CN103214053B - Method for treating wastewater from gallic acid production - Google Patents
Method for treating wastewater from gallic acid production Download PDFInfo
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- CN103214053B CN103214053B CN201310083695.XA CN201310083695A CN103214053B CN 103214053 B CN103214053 B CN 103214053B CN 201310083695 A CN201310083695 A CN 201310083695A CN 103214053 B CN103214053 B CN 103214053B
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Abstract
The invention discloses a method for recovering gallic acid from wastewater in gallic acid production. The method comprises two parts extraction and reverse extraction: first, choosing an appropriate extractant; contacting the extractant with the wastewater in an extraction tank according to a certain phase ratio; extracting gallic acid into an organic phase; then contacting sodium hydroxide with extracted loading organic solvent in a reverse extraction groove; conversing gallic acid into sodium gallate; and subjecting the sodium gallate to reverse extraction to be extracted into an aqueous phase. The method provided by the invention can recover more than 90% of gallic acid in wastewater, and avoids waste of resources; and the extractant can be recycled to reduce reagent consumption. The method has advantages of simple process, high efficiency, environment-friendliness and low operation cost, and is applicable to treatment of gallic acid wastewater.
Description
Technical field
The present invention relates to the recycling of gallic acid production wastewater and the method for purifying treatment, particularly relate to a kind for the treatment of process of Turkey-galls as the waste liquid of raw material production gallic acid of take.
Background technology
Gallic acid is a kind of application industrial chemicals very widely, can be used as food antioxidant, tinting material, scavenging agent, sanitas etc., and has the various biological effects such as antitumor, anti-inflammatory, anti-mutation.
Gallic acid is the hydrolysate of Weibull, and the plant gall that domestic manufacturer's great majority be take containing Hydrolysable Tannins is produced gallic acid as raw material, and 1 ton of gallic acid of every production generally can produce 4-5 ton gallic acid waste liquid.In waste liquid, generally contain the sodium-chlor of 50-100g/L, the gallic acid of 15-20g/L and a large amount of pigment.Although gallic acid itself is minimum to the toxicity of human body, in tap water disinfection by chlorine process, can produce halogenated hydrocarbon material, human body is had to " teratogenesis, carcinogenic, mutagenesis " effect, become drinking water safety control object.If by the direct outer row of these waste liquids, contaminate environment not only, and can lose a large amount of gallic acid (90 kilograms of gallic acids of the approximately outer row's loss of 1 ton of gallic acid product of every production).If gallic acid production wastewater directly adopts biological process to process, gallic acid, owing to there being the effect of sterilization, inhibition microorganism growth, can produce serious influence to biological process treating processes.Therefore, develop efficient gallic acid recovery technology, be conducive to improve the utilization ratio of Natural Resources of Gallnuts, the follow-up qualified discharge that is also conducive to gallic acid waste water is processed, and has good economy and environmental benefit.
About the treatment process of Turkey-galls processing waste water, domestic existing relevant report.
Patent documentation (CN201010281679.8) discloses " a kind of method of processing Turkey-galls processing waste water ", and the method adopts flocculation-UFB(flow lifting type anaerobic composite bed bio-reactor)-electrocoagulation-A/O system-activated carbon filtration art breading waste water.The method does not solve recovery and the affect problem of gallic acid on microorganism of gallic acid.
Patent documentation (CN200610086068.1) discloses a kind of " method for purifying and recovering of gallic acid production wastewater ", the method detailed process is: first with NaOH, be neutralized to pH=4.5～5, again after vacuum evaporation, centrifugal recovery salt, be cooled to 10～15 ℃ and separate out gallic acid crystallization, centrifugal suction filtration obtains crystal gallic acid, and filtrate adds lime slurry neutralization to neutral, after clarification, waste water qualified discharge after biochemistry pool biochemistry after coal mass active carbon decolouring for clear liquid.But the method evaporation concentration energy consumption is high, the gallic acid rate of recovery is lower.
Patent documentation (CN201010136553.1) discloses a kind of method of processing the crude wastewater of gallic acid, adopts following steps: filtration and the catalytic oxidation treatment of (1) gallic acid crude wastewater; (2) waste water after catalytic oxidation treatment carries out pH regulator and precipitation process, then further through charcoal absorption, decolours; (3) by the wastewater dilution suitable multiple after catalytic oxidation treatment and adjusting pH value and precipitation process and adsorption bleaching, carry out the processing of aeration aerobe, last waste discharge reaches the emission standard of trade effluent.The method does not solve the recovery problem of gallic acid yet, and catalytic oxidation treatment cost is high.
