking, out by solvent orange 2 A flash separation and be back to the recycle of step (2) extracting and separating unit, and the solution obtained containing solvent B and hexanolactam sulfuric ester simultaneously;
Wherein, the rearrangement reaction thing curing time is 80 minutes.
(6) in hydrolysis unit, in the solution that step (5) obtains containing solvent B and hexanolactam sulfuric ester, add water be hydrolyzed, obtain mutually light and heavy phase, be gently the B solution containing hexanolactam mutually, heavy phase is the dilution heat of sulfuric acid containing a small amount of hexanolactam;
Wherein, water used is the process water that caprolactam refining unit is discharged; Hydrolysis temperature is 40 DEG C, and the residence time is 35 minutes; After hydrolysis, heavy phase dilute sulphuric acid concentration is 35%(wt%).
(7) in water extraction cells, step (6) is obtained light mutually in add water and extract, obtain the aqueous solution and the solvent B of hexanolactam, the aqueous solution of hexanolactam obtains hexanolactam finished product after sending subsequent cell refining, and solvent B is back to the recycle of step (3) preparation unit;
(8) add ammonia in heavy phase step (6) obtained or ammoniacal liquor carries out neutralization reaction and Crystallization Separation obtains ammonium sulfate and caprolactam water solution, caprolactam water solution prepares hexanolactam finished product after sending subsequent cell refining.
In the present embodiment, rearrangement process, the transformation efficiency of cyclohexanone-oxime is almost 99.92%, be 99.7% to the selectivity of hexanolactam, rearrangement solution colourity 42 breathes out gloomy value, titration value 0.28,290nm light absorption value 0.032, cyclohexanone-oxime content 2ppm(wt%), produce 1.2kg ammonium sulfate/kg cyclohexanone-oxime.
Embodiment 10
(1) at catalysis oximation reaction unit, pimelinketone, hydrogen peroxide, ammonia and TS-1 molecular sieve change the former powder after wetting ability, add continuously from each corresponding charging mouth of pipe of slurry hearth reactor by opening for feed order from top to bottom, carry out continuous catalysis oximation reaction and obtain cyclohexanone-oxime solution;
Wherein, the former powder footpath after TS-1 molecular sieve change wetting ability used is 15.0 μm; The mol ratio of hydrogen peroxide and pimelinketone is 1.0; The mol ratio of ammonia and pimelinketone is 1.5; The concentration 70%(wt% of hydrogen peroxide); Catalysis oximation reaction temperature is 90 DEG C; Pressure is 400KPa (gauge pressure); The internal circulating load of circulation fluid is 1500m3/h; In circulation fluid, catalyst concn is 2.3%(wt%).
(2) at extracting and separating unit, in the cyclohexanone-oxime solution that step (1) obtains, add solvent orange 2 A carry out extracting and separating, obtain the solution A of organic phase cyclohexanone-oxime and the aqueous solution of inorganic phase catalyzer, the aqueous solution of catalyzer after filtering catalyzer is back to step (1) catalysis oximation reaction unit and recycles, the qualified discharge after treatment of the waste water after filtration;
Wherein, solvent for use A is cyclooctane.
(3) at preparation unit, in the solution A of the organic phase cyclohexanone-oxime obtained to step (2), add solvent B, be mixed with by the homogeneous phase solution C containing cyclohexanone-oxime of A, B two kinds of solvent compositions;
Wherein, solvent for use B is 2,4-xylenol; In described homogeneous phase solution C, the content of cyclohexanone-oxime is 35%(wt%); The ratio (vol) of solvent orange 2 A and B is 1.2.
(4) add in the homogeneous phase solution C obtained to step (3) in the reactor of the band premixer of rearrangement reaction unit containing free SO
3oleum, carry out Beckmann rearrangement reaction, obtain rearrangement reaction thing;
(5) at slaking flash evaporation unit, rearrangement reaction thing is stopped certain hour and carries out slaking, out by solvent orange 2 A flash separation and be back to the recycle of step (2) extracting and separating unit, and the solution obtained containing solvent B and hexanolactam sulfuric ester simultaneously;
Wherein, the rearrangement reaction thing curing time is 60 minutes.
