CN104370723B - Hydrolyze the residue produced when producing isophorone and reclaim isophorone and acetone - Google Patents

Abstract

The present invention relates to hydrolyze the residue of generation when producing isophorone and, to reclaim isophorone and acetone, be specifically related to the preparation method of isophorone (3,5,5 trimethyl 2 cyclohexene 1 ketone).

Description

Hydrolyze the residue produced when producing isophorone and reclaim isophorone and acetone

Technical field

The present invention relates to the preparation method of isophorone (3，5，5-trimethylcyclohexen-2-one-1).

The present invention be more particularly directed to extend the preparation method of isophorone to better profit from raw material.Wherein by institute The organic residue produced hydrolyzes (hydrolysis 2) again, in order to returned to by the valuable substance formed in it In technique.In addition to acetone and isophorone, valuable substance also particularly relate to intermediate product phorone, Mesityl oxide and diacetone alcohol.

Background technology

Isophorone is especially used as high boiling point in paint vehicle, printer's ink, adhesives and plant protection product industry Solvent.According to known prior art, isophorone can after further treatment, such as, is processed into different Buddhist That ketone nitrile, isophorone diamine, isophorone diisocyanate or ketone group-isophorone.

So-called isophorone refers to the trimerization condensation product of acetone.The preparation of the isophorone catalysis by acetone Aldol condensation is carried out.

Describing in the patent literature, reaction in the liquid phase is nearly all only in the basic conditions in the temperature improved Carry out under degree and high pressure.

Patent documentation (DE1095818, DE1144 since Hibemia Chemie19 sixties in century 269, DE1205525, DE1165018) in except use low alkali liquid concentration single-phase charging thing/catalyst mix Beyond compound, also describe and carry out post processing by means of hydrolysis tower.Here in pressure reactor, pass through acetone Condensation in the liquid phase, by means of the alkali number (NaOH or KOH) less than 1% as catalyst, with in application Isophorone is prepared less than temperature at 150-250 DEG C under the water yield of 20%.Two phases formed during this reaction, Not only by suitable reaction process (reactor structure, pulse generator), and by using emulsifying agent breast Change, to ensure contact (DE1095818) good between catalyst and reactant.

In addition, DE1205525 also describes the post processing of by-product (so-called condensation substance excessively).? Discharging, in a so-called pressure distillation column, the acetone formed with the aqueous solution of alkali continuously at 120-300 DEG C In the case of, there is the hydrolysis of condensation substance.

By carrying out separated low-boiling-point substance under the pressure identical with carrying out the pressure that is condensed, and by subtracting What the distillation further work-up under little pressure still existed crosses condensation substance, can be from containing isophorone Condensation product obtains pure isophorone (DE1144269).

The application of BP Chemicals is declared, can replace at it by using potassium hydroxide aqueous solution (KOH) Catalyst sodium hydrate aqueous solution (NaOH) common in the case of it, keep identical selective in the case of, Isophorone productivity improves at most 7% (DE2520681).

Furthermore describe, by taking out the material of coloring in the stream of side from this reaction tower, and by distillation Carry out this stream of purification with acidity conversion, the product quality of isophorone can be made to be improved (DE2645281).

Additionally, it is different about preparing to have there is also Daicel Chemical Industries since the nineties in 19th century The application (JP8245485, JP8245486) of phorone.They describe by reducing the water in feed steam dense Degree, and by making aqueous base return to the hydrolyzable moiety of reactive distillation mutually after phase separation, can To improve the conversion ratio of isophorone.

In W02012/076314, the known method preparing isophorone, is to pass through

It is catalyzed the aldol condensation acetone as charging thing,

Post processing product,

Hydrolyze valuable stream (Wertstrom), and be separated into organic fraction (Fraktion) and aqueous fraction, Isophorone is obtained from this organic fraction,

Aqueous fraction carries out distilling post processing, and the steam at distillation equipment for after-treatment top is sent to further This hydrolysis device.

In the method, according to the poised state of the reaction carried out, hydrolysis is crossed decomposing again of condensation substance (Rueckspaltung) carry out the most completely, in the residue therefore occurred at the end of isophorone purification also There is hydrolyzable condensation substance excessively, this crosses condensation substance can be converted into valuable substance by extra hydrolysis. According in the method for W02012/076314, these residues are being burnt.

