CN104447280A - Recycling method of purifying, refining and crystallizing mother liquor of dodecanedioic acid - Google Patents
Recycling method of purifying, refining and crystallizing mother liquor of dodecanedioic acid Download PDFInfo
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- CN104447280A CN104447280A CN201410828673.6A CN201410828673A CN104447280A CN 104447280 A CN104447280 A CN 104447280A CN 201410828673 A CN201410828673 A CN 201410828673A CN 104447280 A CN104447280 A CN 104447280A
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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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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
- C07C29/92—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound by a consecutive conversion and reconstruction
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- 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
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Abstract
The invention provides a recycling method of mother liquor purifying, refining and crystallizing mother liquor of dodecanedioic acid, and belongs to the separation treatment method of non-acyclic dicarboxylic acid containing 12 carbon atoms. The recycling method comprises the steps of (1) recovering a solvent which is methanol; (2) distilling to dissolve and dilute materials residual at the bottom of a kettle; (3) performing acidification under a high temperature, and crystallizing; (4) drying. The recycling method of mother liquor purifying, refining and crystallizing mother liquor of dodecanedioic acid has the advantages that the recovered dodecanedioic acid product has a good color and luster and is of high purity, and moreover, the recovery yield is raised, the device investment is saved, the operation is simple and convenient, the resource can be saved, and the environment is protected; the recovery yield of the dodecanedioic acid product is not less than 97.0%; the product quality meets the technical indexes that the total acid is not less than 99.7wt% (percentage by weight), single acid is not less than 99.3wt%, ash content is not greater than 0.003wt%, the total nitrogen is not greater than 0.004wt%, ferric oxide is not greater than 0.0002wt%, and water content is not greater than 0.17wt%.
Description
Technical field
The present invention is a kind of recoverying and utilizing method of dodecanedioic acid purification crystalline mother solution.Belong to the method for separating and processing of the acyclic di-carboxylic acid having 12 carbon atoms.
Background technology
Dodecanedioic acid (Dodecanedioic Acid) has another name called bay diacid.In long-chain biatomic acid, develop Industrial products comparatively early.Be mainly used in synthesized polymer material, spices, medicine etc.Wherein, synthesizing long carbon chain nylon (also known as polyamide resin) engineering plastics as polycondensation monomer and diamine generation polycondensation, is one of most important purposes.
Nylon is the family macromolecule compound containing acid amides group (-NHCO-) on molecular backbone chain.Due in nylon molecules structure containing a large amount of amide group, macromole end be amino or carboxyl, thus be the strong polarity of a class, intermolecular energy formation hydrogen bond and there is the crystalline polymer of certain reactive behavior.Nylon is the one that in five large-engineering plastics (nylon, polyoxymethylene, polycarbonate, polyphenylene oxide, polybutylene terephthalate), consumption is maximum, kind maximum, purposes is the widest, qualification is the oldest,
The distinctive molecular machinery of long-chain nylon, give the over-all properties that it is good, intensity is higher than metal, excellent mechanical property, thermotolerance, wearability, chemical resistant properties, flame retardant resistance and self lubricity, frictional coefficient is low and easily process, and it can be processed into various plastics, also wire drawing can make fiber, can also make film, coating and tackiness agent etc.Be widely used in automobile, electric, mechanical, communication, the field such as military affairs and aerospace.
Take dodecanedioic acid as raw material, as the long carbon chain nylon that polycondensation monomer and diamine generation polycondensation synthesize, mainly contain nylon 12, nylon 612, nylon 11 12 and nylon 1212 etc.,
In recent years, the demand of dodecanedioic acid on international and domestic market increases sharply, and rises year by year.And, the requirement of the various technical performance index of quality product is improved constantly, more and more harsher.Commercially available dodecanedioic acid can not meet the requirement of long-chain nylon technique to the technical indicator of its purity and visual appearance each side.
