CN107417561A - A kind of preparation method of N lauroyl L lysines - Google Patents
A kind of preparation method of N lauroyl L lysines Download PDFInfo
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- CN107417561A CN107417561A CN201710338603.6A CN201710338603A CN107417561A CN 107417561 A CN107417561 A CN 107417561A CN 201710338603 A CN201710338603 A CN 201710338603A CN 107417561 A CN107417561 A CN 107417561A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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Abstract
A kind of preparation method of N lauroyl L lysines, comprises the following steps：(1) preparation of lysine laruate：Will methanol, laurate, lysine concentrate mix after cool after temperature rising reflux reaction, filter, dry lysine laruate；(2) preparation of lauroyl lysine crude product：Temperature rising reflux reacts after lysine laruate obtained by step (1) and trimethylbenzene are mixed, and reaction cools after terminating, and adds absolute methanol, continues to cool after stirring, then filter, be dried to obtain lauroyl lysine crude product；(3) purifying of crude product：Lauroyl lysine crude product obtained by step (2) is filtered after peracetic acid is recrystallized, activated carbon decolorizing, alcohol are washed, dries obtained N lauroyl L lysine fine work.The preparation method of the present invention achieves higher yield and the purity of obtained product is higher.
Description
Technical field
The invention belongs to chemical products preparation field, and in particular to a kind of preparation method of N- lauroyl -1B.
Background technology
Lauroyl lysine (N-Lauroyl-L-lysine, referred to as：LL, CAS：52315-75-0) it is a kind of chemicals
Matter, molecular formula C18H36N2O3, full name is N- lauroyl -1B.Lauroyl lysine is by laurate and 1B
Synthesize and pass through and isolate and purify gained.Raw material sources have good biological degradability in natural, very safe.
LL with high-lubricity, soft and smooth skin sense, low frictional factor, with antistatic, inoxidizability, it is not soluble in water and more
Number organic solvent, concentrated acid, alkali are dissolved in, but be easily caused decomposition for a long time.LL layered crystal structure make its feel it is smooth it is fine and smooth,
It is as fine as silk, have been used for the surface treatment of high-end cosmetics powder, for foundation cream breast, face cleaning product etc..LL is used for color make-up, made up
Product powder handling, assign powder and paste skin sense, soft and smooth sense and hydrophobicity well.It is high-end that LL can be additionally used in foundation cream breast, rouge liquid etc.
Face cleaning product and mica powder, TiO2Field of surface treatment.
The preparation method of lauroyl lysine is usually by 1B and bay acylating acid, purifies and obtain.Lysine
Direct amidated deficiency is that what is obtained is the mixture of several compounds, and side reaction is more, post-processes pretty troublesome, yield
It is very low, can not or be difficult the lauroyl lysine for obtaining high-quality less than 30%.
The content of the invention
Therefore, it is an object of the invention to provide a kind of preparation method of N- lauroyl -1B.The preparation of the present invention
The purity for N- lauroyl -1B that method obtains is high, product yield high.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：
A kind of preparation method of N- lauroyl -1B, comprises the following steps：
(1) preparation of lysine laruate：Temperature rising reflux reacts after methanol, laurate, lysine concentrate are mixed
After cool, separate, dry lysine laruate；
(2) preparation of lauroyl lysine crude product：Risen after lysine laruate obtained by step (1) and trimethylbenzene are mixed
Warm back flow reaction, reaction cool after terminating, and add absolute methanol, continue to cool after stirring, then separate, be dried to obtain lauroyl
Lysine crude product；
(3) purifying of crude product：Lauroyl lysine crude product obtained by step (2) is recrystallized through peracetic acid, activated carbon decolorizing,
Alcohol separates after washing, and dries obtained N- lauroyl -1B fine work.
The present invention generates intermediate lysine laruate, then passed through again anti-with trimethylbenzene by controlling reaction condition
Lauroyl lysine crude product should be made afterwards, N- lauroyl -1B fine work of obtained high-purity, is avoided directly after purified
Amidatioon obtains the deficiency of a variety of mixtures so that the yield of product greatly improves, and up to more than 50%, product purity is reachable
More than 99%.
Fig. 1 is the intermediate salt synthesis flow schematic diagram in the step (1) of the present invention.
Preferably, being warming up to backflow in step (1), such as 50-80 DEG C is warming up to, preferably 65 DEG C, back flow reaction
Time is more than 4 hours, preferably 5~8 hours, more preferably 6 hours.
Preferably, cooling in two stages, is cooled to 10-30 DEG C, such as room temperature, preferably 20 DEG C of guides, Ran Houzai first
To -5~5 DEG C, preferably 0 DEG C.
Preferably, dry temperature is 50-80 DEG C, preferably 60-65 DEG C.
Separation can use techniques known in the art, such as centrifuge, filtering means.Retortable time of filtrate after separation
Receive methanol.
Back flow reaction can be carried out under agitation.
Preferably, the concentration of lysine is 40-65%, preferably 56% in the lysine concentrate.Lysine concentrates
Liquid is made up of lysine and water.
Preferably, the mol ratio of the laurate and lysine is 1:0.5-2, preferably 1:1.
Preferably, the mass ratio of the laurate and methanol is 1:5-20, preferably 1:8-12.