A series of by-product will be formed when synthesis of isophorone.These by-products e.g. diacetone alcohol, A series of higher level condensation product (mistakes of Mesityl oxide, phorone, 1，3，5-trimethyl-benzene and acetone Condensation substance) (such as xylose ketone and different xylose ketone).For this reason, it is difficult to obtain the high yield of isophorone Rate and high selectivity.

Therefore, the technical purpose of the present invention is to find a kind of method, and it can again improve isophorone and prepare Economic benefit.

Subject of the present invention is the method preparing isophorone through the following steps:

Step 1, catalysis aldol condensation is as the acetone of charging thing；

Step 2, post processing product；

Wherein the post processing in this step 2 is carried out in three kinds of fraction:

A) one of fraction is formed by unconverted acetone, water and low-boiling-point substance, and this fraction is condensed and is then returned to React to reactor；

B) one of fraction, is the most especially enriched with the material of coloring, and wherein this grade of lease making is further purified, and makes Contained valuable substance returns in technique；

C) one of fraction is formed by isophorone, higher level condensation product and water and catalyst, the most valuable Stream, is hydrolyzed 1 the most subsequently to this fraction, byproduct fraction ground or fully in this hydrolytic process It is converted into isophorone, acetone and other valuable product；

Step 3, is wherein separated to post-treated fraction c), is separated into substantially organically fraction d) The most aqueous fraction e)；

Step 4, carries out aqueous fraction e) distilling post processing will be from described distillation equipment for after-treatment top Steam be further introduced into hydrolysis device 1；

Step 5, is following three fraction by organic fraction d) purification:

I) residue,

Ii) pure isophorone,

Iii) low-boiling-point substance remained；Step 6, is hydrolyzed 2 and by produced valuable to residue i) Product returns in technique.

If further hydrolyzed it has been found, surprisingly, that separate laggard row at isophorone, then more effectively The residue that ground hydrolysis is formed when preparing isophorone.(the hydrolysis of hydrolysis again of residue i) in step 6 2) the hydrolyzable composition that there is also in residue can be made to convert further.It is relative that this can improve isophorone Economic benefit prepared by the productivity of the usage amount of acetone and raising isophorone.

The method of the present invention can continuously, discontinuously or semi-continuously be carried out.But preferably it is carried out continuously.

In step 1, the preparation of isophorone is by carrying out as the catalysis aldol condensation of the acetone of charging thing.Its In, at first step, two acetone molecules are reacted under cases of dehydration by intermediate product diacetone alcohol Mesityl oxide.In subsequent reactions, this Mesityl oxide and other acetone are again by dehydration Generate isophorone.

Isophorone refers to the reaction of three acetone molecules condensation in the case of sloughing two hydrones Product.

Because the charging thing (acetone) used and the chemical similarity of (middle) product formed, different The synthesis of phorone is not the most selective.Owing to there is a large amount of emulative aldol reaction, in reaction Under the conditions of in addition to the target molecule isophorone wanted, also obtain a whole series undesirable (higher Level) condensation product (such as xylose ketone and different xylose ketone) and other accessory constituent (such as 1，3，5-trimethyl-benzene).

Therefore, isophorone synthesis is characterised by that reaction network is complicated；Selectivity depends on to a great extent In conversion ratio.In order to the formation of undesirable (higher level) condensation product is minimized, it is necessary to limit third Ketone conversion ratio.Especially in gas phase is reacted, the catalyst used may be by the formation of coking residue Inactivation.

Have been found that the reactant mixture of generation can be particularly economically friendly with ecology by the method for the present invention Post processing becomes isophorone well.

Condensation of acetone reaction generates isophorone (reaction) and preferably carries out with catalytic liquid phase reaction.As an alternative Scheme, it is also possible to by means of gas phase reaction or prepare isophorone by the reaction in supercritical acetone.

Carry out this reaction for the method according to the present invention in the liquid phase, make acetone in the reactor used Portion by catalytic reaction at 100 to 250 DEG C, preferably 150 to 250 DEG C, particularly preferred 180 to 250 DEG C of models The temperature enclosed, and at 5 to 50bar, preferably 10-50bar, in the pressure limit of particularly preferred 20-50bar, Being converted into isophorone, wherein given numerical value can any combination with one another.

Carry out this reaction for the method according to the present invention in the gas phase, make acetone in the reactor used Portion is by catalytic reaction at 100 to 400 DEG C, and the temperature inversion of preferably 200 to 400 DEG C of scopes is isophorone.

