CN102826707A - Three-stage tandem photocatalysis treatment technology of marigold wastewater - Google Patents
Three-stage tandem photocatalysis treatment technology of marigold wastewater Download PDFInfo
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Abstract
According to the invention, marigold production wastewater is processed by the adoption of biodeposition and three-stage tandem photocatalysis treatment technologies. The technology provided by the invention is simple and equipment is simple to manufacture as well. The effluent quality can achieve the first class emission standard in''sewage comprehensive emission standard'' (GB8978-1996). In addition, fertilizers which have great practical values can be obtained from the wastewater and the content of the fertilizers is 1%-2% of the wastewater. The technology provided by the invention has advantages of high efficiency, low cost, convenient operation, green and environmental protection and no secondary pollution, and is suitable for treatment of wastewater generated from lactic acid bacteria fermented marigold processing.
Description
Technical field
The present invention relates to environmental protection industry (epi) resource and Flower of Aztec Marigold industrial sewage treatment process.
Background technology
Along with the domestic and international market must increase natural plant pigment demand; Leaf of Aztec Marigold flavine product has been widely used in aquaculture and the foodstuffs industry as natural colorant; Be one of ideal natural food colour, more and more receive the favor in market, at home and abroad supply falls short of demand in market for related prods.At present, on the world market, the price of 1 gram xenthophylls is suitable with 1 gram gold.In conjunction with the practical situation of China, make raw material with marigold petal and extract xanthophyll-oil to prepare xenthophylls be more promising developing direction.
Flower of Aztec Marigold is the high quality raw material that extract natural carotenol; Natural carotenol is a kind of inhibitor and tinting material of excellent performance; Have characteristics such as lovely luster, stability are strong, acid and alkali-resistance, toxicological harmless, security height; Be widely used in foodstuffs industry and chemical industry fields such as feed, foodstuff additive, medicine, makeup, healthcare products, beverage, tobacco, market outlook are wide.Marigold flower is obtained the dried flower particle after fermentation, dehydration, granulation, drying treatment; Again with normal hexane or other SX oleoresin, product is dissolved in ethanol after removing solvent, use the concentrated base saponification then; Go out crystallized product through spinning, then the recrystallization refined product.Because being the situation with water miscible fatty acid ester of lutein in Flower of Aztec Marigold, xenthophylls exists; When squeezing Flower of Aztec Marigold fermentation petal, there is a large amount of fatty acid ester of lutein to discharge with waste water; Also have nutrients such as lot of organic acids (is main with lactic acid), amino acid, a large amount of VITAMINs, trace element in the waste water simultaneously; Not only waste valuable resource, also polluted environment.When squeezing Flower of Aztec Marigold fermentation petal, have a large amount of waste water to discharge (Flower of Aztec Marigold waste water is called for short in the back), sewage quantity is big, and stink is unpleasant.Exist because xenthophylls is the form with water miscible fatty acid ester of lutein in Flower of Aztec Marigold, a large amount of organism is contained in the inside, and complicated component is high density, high COD, high ammonia nitrogen, bio-refractory sewage.The contaminated wastewater thing is mainly glucide, protein, fat, fiber, xylogen, pectin etc. can be by the material of microbiological degradation, and decomposition will consume a large amount of oxygen, produces organic acid, methane, the CO of different molecular weight
2, malodorous H
2S, mercaptan and 3-methyl azepine indenes materials such as (skatoles) cause that the water body dissolved oxygen is sharp to fall, the water quality acidifying, and aquatic animals and plants is dead, and pathogenic bacteria grows, and the water body blackout is smelly, and body eutrophication or the harm of acid evilization have a strong impact on water quality.If directly can cause then that with biochemical treatment mikrobe self-dissolving and body eutrophication pollute.If directly discharging has not only been wasted valuable resource, and has been polluted environment.Present manufacturing enterprise both domestic and external does not still have sophisticated improvement method, and the problem of Flower of Aztec Marigold contaminated wastewater is perplexing the development of Flower of Aztec Marigold industry always, and the processing of waste water has been very urgent.Solving the problem of concentrating the great deal of high concentration organic waste water that produces in this course of processing is the only way that the xenthophylls industry develops in a healthy way.