Preferably, heating in two stages, is warming up to 100-120 DEG C, preferably 110 DEG C before this in step (2), it is incubated
Reaction without methanol to distillating, and then with 5-15 DEG C/h, preferably 10 DEG C/h are warming up to 150-200 DEG C, preferably 170-180
DEG C, stop reaction when being back to anhydrous abjection.
Preferably, the water generated in reaction, is separated by water knockout drum.
Preferably, reaction cools in two stages after terminating, and is first cooled to 70-90 DEG C, preferably 80 DEG C, guide, then
30-50 DEG C, preferably 40 DEG C are down to again.
Preferably, absolute methanol is added, continues to be cooled to 5-20 DEG C, preferably 10 DEG C after stirring.
Preferably, the mass ratio of lysine laruate and trimethylbenzene is 1:2-10, preferably 1:5 or so.
Preferably, the mass ratio of lysine laruate and methanol is 1:1-5, preferably 1:2 or so.
Separation can use techniques known in the art, such as centrifuge, filtering means.Filtrate after separation is retortable
Reclaim trimethylbenzene and methanol.
Preferably, acetic acid recrystallization process is in step (3)：Heated up after lauroyl lysine crude product and glacial acetic acid mixing
It is back to solid to be completely dissolved, cools, separation.Filtrate after separation can carry out distillation recovery utilization, and filter cake carries out decolorization.
Preferably, to be warming up to 110-130 DEG C, preferably 120 DEG C, the time of backflow is more than 0.5 hour for the heating,
Preferably 1 hour.
Preferably, cooling in two stages, is cooled to 100-110 DEG C, preferably 105 DEG C of guides, then again to 10 first
~20 DEG C, preferably 15 DEG C.Lauramide crude product preferably carries out pickling more than twice, not made in acid cleaning process before decolouring
With activated carbon, the process of material guide while hot is only existed in operation, is the key operation point of acid cleaning process.The process does not have to
Activated carbon decolorizing, it only can pass through 2 pickling, reduce using the filter process after activated carbon, needed if activated carbon is used
Heat filtering is carried out, operation is more complicated, and above-mentioned technique of the invention then simplifies operating procedure, reduces the difficulty of operation.
Preferably, the mass ratio of lauroyl lysine crude product and glacial acetic acid is 1:5-20, preferably 1:10-15.
Preferably, activated carbon decolorizing process is：Acetic acid is recrystallized into separating obtained filter cake to mix with glacial acetic acid, activated carbon
Temperature rising reflux to solid is completely dissolved afterwards, and cooling, thermal release removes activated carbon, then cools, and is placed, separation.Separation can use this
Technology known to field, such as centrifuge, filtering means.Filtrate after separation can carry out distillation recovery utilization, and filter cake is carried out
Alcohol washes processing.
Preferably, to be warming up to 115-130 DEG C, preferably 120 DEG C, the time of backflow is more than 0.5 hour for the heating,
Preferably 1 hour.
Preferably, 100-115 DEG C, preferably 110 DEG C are cooled to for the first time, then are cooled to 10~20 DEG C, preferably 15 DEG C,
The time of placement is more than 3 hours, preferably 5 hours.
Preferably, the amount of activated carbon be filter cake quality 2-5%, preferably 3%.
Preferably, the mass ratio of filter cake and glacial acetic acid is 1:5-15, preferably 1:10.
Preferably, the washed journey of alcohol is：Filter cake obtained by activated carbon decolorizing is added in methanol and stirred, is filtered.
Preferably, the time of stirring is more than 15min, preferably 30min.
Preferably, the mass ratio of filter cake and methanol is 1:3-10, preferably 1:5.
The temperature dried in step (2) and (3) can be 80-90 DEG C.
Filtrate after above-mentioned separation can carry out distillation processing, be reused after recovered.
Feeding intake for liquid material such as lysine concentrate, acetic acid, trimethylbenzene and methanol etc. used is to utilize in the present invention
Vacuum is put into reactor by feeding pipeline.If directly feeding intake, dog-house is located at the top of operating platform, it is necessary to by liquid
Material transportation is on platform；Using vacuum, then material can be put into reactor below platform, it is not necessary to carried, time saving province
Power.
The preparation method of N- lauroyl -1B of the present invention includes the preparation of lysine laruate, lauroyl relies
Three preparation of propylhomoserin crude product, the purifying of crude product steps, by operation temperature (the especially intermediate for reasonably controlling each step
Salt synthesize and crude product synthesis in heating, cooling temperature), time, the condition such as material rate the preparation method of the present invention is obtained
Higher yield, up to more than 50%, product, which is made, has very high purity, and reachable more than 99%.
Brief description of the drawings
Fig. 1 is intermediate salt synthesis flow schematic diagram；
Fig. 2 is crude product synthesis flow schematic diagram；
Fig. 3 is fine work pickling process schematic diagram；
Fig. 4 is fine work decolouring schematic flow sheet.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
Device therefor
Example below device therefor is as shown in Table 1 below.
Table 1
Material used is as follows：
Laurate：Scientific name 12 (alkane) acid, molecular formula：CH3(CH2)10COOH, molecular weight：200.There is the smell of oreodaphene,
White, needle-shaped crystals body.Relative density 0.8679 (50 DEG C).44 DEG C of fusing point.225 DEG C of boiling point (13.3 kPas, 100 millimetress of mercury).
