CN109134287A - The method of purification of byproduct sodium chloride in a kind of glycine betaine or beet alkali hydrochlorate production - Google Patents
The method of purification of byproduct sodium chloride in a kind of glycine betaine or beet alkali hydrochlorate production Download PDFInfo
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- CN109134287A CN109134287A CN201810981182.3A CN201810981182A CN109134287A CN 109134287 A CN109134287 A CN 109134287A CN 201810981182 A CN201810981182 A CN 201810981182A CN 109134287 A CN109134287 A CN 109134287A
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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
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
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- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
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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
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
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Abstract
The present invention relates to the process for separation and purification of byproduct sodium chloride in glycine betaine/beet alkali hydrochlorate production process, merge purifying including reaction mother liquor pretreatment, glycine betaine and the initial gross separation of sodium chloride crude product, secondary purification separation and glycine betaine and sodium chloride merges the processes such as purification and purification.According to the method for the present invention, it is suitble to industrial-scale separating-purifying, is not required to that there is higher economy and the feature of environmental protection by processes such as electrodialysis.Sodium chloride after purification realizes the recycling of by-product up to feed grade standard, and processing method is simple, does not generate secondary pollution.
Description
Technical field
The present invention relates to purification technique field, the especially method of purification of chemical products production sodium chloride byproduct,
The highly effective separation purification method for planting vegetables side product chlorinated sodium in alkali/beet alkali hydrochlorate production process more particularly to one.
Background technique
Glycine betaine also known as trimethylglycine, trimethylglycine etc. are a kind of generally acknowledged nontoxic, harmless, free of contamination
Novel multifunctional additive is widely used in the fields such as food medicine, daily use chemicals chemical industry.It is present in natural plants in nature
In root, stem, leaf and fruit, extractable to obtain, extraction process includes ion method, polyethylene-styrene chromatography, at
This height, it is difficult to be mass produced, therefore glycine betaine generallys use chemical synthesis.Glycine betaine is highly soluble in water, in methyl alcohol molten
Solution property is slightly stronger than ethyl alcohol.Beet alkali hydrochlorate is also known as betaine HCL, be it is a kind of it is efficient, high-quality, economical, be widely used in poultry,
Fowl, aquaculture food attractant-growth promoting auxotype additive.
The chemical synthesis process of glycine betaine or its hydrochloride in this field, generallys use monoxone, sodium hydroxide, trimethylamine
It is neutralized for raw material, aminating reaction, this glycine betaine/beet alkali hydrochlorate production process route is commonly referred to as sodium method production work
Skill is specifically reacted with sodium hydroxide using monoxone and generates sodium chloroacetate, and sodium chloroacetate reacts to obtain glycine betaine with trimethylamine
It is mixed with sodium chloride and completes liquid, after high temperature filters salt, obtained glycine betaine and complete liquid.Under certain temperature, completed in liquid to glycine betaine
Concentrated hydrochloric acid is added, after high temperature filters salt, cools down, filtering obtains beet alkali hydrochlorate.Such as CN101255118 discloses a kind of benefit
It is chemically synthetically produced beet alkali hydrochlorate, the preparation method comprises the following steps: the first step, chloroacetic acid solution is first added into reaction kettle,
Then it is passed through liquid trimethylamine gas into chloroacetic acid solution, temperature is maintained at 30 DEG C hereinafter, be sufficiently stirred, and is then warming up to
It 40-45 DEG C, is sufficiently stirred, then is cooled to 30 DEG C or less；Then sodium hydroxide is added in second step into reaction kettle, be sufficiently stirred
Afterwards, make pH value of solution 5-8, after conventional method concentration, purification and crystallization, can be prepared by glycine betaine, be added into glycine betaine
Hydrochloric acid can be prepared by beet alkali hydrochlorate.
Since the reactions such as hydrolysis, polymerization occur under strongly alkaline conditions for monoxone and sodium chloroacetate, a large amount of sodium chloride are generated
By-product.According to production technology, these a certain amount of glycine betaines of byproduct sodium chloride particle surface adhesion, free ammonia, monoxone/
Sodium chloroacetate, hydroxy acid sodium etc. are usually given up since separation is difficult or as industrial material, cause the waste of sodium chloride resource
And pollution environment.General drop ground, the side product chlorinated sodium that chemical method prepares glycine betaine or beet alkali hydrochlorate account for about glycine betaine and contain
The half of amount, since glycine betaine is soluble easily in water with sodium chloride mixture, it is difficult to separate, containing higher in gained glycine betaine product
The sodium chloride of content remains, and also containing impurity such as a large amount of glycine betaines in sodium chloride crystallization.And the current prior art cannot be very
These defects are overcome well.
The relevant technologies of the preparation of glycine betaine or its hydrochloride and product separation can be listed below in the prior art.
