CN102127017B - Method for fast producing caprolactam by means of strengthening and mixing - Google Patents
Method for fast producing caprolactam by means of strengthening and mixing Download PDFInfo
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Abstract
The invention discloses a method for fast producing caprolactam by means of strengthening and mixing. The method comprises the steps of: mixing solution of cyclohexane oxime-inert solvent with sulfuric acid and sulfur trioxide-containing strongly acid material which is radially added in the manner of dispersing through the axial direction of a specially-designed jet flow mixer in the manner of continuous phase, performing the Beckmann rearrangement reaction, and discharging reaction heat in a gas phase space of a stirring kettle by means of evaporating solvent. At higher linear velocity and lower reaction temperature, the rearrangement can achieve better mass transfer effect and reaction effect, the sulfuric acid consumption is reduced, and the product quality can be improved.
Description
Technical field
The present invention relates to the method that a kind of Beckmann rearrangement of cyclohexanone oxime is equipped with hexanolactam, illustrate further is under the condition that inert solvent exists, cyclohexanone-oxime mixes with the material that contains sulfuric acid and sulphur trioxide by the Special Mixed mode, realize reinforcing mass transfer and rapid reaction, to guarantee the hexanolactam preparation method of high yield and high final product quality.
Background technology
Hexanolactam as the monomer of polyamide 6, is a kind of important petrochemicals, is widely used in making polyamide fibre and engineering plastics.The preparation method of hexanolactam is more, has only several but quality can satisfy the commercial run of polymerization requirement and economical rationality.Present industrial caprolactam production method mainly contains pimelinketone-hydroxylamine assay, photo-nitrosation of cyclohexane process and toluene method etc., wherein preceding two class methods occupy the overwhelming majority of hexanolactam output, all need to prepare cyclohexanone-oxime by benzene, be rearranged into hexanolactam through Beckmann again.
Reset specific to using cyclohexanone-oxime Beckmann, except gas phase was reset technology, the overwhelming majority was to be reaction medium with the oleum.Describe in " caprolactam production and application " book, the liquid phase rearrangement reaction takes place down at 110～120 ℃ in cyclohexanone-oxime, generates the hexanolactam sulfuric ester, and product neutralizes with ammoniacal liquor, gets crude caprolactam and saturated ammonium sulphate solution.The cyclohexanone-oxime transformation efficiency is about 100% in the rearrangement reaction, and the hexanolactam selectivity is greater than 98.5%.
The rearrangement reaction final product is hexanolactam, it is polymer monomer, quality product requires very high, and the change of technology can influence composition and the content of trace impurity, and the assurance of quality product needs rational Beckmann rearrangement reaction technology and corresponding specific equipment.Industrial rearrangement of cyclohexanone-oxime process is to carry out under the condition of lower concentration oleum, peracid oxime ratio and high temperature.So-called lower concentration refers to as the oleum of resetting thinner and catalyzer, its free SO
3Mass percent is about 8%～20%, and it is different and different that concrete numerical value is looked in the cyclohexanone-oxime water-content.The peracid oxime is than the mol ratio (SO in the oleum that refers to sulfuric acid and cyclohexanone-oxime in the rearrangement reaction raw material
3Conversion is sulphur acid meter), be generally about 1.5.
Rearrangement of cyclohexanone-oxime reaction heat comprises oxime solution heat and reaction heat two portions in sulfuric acid, and it is worth up to the 263kJ/mol oxime.Because the rearrangement reaction of cyclohexanone-oxime in the oleum system is a strong exothermic process, if the direct and oleum reaction with cyclohexanone-oxime, SO in keeping system
3Under the condition of concentration and macroscopical sour oxime ratio, the molar fraction of cyclohexanone-oxime in reaction mass is about 0.5, the thermal insulation warming of corresponding material is up to hundreds of degrees centigrade, and obviously general means can't be removed so big heat to guarantee temperature of reaction control within required scope in moment.Therefore, adopted very big recycle ratio in the actual production process, its main purpose is to reduce the branch rate of reactant, takes away reaction heat by the sensible heat of big cycle volume material.Adopt the outer circulation reactor as DSM N. V., oleum joins by recycle pump and resets in the circulation fluid, realize the living Beckmann rearrangement reaction of rapid hybrid concurrency with circulation fluid in the mixing tank of cyclohexanone-oxime in resetting jar, reaction heat causes material to produce about thermal insulation warming to 120 ℃, finally removes the heat that reaction discharges by the outer circulation water cooler.