It is not soluble in water, it is dissolved in ethanol, ether and benzene etc..For alkyd resin processed, wetting agent, detergent, agrochemical.By coconut oil
Separated in aliphatic acid.Lysine：Structural formula is H2NCH2CH2CH2CH2CH(NH2) COOH, molecular formula：C6H14N2O2, molecular weight：
146.Lysine is a kind of amino acid needed by human, and it is nutriment necessary to human body, but body can not oneself production
It is given birth to, it must pass through diet and nutritional supplement obtains.As a kind of amino acid, it is the essential composition of protein
Part.This nutrition serves important function for the appropriate growth of body and development, and it is an important set of carnitine production
Into part.Carnitine is responsible for some unrighted acids being converted into energy, additionally aids reduction cholesterol levels.It seeks with other
Support and form collagen together.Collagen is in connective tissue, bone, muscle, and important angle is played in tendon and articular cartilage
Color.In addition, lysine, which also contributes to body, absorbs calcium.
Methanol：Colourless, inflammable, volatile toxic liquid, to metal non-corrosiveness (except lead, aluminium) under normal temperature, slightly
Alcohol smell.Molecular weight 32.04, relative density 0.792 (20/4 DEG C), -97.8 DEG C of fusing point, 64.5 DEG C of boiling point, the combustion heat
725.76KJ/mol, 12.22 DEG C of flash-point, 463.89 DEG C of self-ignition point, vapour density 1.11, vapour pressure 13.33KPa (100mmHg,
21.2 DEG C), steam and air mixture explosion limit 6~36.5% (volume ratio) can be with water, ethanol, ether, benzene, ketone, halos
Hydrocarbon and many other organic solvents are miscible, but not miscible with petroleum ether, heat, naked light or oxidant easy firing.Volatilization way
In also can be corroded object painted surface.
Trimethylbenzene：It is a kind of mixture of mesitylene and pseudocumene, density：0.8637, fusing point：- 44.7 DEG C, boiling
Point：164.72 DEG C, flash-point：44℃.
Glacial acetic acid：Acetic acid is a kind of colourless liquid for having intense irritation tart flavour at normal temperatures.The fusing point of acetic acid is 16.6
℃(289.6K).Boiling point 117.9 DEG C (391.2K).Relative density 1.05,39 DEG C of flash-point, explosion limit 4%~17% (volume).
Pure acetic acid can be frozen into ice-like crystal when less than fusing point, so anhydrous acetic acid is also known as glacial acetic acid.Acetic acid it is soluble in water and
Ethanol, its aqueous solution are in faintly acid.
Lysine concentrate：Lysine is a kind of amino acid needed by human.Lysine concentrate is by lysine and water group
Into the content 50% or so of lysine.
The preparation method process of the present invention is as follows
1st, the preparation of lysine laruate
Methanol, laurate, lysine concentrate are added in three-necked flask, stirring, heating, backflow is warming up to, flows back
Reaction about 6 hours.Reaction terminates, and is first cooled to 20 DEG C of guides, then is cooled to 0 DEG C, filtering.Methanol filtrate (applying mechanically) is reclaimed, Gu
Body drying, weigh, obtain intermediate salt.
2nd, the preparation of lauroyl lysine
Dehydration：Above-mentioned lysine laruate, trimethylbenzene are added in three-necked flask, water knockout drum is equipped with flask, is stirred
Mix, be warming up to 110 DEG C before this, then insulation reaction is warming up to 170 DEG C or so with 10 DEG C/h, started back to being distillated without methanol
Stream, reacts the water of generation, through water knockout drum, separates water into.Back flow reaction about 6 hours, to reaction is stopped during anhydrous abjection, first drop
Temperature is to 80 DEG C or so guides, then is cooled to 40 DEG C or so, adds absolute methanol, continues to stir, temperature is down to 10 DEG C, then mistake
Filter.Filtrate is collected, it is to be distilled, reclaim trimethylbenzene and methanol.Filter cake is dried, and weighs, and obtains lauramide crude product.
3rd, recrystallize：
Pickling：Crude product and glacial acetic acid are added in three-necked flask, stirring, heating, 120 DEG C or so is warming up to, starts to flow back,
Backflow about 1 hour, is completely dissolved to solid, is cooled to 105 DEG C of guides first, then is cooled to 15 DEG C or so, filters, and collects filter
Liquid, filter cake carry out decolorization.
Decolourize：Filter cake is added in three-necked flask, then adds glacial acetic acid, while adds activated carbon, stirring, heating, is risen
Temperature starts to flow back to 120 DEG C or so, flows back about 1 hour, is completely dissolved to solid, is then cooled to 110 DEG C or so, carries out heat
Filtering, activated carbon is filtered off, collect filtrate, cooling crystallization.Filtrate temperature is down to 15 DEG C or so, places 5 hours, then carries out
Filtering, collects filtrate, and filter cake carries out alcohol and washes processing.
Alcohol is washed：Above-mentioned filter cake is added in flask, while adds methanol, stirring at normal temperature 0.5 hour, then carried out
Filter, collects filtrate, and filter cake is dried processing, obtains N- lauroyl -1B fine work.
Above-mentioned collection, distillation processing can be carried out, after recovered, recycling.
The amount of raw material and purity, yield be as shown in Table 2 below in lauroyl lysine preparation method.Wherein lysine concentrates
The concentration of liquid is 50%.
From table 2 it can be seen that preparation method of the present invention achieves more than 50% yield, the purity of product is made 99%
More than.
