CN103214053A - Method for treating wastewater from gallic acid production - Google Patents
Method for treating wastewater from gallic acid production Download PDFInfo
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- CN103214053A CN103214053A CN201310083695XA CN201310083695A CN103214053A CN 103214053 A CN103214053 A CN 103214053A CN 201310083695X A CN201310083695X A CN 201310083695XA CN 201310083695 A CN201310083695 A CN 201310083695A CN 103214053 A CN103214053 A CN 103214053A
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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 relating to a kind of is the treatment process of the waste liquid of raw material production gallic acid with the Turkey-galls.
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 various biological effects such as antitumor, anti-inflammatory, anti-mutation.
Gallic acid is the hydrolysate of Weibull, and domestic manufacturer's great majority are that raw material is produced gallic acid with the plant gall that contains the hydrolysis tannin, and 1 ton of gallic acid of every production generally can produce 4-5 ton gallic acid waste liquid.Generally contain the sodium-chlor of 50-100g/L, gallic acid and a large amount of pigment of 15-20g/L in the waste liquid.Though gallic acid itself is minimum to the toxicity of human body, in tap water disinfection by chlorine process, can produce the halogenated hydrocarbon material, human body is had " teratogenesis, carcinogenic, mutagenesis " effect, become the drinking water safety controlled member.If these waste liquids are directly effluxed, contaminate environment not only, and can lose a large amount of gallic acid (1 ton of gallic acid product of every production effluxes 90 kilograms of gallic acids of loss approximately).If gallic acid production wastewater directly adopts biological process to handle, gallic acid can produce serious influence to the biological process treating processes because the effect of sterilization, inhibition microorganism growth is arranged.Therefore, develop gallic acid recovery technology efficiently, help improving the utilization ratio of Turkey-galls resource, the follow-up qualified discharge that also helps gallic acid waste water is handled, 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 handling the Turkey-galls processing waste water ", and this method adopts flocculation-UFB(flow lifting type anaerobic composite bed bio-reactor)-electrocoagulation-A/O system-activated carbon filtration art breading waste water.This method does not solve the recovery of gallic acid and the gallic acid problem that influences to microorganism.
Patent documentation (CN200610086068.1) discloses a kind of " method for purifying and recovering of gallic acid production wastewater ", this method detailed process is: be neutralized to pH=4.5～5 with NaOH earlier, after vacuum-evaporation concentrates again, centrifugal recovery salt, be cooled to 10～15 ℃ and separate out the gallic acid crystallization, centrifugal suction filtration gets the crystal gallic acid, and filtrate adds milk of lime and is neutralized to neutrality, after the clarification, waste water qualified discharge behind biochemistry pool biochemistry after clear liquid decolours with coal mass active carbon.But this method evaporation concentration energy consumption height, the gallic acid rate of recovery is lower.
Patent documentation (CN201010136553.1) discloses a kind of method of handling the crude wastewater of gallic acid, adopts following steps: the filtration and the catalytic oxidation treatment of (1) gallic acid crude wastewater; (2) carry out pH regulator and precipitation process through the waste water after the catalytic oxidation treatment, further decolour then through charcoal absorption; (3) will carry out the aeration aerobe and handle through the wastewater dilution suitable multiple behind catalytic oxidation treatment and adjusting pH value and precipitation process and the adsorption bleaching, last waste discharge reaches the emission standard of trade effluent.This method does not solve the recovery problem of gallic acid yet, and catalytic oxidation treatment cost height.
Therefore, existing Turkey-galls deep-processing waste water treatment technology can not satisfy the needs of Turkey-galls industry development, needs to develop the high efficiente callback utilization that helps valuable constituent in the waste water, and the method that reduces the waste water treatment and integral cost.
