CN100410229C - Method of treating hexane diacid preparation waste liquid - Google Patents
Method of treating hexane diacid preparation waste liquid Download PDFInfo
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- CN100410229C CN100410229C CNB2006101069122A CN200610106912A CN100410229C CN 100410229 C CN100410229 C CN 100410229C CN B2006101069122 A CNB2006101069122 A CN B2006101069122A CN 200610106912 A CN200610106912 A CN 200610106912A CN 100410229 C CN100410229 C CN 100410229C
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Abstract
This invention provides a treatment method for waste liquid from adipic acid production with simple process, good effect and low cost. Said method comprises: (1) adding waste liquid from adipic acid production and the extraction agent of ethyl acetate with the same volume as the waste liquid in an extraction equipment, vibrating and extracting, and standing to stratify the water and organic item, and flowing out the water and the remained extract containing three acids (adipic acid, glutaric acid and succinic acid), (2) repeating above steps to extract, (3) distilling the three acids-bearing extract no longer to be treated, evaporating the extraction agent of ethyl acetate, recycling, cooling the remainder and molding to obtain the three acids, and (3) adding alkaline substance to the water no longer to be treated, adjusting its pH within a range of 7-8, and discharging or taking it as liquid fertilizer. The approach is an advanced and mature technology with low energy consumption and no pollution. The three acid obtained have good quality and high efficiency.
Description
Technical field
The present invention relates to a kind of method of handling industrial effluent, specifically, related to a kind of method of handling hexane diacid preparation waste liquid.
Background technology
At present, the large-lot producer that produces hexanodioic acid in China mainly contains 66 salt companies of refreshing horse group of Liaoyang petrochemical industry group and tafelberg, the treatment process of the hexane diacid preparation waste liquid that these two large enterprises produce is basic identical: at first, hexane diacid preparation waste liquid is packed in the acid-resistant reacting kettle, logical steam-heated cal(l)andria is evaporated away moisture and the rare nitric acid produced in the waste liquid; And then, add the lime neutralization to the water of condensation of water vapour and nitric acid, transfer pH value to 7～8, at last discharging; In addition, moisture free useless hexanodioic acid is added admittance deep fat in the pyroreaction still, continue heating,, make the nitric acid that includes resolve into water and NO when temperature reaches 160 ℃～180 ℃
2Be evaporated water vapour and NO
2Mixed gas enters the absorption tower again through cooling tower, sprays sodium hydroxide solution in the absorption tower, and sodium hydroxide and nitrogen peroxide reaction generate SODIUMNITRATE, and reaction reduces NO according to this
2Gas is to atmospheric pollution, the NO in heating useless hexanodioic acid
2After having arranged, emit from reactor, cooling is finished product, and finished product approximately contains Succinic Acid about 5%, about 65% pentanedioic acid and about 20% hexanodioic acid.
Yet there are many problems in this technology, mainly show following some:
1, in this technology, NO
2Assimilation effect be subjected to the influence of factors such as variation of variation, the gas temperature of variation, the gas flow flow velocity of concentration of lye, these factors easily cause NO
2Gas is discharged in a large number, polluted air;
2, about 80% moisture in this arts demand evaporation hexanodioic acid waste liquid is so energy consumption is higher;
3, the high temperature of 160 ℃～180 ℃ of this arts demands produces NO to decompose
2Gas, part Succinic Acid, pentanedioic acid and hexanodioic acid distillation at high temperature run away, and part three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) are decomposed, the energy consumption height, easily loss, the easy coking of product, product colour is dark, of poor quality.
Just because of this, the sector is badly in need of a kind of treatment process of the economical and practical and hexane diacid preparation waste liquid that treatment effect is good.
Summary of the invention
The objective of the invention is to solve the deficiencies in the prior art, thereby the method for the processing hexane diacid preparation waste liquid that a kind of technology is simple, treatment effect good, input cost is low is provided.
