CN101091905A - Preparing multistage adsorbent for difficult degradative organic wastewater in high concentration, and method of use - Google Patents
Preparing multistage adsorbent for difficult degradative organic wastewater in high concentration, and method of use Download PDFInfo
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Abstract
The invention publishes a multistage absorbent preparation of the organic wastewater which is high potency and difficult to degrade, and its application method. The preparation method is as follows: 1) at 100 to 200deg.c., under the oxygen deficit condition, the nature biomass is carbonized for 2 to 6 hours, forming the primary absorbent with the part carbonizes; 2) inputting the primary absorbent of the part carbonized in the high potency organic wastewater, the quality volume ratio of the absorbent and the highly concentrated organic wastewater is 1:500 to 1:10000, after the agitation, removeing the organic pollutant which is at the high potency and difficult to degrade in the waste water; after the precipitation, recycling the primary absorbent of the part carbonize which adsorbs the organic pollutant, after drying, under 400 to 700deg.c. carrying on the further carbonize for 2 to 6 hours, preparing the secondary absorbent. The assignment action mechanism pretreats the organic wastewater which has the high potency and difficult to degrade;and simultaneously uses the strong surface adsorption mechanism of the secondary absorbent which is carbonized completely, the multistage absorbent is suitable to the adsorption treatment in polar and non-polar organic wastewater, and especially suitable to the adsorption treatment of high density organic wastewater in agricultural chemicals waste water, coked waste water and printing waste water and so on.
Description
Technical field
The present invention relates to water technology and application, relate in particular to a kind of multistage adsorbent preparation and using method of high concentration hard-degraded organic waste water.
Background technology
Since the 1950's, along with the develop rapidly of chemical industry, artificial synthetic organism kinds and quantity grow with each passing day.Human chemicals synthetic and that produce has 1,000 ten thousand kinds, has more than 10 ten thousand kinds to enter environment.Persistence organic pollutant (persistent organic pollutants wherein, POPs) extensively be present in the environment such as air, water body, deposit, soil, different with conventional pollutant is, persistence organic pollutant is bigger to human health and natural environment harm: the holdup time is long in natural environment, utmost point difficult degradation, toxicity is extremely strong, can cause global propagation.Taken in the back by organism and be difficult for decomposing, and amplify, the human and animal is endangered huge along food chain is concentrated.That a lot of persistence organic pollutants not only have is carcinogenic, teratogenesis, mutagenicity, but also has the endocrine interference effect.Studies show that persistence organic pollutant can continue several generations to the mankind's influence, human survival procreation and sustainable development are constituted significant threat.For this reason, calendar year 2001, famous " Convention of Stockholm " signed in the representative that comprises more than 90 countries and regions of China in the Stockholm of Sweden, require a signatory to adopt various measures and international cooperation, and the production of control POPs, use, trade and processing are disposed.
In recent years, many countries drop into lot of manpower and material resources in succession, control and the removing method of research and searching POPs.China handles organic wastewater and mainly contains three class methods at present, i.e. biological treatment, physical chemistry are handled and chemical treatment.For the advanced treating research of industrial wastewater with use maximum to be the physical chemistry treatment technology, to comprise technology such as gas is put forward, stripping, absorption, electrolysis, coagulating sedimentation, extraction, flocculation.And main absorption method, Coagulation Method and the extraction etc. of adopting are handled in the materialization of poisonous persistent organic pollutants, and wherein using maximum is absorption method, its key is to search out big capacity, safety, callable efficient sorbing material.
Adsorbent commonly used has active carbon, polymeric adsorbent, active carbon fibre peacekeeping organic modified bentonite.Charcoal absorption is an organic method in the current the most frequently used removal water, usually as the packing material in the purifier.But active carbon does not possess selectivity to organic absorption, and adsorption capacity is little, and is saturated easily, needs constantly regeneration.In addition, bibliographical information is arranged, active carbon is adsorbed with a least concentration to some organic matter in the water, and when being lower than this least concentration, active carbon just can't play a role, and as when organic halogenation substrate concentration in the water during less than 5 μ g/L, active carbon does not produce suction-operated to it.Therefore, active carbon is unsatisfactory to the adsorption effect of low content, lipophilic persistence organic pollutant.The organobentonite absorption property is good, adsorption capacity is big, and the application in organic wastewater with difficult degradation thereby is handled has caused very big concern, existing relevant patent of invention (patent of invention number: ZL03116256.8); But the easy desorption of the surfactant on the organobentonite causes that COD is difficult to qualified discharge in the wastewater treatment.Therefore, the treatment of Organic Wastewater agent that development of new is efficient, cheap, stable, safe is significant.
