CN109481958A - A method of reducing percent hydrolysis of the cyclododecanone oxime in sulfuric acid extraction process - Google Patents
A method of reducing percent hydrolysis of the cyclododecanone oxime in sulfuric acid extraction process Download PDFInfo
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- CN109481958A CN109481958A CN201811445137.2A CN201811445137A CN109481958A CN 109481958 A CN109481958 A CN 109481958A CN 201811445137 A CN201811445137 A CN 201811445137A CN 109481958 A CN109481958 A CN 109481958A
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- B01D11/04—Solvent extraction of solutions which are liquid
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The present invention provides a kind of method of percent hydrolysis of the reduction cyclododecanone oxime in sulfuric acid extraction process, described method includes following steps: a) alkane solution of cyclododecanone oxime is added in extraction reaction kettle, control the temperature and pressure in the extraction reaction kettle, lasting stirring, and the defoaming agent of resistance to strong acid is added into extraction system, so that the water carried secretly in alkane solvent and reaction system in extraction system is evaporated；B) the pretreated concentrated sulfuric acid is added into reaction system to be extracted, the mass fraction of sulfuric acid is 99-100% in the pretreated concentrated sulfuric acid.Cyclododecanone oxime can be effectively reduced in the percent hydrolysis of extraction process in method provided by the invention.
Description
Technical field
The present invention relates to the abstraction technique field of 12 ketoximes, in particular to a kind of reduction cyclododecanone oxime is extracted in sulfuric acid
The method hydrolyzed in the process.
Background technique
Nylon 12 is used as extraordinary nylon product compared with general nylon (such as nylon 6), with water absorption rate is low, toughness is high, resistance to
The advantages that mill, swelling resistance.In the world, nylon 12 (and nylon 11) has substituted metal material, as vehicle fuel pipe,
Air brake hose etc. is indispensable and is difficult to the nonmetallic materials substituted.In addition, in submarine cable, solar energy, medical treatment, 3D printing
Equal fields, nylon 12 all embody superior performance advantage.
It is 12 prior synthesizing method of nylon that cyclododecanone, which obtains nylon 12 through oximate, extraction, rearrangement, polymerization, wherein extracting
Usually the alkane solution of cyclododecanone oxime is mixed with sulfuric acid or oleum, and cyclododecanone oxime is mutually extracted to sulphur from oil
The process of sour phase.Since cyclododecanone oxime has certain polarity, the alkane solution of cyclododecanone oxime usually contains 0.1-0.2wt%
Water, extraction process cyclododecanone oxime occur in acid condition hydrolysis generate cyclododecanone, the following institute of reaction equation
Show, the cyclododecanone for hydrolyzing generation can further be carbonized with sulfuric acid reaction, and carbide can reduce reaction kettle heat transfer coefficient, block up
Pipeline is filled in, and increases later separation difficulty, and influence product quality.
Therefore, cyclododecanone oxime, which how is effectively reduced, becomes the key of extraction reaction in the percent hydrolysis of extraction process.
Summary of the invention
In view of this, the present invention provides a kind of method of cyclododecanone oxime is effectively reduced percent hydrolysis in extraction process.
The present invention be reach its purpose, the technical solution adopted is as follows:
A method of percent hydrolysis of the cyclododecanone oxime in sulfuric acid extraction process being reduced, the method includes walking as follows
It is rapid:
A) alkane solution of cyclododecanone oxime is added in extraction reaction kettle, controls temperature and pressure in the extraction reaction kettle
Power in smooth evaporation system alkane solvent and reaction system in the water carried secretly, carry out continuing stirring, whipping process exists
It is persistently carried out in entire extraction process；The defoaming agent of resistance to strong acid is added into extraction system, to prevent a large amount of gas in evaporation process
The generation of bubble；
B) the pretreated concentrated sulfuric acid is added into extraction system to be extracted, sulfuric acid in the pretreated concentrated sulfuric acid
Mass fraction be 99-100%.
Method provided by the invention evaporates solvent by controlling the temperature and pressure in the extraction reaction kettle, by
The water carried secretly in reaction system since cyclododecanone oxime has certain polarity (for example, make the alkane of cyclododecanone oxime molten
A certain amount of water would generally be contained in liquid) so that water content is also minimized in system, and body can be improved with solvent azeotropic
It is cooling ability；The defoaming agent of resistance to strong acid is added simultaneously, avoids the reduction body having in solvent evaporation process due to cyclododecanone oxime
It is the generation of a large amount of bubbles caused by surface tension performance, to improve the evaporative removal effect and cooling effect of water.Extracting
During taking, while also by the sulfuric acid concentration control of the concentrated sulfuric acid in 99-100%, removal part water can be absorbed, reduce ring 12
The percent hydrolysis of ketoxime, if present inventor has found that sulfuric acid concentration is excessively high, more than 100%, cyclododecanone oxime is oxidized easily, meeting
Reduce the yield of final products lauric lactam；The present invention controls the sulfuric acid concentration for extracting the concentrated sulfuric acid used in 99-100%,
The percent hydrolysis of cyclododecanone oxime is reduced while guaranteeing lauric lactam yield.
In some preferred embodiments, in step b), the pretreated concentrated sulfuric acid is that hair is added into the concentrated sulfuric acid
Cigarette sulfuric acid, and sulfuric acid mass fraction is made to reach 99-100%, the pending pretreated concentrated sulfuric acid used is preferably 98wt% sulphur
Acid；Preferably, the oleum be selected from 20%-65% oleum, such as 20% oleum, 50% oleum and
(20%-65% herein refers to SO 65% oleum3The oleum mass concentration of calculating) one or both of with
On combination, more preferable 20% oleum.When the concentrated sulfuric acid extracts cyclododecanone oxime, the amount ratio of the two is using commonly used in the art
Proportion, such as the mass ratio of the concentrated sulfuric acid and cyclododecanone oxime is 1:1-2.5, preferably 1:2-2.5.
