CN101219946B - Method for recycling waste liquor of ammonium hexanedioic acid and recycling system thereof - Google Patents
Method for recycling waste liquor of ammonium hexanedioic acid and recycling system thereof Download PDFInfo
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- CN101219946B CN101219946B CN200710125602XA CN200710125602A CN101219946B CN 101219946 B CN101219946 B CN 101219946B CN 200710125602X A CN200710125602X A CN 200710125602XA CN 200710125602 A CN200710125602 A CN 200710125602A CN 101219946 B CN101219946 B CN 101219946B
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- ammonium adipate
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Abstract
The invention relates to a method and a system for treating and recovering adipic acid ammonium waste liquid and the recovering method comprises the following steps: A. filtering the solid impurities in the waste liquid; B. controlling the temperature of the filtered waste liquid and acidizing the filtered waste liquid; C. decreasing the temperature of the acidulated waste liquid and crystallizing the acidulated waste liquid; D. collecting adipic acid crystal after solid-liquid separation; E. washing to get adipic acid crystal and collecting the adipic acid crystal after solid-liquid separation. The recovering method and recovering system of the invention have the following advantages that the recovering method and recovering system of the invention are able to acquire a purified adipic acid with standard capacitance and able to be circularly used in the industries such as an electrolytic capacitor, etc. with a simple and efficient technique and obvious economical benefit and environment protection effect.
Description
Technical field
The present invention relates to a kind of recovery method and device systems thereof of organic liquid waste, more particularly, the present invention relates to recovery method and device systems thereof that a kind of aluminium foil changes into waste liquid.
Background technology
Electrical condenser be with must adopting electrolytic solution in the low-voltage aluminium foil formation process, and low pressure to change into the electrolytic solution main component be ammonium adipate.Changing into electrolytic solution uses after for some time owing to wherein sneak into more aluminum ion and some other impurity, the paper tinsel electrical property that changes into that causes producing does not reach predetermined requirement gradually, at this moment just can carry out ordinary production with regard to needing the new ammonium adipate solution of preparation to change electrolytic solution.And if waste and old electrolysis waste solution is arbitrarily toppled over and entered in ambient soil, the water body, then can cause serious environmental to pollute, and cause the wasting of resources.
On the other hand, a large amount of hexanodioic acids are mainly used in production man-made fiber and engineering plastics, are used to produce various ester classes, softening agent; Hexanodioic acid and ammonium adipate also are widely used in the electrolytic condenser industry, are mainly used in the electrolytic solution of low pressure chemical synthesis technology and electrolytic condenser.And, resource growing tension growing along with industry, the market value of hexanodioic acid is day by day surging at present.
Therefore, if can be recycled the discarded electrolytic solution that aluminium foil used in capacitor changes into, not only can be reduced production costs, realize resource circulation utilization, can also be reduced and even eliminate the environmental pollution damage that it causes effectively.
In this regard, number being arranged is that 200480030177.0 Chinese patent application discloses and a kind ofly prepares in the mixture of hexanodioic acid multistep crystalline method in the pimelinketone oxidation and purify and obtain the method for hexanodioic acid; The emphasis of this method is to remove a spot of metal catalyst (as Co) of existing in the preparation process etc., is 95～99.95% hexanodioic acid to reach purity.This technology can not solve the recycling problem of the discarded electrolytic solution that aluminium foil used in capacitor changes into.
Summary of the invention
The problems referred to above at prior art, the objective of the invention is to provide a kind of processing recovery method and recovery system thereof of ammonium adipate waste liquid, this recovery method and recovery system thereof have following advantage: can reclaim the hexanodioic acid that obtains the pure standard of electric capacity, capable of circulationly be used for the electrolytic condenser industry or make other purposes, and technology is simple, effective, and economic benefit and environment protecting are all more remarkable.