CN101323581 provides the synthetic method of a kind of glycine betaine, beet alkali hydrochlorate.Step includes: selection highly basic
Property resin anion (R.A.) be carrier, be processed into oh type；It is eluted with chloroacetic acid solution；Trimethylamine solution recycling elution is used again；
Be washed with distilled water, cleaning solution merges with recycling elution liquid, be atmospherically distilled to it is sticky, continue vacuum distillation obtain powdery or small pieces
The aqueous glycine betaine of shape white；Aqueous glycine betaine is dissolved with ethyl alcohol, and vacuum distillation obtains anhydrous betaine；Above-mentioned vacuum distillation
Hydrochloric acid is added in dope, stirs, and vacuum distillation obtains powdery or strip white beet alkali hydrochlorate.
CN10178696 discloses a kind of preparation method of beet alkali hydrochlorate, and this method is with monoxone, trimethylamine and removes
Aqua is raw material, they are reacted in organic solvent and generates beet alkali hydrochlorate.Its specific process step are as follows: by organic solvent
It puts into reaction kettle, opens stirring, monoxone and deicer is then added, then be passed through trimethylamine at a certain temperature and carry out instead
It answers, through cooling, crystallization, centrifugation, cleaning, dry beet alkali hydrochlorate after having reacted.
CN101863784 discloses the preparation extracting method of a kind of glycine betaine, beet alkali hydrochlorate.The preparation of glycine betaine mentions
It takes method: neutralization reaction first being occurred by sodium hydroxide solution and monoxone, when solution temperature is down to 20-60 DEG C, to reaction kettle
In be passed through liquid trimethylamine, opening stirring reacts it sufficiently；Drying is to remove moisture content；Passed through using anhydrous methanol as extractant
The means such as crystallization treatment extract high-purity glycine betaine crystal.Beet alkali hydrochlorate prepares extracting method: directlying adopt liquid-liquid reactions system
Standby beet alkali hydrochlorate crude product, it is dry to obtain beet alkali hydrochlorate sterling to remove moisture content.
CN106938975 A discloses a kind of method for preparing glycine betaine and beet alkali hydrochlorate.By precipitated calcium carbonate with
Chloroethene aqueous acid, which is mixed, carries out neutralization reaction；After reaction solution is filtered, it is passed through liquid trimethylamine, stirring sends out it sufficiently
Raw aminating reaction；Amination liquid spray drying after concentration obtains glycine betaine.Or after amination liquid is concentrated, hydrochloric acid reaction is added
Crystallization obtains beet alkali hydrochlorate afterwards.
In the preparation method of the prior art, post-processing is preferable using separating effect when the means such as ion exchange resin, still
Speed is slow, is unable to satisfy the industrial requirement of large scale processing, and higher cost, and there are also a large amount of discharge of wastewater when resin regeneration；
When using simple condensing crystallizing means, although post-processing step is simple, inferior separating effect, low efficiency, obtained beet
Alkali purity is not high, and usually gives up side product chlorinated sodium, does not meet the requirement of friendly process production.
Therefore, the prior art lacks in commercial scale to side product chlorinated in glycine betaine/beet alkali hydrochlorate production process
Green high-efficient process for separation and purification of the high-purity of sodium without discharge.
Summary of the invention
The technical problems to be solved by the present invention are: providing by-product in a kind of glycine betaine/beet alkali hydrochlorate production process
The method of the high-purity separating-purifying of object sodium chloride.
The method of the present invention can efficiently separate monoxone and trimethylamine chemical method is prepared in mix products obtained by glycine betaine
Glycine betaine and sodium chloride, wherein sodium chloride purification purity is up to 99% or more, and gained high-purity sodium chloride is only containing low content
Glycine betaine residual, can be directly used for feed grade sodium chloride purposes；Thus realize the sodium chloride byproduct of the impurity containing high-content
It recycling, and recyclable using solvent, treatment process not will form secondary pollution, meanwhile, resulting glycine betaine purity is high,
Be conducive to the beet alkali hydrochlorate for further obtaining high-purity；And separating technology of the present invention is simple, low energy consumption, atom utilization
Height, no by-product and the discharge of three-waste pollution object.
The chemical method preparation that glycine betaine of the present invention/beet alkali hydrochlorate preparation method is well known in the art,
Monoxone is used to be prepared with trimethylamine for reaction raw materials；Specifically, comprising steps of in monoxone and sodium hydroxide progress
Sodium chloroacetate is obtained with reaction, then aminating reaction is carried out with trimethylamine and obtains the mixture containing glycine betaine, sodium chloride.Beet
Alkali salt hydrochlorate is further reacted with equimolar hydrochloric acid by alkali solution of beet to be prepared.