In some preferred embodiments, in step a), the temperature in control extraction reaction kettle is 60-90 DEG C, and pressure is
5-30KPa (A), to reach preferable water evaporation removal effect；And cyclododecanone oxime is precipitated in a solvent in order to prevent, drops simultaneously
Cyclododecanone oxime rearrangement conversion ratio during low-sulfur acid extraction, preferable temperature control are 75-85 DEG C, and pressure control is 10-30KPa
(A).In some embodiments, in the kettle top setting condenser and steam trap of extraction reaction kettle, cooling medium is circulation
Water or chilled water, using the azeotropic nature of water and alkane, water is steamed out of system under above-mentioned temperature and pressure, in extraction process
Drain periodically is carried out to dispenser.
Method of the invention, is evaporated by solvent, can not only reduce system water content, weakens the hydrolysis speed of cyclododecanone oxime
Outside rate, while reaction kettle can be improved and move thermal energy power；Since the sulfuric acid extraction heat of cyclododecanone oxime is larger, 80kJ/mol can reach
(cyclododecanone oxime)；In addition, the rearrangement reaction of cyclododecanone oxime occurs while extraction, the shifting heat for further increasing extraction reaction is difficult
Degree, therefore, how effective cooling becomes the bottleneck that extraction industrialization is amplified.The present invention can effectively improve reaction by evaporating cooling
Kettle cooling ability, guarantee system temperature it is constant, this be also beneficial to reduce cyclododecanone oxime percent hydrolysis, weaken reaction carbonization.
In some preferred embodiments, the pretreated concentrated sulfuric acid be it is described extraction reaction kettle in temperature and
It is just added in the reaction system after pressure is constant.In step b), the feeding temperature of the pretreated concentrated sulfuric acid can be room temperature,
Feed time can be 5-10min.
In order to improve evaporation water removal effect, in step a), by the way that radial paddle and Axial-flow stirrer are arranged in extraction reaction kettle
Dual impellers carry out the stirring；Preferably, the arrangement of the radial direction paddle and Axial-flow stirrer in extraction reaction kettle is the diameter
It is located at upper layer to paddle, the Axial-flow stirrer is located at lower layer.Present inventor's discovery, is stirred using this dual impellers, can
Make in extraction system density contrast greatly oily phase (alkane, density 0.7-0.8g/cm3) and sulfuric acid phase (sulfuric acid and cyclododecanone oxime
Mixture, density 1.3-1.4g/cm3) two-phase system is sufficiently mixed, it can guarantee preferable mass transfer, heat-transfer effect.The radial direction
Paddle preferably≤1.5m at a distance from liquid level, spacing positioned at the radial paddle on upper layer and between the Axial-flow stirrer of lower layer preferably >=
1.2 times of radial paddle diameters, the more preferable spacing are 1.2-3 times of radial paddle diameter；Preferably, controlling speed of agitator in 800rpm
More than, such as 800rpm, 1000rpm, 1100rpm, 120rpm, 1500rpm etc..
There is no particular restriction for the specific type of the radial paddle and Axial-flow stirrer used, can use phase commonly used in the art
Answer radial paddle and Axial-flow stirrer；The radial direction paddle for example can be selected from gear-shaped disk turbo-typed agitating paddle, bouruma gold type agitating paddle, three
Straight leaf cone bottom formula agitating paddle, curved leaf open turbine type agitating paddle, six straight leaves open turbine impeller, the stirring of three leaf swept-backs
The combination of one or more of paddle, arrow leaf formula disc turbine agitating paddle, arc leaf disc turbine impeller and self-priming paddle, it is excellent
Turbine impellers are opened selected from suction paddle and/or six straight leaves.For example optional self-propelled agitating paddle of Axial-flow stirrer, preferably three leaves turn over
Formula promotes paddle, three leaf press-down types to promote paddle, four leaf upper-turn-types that paddle, four leaf press-down types is promoted to promote one or more of paddle
Combination, more preferable four leaves upper-turn-type promotes paddle.
The defoaming agent of resistance to strong acid used in the present invention is preferably modified organic silicon class defoaming agent, the use of the defoaming agent of resistance to strong acid
Amount is preferably the 0.2-0.3wt% (such as 0.2,0.25,0.3wt%) of the alkane solution quality of the cyclododecanone oxime, to reach
To better defoaming effect, conducive to the evaporation and cooling of water.In more preferably some embodiments, the defoaming agent of resistance to strong acid is
The composition of sulfur-bearing carboxyl fluorine containing silicone oil, white carbon black and emulsifier, this defoaming agent are not only resistant to strong acid, and in cyclododecanone oxime
Concentrated sulfuric acid extraction system in have good defoaming effect.It is each based on the defoaming agent of resistance to strong acid in the defoaming agent of resistance to strong acid
The gross mass of component, the mass fraction of the emulsifier are preferably the more preferable 3-5wt% of 1-10wt%, the quality of the white carbon black
Score is preferably 5-10wt%, the defoaming agent formed using optimum ratio, and defoaming effect is more preferable；Preferably, the resistance to strong acid disappears
Infusion by by the sulfur-bearing carboxyl fluorine containing silicone oil, white carbon black and emulsifier at 130-180 DEG C (such as 130,150,180 DEG C etc.)
Lower stirring 2-3h is obtained.