In order to the method according to the present invention carries out this reaction at supercritical region, make acetone at the reactor used Inside is converted by the catalytic reaction temperature 250 to 350 DEG C of scopes and the pressure limit at 50 to 200bar For isophorone.

This catalytic reaction can be carried out with the catalyst mentioned in the prior art, and wherein it both can refer to homogeneously Catalyst, can refer to again heterogeneous catalyst.Homogeneous catalyst is preferably used in the liquid phase, the most preferably Use heterogeneous catalyst.In order to carry out this reaction at supercritical region, it is possible not only to use homogeneous catalyst, also Heterogeneous catalyst can be used.

For the most preferably reacting, isophorone can be by means of alkali number (NaOH or KOH) < 1 Weight %, preferably < 0.5 weight %, particularly preferably < homogeneous catalyst of 0.2 weight % produces.Particularly preferably make With the NaOH that quantity is 0.015 to 0.05 weight % as catalyst.Water concentration used is essentially from rear Process the return stream of technique, should be less than < 40%, preferably < 30% based on total fluid flowmeter water concentration.

This reaction can be at any reactor of prior art, such as tubular reactor, stirred tank, stirred tank Cascade, fixed bed reactors, pressure distillation reactor or reactive distillation, micro-structured reactor, endless tube are anti- Answer in device (Schlaufenreaktor) etc., or carry out in the combination of any reactor.Wherein, the choosing of reactor Select and be not limited to above-mentioned option.

Term pressure distillation reactor is here equal to the equipment carrying out reactive distillation wherein.Reactive Distill to have in technical literature and describe fully, such as at the Encylcopedia of Industrial of Ullmann Chemistry (M.Sakuth, D.Reusch, R.Janowsky:Reactive Distillation2008 Wiley-VCH Verlag GmbH&Co KGaA, Weinheim, DOI: 10.1002/14356007.c22c01.pub2 in).Here and in the document quoted, reactive distillation is described All conventional techniques and equipment.If term reactive distillation tower being used below at this patent text, Then refer to all embodiments of reactive distillation as described in document.

In preferred embodiments, this reaction process is in reactive distillation tower, tubular reactor or fixed bed Reactor is carried out.Particularly preferably tubular reactor.

After this reaction process, this reactant mixture of post processing be separated into each group in step 2 Point.In addition to isophorone, these are so-called low-boiling-point substances, such as acetone, diacetone alcohol and different sub-third Benzylacetone, and condensation of acetone product (crossing condensation substance) (such as the xylose ketone and different xylose of a series of higher level Ketone), water and optional catalyst.The most completely or partially separate.

The separation of each fraction can use all separation methods, such as distill, be evaporated under reduced pressure, crystallize, extract, Sorption, permeate, be separated or the combination of said method, continually or intermittently, single phase or the multistage ground Carry out.This separation is preferably realized in one or more equipment by distillation.

Wherein, distillation can spatially separated with the synthesis of isophorone (reaction) be carried out, or one Individual equipment occurs.The separation of each fraction is preferably preferably carried out by reactive distillation in reactive distillation tower.

This separation particularly preferably synthesize with isophorone (reaction) spatially separatedly, with side stream The reactive distillation tower removed is carried out.

It is separated into three kinds of fraction according to the present invention:

A) one of fraction is by unconverted acetone, water and low-boiling-point substance (such as diacetone alcohol and Mesityl oxide) Composition, this fraction is condensed and is subsequently returned in reactor react.

B) one of fraction, is the most especially enriched with the material of coloring.This level lease making is further purified, and makes institute Return in technique containing valuable substance.

C) one of fraction is made up of isophorone, higher level condensation product and water and optional catalyst especially, It is referred to as valuable stream.Subsequently this fraction is hydrolyzed 1.

In a preferred embodiment, being taken out as vapor stream by fraction a), this stream consists essentially of third Ketone, water and low-boiling-point substance (substantially diacetone alcohol and Mesityl oxide), condensed, and together with raw material acetone, Water adds described reactor together with optional catalyst again.