Table 2
The present invention can also workshop continuous production, yield is up to 40% or so, and cost is in 110,000/ton.
Workshop quantity-produced specific embodiment is as follows：
First, salification process is closed
Close salification process and can be found in Fig. 1, specifically include following process.
1st, material is sketched
Synthesize in salt workshop section, involved material is methanol (solvent), laurate (solid), lysine concentrate (liquid
Body) etc. three kinds of materials.
2nd, safeguard procedures
Protection on methanol operation：Respiratory system protection：When may contact its dust, it should wear anti-poison respirator.Must
Will when wear breathing mask.Eye protection：Wear chemical safety safety goggles.Protective garment：Wear work clothes (anti-corrosion material making).Hand
Protection：Wear rubber gloves.It is other：After work, shower is changed one's clothes.Individually deposit by the clothes of toxic pollution, used again after washing.Keep good
Good hygienic habit.
3rd, feeding operates
Feeding intake for liquid material methanol and lysine concentrate, reactor is pumped into using vavuum pump by feeding tube by material
It is interior；Solid material is lauric to feed intake, and opens reactor manhole kettle cover, directly by quantitative laurate input reactor.
4th, course of reaction operates
(1) after material input 3# reactors, equipment is checked, the scope of examination includes condenser salt solution terminal valve
Door, the exits and entrances valve of reacting kettle jacketing salt solution and recirculated water, the emptying valve etc. of steam exits and entrances valve and reactor, inspection
After the fruit that comes to an end meets the requirements, slowly open steam valve and carry out heat temperature raising.
(2) temperature-rise period, by the control to steam, 65 DEG C or so are warming up within 1.5 hours, backflow phenomenon occurs.Start
After backflow, by controlling quantity of steam, 7 hours or so are maintained the reflux for, after backflow terminates, steam off, ON cycle water is dropped
Temperature.
(3) after temperature is down to room temperature, opens vacuum and carry out guide, material is imported in 4# reactors, and open 4# reactions
The salt solution exits and entrances valve of kettle, cools to material, when temperature is down to below 5 DEG C, carries out centrifugal filtration operation.
(4) after guide terminates, 3# reactors carry out feeding intake for next batch, continue the synthetic reaction of next group.
5th, centrifugal filtration process
(1) it is when temperature is down to less than 5 DEG C, centrifuge is ready when in 4# reactors, and security inspection is carried out,
Then centrifugal filtration is carried out.Low rate start centrifuge, after stabilization of speed, centrifuge is transferred to middling speed, after stabilization of speed,
Open material centrifugation.
(2) in centrifugal process, the flow control of material is exported in Centrifuge filtrate and is defined without solid material, in filtrate clarification and
In the case that flow velocity is fast, dispensing speed is improved as far as possible.If solid material is carried in filtrate, dispensing speed is turned down or of short duration pass
Close dispensing valve.
(3) as defined in reaching when blowing total amount after blowing amount, blowing is stopped, after then middling speed dries 1 hour, by centrifugation speed
Degree is adjusted at a high speed, continue to dry 3 hours, to when being flowed out without filtrate, closes centrifuge step by step.
(4) when discharging, operating personnel, which must match somebody with somebody, to wear a gas mask, while wears plastic gloves, carries out self-protection work.
After discharging, material is weighed, and centrifuge is cleared up, while centrifuge is transferred to next centrifugal filtration state, is treated
Next batch material continues centrifugal filtration.
(5) in centrifugal filtration process, filtrate timely will be got in storage tank in filtrate collecting vessel, forbid filtrate occur overflowing
Go out, situation about causing damage occurs.After centrifugation terminates, record of weighing is carried out to total amount of filtrate of collection.
2nd, dehydration
That is crude product building-up process, reference can be made to Fig. 2, specifically includes following process.
1st, material is sketched
In workshop section is dehydrated, involved material is trimethylbenzene, methanol (solvent), lauroyl lysine salt (solid) etc.
Three kinds of materials.
2nd, safeguard procedures
Protection on trimethylbenzene operation：Respiratory system protection：When concentration is higher in air, filtermask is worn
(half face shield).When emergency situation is rescued or withdrawn, it is proposed that wear air respiratorresuscitator.Eye protection：Wear chemical safety safety goggles.
Body protection：Wear anti-poisonous substance permeable work clothes.Hand protects：Wear rubber gloves.It is other：No smoking for working site, feeds and drinks
Water.Work is finished, and shower is changed one's clothes.Pay attention to personal cleanliness's health.
The protection of methanol is with reference to the methanol operation safeguard procedures during synthesis salt.
3rd, feeding operates
Liquid material trimethylbenzene and methanol are fed intake, and material is pumped into reactor by feeding tube using vavuum pump；Gu
Body material lauroyl lysine feeds intake, and opens reactor manhole kettle cover, quantitative lauroyl lysine directly is put into reaction
In kettle.
In feeding process, it is related to the materials such as trimethylbenzene and methanol, requires, properly protect according to safeguard procedures.
The use of vavuum pump requires to carry out according to the operation of vavuum pump.
4th, course of reaction operates
(1) feed intake after end, check the kettle condition of oily kettle, including kettle in itself, Oil Guide pipeline, electric heating control case, condensation
The situation such as device and motor reducer.