Summary of the invention
It is simple to the purpose of this invention is to provide a kind of technology, and the method for can the high efficiente callback gallic acid producing the gallic acid in the waste liquid.This method can solve gallic acid production waste liquid and contain high salt concentration, and the method for traditional evaporative crystallization recovery gallic acid can't 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 kind of treatment process of 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 the organic phase, obtained extracting the load organic phases of gallic acid;
B, back extraction: load organic phases contacted with NaOH solution strip, make gallic acid be converted into sodium gallate, and enter water from load organic phases, thus the pure gallic acid sodium solution that obtains recycling.
Before the extraction gallic acid production wastewater pH value is adjusted in 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 the 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 that adds in the back extraction process is controlled at 10-120g/L.
The back extraction process adopts the multi-stage countercurrent back extraction, and back extraction progression is the 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 the waste liquid that produces for the raw material production gallic acid with the Turkey-galls.
Although the extraction agent of extraction gallic acid is more from waste water, comprise pure kind of extractants, ketone extraction agent and lipid extraction agent.The difficult point that adopts extracting process to reclaim gallic acid in the waste water is the gallic acid back extraction poor-performing of many extraction agents, and extraction agent can't recycle, does not therefore have actual application value.The present invention is by finding that to the screening of various extraction agents MIBK or TBP extraction agent then 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 the pH value is higher than at 2.0 o'clock, and the recovery of extraction of gallic acid can significantly reduce; Be lower than at 0.5 o'clock if regulate the pH value, reduce of the recovery of extraction not obviously influence of pH value, only can cause the luxus consumption of acid gallic acid.
The present invention adopts the advantage of above-mentioned technical solution to be: the present invention adopts the extracting-back extraction method to reclaim gallic acid from gallic acid production wastewater, because tbp, kerosene solubleness in water are all very little, loss is considerably less in the extraction process, and, can directly recycle through after the back extraction its effect of extracting not being influenced; And because sodium gallate is very little in organic phase and aqueous phase distribution, alkali lye is easy to gallic acid back extraction from organic phase is taken out, and technology is simple and cost is lower; After extracting-back extraction, the gallic acid rate of recovery is higher than 90%, rate of recovery height; The gallic acid concentration that reclaims can reach more than the 100g/L, can directly return conventional gallic acid and produce main flow recovery gallic acid product.
Embodiment
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1
Adopt six grades of extractions---level Four stripping process flow process, with pure MIBK is extracted organic phase, control is compared (organic phase/water) and is 1:1, extraction pH value is 0.5, to the gallic acid concentration through decolouring is that the waste water of 17030mg/L is handled, every grade of mixing time is that 10 minutes, settling time are 30 minutes, contains gallic acid concentration in the raffinate after six grades of extractions and is about 750mg/L, and recovery of extraction is 95.6%; After the extraction, the NaOH solution reaction that adds 1.0mol/L, getting and comparing (organic phase/water) is 5:1, extracted organic phase is carried out back extraction, every grade of mixing time is that 10 minutes, settling time are 40 minutes, gallic acid concentration is 79100mg/L in the strip liquor, and the 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, with 70%MIBK-30%TBP is extraction agent, control is compared (organic phase/water) and is 1:1, extraction pH value is 0.5, to gallic acid concentration is that the waste water of 17030mg/L is handled, every grade of mixing time is that 15 minutes, settling time are 40 minutes, contains gallic acid concentration in the raffinate after six grades of extractions and is about 460mg/L, and recovery of extraction is 97.3%; After the extraction, add the NaOH solution reaction of 1.0mol/L, getting and comparing (organic phase/water) is 5:1, extracted organic phase is carried out back extraction, gallic acid concentration is 79800mg/L in the strip liquor, and the 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, with 30%TBP-70% kerosene is extracted organic phase, control is compared (organic phase/water) and is 1:1, extraction pH value is 0.5, to gallic acid concentration is that the waste water of 17030mg/L is handled, every grade of mixing time is that 15 minutes, settling time are 40 minutes, contains gallic acid concentration in the raffinate after six grades of extractions and is about 870mg/L, and percentage extraction is 94.9%; After the extraction, add the NaOH solution reaction of 1.0mol/L, getting and comparing (organic phase/water) is 5:1, extracted organic phase is carried out back extraction, gallic acid concentration is 77600mg/L in the strip liquor, and the gallic acid back extraction ratio is 96.0%, and the total yield of gallic acid is 91.1%.