Rearrangement product need pass through in the ammonia and could obtain hexanolactam because oleum exists down, and sour oxime is higher than more, and the amount of unit product producing ammonium sulfate byproduct is more big, and technological process is more uneconomical.Existing studies show that reduced the acid amount simply, and the quality of rearrangement product will worsen, and finally influence final product quality.On the other hand, the rearrangement reaction temperature is too high, causes side reaction easily, and the product quality also will worsen.But be subjected to reacting the restriction of thermal insulation warming, the rearrangement reaction temperature is difficult to control than low value.
Because the viscosity with temperature of rearrangement liquid and sour oxime than descending and sharply rising, will cause the part to mix inhomogeneous and influence quality product.As previously mentioned, temperature of reaction is too high will to cause the side reaction aggravation, the corresponding more by-product of the increase of acid amount.Therefore, even if adopt high recycle ratio, cyclohexanone-oxime single-stage Beckmann rearrangement process is difficult to satisfy simultaneously low acid amount and high-quality requirement.
That US Patent No. 5264571, US7358357, US7351820, US7339056 and Chinese patent CN1185218 disclose is multistage (two-stage or more than the two-stage) resets technology: react than oleum under the condition and most oxime at lesser temps with than the peracid oxime, to guarantee that viscosity is unlikely too high under the low temperature, suppress side reaction; Follow-up reacting with the small portion oxime a little more than the previous stage temperature of reaction with under than low sour oxime mol ratio condition, react completely the consumption that reduction is sour with assurance.
Multistage rearrangement needs multistage outer circulation pump, is cost with the energy consumption, and the progression of employing is more many, and energy consumption is more high.On the other hand, multistage rearrangement is not from having in essence to solve owing to mix the problem of the inhomogeneous local superheating that causes.For addressing the above problem, US Patent No. 4257950 discloses the solvent vaporization and has moved the using cyclohexanone-oxime Beckmann rearrangement of heat.Move hot different with the heat accumulating type outer circulation, cyclohexanone-oxime is dissolved in the inert solvent, the hot gasifying solvent of rearrangement reaction produces phase transformation, there is not thermal insulation warming in whole reaction system, and under the situation of solvent abundance, there is not local superheating in theory, reaction control can be carried out under differing temps by regulating gaseous pressure.In addition, adopt solution mode rather than fusion mode to reset, can overcome the susceptible to plugging shortcoming of existing rearrangement technology cyclohexanone-oxime charging, the rearrangement reaction temperature is further reduced becomes possibility.
As previously mentioned, SO
3Resetting with the using cyclohexanone-oxime Beckmann of sulfuric acid system is a fast strong heat-producing chemical reaction, and transmitting (particularly microcosmic mixing behavior) and reaction process condition must mate, and could guarantee higher yield and reliable quality.The Beckmann that moves hot mode at the outer circulation accumulation of heat resets technology, Chinese patent CN200480014248.8 discloses a kind of hybrid reaction method and mixer structure of special use, cyclohexanone-oxime joins in the reaction mixture by one or more passages, under the turbulence state that guarantees enough large Reynold numbers, reaction can obtain very high yield and good final product quality.Yet above-mentioned special hybrid reaction method and mixer structure are applied to that Beckmann that the solvent vaporization moves hot mode is rearranged in the scale operation and are improper, are mainly reflected in:
(1) the solvent vaporization moves under the hot mode, is subjected to the influence of transformation rate, unavoidably contains solvent in the product, and is in its bubble point temperature, is difficult to realize a large amount of reaction mass circulations on the engineering.Therefore, can not reach the effect of control speed of response by a large amount of recycle stock diluting reaction substrate concentrations as the outer circulation accumulation of heat.
(2) the solvent vaporization moves in the hot mode, and cyclohexanone-oxime solution and strongly-acid material directly mix, and the volumetric flow rate difference of two strands of materials is not very big; And the moving in the hot mode of outer circulation accumulation of heat, cyclohexanone-oxime disperses to join in the circulation products, and the latter's flow is much larger than the former.The change of two strands of mass flows will influence mixed effect, thereby finally influence the quality of rearrangement product.