In prior art, the purification process of dodecanedioic acid mainly with the dodecanedioic acid crude product of Production by Microorganism Fermentation for starting raw material, adopt solvent method to carry out purification by recrystallization.The solvent adopted mainly contains Glacial acetic acid and methyl alcohol, weighs the advantages and disadvantages, is better than Glacial acetic acid using methyl alcohol as the method for purification of recrystallisation solvent, but still exists following not enough:
1., because the solubleness of dodecanedioic acid in methyl alcohol is comparatively large, in crystalline mother solution, the residual quantity of dodecanedioic acid is comparatively large, is difficult to separate out.
2., due to methyl alcohol easy and solute dodecanedioic acid generation esterification under acidity and heating condition, therefore, in recrystallizing technology process, the ester that methyl alcohol and dodecanedioic acid are generated by esterification, is present in crystalline mother solution.
3., in prior art, crystalline mother solution is by the distillating method reuse used time, and because the pyrogenic distillation time is longer, the methyl alcohol in process in mother liquor and dodecanedioic acid generate ester by esterification, further increase the content of ester.
4. in prior art, be by distillation, first recycling design methyl alcohol, then, by heavy constituent ester residual at the bottom of still kettle, by the method for plus-minus hydrolysis, finally changes into dodecanedioic acid ester.It is high to there is processing cost in this technique, and the dodecanedioic acid rate of recovery is low, reclaims poor product quality, causes the huge waste of resource.
A kind of dodecanedioic acid product color of recovery is good, purifying is high, reclaims productive rate high, and low equipment investment, easy and simple to handle, economize on resources, the recoverying and utilizing method being conducive to the dodecanedioic acid purification crystalline mother solution of environment protection is that people expected.
Summary of the invention
The object of the invention is to avoid above-mentioned weak point of the prior art; and provide that a kind of dodecanedioic acid product color of recovery is good, purifying is high; recovery productive rate is high; low equipment investment, easy and simple to handle; economize on resources, be conducive to the recoverying and utilizing method of the dodecanedioic acid purification crystalline mother solution of environment protection.
Object of the present invention can be reached by following measure:
The recoverying and utilizing method of dodecanedioic acid purification crystalline mother solution of the present invention, is characterized in that comprising following operation steps:
1.. recycling design methyl alcohol
By the crystalline mother solution that dodecanedioic acid content is 30 ~ 50 grams per liters, drop in Methanol Recovery still kettle, under stirring, first the industrial lye of 30wt% is added, dodecanedioic acid: NaOH (mol ratio)=1:2.5 ~ 2.7, then, heat up distillation, collect and reclaim methyl alcohol, recycle for recrystallization purifying process;
2.. residual material dissolved dilution at the bottom of still kettle
After Methanol Recovery terminates, be dissolved in water residual material at the bottom of still kettle, and dodecanedioic acid content is adjusted to 30 ~ 70 grams per liters, and standby acid out crystallization is used;
3.. high-temperature acid precipitation and crystallization
A. the configuration of dilute sulphuric acid
In dilute sulphuric acid preparation still, add deionized water, under cooling, stirring, slowly drip the vitriol oil of 98.0%, water: the vitriol oil (mass ratio)=1:0.34 ~ 0.44, is cooled to room temperature, standby crystallization is used;
B. acid out crystallization
Residual material at the bottom of still kettle after step being 2. dissolved in water drops in crystallization kettle, be warming up to 98 ~ 102 DEG C, slowly drip the dilution heat of sulfuric acid that a item prepares, along with adding of dilute sulphuric acid, plate crystal is slowly had to generate, when acid adding is to solution acidity pH=3.0, stop acid adding, insulated and stirred is after 15 ~ 20 minutes, slowly decrease temperature crystalline, when being cooled to 50 DEG C, strengthen water coolant, continue fast to be cooled to room temperature, centrifuging, gained filter cake deionized water wash, remove the impurity in filter cake and salt, after having washed, continue centrifuge dripping, washings reclaims, as the dissolved dilution water of next batch, recycle,
4. dry
Filter cake after the step 2. centrifuging of b item, dries at 100 ~ 105 DEG C of temperature;
Obtained High-pure Dodecanedioic Acid crystal; Product recovery rate >=96.3%; Quality product reaches following technical indicator:
In technical scheme of the present invention, before purification crystalline mother solution heats up distillation, namely add liquid caustic soda, solution furnishing alkalescence, restrained effectively in Distillation recovery methanol process, the esterification occurred between solvent methanol and dodecanedioic acid product.Successfully solve the recovery process caused due to the generation of by product ester existed in prior art complicated, reclaim that yield is low, cost recovery is high, reclaim quality product be difficult to reach the market requirement technical problem,
The present invention is after Methanol Recovery terminates, and be dissolved in water residual material at the bottom of still kettle, and adopt at higher temperatures with water as solvent, alkali is molten, prepares the dodecanedioic acid crude product aqueous solution, improves the solubleness of diprotic acid and sodium salt thereof.Be of value to the rate of recovery improving dodecanedioic acid.