The process for separation and purification of byproduct sodium chloride includes in glycine betaine of the present invention/beet alkali hydrochlorate production process
As reaction mother liquor pretreatment, glycine betaine and the initial gross separation of sodium chloride crude product, secondary purification separation and glycine betaine merge purifying and chlorine
It is as follows to change processes, the key steps such as sodium merging purification and purification:
Step S1: will be concentrated under reduced pressure or be evaporated in vacuo containing the reaction mixture of glycine betaine, sodium chloride and a small amount of trimethylamine,
Obtain glycine betaine-sodium chloride crystalline mother solution；Crystalline mother solution is tentatively concentrated by evaporation and is added a small amount of isopropanol, obtains sodium chloride mixed crystal
Crude product obtains sodium chloride primary dcreening operation crude product with 60-70 DEG C of dehydrated alcohol washing impurity-removing；
Step S2: the mother liquor after Isolating chlorinated sodium mixed crystal crude product is subjected to condensing crystallizing, it is thick to obtain glycine betaine-sodium chloride
Product product is dissolved with separation solvent 1 and separates the solid sodium chloride in above-mentioned crude material to obtain sodium chloride crystal product
1；
Step S3: sodium chloride primary dcreening operation crude product is added in separation solvent 2, heating stirring is separated by filtration solid, nothing while hot
Water-ethanol is washed and is dried, and obtains sodium chloride crystal product 2；
Step S4: sodium chloride crystal product 1 is merged with sodium chloride crystal product 2, and anhydrous methanol rinses or elution, later
Washing material 5-10min is boiled with dehydrated alcohol, is filtered while hot, recrystallizing and refining.
Wherein, the separation solvent is the anhydrous methanol prepared in proportion, dehydrated alcohol mixing alcoholic solvent.
Specifically, detailed process is as follows for above steps of the invention:
Step S1 is specific as follows:
(1) glycine betaine is being prepared after reaction using monoxone, trimethylamine as raw material, product mixture is contained into beet
The reaction mixture of alkali, sodium chloride and a small amount of trimethylamine is concentrated under reduced pressure or is atmospherically distilled to precipitation solid, removes trimethylamine and portion
Divide the components such as water, obtains glycine betaine-sodium chloride crystalline mother solution.
(2) above-mentioned mother liquor is preheated in preheater, is preheating to 90-100 DEG C of temperature, then crystallized in industrial evaporation
Concentration is evaporated in device, evaporating temperature is 95-100 DEG C, until stopping when the 50-70% of volume when mother liquor residual volume is preheating
It is concentrated by evaporation, is cooled to 50-60 DEG C, 5-10% isopropanol is added, obtain sodium chloride mixed crystal crude product and remaining mother liquor.It is separated by filtration
The crystal crude product of precipitation, wherein mainly containing sodium chloride and a small amount of glycine betaine；Gained filtrate be containing most of glycine betaine with
And the concentrated mother liquor of a small amount of sodium chloride (not higher than the 40wt% of sodium chloride total amount).
Wherein it is preferred to which the concentrating degree of the evaporative crystallization is to the 50-60% of pre-heated volume.
Optionally, chromatography detection filtrate in sodium chloride content, adjust isopropanol dosage control filtrate in sodium chloride content not
More than 10%, preferably more than 8%.
(3) gained mixed crystal crude product is added in 60-70 DEG C of dehydrated alcohol agitator treating 2-3 times, is wherein adulterated with removing
Glycine betaine filters simultaneously drying solid, obtains sodium chloride crude product, wherein 95% or more sodium chloride content；Then it will contain glycine betaine
Cleaning solution be merged into above-mentioned concentrated mother liquor filtrate, obtain the glycine betaine filtrate 1 containing a small amount of sodium chloride.
Optionally, the sodium chloride crude product also can be used and further be washed with dehydrated alcohol, further to remove surface adhesion
The trace impurities such as glycine betaine, sodium chloroacetate.
Step S2 is specific as follows:
(1) the glycine betaine filtrate 1 containing sodium chloride in above-mentioned steps is continued into evaporative crystallization simultaneously in crystallizing evaporator
Alcohol solvent is recycled, until filtrate volume stops evaporative crystallization when being 10-20%, filters, the filtrate of concentration is transferred to cooling knot
Brilliant kettle is in 0-5 DEG C of crystallisation by cooling, until all solids are precipitated completely, filtering, the solid that merging is obtained by filtration twice, 150-180 DEG C
Drying is glycine betaine-sodium chloride mixed crystal crude material of main component to get glycine betaine；Optionally, remaining crystalline mother solution can
To be merged into next group reaction mixture raw material or glycine betaine filtrate 1 with further multi-cycle separation.
(2) dehydrated alcohol is mixed in a certain ratio preparation with anhydrous methanol and separates solvent 1, by above-mentioned mixed crystal crude product and divided
Separation solvent is added in the ratio that exsolution agent mass ratio is 1:2-3, and continuously adds and account for separation total solvent volume 1-2% (v/v)
Deionized water is then heated to 60-65 DEG C to increase solution polarity, is thoroughly mixed 5-15min and is completely dissolved to glycine betaine,
It is centrifuged when remaining solid does not continue to dissolution or filters while hot, separatin non-soluble solid, obtained solid washs 2-3 with dehydrated alcohol
It is secondary, to remove the alkali solution of beet wherein adhered to, the ethyl alcohol after washing is merged into filtrate；Obtained solid dries drying, from
And obtain sodium chloride crystal product 1.