The technical scheme of the processing hexane diacid preparation waste liquid that the present invention proposes comprises the steps:
(1), takes by weighing the ethyl acetate extraction agent of the hexane diacid preparation waste liquid and the V volume of V volume, together add in the extraction equipment 1, under the normal temperature and pressure, carry out oscillation extraction, static then, after organic phase and water layering, in extraction equipment 1, flow out water, be called 1b, the remaining extraction liquid that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) is called 1a;
(2), take by weighing the hexane diacid preparation waste liquid of V volume again, pour in the extraction equipment 2, pour the extraction liquid 1a that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) again into, under the normal temperature and pressure, carry out oscillation extraction, static then, after organic phase and water layering, flow out water in extraction equipment 2, be called 2b, the remaining extraction liquid that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) is called 2a;
(3), take by weighing the hexane diacid preparation waste liquid of V volume again, pour in the extraction equipment 3, pour the extraction liquid 2a that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) again into, under the normal temperature and pressure, carry out oscillation extraction, static then, after organic phase and water layering, flow out water in extraction equipment 3, be called 3b, the remaining extraction liquid that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) is called 3a;
(4), then, water 1b is poured in the extraction equipment 4, adding is with the ethyl acetate extraction agent of volume, under the normal temperature and pressure, carry out oscillation extraction, static then, after organic phase and water layering, flow out water from extraction equipment 4, be called 4b, the remaining extraction liquid that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) is called 4a;
(5), again extraction liquid 4a is mixed with water 3b and pour in the extraction equipment 5, under the normal temperature and pressure, carry out oscillation extraction, after organic phase and water layering, flow out water in extraction equipment 5, be called 5b, the remaining extraction liquid that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) is called 5a;
(6), water 4b is poured in the extraction equipment 6, adding is with the ethyl acetate extraction agent of volume, under the normal temperature and pressure, carry out oscillation extraction, after organic phase and water layering, flow out water in extraction equipment 6, be called 6b, the remaining extraction liquid that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) is called 6a;
(7), again extraction liquid 5a is mixed with water 2b and pour in the extraction equipment 7, under the normal temperature and pressure, carry out oscillation extraction, after organic phase and water layering, flow out water in extraction equipment 7, be called 7b, the remaining extraction liquid that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) is called 7a;
(8), extraction liquid 6a mixed with water 7b pours in the extraction equipment 8, under the normal temperature and pressure, carry out oscillation extraction, after organic phase and water layering, flow out water in extraction equipment 8, be called 8b, the remaining extraction liquid that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) is called 8a;
(9), the extraction liquid of no longer handling in step (3), (7) and (8) that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) is distilled, make ethyl acetate extraction agent evaporation, reclaim, then, make the surplus materials cooling forming, obtain three acid (hexanodioic acid, pentanedioic acid and Succinic Acid);
(10), the aqueous phase no longer handled in step (5), (6) and (8) is added alkaline matter, transfer its pH value in 7～8 scope, discharge or do liquid fertilizer then.
Based on the above, replace ethyl acetate with Isoamyl Acetate FCC, butylacetate, benzene, dimethylbenzene or chloroform.
The present invention has outstanding substantive distinguishing features and obvious improvement, and specifically, its most tangible advantage is:
1, in this treatment process, do not need to evaporate 80% moisture, so energy consumption is low;
2, adopt method of extraction, make to extract in the organic phase of back and do not contain nitric acid, so when extraction liquid adds thermal distillation, there is not NO
2Gas is emitted, and can not pollute atmosphere;
Temperature control was low when 3, extraction liquid added thermal distillation, do not surpass 160 ℃ usually, avoided the distillation or the decomposition of three acid as far as possible, reduced loss, and not coking of product, of light color, quality good;
4, this technology does not need to drop into a large amount of treatment facilities, and technology is simple, advanced, and technology maturation is easy to operate, and extraction agent is also recyclable to be utilized again, and processing cost is low, high efficiency;
5, adopt measured three acid of the recyclable a large amount of matter of this technology (hexanodioic acid, pentanedioic acid and Succinic Acid) product, utility value after its reprocessing is very high, in addition, can be used as fertilizer after waste liquid is handled through acid base equilibrium and use, have considerable economic and social benefit.
Description of drawings
Fig. 1 is a treatment scheme synoptic diagram of the present invention.