In preferable some embodiments, the sulfur-bearing carboxyl fluorine containing silicone oil used in the defoaming agent of resistance to strong acid is used
The method preparation included the following steps:
1) the fluorine-containing methyl-silicone oil of formula (I) and the tetramethyl-ring tetrasiloxane of formula (II) are reacted, obtains containing for formula (III)
Fluorine containing hydrogen silicone oil；The reaction temperature of the reaction is preferably 60-80 DEG C, reaction pressure normal pressure, and the reaction time can be 4-8h
(such as 4,5,6,8h).
2) the sulfur-bearing carboxyl that the fluorine-containing containing hydrogen silicone oil of formula (III) reacts to obtain formula (V) with the alkenyl thionothiolic acid of formula (IV) contains
Fluorosilicon oil；The reaction of step 2) preferably carries out in acid condition, such as the concentrated sulfuric acid, salt are added in the reaction system of the step
The inorganic acids such as acid, nitric acid, phosphoric acid are, it is preferable to use the concentrated sulfuric acid, such as the 98wt% concentrated sulfuric acid；In some embodiments, should
The amount that inorganic acid (such as 98wt% concentrated sulfuric acid) is added into reaction system for step reaction is the 0.01- of reaction solution gross mass
0.02wt%；It is preferred that the reaction temperature of step reaction is 90-100 DEG C, and reaction pressure normal pressure, reaction time 2.5-4h；Reaction knot
Shu Hou, reaction solution directly can be mixed with the defoaming agent of resistance to strong acid with white carbon black and emulsifier, using this without the post-processing such as degassing
Sulfur-bearing carboxyl fluorine containing silicone oil made from method combines the defoaming agent constituted with white carbon black and emulsifier and is highly suitable for concentrated sulfuric acid extraction
Take the defoaming in cyclododecanone oxime system, not only resistance to strong acid, and defoaming effect is very good, it is ensured that evaporation cooling be able to smoothly into
The percent hydrolysis of extraction reaction kettle gas holdup and cyclododecanone oxime during evaporation cooling is greatly reduced in row；And it is subsequent can be with
It is reused in such a way that rectifying is recycled.
In above each structural formula, x=1-30, y=1-40, z=4-20, n=2-8.In above-mentioned reaction process, contain methyl fluoride
The feeding quantity of silicone oil, tetramethyl-ring tetrasiloxane and alkenyl thionothiolic acid is subject to the molecular formula requirement for being able to satisfy final products.
In the defoaming agent of resistance to strong acid, the emulsifier used is preferably selected from organic carboxyl acid, organic sulfonic acid, organic sub- sulphur
The combination of one or more of sour, organic thionothiolic acid, preferably adipic acid, decanedioic acid, p-methyl benzenesulfonic acid, dodecyl carboxylic
One of acid, dodecyl thionothiolic acid, dodecyl sodium sulfonate, octadecyl carboxylic acid, octadecyl sulfonic acid, dodecanedioic acid or
Two or more combinations, more preferable dodecanedioic acid, dodecyl carboxylic acid, dodecyl thionothiolic acid and dodecyl sodium sulfonate one
Kind or two or more combinations.Mass ratio of the emulsifier in the emulsifier of resistance to strong acid is 1-10wt%, in order to guarantee more preferably
Emulsification and defoaming effect, preferably 3-5wt%.
The precipitation of cyclododecanone oxime in order to prevent, while the production capacity of extraction reaction unit is improved, solvent separating energy consumption is reduced,
In the alkane solution of the cyclododecanone oxime, the concentration of cyclododecanone oxime is 10-30wt%, preferably 15-20wt%；The ring ten
In the alkane solution of two ketoximes, there is no particular restriction for solvent for use alkane, and the applicable coordinative solvent alkane in this field is applicable,
In some embodiments, the solvent alkane in the alkane solution can be but be not limited to ethyl cyclohexane and/or different
Propyl cyclohexane.
Technical solution provided by the invention has the following beneficial effects:
It using method of the invention, is kept stirring in extraction process, and evaporates the water carried secretly in extraction system constantly,
The defoaming agent of resistance to strong acid is added in system and the mass fraction for controlling the sulfuric acid of the extraction concentrated sulfuric acid used is 99-100%, it can be effective
Slave cyclododecanone oxime sulfuric acid extraction process in evaporate cooling, reduce evaporation cooling process extraction kettle gas holdup, and reduce
Percent hydrolysis of the cyclododecanone oxime in sulfuric acid extraction process, in some preferred embodiments, percent hydrolysis can be reduced to 0.1% with
Under.
In a preferred approach, by using preferred method synthesis as formula (V) sulfur-bearing carboxyl fluorine containing silicone oil, and with emulsification
Agent and white carbon black combination are used as acid and alkali-resistance defoaming agent, and evaporation cooling process extraction kettle gas holdup can be greatly reduced, can be by 50-70%
It is reduced to 10-20%, evaporation cooling scheme is smoothly realized, guarantees cyclododecanone oxime lower water in sulfuric acid extraction process
Solution rate.
Detailed description of the invention
Fig. 1-3 respectively be formula involved in embodiment one to three (I), (III), (V) compound H-1NMR map.
Specific embodiment
For a better understanding of the technical solution of the present invention, below with reference to the embodiment content that the present invention is further explained,
But the contents of the present invention are not limited only to following embodiment.
Used detection method in embodiment:
One, gas-chromatography (GC)
Gas chromatograph (is equipped with split sampling mouth, temperature programming column oven, flame ionization ditector), capillary color
Spectrum column is DB-5 (30m × 0.25mm × 0.25um).
Chromatographiccondition:
Instrument model: Shimadzu GC2010；
Chromatographic column: DB-5 (30 × 0.32 × 0.25)；
Column temperature: temperature programming (then 50 DEG C of holding 3min rise to 100 DEG C with the heating rate of 5 DEG C/min, then with 15 DEG C/
The heating rate of min rises to 300 DEG C, and keeps 5min)；
Injector temperature: 250 DEG C；
FID temperature: 300 DEG C；
N2Flow: 1mL/min；
H2Flow: 40mL/min；
Dottle pin purges (N2) flow velocity: 3mL/min；
Carrier gas (N2) flow velocity: 1mL/min；
Split sampling, split ratio: 50；
Sample volume: 0.2 μ L.