For this reason, one of technical solution of the present invention is a kind of processing recovery method of ammonium adipate waste liquid, and described recovery method comprises the steps: solid impurity in A, the filtering waste liquid, B, to the filter after waste liquid carry out the temperature control acidifying, souring temperature is controlled at 55-75 ℃, pH is controlled at the 2-3 scope, C, the waste liquid after the acidifying is carried out decrease temperature crystalline, D, solid-liquid separation are collected crystallization of adipic acid, the crystallization of adipic acid that E, cleaning obtain, and solid-liquid separation is collected crystallization of adipic acid.
The ammonium adipate that adopts in changing into electrolytic solution is the pure grade of electric capacity, but aluminum ion and other some impurity have been sneaked in process of production, analysis revealed, change into and mainly contain ammonium adipate and more above-mentioned ions and metallic element in the waste liquid, in this solution, directly ammonium adipate is carried out recrystallization and then compare difficulty with the impurity of removing wherein, because it is the solubleness of ammonium adipate can reach 50～70g/100g water at normal temperatures, difficult to take crystallization method that ammonium adipate is reclaimed, utilizes.The thinking of Japan's some process using solubility product of industry competition: interpolation can produce the ion of difficulty soluble salt such as calcium ion and wait and make hexanodioic acid separate with ammonium and generate lower salt of solubility product and then solid-liquid separation enrichment hexanodioic acid root, and then acidifying obtains the hexanodioic acid of purifying.Such technology will be used excessive easily molten strong acid calcium salt, so behind crystallization of adipic acid, can sneak into the strong acid root and the calcium ion of excessive part simultaneously, should wash-out or in and the strong acid root, also to remove calcium ion, have ambilateral separating difficulty and workload, organic efficiency and economic benefit all are subjected to very big influence.
Recognize the above-mentioned shortcoming of existing Technology, the present invention is conceived to reduce the aftertreatment workload, sharp and recognize: the slope that the solubility with temperature of hexanodioic acid changes is very violent: be 3.01g/100g water during the 303K temperature originally, then reach 160g/100g water during 373K, process evidence: electrical condenser is changed into waste liquid carry out acidifying with diluted acid, regulate pH at suitable scope, control waste liquid under proper temperature, allow it fully react, with nitric acid following reaction take place as ammonium adipate in the waste liquid and acidifying:
H
4NOOC-(CH
2)
4-COONH
4+2HNO
3→HOOC-(CH
2)
4-COOH+2NH
4NO
3
Temperature-solubility curve in conjunction with hexanodioic acid, just can infer: after hexanodioic acid in the waste liquid fully generates, just can then adopt the cooling crystallization method hexanodioic acid of purifying, if above-mentioned thinking is possible, just ambilateral separating difficulty and workload an aspect be can be reduced to, thereby organic efficiency, environmental benefit and economic benefit significantly improved.In contrast to this, ammonia salt such as ammonium nitrate NH
4NO
3Solubleness be: be 242g/100g water during the 303K temperature, then reach 870g/100g water during 373K, its solubleness is very big under the room temperature, also is difficult to crystallization, and it can not influence the purity of hexanodioic acid.
For this reason, the treatment process that the present invention gropes integral body is: take to filter directly acidifying processing step of back, make ammonium adipate be converted into hexanodioic acid heating, separating with the ammonium root under the acidic conditions; Utilize then and reduce method of temperature, make the hexanodioic acid direct crystallization generate the solid adipic acid crystallization, the crystallization of adipic acid that obtains is washed, to remove the foreign ion that wherein is mingled with pure water; During this time impurity, the purity of hexanodioic acid are measured, reached corresponding standard and can send into the workshop and be back to production, the underproof pure water that then adds once more carries out recrystallization, until reaching standard.Experimental results show that; This technology is very high to the recovery productive rate of hexanodioic acid in the waste liquid, reaches more than 90%, and purity can reach 99.5% even higher; Hexanodioic acid after the present invention purifies adds ammoniacal liquor generation ammonium adipate and can be used further to change in the electrolytic solution.Therefore recovery method technology of the present invention is simple, recovery is effective, reclaims product and can be recycled and reused for production, has reduced the discharging of waste electrolyte, has reduced production cost; Efficiency of cycling economy and environment protecting are all very remarkable.