(6) in hydrolysis unit, in the solution that step (5) obtains containing solvent B and hexanolactam sulfuric ester, add water be hydrolyzed, obtain mutually light and heavy phase, be gently the B solution containing hexanolactam mutually, heavy phase is the dilution heat of sulfuric acid containing a small amount of hexanolactam;
At this unit, water used is the process water that caprolactam refining unit is discharged; Hydrolysis temperature is 40 DEG C, and the residence time is 30 minutes; After hydrolysis, heavy phase dilute sulphuric acid concentration is 35%(wt%).
(7) in water extraction cells, step (6) is obtained light mutually in add water and extract, obtain the aqueous solution and the solvent B of hexanolactam, the aqueous solution of hexanolactam obtains hexanolactam finished product after sending subsequent cell refining, and solvent B is back to the recycle of step (3) preparation unit;
(8) add ammonia in heavy phase step (6) obtained or ammoniacal liquor carries out neutralization reaction and Crystallization Separation obtains ammonium sulfate and caprolactam water solution, caprolactam water solution prepares hexanolactam finished product after sending subsequent cell refining.
In the present embodiment, rearrangement process, the transformation efficiency of cyclohexanone-oxime is almost 100%, be 99.9% to the selectivity of hexanolactam, rearrangement solution colourity 37 breathes out gloomy value, titration value 0.37,290nm light absorption value 0.034, cyclohexanone-oxime content 1ppm(wt%), produce 1.2kg ammonium sulfate/kg cyclohexanone-oxime.
Claims (10)
1. prepare a method for hexanolactam, it is characterized in that comprising the following steps:
(1) at catalysis oximation reaction unit, under HTS existent condition, with pimelinketone, hydrogen peroxide and ammonia for raw material, cyclohexanone-oxime solution is obtained by catalysis oximation reaction;
Wherein, the HTS adopted is that TS-1 molecular sieve changes the former powder after wetting ability or shaping TS-1 catalyzer; The mol ratio of hydrogen peroxide and pimelinketone is 0.5 ~ 6.0; The mol ratio of ammonia and pimelinketone is 0.5 ~ 8.0; Oximation reaction temperature is 30 ~ 120 DEG C; Pressure is 0.10 ~ 0.60MPa(gauge pressure); The recycle ratio 10 ~ 100 of oximation reaction, in circulation fluid, the massfraction of catalyzer is 0.5% ~ 5%;
(2) at extracting and separating unit, in the cyclohexanone-oxime solution that step (1) obtains, add solvent orange 2 A carry out extracting and separating, obtain the solution A of organic phase cyclohexanone-oxime and the aqueous solution of inorganic phase catalyzer, the aqueous solution of catalyzer after filtering catalyzer is back to step (1) catalysis oximation reaction unit and recycles, the qualified discharge after treatment of the waste water after filtration;
Wherein, solvent orange 2 A is paraffinic hydrocarbons or naphthenic hydrocarbon, or their mixture;
(3) at preparation unit, in the solution A of the organic phase cyclohexanone-oxime obtained to step (2), add solvent B, be mixed with by the homogeneous phase solution C containing cyclohexanone-oxime of A, B two kinds of solvent compositions;
Wherein, solvent B is cycloalkane-carboxylic acid or alkylphenol, or their mixture;
In homogeneous phase solution C, the massfraction of cyclohexanone-oxime is 5% ~ 80%; The volume ratio of solvent orange 2 A and B is 0.4 ~ 5.0;
(4) at rearrangement reaction unit, in the homogeneous phase solution C that step (3) obtains, add oleum carry out Beckmann rearrangement reaction, obtain rearrangement reaction thing;
Wherein, the mol ratio of oleum and cyclohexanone-oxime is 0.5 ~ 3.0; Free SO in oleum used
3massfraction be 5% ~ 65%; Rearrangement reaction temperature is 40 ~ 140 DEG C; Rearrangement reaction pressure is-20KPa ~ 500KPa (gauge pressure);
(5) at slaking flash evaporation unit, rearrangement reaction thing is stopped certain hour and carries out slaking, out by solvent orange 2 A flash separation and be back to the recycle of step (2) extracting and separating unit, and the solution obtained containing solvent B and hexanolactam sulfuric ester simultaneously;
Wherein, the rearrangement reaction thing curing time is 1 ~ 120 minute;
(6) in hydrolysis unit, in the solution that step (5) obtains containing solvent B and hexanolactam sulfuric ester, add water be hydrolyzed, obtain mutually light and heavy phase, be gently the B solution containing hexanolactam mutually, heavy phase is the dilution heat of sulfuric acid containing a small amount of hexanolactam;
Wherein, hydrolysis temperature is 10 ~ 80 DEG C; The hydrolysis residence time is 20 ~ 80 minutes; After hydrolysis, the massfraction of heavy phase dilute sulphuric acid is 5% ~ 60%;
(7) in water extraction cells, step (6) is obtained light mutually in add water and extract, obtain the aqueous solution and the solvent B of hexanolactam, the aqueous solution of hexanolactam obtains hexanolactam finished product after sending subsequent cell refining, and solvent B is back to the recycle of step (3) preparation unit;
(8) add ammonia in heavy phase step (6) obtained or ammoniacal liquor carries out neutralization reaction and Crystallization Separation obtains ammonium sulfate and caprolactam water solution, caprolactam water solution prepares hexanolactam finished product after sending subsequent cell refining.