Dodecanedioic acid content is adjusted to 30 ~ 70 grams per liters.Be applicable to acid out crystallization.
The present invention at 98 ~ 102 DEG C of temperature, acid out crystallization, acid out temperature is higher, reduce the speed that crystal is separated out, be conducive to the growth of nucleus, be easy to obtain regular crystal, decrease for the coated of impurity and carrying secretly in product crystal, thus increase grain-size, improve the purity of product.The dodecanedioic acid quality product reclaimed can meet the requirement of long-chain nylon technique to the technical indicator of its purity and visual appearance each side.
The present invention adopts deionization water as solvent, deionized water is cheap and easy to get, nonpoisonous and tasteless, environmental protection, to avoid in prior art Glacial acetic acid and alcohol organic solvent to the pollution of environment, and the solubleness of dodecanedioic acid in water is very little, product residual in last mother liquor is few, create the effect that product yield is significantly improved, synchronously reduce production cost.Significantly improve the economic benefit of enterprise, facilitate the development of dodecanedioic acid industry effectively.Recycling for waste liquid opens a new way, has effectively saved resource, has protected environment.Thus complete task of the present invention.
Object of the present invention can also be reached by following measure:
The recoverying and utilizing method of dodecanedioic acid purification crystalline mother solution of the present invention, is characterized in that step 1. in the whole process of recycling design methyl alcohol, regulates the pH value of the material in Methanol Recovery still kettle, pH >=8 remained with industrial lye.It is preferred technical scheme.
The recoverying and utilizing method of dodecanedioic acid purification crystalline mother solution of the present invention, it is characterized in that step is 2.. residual material dissolved dilution at the bottom of still kettle, after methyl alcohol all steams, be dissolved in water residual material at the bottom of dilution still kettle, dodecanedioic acid content is adjusted to 60 ~ 70 grams per liters, and standby acid out crystallization is used.It is preferred technical scheme.
The recoverying and utilizing method of dodecanedioic acid purification crystalline mother solution of the present invention, is characterized in that the mass percentage concentration of the dilute sulphuric acid that 1. step is prepared is 25 ~ 30%.It is preferred technical scheme.
The recoverying and utilizing method of dodecanedioic acid purification crystalline mother solution of the present invention, it is characterized in that step 3. in c item washing water used be deionized water, its electricity Dao Shuais≤20 μ S/cm, when the effluent liquid electricity Dao after washing leaching cake Shuai≤300 μ S/cm time be washing terminal.It is preferred technical scheme.
The recoverying and utilizing method of dodecanedioic acid purification crystalline mother solution of the present invention, is characterized in that comprising following operation steps:
1.. recycling design methyl alcohol
By the crystalline mother solution that dodecanedioic acid content is 30 ~ 50 grams per liters, drop in Methanol Recovery still kettle, under stirring, first the industrial lye of 30wt% is added, dodecanedioic acid: NaOH (mol ratio)=1:2.5, then, heat up distillation, collect and reclaim methyl alcohol, recycle for recrystallization purifying process; In the whole process of recycling design methyl alcohol, regulate the pH value of the material in Methanol Recovery still kettle with industrial lye, pH >=8 remained.
