CN108003014A - The process for refining and purifying of tridecandioic acid - Google Patents
The process for refining and purifying of tridecandioic acid Download PDFInfo
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- CN108003014A CN108003014A CN201711410679.1A CN201711410679A CN108003014A CN 108003014 A CN108003014 A CN 108003014A CN 201711410679 A CN201711410679 A CN 201711410679A CN 108003014 A CN108003014 A CN 108003014A
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- acid
- filter cake
- acetic acid
- water
- tridecandioic
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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
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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
Abstract
The present invention is the process for refining and purifying of tridecandioic acid, 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 tridecandioic acid of high-purity.Tridecandioic acid total acid content after refined purification reaches 99.90%, and mono-acid content reaches 99.42%, and total nitrogen reaches 10ppm, and iron ion content reaches 0.5ppm, content of ashes≤10ppm, water capacity≤0.10%.Purification comprehensive yield reaches 98.62%.Every quality and technical index meets user demand.
Description
Technical field
The present invention is a kind of process for refining and purifying of tridecandioic acid.Belonging to has the acyclic binary carboxylic of more than 10 carbon atoms
The purification process of acid.
Background technology
Tridecandioic acid (1,13-Tridecanedioic Acid) also known as brassylic acid (Brassylic Acid) are long
Industrial products important earlier are developed in chain binary acid.It is mainly used for synthesizing high molecular material, spices, medicine etc..For example, make
The high performance lubricant long carbochain biatomic acid dibasic ester required for the primary raw material of musk ambrette ketone, synthesis with property
Raw material, synthesized high-performance polyamide hot melt type adhesive polycondensation monomer, and it is anti-as polycondensation monomer and diamine generation polycondensation
Long carbon chain nylon 1313 etc. should be synthesized, is applied in numerous areas.
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.
In recent years, demand of the tridecandioic acid on international and domestic market increases sharply, and rises year by year.It is moreover, right
The requirement of the various technical performance indexs of product quality is continuously improved, increasingly harsher.Commercially available tridecandioic acid cannot meet long-chain
The requirement of nylon industry and other downstream product to the technical indicator of its purity and presentation quality each side.
Tridecandioic acid, nature are not present, and mainly using organic synthesis method, prepared by biological fermentation process, using organic conjunction
Cheng Fa, 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 tridecandioic acid of Production by Microorganism Fermentation, mainly carries out purification using solvent method by recrystallizing.
Solvent is mainly using acetic acid and methanol etc..Experiment and production practices show, no matter in Refining times, refining solvent dosage and crystallization
In product purity, acetic acid is better than other organic solvents.
In the prior art, the tridecandioic 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 tridecandioic 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 tridecandioic 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 tridecandioic acid of about 5wt%~6wt% in the mother liquor after decoloration crystallization, separation, this partial mother liquid is not
Through processing, it is sent directly into rectifying column and carries out rectifying, discarded the raw material in mother liquor.Product yield is reduced, improves and is produced into
This.
Since the prior art has deficiency above, so tridecandioic 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 tridecandioic 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 tridecandioic acid of high-purity is people institute
Expect.
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 tridecandioic acid 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 tridecandioic acid of the present invention, using the tridecandioic acid crude product of fermentation method preparation as raw material,
Acetic acid is used as solvent, refined purification is handled by recrystallizing, including dissolving, decolorization filtering, decrease temperature crystalline, centrifugal filtration, filter
Cake washs and stoving process step, it is characterised in that：
1. tridecandioic 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.
Tridecandioic 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 tridecandioic acid crude product moisture within 1%, acetic acid Pureness control significantly improves solvent acetic acid more than 95%
To the dissolubility of the tridecandioic acid in crude product and soluble impurity component, the refined receipts of tridecandioic acid are improved from source
Rate, avoids of the prior art, and some undissolved good impurity molecules become crystal seed in crystallization process, caused
Heterogeneous nucleation phenomenon produces.So as to improve purification effect.
Reduce heterogeneous nucleation problem of the tridecandioic acid solution in decrease temperature crystalline, reduce the bag of crystals impurity
The amount of covering, not only improves crystal habit, but also improves 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 tridecandioic acid of the present invention, 1. described in recycling of the solvent acetic acid described in 4.
Acetic acid, insufficient section are supplied with industrial acetic.It is preferable technical solution.
The present invention tridecandioic acid process for refining and purifying, 2. described in decolorization filtering use level Four filter operation,
Material after decoloration, successively successively using closed delivery plate and frame filter press, bag filter, metal stud filter, stacked
Filter level Four filters, separation of solid and liquid, and filtrate is sent into crystallization kettle.It is preferable technical solution.