At present; The treatment technology of Flower of Aztec Marigold factory effluent is still rare, can find be Rong Haihong be published in 2007 the 5th article-fresh Flos Tagetis Erectae fermented waste fluids on the phase chemical engineer the comprehensive regulation and in August, 2007 people such as Li Li patent of invention-Flower of Aztec Marigold fermentation pressed liquor reclaim the raw material and the measure of comprehensive of producing xenthophylls.The article employing DDGS of Rong Haihong or DDG method, photosynthetic bacterium method, supercritical water oxidation method, flocculence secondary treatment, membrane filter method are handled the Flower of Aztec Marigold factory effluent; And its treatment effect compared, find that membrane processing method has vast potential for future development.And people's such as Li Li patent of invention-Flower of Aztec Marigold fermentation pressed liquor reclaims the raw material and the measure of comprehensive of producing xenthophylls; At first pass through nanofiltration device to the Flower of Aztec Marigold fermented liquid; Xenthophylls lipid acid is held back in nanofiltration device and is concentrated; Obtain producing the raw material of Flower of Aztec Marigold through vacuum dryer again, and another part material enters into next device-reverse osmosis unit with moisture, through reverse osmosis unit; Part material such as organic acid, amino acid, VITAMINs, trace element, inorganic salt etc. are concentrated, and then are processed as fertilizer; And the water of discharging through reverse osmosis unit has obtained improvement, has reached discharging standards.And film processing, nanofiltration device and reverse osmosis unit mainly are the methods of utilizing physics---through holding back the molecular weight of different range, thereby the material of macromolecule and the material of small molecular weight are separated.At present, its application and report are not arranged as yet in the industry.And the method that we mainly adopt different with preceding two kinds of methods, we adopted mainly is to utilize method such as photochemical catalysis that Flower of Aztec Marigold waste water is handled, photocatalysis principle is exactly that some semiconductor materials are (like TiO briefly
2) the charged son in rank can be excited to conduction band under visible light or ultraviolet irradiation, thereby produce electronics (e) hole (h with very strong reactive behavior
+) right; After these electron-hole pairs are moved to semiconductor surface; Under photocatalysis, produce hydroxyl (OH) and super-oxide ion; Under the situation of not using any chemicals, with the organism in the water, bacterium, virus and other pathogen be completely oxidized to carbonic acid gas, water and inorganic molecules, reached the purpose of purification, sterilization and degradation of contaminant.And we handle Flower of Aztec Marigold waste water through three grades of tandem photocatalysis treatment technologies; This technology is when the Flower of Aztec Marigold waste water of handling; Adding is that the mesopore titania photocatalyst of template preparation is as pretreating agent with plant peel, film or photosensitive activity thing; This material can adsorb organic waste molecule and the inorganic harmful ion in the Flower of Aztec Marigold waste water efficiently, cheaply, thereby reaches the purpose of degradation of contaminant.Macromolecular substance in view of containing macromolecular substance or difficult degradation in the Flower of Aztec Marigold waste water need carry out thermal pretreatment, and waste water is heated to 50-100 ℃, purpose be for mesopore titania photocatalyst in the light-catalyzed reaction (like TiO
2) the charged son in rank be excited to conduction band certain energy be provided, thereby produce hydroxyl (OH) and super-oxide ion with very strong reactive behavior so that make light-catalyzed reaction reach very effective result.Handle Flower of Aztec Marigold waste water at first through biological settling bowl, at last through three grades of tandem photochemical catalysis device processes, the macromolecular substance in the Flower of Aztec Marigold waste water is discharged through three grades of tandem photochemical catalysis equipment generation small molecules and then with gas form.Can reach the first discharge standard among the GB8978-1996 " integrated wastewater discharge standard ".Technology of the present invention not only cost is low, technical process and simple to operate, and need not too much complex chemical treatment method, be convenient to realize industriallization.