2.. residual material dissolved dilution at the bottom of still kettle
After Methanol Recovery terminates, be dissolved in water residual material at the bottom of still kettle, and dodecanedioic acid content is adjusted to 60 ~ 70 grams per liters, and standby acid out crystallization is used;
3.. high-temperature acid precipitation and crystallization
A. the configuration of dilute sulphuric acid
In dilute sulphuric acid preparation still, add deionized water, under cooling, stirring, slowly drip the vitriol oil of 98.0%, water: the vitriol oil (mass ratio)=1:0.34 ~ 0.44, the mass percentage concentration of the dilute sulphuric acid of preparation is 25 ~ 30%, be cooled to room temperature, standby crystallization is used;
B. acid out crystallization
Residual material at the bottom of still kettle after step being 2. dissolved in water drops in crystallization kettle, be warming up to 98 ~ 102 DEG C, slowly drip the dilution heat of sulfuric acid that a item prepares, along with adding of dilute sulphuric acid, plate crystal is slowly had to generate, when acid adding is to solution acidity pH=3.0, stop acid adding, insulated and stirred is after 15 ~ 20 minutes, slowly decrease temperature crystalline, when being cooled to 50 DEG C, strengthen water coolant, continue fast to be cooled to room temperature, centrifuging, gained filter cake deionized water wash, remove the impurity in filter cake and salt, washing water used are deionized water, its specific conductivity≤20 μ S/cm, it is washing terminal as effluent liquid specific conductivity≤300 μ S/cm after washing leaching cake, after having washed, continue centrifuge dripping, washings reclaims, as the dissolved dilution water of next batch, recycle,
4. dry
Filter cake after the step 2. centrifuging of b item, dries at 100 ~ 105 DEG C of temperature; Obtained High-pure Dodecanedioic Acid crystal; Product recovery rate >=97.0%; Quality product reaches following technical indicator:
It is preferred technical scheme.
The application of the dodecanedioic acid product reclaimed according to the recoverying and utilizing method of dodecanedioic acid purification crystalline mother solution of the present invention, is characterized in that being applicable to synthesize long carbon chain nylon as polycondensation monomer and diamine generation polycondensation; Also the raw material of synthetic perfume, medicine is applicable to.
The recoverying and utilizing method of dodecanedioic acid purification crystalline mother solution of the present invention, has following positively effect compared to existing technology:
1. the dodecanedioic acid product color providing a kind of recovery is good, purifying is high, reclaims productive rate high, low equipment investment, easy and simple to handle, economizes on resources, is conducive to the recoverying and utilizing method of the dodecanedioic acid purification crystalline mother solution of environment protection.
2. in technical scheme of the present invention, before purification crystalline mother solution heats up distillation, namely add liquid caustic soda, solution furnishing alkalescence, restrained effectively in Distillation recovery methanol process, the esterification occurred between solvent methanol and dodecanedioic acid product.Successfully solve the recovery process caused due to the generation of by product ester existed in prior art complicated, reclaim that yield is low, cost recovery is high, reclaim the technical problem that quality product is difficult to reach the market requirement.
3. the present invention is after Methanol Recovery terminates, and be dissolved in water residual material at the bottom of still kettle, and adopt at higher temperatures with water as solvent, alkali is molten, prepares the dodecanedioic acid crude product aqueous solution, improves the solubleness of diprotic acid and sodium salt thereof.Be of value to the rate of recovery improving dodecanedioic acid.
4. dodecanedioic acid content is adjusted to 30 ~ 70 grams per liters.Be applicable to acid out crystallization.
5. the present invention is at 98 ~ 102 DEG C of temperature, acid out crystallization, acid out temperature is higher, reduce the speed that crystal is separated out, be conducive to the growth of nucleus, be easy to obtain regular crystal, decrease in product crystal for the coated of impurity and carrying secretly, thus increase grain-size, improve the purity of product.The dodecanedioic acid quality product reclaimed can meet the requirement of long-chain nylon technique to the technical indicator of its purity and visual appearance each side.