Wherein, volume ratio shared by dehydrated alcohol is 50-90%, preferably 70-90% in the separation solvent；
(3) the filtrate rotary evaporation concentration by above-mentioned containing glycine betaine and recycling design, 45 DEG C -50 DEG C of evaporating temperature, until brilliant
Concentrate is filtered and be dried to obtain glycine betaine crystal 1 in 0-4 DEG C of low temperature crystallization when body starts to be precipitated, by crystalline mother solution and is returned
The solvent of receipts merges, and the mixing alcoholic solvent containing anhydrous methanol and dehydrated alcohol component is distilled to recover, to obtain ethanol content more
High separation solvent 2, the concentration residue mother liquor after recycling design are spare.
Step S3 is specific as follows:
(1) the sodium chloride crude product that step (S1) obtains is added in the separation solvent 2 of above-mentioned recycling of 1-2 times of quality,
It is heated to 60-65 DEG C of temperature while stirring, is thoroughly mixed 10-15min；Then it is separated by filtration solid while hot, with anhydrous second
Alcohol washs solid product and drying, obtains sodium chloride crystal product 2.
(2) ethanol washes are merged into filtrate, and it is remaining female that the concentration in above-mentioned steps S2 after recycling design is added
Liquid is evaporated concentration using such as condensing Rotary Evaporators etc., and recycling design is precipitated with recycling to gained concentrate
Stop concentration after most of solid, in 0-5 DEG C of decrease temperature crystalline, filtering obtains glycine betaine crystal 2, and gained crystal is dry, and with
The glycine betaine crystal 1 of above-mentioned acquisition merges to obtain total glycine betaine crystalline product, and purity is up to 98% or more.
Preferably, the glycine betaine crystal of acquisition can be carried out recrystallization purifying 1-2 times, to obtain 99% or more purity
Glycine betaine crystal product is refined, residual rate of burning is lower than 0.3%, 226.7-227.6 DEG C of melting range.
Step S4 is specific as follows:
(1) sodium chloride crystal product 1 made from above-mentioned steps is mixed with sodium chloride crystal product 2, with 0.5-1 times of quality
55-60 DEG C of anhydrous methanol rinse or elution 1-2 time, recycling methanol, 150-180 DEG C of dry solid sodium chloride；
(2) 2-3 times of quality dehydrated alcohol is added in the solid sodium chloride after drying and heated, be heated to 75-78 DEG C of stirring
And boil and wash sodium chloride material 5-10min, it filters while hot, gained solid sodium chloride is dried into drying, and recycle alcohol solvent, gained
Sodium chloride content is up to 99% or more in solid；
(3) by the deionized water dissolving of 3-5 times of quality of the sodium chloride after washing and drying, it is stirred and heated to temperature
It 80-90 DEG C, is stirred well to and is completely dissolved, vacuum evaporation, until there is solid to be precipitated to obtain saturated solution；
(4) saturated solution is continued to be concentrated by evaporation to the 20-30% of saturated solution volume, stops being concentrated by evaporation, is cooled to room temperature
In 0-4 DEG C of low temperature crystallization, filtering, filtrate is continued evaporative crystallization and is precipitated completely to solid, and gained is crystallized and is dried, is refined
White sodium chloride crystal, wherein beet alkali content is no more than 0.4%, without recrystallization, can be directly used for feed applications.
The method of the present invention obtain sodium chloride crystal after refining purity be not less than 99.0%, purification efficiency up to 90% with
On.
Compared with prior art, the present invention at least has the following beneficial effects:
1. the method for the present invention purifies sodium chloride byproduct, compared with direct solvent partition method for crystallising, high with yield,
Product purity is high and feature that impurity content is low；In step s 2, creatively use the separation based on dehydrated alcohol molten
Agent is aided with the stronger deionized water of polarity of bigger polarity, the higher methanol of beet alkali solubility and 1-2% volume；Through trying
Verify bright, which is optimal separation dissolution combination, and effect is optimal.Wherein, test proves that sodium chloride is 96% or more
It is presence that is insoluble,practically, and separating the water of low content in solvent in the alcohol solvent of purity, compares anhydrous alcoholic solvent, then can
The dissolution for further promoting glycine betaine, makes it more effectively access filtrate, purity and yield are higher.
2. in mixed crystal purification step S2-S3, using gradient separations solvent method, i.e., by merge ethanol washes to by
The ethanol content in separation solvent is gradually increased, ethanol washes on the one hand can be recycled, on the other hand can guarantee sweet tea
Virose methanol content is gradually decreased on the basis of dish alkali highly dissoluble；It can more effectively realize glycine betaine and sodium chloride
Depth separation.
3. the method for the present invention cost is more compared with all kinds of methods such as conventional vacuum distillation method, ion-exchange, UF membrane
It is low, it is suitble to industrialization large scale processing, gained glycine betaine can reach 98% or more purity without recrystallization；After recrystallizing and refining
For glycine betaine purity up to 99% or more, sodium chloride content is not higher than 0.3%.And it gained sodium chloride crystal purity >=99.0%, mentions
Pure yield >=90% realizes glycine betaine product and efficiently separates and the recycling of the high-purity of sodium chloride.