Summary of the invention
The purpose of this invention is to provide a kind of efficient, low investment, easy to operate Flower of Aztec Marigold production wastewater treatment technology, and environment is not caused secondary pollution.The water sample of research is taken from the chemical plant, Yunnan Province; Not only effluent quality is up to standard after treatment; And the organic acid that contains in the Flower of Aztec Marigold fermentation pressed liquor, amino acid, VITAMINs, trace element etc., mainly be that the material of the inside has obtained good use-as fertilizer sources.Relate to three patent of having applied for: Wang Jiaqiang among the present invention, photocatalytic vacuum gas-liquid-solid three-phase high efficiency separation art breading high salt and high concentrated organic wastewater patent of invention (application number: 201010039195.2); With plant peel, film is that the method that template prepares mesopore titania photocatalyst (is authorized: ZL200710065939.6); With the photosensitive activity thing is the preparation method of the mesoporous crystal titanium dioxide of template, and patent of invention (is authorized: ZL200710065747.5).
The present invention compares the facture in the background technology, and following advantage is arranged:
Cost is low, and technical process and simple to operate need not too much complex chemical treatment method, is convenient to realize industriallization.
Through after this art breading, effluent quality can reach the first discharge standard among the GB8978-1996 " integrated wastewater discharge standard ".
Materials such as the organic acid that warp is discharged, amino acid, VITAMINs, trace element are liquid concentrator, and its directly as fertilizer sources or recycling has practical value.
From waste water, can reclaim in this technology and obtain fertilizer, turn waste into wealth, have the very big economic worth and the value of environmental protection.
Technical scheme of the present invention is: the first step, biological sedimentation pre-treatment; Second step, adopt three grades of tandem photochemical catalysis technologies that waste water is handled, wherein three grades are respectively one-level pre-treatment, secondary light catalytic treatment and three grades of advanced treatment.
Biological sedimentation pre-treatment promptly adds active sludge and aeration in the pond; Planting aquatic plants in the pond.
Pretreating agent in the one-level pre-treatment can be mesoporous titanium dioxide photocatalytic material, oxygenant or flocculation agent, and it is 1 with the wastewater quality ratio: 50-1: 1000, and waste water is heated to 50-100 ℃.
The secondary light catalytic treatment is for to be coated with last layer in photocatalysis apparatus inside be the mesoporous crystal titanium dioxide of masterplate with plant peel, film or photosensitive activity thing and insert a 40-1000W ultraviolet source.
The oxygenant that adds in three grades of advanced treatment is O
3Or newborn Manganse Dioxide, Fenton reagent, from then on the water of qualified discharge discharge.
Figure of description is seen in technical process, specifies technical scheme of the present invention at present:
The biological sedimentation of the first step
At first, the Flower of Aztec Marigold factory effluent is introduced biological settling bowl, in the pond, add active sludge and aeration, utilize the mikrobe in the active sludge under aerobic condition, to be to consume foodstuff ramp propagation organism waste water is purified with the organism; Or in the pond planting aquatic plants, utilize the growth of waterplant to reduce the objectionable impurities in the water.
Second step adopted three grades of tandem photochemical catalysis technologies that waste water is handled
The one-level pre-treatment
The Flower of Aztec Marigold factory effluent is introduced pretreatment pool,, its objective is in order to prevent that processing unit afterwards from stopping up through removing the suspended substance of larger particles after the grid in the pond.Add mesopore titania photocatalyst or flocculation agent then, stirring and dissolving gets final product.Mesoporous material is compared with the micro porous molecular sieve of classics, and mesoporous material has the following advantages:
1) has regular pore passage structure;
2) pore size distribution is narrow, and the aperture can be regulated between 1.5-10nm;
3) through after optimizing synthesis condition or processing, have good thermostability and hydrothermal stability;
4) has higher specific surface area (1000-1500m
2/ g);
5) particle has regular profile, and in nanoscale, keeps the duct order of height.