6. the present invention is at 98 ~ 102 DEG C of temperature, acid out crystallization, acid out temperature is higher, reduce the speed that crystal is separated out, be conducive to the growth of nucleus, be easy to obtain regular crystal, decrease in product crystal for the coated of impurity and carrying secretly, thus increase grain-size, improve the purity of product.The dodecanedioic acid quality product reclaimed can meet the requirement of long-chain nylon technique to the technical indicator of its purity and visual appearance each side.
7. the present invention adopts deionization water as solvent, deionized water is cheap and easy to get, nonpoisonous and tasteless, environmental protection, to avoid in prior art Glacial acetic acid and alcohol organic solvent to the pollution of environment, and the solubleness of dodecanedioic acid in water is very little, product residual in last mother liquor is few, create the effect that product yield is significantly improved, synchronously reduce production cost.Significantly improve the economic benefit of enterprise, facilitate the development of dodecanedioic acid industry effectively.Recycling for waste liquid opens a new way, has effectively saved resource, has protected environment.
8. adopt method of the present invention, dodecanedioic acid product recovery rate >=97.0%.Quality product reaches following technical indicator:
Embodiment
The present invention will now be further detailed embodiment:
Embodiment 1
The recoverying and utilizing method of a kind of dodecanedioic acid purification crystalline mother solution of the present invention, comprises following operation steps:
1.. recycling design methyl alcohol
It is the crystalline mother solution 2000 liters of 30 grams per liters by dodecanedioic acid content, drop in Methanol Recovery still kettle, under stirring, first the industrial lye of 30wt% is added, dodecanedioic acid: NaOH (mol ratio)=1:2.5, then, heat up distillation, collect and reclaim methyl alcohol, recycle for recrystallization purifying process; In the whole process of recycling design methyl alcohol, regulate the pH value of the material in Methanol Recovery still kettle with industrial lye, pH >=8 remained.
2.. residual material dissolved dilution at the bottom of still kettle
After Methanol Recovery terminates, be dissolved in water residual material at the bottom of still kettle, and dodecanedioic acid content is adjusted to 60 grams per liters, and standby acid out crystallization is used;
3.. high-temperature acid precipitation and crystallization
A. the configuration of dilute sulphuric acid
In dilute sulphuric acid preparation still, add deionized water, under cooling, stirring, slowly drip the vitriol oil of 98.0%, water: the vitriol oil (mass ratio)=1:0.34, the mass percentage concentration of the dilute sulphuric acid of preparation is 25.3%, is cooled to room temperature, and standby crystallization is used;
B. acid out crystallization
Residual material at the bottom of still kettle after step being 2. dissolved in water drops in crystallization kettle, be warming up to 98 DEG C, slowly drip the dilution heat of sulfuric acid that a item prepares, along with adding of dilute sulphuric acid, plate crystal is slowly had to generate, when acid adding is to solution acidity pH=3.0, stop acid adding, insulated and stirred is after 15 minutes, slowly decrease temperature crystalline, when being cooled to 50 DEG C, strengthen water coolant, continue fast to be cooled to room temperature, centrifuging, gained filter cake deionized water wash, remove the impurity in filter cake and salt, washing water used are deionized water, its specific conductivity≤20 μ S/cm, it is washing terminal as effluent liquid specific conductivity≤280 μ S/cm after washing leaching cake, after having washed, continue centrifuge dripping, washings reclaims, as the dissolved dilution water of next batch, recycle,
4. dry
Filter cake after the step 2. centrifuging of b item, dries at 100 ~ 105 DEG C of temperature; Obtained 58 kilograms, High-pure Dodecanedioic Acid crystal; Product recovery rate 96.7%; Quality product reaches following technical indicator:
Embodiment 2
The recoverying and utilizing method of a kind of dodecanedioic acid purification crystalline mother solution of the present invention, comprises following operation steps:
1.. recycling design methyl alcohol
It is the crystalline mother solution 2000 liters of 40 grams per liters by dodecanedioic acid content, drop in Methanol Recovery still kettle, under stirring, first the industrial lye of 30wt% is added, dodecanedioic acid: NaOH (mol ratio)=1:2.6, then, heat up distillation, collect and reclaim methyl alcohol, recycle for recrystallization purifying process; In the whole process of recycling design methyl alcohol, regulate the pH value of the material in Methanol Recovery still kettle with industrial lye, pH >=8 remained.