4. method of purification of the present invention has low, easily operated, the solvent-free waste of simple process, production cost, to environment friend
The advantages that good, gained can be directly used in animal husbandry containing the sodium chloride of micro glycine betaine, compared to pure sodium chloride, have
The glycine betaine effect of additive and economic value of benefit.
5. the method for the present invention not only solves the environmental pollution of by-product salt, and takes full advantage of resource, in treatment process
The equal recoverable of solvent for use, filtered fluid is Ke Xunhuanliyong, therefore discharges without waste water and gas, does not form secondary pollution, and locate
It is low to manage process cost.
Specific embodiment
Below by specific preparation example and embodiment, the present invention is described in detail, but these exemplary embodiments
Purposes and purpose be only used to enumerate the present invention, any type of any limit not is constituted to real protection scope of the invention
It is fixed, it is more non-that protection scope of the present invention is confined to this.
The detailed description of preferred implementation method of the invention below and including embodiment can be more easily to understand it is of the invention
Content.Unless otherwise defined, all technologies used herein and scientific term have and fields ordinary skill of the present invention
The normally understood identical meaning of personnel.When there is a conflict, the definition in this specification shall prevail.
Embodiment 1
(1) glycine betaine is prepared after reaction, by the reaction mixture containing glycine betaine, sodium chloride and a small amount of trimethylamine
1.28kg is concentrated under reduced pressure into crystal precipitation, removes the components such as trimethylamine and water, obtains glycine betaine-sodium chloride crystalline mother solution；It will be upper
Mother liquor is stated to carry out being evaporated concentration, evaporating temperature 98 after being preheating to 90 DEG C of temperature in crystallizing evaporator in preheater
DEG C, until stopping being concentrated by evaporation when mother liquor volume is about half, 50 DEG C are cooled to, the isopropanol that 10% volume is added continues crystallization,
Sodium chloride coarse-grain and remaining mother liquor are obtained, solid is separated by filtration.It is 60 DEG C of dehydrated alcohol that obtained solid is first used to 180ml temperature
Washing, filtering, solid are washed with 60 DEG C of 120ml of dehydrated alcohol again, filter and obtained solid is dry, it is thick to obtain sodium chloride
Product about 121g, wherein ion chromatography measures sodium chloride content 96.3%；Then the ethanol washes containing glycine betaine are merged into
In above-mentioned residue mother liquid filtrate, glycine betaine filtrate 1 is obtained.
(2) above-mentioned glycine betaine filtrate 1 is continued into rotary evaporation crystallizer evaporative crystallization, and recycles ethyl alcohol, isopropanol
Solvent, until filtrate volume residue stops evaporative crystallization when being about 10%, filtering, and the filtrate of concentration is transferred to crystallisation by cooling kettle
It is precipitated, filters completely to solid in 5 DEG C of crystallisation by cooling, obtained solid is filtered in merging twice, dries at 150 DEG C to get glycine betaine
For glycine betaine-sodium chloride mixed crystal crude material 381g of main component；Remaining mother liquor is merged into the reaction in next group step (1)
To further separate in mixture material or glycine betaine filtrate 1.
(3) dehydrated alcohol is mixed by the volume ratio of 7:3 as solvent is separated with anhydrous methanol, above-mentioned mixed crystal crude product is added
Into 850ml separation solvent, and 15ml deionized water is added to increase solution polarity, is then heated to 62-63 DEG C and is sufficiently stirred
10min is mixed, filters while hot, separatin non-soluble solid sodium chloride, washs 2 glycine betaines to remove attachment removal with dehydrated alcohol,
Ethyl alcohol after washing is merged into filtrate；Obtained solid dries drying, to obtain sodium chloride crystal product 1.
The above-mentioned filtrate containing glycine betaine is evaporated under reduced pressure at 50 DEG C and is concentrated and recycles separation solvent, until crystal will after being precipitated
Concentrate filters and is dried to obtain glycine betaine crystal 1 in 0-4 DEG C of low temperature crystallization, and crystalline mother solution is merged with recovered solvent, steams
Mixing alcoholic solvent of the recycling containing anhydrous methanol and dehydrated alcohol component is evaporated, as separation solvent 2；Glycine betaine knot after recycling design
Brilliant mother liquor is spare.
(4) the sodium chloride crude product that step (1) obtains is added in the above-mentioned separation solvent 2 of 155g, is heated to while stirring
Temperature 60 C is thoroughly mixed 10min；Then it is separated by filtration solid sodium chloride while hot, washs solid product with dehydrated alcohol
And it is dry, obtain sodium chloride crystal product 2.Ethanol washes are merged into filtrate, and the sweet tea after above-mentioned recycling design is added
Dish alkali crystalline mother solution concentrate is concentrated by evaporation using condensing Rotary Evaporators, and recycling design is concentrated with recycling to gained
Liquid starts to stop concentration after solid is precipitated, and in 0 DEG C of decrease temperature crystalline, filtering obtains glycine betaine crystal 2, the beet with above-mentioned acquisition
Alkali crystal 1 merges, is dry, obtains total glycine betaine product 338.7g, and 226.7-227.6 DEG C of melting range, HPLC purity 98.6%.