Because orderly structure is unique advantages very, can be used as functional materials, sorbent material, catalyzer and carrier thereof, has not only remedied the deficiency of micro-pore zeolite molecular sieve, can also utilize order mesoporous " microreactor " as nanoparticle.Therefore in various fields such as chemical industry, energy and environment, biotechnology, fractionation by adsorption, catalysis and light, electricity, magnetic vast potential for future development is arranged.This material can adsorb organic waste molecule and the inorganic harmful ion in the Flower of Aztec Marigold waste water efficiently, cheaply, thereby reaches the purpose of degradation of contaminant.Macromolecular substance in view of containing macromolecular substance or difficult degradation in the Flower of Aztec Marigold waste water need carry out thermal pretreatment, and waste water is heated to 50-100 ℃, purpose be for mesopore titania photocatalyst in the light-catalyzed reaction (like TiO
2) the charged son in rank be excited to conduction band certain energy be provided, thereby produce hydroxyl (OH) and super-oxide ion with very strong reactive behavior so that make light-catalyzed reaction reach very effective result.
The secondary light catalytic treatment
Through after the pre-treatment, to open light source and carry out the photochemical catalysis pre-treatment by it, photocatalysis principle is exactly that some semiconductor materials are (like TiO briefly
2) the charged son in rank can be excited to conduction band under visible light or ultraviolet irradiation, thereby produce electronics (e) hole (h with very strong reactive behavior
+) right; After these electron-hole pairs are moved to semiconductor surface; Under photocatalysis, produce hydroxyl (OH) and super-oxide ion; Under the situation of not using any chemicals, with the organism in the water, bacterium, virus and other pathogen be completely oxidized to carbonic acid gas, water and inorganic molecules, reached the purpose of purification, sterilization and degradation of contaminant.In these semiconductor catalysts, TiO
2Chemical property is stable, indissoluble, nontoxic, cost is low, catalytic efficiency (is high, and is very effective for hardly degraded organic substance.In a word; Flower of Aztec Marigold waste water can reach good decolouring and degradation effect after the secondary light catalytic treatment, simultaneously can also the organism of difficult degradation be combined together to form the residue of density greater than water, and is thick in the organic phase of this discharge; Can directly be used as fertilizer, also recyclable other purposes of work.
Three grades of advanced treatment
Waste water after photocatalysis treatment is introduced the advanced treatment device, add O
3, newborn Manganse Dioxide or Fenton reagent, the organic content of reaction back water outlet is lower.Effluent quality can reach the first discharge standard among the GB8978-1996 " integrated wastewater discharge standard ".
Description of drawings
Accompanying drawing is this process flow sheet
Embodiment
Specific embodiment 1:
COD is about 50000mg/L, NH
3It is that 4.5 Flower of Aztec Marigold waste water is sent into biological settling bowl that-N is about 756mg/L, pH value; Afterwards factory effluent is sent into pretreatment pool; To add the mesoporous catalytic material a of 1g/L after removing the larger particles suspended substance, pass through preheater afterwards, send into photo catalysis reactor more continuously; Carry out successive reaction, send into advanced treatment apparatus and feed O
3, through the water of discharging, the COD of last sewage is 80mg/L, NH
3-N is that 11mg/L, pH value are 7.5, colourity is less than 50, reaches the first discharge standard among the GB8978-1996 " integrated wastewater discharge standard ".
Specific embodiment 2:
COD is about 50000mg/L, NH
3It is that 4.5 Flower of Aztec Marigold waste water is sent into biological settling bowl that-N is about 756mg/L, pH value, afterwards factory effluent is sent into pretreatment pool, it is added the mesoporous catalytic material b of 1g/L after removing the larger particles suspended substance; Pass through preheater afterwards; Send into photo catalysis reactor more continuously, carry out successive reaction, send into advanced treatment apparatus and add newborn Manganse Dioxide; Through the water of discharging, the COD of last water outlet is 89mg/L, NH
3-N is that 15mg/L, pH value are 7.5, colourity is less than 50, reaches the first discharge standard among the GB8978-1996 " integrated wastewater discharge standard ".