2.. residual material dissolved dilution at the bottom of still kettle
After Methanol Recovery terminates, be dissolved in water residual material at the bottom of still kettle, and dodecanedioic acid content is adjusted to 66 grams per liters, and standby acid out crystallization is used;
3.. high-temperature acid precipitation and crystallization
A. the configuration of dilute sulphuric acid
In dilute sulphuric acid preparation still, add deionized water, under cooling, stirring, slowly drip the vitriol oil of 98.0%, water: the vitriol oil (mass ratio)=1:0.40, the mass percentage concentration of the dilute sulphuric acid of preparation is 27.8%, is cooled to room temperature, and standby crystallization is used;
B. acid out crystallization
Residual material at the bottom of still kettle after step being 2. dissolved in water drops in crystallization kettle, be warming up to 100 DEG C, slowly drip the dilution heat of sulfuric acid that a item prepares, along with adding of dilute sulphuric acid, plate crystal is slowly had to generate, when acid adding is to solution acidity pH=3.0, stop acid adding, insulated and stirred is after 20 minutes, slowly decrease temperature crystalline, when being cooled to 50 DEG C, strengthen water coolant, continue fast to be cooled to room temperature, centrifuging, gained filter cake deionized water wash, remove the impurity in filter cake and salt, washing water used are deionized water, its specific conductivity≤20 μ S/cm, it is washing terminal as effluent liquid specific conductivity≤290 μ S/cm after washing leaching cake, after having washed, continue centrifuge dripping, washings reclaims, as the dissolved dilution water of next batch, recycle,
4. dry
Filter cake after the step 2. centrifuging of b item, dries at 100 ~ 105 DEG C of temperature; Obtained 77 kilograms, High-pure Dodecanedioic Acid crystal; Product recovery rate 96.3%; Quality product reaches following technical indicator:
Embodiment 3
The recoverying and utilizing method of a kind of dodecanedioic acid purification crystalline mother solution of the present invention, comprises following operation steps:
1.. recycling design methyl alcohol
It is the crystalline mother solution 2000 liters of 50 grams per liters by dodecanedioic acid content, drop in Methanol Recovery still kettle, under stirring, first the industrial lye of 30wt% is added, dodecanedioic acid: NaOH (mol ratio)=1:2.7, then, heat up distillation, collect and reclaim methyl alcohol, recycle for recrystallization purifying process; In the whole process of recycling design methyl alcohol, regulate the pH value of the material in Methanol Recovery still kettle with industrial lye, pH >=8 remained.
2.. residual material dissolved dilution at the bottom of still kettle
After Methanol Recovery terminates, be dissolved in water residual material at the bottom of still kettle, and dodecanedioic acid content is adjusted to 70 grams per liters, and standby acid out crystallization is used;
3.. high-temperature acid precipitation and crystallization
A. the configuration of dilute sulphuric acid
In dilute sulphuric acid preparation still, add deionized water, under cooling, stirring, slowly drip the vitriol oil of 98.0%, water: the vitriol oil (mass ratio)=1:0.44, the mass percentage concentration of the dilute sulphuric acid of preparation is 29.7%, is cooled to room temperature, and standby crystallization is used;
B. acid out crystallization
Residual material at the bottom of still kettle after step being 2. dissolved in water drops in crystallization kettle, be warming up to 102 DEG C, slowly drip the dilution heat of sulfuric acid that a item prepares, along with adding of dilute sulphuric acid, plate crystal is slowly had to generate, when acid adding is to solution acidity pH=3.0, stop acid adding, insulated and stirred is after 18 minutes, slowly decrease temperature crystalline, when being cooled to 50 DEG C, strengthen water coolant, continue fast to be cooled to room temperature, centrifuging, gained filter cake deionized water wash, remove the impurity in filter cake and salt, washing water used are deionized water, its specific conductivity≤20 μ S/cm, it is washing terminal as effluent liquid specific conductivity≤285 μ S/cm after washing leaching cake, after having washed, continue centrifuge dripping, washings reclaims, as the dissolved dilution water of next batch, recycle,