The present invention tridecandioic acid 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 tridecandioic acid of the present invention, it is characterised in that three sections of gradient coolings described in 3. are：
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, tridecandioic acid induction crystal seed is added, then proceedes to Temperature fall
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 present invention tridecandioic acid process for refining and purifying, it is characterised in that the method for the azeotropic distillation described in 4. with
Isopropyl acetate is azeotropy dehydrant.It is a preferable technical solution.
The process for refining and purifying of the tridecandioic acid of the present invention, it is characterised in that produced in the subtractive process described in 5.
Cleaning solution and mother liquor recycling method are：
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 tridecandioic acid 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, tridecandioic acid induction crystal seed is added, then proceedes to Temperature fall
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；
Tridecandioic acid after purification reaches following technical indicator：
The process for refining and purifying of the tridecandioic acid 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, tridecandioic 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 tridecandioic acid；
Tridecandioic acid after purification reaches following technical indicator：
It is optimal technical solution.
The process for refining and purifying of the tridecandioic acid of the present invention, it is characterised in that the step 5. adopt by the drying unit
With vacuum dryer or blade drier.
Technical solution disclosed in the process for refining and purifying of the tridecandioic acid of the present invention, can produce such as compared with prior art
Lower good effect：
1. it is high to provide a kind of product yield, refined cost is relatively low, the process for refining and purifying of the tridecandioic acid of high-purity.
2. by the way that by the control of tridecandioic acid crude product moisture, within 1%, acetic acid Pureness control reduces more than 95%
Heterogeneous nucleation problem of the tridecandioic acid solution in decrease temperature crystalline, reduces the covering amount of crystals impurity, both improved
Crystal habit, and improve 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 the tridecandioic acid total acid content after refined purification reaches 99.90%, mono-acid content
Reaching 99.42%, total nitrogen reaches 10ppm, and iron ion content reaches 0.5ppm, content of ashes≤10ppm, water capacity≤
0.10%,.Purification comprehensive yield reaches 98.62%.Every quality and technical 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 tridecandioic acid of the present invention
In 3000L dissolves decoloring reaction kettle, 98% acetic acid solution 2000L, tridecandioic 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 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 78 DEG C, closes temperature lowering water, is naturally cooling to 75 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 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 tridecandioic 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 tridecandioic acid 108kg is obtained through plate-frame filtering, vacuum drying.
Embodiment 2
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 1800L, tridecandioic 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 tridecane 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
Tridecandioic 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 tridecandioic 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 tridecandioic acid 108kg is obtained through plate-frame filtering, vacuum drying.
Embodiment 3
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.
Claims (10)
1. a kind of process for refining and purifying of tridecandioic acid, the tridecandioic acid crude product prepared using fermentation method is raw material, using second
Acid is solvent, and refined purification is handled by recrystallizing, including dissolving, decolorization filtering, decrease temperature crystalline, centrifugal filtration, Washing of Filter Cake
With stoving process step, it is characterised in that：
1. tridecandioic 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 tridecandioic acid according to claim 1, it is characterised in that the solvent acetic acid described in 1. is come
Recycling acetic acid described in 4., insufficient section are supplied with industrial acetic.
3. the process for refining and purifying of the tridecandioic acid according to claim 1, it is characterised in that the decolorization filtering described in 2. is adopted
With level Four filter operation, the material after decoloration, successively successively using closed delivery plate and frame filter press, bag filter, Titanium
Rod filter, the filtering of cascading type filter level Four, separation of solid and liquid, filtrate are sent into crystallization kettle.
4. the process for refining and purifying of the tridecandioic acid according to claim 1, it is characterised in that the induction crystal seed described in 3. is
Purity is more than or equal to 99.8% refined tridecandioic acid, and induction seed load is long-chain binary hydroxy acid crude product dosage
0.1%~1%.
5. the process for refining and purifying of the tridecandioic acid according to claim 1, it is characterised in that three sections of gradients drop described in 3.
Wen Shi：
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, tridecandioic 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.
6. the process for refining and purifying of the tridecandioic acid according to claim 1, it is characterised in that azeotropic distillation described in 4.
Method is using isopropyl acetate as azeotropy dehydrant.
7. the process for refining and purifying of the tridecandioic acid according to claim 1, it is characterised in that in the subtractive process described in 5.
The cleaning solution and mother liquor recycling method of generation 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.
8. the process for refining and purifying of the tridecandioic acid 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, tridecandioic 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 tridecandioic acid；
Tridecandioic acid after purification reaches following technical indicator：
9. the process for refining and purifying of the tridecandioic acid 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, tridecandioic 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 tridecandioic acid；
Tridecandioic acid after purification reaches following technical indicator：
10. according to claim 8 or the process for refining and purifying of the tridecandioic acid of claim 9, it is characterised in that the step
5. the drying unit uses vacuum dryer or blade drier.
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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 |
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| 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 |
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