Therefore, existing Turkey-galls deep-processing waste water treatment technology can not meet the needs of Turkey-galls industry development, needs to develop the high efficiente callback utilization that is conducive to valuable constituent in waste water, and the method that reduces waste water treatment and integral cost.
Summary of the invention
The object of this invention is to provide a kind of technique simple, and the method for can high efficiente callback gallic acid producing the gallic acid in waste liquid.The method can solve gallic acid production waste liquid and contain high salt concentration, and the method for traditional evaporative crystallization recovery gallic acid cannot realize the problem of the high efficiency separation of gallic acid and salt.
In order to solve the problems of the technologies described above, the present invention implements by following technical solution:
A treatment process for gallic acid production wastewater, comprises the steps:
A, extraction: gallic acid production wastewater and organic phase methyl iso-butyl ketone (MIBK) or methyl iso-butyl ketone (MIBK)-tbp or tbp-kerosene are contacted, gallic acid is extracted in organic phase, be extracted the load organic phases of gallic acid;
B, back extraction: load organic phases is contacted and stripped with NaOH solution, make gallic acid be converted into sodium gallate, and enter water from load organic phases, thereby be recycled the pure gallic acid sodium solution of utilization.
Before extraction, gallic acid production wastewater pH value is adjusted in to 0.5-2.0.
Organic phase methyl iso-butyl ketone (MIBK) and tbp volume ratio are controlled at 1/0～2/1; Tbp and kerosene volume ratio are controlled at 1/4～1/1.
Extraction process adopts multi-stage counter current extraction, and extraction progression is 3-6 level, and every grade of mixing time is 10-30 minute, and every grade of settling time is 20-60 minute.
The NaOH concentration adding in back extraction process is controlled at 10-120g/L.
Back extraction process adopts multi-stage countercurrent back extraction, and back extraction progression is 2-4 level, and every grade of mixing time is 10-30 minute, and every grade of settling time is 20-60 minute.
Described gallic acid production wastewater is to take the waste liquid that Turkey-galls produces as raw material production gallic acid.
Although more from the extraction agent of Wastewater by Solvent Extraction gallic acid, comprise alcohol kind of extractants, ketone extraction agent and lipid extraction agent.The difficult point that adopts extracting process to reclaim gallic acid in waste water is the gallic acid back extraction poor-performing of many extraction agents, and extraction agent cannot recycle, therefore there is no actual application value.The present invention finds that by the screening to various extraction agents MIBK or TBP extraction agent have good extraction ability and back extraction performance to gallic acid simultaneously.
The extraction pH of gallic acid production wastewater is controlled at 0.5-2.0, and pH value was higher than 2.0 o'clock, and the recovery of extraction of gallic acid can significantly reduce; If regulate pH value lower than 0.5 o'clock, reduce pH value the recovery of extraction of gallic acid is not had a significant effect, only can cause sour luxus consumption.
The present invention adopts the advantage of above-mentioned technical solution to be: the present invention adopts extracting-back extraction method from gallic acid production wastewater, to reclaim gallic acid, because tbp, kerosene solubleness in water is all very little, in extraction process, lose considerably less, and on the not impact of its effect of extracting, can use by direct circulation after back extraction; And because sodium gallate distributes very littlely in organic phase and water, alkali lye is easy to gallic acid back extraction from organic phase to take out, technique is simple and cost is lower; After extracting-back extraction, the gallic acid rate of recovery is higher than 90%, and the rate of recovery is high; More than the gallic acid concentration reclaiming can reach 100g/L, can directly return to conventional gallic acid and produce main flow recovery gallic acid product.
Embodiment
Below in conjunction with embodiment, be intended to further illustrate the present invention, and unrestricted the present invention.
Embodiment 1
Adopt six grades of extractions---level Four stripping process flow process, take pure MIBK as extracted organic phase, control is compared (organic phase/water) for 1:1, extraction pH value is 0.5, the waste water that is 17030mg/L to the gallic acid concentration through decolouring is processed, every grade of mixing time is that 10 minutes, settling time are 30 minutes, contains gallic acid concentration and be about 750mg/L after six grades of extractions in raffinate, and recovery of extraction is 95.6%; After extraction, the NaOH solution reaction that adds 1.0mol/L, get and compare (organic phase/water) for 5:1, extracted organic phase is carried out to back extraction, every grade of mixing time is that 10 minutes, settling time are 40 minutes, in strip liquor, gallic acid concentration is 79100mg/L, and gallic acid back extraction ratio is 97.2%, and the total yield of gallic acid is 92.9%.