This shows, the Beckmann rearrangement technology that the outer circulation accumulation of heat moves hot mode has its supporting hybrid technology and structure formation, but the rearrangement that vaporization moves hot mode for solvent, because the difficult point place of above-mentioned engineering problem, at present none preferably solution guarantee to react coupling with mass transfer.
Summary of the invention
Purpose of the present invention aims to provide a kind of Beckmann and resets the method that prepare hexanolactam, and when guaranteeing that cyclohexanone-oxime thoroughly transforms, inhibition side reaction process is cut down the consumption of raw materials and guaranteed quality product.
A kind of method of producing hexanolactam of mixing, the equipment that adopts comprises jet mixer and stirring tank, the axial passage outlet of jet mixer is arranged at stirring tank gas-phase space outer peripheral edges; The solution of cyclohexanone-oxime-inert organic solvents passes through the jet mixer axial passage as external phase, contain the strongly-acid material of sulfuric acid and sulphur trioxide as disperse phase by jet mixer radially, the Beckmann rearrangement reaction takes place after external phase and the disperse phase short mix, product obtains the hexanolactam sulfuric ester realize gas-liquid separation in follow-up stirring tank after.
In the jet mixer by contriver institute particular design, the solution of cyclohexanone-oxime-inert organic solvents and the material short mix that contains sulfuric acid and sulphur trioxide because Beckmann rearrangement speed is very fast, is reflected in the mixing tank and just carries out immediately.The outlet of jet mixer axial passage is tangent with stirred autoclave gas-phase space circumference, after the reaction product mixture gas-liquid separation, obtains the hexanolactam sulfuric ester.Jet mixer is similar Venturi-type throat tubular construction, and the material that contains cyclohexanone-oxime and inert solvent passes through the jet mixer axial passage at a high speed vertically with main body speed U, forms a highly disorderly field of turbulent flow.Be that the narrowest place of jet mixer axial passage circumference has the micropore that a plurality of apertures are d at trunnion, perhaps have the annular space that spacing is d, the strongly-acid material that contains sulfuric acid and sulphur trioxide radially sprays into the field of turbulent flow from micropore or annular space with relative less flow, and linear velocity is u
0
By regulating axial flow or changing jet mixer axial passage diameter, the material that can guarantee to contain cyclohexanone-oxime has enough big main body speed during by trunnion, can form negative pressure behind the fluid expansion, effectively the strongly-acid material that sprays into is entrainmented.Material constantly is dispersed into micelle and is transported to the more external region of big scale on the macroscopic view, and viscous yielding power is stretched micelle on the microcosmic, reaches mixed effect preferably.
The contriver is by discovering, in the quick enhancing mixed method of Beckmann rearrangement reaction of the present invention, axial main body speed and radial fluid linear velocity and ratio thereof are the keys that guarantees short mix and mass transfer effect.For guaranteeing that enough big speed is axially arranged, it is the axial passage of jet mixer by trunnion as external phase vertically that the contriver chooses the bigger reaction mass of flow.For the Beckmann rearrangement reaction of solvent heat-obtaining mode, contain the inertia alkane solution flow of cyclohexanone-oxime greater than the strongly-acid material that contains sulfuric acid and sulphur trioxide, therefore select for use cyclohexanone-oxime solution as external phase, the strongly-acid material is as disperse phase.However, axial main body speed still may be on the low side, can perhaps change the cyclohexanone-oxime strength of solution, to obtain higher mixing velocity by changing throat pipe diameter or shape.
In the quick enhancing mixed method of described Beckmann rearrangement reaction, the trunnion cross section is the circle that is shaped as of jet mixer axial cross section, perhaps annular.When the cross section is circle, reduces circular inner diameter and can under the situation of constant flow, improve axial main body speed U.But the reducing of internal diameter also causes reducing of trunnion circumference, may offer abundant aperture inadequately, perhaps at hole count, aperture or annular space width one regularly, and the linear velocity u of strongly-acid material radially
0Too high, axially influence mixed effect with radial velocity than imbalance.Adoptable solution is for to arrange circular plug at the jet mixer axial passage, and then corresponding trunnion cross section is annular, under the prerequisite that does not change trunnion circumference and flow, can improve axial main body speed efficiently.