The processing recovery method of ammonium adipate waste liquid of the present invention also further comprises following concrete improvement:
The crystallization of adipic acid that solid-liquid separation is obtained carries out step F: dehydrates recovery and makes the hexanodioic acid finished product,
So not only can use by oneself, can also be as production marketing, and be easy to preserve.
Aforementioned crystalline mother liquor, rinse water are carried out centralized collection; and heating, crystallization; can generate for example ammonium nitrate of ammonium salt of strong acid; these ammonium salt reusable edibles are as industrial chemicals or as fertilizer sources; to reduce production cost; better protection environment, for example: described recovery method also comprises the steps: G, carries out evaporation concentration with separating the liquid that obtains among step D, the E, removes moisture and obtains ammonium salt.
Among the described step B, acidifying adopts nitric acid, sulfuric acid, hydrochloric acid wherein a kind of.
Too much to electrical condenser or change into deleterious sulfate radical, chlorion for fear of carrying secretly in reclaiming the hexanodioic acid of purifying, among the described step B, rare nitric acid is preferably adopted in acidifying, and temperature is controlled at 55-75 ℃, and pH is controlled at the 2-3 scope.
Described step C also comprises the described acidifying waste liquid of evaporation concentration, makes the density of waste liquid reach 1.1-1.3g/cm
3, be cooled to room temperature then and carry out crystallization, the preferred mode that leaves standstill, the easy like this needle crystals that obtains of adopting in the described decrease temperature crystalline process.
In the described step e, impurity on the pure water eccysis crystallization of adipic acid of employing resistivity 〉=2M Ω cm, detect its impurity and purity then: as reach corresponding standard, make the finished product hexanodioic acid after F dehydrates set by step or directly recycle, otherwise add that pure water heats, recycle behind the recrystallization.
In the described step F, dehydrate to be controlled at and carry out the exhausting drying under 40～50 ℃.
Correspondingly, another technical solution of the present invention is a kind ofly to be used for the as above ammonium adipate Mead-Bauer recovery system of recovery method, and described recovery system comprises in regular turn as lower member: the acidifier of waste liquid tank, strainer, band heating unit, temperature control crystallizer, solid-liquid separator 1, washing bath, solid-liquid separator 2, exhausting moisture eliminator; Mainly the advancing of above-mentioned each parts/discharge port directly or indirectly is connected mutually by the transmission utensil.
As previously mentioned, ammonium adipate Mead-Bauer recovery system of the present invention can be efficiently, environmental protection ground reclaims the pure hexanodioic acid that obtains capacity standard, and circulation is used for electrical condenser and changes into industry, and technology is simple, effect is remarkable.
For quality product is reclaimed in the environmental benefit and the assurance that further improve recovery system, described recovery system also comprise in regular turn to liquid carries out evaporation concentration vaporizer, collect the solid-liquid separator and the moisture eliminator of ammonium salt, mainly the advancing of above-mentioned each parts/discharge port directly or indirectly is connected mutually by the transmission utensil; Also be provided with well heater between described solid-liquid separator 2 and the crystallizer.
The present invention will be further described below in conjunction with the drawings and specific embodiments.
Description of drawings
Fig. 1 is the structural representation of ammonium adipate Mead-Bauer recovery system of the present invention.
Fig. 2 is the schematic process flow diagram of the processing recovery method of ammonium adipate waste liquid of the present invention.