(2) after the above situation meets reaction safety operation requirement, open stirring motor, open one group of electrically heated rod, it is right
Oily kettle carries out heat temperature raising.The initial temperature of control cabinet is set in 100 DEG C,
(3) after oil temperature is raised to 100 DEG C, 2 hours are incubated, until temperature in the kettle is stable, and the temperature of temperature in the kettle and oil temperature
Difference is no more than 15 DEG C.
(4) after temperature in the kettle is stable, electric heating system is adjusted, continues to heat up.Each design temperature improves than original temperature
10 DEG C, and after temperature rises to design temperature, insulation reaction 1 hour.10 DEG C of regulation heating is then proceeded to, until temperature rises to
Stop at 180 DEG C.
(5) in temperature-rise period, constantly the water layer in water knockout drum to be released.After rising to set point of temperature, insulation reaction 6 is small
When.After reaction terminates, electrically heated rod is closed, opens Oil Guide pump, carries out cold oil, hot-oil circulation cooling.
(6) temperature be down to after set point of temperature, it is specified that temperature be 85 DEG C, by material in kettle carry out using vacuum import 8# cooling
In kettle.Guide front opening salt solution valve is cooled.
(7) after material imports 8# reactors, carry out being cooled to 40 DEG C using salt solution, then open vacuum by feeding tube,
Methanol is squeezed into kettle.During operation, to be protected according to the operation safeguard procedures of methanol.
(8) when reactor temperature is down to 10 DEG C or so, centrifugal filtration work is prepared.
5th, centrifugal filtration process
(1) it is when temperature is down to less than 10 DEG C, centrifuge is ready when in 8# reactors, and security inspection is carried out,
Then centrifugal filtration is carried out.Low rate start centrifuge, after stabilization of speed, centrifuge is transferred to middling speed, after stabilization of speed,
Open material centrifugation.
(2) in centrifugal process, the flow control of material is exported in Centrifuge filtrate and is defined without solid material, in filtrate clarification and
In the case that flow velocity is fast, dispensing speed is improved as far as possible.If solid material is carried in filtrate, dispensing speed is turned down or of short duration pass
Close dispensing valve.
(3) as defined in reaching when blowing total amount after blowing amount, blowing is stopped, after then middling speed dries 1 hour, by centrifugation speed
Degree is adjusted at a high speed, continue to dry 3 hours, to when being flowed out without filtrate, closes centrifuge step by step.
(4) when discharging, operating personnel, which must match somebody with somebody, to wear a gas mask, while wears plastic gloves, according to trimethylbenzene and methanol
Requirement of shelter, carry out self-protection work.After discharging, material is weighed, and centrifuge is cleared up, while will be from
Next centrifugal filtration state is transferred in scheming, treats that next batch material continues centrifugal filtration.
(5) in centrifugal filtration process, filtrate timely will be got in storage tank in filtrate collecting vessel, forbid filtrate occur overflowing
Go out, situation about causing damage occurs.After centrifugation terminates, record of weighing is carried out to total amount of filtrate of collection.
3rd, recrystallization process
1st, material is sketched
In recrystallization process, involved material is acetic acid (solvent), lauramide crude product and activated carbon (solid)
Deng three kinds of materials.
2nd, feeding operates
The feeding of liquid acetic, by feeding tube, material is put into reactor using vacuum.Protection is worn when feeding intake
Mask, glasses and wear plastic gloves and protected, prevent acetic acid from being contacted with skin and clothes.Solid lauramide crude product and
Activated carbon is put into kettle by reactor entrance, when feeding intake, to prevent kettle internal solvent from spilling outside kettle, using suitable feeding mode
And safeguard procedures.
3rd, course of reaction operates
(1), acid cleaning process
Acid cleaning process can be found in Fig. 3, specifically include following process.
Lauramide crude product before decolouring, it is necessary to carry out pickling twice, without using activated carbon in acid cleaning process, in operation only
It is the key operation point of acid cleaning process in the presence of the process of material guide while hot.
(1) in acid cleaning process, after material, check that reactor kettle and condenser situation, inspection meet
After safety requirements and operation require, stirring motor is opened, slowly opens steam valve, heat temperature raising is carried out to material.Lead to simultaneously
Control steam valve is crossed, steam flow is controlled, so as to control the speed of heat temperature raising.
(2) heating-up time controls 4 hours or so, and temperature rises to acetic acid and starts to flow back, and about 110 DEG C or so, then somewhat closes
Steam valve is closed, maintains the reflux for reaction 1 hour.
(3) after back flow reaction terminates, material is imported in 5# reactors using vacuum.0.5 hour before guide, to open and lead
The steam heating of batch can, guide tank is preheated, 2 pressure of Steam pressure control or so.Before starting guide, it is anti-to open 5#
The salt solution exits and entrances valve of kettle is answered, after material is imported in kettle, material is cooled.
(4) after guide terminates, 5# reactors continue to cool, and when being down between 15-20 DEG C of temperature in the kettle, are ready for
Centrifugal filtration operates.
(5) during guide, because temperature of charge is high, safety prevention measure is carried out.Hot acetic acid is prevented to human body and is set
It is standby etc. to damage and corrode.
(6) acid cleaning process and guide process terminate, and cleaning finisher is carried out to kettle, material guide device and surrounding instrument
Make.The pickling that 5# according to circumstances carries out next batch feeds intake and temperature rising reflux.
(2) heat filtering decolorization
Decolorization can be found in Fig. 1, specifically include following process.