In the quick enhancing mixed method of described Beckmann rearrangement reaction, by axially entering mixing tank, axially circular inner diameter is 10～200mm to cyclohexanone-oxime solution, when circular plug is set as external phase, axially the annulus external diameter is 40～200mm, and the external diameter difference is 1～10mm in the annulus.
In the quick enhancing mixed method of described Beckmann rearrangement reaction, the strongly-acid material of sulfur acid and sulphur trioxide as disperse phase by radially entering mixing tank, offer a plurality of apertures on the axial shell of jet mixer, each hole evenly distributes, the circular hole number is 2～100, the circular hole inner diameter d is 1～10mm, perhaps offers annular gap on the axial shell of jet mixer, and annular space width d is 1～10mm.
Described a plurality of circular hole or annular gap are arranged at the peripheral region of axial shell minimum diameter.
In the quick enhancing mixed method of described Beckmann rearrangement reaction, there is an OK range in the axial and radial fluid speed of jet mixer: external phase cyclohexanone-oxime solution main body speed U is 1～40m/s, and the disperse phase linear velocity uo of strongly-acid materials such as sulfur acid and sulphur trioxide is 1～40m/s.Underspeed will cause local mixing inhomogeneous, and the rearrangement reaction yield is on the low side, and final product quality descends; Speed is too high will to cause residence time deficiency, and the cyclohexanone-oxime transformation efficiency is on the low side in the mixing tank, finally also influence final product quality.External phase is 0.2: 1～5: 1 with disperse phase proper speed ratio.
In the quick enhancing mixed method of described Beckmann rearrangement reaction, axial rings hexanone oxime-inertia alkane solution refers to that it is 4～10 alkane that cyclohexanone-oxime is dissolved in carbonatoms, or naphthenic hydrocarbon, or in their mixture.The carbon chain lengths difference of alkane, corresponding normal transformation temperature difference, rearrangement reaction is carried out with regard to controlling under differing temps.
In the short mix method of described Beckmann rearrangement reaction, the cyclohexanone-oxime mass percent of axial rings hexanone oxime-inertia alkane solution is 5%～50%, specifically depends on selected solvent types.Strength of solution is too high, and there is tangible thermal insulation warming in rearrangement reaction, is difficult to control at steady state operation; Strength of solution is low excessively, will increase the energy consumption of follow-up solvent recuperation.
In the short mix method of described Beckmann rearrangement reaction, radially the strongly-acid material is the mixture that contains sulfuric acid and sulphur trioxide.The different oleum of sulfur trioxide content is the preferred feedstock that the solvent vaporization moves hot mode Beckmann rearrangement reaction.The Beckmann rearrangement reaction also can take place with cyclohexanone-oxime in the hexanolactam sulfuric ester that contains sulfuric acid and sulphur trioxide, this mode can be applicable to multistage rearrangement process back what.The nitrosifying product of hexahydrobenzoic acid in the toluene method caprolactam technology also suits as the raw material of rearrangement reaction owing to contain sulfuric acid, sulphur trioxide and hexanolactam.
In the short mix method of described Beckmann rearrangement reaction, radially the strongly-acid material comes the source category difference according to it, and the mass percent of sulphur trioxide is 3%～65%.
The present invention is based on solvent is moved the following understanding that the hot mode using cyclohexanone-oxime Beckmann is reset:
(1) Fan Ying transformation period approaches with the transformation period of mixing or is littler, and its intrinsic speed is greater than mixing rate, and namely before the even mixing that reaches molecular scale, reaction may have been finished quite most of.Therefore, improve rate of mass transfer by enhancing mixed and can effectively reduce the local non-homogeneous state of reaction mass, thereby avoid contingent side reaction.
(2) solvent moves the relative outer circulation accumulation of heat of hot mode rearrangement reaction temperature and moves hot mode to reset technology lower, therefore, need guarantee enough residence time in enhancing mixed, to guarantee high cyclohexanone-oxime transformation efficiency.