Two, determination of moisture
Ti-Touch 915-KF is led in moisture teller model Switzerland ten thousand, using the karl Fischer reagent that can survey aldehyde ketone, takes off
Water reagent (molecular sieve are as follows: MOLECULAR SIEVE 250GR molecular sieve, silica gel are as follows: the discoloration silica gel of traditional Chinese medicines 10018360.)
Three, H-1NMR map detects
Nuclear-magnetism instrument model: Bruker 400M, instrument frequency 400MHz, sampling number 16 times, sample uses deuterated chloroform
Dissolution.
Raw material sources:
Ethyl cyclohexane, isopropyl cyclohexane, South Korea SK；
Sulfuric acid, oleum, Zibo Jianlong Chemical Co., Ltd.；
Dodecanedioic acid, Shandong Caesar biology；
White carbon black, Shandong Li Hua new material Co., Ltd；
Fluorine-containing methyl-silicone oil, Dow corning；
Hexenyl thionothiolic acid, laurylene base thionothiolic acid, Jiangsu Xin Nuoke Co., Ltd；
Cyclododecanone oxime, Germany win wound；It can also make by oneself to obtain, such as: use the ethyl cyclohexane of cyclododecanone or different
Propyl cyclohexane solution and hydroxyl sulfate (Jiangsu Ai Kewei Science and Technology Ltd.) reactant aqueous solution, 90-95 DEG C of reaction temperature, instead
Pressure 0.1MPa, reaction time 4-10h such as 6h are answered, cyclododecanone oxime solid is obtained by filtration in reaction solution decrease temperature crystalline after reaction.
Embodiment one:
The preparation of modified organic silicon defoaming agent (that is, sulfur-bearing carboxyl fluorine containing silicone oil of formula (V)):
60 DEG C, under normal pressure, by the fluorine-containing methyl-silicone oil of 39.2g (x=1, y=1, formula (I) compound) and 24g tetramethyl cyclotetrasiloxane
Siloxanes (formula (II) compound) is stirred reaction 4h, obtains fluorine-containing containing hydrogen silicone oil (formula (III) compound)；
52g hexenyl thionothiolic acid (formula (IV) compound, n=2) and 98% concentrated sulfuric acid of 0.0115g are added into reaction solution
(0.01wt%), the reaction was continued that 2.5h obtains modified organic silicon defoaming agent (x=1, y=1, z after reaction in 90 DEG C
=4, n=2, formula (V) compound)；
5.76g white carbon black and 3.63g dodecanedioic acid is added to reaction solution, can be obtained in 130 DEG C of stirring 2h can be used for
The defoaming agent of resistance to strong acid of concentrated sulfuric acid system, wherein white carbon black mass percent used is 5wt%, dodecanedioic acid mass percent
For 3wt%.
Fluorine-containing methyl-silicone oil, fluorine-containing containing hydrogen silicone oil and the obtained organic silicon defoaming agent being related to the embodiment carry out core
Magnetic characterization, H-1NMR map is referring to Fig. 1, it is seen that compared with compound (I), compound (III) is in the position that chemical shift is 0.19
There is the peak Si-H, illustrates that fluorine-containing methyl-silicone oil reacts with tetramethyl-ring tetrasiloxane, synthesized fluorine-containing containing hydrogen silicone oil；With change
It closes object (III) to compare, compound (V) disappears at the peak Si-H that chemical shift is 0.19 position, illustrates hydrogen atom by hexenyl sulphur carboxylic
Acid replaces, while generating the peak C-H that chemical shift is 1.29,1.3,1.58,2.4 to get fluorine-containing organic of sulfur-bearing carboxyl has been arrived
Silicon class defoaming agent.
Extraction process:
The ethyl cyclohexane solution for the cyclododecanone oxime that 1000g mass concentration is 15wt% is added in 2L reaction kettle,
Cyclododecanone oxime mass fraction determines that the water content of the ethyl cyclohexane solution of cyclododecanone oxime is through dividing by gas chromatographic analysis
Analysis is measured as 0.2%.Reaction kettle uses oil bath heating, controls 80 DEG C of oil bath temperature, opens stirring, and stirring pattern is upper layer self-priming
Paddle and four leaf upper-turn-type of lower layer promote the combination of paddle, and it is 65mm, paddle spacing that self-priming paddle and four leaf upper-turn-types, which promote the diameter of paddle,
For 78mm, upper-layer paddle is away from liquid level 70mm, speed of agitator 800rpm.
The above-mentioned defoaming agent of resistance to strong acid 2g (0.2wt%) is added to reaction system, vacuum pump pressure 20KPa is set, to reaction
System takes out negative pressure, and kettle top condenser cooling medium is recirculated water, and measuring extraction kettle gas holdup by volume expansion method is 13%.
After stable system, the pretreated concentrated sulfuric acid is added dropwise to reaction kettle, the pretreated concentrated sulfuric acid is through 20% hair
The 98wt% sulfuric acid of cigarette sulfur acid pretreatment, sulfuric acid concentration 99wt%, sulphuric acid 74.6g, feed time 5min, into
Pass through the percent hydrolysis of gas Chromatographic Determination cyclododecanone oxime after material, the percent hydrolysis of cyclododecanone oxime is 0.08%.