(1) in heat filtering decolorization, appropriate activated carbon is heated into kettle, adsorption bleaching is carried out to material.Heating
Process and back flow reaction process are identical with acid cleaning process, are operated according to acid cleaning process during operation.
(2) during back flow reaction, the heat filtering equipment such as filter and filter cloth will be put into guide tank, while in heat filtering
First 0.5 hour, the steam valve of guide tank is opened, steam preheating is carried out to guide tank.
(3) after heat filtering ER equipment ready, 5# kettles vacuum, guide pipeline valve are opened, while control the blowing of 6# kettles
Valve, dispensing speed is controlled, carry out heat filtering.
(4) dispensing speed control exists, in heat filtering kettle on the basis of no liquid residual.The situation that no liquid remains in kettle,
Quickening dispensing speed as far as possible.
(5) during heat filtering, the insulation of appropriateness is carried out to 6# reactors, keeps the temperature stabilization in reactor.
(6) during heat filtering, because temperature of charge is high, to carry out safety prevention measure, prevent hot acetic acid to human body and
Equipment etc. is damaged and corroded.
(7) after heat filtering terminates, continue to carry out salt solution cooling to 5# reactors, after temperature is down to 15-20 DEG C, prepare filtering
Centrifugally operated.
(8) after heat filtering terminates, after temperature is down to room temperature in guide tank, the activated carbon in guide tank is cleared up and collected.
During operation, because solid contains acetic acid, safety prevention measure is carried out according to the requirement of shelter of acetic acid.Filter cake after decolouring enters
Row alcohol is washed.
(9) after heat filtering process terminates, heat filtering device is subjected to cleaning arrangement, is ready for the production exercise of next batch
Make.
5th, centrifugal filtration process
(1) when in 5# reactors, temperature be down to 15-20 DEG C between when, it is centrifuge is ready, and carry out security inspection
Look into, then carry out centrifugal filtration.Low rate start centrifuge, after stabilization of speed, centrifuge is transferred to middling speed, etc. stabilization of speed
Afterwards, open material centrifugation.
(2) in centrifugal process, the flow control of material is exported in Centrifuge filtrate and is defined without solid material, in filtrate clarification and
In the case that flow velocity is fast, dispensing speed is improved as far as possible.If solid material is carried in filtrate, dispensing speed is turned down or of short duration pass
Close dispensing valve.
(3) as defined in reaching when blowing total amount after blowing amount, blowing is stopped, after then middling speed dries 1 hour, by centrifugation speed
Degree is adjusted at a high speed, continue to dry 3 hours, to when being flowed out without filtrate, closes centrifuge step by step.
(4) when discharging, operating personnel, which must match somebody with somebody, to wear a gas mask, while wears plastic gloves, will according to the protection of acetic acid
Ask, carry out self-protection work.After discharging, material is weighed, and centrifuge is cleared up, while centrifuge is transferred to
Next centrifugal filtration state, treat that next batch material continues centrifugal filtration.
(5) in centrifugal filtration process, filtrate timely will be got in storage tank in filtrate collecting vessel, forbid filtrate occur overflowing
Go out, situation about causing damage occurs.After centrifugation terminates, record of weighing is carried out to total amount of filtrate of collection.
4th, still-process
1st, the distillation recovery of methanol
(1) it is methanol, water and the part of dissolving lauroyl lysine salt to synthesize the filtrate reclaimed in salt centrifugal filtration process,
Methanol is recovered by distillation, wherein methanol contains a small amount of moisture.The content of initial moisture is distilled 3% or so, with distillation
Progress, temperature constantly raises, and in the methanol of recovery, the content of moisture also gradually rises, when the content of moisture is more than 8%
When, stop distillation, or another a batch of filtrate is added into reactor, continue to distill.
(2) in still-process, control the amount of steam can not be excessive, cause the too high levels of moisture in methanol.Steaming simultaneously
Evaporate the later stage, material must not occur the situation of foam in kettle.
(3) in still-process, water content detection regularly is carried out to methanol fraction, and the methanol of recovery is weighed.
The methanol of recovery can continue on in the course of reaction of synthesis salt.
(4) distillation terminate after, by kettle material carry out salt solution cooling, when temperature is down to 5 DEG C or so, material is carried out from
The heart filters.Centrifugal filtration process is with reference to the material centrifugal filtration process operation in salt building-up process.
(5) solid centrifugally filtered out can be dewatered reaction, produce crude product.The filtrate centrifugally filtered out mainly contains
Methanol, the lauroyl lysine salt of water and dissolving in a liquid, can directly be discharged into biochemistry pool, carry out at biochemical degradation
Reason.
2nd, the distillation recovery of trimethylbenzene
(1) filtrate of the 8# material in reactor after centrifugal filtration is trimethylbenzene, methanol and the bay being dissolved in solvent
Crude amide.Filtrate is squeezed into 10# reactors after collection and carries out being distilled to recover methanol and trimethylbenzene, while phase after distillation,
Material is subjected to centrifugal filtration and collects solid.
(2) after filtrate adds 10# kettles, steam valve is slowly opened, carries out heat temperature raising, while collect temperature and be less than
110 DEG C of cut, the cut are methanol, contain a small amount of trimethylbenzene.
(3) when 110 DEG C of temperature, when cut is seldom, stop the collection of methanol, close reactor steam, while open folder
The recirculated water exits and entrances valve of set, cools to material, when temperature is down to 85 DEG C, closes recirculated water exits and entrances valve, opens
Ability of swimming vavuum pump and two stage pump, by controlling vacuum, material is carried out to be evaporated under reduced pressure recovery front three benzene fraction.