Based on above-mentioned cognition, by choosing suitable cyclohexanone-oxime-inertia alkane solution concentration value, realize the balance between Beckmann rearrangement reaction heat and the inertia alkane vaporization heat of phase transformation; By designing special mixing tank reinforcing mass transfer, realize the coupling of transmission speed and speed of response, guarantee that most cyclohexanone-oximes mix in mixing tank, react completely, constant temperature and controlled is to guarantee the rearrangement product reliable in quality.
Contrast the processing method that the existing Beckmann rearrangement of cyclohexanone oxime that relates under the oleum effect is equipped with hexanolactam, method provided by the present invention mainly embodies following difference:
(1) industrial technology of existing cyclohexanone-oxime and oleum Beckmann rearrangement all adopts big cycle volume material heat storage type to remove exothermic heat of reaction, by rearrangement product diluting reaction substrate concentration, utilizes the thermal insulation warming of the internal circulating load control reaction of material; Be that cyclohexanone-oxime-inertia alkane solution vaporization mode is removed exothermic heat of reaction and the present invention adopts, by inert solvent diluting reaction substrate concentration, utilize the thermal insulation warming of the heat of phase transformation control reaction of solvent.
(2) in the industrial technology that existing cyclohexanone-oxime and oleum Beckmann reset, cyclohexanone-oxime and rearrangement product hexanolactam sulfuric ester react in the mixing tank, and the circulation line of oleum outside mixing tank adds; And cyclohexanone-oxime among the present invention-inertia alkane solution and the strongly-acid material that contains sulfuric acid and sulphur trioxide directly living rearrangement reaction of hybrid concurrency in mixing tank.
(3) in the industrial technology that existing cyclohexanone-oxime and oleum Beckmann reset, for guaranteeing mass transfer effect, the rearrangement product hexanolactam sulfuric ester of big relatively flow is that external phase is passed through mixing tank, and the fusion cyclohexanone-oxime is that disperse phase joins in the mixing tank; And the cyclohexanone-oxime-inertia alkane solution with big relatively flow is external phase among the present invention, and the strongly-acid material that contains sulfuric acid and sulphur trioxide is disperse phase.
(4) in the industrial technology that existing cyclohexanone-oxime and oleum Beckmann reset, continuity is round trunnion by the cross section vertically, and disperse phase adopts the porous spray regime radially to add; And be assurance blend speed among the present invention, and the cross section that the axial external phase that adds is passed through is round or circular ring type, radially the disperse phase that adds adopts porous injection or annular space spray regime.
Crucial innovative point of the present invention can overcome the difficult point of Beckmann rearrangement reaction in course of industrialization that the solvent vaporization moves hot mode, realizes the engineering amplification.Simultaneously, moving hot mode rearrangement technology with respect to existing outer circulation accumulation of heat has remarkable improvement, can reduce sulfuric acid consumption, improves the quality of products, and produces good economic worth, is mainly reflected in following aspect:
(1) cyclohexanone-oxime solution feed mode can solve the problems such as viscosity rising that rearrangement reaction brings, and need not to reduce material viscosity by excess sulfuric acid, is beneficial to the minimizing sulfuric acid consumption.
(2) vaporization that directly mixes moves hot mode Beckmann rearrangement because temperature of reaction is lower, and the titration value of resetting after product descends, and the PM value of corresponding finished product rises, optical density value decline, and quality is more guaranteed.
(3) hybrid mode of particular design is in reinforcing mass transfer, guaranteed residence time of reacting required, can improve the transformation efficiency of cyclohexanone-oxime, guarantees product quality effectively.
Reaction process provided by the present invention can obtain higher yield and better products quality in following processing range:
The inert organic solvents of selecting for use is alkane or the naphthenic hydrocarbon of carbonatoms 4～10, or their mixture, preferred hexanaphthene, normal hexane or both mixtures.
The concentration of cyclohexanone-oxime-inert organic solvents is 5%～50%, preferred 10%～20%.
Selecting the strongly-acid material for use is oleum, or the hexanolactam sulfuric ester, or hexahydrobenzoic acid nitrosification product, and preferred sulphur trioxide mass fraction is 8%～20% oleum.
The solution of cyclohexanone-oxime-inert organic solvents as external phase by mixer shafts to, the strongly-acid material that contains sulfuric acid and sulphur trioxide is as disperse phase by mixing tank radially.