Embodiment
System embodiment:
As Fig. 1, be depicted as the structural representation of ammonium adipate Mead-Bauer recovery system of the present invention.It comprises mainly/discharge port directly or indirectly be connected in regular turn as lower member: acidifier 12, temperature control crystallizer 13, solid-liquid separator 1-14A, washing bath 15, solid-liquid separator 2-14B, the exhausting moisture eliminator 16 of waste liquid tank 10, strainer 11, band heating unit, the well heater 17 of the promising recrystallization of returning apparatus between solid-liquid separator 2-14B and temperature control crystallizer 13 carries out crystallization purifying once more after being used for the crystallization of disqualified upon inspection dissolved; Also be provided with the pipeline T of band switching valve between solid-liquid separator 1-14A and exhausting moisture eliminator 16, the band liquid crystallization that is used for being purified once more behind the recrystallization directly is transported to solid-liquid separator 1-14A and carries out disposable solid-liquid separation.Described recovery system also comprises in regular turn carries out the vaporizer 18 of evaporation concentration, solid-liquid separator 19, the moisture eliminator 20 of collection ammonium salt to acidic liquid; Mainly the advancing of this vaporizer 18, solid-liquid separator 19, moisture eliminator 20/discharge port directly or indirectly is connected in regular turn.Above-mentioned solid-liquid separator all can adopt centrifuge separator.
Method embodiment:
As Fig. 2, be depicted as the schematic process flow diagram of the processing recovery method of ammonium adipate waste liquid of the present invention.Recovery method adopts recovery system embodiment of the present invention, carry out following steps comprises: depleted ammonium adipate solution between A0, collecting cart, A, filter, and remove suspended substance wherein; B, clarifying filtrate being heated to 60 ℃ ± 5 ℃, is 0.5mol/L ± 0.1mol/L nitric acid with the good concentration of oneself dilution, slowly adds wherein, regulates pH to 2-3, fully stirs simultaneously, heating, evaporation concentration solution, and solution density is controlled at 1.1～1.3g/cm
3C, leave standstill solution and cooling solution, come controlled chilling speed according to the crystalline shape therebetween, generate needle crystal to room temperature, D, solidliquid mixture is done to collect crystallization after the solid-liquid separation, E1, crystallization is cleaned, remove impurity, collect crystallization after E2, the solid-liquid separation with pure water; The purity that detects hexanodioic acid reaches more than 99.5%, foreign ion (mainly being nitrate radical, chlorion etc.) also satisfies the pure requirement of electric capacity, can be mixed with once more to change into that liquid is produced or carry out step F: will detect qualified crystallization of adipic acid and can pack after 40～50 ℃ of exhausting oven dry; The purity that detects hexanodioic acid is defective, carry out E3: defective crystallization of adipic acid is carried out heating for dissolving, and then carry out step C: leave standstill solution and cooling solution to room temperature, carry out crystallization once more, solid-liquid separation D, detect and directly carry out step F after qualified and reclaim crystallization of adipic acid.
And the mother liquor that above-mentioned solid-liquid separation obtains after the crystallization is made centralized collection, G1, carry out evaporation concentration as the case may be.G2, centrifugation are reclaimed behind G3, the drying crystalline and are obtained particle ammonium nitrate.
Claims (9)
1. the processing recovery method of an ammonium adipate waste liquid, it is characterized in that: described recovery method comprises the steps: solid impurity in A, the filtering waste liquid, B, to the filter after waste liquid carry out the temperature control acidifying, souring temperature is controlled at 55-75 ℃, pH is controlled at the 2-3 scope, C, the waste liquid after the acidifying is carried out decrease temperature crystalline, and D, solid-liquid separation are collected crystallization of adipic acid, E, cleaning crystallization of adipic acid, solid-liquid separation is collected crystallization of adipic acid.
2. the processing recovery method of ammonium adipate waste liquid according to claim 1 is characterized in that: described recovery method also comprises the steps: F, make the finished product hexanodioic acid after dehydrating.
3. the processing recovery method of ammonium adipate waste liquid according to claim 1, it is characterized in that: described recovery method also comprises the steps: G, carries out evaporation concentration with separating the liquid that obtains among step D, the E, removes moisture and obtains corresponding ammonium salt.