(4) in still-process, when temperature is too low, cut it is seldom or without cut in the case of, appropriate regulation steam
Valve, material is heated up, maintain the cut of trimethylbenzene stable.
(5) later stage is distilled, when cut is seldom, the material in reactor can be cooled, will another a batch of filter
In liquid input kettle, continue to be distilled to recover methanol and trimethylbenzene.
(6) after distillation terminates, there is solid precipitation in liquid in reactor, material is relatively sticky, then will be squeezed into kettle
A certain amount of water, it is stirred dilution.Then after temperature is down to room temperature, centrifugal filtration is carried out.Solid material is collected to be dried
Dry-cure, the fraction solids are lauramide crude product.
(7) filtrate is trimethylbenzene, water and a small amount of lauramide crude product of dissolving.Due to trimethylbenzene non-degradable, the part
Waste water is, it is necessary to carry out burning disposal.
3rd, the distillation recovery of acetic acid
(1) for 5# material in reactor after centrifugal filtration, obtained filtrate is acetic acid, has wherein been dissolved in acetic acid on a small quantity
Lauramide and some impurity etc..The filtrate needs to carry out distillation recovery acetic acid, and the acetic acid after recovery can continue to put into acid
Wash and decolourize in producing.
(2) after the filtrate input 11# kettles collected, heating air-distillation is proceeded by, distills initial stage, cut is smaller to be controlled
The flow of condenser salt solution, prevent acetic acid from freezing to block condenser, so as to cause reacting kettle inner pressure to increase, safe thing occurs
Therefore.
(3) about 100 DEG C or so of the vapo(u)rizing temperature of acetic acid, after cut is stable, the valve of steam can be controlled, keeps distillation
The stabilization of process.
(4) in still-process, with the increase of cut, cut can be controlled by the disengaging valve of condenser salt solution
Temperature, prevent the too high loss for causing solvent of cut temperature, prevent that the temperature of cut is too low again, cause acetic acid to freeze etc. existing
The generation of elephant.Visor below condenser will carry out inspection, if any it is abnormal will timely mistake manage everywhere.
(5) later stage is distilled, when material is less in kettle, can be cooled with steam off, ON cycle water, temperature is down to
After 30 DEG C, another a batch of acetic acid filtrate can be squeezed into kettle, continue air-distillation.
(6) repeatedly after distillation, the content of solid increases in material in kettle, distills the later stage, after material is sticky, is beaten into kettle
Enter certain water, be then stirred cooling.After temperature is down to room temperature, centrifugal filtration is carried out to material, collects solid material.
(7) because acetic acid can carry out biochemical degradation, the filtrate of centrifugal filtration can be directly discharged into sewer pipe and enter life
Change pond and carry out biochemical treatment.
5th, feeding guide process
1st, feeding operates
(1), the feeding of liquid material
(1) process that feeds intake of liquid material, it is to be put into using vacuum by feeding pipeline in reactor.
(2) liquid material involved by is the filtrate of methanol, front three ALPHA Tolylic acid and solvent, is fed intake in liquid material
When, to take corresponding safeguard procedures for different materials, it is ensured that the personal safety during feeding intake.
(3) during feeding, name of material is checked first, while clearly goes up doses, and the information of correlation is entered
Row record, forbid upper wrong material occur or the situation of mistake occurs in feeding amount.
(4) feeding process, the bottom valve of reactor, baiting valve and emptying valve are closed first, while by vacuum pipe
And the emptying valve of vavuum pump is closed.Vavuum pump is then turned on, slowly opens feeding valve, carries out feeding.
(5) after feeding terminates, feeding valve is closed, opens reactor emptying valve, and the emptying valve of vavuum pump, so
After close vavuum pump.
(6) after feeding terminates, leftover materials are placed into defined region, and feeding instrument and equipment are cleared up
Arrange.
(2) feeding of solid material
(1) in Workshop Production, feeding intake for solid material is to be put into by manhole in reactor.
(2) involved material is laurate, lauroyl lysine salt and lauramide crude product etc. in producing.
(3) when feeding intake, reactor manhole cover can be opened, is then put into material in reactor, feed intake end, by manhole
Lid covers, and carries out sealing fastening.
(4) when feeding intake, name of material and charged material weight are checked, forbids the wrong situation that feeds intake occur, and it is right
Feed intake and recorded accordingly.
(5) feed intake after end, leftover materials are placed into defined region, and feeding instrument and equipment are cleared up
Arrange.
2nd, guide operates
(1) before guide, guide kettle and guide pipeline are checked, checks guide bottom valve, baiting valve and kettle
Whether emptying valve closes, and whether the valve of guide pipeline is opened.
(2) vacuum vent valve, and the emptying valve of vacuum pipe are closed, opens vavuum pump.
(3) bottom valve and dispensing valve of blowing kettle are opened, material is imported in guide kettle.Peace is carried out during guide
Full protection works.And the salt solution exits and entrances valve of guide kettle chuck is opened, while condenser Inlet and outlet water valve is opened, to hot thing
Material carries out cooling backflow.
(4) guide terminates, and closes the dispensing valve and bottom valve of blowing, opens the emptying valve of guide kettle and vacuum pipe,
And the emptying valve of vavuum pump, it is then shut off vavuum pump.