Embodiment 2
Adopt six grades of extractions---level Four stripping process flow process, take 70%MIBK-30%TBP as extraction agent, control is compared (organic phase/water) for 1:1, extraction pH value is 0.5, the waste water that is 17030mg/L to gallic acid concentration is processed, every grade of mixing time is that 15 minutes, settling time are 40 minutes, contains gallic acid concentration and be about 460mg/L after six grades of extractions in raffinate, and recovery of extraction is 97.3%; After extraction, add the NaOH solution reaction of 1.0mol/L, get and compare (organic phase/water) for 5:1, extracted organic phase is carried out to back extraction, in strip liquor, gallic acid concentration is 79800mg/L, and gallic acid back extraction ratio is 96.3%, and the total yield of gallic acid is 93.7%.
Embodiment 3
Adopt six grades of extractions---level Four stripping process flow process, take 30%TBP-70% kerosene as extracted organic phase, control is compared (organic phase/water) for 1:1, extraction pH value is 0.5, the waste water that is 17030mg/L to gallic acid concentration is processed, every grade of mixing time is that 15 minutes, settling time are 40 minutes, contains gallic acid concentration and be about 870mg/L after six grades of extractions in raffinate, and percentage extraction is 94.9%; After extraction, add the NaOH solution reaction of 1.0mol/L, get and compare (organic phase/water) for 5:1, extracted organic phase is carried out to back extraction, in strip liquor, gallic acid concentration is 77600mg/L, and gallic acid back extraction ratio is 96.0%, and the total yield of gallic acid is 91.1%.
Claims (4)
1. a treatment process for gallic acid production wastewater, is characterized in that, comprises the steps:
A, described gallic acid production wastewater are to take the waste liquid that Turkey-galls produces as raw material production gallic acid; Before extraction, gallic acid production wastewater pH value is adjusted in to 0.5-2.0;
B, extraction: gallic acid production wastewater is contacted with organic phase methyl iso-butyl ketone (MIBK)-tbp or tbp-kerosene, gallic acid is extracted in organic phase, be extracted the load organic phases of gallic acid; Organic phase methyl iso-butyl ketone (MIBK) and tbp volume ratio are controlled at 2/1-7/3; Tbp and kerosene volume ratio are controlled at 1/4～1/1;
C, back extraction: load organic phases is contacted and stripped with NaOH solution, make gallic acid be converted into sodium gallate, and enter water from load organic phases, thereby be recycled the pure gallic acid sodium solution of utilization.
2. method according to claim 1, is characterized in that: extraction process adopts multi-stage counter current extraction, and extraction progression is 3-6 level, and every grade of mixing time is 10-30 minute, and every grade of settling time is 20-60 minute.
3. method according to claim 1, is characterized in that: the NaOH concentration adding in back extraction process is controlled at 10-120g/L.
4. according to the method described in claim 1 or 3, it is characterized in that: back extraction process adopts multi-stage countercurrent back extraction, and back extraction progression is 2-4 level, and every grade of mixing time is 10-30 minute, and every grade of settling time is 20-60 minute.
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| US20170203978A1 (en) * | 2016-01-19 | 2017-07-20 | Guangdong Shunde Tianxin Environmental Protection Technologies Co. Ltd. | Treatment methods for recycling dyeing residual liquids |
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| CN103803753B (en) * | 2014-02-28 | 2016-04-27 | 南京大学盐城环保技术与工程研究院 | A kind of synthetical recovery treatment process of H acid trade effluent |
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| US2723992A (en) * | 1952-04-19 | 1955-11-15 | Mallinckrodt Chemical Works | Preparation of gallic acid from tannincontaining materials |
| CN1317199C (en) * | 2005-04-01 | 2007-05-23 | 上海洁申实业有限公司 | Method for retrieving organic compound from photoresist and/or desquamation fluid |
| DE102009001008A1 (en) * | 2009-02-19 | 2010-08-26 | Evonik Degussa Gmbh | Reactive extraction of free organic acids from their ammonium salts |
| CN102850211B (en) * | 2012-09-19 | 2014-06-11 | 湖南洪江棓雅生物科技有限公司 | Gallic acid and clean and efficient production process thereof |
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| US20170203978A1 (en) * | 2016-01-19 | 2017-07-20 | Guangdong Shunde Tianxin Environmental Protection Technologies Co. Ltd. | Treatment methods for recycling dyeing residual liquids |
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