CN108003015A - The process for refining and purifying of Long carbon chain dicarboxylic acids - Google Patents
The process for refining and purifying of Long carbon chain dicarboxylic acids Download PDFInfo
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- CN108003015A CN108003015A CN201711410722.4A CN201711410722A CN108003015A CN 108003015 A CN108003015 A CN 108003015A CN 201711410722 A CN201711410722 A CN 201711410722A CN 108003015 A CN108003015 A CN 108003015A
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- filter cake
- acetic acid
- acid
- water
- dicarboxylic acids
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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
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
Abstract
The present invention is the process for refining and purifying of Long carbon chain dicarboxylic acids, it is characterised in that control long-chain biatomic acid crude material moisture≤1.0wt%；Solvent acetic acid content >=95.0wt%；Crystallization processes use three sections of gradient coolings, and induction crystal seed is added after second segment cooling, induction crystallization；Crystalli-zation cake acetic acid first elutes, then through water wash, centrifugal filtration；Then filter cake water washing at ambient temperature；The method that the acetic acid solvent that subtractive process produces uses azeotropic distillation, all recycling, recycles；The cleaning solution and mother liquor that subtractive process produces recycle completely, recycle.It is high to provide a kind of product yield, refined cost is relatively low, the process for refining and purifying of the Long carbon chain dicarboxylic acids of high-purity.Long carbochain biatomic acid total acid content after refined purification reaches 99.90%, and mono-acid content reaches 99.45%, and total nitrogen reaches 6ppm, and iron ion content reaches 0.5ppm, and content of ashes≤10ppm, water capacity≤0.16%, reaches 0.16%.Purification comprehensive yield reaches 98.64%.Every quality and technical index meets user demand.
Description
Technical field
The present invention is a kind of process for refining and purifying of Long carbon chain dicarboxylic acids.Belonging to has acyclic the two of more than 10 carbon atoms
The purification process of first carboxylic acid.
Background technology
It is former containing more than 10 carbon in Long carbon chain dicarboxylic acids (along-chain dicarboxylic acid)-carbochain
The straight-chain dicarboxylic acid of son, is a kind of important fine chemical product.For synthesizing polyamides resin, polyester resin, hot melt adhesive,
The primary raw material of the products such as spices, weatherability plasticizer, lube oil additive, coating, liquid crystal.
Main commercial Application includes synthetic musk ketone；The coil adhesive of the long-time service at 100 DEG C；Garment setting
Use thermosol；Fire-resistant lubricants can not only be manufactured, moreover it is possible to which manufacture can realize the profit of effectively lubricating under -45 DEG C of low temperature
Lubrication prescription；The high-performance coating manufactured with long carbochain biatomic acid has bright in color, wearability is good, impact strength is high, adhesive force
By force, the features such as pliability is good, long-time UV resistant irradiates.Suitable for car and upholstered furniture, national defence tent and military operation
And means of transport coating.Long carbochain biatomic acid can also synthesize the excellent plasticizer of cold tolerance, add this plasticizer manufacture
Plastic film can be used for a long time in cold environment.
Nylon is a kind of high-molecular compound for containing acid amides group (- NHCO-) on molecular backbone.Due to nylon molecules knot
Contain a large amount of amide groups in structure, macromolecular end is amino or carboxyl, so be a kind of highly polar, intermolecular energy formed hydrogen bond and
Crystalline polymer with certain reactivity.Nylon is five large-engineering plastics (nylon, polyformaldehyde, makrolon, polyphenyl
Ether, polybutylene terephthalate (PBT)) in consumption is maximum, kind at most, one kind that purposes is most wide, qualification is oldest,
The distinctive molecular machinery of long-chain nylon, assigns its good comprehensive performance, and intensity is higher than metal, excellent mechanicalness
Energy, heat resistance, wear resistance, chemical resistance, anti-flammability and self lubricity, friction coefficient is low and is easily worked, it can add
Work be made various plastic products, can also wire drawing fiber is made, film, coating and adhesive etc. can also be made.It is widely used in
The field such as automobile, electric, mechanical, communication, military and aerospace.
Using Long carbon chain dicarboxylic acids as raw material, the Long carbon chain Buddhist nun that polycondensation reaction synthesizes occurs as polycondensation monomer and diamine
Dragon, mainly have nylon 11, nylon 12, nylon 612, nylon 11 11, nylon 11 12, nylon 1212, nylon 1213, nylon 1314,
Nylon 1414, nylon 512 and nylon 614 etc..
In recent years, demand of the long carbochain biatomic acid on international and domestic market increases sharply, and rises year by year.Moreover,
Requirement to the various technical performance indexs of product quality is continuously improved, increasingly harsher.Commercially available long carbochain biatomic acid cannot meet
The requirement of long-chain nylon and other downstream product to the technical indicator of its purity and presentation quality each side.
Long carbon chain dicarboxylic acids, nature are not present, and mainly using organic synthesis method, prepared by biological fermentation process, using having
Machine synthetic method, process route length is of high cost, yield is low, and there are security risk and pollution environment.
Biological fermentation process is mainly with C11~C18N-alkane is raw material, is fermented by Candida, by single alkane transformations
Into long-chain biatomic acid, then through thick purification and refine, obtain long-chain biatomic acid crystalline product.The normal alkane is fractionated in petroleum refining
What is gone out contains carbon atom C11~C18Component, be using urea technique to oil carry out degreasing obtained by accessory substance, be commonly called as liquid
Paraffin.Therefore, the long-chain biatomic acid of method production has that raw material sources are wide, simple production process, and investment is small, production cost is low.
Therefore, presently commercially available long carbochain biatomic acid is mostly the product of biological fermentation process production.
Due to containing the impurity such as a small amount of mycoprotein, pigment, ferric ion compounds in tunning, product is seriously affected
Purity and appearance.Therefore, polishing purification technique is the vital link that microbial fermentation prepares Long carbon chain dicarboxylic acids.
The Long carbon chain dicarboxylic acids of Production by Microorganism Fermentation, mainly carries out purification essence using solvent method by recrystallizing
System.Solvent is mainly using acetic acid and methanol etc..Experiment and production practices show, no matter Refining times, refining solvent dosage and
In crystalline product purity, acetic acid is better than other organic solvents.
In the prior art, the long-chain biatomic acid crude product prepared using fermentation method as raw material, use the acetic acid of more than 90wt% for
Solvent, is decolourized, is filtered first, and filtrate cooling, Crystallization Separation, gained filter cake keep the temperature 120 points in 70 DEG C~100 DEG C hot water
Clock, cools down 20 DEG C~30 DEG C, centrifuges, drying.There are following deficiency：
1. dissolving, bleaching workshop section directly use the long-chain biatomic acid crude product of water content 5wt%~25wt% as raw material, solvent
Using more than 90% acetic acid aqueous solution.The moisture brought into raw material and solvent, reduces acetic acid for long-chain biatomic acid crude product
And the solubility property of some impurity wherein mixed.Cause some impurity by it is atomic it is short grained in the form of enter solution to be crystallized,
In crystallization process, under proper temperature, these impurity molecules become crystal seed, cause heterogeneous nucleation phenomenon to produce, are wrapped by
In long-chain biatomic acid crystallization.Removal to impurity adds difficulty.Meanwhile the purification for also reducing long carbochain biatomic acid is received
Rate.
2. cool down spontaneous nucleation method, the crystalline mother solution remained in decoloration filter cake also is not replaced out, that is, carries out high temperature
Water washing, when a large amount of water are contacted with the crystalline mother solution remained in filter cake, due to the deliquescent influence of water Dichlorodiphenyl Acetate, makes in mother liquor
Dissolved impurity moment separates out, and residues in filter cake and is difficult to remove in subsequent technique.