(5) sodium chloride crystal product 1 made from above-mentioned steps is mixed with sodium chloride crystal product 2, with 0.5 times of quality
55 DEG C of anhydrous methanols rinse washing, recycle methanol, and in 180 DEG C of dry gained solid sodium chlorides；Sodium chloride after drying is consolidated
Body is added in 2 times of quality dehydrated alcohol and is heated to 75 DEG C, and stirring, which is boiled, washes sodium chloride material 5min, filters while hot, by gained
Solid sodium chloride dries drying, and recycles alcohol solvent.
(6) by the deionized water dissolving of 4 times of quality of the sodium chloride after washing and drying, 90 DEG C of temperature are heated to, sufficiently
To being completely dissolved, vacuum evaporation obtains saturated solution when until there is solid precipitation for stirring；Saturated solution is continued to be concentrated by evaporation to full
Stop being concentrated by evaporation with about the 30% of liquid product, in 0 DEG C of low temperature crystallization, filtering, filtrate is continued evaporative crystallization and analysed completely to solid
Out, it combining solid and dries, the sodium chloride crystal 159.6g, HPLC refined measures purity 99.4%, and wherein glycine betaine contains
Amount 0.32%, purification efficiency 91.4%.
Embodiment 2
(1) by the reaction mixture 132.7kg containing glycine betaine, sodium chloride and a small amount of trimethylamine in vacuum distillation tower into
Row distillation, tower top temperature is 65 DEG C, column bottom temperature is 95 DEG C, removes the components such as trimethylamine and water, obtains glycine betaine-sodium chloride knot
Brilliant mother liquor；Above-mentioned mother liquor is carried out to be preheating to after 95 DEG C of temperature in preheater be evaporated in industrial evaporation crystallizer it is dense
Contracting, evaporating temperature are 95 DEG C, until stopping being concentrated by evaporation when mother liquor volume is about half, are cooled to 50 DEG C, the different of 5% volume is added
Propyl alcohol continues crystallization, obtains sodium chloride coarse-grain and remaining mother liquor, is separated by filtration solid.Obtained solid is anhydrous with 60 DEG C of 18L
Ethanol washing filters, dry, obtains sodium chloride crude product；Then the ethanol washes containing glycine betaine are merged into above-mentioned residue
In mother liquid filtrate, glycine betaine filtrate 1 is obtained.
(2) above-mentioned glycine betaine filtrate 1 is crystallized in crystallizing evaporator, and recycles ethyl alcohol, isopropanol solvent, filtering gained
Crystalline mother solution after evaporative crystallization is transferred to crystallisation by cooling kettle in 0 DEG C of crystallisation by cooling by solid, and filtering merges and filters institute twice
Solid is obtained, it is dry, obtain glycine betaine-sodium chloride mixed crystal crude material 40.2kg.
(3) dehydrated alcohol is mixed by the volume ratio of 8:2 as solvent is separated with anhydrous methanol, above-mentioned mixed crystal crude product is added
Into 82L separation solvent, and 1.2L deionized water is added, is then heated to 65 DEG C of stirring 10min, filters separatin non-soluble while hot
Solid sodium chloride is washed to remove the glycine betaine of attachment removal with dehydrated alcohol, the ethyl alcohol after washing is merged into filtrate；Gained chlorine
Change sodium solid and dry drying, to obtain sodium chloride crystal product 1.The above-mentioned filtrate decompression containing glycine betaine is distilled and is recycled point
Exsolution agent, and the concentrate after crystal is precipitated is in 0-4 DEG C of continuation low temperature crystallization, is filtered and drying solid, obtains glycine betaine crystalline substance
Body 1 merges crystalline mother solution with recovered solvent, is distilled to recover the mixing alcoholic solvent containing anhydrous methanol and dehydrated alcohol component,
As separation solvent 2；Glycine betaine crystalline mother solution after recycling design is spare.
(4) the sodium chloride crude product that step (1) obtains is added in the above-mentioned separation solvent 2 of 16Kg, is heated to while stirring
Temperature 60 C is stirred 10min；Then it is separated by filtration solid sodium chloride while hot, washed with dehydrated alcohol and dries, obtains chlorine
Change sodium crystal product 2.Ethanol washes are merged into filtrate, and it is dense that the glycine betaine crystalline mother solution after above-mentioned recycling design is added
Mixed liquor is concentrated by evaporation simultaneously recycling design by contracting liquid, stops concentration, 0 DEG C of cooling knot after gained concentrate starts that solid is precipitated
Crystalline substance, filtering, obtains glycine betaine crystal 2, merges with the glycine betaine crystal 1 of above-mentioned acquisition, is dry, obtaining total glycine betaine product
35.3kg, HPLC purity 98.1%.