Embodiment two:
The preparation of modified organic silicon defoaming agent (that is, sulfur-bearing carboxyl fluorine containing silicone oil of formula (V)):
80 DEG C, under normal pressure, by the fluorine-containing methyl-silicone oil of 78.02g (x=30, y=40, formula (I) compound) and 12g tetramethyl
Cyclotetrasiloxane (formula (II) compound) is stirred reaction 5h, obtains fluorine-containing containing hydrogen silicone oil (formula (III) compound)；
42.8g laurylene base thionothiolic acid (formula (IV) compound, n=8) is added into reaction solution and 0.0266g 98% is dense
Sulfuric acid (0.02wt%), the reaction was continued that 3h obtains modified organic silicon defoaming agent (x=30, y after reaction in 100 DEG C
=40, z=20, n=8, formula (V) compound)；
13.28g white carbon black and 7.31g dodecyl carboxylic acid is added to reaction solution, can be obtained in 180 DEG C of stirring 3h available
In the defoaming agent of resistance to strong acid of the modification of concentrated sulfuric acid system, wherein the mass percent of white carbon black used is 10wt%, 12 carbon two
The mass percent of acid is 5wt%.
Fluorine-containing methyl-silicone oil, fluorine-containing containing hydrogen silicone oil and the obtained organic silicon defoaming agent being related to the embodiment carry out core
Magnetic characterization, referring to fig. 2 from H-1NMR map, it is seen then that compared with compound (I), compound (III) is 0.19 in chemical shift
There is the peak Si-H in position, illustrates that fluorine-containing methyl-silicone oil reacts with tetramethyl-ring tetrasiloxane, has synthesized fluorine-containing containing hydrogen silicone oil；
Compared with compound (III), compound (V) disappears at the peak Si-H that chemical shift is 0.19 position, illustrates hydrogen atom by laurylene
Base thionothiolic acid replaces, while generating chemical shift is that 1.3 neighbouring, 1.58,2.4 the peaks C-H are fluorine-containing to get sulfur-bearing carboxyl has been arrived
Organic silicon defoaming agent.
Extraction process:
The ethyl cyclohexane solution of 1000g 20wt% cyclododecanone oxime is added in 2L reaction kettle, cyclododecanone oxime matter
It measures score to determine by gas chromatographic analysis, the water content of the ethyl cyclohexane solution of cyclododecanone oxime is measured as through analysis
0.3%.Reaction kettle uses oil bath heating, controls 80 DEG C of oil bath temperature, opens stirring, and stirring pattern is the unlatching of the straight leaf in upper layer six
Turbine impeller and four leaf upper-turn-type of lower layer promote the combination of paddle, and six straight leaves open turbine impeller and four leaf upper-turn-types promote
The diameter of paddle is 65mm, and paddle spacing is 80mm, and upper-layer paddle is away from liquid level 68mm, speed of agitator 1000rpm.
The above-mentioned defoaming agent of resistance to strong acid 2g (0.2wt%) is added to reaction system, vacuum pump pressure 20KPa is set, to reaction
System takes out negative pressure, and kettle top condenser cooling medium is chilled water, and measuring extraction kettle gas holdup by volume expansion method is 17%.
After stable system, the pretreated concentrated sulfuric acid is added dropwise to reaction kettle, the pretreated concentrated sulfuric acid is through 20% hair
The 98wt% sulfuric acid of cigarette sulfur acid pretreatment, sulfuric acid concentration 100wt%, sulphuric acid 99.5g, feed time 10min,
Pass through the percent hydrolysis of gas Chromatographic Determination cyclododecanone oxime after charging, the percent hydrolysis of cyclododecanone oxime is 0.06%.
Embodiment three:
The preparation of modified organic silicon defoaming agent (that is, sulfur-bearing carboxyl fluorine containing silicone oil of formula (V)):
70 DEG C, under normal pressure, by the fluorine-containing methyl-silicone oil of 24.62g (x=10, y=10, formula (I) compound) and 7.2g tetramethyl
Cyclotetrasiloxane (formula (II) compound) is stirred reaction 8h, obtains fluorine-containing containing hydrogen silicone oil (formula (III) compound)；
15.6g hexenyl thionothiolic acid (formula (IV) compound, n=2) and the dense sulphur of 0.0071g 98% are added into reaction solution
Sour (0.015wt%), the reaction was continued that 4h obtains modified organic silicon defoaming agent (x=10, y=after reaction in 95 DEG C
10, z=12, n=2, formula (V) compound)；
3.79g white carbon black and 1.9g dodecanedioic acid is added to reaction solution, can be obtained in 150 DEG C of stirring 2.5h can be used for
The defoaming agent of resistance to strong acid of concentrated sulfuric acid system, wherein the mass percent of white carbon black used is 8wt%, the quality hundred of dodecanedioic acid
Divide than being 4wt%.
Fluorine-containing methyl-silicone oil, fluorine-containing containing hydrogen silicone oil and the obtained organic silicon defoaming agent being related to the embodiment carry out core
Magnetic characterization, from H-1NMR map referring to Fig. 3, it is seen then that compared with compound (I), compound (III) is 0.19 in chemical shift
There is the peak Si-H in position, illustrates that fluorine-containing methyl-silicone oil reacts with tetramethyl-ring tetrasiloxane, has synthesized fluorine-containing containing hydrogen silicone oil；
Compared with compound (III), compound (V) disappears at the peak Si-H that chemical shift is 0.19 position, illustrates hydrogen atom by hexenyl
Thionothiolic acid replaces, at the same generate chemical shift be 1.3 nearby, sulfur-bearing carboxyl is fluorine-containing to be had to get having arrived for 1.58,2.4 peak C-H
Machine silicon class defoaming agent.