4. the processing recovery method of ammonium adipate waste liquid according to claim 1 is characterized in that: among the described step B, acidifying adopts nitric acid, sulfuric acid, hydrochloric acid wherein a kind of.
5. the processing recovery method of ammonium adipate waste liquid according to claim 1, it is characterized in that: described step C also comprises the described acidifying waste liquid of evaporation concentration, makes the density of waste liquid reach 1.1-1.3g/cm
3, be cooled to room temperature then and carry out crystallization.
6. the processing recovery method of ammonium adipate waste liquid according to claim 1, it is characterized in that: in the described step e, impurity on the pure water eccysis crystallization of adipic acid of employing resistivity 〉=2M Ω cm, detect its impurity and purity then: as reach corresponding standard, make the finished product hexanodioic acid after F dehydrates set by step or directly recycle, otherwise add that pure water heats, recycle behind the recrystallization.
7. as the processing recovery method of ammonium adipate waste liquid as described in the claim 2, it is characterized in that: in the described step F, dehydrate to be controlled at and carry out the exhausting drying under 40～50 ℃.
8. ammonium adipate Mead-Bauer recovery system that is used for as one of claim 1-7 recovery method, it is characterized in that: described recovery system comprises in regular turn as lower member: the acidifier of waste liquid tank, strainer, band heating unit, temperature control crystallizer, solid-liquid separator 1, washing bath, solid-liquid separator 2, exhausting moisture eliminator; Mainly the advancing of above-mentioned each parts/discharge port directly or indirectly is connected mutually by the transmission utensil.
9. as ammonium adipate Mead-Bauer recovery system as described in the claim 8, it is characterized in that: described recovery system also comprise in regular turn to liquid carries out evaporation concentration vaporizer, collect the solid-liquid separator and the moisture eliminator of ammonium salt, mainly the advancing of above-mentioned each parts/discharge port directly or indirectly is connected mutually by the transmission utensil; Also be provided with well heater between described solid-liquid separator 2 and the crystallizer.
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| CN200710125602XA CN101219946B (en) | 2007-12-25 | 2007-12-25 | Method for recycling waste liquor of ammonium hexanedioic acid and recycling system thereof |
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| CN200710125602XA CN101219946B (en) | 2007-12-25 | 2007-12-25 | Method for recycling waste liquor of ammonium hexanedioic acid and recycling system thereof |
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| CN101219946A CN101219946A (en) | 2008-07-16 |
| CN101219946B true CN101219946B (en) | 2010-08-11 |
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| CN103508596B (en) * | 2012-06-29 | 2015-01-07 | 温州大学 | Treatment system and recycling method of ammonium adipate cleansing wastewater |
| CN103588632B (en) * | 2013-10-17 | 2015-07-15 | 仲恺农业工程学院 | Method and equipment for efficiently synthesizing adipate crystal from ammonium adipate formation waste liquid |
| RU2635106C1 (en) * | 2017-02-20 | 2017-11-09 | Федеральное автономное учреждение "25 Государственный научно-исследовательский институт химмотологии Министерства обороны Российской Федерации" | Method of producing concentrate of adipic acid and sodium alkaline from alkaline drains of caprolactam production |
| CN109053423B (en) * | 2018-10-12 | 2021-07-27 | 温州大学新材料与产业技术研究院 | Purification method of ammonium adipate waste liquid and recovery processing device thereof |
| CN110746291A (en) * | 2019-09-18 | 2020-02-04 | 山东凯米科环保科技有限公司 | Purification method of ammonium adipate waste liquid and recovery processing device thereof |
| CN110759554A (en) * | 2019-11-01 | 2020-02-07 | 扬州宏远电子股份有限公司 | Recycling and zero-discharge treatment method for ammonium adipate wastewater generated in aluminum foil formation |
| CN115141095A (en) * | 2022-07-01 | 2022-10-04 | 浙江贝诺机械有限公司 | Process for re-melting, purifying and recrystallizing adipic acid |
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