(5) sodium chloride crystal product 1 made from above-mentioned steps is mixed with sodium chloride crystal product 2, with 0.5 times of quality
55 DEG C of anhydrous methanols rinse washing, recycle methanol, and in 180 DEG C of dry gained solid sodium chlorides；Sodium chloride after drying is consolidated
Body is added in 2 times of quality dehydrated alcohol and is heated to 75 DEG C, and stirring, which is boiled, washes sodium chloride material 5min, filters while hot, by gained
Solid sodium chloride dries drying, and recycles alcohol solvent；
(6) by the deionized water dissolving of the sodium chloride 82.6Kg after washing and drying, 90 DEG C of temperature is heated to, is sufficiently stirred
It mixes to being completely dissolved, vacuum evaporation, in 0 DEG C of low temperature crystallization, filters, filtrate until stopping being concentrated by evaporation when concentrate about 25L
Continue evaporative crystallization to be precipitated completely to solid sodium chloride, combining solid is simultaneously dried, and the sodium chloride crystal of purity 99.1% is obtained
16.8kg, HPLC measure beet alkali content 0.38%, purification efficiency 90.8%.
Comparative example 1
(that is, by anti-other than glycine betaine-sodium chloride mixed crystal being obtained with direct evaporative crystallization to replace step (1)-(2)
Answer product mixture to be directly concentrated by evaporation and obtain glycine betaine-sodium chloride mixed crystal product, without including pre-separation sodium chloride step),
Remaining step is same as Example 1, so that comparative example 1 is implemented, beet alkali content in obtained sodium chloride crystal
2.86%.
Comparative example 2
Other than separation solvent is replaced with the dehydrated alcohol of equivalent and is added without deionized water increasing, remaining step and reality
It is identical to apply example 1, so that comparative example 2 is implemented, beet alkali content 1.17% in obtained sodium chloride crystal.
Comparative example 3
In addition to without containing other than step (5) (that is, methanol flushing-ethyl alcohol without sodium chloride crystal product boils and washes operation, and
It is directly to recrystallize combined sodium chloride product), remaining step is same as Example 1, so that comparative example 3 is implemented,
Beet alkali content 1.68% in obtained sodium chloride crystal.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (8)
1. the process for separation and purification of side product chlorinated sodium in a kind of glycine betaine/beet alkali hydrochlorate production process, including reaction solution
Pre-separation processing, glycine betaine and the separation of sodium chloride mixed crystal crude product, secondary purification separation and glycine betaine merge purifying and sodium chloride
Merge the processes such as purification and purification；Characterized by comprising the following steps:
Step S1: it will be concentrated under reduced pressure or be evaporated in vacuo containing the reaction mixture of glycine betaine, sodium chloride and a small amount of trimethylamine, obtain
Glycine betaine-sodium chloride crystalline mother solution；Crystalline mother solution is tentatively concentrated by evaporation and is added a small amount of isopropanol, and it is thick to obtain sodium chloride mixed crystal
Product obtain sodium chloride primary dcreening operation crude product with 60-70 DEG C of dehydrated alcohol washing impurity-removing；
Step S2: carrying out condensing crystallizing for the mother liquor after Isolating chlorinated sodium mixed crystal crude product, obtains glycine betaine-sodium chloride crude product and produces
Object is dissolved with separation solvent 1 and separates the solid sodium chloride in above-mentioned crude material to obtain sodium chloride crystal product 1；
Step S3: sodium chloride primary dcreening operation crude product is added in separation solvent 2, heating stirring is separated by filtration solid, anhydrous second while hot
Alcohol is washed and is dried, and obtains sodium chloride crystal product 2；
Step S4: sodium chloride crystal product 1 is merged with sodium chloride crystal product 2, and anhydrous methanol rinses or elution, uses nothing later
Water-ethanol boils washing material 5-10min, filters while hot, recrystallizing and refining.
2. the method according to claim 1, wherein detailed process is as follows by the step S1:
(1) it is being that chemically prepares glycine betaine after reaction with monoxone, trimethylamine etc., product mixture is being contained
The reaction mixture of glycine betaine, sodium chloride and a small amount of trimethylamine is concentrated under reduced pressure or is atmospherically distilled to precipitation solid, removes trimethylamine
With the components such as part water, glycine betaine-sodium chloride crystalline mother solution is obtained；
(2) above-mentioned mother liquor is preheated in preheater, is preheating to 90-100 DEG C of temperature, then carried out in crystallizing evaporator
It being concentrated by evaporation, evaporating temperature is 95-100 DEG C, until stop concentration when mother liquor residual volume is preheating when the 50-70% of volume, it is cold
But to 50-60 DEG C, 5-10% isopropanol is added, obtains sodium chloride mixed crystal crude product and remaining mother liquor；
(3) it is separated by filtration the solid crude product of precipitation, wherein mainly containing sodium chloride, and the impurity such as a small amount of glycine betaine；By gained
Mixed crystal crude product is added in 60-70 DEG C of dehydrated alcohol agitator treating 2-3 times, to remove the organic components such as the glycine betaine wherein adulterated,
Simultaneously drying solid is filtered, sodium chloride crude product is obtained；Cleaning solution containing glycine betaine is merged into above-mentioned filtrate, glycine betaine is obtained
Filtrate 1.