Extraction process:
The ethyl cyclohexane solution of 1000g 17wt% cyclododecanone oxime is added in 2L reaction kettle, cyclododecanone oxime matter
It measures score to determine by gas chromatographic analysis, the water content of the ethyl cyclohexane solution of cyclododecanone oxime is measured as through analysis
0.25%.Reaction kettle controls 80 DEG C of oil bath temperature using oil bath heating, opens stirring, and stirring pattern is upper layer self-priming paddle under
Four leaf upper-turn-type of layer promote the combination of paddle, and it is 65mm that self-priming paddle and four leaf upper-turn-types, which promote the diameter of paddle, and paddle spacing is 79mm,
Upper-layer paddle is away from liquid level 72mm, speed of agitator 900rpm.
The above-mentioned defoaming agent of resistance to strong acid 3g (0.3wt%) is added to reaction system, vacuum pump pressure 20KPa is set, to reaction
System takes out negative pressure, and kettle top condenser cooling medium is recirculated water, and measuring extraction kettle gas holdup by volume expansion method is 15%.
After stable system, the pretreated concentrated sulfuric acid is added dropwise to reaction kettle, the pretreated concentrated sulfuric acid is through 20% hair
The 98wt% sulfuric acid of cigarette sulfur acid pretreatment, sulfuric acid concentration 99.3wt%, sulphuric acid 86g, feed time 5min, into
Pass through the percent hydrolysis of gas Chromatographic Determination cyclododecanone oxime after material, the percent hydrolysis of cyclododecanone oxime is 0.05%.
Comparative example one: (not plus defoaming agent)
The ethyl cyclohexane solution of 1000g 15wt% cyclododecanone oxime is added in 2L reaction kettle, cyclododecanone oxime matter
It measures score to determine by gas chromatographic analysis, the water content of the ethyl cyclohexane solution of cyclododecanone oxime is measured as through analysis
0.2%.Reaction kettle uses oil bath heating, controls 80 DEG C of oil bath temperature, opens stirring, and stirring pattern is upper layer self-priming paddle and lower layer
Four leaf upper-turn-types promote the combination of paddle, and it is 65mm that self-priming paddle and four leaf upper-turn-types, which promote the diameter of paddle, and paddle spacing is 78mm, on
Layer pitch liquid level 70mm, speed of agitator 800rpm.Defoaming agent is not added, vacuum pump pressure 20KPa is set, reaction system is taken out negative
Pressure, kettle top condenser cooling medium are recirculated water, and measuring extraction kettle gas holdup by volume expansion method is 65%.
Comparative example two: (not plus defoaming agent, do not evaporate cooling)
The ethyl cyclohexane solution of 1000g 20wt% cyclododecanone oxime is added in 2L reaction kettle, cyclododecanone oxime matter
It measures score to determine by gas chromatographic analysis, the water content of the ethyl cyclohexane solution of cyclododecanone oxime is measured as through analysis
0.3%.Reaction kettle uses oil bath heating, controls 80 DEG C of oil bath temperature, opens stirring, and stirring pattern is the unlatching of the straight leaf in upper layer six
Turbine impeller and four leaf upper-turn-type of lower layer promote the combination of paddle, and six straight leaves open turbine impeller and four leaf upper-turn-types promote
The diameter of paddle is 65mm, and paddle spacing is 80mm, and upper-layer paddle is away from liquid level 68mm, speed of agitator 1000rpm.Sulphur is added dropwise to reaction kettle
Acid, sulfuric acid are through the pretreated 98wt% sulfuric acid of 20% oleum, sulfuric acid concentration 100wt%, and sulphuric acid is
99.5g, feed time 10min pass through the percent hydrolysis of gas Chromatographic Determination cyclododecanone oxime, cyclododecanone oxime after charging
Percent hydrolysis be 0.8%.
Comparative example three: (not plus defoaming agent, do not pre-process the concentrated sulfuric acid)
The ethyl cyclohexane solution of 1000g 20wt% cyclododecanone oxime is added in 2L reaction kettle, cyclododecanone oxime matter
It measures score to determine by gas chromatographic analysis, the water content of the ethyl cyclohexane solution of cyclododecanone oxime is measured as through analysis
0.3%.Reaction kettle uses oil bath heating, controls 80 DEG C of oil bath temperature, opens stirring, and stirring pattern is the unlatching of the straight leaf in upper layer six
Turbine impeller and four leaf upper-turn-type of lower layer promote the combination of paddle, and six straight leaves open turbine impeller and four leaf upper-turn-types promote
The diameter of paddle is 65mm, and paddle spacing is 80mm, and upper-layer paddle is away from liquid level 68mm, speed of agitator 1000rpm.It is added dropwise to reaction kettle
98wt% sulfuric acid, feed time 10min pass through the percent hydrolysis of gas Chromatographic Determination cyclododecanone oxime, ring ten after charging
The percent hydrolysis of two ketoximes is 1.2%.
Example IV: (bilayer paddle is not used)
The ethyl cyclohexane solution of 1000g 15wt% cyclododecanone oxime is added in 2L reaction kettle, cyclododecanone oxime matter
It measures score to determine by gas chromatographic analysis, the water content of the ethyl cyclohexane solution of cyclododecanone oxime is measured as through analysis
0.21%.Reaction kettle uses oil bath heating, controls 80 DEG C of oil bath temperature, opens stirring, and stirring pattern is the propulsion of four leaf upper-turn-types
Paddle single-blade, speed of agitator 800rpm.
The defoaming agent of resistance to strong acid 2g (0.2wt%) in embodiment 1 is added to reaction system, vacuum pump pressure 20KPa is set, it is right
Reaction system takes out negative pressure, and kettle top condenser cooling medium is recirculated water, measures extraction kettle gas holdup by volume expansion method and is
13%.