4. dry
Filter cake after the step 2. centrifuging of b item, dries at 100 ~ 105 DEG C of temperature; Obtained 97 kilograms, High-pure Dodecanedioic Acid crystal; Product recovery rate 97.0%; Quality product reaches following technical indicator:
Claims (7)
1. a recoverying and utilizing method for dodecanedioic acid purification crystalline mother solution, is characterized in that comprising following operation steps:
1.. recycling design methyl alcohol
By the crystalline mother solution that dodecanedioic acid content is 30 ~ 50 grams per liters, drop in Methanol Recovery still kettle, under stirring, first the industrial lye of 30wt% is added, dodecanedioic acid: NaOH (mol ratio)=1:2.5 ~ 2.7, then, heat up distillation, collect and reclaim methyl alcohol, recycle for recrystallization purifying process;
2.. residual material dissolved dilution at the bottom of still kettle
After Methanol Recovery terminates, be dissolved in water residual material at the bottom of still kettle, and dodecanedioic acid content is adjusted to 30 ~ 70 grams per liters, and standby acid out crystallization is used;
3.. high-temperature acid precipitation and crystallization
A. the configuration of dilute sulphuric acid
In dilute sulphuric acid preparation still, add deionized water, under cooling, stirring, slowly drip the vitriol oil of 98.0%, water: the vitriol oil (mass ratio)=1:0.34 ~ 0.44, is cooled to room temperature, standby crystallization is used;
B. acid out crystallization
Residual material at the bottom of still kettle after step being 2. dissolved in water drops in crystallization kettle, be warming up to 98 ~ 102 DEG C, slowly drip the dilution heat of sulfuric acid that a item prepares, along with adding of dilute sulphuric acid, plate crystal is slowly had to generate, when acid adding is to solution acidity pH=3.0, stop acid adding, insulated and stirred is after 15 ~ 20 minutes, slowly decrease temperature crystalline, when being cooled to 50 DEG C, strengthen water coolant, continue fast to be cooled to room temperature, centrifuging, gained filter cake deionized water wash, remove the impurity in filter cake and salt, after having washed, continue centrifuge dripping, washings reclaims, as the dissolved dilution water of next batch, recycle,
4. dry
Filter cake after the step 2. centrifuging of b item, dries at 100 ~ 105 DEG C of temperature;
Obtained High-pure Dodecanedioic Acid crystal; Product recovery rate >=96.3%; Quality product reaches following technical indicator:
2. according to the recoverying and utilizing method of the dodecanedioic acid purification crystalline mother solution of claim 1, it is characterized in that step 1. in the whole process of recycling design methyl alcohol, regulate the pH value of the material in Methanol Recovery still kettle with industrial lye, pH >=8 remained.
3. according to the recoverying and utilizing method of the dodecanedioic acid purification crystalline mother solution of claim 1, it is characterized in that step is 2.. residual material dissolved dilution at the bottom of still kettle, after methyl alcohol all steams, be dissolved in water residual material at the bottom of dilution still kettle, dodecanedioic acid content is adjusted to 60 ~ 70 grams per liters, and standby acid out crystallization is used.
4., according to the recoverying and utilizing method of the dodecanedioic acid purification crystalline mother solution of claim 1, it is characterized in that the mass percentage concentration of the dilute sulphuric acid that 1. step is prepared is 25 ~ 30%.
5. according to the recoverying and utilizing method of the dodecanedioic acid purification crystalline mother solution of claim 1, it is characterized in that step 3. in c item washing water used be deionized water, its specific conductivity≤20 μ S/cm is washing terminal as effluent liquid specific conductivity≤300 μ S/cm after washing leaching cake.