In preferred embodiments, using fraction b) as distillation column, the side stream of preferred reactive distillation column Remove, optionally neutralize and further work-up.Wherein, all conventional separation sides can be applied during post processing Method, such as, distill, be evaporated under reduced pressure, crystallize, extract, sorption, permeate, be separated or above-mentioned every group Close.Purification can continuously or intermittently, single phase or the multistage ground carry out.Purify preferably by distillation Realize.Purify particularly preferably by neutralizing or extract and the combination of distillation subsequently, preferably at reactive distillation Tower realizes.Preferably by with the valuable product being made up of isophorone, high-boiling components and optional catalyst Post-treated being delivered to mutually in hydrolysis device.Another phase that will be obtained by valuable product, substantially Including acetone, diacetone alcohol and Mesityl oxide, it is preferably returned in reaction.The residue optionally produced It is transported to heat utilization.

Fraction c) is hydrolyzed 1.The purpose of hydrolysis 1 is, makes byproduct fraction ground or is completely converted into Isophorone, acetone and other valuable product.Hydrolysis can be described above all conventional anti- Answer in device or distillation column or a combination of both and carry out.Hydrolysis is preferably carried out by reactive distillation, is wherein produced Raw low-boiling-point substance (consisting essentially of acetone, diacetone alcohol and Mesityl oxide) is directly discharged from hydrolysis area, And return in reaction, and it is no longer used to the side reaction in hydrolysis with this.

The hydrolysis 1 of fraction c) is carried out by reactive distillation the most in a device, preferably in reaction Property distillation column is carried out, reactant mixture is separated into fraction a to c the most simultaneously) so that produced product Thing the most correspondingly separates, and is hydrolyzed fraction c).

Optionally, hydrolysis 1 and separated can also synthesize (reaction) with isophorone within one device Rise and carry out.

Hydrolysis 1 can be entered in the case of with or without catalyst with all mixed proportions of organic component and water OK.Wherein, the water concentration in hydrolysis is 0.1-99.9 weight %, preferably 30-90 weight %.In homogeneous catalysis In the case of, the catalyst that also in reactive moieties use is preferably used during hydrolysis.Catalyst concn is preferably 0.001-10 weight %, particularly preferred 0.05-1 weight %.Pressure in hydrolysis reactor is 1-200bar, excellent Select 20-60bar, carry out under the hydrolysis the most also pressure in isophorone synthesis step (reaction). The temperature of hydrolysis is 100-300 DEG C, preferably 210-260 DEG C.Particularly preferably adjust when application response distillation column Whole temperature or temperature curve, this temperature curve corresponding to separating column plate or reacting column plate at the bottom of tower with each Boiling temperature.

Hydrolysis 1 can be carried out to single phase or multistage in one or more equipment.

The most post-treated fraction c) then separates from hydrolysis reactor 1 or reactive distillation tower, cold But and be separated.

Being separated into substantially organically fraction d) and the most aqueous fraction e), the latter is when homogeneous catalysis Possibly together with catalyst.Wherein it is possible to use band and the phase separation container without embedded component (Einbaute).Divide mutually From at 0-200 DEG C, preferably 0-100 DEG C, the temperature of particularly preferred 20-70 DEG C and at 1-150bar, preferably 20-60bar, the most also pressure when hydrolysis are carried out.

Substantially organically fraction d) with target product isophorone is the most neutralized, and with general side Method purifies, in order to obtain the isophorone with required purity and colour stability.Wherein it is possible to use institute There is conventional separation method, such as, distill, be evaporated under reduced pressure, crystallize, extract, sorption, infiltration, divide mutually From or above-mentioned every combination.Purification can continually or intermittently, and single phase or multistage ground, at pressure Down or carry out in a vacuum.

It is following three fraction by organic fraction d) purification:

I) residue,

Ii) pure isophorone,

Iii) low-boiling-point substance remained.

Purify and preferably realized by distillation.Purify particularly preferably by neutralizing or extract and the group of follow-up distillation Close and realize.

Fraction i) residue is carried out the hydrolysis (hydrolysis 2) of other step 6.

Hydrolysis 2 (steps 6) are carried out under conditions of identical with hydrolysis 1.Hydrolysis 2 can with organic component and All mixed proportions of water are carried out in the case of with or without catalyst.Wherein, the water concentration in hydrolysis is 0.1-99.9 weight %, preferably 30-90 weight %.In case of homogeneous hydrogenation, it is preferably used during hydrolysis also The catalyst used in reactive moieties.Catalyst concn is preferably 0.001-10 weight %, particularly preferably 0.05-1 weight %.Pressure in hydrolysis reactor is 1-200bar, preferably 20-60bar, and the temperature of hydrolysis is 100-300 DEG C, preferably 210-260 DEG C.