3. high temperature water washing simply accelerates washing speed, more impurity, refining effect can not be washed off than room temperature
It is little, and thermal energy is consumed, add wastewater discharge.Improve production cost.
4. containing the Long carbon chain dicarboxylic acids of about 5wt%~6wt% in the mother liquor after decoloration crystallization, separation, this part is female
Liquid is unprocessed, is sent directly into rectifying column and carries out rectifying, has discarded the raw material in mother liquor.Product yield is reduced, improves life
Produce cost.
Since the prior art has deficiency above, so long-chain biatomic acid product total acid content and mono-acid content after refined
It is not high enough, it is impossible to meet that long-chain nylon i.e. biological poly nylon industry is wanted for the harsh of long-chain biatomic acid product purity
Ask.
A kind of product yield is high, and refined cost is relatively low, and the process for refining and purifying of the Long carbon chain dicarboxylic acids of high-purity is people
Expected.
The content of the invention
It is an object of the invention to avoid above-mentioned shortcoming of the prior art, and a kind of product yield height is provided, essence
Relatively low a, process for refining and purifying for the Long carbon chain dicarboxylic acids of high-purity is made.
The purpose of the present invention can be reached by following measure：
The process for refining and purifying of the Long carbon chain dicarboxylic acids of the present invention, using long-chain biatomic acid crude product prepared by fermentation method as original
Material, uses acetic acid as solvent, and refined purification is handled by recrystallizing, including dissolving, decolorization filtering, decrease temperature crystalline, centrifugal filtration,
Washing of Filter Cake and stoving process step, it is characterised in that：
1. long-chain biatomic acid crude material described in is after drying to moisture≤1.0wt%, anti-into dissolving, decoloration
Answer kettle；Solvent acetic acid content >=the 95.0wt%；
2. decolorization filtering described in uses two-stage above Multistage filtering device；
3. decrease temperature crystalline technique is described in, using three sections of gradient coolings, and induction crystal seed is added after second segment cooling,
Induction crystallization, centrifugal filtration；
4. Washing of Filter Cake step is described in, acetic acid elutes first, then after water wash, centrifugal filtration；Then filter cake is in ring
Water washing at a temperature of border；
5. the method that the acetic acid solvent that subtractive processes produce uses azeotropic distillation, all recycling, recycles；
6. cleaning solution and mother liquor that subtractive processes produce recycle completely, recycle.
Long-chain biatomic acid crude material is vacuum dried to after moisture≤1.0wt%, into dissolving, decoloring reaction
Kettle；Solvent acetic acid content >=the 95.0wt%；It is the technical characteristic that outstanding contributions are made for completing the task of the present invention.It is logical
Cross by the control of Long carbon chain dicarboxylic acids crude product moisture within 1%, acetic acid Pureness control significantly improves solvent more than 95%
Acetic acid improves Long carbon chain binary to Long carbon chain dicarboxylic acids and the dissolubility of soluble impurity component in crude product from source
The refined yield of carboxylic acid, avoids of the prior art, and some undissolved good impurity molecules become in crystallization process
Crystal seed, caused heterogeneous nucleation phenomenon produce.So as to improve purification effect.
Reduce heterogeneous nucleation problem of the Long carbon chain dicarboxylic acids solution in decrease temperature crystalline, reduce crystals impurity
Covering amount, not only improve crystal habit, but also improve purity.
Decolorization filtering uses two-stage above Multistage filtering device, retained to greatest extent dissolving bleaching workshop section because raw material,
All impurity that solvent and decolorising agent are brought into, further increase purification effect.
In crystallization process, using three sections of gradient coolings, and induction crystal seed is added after second segment cooling, induction crystallization,
Centrifugal filtration；It is the technical characteristic that outstanding contributions are made for completing the task of the present invention.
Heterogeneous nucleation problem of the Long carbon chain binary carboxylic solution in decrease temperature crystalline is avoided, reduces crystals impurity
Covering amount, the crystal grain increase of formation, and also crystal form is more regular, is undoubtedly beneficial to the raising of product purity.
Washing of Filter Cake step after crystallization is that acetic acid elutes first, then through water wash；Filter cake at ambient temperature, is washed
Wash；Operating procedure method, be to make the technical characteristics of outstanding contributions for completing the task of the present invention.
Filter cake is first eluted in centrifuge with acetic acid, displaces remaining crystalline mother solution in filter cake, then with water wash,
Most acetic acid in filter cake is displaced, then through centrifugal filtration, filter cake is through room temperature water washing.Successfully solve the prior art
In, the crystalline mother solution remained in decoloration filter cake also is not replaced out, that is, carries out high temperature water washing, a large amount of water are with remaining in filter
When crystalline mother solution in cake contacts, due to the deliquescent influence of water Dichlorodiphenyl Acetate, separate out dissolved impurity moment in mother liquor, residual
It is difficult to the technical problem removed in subsequent technique in filter cake.Substantially increase the purity of product.Refined yield is also improved,
Energy consumption is reduced, while reduces production cost.
The method that the acetic acid solvent that subtractive process produces uses azeotropic distillation, all recycling, recycles；Subtractive process is produced
Raw cleaning solution and mother liquor recycles completely, recycles.Raw material and water resource have been saved, has reduced production cost, has been reduced useless
The load of water process, environmentally friendly protection.
The purpose of the present invention can also be reached by following measure：
The process for refining and purifying of the Long carbon chain dicarboxylic acids of the present invention, the Long carbon chain dicarboxylic acids is C11~C18Directly
Chain dicarboxylic acids.
The process for refining and purifying of the Long carbon chain dicarboxylic acids of the present invention, 1. described in solvent acetic acid described in 4.
Acetic acid is recycled, insufficient section is supplied with industrial acetic.It is preferable technical solution.
The present invention Long carbon chain dicarboxylic acids process for refining and purifying, 2. described in decolorization filtering using level Four filtering behaviour
Make, the material after decoloration, successively successively using closed delivery plate and frame filter press, bag filter, metal stud filter, stacking
Formula filter level Four filters, separation of solid and liquid, and filtrate is sent into crystallization kettle.It is preferable technical solution.
The present invention Long carbon chain dicarboxylic acids process for refining and purifying, 3. described in induction crystal seed be more than or equal to for purity
99.8% refined long carbochain biatomic acid, induction seed load is the 0.1%~1% of long-chain binary hydroxy acid crude product dosage.
It is preferable technical solution.
The process for refining and purifying of the Long carbon chain dicarboxylic acids of the present invention, it is characterised in that three sections of gradient coolings described in 3.
It is：
A. one section of cooling
Under stirring, interlayer temperature lowering water is opened, the filtrate after decolorization is down to 75 DEG C~80 DEG C；
B. two sections of coolings, induction crystallization
Under stirring, after being naturally cooling to 71 DEG C~75 DEG C, long carbochain biatomic acid induction crystal seed is added, then proceedes to nature drop
Temperature is to 68 DEG C~70 DEG C；
C. three sections of coolings
Interlayer temperature lowering water is opened, adjusts cooling water flow, crystallization feed temperature is down to 20 DEG C~30 DEG C.
It is preferable technical solution.
The process for refining and purifying of the Long carbon chain dicarboxylic acids of the present invention, it is characterised in that the side of the azeotropic distillation described in 4.
Method is using isopropyl acetate as azeotropy dehydrant.It is a preferable technical solution.
The process for refining and purifying of the Long carbon chain dicarboxylic acids of the present invention, it is characterised in that produced in the subtractive process described in 5.