After stable system, the pretreated concentrated sulfuric acid is added dropwise to reaction kettle, the pretreated concentrated sulfuric acid is through 20% hair
The 98wt% sulfuric acid of cigarette sulfur acid pretreatment, sulfuric acid concentration 99wt%, sulphuric acid 74.6g, feed time 5min, into
Pass through the percent hydrolysis of gas Chromatographic Determination cyclododecanone oxime after material, the percent hydrolysis of cyclododecanone oxime is 0.53%.
Embodiment five: (changing defoaming agent dosage)
The ethyl cyclohexane solution of 1000g 20wt% cyclododecanone oxime is added in 2L reaction kettle, cyclododecanone oxime matter
It measures score to determine by gas chromatographic analysis, the water content of the ethyl cyclohexane solution of cyclododecanone oxime is measured as through analysis
0.28%.Reaction kettle uses oil bath heating, controls 80 DEG C of oil bath temperature, opens stirring, and stirring pattern is that the straight leaf in upper layer six is opened
It opens turbine impeller and four leaf upper-turn-type of lower layer promotes the combination of paddle, six straight leaves open turbine impeller and four leaf upper-turn-types push away
Diameter into paddle is 65mm, and paddle spacing is 80mm, and upper-layer paddle is away from liquid level 68mm, speed of agitator 1000rpm.
The defoaming agent of resistance to strong acid 1g (0.1wt%) in embodiment 2 is added to reaction system, vacuum pump pressure 20KPa is set, it is right
Reaction system takes out negative pressure, and kettle top condenser cooling medium is chilled water, measures extraction kettle gas holdup by volume expansion method and is
65%.
After stable system, the pretreated concentrated sulfuric acid is added dropwise to reaction kettle, the pretreated concentrated sulfuric acid is through 20% hair
The 98wt% sulfuric acid of cigarette sulfur acid pretreatment, sulfuric acid concentration 100wt%, sulphuric acid 99.5g, feed time 10min,
Pass through the percent hydrolysis of gas Chromatographic Determination cyclododecanone oxime after charging, the percent hydrolysis of cyclododecanone oxime is 0.12%.
Embodiment six: (changing extraction temperature and pressure)
The ethyl cyclohexane solution of 1000g 17wt% cyclododecanone oxime is added in 2L reaction kettle, cyclododecanone oxime matter
It measures score to determine by gas chromatographic analysis, the water content of the ethyl cyclohexane solution of cyclododecanone oxime is measured as through analysis
0.24%.Reaction kettle controls 90 DEG C of oil bath temperature using oil bath heating, opens stirring, and stirring pattern is upper layer self-priming paddle under
Four leaf upper-turn-type of layer promote the combination of paddle, and it is 65mm that self-priming paddle and four leaf upper-turn-types, which promote the diameter of paddle, and paddle spacing is 79mm,
Upper-layer paddle is away from liquid level 72mm, speed of agitator 900rpm.
The defoaming agent of resistance to strong acid 3g (0.3wt%) in embodiment 3 is added to reaction system, vacuum pump pressure 28.8KPa is set,
Negative pressure is taken out to reaction system, kettle top condenser cooling medium is recirculated water, measures extraction kettle gas holdup by volume expansion method and is
16%.
After stable system, the pretreated concentrated sulfuric acid is added dropwise to reaction kettle, the pretreated concentrated sulfuric acid is through 20% hair
The 98wt% sulfuric acid of cigarette sulfur acid pretreatment, sulfuric acid concentration 99.4wt%, sulphuric acid 86g, feed time 5min, into
Pass through the percent hydrolysis of gas Chromatographic Determination cyclododecanone oxime after material, the percent hydrolysis of cyclododecanone oxime is 0.26%.
Embodiment seven: (changing type of anti-foam agent)
The ethyl cyclohexane solution of 1000g 15wt% cyclododecanone oxime is added in 2L reaction kettle, cyclododecanone oxime matter
It measures score to determine by gas chromatographic analysis, the water content of the ethyl cyclohexane solution of cyclododecanone oxime is measured as through analysis
0.23%.Reaction kettle controls 80 DEG C of oil bath temperature using oil bath heating, opens stirring, and stirring pattern is upper layer self-priming paddle under
Four leaf upper-turn-type of layer promote the combination of paddle, and it is 65mm that self-priming paddle and four leaf upper-turn-types, which promote the diameter of paddle, and paddle spacing is 78mm,
Upper-layer paddle is away from liquid level 70mm, speed of agitator 800rpm.
Dimethicone 2g (0.2wt%) is added to reaction system, vacuum pump pressure 20KPa is set, reaction system is taken out
Negative pressure, kettle top condenser cooling medium are recirculated water, and measuring extraction kettle gas holdup by volume expansion method is 59%.
After stable system, the pretreated concentrated sulfuric acid is added dropwise to reaction kettle, the pretreated concentrated sulfuric acid is through 20% hair
The 98wt% sulfuric acid of cigarette sulfur acid pretreatment, sulfuric acid concentration 99.4wt%, sulphuric acid 74.6g, feed time 5min,
Pass through the percent hydrolysis of gas Chromatographic Determination cyclododecanone oxime after charging, the percent hydrolysis of cyclododecanone oxime is 0.46%.
From the above experimental result as it can be seen that making solvent and water evaporation in extraction system by control temperature and pressure, add simultaneously
Enter the defoaming agent of resistance to strong acid, and using pretreatment concentration reaches the concentrated sulfuric acid of 99-100% to carry out the extraction of cyclododecanone oxime, it can
With timely cooling, and cyclododecanone oxime percent hydrolysis significantly reduces.And Axial-flow stirrer and radial paddle combination stirring are used, using preferred
Acid and alkali-resistance defoaming agent can further significantly reduce percent hydrolysis.
It will be understood by those skilled in the art that under the introduction of this specification, the present invention can be made some modifications or
Adjustment.These modifications or adjustment should also be as within the scope of the claims in the present invention.