Hydrolysis 2 can be carried out to single phase or multistage in one or more equipment.

Hydrolysis 2 can be in all of common reactor having been explained above or at distillation column or two In the combination of person, preferably carry out at least one reactive distillation tower.

In addition to isophorone and acetone, the low-boiling-point substance of other be converted into isophorone, the most double third Keto-alcohol, Mesityl oxide and phorone broadly fall in the hydrolysis 2 of residue i) formed steam in have valency Value product.And then the valuable product formed returns in technique and is therefore utilized on material.Preferably Return to hydrolyze in 1.Preferably the steam at hydrolysis device 2 top is further introduced in hydrolysis device 1.Water Carry out in reactive distillation tower with solving for 2 particularly preferred single phases.

Compared with the technique of WO2012/076314, owing to residue i) hydrolysis in step 6 creates excellent Point.Be hydrolyzed 2 residue be practically free of isophorone, this hydrolysis compared with fraction c) (hydrolysis 1) produces The more favo(u)red state of molecular balance, thus hydrolysis can be carried out more completely.

Here will describe more accurately aqueous fraction e) distillation post processing (waste-water purification) and distillation after locate The steam at reason equipment top be further incorporated into hydrolysis device 1.

The most aqueous fraction e) is preferably carried out waste-water purification.Here the reaction as key component is carried out Water and optional catalyst and the organic component optionally still dissolved be (such as isophorone, acetone and higher level Condensation product) separation.Waste-water purification described in W02012/076314 exactly.

Waste-water purification is preferably carried out in one or more distillation column.Wherein, according to the present invention it is necessary that The steam of waste water tower is delivered directly to hydrolyze wherein in the equipment of 1.Solve currently existing the most simultaneously Multiple problems of technology:

1) because this steam is substantially made up of water, hydrolyzable moiety be adjusted to required, sufficiently high water is dense Degree, in order to additional fresh water need not be added to hydrolysis.

2) it is dissolved in the organic principle in fraction e) and partially or completely returns to this technique by the steam of waste water tower In.Organic substance carrying capacity in this waste water is minimized, and because described Organic substance is substantially different Fo Er Ketone, so improve the gross production rate of technique.Therefore, this novel misconnection of waste water tower is to ecological and economy Process makes major contribution.

3) additionally, the heat required for the hydrolysis of reactant mixture or separated is provided by steam, thus nothing Need single heater.

Pressure in waste water tower is 1-200bar, preferably 20-60bar.Steam at waste water tower is delivered directly to During the hydrolyzable moiety of reactive distillation, the system pressure particularly preferably set in whole hydrolysis/waste water Tower System Lower work.Temperature in waste water tower is consistent with the boiling temperature of fraction e) under this pressure condition.Preferably steam Temperature is 200-300 DEG C.

It is described in more detail below and how the water from aqueous fraction distillation rear treating groove is evaporated under reduced pressure, How to return to prepare with produced purified water in the technique of isophorone.

(stream f) can cool down and discard the waste water produced at the bottom of waste water tower tower.But preferably waste water f) is subtracted Pressure evaporation also separates further with this.The steam g) (being substantially made up of pure water) in reduction vaporization stage is permissible Condensation also returns in technique as water, is preferably returned in reaction, such as, be used for diluting used catalysis Agent (in case of homogeneous hydrogenation).Wastewater flow rate is reduced again with this.Reduction vaporization can single phase or many Stage, located continuously or discontinuously carry out.In any case in the below waste water tower of the pressure in reduction vaporization Pressure.In the method according to the invention, advantageous applications is evaporated under reduced pressure.

Whole distilation steps and reactions steps in described technique can be with or without embedded component (such as fractional distillation Tower, irregular embedded component or windrow, the embedded component of rule or filler, with or without forced conveyance Column plate) reactor or equipment in carry out.

All metal materials contacted with product for reaction and the equipment being made up of metal material and embedded Part all must resistance to alkali liquor.Wherein it is possible to propose various life requirements according to danger.For durability, It is directed not only to chemistry and/or mechanical property, and relates to the evaluation mark of preparation method to be used and inspection period Accurate.