Industries such as alcohol, monosodium glutamate, pharmacy, citric acid, starch, yeast and food produce a large amount of high concentrated organic wastewaters.At present, to this class waste water preferably processing method be to adopt the anaerobic-aerobic combined treatment process.Wherein, the Anaerobic Treatment technology can be removed the organic pollution in the waste water effectively, and organic pollution is converted into biogas; Aerobic Process for Treatment is then further thoroughly degraded the hard-degraded substance in the waste water, makes it qualified discharge.The integrated Waste Water Treatment of anaerobic-hypoxia-anaerobic-aerobic (Anarebic-Low oxic-Anareobicsystem, be called for short ALAO system), this system is with anaerobism, hypoxemia, anaerobism, the aerobic operating unit that waits is combined, treatment effeciency is higher, floor space is few, reduced investment, and operating cost is low.But this technology is difficult to remove persistence organic pollutant in the waste water.
Summary of the invention
The multistage adsorbent preparation and the using method that the purpose of this invention is to provide a kind of high concentration hard-degraded organic waste water.
The multistage preparation of adsorbent method of high concentration hard-degraded organic waste water comprises the steps:
1) at 100～200 ℃, the charing natural biomass is 2～6 hours under the condition of anoxic, makes the elementary adsorbent of part charing;
2) the elementary adsorbent of part charing is dropped in the high concentrated organic wastewater, the mass volume ratio of adsorbent and high concentrated organic wastewater is 1: 500～1: 10000, through stirring, removes waste water middle and high concentration organic pollution; Post precipitation reclaims the elementary adsorbent of part charing that is adsorbed with organic pollution, drying, and further charing is 2～6 hours under 400～700 ℃, makes the secondary adsorbent of complete charing.
Described natural biomass is pine needle, orange peel, shell.The granularity of natural biomass is 40～200 orders.
The carbonization temperature of the elementary adsorbent of part charing is 100～150 ℃.The mass volume ratio of adsorbent and pending organic wastewater is 1: 1000～1: 5000.Persistent organic pollutants in the high concentrated organic wastewater are naphthalene, pyrene, phenanthrene, alpha naphthol, organic agricultural chemicals or dyestuff.
The using method of the multistage adsorbent of high-concentration hardly-degradable organic polluting water comprises the steps:
1) the elementary adsorbent of part charing is added in the high concentrated organic wastewater, the mass volume ratio of the elementary adsorbent of part charing and high concentrated organic wastewater is 1: 500～1: 10000, through stirring, the organic wastewater of high concentration is carried out preliminary treatment;
2) the more secondary adsorbent of complete charing is added in pretreated organic wastewater, through stir, precipitation, carry out advanced treating, qualified discharge.
The present invention utilizes natural biomass charings such as discarded pine needle, orange peel, shell to produce high-efficiency adsorbent, according to the difference of carbonizing production under the different temperatures, adopt two-step process absorption to remove persistent organic pollutants in the water to the mechanism of organic pollution absorption.Discover that the low-temperature carbonization product is distributional effects to the main adsorption mechanism of high concentration organic contaminant, have good adsorption effect, adsorption capacity is big, and is irrelevant with the initial concentration of organic pollution, is suitable for the preliminary treatment of high concentrated organic wastewater; And the adsorption mechanism of high temperature carbonization product is surface absorption, is fit to the advanced treating of light concentration organic pollutant, and clearance is up to 99%.In addition, the advantage of this technology also has adsorbent to reuse, and regeneration is convenient, only need heat charing again and get final product.
Description of drawings
Accompanying drawing is a kind of multistage adsorbent preparation of high concentration hard-degraded organic waste water and the flow chart of using method.
The specific embodiment
The present invention is that promptly the low-temperature carbonization product produces distributional effects to the high concentration persistence organic pollutant, has very high adsorption capacity according to high concentration distributional effects-adsorbing principle in low concentration surface; And the high temperature carbonization product produces surperficial suction-operated to the low concentration persistence organic pollutant, has very strong adsorption effect; The carbonizing production that produces under the different temperatures is made multistage adsorbent, divide two stages to drop in the organic wastewater.Simple, green, the non-secondary pollution of this high-efficiency adsorbent preparation, and absorption property is strong, applied widely.
The present invention is fit to the adsorption treatment of high-concentration and low-concentration organic wastewater.Because carbonizing production also constantly increases with its hydrophobicity of rising of temperature, this water treatment technology is fit to the adsorption treatment of polarity and nonpolar organic wastewater; The adsorbent stable in properties, the high temperature carbonization product is difficult for desorption in wastewater treatment process, is suitable for the adsorption treatment of high concentration organic wastewaters such as agricultural chemicals waste water, coking chemical waste water and dyeing waste water, is particularly suitable for the adsorption treatment of micro quantity organic pollutant in the drinking water.Handling the back easy reclaiming of adsorbent uses.