Raw cleaning solution and mother liquor recycling method be：
A. crystalline mother solution is all collected, filtered, and filtrate enters acetic acid solvent azeotropic distillation recovery system；Filter cake is as binary
Acid crude raw material is reused；
B. 4. described in Washing of Filter Cake step in, through acetic acid elution produce washing and centrifuge mother liquor, be directly used as molten
Solution, decoloration solvent, recycle；
C. 4. described in again after water wash, centrifugal filtration, the washing of generation and centrifuge mother liquor are all collected, filtering,
Filtrate enters acetic acid solvent azeotropic distillation recovery system；Filter cake is reused as binary acid crude material；
D. 4. described in filter cake at ambient temperature, after water washing, centrifugal filtration, caused filtrate be used as lower batch 4. in
The water wash is washed with water, recycling.It is preferable technical solution.
The process for refining and purifying of the Long carbon chain dicarboxylic acids of the present invention, it is characterised in that include the following steps：
1. dissolvings, decoloration
At room temperature, by long-chain binary hydroxy acid crude product, acetic acid, activated carbon input decoloring reaction kettle, 90~95 DEG C are warming up to,
Insulation 10~30 minutes, successively through closed delivery plate and frame filter press, bag filter, metal stud filter, cascading type filter
Level Four filters, separation of solid and liquid, and filtrate is sent into crystallization kettle, standby crystallization.
The mass ratio that feeds intake is as follows：
Dicarboxylic acids crude product：Solvent (mass ratio) 1：2.2~3.5
Activated carbon：Dicarboxylic acids crude product (mass ratio) 1：60~150
2. gradient coolings, induction crystallization
A. one section of cooling
In crystallization kettle, under stirring, interlayer temperature lowering water is opened, the decoloration filtrate from step 1. is down to 75 DEG C~80
℃；
B. two sections of coolings, induction crystallization
Under stirring, after being naturally cooling to 71 DEG C~75 DEG C, long carbochain biatomic acid induction crystal seed is added, then proceedes to nature drop
Temperature is to 68 DEG C~70 DEG C；
C. three sections of coolings
Interlayer temperature lowering water is opened, adjusts cooling water flow, crystallization feed temperature is down to 20 DEG C~30 DEG C；
D. centrifuge, filter
From the complete material of crystallization c above-mentioned, centrifugal filtration；The standby elution of filter cake, mother liquor are all collected, filtered, filter
Liquid enters acetic acid solvent azeotropic distillation recovery system；Filter cake is reused as binary acid crude material；
3. centrifugal filtrations, elution
A. acetic acid elutes
Filter cake after 2. step centrifuges, in centrifuge, first with a small amount of acetic acid elute, lessivation produce from
Heart mother liquor, is directly used in dissolving, decoloration solvent, recycles；Filter cake after drying stays in standby deionized water in centrifuge and elutes；
Elute acetic acid dosage for step 1. acetic acid dosage 5%~100%.
B. water wash
Filter cake in centrifuge, the centrifuge mother liquor 4. produced with deionized water or subsequent step elute, again centrifuge dripping
Afterwards, filter cake is washed for room temperature and used；Cleaning solution, the mother liquor produced in lessivation is all collected, filtering, and filtrate enters acetic acid solvent
Azeotropic distillation recovery system；Filter cake is reused as binary acid crude material；
4. room temperatures are washed, centrifugation
Filter cake from step 3., after slurries are made with deionized water, is sent into water washing tank, adds deionized water and is stirred
Washing 30 minutes, centrifugal filtration, separation of solid and liquid, filter cake are standby dry；Filtrate is used as elution of the lower batch of production stage 3. needed for b and uses
Water, recycles；
Add in water washing tank the amount of pure water for step 1. quality of acetic acid used 70%~120%；
5. is dried
The filter cake drying of step 4., obtains refined long carbochain biatomic acid；
Long carbon chain dicarboxylic acids after purification reaches following technical indicator：
The process for refining and purifying of the Long carbon chain dicarboxylic acids of the present invention, it is characterised in that include the following steps：
1. dissolvings, decoloration
At room temperature, by long-chain binary hydroxy acid crude product, acetic acid, activated carbon input decoloring reaction kettle, 90~95 DEG C are warming up to,
Insulation 10~30 minutes, successively through closed delivery plate and frame filter press, bag filter, metal stud filter, cascading type filter
Level Four filters, separation of solid and liquid, and filtrate is sent into crystallization kettle, standby crystallization.
The mass ratio that feeds intake is as follows：
Dicarboxylic acids crude product：Solvent (mass ratio) 1：2.5~3.5
Activated carbon：Dicarboxylic acids crude product (mass ratio) 1：80~100
2. gradient coolings, induction crystallization
A. one section of cooling
In crystallization kettle, under stirring, interlayer temperature lowering water is opened, the decoloration filtrate from step 1. is down to 77 DEG C；
B. two sections of coolings, induction crystallization
Under stirring, after being naturally cooling to 74 DEG C, long carbochain biatomic acid induction crystal seed is added, then proceedes to be cooled to 68 DEG C；
C. three sections of coolings
Interlayer temperature lowering water is opened, adjusts cooling water flow, crystallization feed temperature is down to 25 DEG C~30 DEG C；
D. centrifuge, filter
From the complete material of crystallization c above-mentioned, centrifugal filtration；The standby elution of filter cake, mother liquor are all collected, filtered, filter
Liquid enters acetic acid solvent azeotropic distillation recovery system；Filter cake is reused as binary acid crude material；
3. centrifugal filtrations, elution
A. acetic acid elutes
Filter cake after 2. step centrifuges, in centrifuge, first with a small amount of acetic acid elute, lessivation produce from
Heart mother liquor, is directly used in dissolving, decoloration solvent, recycles；Filter cake after drying stays in standby deionized water in centrifuge and elutes；
Elute acetic acid dosage for step 1. acetic acid dosage 5%~100%.
B. water wash
Filter cake in centrifuge, the centrifuge mother liquor 4. produced with deionized water or subsequent step elute, again centrifuge dripping
Afterwards, filter cake is washed for room temperature and used；Cleaning solution, the mother liquor produced in lessivation is all collected, filtering, and filtrate enters acetic acid solvent
Azeotropic distillation recovery system；Filter cake is reused as binary acid crude material；
4. room temperatures are washed, centrifugation
Filter cake from step 3., after slurries are made with deionized water, is sent into water washing tank, adds deionized water and is stirred
Wash half an hour, centrifugal filtration, separation of solid and liquid, filter cake is standby dry；Filtrate is used as elution of the lower batch of production stage 3. needed for b and uses
Water, recycles；
Add in water washing tank the amount of pure water for step 1. quality of acetic acid used 70%~120%；
5. is dried
The filter cake drying of step 4., obtains refined long carbochain biatomic acid；
Long carbon chain dicarboxylic acids after purification reaches following technical indicator：
It is optimal technical solution.
The process for refining and purifying of the Long carbon chain dicarboxylic acids of the present invention, it is characterised in that the step 5. described drying dress
Put and use vacuum dryer or blade drier.
Technical solution disclosed in the process for refining and purifying of the Long carbon chain dicarboxylic acids of the present invention, can produce compared with prior art
Raw following good effect：
1. it is high to provide a kind of product yield, refined cost is relatively low, the refined purification of the Long carbon chain dicarboxylic acids of high-purity
Method.