For metal material part with reference in November, 2008 publish AD2000-Merkblatt HP0 (Allgemeine F ü r Auslegung, Herstellung und damit verbundene Pr ü fungen (design, produce and the general standard of inspection related to this)) and the DIN EN of in July, 2000 publication 10020(Begriffsbestimmung fur die Einteilung der(the term definition of steel classification)). For accurate expression term (such as austenitic stainless steel), the material packet that citation there is listed.If technology Upper suitable, described in assert for have comparability compared with resistance to alkali liquid corrosion material technology on operational Flexible program (such as, forging flexible program, rolling flexible program and casting flexible program) is the most effective.

A) for assembly that is that bear pressure and that contact with product, any suitable material of prior art can be applied Material, such as:

● heat resisting steel (such as, according to the material subgroup 5.1 to 5.4 and 6.1 to 6.4 of AD2000HP0)

● austenitic stainless steel (such as, according to the material subgroup 8.1 to 8.2 of AD2000HP0)

● without ferrite austenitic stainless steel (such as, according to AD2000HP0 material subgroup 8.1 to 8.2)

● ferritic-austenitic stainless steel (such as, according to AD2000HP0 material subgroup 10.1 to 10.2)

● nickel and nickel alloy (such as, according to the material subgroup 41 to 46 of AD2000HP0)

The combination of above-mentioned material can also be applied.Wherein, the selection of material is not limited to above-mentioned option and also bag Include on corrosion technology the of equal value or scheme of higher level.Preferably according to prior art consider loading condiction and To the material that the commercial viability of alkali liquor is excellent in the case of danger.When changing alkali in unallowed mode During the commercial viability of liquid, it is not possible to abandon heat treatment.

B) any suitable material of prior art can be applied for assembly that is that be not subject to pressure and that contact with product Material, such as:

● all materials enumerated under a) item

● non-alloyed steel (such as, according to AD2000HP0 material subgroup 1.1 to 1.2)

● non-alloyed steel and other steel alloy (such as, according to DIN EN10020)

The combination of above-mentioned material can also be applied.Wherein, the selection of material is not limited to above-mentioned option, but also Be included on corrosion technology equivalence or the variant of higher level.Considering requirement condition and dangerous situation Under, preferably prior art has the material of enough durability to alkali liquor.For being not subject to the assembly of pressure, depend on The most interim durability can be tolerated in danger.When changing the industry to alkali liquor in unallowed mode During durability, it is not possible to abandon heat treatment.

C) changing material behavior by suitable preparation method, these preparation methoies were below with respect to 2003 JIUYUE publish DIN8580 (Fertigungsverfahren-Begriffe, Einteilung (preparation method term, Classification)) in the term mentioned be described.Following preparation method can be used to power work metal material, such as:

● shape (such as, casting)

● deformation (Umformen) (such as cold forming and thermoforming)

● cut off (the Tool in Cutting that such as, determines and cutting with the uncertain cutter of geometry with geometry Cut)

● engage (such as, melting welding)

● coating (such as, the coating of liquid, melt immersion, plating, thermal spraying, sinter, electroplate coating, Chemistry coating and gaseous state and the coating of vaporous)

● change material behavior preparation method (by strain hardening, described deformation is such as forged, roll-in, Irradiation；Heat treatment is the most quenched, recrystallization annealing, low stress annealing, normalization annealing (Normaisierungsgl ühen)；The combination of thermo-mechanical processi, such as heat treatment and deformation process；Sintering and calcining)

The combination of above-mentioned preparation method can also be applied.Wherein, the selection of preparation method is not limited to above-mentioned option. Preferably according to the method for the alkali liquor durability required by the prior art each material and facility of guarantee.

D) can apply following to equipment and embedded component and particularly inspection to solder bond, such as:

● magnetic powder test MT

● penetrating inspection PT

● ray inspection RT

● ultrasonic examination UT

● visual inspection VT

● Hardness Surveillance HT

● alloy analysis

The combination of the above-mentioned method of inspection can also be used.Wherein, the selection of the method for inspection is not limited to above-mentioned option. It is preferably to ensure the method for inspection that the alkali liquor durability required by each assembly makes contributions and comment according to prior art Valency basis.

According to the embodiment of the present invention:

The preparation of isophorone is carried out according to step the most disclosed in the specification.Fraction d) is distilled Post processing.The isophorone often producing 1kg will produce the residue i) of 0.12kg.

Residue i) from post processing is carried out extra hydrolysis 2.