Embodiment 1
1) at 100 ℃, the charing pine needle is 2 hours under the condition of anoxic, makes the elementary adsorbent of part charing;
2) the elementary adsorbent of part charing is dropped in the high concentrated organic wastewater, the mass volume ratio of adsorbent and high concentrated organic wastewater is 1: 500, through stirring, removes waste water middle and high concentration organic pollution; Post precipitation reclaims the elementary adsorbent of part charing that is adsorbed with organic pollution, drying, and further charing is 2 hours under 400 ℃, makes the secondary adsorbent of complete charing.
Embodiment 2
1) at 200 ℃, the charing orange peel is 6 hours under the condition of anoxic, makes the elementary adsorbent of part charing;
2) the elementary adsorbent of part charing is dropped in the high concentrated organic wastewater, the mass volume ratio of adsorbent and high concentrated organic wastewater is 1: 10000, through stirring, removes waste water middle and high concentration organic pollution; Post precipitation reclaims the elementary adsorbent of part charing that is adsorbed with organic pollution, drying, and further charing is 6 hours under 700 ℃, makes the secondary adsorbent of complete charing.
Embodiment 3
1) at 150 ℃, the charing shell is 4 hours under the condition of anoxic, makes the elementary adsorbent of part charing;
2) the elementary adsorbent of part charing is dropped in the high concentrated organic wastewater, the mass volume ratio of adsorbent and high concentrated organic wastewater is 1: 800, through stirring, removes waste water middle and high concentration organic pollution; Post precipitation reclaims the elementary adsorbent of part charing that is adsorbed with organic pollution, drying, and further charing is 4 hours under 600 ℃, makes the secondary adsorbent of complete charing.
Embodiment 4
1) the elementary adsorbent of part charing is added in the high concentrated organic wastewater, the mass volume ratio of the elementary adsorbent of part charing and high concentrated organic wastewater is 1: 500, through stirring, the organic wastewater of high concentration is carried out preliminary treatment;
2) the more secondary adsorbent of complete charing is added in pretreated organic wastewater, through stir, precipitation, carry out advanced treating, qualified discharge.
Embodiment 5
1) the elementary adsorbent of part charing is added in the high concentrated organic wastewater, the mass volume ratio of the elementary adsorbent of part charing and high concentrated organic wastewater is 1: 10000, through stirring, the organic wastewater of high concentration is carried out preliminary treatment;
2) the more secondary adsorbent of complete charing is added in pretreated organic wastewater, through stir, precipitation, carry out advanced treating, qualified discharge.
Embodiment 6
1) the elementary adsorbent of part charing is added in the high concentrated organic wastewater, the mass volume ratio of the elementary adsorbent of part charing and high concentrated organic wastewater is 1: 800, through stirring, the organic wastewater of high concentration is carried out preliminary treatment;
2) the more secondary adsorbent of complete charing is added in pretreated organic wastewater, through stir, precipitation, carry out advanced treating, qualified discharge.
Embodiment 6
The naphthalene solution (the Tu Shui ratio is about 1: 500) of getting elementary adsorbent of 20mg part charing and 10ml adds in the sample bottle of 10ml, 25 ℃ of 24 hours (absorption reach balance) of vibrating down.The concentration range of naphthalene: 10-28 μ g/mL.Experiment records clearance＞40% of naphthalene.
Embodiment 7
Get in the sample bottle of the secondary adsorbent of the complete charing of 10mg and the naphthalene solution of 10ml (the Tu Shui ratio is about 1: 1000) adding 10ml 25 ℃ of 24 hours (absorption reach balance) of vibrating down.The concentration range of naphthalene: 0.02-5 μ g/mL.Experiment records clearance＞90% of naphthalene.
Embodiment 8
The luxuriant and rich with fragrance solution (the Tu Shui ratio is about 1: 1000) of getting elementary adsorbent of 10mg part charing and 10ml adds in the sample bottle of 10ml, 25 ℃ of 24 hours (absorption reach balance) of vibrating down.Luxuriant and rich with fragrance concentration range: 0.001-1.0 μ g/mL.Experiment records luxuriant and rich with fragrance clearance greater than 65%.The high adsorption capacity of its China and Philippines can reach 7mg/g.
Embodiment 9
Get in the sample bottle of the secondary adsorbent of the complete charing of 5mg and the luxuriant and rich with fragrance solution of 10ml (the Tu Shui ratio is about 1: 2000) adding 10ml 25 ℃ of 24 hours (absorption reach balance) of vibrating down.Luxuriant and rich with fragrance concentration range: 0.001-1.0 μ g/mL.Experiment records luxuriant and rich with fragrance clearance greater than 95%.The high adsorption capacity of its China and Philippines can reach 7mg/g.