2. by the way that by the control of Long carbon chain dicarboxylic acids crude product moisture, within 1%, acetic acid Pureness control subtracts more than 95%
Lack heterogeneous nucleation problem of the Long carbon chain dicarboxylic acids solution in decrease temperature crystalline, reduce the covering amount of crystals impurity,
Not only crystal habit is improved, but also improves purity.
3.. decolorization filtering uses two-stage above Multistage filtering device, has retained dissolving bleaching workshop section to greatest extent because of original
All impurity that material, solvent and decolorising agent are brought into, further increase purification effect.
4. in crystallization process, using three sections of gradient coolings, and induction crystal seed is added after second segment cooling, induction knot
Crystalline substance, centrifugal filtration；Heterogeneous nucleation problem of the Long carbon chain binary carboxylic solution in decrease temperature crystalline is further avoid, reduces crystal
The covering amount of internal impurity, the crystal grain increase of formation, and also crystal form is more regular, is undoubtedly beneficial to the raising of product purity.
5. crystallization filtering gained filter cake, in centrifuge, is first eluted with acetic acid, it is female to displace remaining crystallization in filter cake
Liquid, then with water wash, displaces most acetic acid in filter cake, then through centrifugal filtration, improve washing effect, improve production
Product purity.
6. the method that the acetic acid solvent that subtractive process produces uses azeotropic distillation, all recycling, recycles；Subtractive process
The cleaning solution and mother liquor of generation recycle completely, recycle.Raw material and water resource have been saved, has reduced production cost, has been reduced
The load of wastewater treatment, environmentally friendly protection.
7 improve the purity of product, and total acid content >=99.80%, reaches 99.90%；Mono-acid content >=99.36%, reaches
To 99.45%；Total nitrogen content≤10ppm, reaches 6ppm；Iron ion content≤0.6ppm, reaches 0.5ppm；Content of ashes≤
10ppm, water capacity≤0.16%, reaches 0.16%.It is >=98.5% to purify comprehensive yield, reaches 98.64%.Every quality skill
Art index meets user demand.
Embodiment
The present invention will now be further detailed embodiment：
Embodiment 1
A kind of process for refining and purifying of dodecanedioic acid of the present invention
In 3000L dissolves decoloring reaction kettle, 98% acetic acid solution 2000L, dodecanedioic acid crude product 800kg are put into,
Activated carbon 6kg, stirs evenly, and is warming up to 95 DEG C, 20 minutes is kept the temperature, through closed delivery plate and frame filter press, bag filter, metal stud
The dodecanedioic acid solution that filter, cascading type filter level Four filtration system are obtained by filtration enters crystallization kettle, in crystallization kettle
Quick uniform is cooled to 78 DEG C, closes temperature lowering water, is naturally cooling to 75 DEG C, adds dodecanedioic acid of the purity more than 99.8% and makees
For crystal seed, mixing speed 40r/min is controlled, crystallization temperature in the kettle recoils to 77 DEG C, then progressively declines, temperature drops to naturally
At 68 DEG C, temperature lowering water is slowly opened, control cooling rate is finally cooled to 25 DEG C, whole temperature-fall period control drop by slow-to-fast
When warm time 6~8 is small.Crystal solution centrifuges, and is used when filtrate is for disposing mother liquor, and filter cake, which stays in, uses 200L purity in centrifuge
98% acetic acid solution is eluted, and is centrifuged 15 minutes after elution, filtrate makees the solvent of material addition step for lower production cycle
With；Filter cake in centrifuge is eluted with 2000L deionized waters again, is centrifuged 15 minutes after elution, filtrate is returned for mother liquor
Time receiving uses.The filter cake of material solid content 84% is obtained, filter cake is squeezed into room temperature with pump after being sized mixing with 1200L deionized waters and washed
Tank, adds deionized water 800L, stirs half an hour, centrifugal filtration, and filtrate is used for lower production cycle elution centrifuge；Filter cake is through bipyramid
Vacuum drier is dried to obtain refined dodecanedioic acid 680kg.Neutralization titration surveys total acid content 99.86%, gas chromatography
Survey mono-acid content 99.38%, total nitrogen content 10ppm, iron ion content 0.5ppm, content of ashes 10ppm, water capacity 0.10%.
It is 98.5% to purify comprehensive yield.
By the filtrate that crystal solution is centrifugally separating to obtain and water mutually elute centrifuge generation filtrate mix after be warming up to 85 DEG C,
Then 25 DEG C are cooled to be recrystallized, crude product dodecanedioic acid 108kg is obtained through plate-frame filtering, vacuum drying.
Embodiment 2
A kind of process for refining and purifying of dodecanedioic acid of the present invention
In 3000L dissolves decoloring reaction kettle, 98% acetic acid solution 1800L, dodecanedioic acid crude product 760kg are put into,
Activated carbon 6kg, gained acetic acid elution filtrate 200L is stirred evenly in embodiment 1, is warming up to 95 DEG C, 20 minutes is kept the temperature, through closed delivery
The dodecane that plate and frame filter press, bag filter, metal stud filter, cascading type filter level Four filtration system are obtained by filtration
Diacid solution enters crystallization kettle, and Quick uniform is cooled to 77 DEG C in crystallization kettle, closes temperature lowering water, is naturally cooling to 73 DEG C, throws
Dodecanedioic acid of the purity more than 99.8% is added to control mixing speed 40r/min, crystallization temperature in the kettle recoils to 75 as crystal seed
DEG C, then progressively decline, when temperature drops to 68 DEG C naturally, slowly open temperature lowering water, control cooling rate is by slow-to-fast, finally
It is cooled to 25 DEG C, when whole temperature-fall period controls temperature fall time 6~8 small.Crystal solution centrifuges, and makes when filtrate is for disposing mother liquor
With filter cake is stayed in centrifuge and eluted with the acetic acid solution of 300L purity 98%, is centrifuged 15 minutes after elution, filtrate
The solvent that material addition step is done in standby lower production cycle is used；Again with the 2000L room temperature water washing liquors obtained in embodiment 1 in centrifuge
Filter cake is eluted, and is centrifuged 15 minutes after elution, is used when filtrate is for disposing mother liquor.Obtain the filter of material solid content 86%
Cake, filter cake with pump squeeze into room temperature water washing tank after being sized mixing with 1200L deionized waters, add deionized water 800L, stir half an hour, centrifugation
Filtering, filtrate are used for lower production cycle elution centrifuge；Filter cake is dried to obtain refined dodecanedioic acid through double-cone vacuum dryer
685kg.Neutralization titration surveys total acid content 99.90%, and gas chromatography surveys mono-acid content 99.42%, total nitrogen content 10ppm,
Iron ion content 0.6ppm, content of ashes 11ppm, water capacity 0.11%.It is 98.62% to purify comprehensive yield.
By the filtrate that crystal solution is centrifugally separating to obtain and water mutually elute centrifuge generation filtrate mix after be warming up to 85 DEG C,
Then 25 DEG C are cooled to be recrystallized, crude product dodecanedioic acid 108kg is obtained through plate-frame filtering, vacuum drying.