Claims (7)
1. the treatment process of a gallic acid production wastewater is characterized in that, 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 the organic phase, obtained extracting the load organic phases of gallic acid;
B, back extraction: load organic phases contacted with NaOH solution strip, make gallic acid be converted into sodium gallate, and enter water from load organic phases, thus the pure gallic acid sodium solution that obtains recycling.
2. method according to claim 1 is characterized in that: before the extraction gallic acid production wastewater pH value is adjusted in 0.5-2.0.
3. method according to claim 1 is characterized in that: 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.
4. according to claim 1 or 3 described methods, it is characterized in that: extraction process adopts multi-stage counter current extraction, and extraction progression is the 3-6 level, and every grade of mixing time is 10-30 minute, and every grade of settling time is 20-60 minute.
5. method according to claim 1 is characterized in that: the NaOH concentration that adds in the back extraction process is controlled at 10-120g/L.
6. method according to claim 1 or 5, it is characterized in that: the back extraction process adopts the multi-stage countercurrent back extraction, and back extraction progression is the 2-4 level, and every grade of mixing time is 10-30 minute, and every grade of settling time is 20-60 minute.
7. method according to claim 1 is characterized in that: described gallic acid production wastewater is the waste liquid that produces for the raw material production gallic acid with the Turkey-galls.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103803753A (en) * | 2014-02-28 | 2014-05-21 | 南京大学盐城环保技术与工程研究院 | Comprehensive recovery treatment method for H acid industrial waste water |
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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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2723992A (en) * | 1952-04-19 | 1955-11-15 | Mallinckrodt Chemical Works | Preparation of gallic acid from tannincontaining materials |
| CN1696065A (en) * | 2005-04-01 | 2005-11-16 | 上海洁申实业有限公司 | Method for retrieving organic compound from photoresist and/or desquamation fluid |
| CN102325746A (en) * | 2009-02-19 | 2012-01-18 | 赢创德固赛有限公司 | Reactive extraction of free organic acids from ammonium salts thereof |
| CN102850211A (en) * | 2012-09-19 | 2013-01-02 | 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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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2723992A (en) * | 1952-04-19 | 1955-11-15 | Mallinckrodt Chemical Works | Preparation of gallic acid from tannincontaining materials |
| CN1696065A (en) * | 2005-04-01 | 2005-11-16 | 上海洁申实业有限公司 | Method for retrieving organic compound from photoresist and/or desquamation fluid |
| CN102325746A (en) * | 2009-02-19 | 2012-01-18 | 赢创德固赛有限公司 | Reactive extraction of free organic acids from ammonium salts thereof |
| CN102850211A (en) * | 2012-09-19 | 2013-01-02 | 湖南洪江棓雅生物科技有限公司 | Gallic acid and clean and efficient production process thereof |
Non-Patent Citations (1)
| Title |
|---|
| 梅帆等: "苯甲酸稀溶液的萃取特性", 《应用化学》, vol. 19, no. 6, 30 June 2002 (2002-06-30), pages 517 - 520 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103803753A (en) * | 2014-02-28 | 2014-05-21 | 南京大学盐城环保技术与工程研究院 | Comprehensive recovery treatment method for H acid industrial waste water |
| 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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Effective date of registration: 20170601 Address after: 410205 Hunan city high tech Development Zone Changsha Changsha Wenxuan Road No. 27 Lu Valley Yuyuan C2 building N unit 6 layer 607. Patentee after: Hunan in south of the Five Ridges golden Union Environmental Protection Technology Co., Ltd. Address before: 410013, Changsha, Hunan hi tech Development Zone, national hi tech Industrial Development Zone, torch City, M0 group, South 2 floor Patentee before: Hunan Yoursun Environmental Protection Technology Co., Ltd. |
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