Embodiment
For the plurality of advantages of technical scheme of the present invention and existence can better be described, now provide concrete embodiment:
A kind of method of handling hexane diacid preparation waste liquid comprises the steps:
(1), takes by weighing the ethyl acetate extraction agent of the hexane diacid preparation waste liquid and the V volume of V volume, together add in the extraction equipment 1, under the normal temperature and pressure, carry out oscillation extraction, static then, after organic phase and water layering, in extraction equipment 1, flow out water, be called 1b, the remaining extraction liquid that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) is called 1a;
(2), take by weighing the hexane diacid preparation waste liquid of V volume again, pour in the extraction equipment 2, pour the extraction liquid 1a that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) by a certain percentage again into, under the normal temperature and pressure, carry out oscillation extraction, static then, after organic phase and water layering, flow out water in extraction equipment 2, be called 2b, the remaining extraction liquid that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) is called 2a;
(3), take by weighing the hexane diacid preparation waste liquid of V volume again, pour in the extraction equipment 3, pour the extraction liquid 2a that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) by a certain percentage again into, under the normal temperature and pressure, carry out oscillation extraction, static then, after organic phase and water layering, flow out water in extraction equipment 3, be called 3b, the remaining extraction liquid that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) is called 3a;
(4), then, water 1b is poured in the extraction equipment 4, adding is with the ethyl acetate extraction agent of volume, under the normal temperature and pressure, carry out oscillation extraction, static then, after organic phase and water layering, flow out water from extraction equipment 4, be called 4b, the remaining extraction liquid that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) is called 4a;
(5), extraction liquid 4a and water 3b are mixed by a certain percentage pour in the extraction equipment 5 again, under the normal temperature and pressure, carry out oscillation extraction, after organic phase and water layering, in extraction equipment 5, flow out water, be called 5b, the remaining extraction liquid that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) is called 5a;
(6), water 4b is poured in the extraction equipment 6, adding is with the ethyl acetate extraction agent of volume, under the normal temperature and pressure, carry out oscillation extraction, after organic phase and water layering, flow out water in extraction equipment 6, be called 6b, the remaining extraction liquid that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) is called 6a;
(7), extraction liquid 5a and water 2b are mixed by a certain percentage pour in the extraction equipment 7 again, under the normal temperature and pressure, carry out oscillation extraction, after organic phase and water layering, in extraction equipment 7, flow out water, be called 7b, the remaining extraction liquid that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) is called 7a;
(8), extraction liquid 6a and water 7b are mixed by a certain percentage pour in the extraction equipment 8, under the normal temperature and pressure, carry out oscillation extraction, after organic phase and water layering, in extraction equipment 8, flow out water, be called 8b, the remaining extraction liquid that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) is called 8a;
(9), extraction liquid 3a, 7a and the 8a that contains three acid (hexanodioic acid, pentanedioic acid and Succinic Acid) carried out low temperature (temperature is no more than 160 ℃ usually) distillation, make ethyl acetate extraction agent evaporation, reclaim, then, make the surplus materials cooling forming, obtain three acid (hexanodioic acid, pentanedioic acid and Succinic Acid);
(10), in water 5b, 6b and 8b, add lime, transfer its pH value in 7～8 scope, can directly discharge or do liquid fertilizer then.
Wherein, the above extraction agent also can be organic solvents such as ester classes such as Isoamyl Acetate FCC, butylacetate or benzene, dimethylbenzene, chloroform.
The water process is above repeatedly, the extraction of eclipsed form, hexanodioic acid in the former hexane diacid preparation waste liquid, pentanedioic acid and Succinic Acid are by the basic extraction of organic phase (ethyl acetate) fully, percentage extraction is up to more than 98%, and rare nitric acid still is present in aqueous phase, this time in water discharging pond, add lime or other alkaline matters with in and nitric acid, and adjust the pH value in 7～8 scope, at this moment, water can discharge, and also can make liquid fertilizer and use.
Repeatedly, eclipsed extraction mode finally makes three acid (hexanodioic acid, pentanedioic acid and the Succinic Acid) concentration of aqueous phase fewer and feweri, three acid in the organic extract (hexanodioic acid, pentanedioic acid and Succinic Acid) concentration is more and more.