3. according to the method described in claim 2, it is characterized in that, controlling the degree of the evaporative crystallization to remaining concentrated liquid
The 50-60% of volume when product is preheats.
4. the method according to claim 1, wherein detailed process is as follows by the step S2:
(1) the glycine betaine filtrate 1 in above-mentioned steps is continued to evaporative crystallization in crystallizing evaporator and recycles alcohol solvent, until filter
Liquid product stops evaporative crystallization when being 10-20%, filters, and the filtrate of concentration is transferred to crystallisation by cooling kettle in 0-5 DEG C of cooling knot
Crystalline substance, until all solids are precipitated completely, filtering merges the solid being obtained by filtration twice, and 150-180 DEG C of drying obtains glycine betaine-chlorination
Sodium mixed crystal crude material；
(2) by dehydrated alcohol, example mixed preparing separates solvent 1 according to a certain volume with anhydrous methanol, by above-mentioned mixed crystal crude product and divides
Separation solvent 1 is added in the ratio that exsolution agent mass ratio is 1:2-3, and the deionized water for accounting for separation total solvent volume 1-2% is added
To increase solution polarity, it is then heated to 60-65 DEG C, is thoroughly mixed 5-15min, separatin non-soluble solid, obtained solid
It is washed 2-3 times with dehydrated alcohol, to remove the alkali solution of beet of attachment removal, the ethyl alcohol after washing is merged into filtrate；Gained is solid
Body dries drying, obtains sodium chloride crystal product 1；
(3) filtrate by above-mentioned containing glycine betaine is concentrated by evaporation simultaneously recycling design, and 45-50 DEG C of evaporating temperature, crystal will be dense when being precipitated
Contracting liquid filters and is dried to obtain glycine betaine crystal 1 in 0-4 DEG C of low temperature crystallization, and crystalline mother solution is merged with recovered solvent, recycling
Mixing alcoholic solvent containing methanol and ethanol component, it is spare as separation solvent 2.
5. according to the method described in claim 4, it is characterized in that, separating body shared by dehydrated alcohol in solvent 1 as described in wherein
Product is than being 50-90%, preferably 70-90%.
6. the method according to claim 1, wherein detailed process is as follows by the step S3:
(1) the sodium chloride crude product that step (S1) obtains is added in the separation solvent 2 of 1-2 times of quality, is heated to while stirring
60-65 DEG C of temperature, it is thoroughly mixed 10-15min；Then it is separated by filtration solid while hot, washs solid product with dehydrated alcohol
And it is dry, obtain sodium chloride crystal product 2；
(2) ethanol washes are merged into filtrate, are concentrated by evaporation and recycling design is to recycle, is precipitated to gained concentrate
Stop concentration after big semisolid, in 0-5 DEG C of decrease temperature crystalline, filtering obtains glycine betaine crystal 2, brilliant with the glycine betaine of above-mentioned acquisition
Body 1 merges dry to obtain total glycine betaine product.
7. the method according to claim 1, wherein detailed process is as follows by the step S4:
(1) sodium chloride crystal product 1 made from above-mentioned steps is mixed with sodium chloride crystal product 2, with 55-60 DEG C of anhydrous methanol
It rinses or elutes 1-2 times, recycle methanol, the solid sodium chloride being dried to obtain；
(2) solid sodium chloride after drying is added to absolute ethanol and is heated to 75-78 DEG C, stirring, which is boiled, washes sodium chloride material 5-
10min is filtered while hot, gained solid sodium chloride is dried drying, and recycle alcohol solvent；
(3) by the deionized water dissolving of 3-5 times of quality of the sodium chloride after washing and drying, it is stirred and heated to temperature 80-90
DEG C, it is stirred well to and is completely dissolved, vacuum evaporation is precipitated to obtain saturated solution to solid；
(4) saturated solution is continued to be concentrated by evaporation to the 20-30% of saturated solution volume, stops being concentrated by evaporation, is cooled to room temperature in 0-4
DEG C low temperature crystallization, filtering, filtrate are continued evaporative crystallization and are precipitated completely to solid, gained is crystallized and is dried, the feed refined
Grade sodium chloride crystal, wherein beet alkali content is no more than 0.4%.
8. the purposes that the sodium chloride containing micro glycine betaine that -7 the methods obtain according to claim 1 is used for feed.
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| CN112174843A (en) * | 2020-10-10 | 2021-01-05 | 衢州学院 | Preparation method for low-ignition residue betaine hydrochloride and co-production sodium fluosilicate |
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| CN114835157A (en) * | 2022-04-20 | 2022-08-02 | 柳州华锡有色设计研究院有限责任公司 | Method for reducing chloride ion content in sodium stannate production process |
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