Embodiment 3
A kind of process for refining and purifying of tetracosandioic acid of the present invention
In 3000L dissolves decoloring reaction kettle, 98% acetic acid solution 2000L, tetracosandioic acid crude product 660kg are put into,
Activated carbon 6kg, stirs evenly, and is warming up to 95 DEG C, 20 minutes is kept the temperature, through closed delivery plate and frame filter press, bag filter, metal stud
The tetracosandioic acid solution that filter, cascading type filter level Four filtration system are obtained by filtration enters crystallization kettle, in crystallization kettle
Quick uniform is cooled to 78 DEG C, closes temperature lowering water, is naturally cooling to 75 DEG C, adds tetracosandioic acid of the purity more than 99.8% and makees
For crystal seed, mixing speed 40r/min is controlled, crystallization temperature in the kettle recoils to 77 DEG C, then progressively declines, temperature drops to naturally
At 68 DEG C, temperature lowering water is slowly opened, control cooling rate is finally cooled to 25 DEG C, whole temperature-fall period control drop by slow-to-fast
When warm time 6~8 is small.Crystal solution centrifuges, and is used when filtrate is for disposing mother liquor, and filter cake, which stays in, uses 300L purity in centrifuge
98% acetic acid solution is eluted, and is centrifuged 15 minutes after elution, filtrate makees the solvent of material addition step for lower production cycle
With；Filter cake in centrifuge is eluted with 2000L deionized waters again, is centrifuged 15 minutes after elution, filtrate is returned for mother liquor
Time receiving uses.The filter cake of material solid content 85% is obtained, filter cake is squeezed into room temperature with pump after being sized mixing with 1200L deionized waters and washed
Tank, adds deionized water 800L, stirs half an hour, centrifugal filtration, and filtrate is used for lower production cycle elution centrifuge；Filter cake is through bipyramid
Vacuum drier is dried to obtain refined tetracosandioic acid 560kg.Neutralization titration surveys total acid content 99.80%, gas chromatography
Survey mono-acid content 99.36%, total nitrogen content 12ppm, iron ion content 0.6ppm, content of ashes 14ppm, water capacity 0.16%.
It is 98.64% to purify comprehensive yield.
By the filtrate that crystal solution is centrifugally separating to obtain and water mutually elute centrifuge generation filtrate mix after be warming up to 85 DEG C,
Then 25 DEG C are cooled to be recrystallized, crude product tetracosandioic acid 91kg is obtained through plate-frame filtering, vacuum drying.
Embodiment 4
A kind of process for refining and purifying of tridecandioic acid of the present invention
In 3000L dissolves decoloring reaction kettle, 98% acetic acid solution 2000L, tridecandioic acid crude product 680kg are put into,
Activated carbon 6kg, stirs evenly, and is warming up to 95 DEG C, 20 minutes is kept the temperature, through closed delivery plate and frame filter press, bag filter, metal stud
The tridecandioic acid solution that filter, cascading type filter level Four filtration system are obtained by filtration enters crystallization kettle, in crystallization kettle
Quick uniform is cooled to 76 DEG C, closes temperature lowering water, is naturally cooling to 72 DEG C, adds tridecandioic acid of the purity more than 99.8% and makees
For crystal seed, mixing speed 40r/min is controlled, crystallization temperature in the kettle recoils to 74 DEG C, then progressively declines, temperature drops to naturally
At 68 DEG C, temperature lowering water is slowly opened, control cooling rate is finally cooled to 25 DEG C, whole temperature-fall period control drop by slow-to-fast
When warm time 6~8 is small.Crystal solution centrifuges, and is used when filtrate is for disposing mother liquor, and filter cake, which stays in, uses 300L purity in centrifuge
98% acetic acid solution is eluted, and is centrifuged 15 minutes after elution, filtrate makees the solvent of material addition step for lower production cycle
With；Filter cake in centrifuge is eluted with 2000L deionized waters again, is centrifuged 15 minutes after elution, filtrate is returned for mother liquor
Time receiving uses.The filter cake of material solid content 85% is obtained, filter cake is squeezed into room temperature with pump after being sized mixing with 1200L deionized waters and washed
Tank, adds deionized water 800L, stirs half an hour, centrifugal filtration, and filtrate is used for lower production cycle elution centrifuge；Filter cake is through bipyramid
Vacuum drier is dried to obtain refined tridecandioic acid 578kg.Neutralization titration surveys total acid content 99.84%, gas chromatography
Survey mono-acid content 99.40%, total nitrogen content 13ppm, iron ion content 0.6ppm, content of ashes 10ppm, water capacity 0.10%.
It is 98.53% to purify comprehensive yield.
By the filtrate that crystal solution is centrifugally separating to obtain and water mutually elute centrifuge generation filtrate mix after be warming up to 85 DEG C,
Then 25 DEG C are cooled to be recrystallized, crude product tridecandioic acid 92kg is obtained through plate-frame filtering, vacuum drying.
Embodiment 5
A kind of process for refining and purifying of heneicosanedioic acid of the present invention
In 3000L dissolves decoloring reaction kettle, 98% acetic acid solution 2000L, heneicosanedioic acid crude product 780kg are put into,
Activated carbon 6kg, stirs evenly, and is warming up to 95 DEG C, 20 minutes is kept the temperature, through closed delivery plate and frame filter press, bag filter, metal stud
The heneicosanedioic acid solution that filter, cascading type filter level Four filtration system are obtained by filtration enters crystallization kettle, in crystallization kettle
Quick uniform is cooled to 76 DEG C, closes temperature lowering water, is naturally cooling to 72 DEG C, adds heneicosanedioic acid of the purity more than 99.8% and makees
For crystal seed, mixing speed 40r/min is controlled, crystallization temperature in the kettle recoils to 74 DEG C, then progressively declines, temperature drops to naturally
At 68 DEG C, temperature lowering water is slowly opened, control cooling rate is finally cooled to 25 DEG C, whole temperature-fall period control drop by slow-to-fast
When warm time 6~8 is small.Crystal solution centrifuges, and is used when filtrate is for disposing mother liquor, and filter cake, which stays in, uses 300L purity in centrifuge
98% acetic acid solution is eluted, and is centrifuged 15 minutes after elution, filtrate makees the solvent of material addition step for lower production cycle
With；Filter cake in centrifuge is eluted with 2000L deionized waters again, is centrifuged 15 minutes after elution, filtrate is returned for mother liquor
Time receiving uses.The filter cake of material solid content 85% is obtained, filter cake is squeezed into room temperature with pump after being sized mixing with 1200L deionized waters and washed
Tank, adds deionized water 800L, stirs half an hour, centrifugal filtration, and filtrate is used for lower production cycle elution centrifuge；Filter cake is through bipyramid
Vacuum drier is dried to obtain refined heneicosanedioic acid 660kg.Neutralization titration surveys total acid content 99.89%, gas chromatography
Survey mono-acid content 99.45%, total nitrogen content 6ppm, iron ion content 0.6ppm, content of ashes 13ppm, water capacity 0.12%.Carry
Pure comprehensive yield is 98.59%.
By the filtrate that crystal solution is centrifugally separating to obtain and water mutually elute centrifuge generation filtrate mix after be warming up to 85 DEG C,
Then 25 DEG C are cooled to be recrystallized, crude product heneicosanedioic acid 109kg is obtained through plate-frame filtering, vacuum drying.