Embodiment 10
Get in the sample bottle of the secondary adsorbent of the complete charing of 1mg and the pyrene solution of 10ml (the Tu Shui ratio is about 1: 10000) adding 10ml 25 ℃ of 24 hours (absorption reach balance) of vibrating down.The concentration range of pyrene: 0.001-0.1 μ g/mL.Experiment records the clearance of pyrene greater than 99%.Wherein the high adsorption capacity of pyrene can reach 5mg/g; Be that the secondary adsorbent of the complete charing of 1g can be used for adsorption treatment 50L and contains pyrene organic wastewater (0.1 μ g/mL).
Embodiment 11
The alpha naphthol solution (the Tu Shui ratio is about 1: 500) of getting elementary adsorbent of 20mg part charing and 10mL adds in the sample bottle of 10ml, 25 ℃ of 24 hours (absorption reach balance) of vibrating down.The concentration range of alpha naphthol: 17-600 μ g/mL.Experiment records clearance＞50% of alpha naphthol.
Embodiment 12
Get in the sample bottle of the secondary adsorbent of the complete charing of 10mg and the alpha naphthol solution of 10mL (the Tu Shui ratio is about 1: 1000) adding 10mL 25 ℃ of 24 hours (absorption reach balance) of vibrating down.The concentration range of alpha naphthol: 0.02-17 μ g/mL.Experiment records clearance＞95% of alpha naphthol.
Claims (7)
1. the multistage adsorbent preparation method of a high concentration hard-degraded organic waste water is characterized in that, comprises the steps:
1) at 100～200 ℃, the charing natural biomass is 2～6 hours under the condition of anoxic, makes the elementary adsorbent of part charing;
2) the elementary adsorbent of part charing is dropped in the high concentrated organic wastewater, the mass volume ratio of adsorbent and high concentrated organic wastewater is 1: 500～1: 10000, through stirring, removes waste water middle and high concentration organic pollution; Post precipitation reclaims the elementary adsorbent of part charing that is adsorbed with organic pollution, drying, and further charing is 2～6 hours under 400～700 ℃, makes the secondary adsorbent of complete charing.
2. the multistage adsorbent preparation method of a kind of high concentration hard-degraded organic waste water according to claim 1 is characterized in that described natural biomass is pine needle, orange peel, shell.
3. the multistage adsorbent preparation method of a kind of high concentration hard-degraded organic waste water according to claim 1, the granularity that it is characterized in that described natural biomass is 40～200 orders.
4. the multistage adsorbent preparation method of a kind of high concentration hard-degraded organic waste water according to claim 1, the carbonization temperature that it is characterized in that the elementary adsorbent of described part charing is 100～150 ℃.
5. the adsorption treatment process of a kind of high concentration hard-degraded organic waste water according to claim 1, the mass volume ratio that it is characterized in that described adsorbent and pending organic wastewater is 1: 1000～1: 5000.
6. the multistage adsorbent preparation method of a kind of high-concentration hardly-degradable organic polluting water according to claim 1 is characterized in that the persistent organic pollutants in the described high concentrated organic wastewater are naphthalene, pyrene, phenanthrene, alpha naphthol, organic agricultural chemicals or dyestuff.
7. the using method of the multistage adsorbent of a high concentration hard-degraded organic waste water as claimed in claim 1 is characterized in that, comprises the steps:
1) the elementary adsorbent of part charing is added in the high concentrated organic wastewater, the mass volume ratio of the elementary adsorbent of part charing and high concentrated organic wastewater is 1: 500～1: 10000, through stirring, the organic wastewater of high concentration is carried out preliminary treatment;
2) the more secondary adsorbent of complete charing is added in pretreated organic wastewater, through stir, precipitation, carry out advanced treating, discharge behind the wastewater to reach standard.
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| CN102921383B (en) * | 2012-11-26 | 2014-07-09 | 四川大学 | Absorbent for cationic dyes in waste water and preparation method of absorbent |
| CN103058473A (en) * | 2012-12-31 | 2013-04-24 | 东莞市粤源包装有限公司 | Low-cost method capable of continuously cleaning river sludge |
| CN103466810A (en) * | 2013-09-30 | 2013-12-25 | 东莞市粤源包装有限公司 | Method for polluted river comprehensive treatment |
| CN103482799A (en) * | 2013-10-15 | 2014-01-01 | 无锡艾科瑞思产品设计与研究有限公司 | Method for adsorbing copper ions in water by use of melon seed peels |
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