The mixing tank cross section that preferred external phase is passed through is circular ring type, and linear velocity is 5～20m/s.
The mixing tank cross section that preferred disperse phase passes through is a plurality of circular holes, and the aperture is 2～3mm, and linear velocity is 5～20m/s.
The present invention also provides a kind of equipment for aforesaid method, and the equipment that adopts comprises jet mixer and stirring tank, and the axial passage outlet of jet mixer is arranged at stirring tank gas-phase space outer peripheral edges; Equally distributed on the axial shell of described jet mixer have a plurality of circular holes or an annular gap, has the radial passage to be communicated with it at circular hole or annular gap place; It is minimum diameter that the axial passage of described jet mixer has a place, and the axial cross section at this place is circle or circular ring type.
What described jet mixer axial cross section was that annulus adopts is to be provided with a circular plug in the middle of the cross section present position.
Described a plurality of circular hole or annular gap are arranged at the peripheral region of the axial passage minimum diameter of jet mixer.
Described circular inner diameter is 10～200mm, and perhaps the annulus external diameter is 40～200mm, and the external diameter difference is 1～10mm in the annulus.
Description of drawings
Fig. 1 is device structure synoptic diagram of the present invention.
Fig. 2 is the vertical view of Fig. 1.
Fig. 3 is the structure iron of jet mixer of the present invention.
The axial shell 3-axial passage outlet of 1-jet mixer 2-jet mixer
4-stirring tank 5-gas-phase space 6-plug
The radial passage 9-jet mixer axial passage of 7-circular hole 8-jet mixer
The solution of A-external phase cyclohexanone-oxime-inert organic solvents;
The B-disperse phase contains the strongly-acid material of sulfuric acid and sulphur trioxide.
Embodiment
The present invention will be further described below in conjunction with embodiment, and embodiment should not be interpreted as limitation of the scope of the invention.
Rearrangement product subsequent disposal: get sample 5g to be analyzed (being accurate to 0.0001g), add the 15g mixture of ice and water and stir, make its abundant hydrolysis.Add the 20g frozen water, the NaoH that adds 4mol/L under the violent stirring is neutralized to PH=7-8, and the sample that will neutralize is afterwards put to the 100ml volumetric flask, with distilled water diluting to scale.
Adopt high-efficient liquid phase chromatogram technique analysis cyclohexanone-oxime concentration.
Adopt redox titration to measure reducing substances total amount, i.e. titration value.Get the 100ml beaker of clean dried, on electronic balance, take by weighing 1.0g (being accurate to 0.0001) neutralized rearrangement mixture sample, put into 20ml distilled water, 20ml sulfuric acid, stir at magnetic stirring apparatus, use the 0.1mol/L permanganate titration, to the red-purple of potassium permanganate keep 30 seconds colour-fast till.Titration value=A/W, wherein
The milliliter number of the potassium permanganate that A---titration consumes;
W---sample grams.
Embodiment 1:
Be acid source with the oleum, the catalysis of pimelinketone oxime rearrangement is produced hexanolactam, realizes mass transfer and reaction by the one-jet mixing tank, and the solvent vaporization moves the thermal control temperature of reaction.Cyclohexanone-oxime fully mixes with the normal hexane of 68500.6kg/h with the flow of 12087.7kg/h, obtains 15%wt cyclohexanone-oxime-hexane solution that cyclohexanone-oxime concentration is, its mass flow rate and volumetric flow rate are respectively and are 80588.3kg/h and 120.55m
3/ h.To entering, the trunnion internal diameter is 45mm to cyclohexanone-oxime solution by mixer shafts, the about 21.0m/s of trunnion speed.