Embodiment 6
A kind of process for refining and purifying of pentacosandioic acid of the present invention
In 3000L dissolves decoloring reaction kettle, 98% acetic acid solution 2000L, pentacosandioic acid crude product 660kg are put into,
Activated carbon 6kg, stirs evenly, and is warming up to 95 DEG C, 20 minutes is kept the temperature, through closed delivery plate and frame filter press, bag filter, metal stud
The pentacosandioic acid solution that filter, cascading type filter level Four filtration system are obtained by filtration enters crystallization kettle, in crystallization kettle
Quick uniform is cooled to 78 DEG C, closes temperature lowering water, is naturally cooling to 75 DEG C, adds pentacosandioic acid of the purity more than 99.8% and makees
For crystal seed, mixing speed 40r/min is controlled, crystallization temperature in the kettle recoils to 77 DEG C, then progressively declines, temperature drops to naturally
At 69 DEG C, temperature lowering water is slowly opened, control cooling rate is finally cooled to 25 DEG C, whole temperature-fall period control drop by slow-to-fast
When warm time 6~8 is small.Crystal solution centrifuges, and is used when filtrate is for disposing mother liquor, and filter cake, which stays in, uses 300L purity in centrifuge
98% acetic acid solution is eluted, and is centrifuged 15 minutes after elution, filtrate makees the solvent of material addition step for lower production cycle
With；Filter cake in centrifuge is eluted with 2000L deionized waters again, is centrifuged 15 minutes after elution, filtrate is returned for mother liquor
Time receiving uses.The filter cake of material solid content 85% is obtained, filter cake is squeezed into room temperature with pump after being sized mixing with 1200L deionized waters and washed
Tank, adds deionized water 800L, stirs half an hour, centrifugal filtration, and filtrate is used for lower production cycle elution centrifuge；Filter cake is through bipyramid
Vacuum drier is dried to obtain refined pentacosandioic acid 562kg.Neutralization titration surveys total acid content 99.80%, gas chromatography
Survey mono-acid content 99.33%, total nitrogen content 11ppm, iron ion content 0.5ppm, content of ashes 16ppm, water capacity 0.18%.
It is 98.63% to purify comprehensive yield.
By the filtrate that crystal solution is centrifugally separating to obtain and water mutually elute centrifuge generation filtrate mix after be warming up to 85 DEG C,
Then 25 DEG C are cooled to be recrystallized, crude product pentacosandioic acid 89kg is obtained through plate-frame filtering, vacuum drying.
Embodiment 7
A kind of process for refining and purifying of hexadecandioic acid (hexadecane diacid) of the present invention
In 3000L dissolves decoloring reaction kettle, 98% acetic acid solution 2000L, hexadecandioic acid (hexadecane diacid) crude product 650kg are put into,
Activated carbon 6kg, stirs evenly, and is warming up to 95 DEG C, 20 minutes is kept the temperature, through closed delivery plate and frame filter press, bag filter, metal stud
The hexadecandioic acid (hexadecane diacid) solution that filter, cascading type filter level Four filtration system are obtained by filtration enters crystallization kettle, in crystallization kettle
Quick uniform is cooled to 79 DEG C, closes temperature lowering water, is naturally cooling to 75 DEG C, adds hexadecandioic acid (hexadecane diacid) of the purity more than 99.8% and makees
For crystal seed, mixing speed 40r/min is controlled, crystallization temperature in the kettle recoils to 77 DEG C, then progressively declines, temperature drops to naturally
At 69 DEG C, temperature lowering water is slowly opened, control cooling rate is finally cooled to 25 DEG C, whole temperature-fall period control drop by slow-to-fast
When warm time 6~8 is small.Crystal solution centrifuges, and is used when filtrate is for disposing mother liquor, and filter cake, which stays in, uses 300L purity in centrifuge
98% acetic acid solution is eluted, and is centrifuged 15 minutes after elution, filtrate makees the solvent of material addition step for lower production cycle
With；Filter cake in centrifuge is eluted with 2000L deionized waters again, is centrifuged 15 minutes after elution, filtrate is returned for mother liquor
Time receiving uses.The filter cake of material solid content 85% is obtained, filter cake is squeezed into room temperature with pump after being sized mixing with 1200L deionized waters and washed
Tank, adds deionized water 800L, stirs half an hour, centrifugal filtration, and filtrate is used for lower production cycle elution centrifuge；Filter cake is through bipyramid
Vacuum drier is dried to obtain refined hexadecandioic acid (hexadecane diacid) 555kg.Neutralization titration surveys total acid content 99.80%, gas chromatography
Survey mono-acid content 99.37%, total nitrogen content 13ppm, iron ion content 0.5ppm, content of ashes 15ppm, water capacity 0.15%.
It is 98.62% to purify comprehensive yield.
By the filtrate that crystal solution is centrifugally separating to obtain and water mutually elute centrifuge generation filtrate mix after be warming up to 85 DEG C,
Then 25 DEG C are cooled to be recrystallized, crude product hexadecandioic acid (hexadecane diacid) 86kg is obtained through plate-frame filtering, vacuum drying.
Embodiment 8
A kind of process for refining and purifying of heptadecane diacid of the present invention
In 3000L dissolves decoloring reaction kettle, 98% acetic acid solution 2000L, heptadecane diacid crude product 640kg are put into,
Activated carbon 6kg, stirs evenly, and is warming up to 95 DEG C, 20 minutes is kept the temperature, through closed delivery plate and frame filter press, bag filter, metal stud
The heptadecane diacid solution that filter, cascading type filter level Four filtration system are obtained by filtration enters crystallization kettle, in crystallization kettle
Quick uniform is cooled to 79 DEG C, closes temperature lowering water, is naturally cooling to 75 DEG C, adds heptadecane diacid of the purity more than 99.8% and makees
For crystal seed, mixing speed 40r/min is controlled, crystallization temperature in the kettle recoils to 77 DEG C, then progressively declines, temperature drops to naturally
At 69 DEG C, temperature lowering water is slowly opened, control cooling rate is finally cooled to 25 DEG C, whole temperature-fall period control drop by slow-to-fast
When warm time 6~8 is small.Crystal solution centrifuges, and is used when filtrate is for disposing mother liquor, and filter cake, which stays in, uses 300L purity in centrifuge
98% acetic acid solution is eluted, and is centrifuged 15 minutes after elution, filtrate makees the solvent of material addition step for lower production cycle
With；Filter cake in centrifuge is eluted with 2000L deionized waters again, is centrifuged 15 minutes after elution, filtrate is returned for mother liquor
Time receiving uses.The filter cake of material solid content 85% is obtained, filter cake is squeezed into room temperature with pump after being sized mixing with 1200L deionized waters and washed
Tank, adds deionized water 800L, stirs half an hour, centrifugal filtration, and filtrate is used for lower production cycle elution centrifuge；Filter cake is through bipyramid
Vacuum drier is dried to obtain refined heptadecane diacid 551kg.Neutralization titration surveys total acid content 99.85%, gas chromatography
Survey mono-acid content 99.33%, total nitrogen content 12ppm, iron ion content 0.6ppm, content of ashes 11ppm, water capacity 0.18%.
It is 98.59% to purify comprehensive yield.
By the filtrate that crystal solution is centrifugally separating to obtain and water mutually elute centrifuge generation filtrate mix after be warming up to 85 DEG C,
Then 25 DEG C are cooled to be recrystallized, crude product heptadecane diacid 80kg is obtained through plate-frame filtering, vacuum drying.