2. method according to claim 1, is characterized in that at catalysis oximation reaction unit, and the oximation reaction device adopted is microreactor or multi-stage type tubular reactor or slurry hearth reactor;
The catalyst particle size scope adopted is 0.1 ~ 30.0 μm; The mol ratio of hydrogen peroxide and pimelinketone is 1.0 ~ 1.2, and the mol ratio of ammonia and pimelinketone is 1.0 ~ 1.5; The massfraction 15% ~ 70% of hydrogen peroxide; Oximation reaction temperature is 60 ~ 95 DEG C; Pressure is 0.20 ~ 0.40MPa (gauge pressure); The recycle ratio 20 ~ 50 of oximation reaction.
3. method according to claim 1, is characterized in that at extracting and separating unit, and solvent orange 2 A is the naphthenic hydrocarbon of carbonatoms 4 ~ 8.
4. method according to claim 1, is characterized in that preparing the alkylphenol that unit solvent B is carbonatoms 7 ~ 12;
In homogeneous phase solution C, the massfraction 10% ~ 50% of cyclohexanone-oxime; The volume ratio of solvent orange 2 A and B is
0.6～3.0。
5. the method according to claim 1 or 4, is characterized in that the massfraction 15% ~ 35% of cyclohexanone-oxime.
6. the method according to claim 1 or 4, is characterized in that the volume ratio of solvent orange 2 A and B is 0.8 ~ 2.0.
7. method according to claim 1, is characterized in that adopting the tubular reactor of microreactor or multi-stage type tubular reactor or high-shear mixer or the reactor of band premixer at rearrangement reaction unit rearrangement reactor.
8. method according to claim 1, is characterized in that at rearrangement reaction unit, and the mol ratio of oleum and cyclohexanone-oxime is 0.6 ~ 1.1;
Free SO in oleum
3massfraction be 5% ~ 25%; Rearrangement reaction temperature is 60 ~ 120 DEG C; Rearrangement reaction pressure is 10KPa ~ 300KPa (gauge pressure).
9. method according to claim 1, is characterized in that at slaking unit, and the rearrangement reaction thing curing time is 3 ~ 80 minutes.
10. method according to claim 1, it is characterized in that at the water that hydrolysis unit is used be the process water that secondary de-salted water or caprolactam refining unit are discharged, hydrolysis temperature is 30 ~ 40 DEG C, the hydrolysis residence time is 30 ~ 40 minutes, and after hydrolysis, the massfraction of heavy phase dilute sulphuric acid is 30% ~ 40%.
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| CN107556213B (en) * | 2016-08-16 | 2019-11-22 | 沧州旭阳化工有限公司 | A kind of technique of cyclohexanone oxamidinating and the technique for manufacturing caprolactam |
| CN106831486A (en) * | 2017-03-03 | 2017-06-13 | 山东省化工研究院 | A kind of process for synthesizing ketoxime |
| CN109776418A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | A method of reducing hexanolactam hydrogenation catalyst amount |
| CN108358823A (en) * | 2018-04-20 | 2018-08-03 | 陕西宏元化工技术有限公司 | A method of with organic solvent crystal refining caprolactam |
| CN110295074A (en) * | 2019-07-18 | 2019-10-01 | 北京石油化工工程有限公司 | The system and method for hydrogen resources comprehensive utilization in a kind of oven gas |
| CN114671808A (en) * | 2022-04-28 | 2022-06-28 | 武亚梅 | Preparation method of caprolactam |
| WO2024000849A1 (en) * | 2022-06-29 | 2024-01-04 | 中国天辰工程有限公司 | Method for synthesizing caprolactam by means of beckmann rearrangement reaction |
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