Obviously, above-described embodiment is only intended to clearly illustrate example, and is not the restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (10)
1. a kind of preparation method of N- lauroyl -1B, comprises the following steps：
(1) preparation of lysine laruate：Dropped after methanol, laurate, lysine concentrate are mixed after temperature rising reflux reaction
Temperature, filtering, dry lysine laruate；
(2) preparation of lauroyl lysine crude product：Heated up back after lysine laruate obtained by step (1) and trimethylbenzene are mixed
Stream reaction, reaction cool after terminating, and add absolute methanol, continue to cool after stirring, then filter, and are dried to obtain lauroyl and rely ammonia
Acid crude；
(3) purifying of crude product：By lauroyl lysine crude product is recrystallized through peracetic acid, activated carbon decolorizing, alcohol are washed obtained by step (2)
After filter, dry obtained N- lauroyl -1B fine work.
2. preparation method according to claim 1, it is characterised in that be warming up to backflow in step (1), back flow reaction when
Between be more than 4 hours；
Preferably, cooling in two stages, is cooled to 10-30 DEG C of guide first, then again to -5~5 DEG C；
Preferably, dry temperature is 50-80 DEG C；
Preferably, the concentration of lysine is 40-65% in the lysine concentrate；
Preferably, the mol ratio of the laurate and lysine is 1:0.5-2；
Preferably, the mass ratio of the laurate and methanol is 1:5-20.
3. preparation method according to claim 1 or 2, it is characterised in that heated up in two stages, before this in step (2)
100-120 DEG C is warming up to, then insulation reaction is warming up to 150-200 DEG C with 5-15 DEG C/h, be back to being distillated without methanol
Stop reaction during anhydrous abjection；
Preferably, reaction cools in two stages after terminating, and is first cooled to 70-90 DEG C of guide, is then down to 30-50 DEG C again；
Preferably, absolute methanol is added, continues to be cooled to 5-20 DEG C after stirring；
Preferably, the mass ratio of lysine laruate and trimethylbenzene is 1:2-10；
Preferably, the mass ratio of lysine laruate and methanol is 1:1-5.
4. according to the preparation method described in claim any one of 1-3, it is characterised in that acetic acid recrystallization process in step (3)
For：Temperature rising reflux to solid is completely dissolved after lauroyl lysine crude product and glacial acetic acid mixing, is cooled, filtering.
5. preparation method according to claim 4, it is characterised in that the heating is is warming up to 115-130 DEG C, preferably
120 DEG C, the time of backflow is more than 0.5 hour, preferably 1 hour；
Preferably, cooling in two stages, is cooled to 100-110 DEG C, preferably 105 DEG C of guides, then again to 10~20 first
DEG C, preferably 15 DEG C；
Preferably, the mass ratio of lauroyl lysine crude product and glacial acetic acid is 1:5-20.
6. according to the preparation method described in claim any one of 1-5, it is characterised in that activated carbon decolorizing process in step (3)
For：Acetic acid is recrystallized into temperature rising reflux to solid after filtering gained filter cake mixes with glacial acetic acid, activated carbon to be completely dissolved, cooled,
Heat filtering filters off activated carbon, then cools, and places, filtering.
7. preparation method according to claim 6, it is characterised in that the heating is to be warming up to 110-130 DEG C, backflow
Time is more than 0.5 hour；
Preferably, 100-115 DEG C is cooled to for the first time, then is cooled to 10~20 DEG C, and the time of placement is more than 3 hours.
8. the preparation method according to claim 6 or 7, it is characterised in that the amount of activated carbon is the 2-5% of filter cake quality；
Preferably, the mass ratio of filter cake and glacial acetic acid is 1:5-15.
9. according to the preparation method described in claim any one of 1-8, it is characterised in that the washed journey of alcohol is in step (3)：Will be living
Property carbon decoloring obtained by filter cake add methanol in stir, filter.
10. preparation method according to claim 9, it is characterised in that the time of stirring is more than 15min；
Preferably, the mass ratio of filter cake and methanol is 1:3-10.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761857A (en) * | 2019-03-04 | 2019-05-17 | 浙江华贝药业有限责任公司 | N-2- palmityl-N-6- fluorenylmethyloxycarbonyl-L-lysine method of purification |
| CN114933545A (en) * | 2022-03-02 | 2022-08-23 | 上海常丰生物医药科技有限公司 | Method for synthesizing lauroyl lysine |
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| US3897466A (en) * | 1972-04-25 | 1975-07-29 | Ajinomoto Kk | Method of preparing N{302 -acyl basic amino acids |
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2017
- 2017-05-15 CN CN201710338603.6A patent/CN107417561A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3897466A (en) * | 1972-04-25 | 1975-07-29 | Ajinomoto Kk | Method of preparing N{302 -acyl basic amino acids |
Non-Patent Citations (1)
| Title |
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| 王致果等: "《新型化妆品用功能性粉体--N-月桂酸基-L-赖氛酸的合成》", 《日用化学工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761857A (en) * | 2019-03-04 | 2019-05-17 | 浙江华贝药业有限责任公司 | N-2- palmityl-N-6- fluorenylmethyloxycarbonyl-L-lysine method of purification |
| CN114933545A (en) * | 2022-03-02 | 2022-08-23 | 上海常丰生物医药科技有限公司 | Method for synthesizing lauroyl lysine |
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Application publication date: 20171201 |