Hydrolysis 2 principle according to reactive distillation in the distillation equipment of single phase is carried out.In order to by steam Or nitrogen introduces in container, this equipment is made up of stirring container and two conveying pipes of a heating.In addition One is had to connect for exporting, condense and collect formed steam.Test under the following conditions: 300g residue i) and 1500g water are added in reactor, and under agitation (about 400U/min) heating. Now nitrogen stream is adjusted to 10g/h, equipment pressure is adjusted to 36bar.Reactor be heated to 240 DEG C it After, the soda lye by 25% is pressed in reactor by pressure apparatus, the water of this pressure apparatus 188g Rinse.The valuable substance of 23 weight % is obtained by residue i).The valuable substance formed have acetone, Isophorone, phorone, diacetone alcohol and Mesityl oxide.

Comparison with the preparation according to WO2012/076314

By above-mentioned extra hydrolysis, the isophorone often preparing lkg therefore can be according to step 1-6 Whole technique in save the acetone of 0.04kg.According in the whole technique of step 1-6, by isophorone Productivity improve 3 weight %.

Claims (34)

1. The method preparing isophorone the most through the following steps:

   Step 1, catalysis aldol condensation is as the acetone of charging thing；

   Step 2, post processing product；

   Wherein the post processing in this step 2 is carried out in three kinds of fraction:

   A) one of fraction is formed by unconverted acetone, water and low-boiling-point substance, and this fraction is condensed and is then returned to React to reactor；

   B) one of fraction, is the most especially enriched with the material of coloring, and wherein this grade of lease making is further purified, and makes Contained valuable substance returns in technique；

   C) one of fraction is formed by isophorone, higher level condensation product and water and catalyst, the most valuable Stream, is hydrolyzed 1 the most subsequently to this fraction, byproduct fraction ground or fully in this hydrolytic process It is converted into isophorone, acetone and other valuable product；

   Step 3, is wherein separated to post-treated fraction c), is separated into substantially organically fraction d) The most aqueous fraction e)；

   Step 4, carries out aqueous fraction e) distilling post processing will be from described distillation equipment for after-treatment top Steam be further introduced into hydrolysis device 1；

   Step 5, is following three fraction by organic fraction d) purification:

   I) residue,

   Ii) pure isophorone,

   Iii) low-boiling-point substance remained；

   Step 6, is hydrolyzed 2 and returned in technique by produced valuable product to residue i).
2. 2. according to the method preparing isophorone of claim 1, it is characterised in that to from aqueous fraction E) water bottom distillation post processing is evaporated under reduced pressure, and returns to produced purified water for preparing different Buddhist In the technique of your ketone.
3. 3. according to the method preparing isophorone of claim 1 or 2, it is characterised in that this reaction process Carry out in the liquid phase, wherein at 100 to 250 DEG C with in the pressure limit of 5 to 50bar, make acetone pass through to urge Changing reaction and be converted into isophorone, the value be wherein given can at random combination with one another.
4. 4. according to the method preparing isophorone of claim 1 or 2, it is characterised in that this reaction process Carry out in the gas phase, wherein in the temperature of 100 to 400 DEG C of scopes, make acetone be converted into by catalytic reaction different Phorone.
5. 5. according to the method preparing isophorone of claim 1 or 2, it is characterised in that this process is super Critical zone is carried out, and wherein in temperature and the pressure limit of 50 to 200bar of 250 to 350 DEG C of scopes, makes third Ketone is converted into isophorone by catalytic reaction.
6. 6. according to the method preparing isophorone of claim 1 or 2, it is characterised in that use homogeneous or Heterogeneous catalyst.
7. 7. according to the method preparing isophorone of claim 1 or 2, it is characterised in that this reaction is at liquid Carry out by homogeneous catalyst in mutually.
8. 8. according to the method preparing isophorone of claim 7, it is characterised in that use < 1 weight % Alkali number is as catalyst.
9. 9. according to the method preparing isophorone of claim 1 or 2, it is characterised in that described reaction exists Selected from tubular reactor, stirred tank, stirred tank cascade, fixed bed reactors, reactive distillation tower, micro-knot Structure reactor, annular-pipe reactor reactor in or the combination of these reactors in carry out.
10. 10. according to the method preparing isophorone of claim 1 or 2, it is characterised in that this reaction exists Reactive distillation tower, tubular reactor or fixed bed reactors are carried out.
11. 11. according to the method preparing isophorone of claim 1 or 2, it is characterised in that in step 2 The separation of each fraction is by separation method continually or intermittently, carry out to single phase or multistage.
12. 12. according to the method preparing isophorone of claim 1 or 2, it is characterised in that this step 2 In synthesize spatially separated carrying out by separation and the isophorone of distillation, or in a reaction unit Occur.
13. 13. according to the method preparing isophorone of claim 1 or 2, it is characterised in that this step 2 In the synthesis of separation and isophorone spatially separatedly, by the reactive distillation removed with side stream Carry out.
14. 14. according to the method preparing isophorone of claim 1 or 2, it is characterised in that described fraction A) as vapor stream take out, condensed, and again add together with raw material acetone, water and catalyst described instead Device, described vapor stream is answered to consist essentially of acetone, water and low-boiling-point substance, described low-boiling-point substance the most double third Keto-alcohol and Mesityl oxide.
15. 15. according to the method preparing isophorone of claim 1 or 2, it is characterised in that described fraction B) the side stream as distillation column removes.
16. 16. according to the method preparing isophorone of claim 1 or 2, it is characterised in that fraction b's) It is purified by neutralizing or extract to combine with distillation subsequently carrying out in reactive distillation tower.
17. 17. according to the method preparing isophorone of claim 1 or 2, it is characterised in that by fraction b) Post-treated have the mutually defeated of the valuable product that is made up of isophorone, high-boiling components with optional catalyst Deliver to hydrolytic process.
18. 18. according to the method preparing isophorone of claim 1 or 2, it is characterised in that by fraction b) What another obtained is made up of the valuable product substantially containing acetone, diacetone alcohol and Mesityl oxide It is back to mutually in described reaction.
19. 19. according to the method preparing isophorone of claim 1 or 2, it is characterised in that described hydrolysis C) carry out in reactive distillation tower.
20. 20. according to the method preparing isophorone of claim 1 or 2, it is characterised in that hydrolysis c) exists The hydrolysis of 0.1-99.9 weight % is carried out under water concentration.
21. 21. according to the method preparing isophorone of claim 1 or 2, it is characterised in that hydrolysis c) exists Carry out under the catalyst concn of 0.001-10 weight %.
22. 22. according to the method preparing isophorone of claim 1 or 2, it is characterised in that hydrolysis c) exists Carry out under pressure in the hydrolysis reactor of 1-200bar.
23. 23. according to the method preparing isophorone of claim 1 or 2, it is characterised in that hydrolysis c) exists The temperature of 100-300 DEG C is carried out.
24. 24. according to the method preparing isophorone of claim 1 or 2, it is characterised in that organic fraction D) purification is carried out by distillation.
25. 25. according to the method preparing isophorone of claim 1 or 2, it is characterised in that step 6 Hydrolysis is carried out under water concentration in the hydrolysis of 0.1-99.9 weight %.
26. 26. according to the method preparing isophorone of claim 1 or 2, it is characterised in that step 6 Hydrolysis is carried out under the catalyst concn of 0.001-10 weight %.
27. 27. according to the method preparing isophorone of claim 1 or 2, it is characterised in that step 6 Hydrolysis is carried out under the pressure in the hydrolysis reactor of 1-200bar.
28. 28. according to the method preparing isophorone of claim 1 or 2, it is characterised in that step 6 Hydrolyze the temperature at 100-300 DEG C to carry out.
29. 29. according to the method preparing isophorone of claim 1 or 2, it is characterised in that step 6 Hydrolysis is carried out to single phase or multistage in one or more equipment.
30. 30. according to the method preparing isophorone of claim 1 or 2, it is characterised in that by step 6 The steam at middle hydrolysis device top is further introduced into hydrolysis device 1.
31. 31. according to the method preparing isophorone of claim 1 or 2, it is characterised in that step 6 Hydrolysis is carried out at least one reactive distillation tower.
32. 32. according to the method preparing isophorone of claim 1 or 2, it is characterised in that step 6 Hydrolysis single phase ground is carried out in reactive distillation tower.
33. 33. according to the method preparing isophorone of claim 1 or 2, it is characterised in that to aqueous level Divide and e) carry out distilling post processing and the steam from described distillation equipment for after-treatment top being further introduced into hydrolysis In equipment 1, wherein this distillation post processing is preferably carried out in one or more distillation column.
34. 34. according to the method preparing isophorone of claim 33, it is characterised in that produce in bottom Waste water stream f carry out being evaporated under reduced pressure and separating further.