Embodiment 9
A kind of process for refining and purifying of octadecane diacid of the present invention
In 3000L dissolves decoloring reaction kettle, 98% acetic acid solution 2000L, octadecane diacid crude product 630kg are put into,
Activated carbon 6kg, stirs evenly, and is warming up to 95 DEG C, 20 minutes is kept the temperature, through closed delivery plate and frame filter press, bag filter, metal stud
The octadecane diacid solution that filter, cascading type filter level Four filtration system are obtained by filtration enters crystallization kettle, in crystallization kettle
Quick uniform is cooled to 80 DEG C, closes temperature lowering water, is naturally cooling to 75 DEG C, adds octadecane diacid of the purity more than 99.8% and makees
For crystal seed, mixing speed 40r/min is controlled, crystallization temperature in the kettle recoils to 77 DEG C, then progressively declines, temperature drops to naturally
At 69 DEG C, temperature lowering water is slowly opened, control cooling rate is finally cooled to 25 DEG C, whole temperature-fall period control drop by slow-to-fast
When warm time 6~8 is small.Crystal solution centrifuges, and is used when filtrate is for disposing mother liquor, and filter cake, which stays in, uses 300L purity in centrifuge
98% acetic acid solution is eluted, and is centrifuged 15 minutes after elution, filtrate makees the solvent of material addition step for lower production cycle
With；Filter cake in centrifuge is eluted with 2000L deionized waters again, is centrifuged 15 minutes after elution, filtrate is returned for mother liquor
Time receiving uses.The filter cake of material solid content 86% is obtained, filter cake is squeezed into room temperature with pump after being sized mixing with 1200L deionized waters and washed
Tank, adds deionized water 800L, stirs half an hour, centrifugal filtration, and filtrate is used for lower production cycle elution centrifuge；Filter cake is through bipyramid
Vacuum drier is dried to obtain refined octadecane diacid 546kg.Neutralization titration surveys total acid content 99.82%, gas chromatography
Survey mono-acid content 99.38%, total nitrogen content 12ppm, iron ion content 0.6ppm, content of ashes 10ppm, water capacity 0.16%.
It is 98.57% to purify comprehensive yield.
By the filtrate that crystal solution is centrifugally separating to obtain and water mutually elute centrifuge generation filtrate mix after be warming up to 85 DEG C,
Then 25 DEG C are cooled to be recrystallized, crude product octadecane diacid 75kg is obtained through plate-frame filtering, vacuum drying.
Claims (11)
1. a kind of process for refining and purifying of Long carbon chain dicarboxylic acids, the long-chain biatomic acid crude product prepared using fermentation method is adopted as raw material
It is solvent with acetic acid, refined purification is handled by recrystallizing, including dissolving, decolorization filtering, decrease temperature crystalline, centrifugal filtration, filter cake
Washing and stoving process step, it is characterised in that：
1. long-chain biatomic acid crude material described in is after drying to moisture≤1.0wt%, into dissolving, decoloring reaction kettle；
Solvent acetic acid content >=the 95.0wt%；
2. decolorization filtering described in uses two-stage above Multistage filtering device；
3. decrease temperature crystalline technique is described in, using three sections of gradient coolings, and induction crystal seed, induction are added after second segment cooling
Crystallization, centrifugal filtration；
4. Washing of Filter Cake step is described in, acetic acid elutes first, then through water wash, centrifugal filtration；Then filter cake is in environment temperature
Lower water washing；
5. the method that the acetic acid solvent that subtractive processes produce uses azeotropic distillation, all recycling, recycles；
6. cleaning solution and mother liquor that subtractive processes produce recycle completely, recycle.
2. the process for refining and purifying of the Long carbon chain dicarboxylic acids according to claim 1, it is characterised in that the Long carbon chain binary
Carboxylic acid is C11~C18Straight-chain dicarboxylic acid.
3. the process for refining and purifying of the Long carbon chain dicarboxylic acids according to claim 1, it is characterised in that the solvent second described in 1.
Recycling acetic acid of the acid described in 4., insufficient section are supplied with industrial acetic.
4. the process for refining and purifying of the Long carbon chain dicarboxylic acids according to claim 1, it is characterised in that the decoloration described in 2.
Filter uses level Four filter operation, the material after decoloration, successively successively using closed delivery plate and frame filter press, bag filter, gold
Belong to stud filter, the filtering of cascading type filter level Four, separation of solid and liquid, filtrate is sent into crystallization kettle.
5. the process for refining and purifying of the Long carbon chain dicarboxylic acids according to claim 1, it is characterised in that the induction described in 3. is brilliant
Kind is more than or equal to 99.8% refined long carbochain biatomic acid for purity, and induction seed load is that long-chain binary hydroxy acid crude product adds
The 0.1%~1% of amount.
6. the process for refining and purifying of the Long carbon chain dicarboxylic acids according to claim 1, it is characterised in that three sections of ladders described in 3.
Spending cooling is：
A. one section of cooling
Under stirring, interlayer temperature lowering water is opened, the filtrate after decolorization is down to 75 DEG C~80 DEG C；
B. two sections of coolings, induction crystallization
Under stirring, after being naturally cooling to 71 DEG C~75 DEG C, long carbochain biatomic acid induction crystal seed is added, then proceedes to be naturally cooling to
68 DEG C~70 DEG C；
C. three sections of coolings
Interlayer temperature lowering water is opened, adjusts cooling water flow, crystallization feed temperature is down to 20 DEG C~30 DEG C.
7. the process for refining and purifying of the Long carbon chain dicarboxylic acids according to claim 1, it is characterised in that the azeotropic essence described in 4.
The method evaporated is using isopropyl acetate as azeotropy dehydrant.
8. the process for refining and purifying of the Long carbon chain dicarboxylic acids according to claim 1, it is characterised in that refining described in 5.
The cleaning solution and mother liquor recycling method produced in journey be：
A. crystalline mother solution is all collected, filtered, and filtrate enters acetic acid solvent azeotropic distillation recovery system；Filter cake is thick as binary acid
Product raw material is reused；
B. 4. described in Washing of Filter Cake step in, through acetic acid elution produce washing and centrifuge mother liquor, be directly used as dissolving, take off
Color solvent, recycles；
C. 4. described in again after water wash, centrifugal filtration, the washing of generation and centrifuge mother liquor are all collected, filtering, filtrate
Into acetic acid solvent azeotropic distillation recovery system；Filter cake is reused as binary acid crude material；
D. 4. described in filter cake at ambient temperature, after water washing, centrifugal filtration, caused filtrate be used as lower batch 4. described in
Water wash wash with water, recycle.
9. the process for refining and purifying of the Long carbon chain dicarboxylic acids according to claim 1, it is characterised in that include the following steps：
1. dissolvings, decoloration
At room temperature, by long-chain binary hydroxy acid crude product, acetic acid, activated carbon input decoloring reaction kettle, 90~95 DEG C are warming up to, insulation
10~30 minutes, successively through closed delivery plate and frame filter press, bag filter, metal stud filter, cascading type filter level Four
Filtering, separation of solid and liquid, filtrate are sent into crystallization kettle, standby crystallization.
The mass ratio that feeds intake is as follows：
Dicarboxylic acids crude product：Solvent (mass ratio) 1：2.2~3.5
Activated carbon：Dicarboxylic acids crude product (mass ratio) 1：60~150
2. gradient coolings, induction crystallization
A. one section of cooling
In crystallization kettle, under stirring, interlayer temperature lowering water is opened, the decoloration filtrate from step 1. is down to 75 DEG C~80 DEG C；
B. two sections of coolings, induction crystallization
Under stirring, after being naturally cooling to 71 DEG C~75 DEG C, long carbochain biatomic acid induction crystal seed is added, then proceedes to be naturally cooling to
68 DEG C~70 DEG C；
C. three sections of coolings
Interlayer temperature lowering water is opened, adjusts cooling water flow, crystallization feed temperature is down to 20 DEG C~30 DEG C；
D. centrifuge, filter
From the complete material of crystallization c above-mentioned, centrifugal filtration；The standby elution of filter cake, mother liquor are all collected, filtering, filtrate into
Enter acetic acid solvent azeotropic distillation recovery system；Filter cake is reused as binary acid crude material；
3. centrifugal filtrations, elution
A. acetic acid elutes
Filter cake after 2. step centrifuges, in centrifuge, is first eluted, the centrifugation that lessivation produces is female with a small amount of acetic acid
Liquid, is directly used in dissolving, decoloration solvent, recycles；Filter cake after drying stays in standby deionized water in centrifuge and elutes；Elution
Acetic acid dosage for step 1. acetic acid dosage 5%~100%.