6., according to the recoverying and utilizing method of the dodecanedioic acid purification crystalline mother solution of claim 1, it is characterized in that comprising following operation steps:
1.. recycling design methyl alcohol
By the crystalline mother solution that dodecanedioic acid content is 30 ~ 50 grams per liters, drop in Methanol Recovery still kettle, under stirring, first the industrial lye of 30wt% is added, dodecanedioic acid: NaOH (mol ratio)=1:2.5, then, heat up distillation, collect and reclaim methyl alcohol, recycle for recrystallization purifying process; In the whole process of recycling design methyl alcohol, regulate the pH value of the material in Methanol Recovery still kettle with industrial lye, pH >=8 remained;
2.. residual material dissolved dilution at the bottom of still kettle
After Methanol Recovery terminates, be dissolved in water residual material at the bottom of still kettle, and dodecanedioic acid content is adjusted to 60 ~ 70 grams per liters, and standby acid out crystallization is used;
3.. high-temperature acid precipitation and crystallization
A. the configuration of dilute sulphuric acid
In dilute sulphuric acid preparation still, add deionized water, under cooling, stirring, slowly drip the vitriol oil of 98.0%, water: the vitriol oil (mass ratio)=1:0.34 ~ 0.44, the mass percentage concentration of the dilute sulphuric acid of preparation is 25 ~ 30%, be cooled to room temperature, standby crystallization is used;
B. acid out crystallization
Residual material at the bottom of still kettle after step being 2. dissolved in water drops in crystallization kettle, be warming up to 98 ~ 102 DEG C, slowly drip the dilution heat of sulfuric acid that a item prepares, along with adding of dilute sulphuric acid, plate crystal is slowly had to generate, when acid adding is to solution acidity pH=3.0, stop acid adding, insulated and stirred is after 15 ~ 20 minutes, slowly decrease temperature crystalline, when being cooled to 50 DEG C, strengthen water coolant, continue fast to be cooled to room temperature, centrifuging, gained filter cake deionized water wash, remove the impurity in filter cake and salt, washing water used are deionized water, its electricity Dao Shuais≤20 μ S/cm, when the effluent liquid electricity Dao after washing leaching cake Shuai≤300 μ S/cm time for washing terminal, after having washed, continue centrifuge dripping, washings reclaims, as the dissolved dilution water of next batch, recycle,
4. dry
Filter cake after the step 2. centrifuging of b item, dries at 100 ~ 105 DEG C of temperature; Obtained High-pure Dodecanedioic Acid crystal; Product recovery rate >=97.0%; Quality product reaches following technical indicator:
7. the application of the dodecanedioic acid product reclaimed according to the recoverying and utilizing method of the dodecanedioic acid purification crystalline mother solution of claim 1, is characterized in that being applicable to synthesize long carbon chain nylon as polycondensation monomer and diamine generation polycondensation; Also the raw material of synthetic perfume, medicine is applicable to.
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| WO2017088218A1 (en) | 2015-11-27 | 2017-06-01 | 希锐科技（北京）有限公司 | Method of co-producing long chain amino acid and dibasic acid |
| US10239821B2 (en) | 2015-11-27 | 2019-03-26 | Vitaworks Ip, Llc | Process for the co-production of long chain amino acids and dibasic acids |
| US10065921B1 (en) | 2017-07-07 | 2018-09-04 | Vitaworks Ip, Llc | Process for producing long chain amino acids and dibasic acids |
| US10343978B2 (en) | 2017-07-07 | 2019-07-09 | Vitaworks Ip, Llc | Process for producing long chain amino acids and dibasic acids |
| US10822300B2 (en) | 2017-07-07 | 2020-11-03 | Vitaworks Ip, Llc | Process for producing long chain amino acids and dibasic acids |
| WO2020251613A1 (en) | 2019-06-10 | 2020-12-17 | Vitaworks Ip, Llc | Producing long chain amino and dibasic acids |
| CN111087298A (en) * | 2019-12-31 | 2020-05-01 | 淄博广通化工有限责任公司 | Mixed long carbon chain dicarboxylic acid and preparation method thereof |
| CN116239488A (en) * | 2021-12-08 | 2023-06-09 | 江苏万年长药业有限公司 | Method for recycling N, N-dimethyl capramide byproducts |
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