The narrowest place of mixing tank trunnion circumference is a plurality of apertures of distribution evenly.Another raw material of rearrangement reaction is SO
3Content is the oleum of 20.0% (mass fraction), radially enters nozzle interior with the flow passing hole channel of 15047.6kg/h, gives birth to reaction with the axial admission hybrid concurrency, and the respective volume flow rate is 8.13m
3/ h.Hole diameter is 2mm, and hole count is 45 o'clock, the about 16.0m/s of oleum linear velocity.Jet mixer outlet is connected with static mixer, and length is 800mm, and circumference is tangent on its axial and stirred autoclave gas phase expanding reach.Product carries out gas-liquid separation at the stirred autoclave gas-phase space, stirred autoclave effective volume 1.0m
3
At above-mentioned flow with under forming, about 0.05 second of the residence time in the mixing tank, about 3min of the residence time in the stirring tank, the rearrangement reaction temperature is 68 ℃, sour oxime mol ratio is about 1.50.Cyclohexanone-oxime is less than 1 μ g/g in the high performance liquid chromatography detection rearrangement product, and resetting the drop definite value is 0.8, and after follow-up neutralization, extraction, distillation, finished product hexanolactam 290nm light absorption value is 0.05.
Embodiment 2:
Be acid source with hexahydrobenzoic acid nitrosification product, its classical group becomes: hexahydrobenzoic acid 23.1% (mass percent, down with), and sulphur trioxide 11.3%, sulfuric acid 28.2%, normal hexane 18.3%, hexanolactam 16.0%, all the other are by product.Further the catalysis of pimelinketone oxime rearrangement is produced hexanolactam, to reduce the ammonium sulfate by-product amount of unit hexanolactam.
Adopt the dual-jet mixing tank, axial admission is the cyclohexanone-oxime solution of 15%wt, and its mass flow rate is 80602kg/h, respective volume flow rate 120.6m3/h.The material viscosity of trunnion charging is 0.873mPas, and temperature is 39.3 ℃, and the trunnion internal diameter is 79mm, and the plug diameter is 70mm, the about 16m/s of trunnion speed,
The narrowest place of mixing tank trunnion circumference offers annular space, and hexahydrobenzoic acid nitrosification product is evenly distributed along circumference by trunnion annular space place and enters mixing tank, and its mass flow rate is 56746kg/h, respective volume flow rate 53.48m
3/ h.The material viscosity of ring bits charging is 3.1mPas, and temperature is 71 ℃.When the annular space width was 3mm, nitrosification product linear velocity was about 10m/s.Each mixer outlet all is connected with static mixer, and length is 1000mm, its axially and on the stirred autoclave gas phase expanding reach circumference tangent.Product carries out gas-liquid separation at the stirred autoclave gas-phase space, stirred autoclave effective volume 2.3m
3
At above-mentioned flow with under forming, about 0.1 second of the residence time in the mixing tank, about 3min of the residence time in the stirring tank, the rearrangement reaction temperature is 73 ℃, sour oxime mol ratio is about 1.35.High performance liquid chromatography detects the about 2 μ g/g of cyclohexanone-oxime in the rearrangement product, and resetting the drop definite value is 2.3, and after follow-up neutralization, extraction, distillation, finished product hexanolactam 290nm light absorption value is 0.10.
Embodiment 3:
Be acid source with hexahydrobenzoic acid nitrosification product, at first adopt the method for centrifugation to deviate from light phase normal hexane, heavy phase consists of: hexahydrobenzoic acid 28.1% (mass percent, down together), sulphur trioxide 13.0%, sulfuric acid 34.6%, hexanolactam 19.8%, all the other are by product.Further the catalysis of pimelinketone oxime rearrangement is produced hexanolactam, to reduce the ammonium sulfate by-product amount of unit hexanolactam.