Claims (2)
1. a method of handling hexane diacid preparation waste liquid is characterized in that, comprises the steps:
(1), takes by weighing the ethyl acetate extraction agent of the hexane diacid preparation waste liquid and the V volume of V volume, together add in the extraction equipment 1, under the normal temperature and pressure, carry out oscillation extraction, static then, after organic phase and water layering, in extraction equipment 1, flow out water, be called 1b, the remaining extraction liquid that contains hexanodioic acid, pentanedioic acid and Succinic Acid is called 1a;
(2), take by weighing the hexane diacid preparation waste liquid of V volume again, pour in the extraction equipment 2, pour the extraction liquid 1a that contains hexanodioic acid, pentanedioic acid and Succinic Acid again into, under the normal temperature and pressure, carry out oscillation extraction, static then, after organic phase and water layering, flow out water in extraction equipment 2, be called 2b, the remaining extraction liquid that contains hexanodioic acid, pentanedioic acid and Succinic Acid is called 2a;
(3), take by weighing the hexane diacid preparation waste liquid of V volume again, pour in the extraction equipment 3, pour the extraction liquid 2a that contains hexanodioic acid, pentanedioic acid and Succinic Acid again into, under the normal temperature and pressure, carry out oscillation extraction, static then, after organic phase and water layering, flow out water in extraction equipment 3, be called 3b, the remaining extraction liquid that contains hexanodioic acid, pentanedioic acid and Succinic Acid is called 3a;
(4), then, water 1b is poured in the extraction equipment 4, adding is with the ethyl acetate extraction agent of volume, under the normal temperature and pressure, carry out oscillation extraction, static then, after organic phase and water layering, flow out water from extraction equipment 4, be called 4b, the remaining extraction liquid that contains hexanodioic acid, pentanedioic acid and Succinic Acid is called 4a;
(5), again extraction liquid 4a is mixed with water 3b and pour in the extraction equipment 5, under the normal temperature and pressure, carry out oscillation extraction, after organic phase and water layering, flow out water in extraction equipment 5, be called 5b, the remaining extraction liquid that contains hexanodioic acid, pentanedioic acid and Succinic Acid is called 5a;
(6), water 4b is poured in the extraction equipment 6, add ethyl acetate extraction agent, under the normal temperature and pressure with volume, carry out oscillation extraction, after organic phase and water layering, in extraction equipment 6, flow out water, be called 6b, the remaining extraction liquid that contains hexanodioic acid, pentanedioic acid and Succinic Acid is called 6a;
(7), again extraction liquid 5a is mixed with water 2b and pour in the extraction equipment 7, under the normal temperature and pressure, carry out oscillation extraction, after organic phase and water layering, flow out water in extraction equipment 7, be called 7b, the remaining extraction liquid that contains hexanodioic acid, pentanedioic acid and Succinic Acid is called 7a;
(8), extraction liquid 6a mixed with water 7b pours in the extraction equipment 8, under the normal temperature and pressure, carry out oscillation extraction, after organic phase and water layering, flow out water in extraction equipment 8, be called 8b, the remaining extraction liquid that contains hexanodioic acid, pentanedioic acid and Succinic Acid is called 8a;
(9), the extraction liquid of no longer handling in step (3), (7) and (8) that contains hexanodioic acid, pentanedioic acid and Succinic Acid is distilled, make ethyl acetate extraction agent evaporation, reclaim, then, make the surplus materials cooling forming, obtain hexanodioic acid, pentanedioic acid and Succinic Acid;
(10), the aqueous phase no longer handled in step (5), (6) and (8) is added alkaline matter, transfer its pH value in 7～8 scope, discharge or do liquid fertilizer then.
2. a kind of method of handling hexane diacid preparation waste liquid according to claim 1 is characterized in that replacing ethyl acetate with Isoamyl Acetate FCC, butylacetate, benzene, dimethylbenzene or chloroform.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006101069122A CN100410229C (en) | 2006-08-18 | 2006-08-18 | Method of treating hexane diacid preparation waste liquid |
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| CNB2006101069122A CN100410229C (en) | 2006-08-18 | 2006-08-18 | Method of treating hexane diacid preparation waste liquid |
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| CN101786697B (en) * | 2010-02-11 | 2013-07-17 | 山东鲁北企业集团总公司 | Processing method and device for purifying acidic sewage by gypsum acid preparation furnace gas |
| CN101792227B (en) * | 2010-03-30 | 2012-01-11 | 兖矿鲁南化肥厂 | Process equipment containing polyethyleneglycol dimethyl ether and method |
| CN102372622A (en) * | 2010-08-17 | 2012-03-14 | 山东洪业化工集团股份有限公司 | New technology for extracting adipic acid from diacid mixed solution |
| CN102211992B (en) * | 2011-04-18 | 2013-04-24 | 湖南百利工程科技股份有限公司 | Process for reclaiming dibasic acid from adipic acid production waste solution |
| CN115246692B (en) * | 2021-04-25 | 2023-08-08 | 中国石油化工股份有限公司 | Treatment method of adipic acid production process wastewater |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067046A (en) * | 1992-01-15 | 1992-12-16 | 黄玉龙 | Method for extracting dicarboxylic acid and esters thereof from adipic acid production waste liquid |
| EP0712830A1 (en) * | 1994-11-18 | 1996-05-22 | Bayer Ag | Process for the recovery of adipic acid |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067046A (en) * | 1992-01-15 | 1992-12-16 | 黄玉龙 | Method for extracting dicarboxylic acid and esters thereof from adipic acid production waste liquid |
| EP0712830A1 (en) * | 1994-11-18 | 1996-05-22 | Bayer Ag | Process for the recovery of adipic acid |
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