B. water wash
Filter cake in centrifuge, the centrifuge mother liquor 4. produced with deionized water or subsequent step elutes, again after centrifuge dripping, filter
Cake is washed for room temperature and used；Cleaning solution, the mother liquor produced in lessivation is all collected, filtering, and filtrate enters acetic acid solvent azeotropic
Rectifying recovery system；Filter cake is reused as binary acid crude material；
4. room temperatures are washed, centrifugation
Filter cake from step 3., after slurries are made with deionized water, is sent into water washing tank, adds deionized water and is followed by stirring and washing
30 minutes, centrifugal filtration, separation of solid and liquid, the standby drying of filter cake；Filtrate is used as the lower batch of production stage 3. leaching scouring water needed for b, follows
Ring uses；
Add in water washing tank the amount of pure water for step 1. quality of acetic acid used 70%~120%；
5. is dried
The filter cake drying of step 4., obtains refined long carbochain biatomic acid；
Long carbon chain dicarboxylic acids after purification reaches following technical indicator：
10. the process for refining and purifying of the Long carbon chain dicarboxylic acids according to claim 1, it is characterised in that include the following steps：
1. dissolvings, decoloration
At room temperature, by long-chain binary hydroxy acid crude product, acetic acid, activated carbon input decoloring reaction kettle, 90~95 DEG C are warming up to, insulation
10~30 minutes, successively through closed delivery plate and frame filter press, bag filter, metal stud filter, cascading type filter level Four
Filtering, separation of solid and liquid, filtrate are sent into crystallization kettle, standby crystallization.
The mass ratio that feeds intake is as follows：
Dicarboxylic acids crude product：Solvent (mass ratio) 1：2.5~3.5
Activated carbon：Dicarboxylic acids crude product (mass ratio) 1：80~100
2. gradient coolings, induction crystallization
A. one section of cooling
In crystallization kettle, under stirring, interlayer temperature lowering water is opened, the decoloration filtrate from step 1. is down to 77 DEG C；
B. two sections of coolings, induction crystallization
Under stirring, after being naturally cooling to 74 DEG C, long carbochain biatomic acid induction crystal seed is added, then proceedes to be cooled to 68 DEG C；
C. three sections of coolings
Interlayer temperature lowering water is opened, adjusts cooling water flow, crystallization feed temperature is down to 25 DEG C~30 DEG C；
D. centrifuge, filter
From the complete material of crystallization c above-mentioned, centrifugal filtration；The standby elution of filter cake, mother liquor are all collected, filtering, filtrate into
Enter acetic acid solvent azeotropic distillation recovery system；Filter cake is reused as binary acid crude material；
3. centrifugal filtrations, elution
A. acetic acid elutes
Filter cake after 2. step centrifuges, in centrifuge, is first eluted, the centrifugation that lessivation produces is female with a small amount of acetic acid
Liquid, is directly used in dissolving, decoloration solvent, recycles；Filter cake after drying stays in standby deionized water in centrifuge and elutes；Elution
Acetic acid dosage for step 1. acetic acid dosage 5%~100%.
B. water wash
Filter cake in centrifuge, the centrifuge mother liquor 4. produced with deionized water or subsequent step elutes, again after centrifuge dripping, filter
Cake is washed for room temperature and used；Cleaning solution, the mother liquor produced in lessivation is all collected, filtering, and filtrate enters acetic acid solvent azeotropic
Rectifying recovery system；Filter cake is reused as binary acid crude material；
4. room temperatures are washed, centrifugation
Filter cake from step 3., after slurries are made with deionized water, is sent into water washing tank, adds deionized water and is followed by stirring and washing
Half an hour, centrifugal filtration, separation of solid and liquid, filter cake are standby dry；Filtrate is used as the lower batch of production stage 3. leaching scouring water needed for b, follows
Ring uses；
Add in water washing tank the amount of pure water for step 1. quality of acetic acid used 70%~120%；
5. is dried
The filter cake drying of step 4., obtains refined long carbochain biatomic acid；
Long carbon chain dicarboxylic acids after purification reaches following technical indicator：
11. according to claim 9 or the process for refining and purifying of the Long carbon chain dicarboxylic acids of claim 10, it is characterised in that described
5. the drying unit uses vacuum dryer or blade drier to step.
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| CN110002992A (en) * | 2019-03-24 | 2019-07-12 | 张艾琳 | A kind of refining methd of positive long-chain biatomic acid |
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| CN111099990A (en) * | 2019-12-31 | 2020-05-05 | 淄博广通化工有限责任公司 | Method for recycling mother liquor of long carbon chain dicarboxylic acid refining crystallization |
| CN111099991A (en) * | 2019-12-31 | 2020-05-05 | 淄博广通化工有限责任公司 | Refining and purifying method for long carbon chain dicarboxylic acid with high yield and low cost |
| CN112321418A (en) * | 2020-11-24 | 2021-02-05 | 淮安清江石油化工有限责任公司 | Refining method of long-chain dibasic acid |
| CN114426479A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Method and device for refining long-chain dicarboxylic acid |
| CN114685267A (en) * | 2020-12-29 | 2022-07-01 | 中国石油化工股份有限公司 | Method for crystallizing long-chain dicarboxylic acid and method for purifying long-chain dicarboxylic acid |
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| CN110041193A (en) * | 2019-03-24 | 2019-07-23 | 张艾琳 | A kind of refining methd of positive long-chain biatomic acid under inert gas shielding |
| CN110002992A (en) * | 2019-03-24 | 2019-07-12 | 张艾琳 | A kind of refining methd of positive long-chain biatomic acid |
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| CN111099991A (en) * | 2019-12-31 | 2020-05-05 | 淄博广通化工有限责任公司 | Refining and purifying method for long carbon chain dicarboxylic acid with high yield and low cost |
| CN111099990B (en) * | 2019-12-31 | 2023-12-26 | 山东广通新材料有限公司 | Recycling method of long carbon chain dicarboxylic acid refined crystallization mother liquor |
| CN114426479A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Method and device for refining long-chain dicarboxylic acid |
| CN112321418A (en) * | 2020-11-24 | 2021-02-05 | 淮安清江石油化工有限责任公司 | Refining method of long-chain dibasic acid |
| CN114685259A (en) * | 2020-12-29 | 2022-07-01 | 中国石油化工股份有限公司 | Crystallization method of long-chain dicarboxylic acid and refining method of long-chain dicarboxylic acid |
| CN114685261A (en) * | 2020-12-29 | 2022-07-01 | 中国石油化工股份有限公司 | Refining method of long-chain dicarboxylic acid |
| CN114685260A (en) * | 2020-12-29 | 2022-07-01 | 中国石油化工股份有限公司 | Method for purifying long-chain dicarboxylic acid |
| CN114685267A (en) * | 2020-12-29 | 2022-07-01 | 中国石油化工股份有限公司 | Method for crystallizing long-chain dicarboxylic acid and method for purifying long-chain dicarboxylic acid |
| CN114853596A (en) * | 2021-02-04 | 2022-08-05 | 青岛智库生物技术有限公司 | Long-chain dicarboxylic acid refining method and device |
| CN117326936A (en) * | 2023-12-01 | 2024-01-02 | 山东归源生物科技有限公司 | Refining method and device for long carbon chain dibasic acid |
| CN117326936B (en) * | 2023-12-01 | 2024-02-02 | 山东归源生物科技有限公司 | Refining method and device for long carbon chain dibasic acid |
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