Adopt the dual-jet mixing tank, the axial admission of nozzle is the cyclohexanone-oxime solution of 12%wt, and its mass flow rate is 100730kg/h, respective volume flow rate 150.68m
3/ h.The trunnion internal diameter is 51mm, and the plug diameter is 41mm, the about 29.0m/s of trunnion speed,
Axially be whole except plug, the narrowest place of trunnion radially opens 40 3 holes and evenly distributes, and hexahydrobenzoic acid nitrosification product enters nozzle interior by the trunnion duct along circumference, gives birth to reaction with the axial admission hybrid concurrency, its mass flow rate is 46375kg/h, respective volume flow rate 33.13m
3/ h, the about 16.3m/s of nitrosification product linear velocity.Each mixer outlet all is connected with static mixer, and length is 1000mm, its axially and on the stirred autoclave gas phase expanding reach circumference tangent.Product carries out gas-liquid separation at the stirred autoclave gas-phase space, stirred autoclave effective volume 2.3m
3
Claims (13)
1. one kind is mixed the method for producing the hexanolactam sulfuric ester, and the equipment that adopts comprises jet mixer and stirring tank, and the axial passage outlet of jet mixer is arranged at stirring tank gas-phase space outer peripheral edges; The solution of cyclohexanone-oxime-inert organic solvents passes through the jet mixer axial passage as external phase, contain the strongly-acid material of sulfuric acid and sulphur trioxide as disperse phase by jet mixer radially, the Beckmann rearrangement reaction takes place after external phase and the disperse phase short mix, the cross section that the external phase of described axial adding is passed through is round or circular ring type, and radially the disperse phase that adds adopts porous to spray or the annular space spray regime; Product obtains the hexanolactam sulfuric ester realize gas-liquid separation in follow-up stirring tank after; Offer a plurality of circular holes or annular gap on the axial shell of described jet mixer; Have the radial passage to be communicated with it at circular hole or annular gap place, described a plurality of circular holes or annular gap are arranged at the peripheral region of axial shell minimum diameter; The velocity ratio of external phase and disperse phase is 0.2:1～5:1.
2. method according to claim 1, described external phase main body speed is 1～40m/s, described disperse phase linear velocity is 1～40m/s.
3. method according to claim 1, the place that axially has of described jet mixer is minimum diameter, and the axial cross section at this place is circle or circular ring type.
4. method according to claim 3 is provided with a circular plug at the axial passage of jet mixer and makes that the jet mixer axial cross section is circular ring type.
5. method according to claim 3, described circular inner diameter is 10～200mm, and perhaps the annulus external diameter is 40～200mm, and the external diameter difference is 1～10mm in the annulus.
6. according to each described method of claim 3-5, external phase is that the linear velocity of circular ring type jet mixer is 5～20m/s by cross section; The linear velocity of disperse phase is 5～20m/s; The axial shell of jet mixer is a plurality of circular holes, and the aperture is 2～3mm.
7. method according to claim 1, in the solution of described external phase cyclohexanone-oxime-inert organic solvents, the mass percent of cyclohexanone-oxime is 5%～50%.
8. method according to claim 1, described inert organic solvents is alkane or the naphthenic hydrocarbon of carbonatoms 4～10, or their mixture.
9. method according to claim 1, the strongly-acid material that described disperse phase contains sulfuric acid and sulphur trioxide is oleum, or the hexanolactam sulfuric ester, or hexahydrobenzoic acid nitrosification product.
10. method according to claim 1, the mass percent of sulphur trioxide is 3%～65% in the described disperse phase.
11. an equipment that is used for each described method of claim 1-10, the equipment that adopts comprises jet mixer and stirring tank, and the axial passage outlet of jet mixer is arranged at stirring tank gas-phase space outer peripheral edges; It is minimum diameter that the axial passage of described jet mixer has a place, and the axial cross section at this place is round or circular ring type, and axially equally distributed on the shell have a plurality of circular holes or an annular gap, has the radial passage to be communicated with it at circular hole or annular gap place; It is minimum diameter that the axial passage of described jet mixer has a place, and the axial cross section at this place is circle or circular ring type; Described a plurality of circular hole or annular gap are arranged at the peripheral region of the axial passage minimum diameter of jet mixer.
What adopt is to be provided with a circular plug in the middle of the cross section present position 12. equipment according to claim 11, described jet mixer axial cross section are annulus.
13. equipment according to claim 11, described circular inner diameter are 10～200mm, perhaps the annulus external diameter is 40～200mm, and the external diameter difference is 1～10mm in the annulus.
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| CN103007869B (en) * | 2011-09-20 | 2015-02-25 | 中国石油化工股份有限公司 | Three liquid phase material feeding nozzle for caprolactam rearrangement reaction |
| CN103073497B (en) * | 2011-10-26 | 2015-04-22 | 中国石油化工股份有限公司 | Method and device for preparing caprolactam through cyclohexanone oxime rearrangement reaction |
| CN105085354B (en) * | 2014-05-07 | 2018-09-28 | 中国石油化工股份有限公司 | A kind of caprolactam preparation method |
| CN107200698A (en) * | 2016-03-16 | 2017-09-26 | 山东大明精细化工有限公司 | A kind of method for removing sulfonating reaction heat |
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