Claims (10)
1. a kind of method of percent hydrolysis of reduction cyclododecanone oxime in sulfuric acid extraction process, which is characterized in that the method packet
Include following steps:
A) alkane solution of cyclododecanone oxime is added in extraction reaction kettle, controls the temperature and pressure in the extraction reaction kettle,
Lasting stirring, and the defoaming agent of resistance to strong acid is added into extraction system, make to press from both sides in alkane solvent and reaction system in extraction system
The water of band is evaporated；
B) the pretreated concentrated sulfuric acid is added into extraction system to be extracted, the matter of sulfuric acid in the pretreated concentrated sulfuric acid
Amount score is 99-100%.
2. the method according to claim 1, wherein the pretreated concentrated sulfuric acid is to dense in step b)
Oleum is added in sulfuric acid, sulfuric acid mass fraction is made to reach 99-100%；Preferably, the oleum is selected from 20%-
65% oleum is preferably selected from the combination of one or more of 20%, 50%, 65% oleum.
3. method according to claim 1 or 2, which is characterized in that in step a), the temperature in control extraction reaction kettle is
60-90 DEG C, pressure is 5-30KPa (A)；Preferable temperature is 75-85 DEG C, and pressure is 10-30KPa (A).
4. according to the method described in claim 3, it is characterized in that, the pretreated concentrated sulfuric acid is reacted in the extraction
It is just added in the extraction system after temperature and pressure in kettle is constant.
5. the method according to claim 1, wherein passing through the setting radial direction in extraction reaction kettle in step a)
The dual impellers of paddle and Axial-flow stirrer carry out the stirring；
Preferably, the arrangement of the radial paddle and Axial-flow stirrer in extraction reaction kettle is that the radial paddle is located at upper layer, institute
It states Axial-flow stirrer and is located at lower layer, described radial direction paddle preferably≤1.5m at a distance from liquid level, positioned at the radial paddle on upper layer and positioned at lower layer
Axial-flow stirrer between spacing preferably >=1.2 times of radial paddle diameters, the more preferable spacing is 1.2-3 times radial direction paddle diameter；
Preferably, the radial paddle is selected from gear-shaped disk turbo-typed agitating paddle, bouruma gold type agitating paddle, three straight leaf cone bottom formulas and stirs
Mix paddle, curved leaf opens turbine type agitating paddle, six straight leaves open turbine impeller, three leaf swept-back agitating paddles, arrow leaf formula disk
The combination of one or more of turbine impeller, arc leaf disc turbine impeller and self-priming paddle, preferably self-priming paddle and/or
Six straight leaves open turbine impeller；Axial-flow stirrer is selected from pusher agitating paddle, and preferably three leaf upper-turn-types promote paddle, three leaf press-down types
Promote paddle, four leaf upper-turn-types that paddle, four leaf press-down types is promoted to promote the combination of one or more of paddle, on more preferable four leaf
It turns over formula and promotes paddle.
6. method according to claim 1-5, which is characterized in that the defoaming agent of resistance to strong acid is modified organic silicon
Class defoaming agent, the dosage of the defoaming agent of resistance to strong acid are preferably the 0.2- of the alkane solution quality of the cyclododecanone oxime
0.3wt%.
7. according to the method described in claim 6, it is characterized in that, the defoaming agent of resistance to strong acid be sulfur-bearing carboxyl fluorine containing silicone oil,
The composition of white carbon black and emulsifier；In the defoaming agent of resistance to strong acid, based on the gross mass of the defoaming agent of resistance to strong acid each component, institute
The mass fraction for stating emulsifier is preferably the more preferable 3-5wt% of 1-10wt%, and the mass fraction of the white carbon black is preferably 5-
10wt%；
Preferably, the defoaming agent of resistance to strong acid by by the sulfur-bearing carboxyl fluorine containing silicone oil, white carbon black and emulsifier in 130-180
2-3h is stirred at DEG C to obtain.
8. including the following steps the method according to the description of claim 7 is characterized in that the sulfur-bearing carboxyl fluorine containing silicone oil uses
Method preparation:
1) the fluorine-containing methyl-silicone oil of formula (I) and the tetramethyl-ring tetrasiloxane of formula (II) are reacted, obtains fluorine-containing the containing of formula (III)
Hydrogen silicone oil；Preferable reaction temperature is 60-80 DEG C；
2) the fluorine-containing containing hydrogen silicone oil of formula (III) reacts to obtain the sulfur-bearing carboxyl fluorine silicon of formula (V) with the alkenyl thionothiolic acid of formula (IV)
Oil；Preferred steps 2) reaction carry out in acid condition；Reaction temperature is preferably 90-100 DEG C；
In the above structural formula, x=1-30, y=1-40, z=4-20, n=2-8.
9. method according to claim 7 or 8, which is characterized in that the emulsifier be selected from organic carboxyl acid, organic sulfonic acid,
The combination of one or more of organic sulfinic acid, organic thionothiolic acid, preferably adipic acid, decanedioic acid, p-methyl benzenesulfonic acid, ten
Dialkyl carboxylic acid, dodecyl thionothiolic acid, dodecyl sodium sulfonate, octadecyl carboxylic acid, octadecyl sulfonic acid, in dodecanedioic acid
A combination of one or more, more preferable dodecanedioic acid, dodecyl carboxylic acid, dodecyl thionothiolic acid and dodecyl
The a combination of one or more of sulfonic acid.
10. -9 described in any item methods according to claim 1, which is characterized in that in the alkane solution of the cyclododecanone oxime,
The concentration of cyclododecanone oxime is 10-30wt%, preferably 15-20wt%；Solvent alkane in the alkane solution is cyclohexyl
Alkane and/or isopropyl cyclohexane.
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