Specific embodiment 3:
COD is about 50000mg/L, NH
3It is that 4.5 Flower of Aztec Marigold waste water is sent into biological settling bowl that-N is about 756mg/L, pH value, afterwards factory effluent is sent into pretreatment pool, it is added the mesoporous catalytic material c of 1g/L after removing the larger particles suspended substance; Pass through preheater afterwards; Send into photo catalysis reactor more continuously, carry out successive reaction, send into advanced treatment apparatus; Through the water of discharging, the COD of last water outlet is 82mg/L, NH
3-N is that 11mg/L, pH value are 7.5, colourity is less than 50, reaches the first discharge standard among the GB8978-1996 " integrated wastewater discharge standard ".
Specific embodiment 4:
COD is about 50000mg/L, NH
3It is that 4.5 Flower of Aztec Marigold waste water is sent into biological settling bowl that-N is about 756mg/L, pH value, afterwards factory effluent is sent into pretreatment pool, remove behind the larger particles suspended substance it is added the mesoporous catalytic material d of 2.0g/L after; Add 0.5g aluminium salt and the sedimentation of molysite mixed flocculation again, pass through preheater afterwards, send into photo catalysis reactor more continuously; Carry out successive reaction; Send into advanced treatment apparatus and add Fenton reagent, through the water of discharging, the COD of last water outlet is 83mg/L, NH
3-N is that 9mg/L, pH value are 7.5, colourity is less than 50, reaches the first discharge standard among the GB8978-1996 " integrated wastewater discharge standard ".
Claims (5)
1. the treatment process of a Flower of Aztec Marigold factory effluent is characterized in that treatment step is following: the first step, biological sedimentation pre-treatment; Second step, adopt three grades of tandem photochemical catalysis technologies that waste water is handled, wherein three grades are respectively one-level pre-treatment, secondary light catalytic treatment and three grades of advanced treatment.
2. according to the treatment process of claim 1, it is characterized in that described biological sedimentation pre-treatment promptly adds active sludge and aeration in the pond; Planting aquatic plants in the pond.
3. according to the treatment process of claim 1; It is characterized in that it is the mesoporous catalytic material of masterplate, oxygenant or flocculation agent that pretreating agent in the described one-level pre-treatment can be with plant peel, film or photosensitive activity thing; The mass ratio of itself and waste water is 1: 50-1: 1000, and waste water is heated to 50-100 ℃.
4. according to the treatment process of claim 1, its characteristic for to be coated with last layer with mesopore molecular sieve in photocatalysis apparatus inside, and inserts a 40-1000W ultraviolet source in described secondary light catalytic treatment.
5. according to the treatment process of claim 1, it is characterized in that the oxygenant that adds in described three grades of advanced treatment is O
3Or newborn Manganse Dioxide, Fenton reagent, from then on the water of qualified discharge discharge.
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| CN103739129A (en) * | 2013-12-13 | 2014-04-23 | 云南中烟昆船瑞升科技有限公司 | Method for strong oxidation treatment of high-concentration waste water |
| CN104086038A (en) * | 2014-05-26 | 2014-10-08 | 华中农业大学 | Comprehensive processing method for squeezing sewage generated in process of extracting xanthophyll from tagetes erecta |
| CN104445839A (en) * | 2014-12-30 | 2015-03-25 | 云南大学 | Three-stage series type photocatalytic treatment process of coal tar wastewater |
| CN105254091A (en) * | 2015-10-30 | 2016-01-20 | 无锡市嘉邦电力管道厂 | Method for treating organic wastewater difficult to biochemically degrade |
| CN102976567B (en) * | 2012-12-31 | 2017-03-29 | 云南大学 | A kind of technique of the multistage photocatalysis treatment paint waste water of ultraviolet visible light |
| CN109592857A (en) * | 2019-01-28 | 2019-04-09 | 云南鼎易环保科技工程有限公司 | The processing method of marigold squeezing waste water |
| CN113149344A (en) * | 2021-03-29 | 2021-07-23 | 昆明理工大学 | Processing method of vegetable juice stock solution |
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| CN113149344A (en) * | 2021-03-29 | 2021-07-23 | 昆明理工大学 | Processing method of vegetable juice stock solution |
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Application publication date: 20121219 |