CN100446851C - Preparation and using method of plant bionic high efficient adsorbent for removing difficult degradation organic pollutant - Google Patents
Preparation and using method of plant bionic high efficient adsorbent for removing difficult degradation organic pollutant Download PDFInfo
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- CN100446851C CN100446851C CNB2007100677820A CN200710067782A CN100446851C CN 100446851 C CN100446851 C CN 100446851C CN B2007100677820 A CNB2007100677820 A CN B2007100677820A CN 200710067782 A CN200710067782 A CN 200710067782A CN 100446851 C CN100446851 C CN 100446851C
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Abstract
An efficient bionic vegetative adsorbent for removing the organic pollutants difficult to be degradated from water is prepared through providing vegetative skin, extracting to obtain waxy liquid, proportionally mixing it with clay mineral, oscillating, filtering, drying the filtered cake in the air, baking, grinding and sieving. Its application method is also disclosed.
Description
Technical field
The present invention relates to water technology and application, relate in particular to a kind of plant bionic high efficient adsorbent preparation and using method of removing hardly degraded organic substance in the water.
Background technology
Since the 1950's, the chemical industry develop rapidly is that 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) great majority have carcinogenic, cause rugged, mutagenicity, extensively be present in the environment such as air, water body, deposit, soil, and in environment, be difficult to degraded, can transmit in vivo and accumulate by food chain, health and ecological environment are constituted a serious threat.For this reason, famous " Convention of Stockholm " signed in calendar year 2001s 122 representative of country in the Stockholm of Sweden, requires a signatory to adopt various measures and international cooperation, and the production of control POP, 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.Main both at home and abroad at present employing charcoal absorption, activated carbon has the good treatment effect to the dissolubility organic pollution, but its adsorption mechanism is surface absorption, adsorption capacity is little, and is saturated easily, causes the use cost height.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.
The plant cuticula is the membrane structure that plant surface is made up of cutin and wax, and is linked by pectic substance, covers on the cell membrane of epidermal cell outer surface, and plant is played a part mechanical protection and dehydration protection, is the outermost layer that plant is resisted pollution; Wherein waxy component plays a decisive role to cuticular transmission course, there are some researches show, removes waxy component, and hydrone and the organic matter permeability in cuticula improves 10-1000 doubly.Waxy component stable in properties in the plant cuticula, difficult degraded are the main positions of lipophilicity persistence organic pollutant in the plant accumulation air.
Summary of the invention
The purpose of this invention is to provide a kind of preparation and using method of removing the plant bionic high efficient adsorbent of persistent organic pollutants in the water.
The preparation method who removes the plant bionic high efficient adsorbent of persistent organic pollutants in the water comprises the steps:
1) utilizes discarded plant epidermis, behind the removal pulp wherein, obtain plant epidermis, extract, obtain natural wax extract through the Soxhlet method;
2) the wax extract is mixed natural clay mineral and wax extract mass volume ratio 1: 3-1 with the natural clay mineral: 80, normal temperature vibrated 1～6 hour down, filtered;
3) filter cake is air-dry under normal temperature, and dries 1～2 hour down at 80～90 ℃, grinds, and the 40-200 order that sieves obtains plant bionic high efficient adsorbent; Filtrate recovery is reused.
Described natural clay mineral are calcium-base bentonite original soil or sodium bentonite original soil.The granularity of natural clay mineral is 40～200 orders.Plant cuticular wax content is 0.1%～60% in the plant bionic high efficient adsorbent.Discarded plant epidermis is the epidermis of tomato, apple, green pepper, orange, potato, wax gourd.
Remove the using method of the plant bionic high efficient adsorbent of persistent organic pollutants in the water: adsorbent is added in the organic wastewater pond, stirs, precipitate, the ratio of the consumption of adsorbent and pending organic wastewater amount is 1: 1000～1: 10000.Persistent organic pollutants in the described organic wastewater are naphthalene, pyrene, phenanthrene, naphthols.
The present invention is the principle according to plant surface wax strong absorption persistence organic pollutant, the cuticular waxy component of plant is loaded to the natural clay mineral surfaces form the plant bionic organic matter.Simple, green, the non-secondary pollution of this plant bionic adsorbent preparation, and absorption property is strong.
This plant bionic adsorbent has hydrophobic plant wax and hydrophilic natural clay mineral, is fit to the adsorption treatment of polarity and nonpolar organic wastewater; The adsorbent stable in properties, waxy component is difficult for desorption in wastewater treatment process, is particularly suitable for the adsorption treatment of micro quantity organic pollutant in the drinking water.This plant bionic adsorbent adjustable density, the plant wax content was greater than 10% o'clock in the plant bionic high efficient adsorbent, and the density of adsorbent is just used with waste water treatment engineering greater than the density (1g/mL) of water; Handling the back easy reclaiming of adsorbent uses.Used montmorillonite mineral is that a kind of specific area is big, the very wide clay mineral that distributes, and aboundresources, cost is low.
Description of drawings
Accompanying drawing is preparation method's flow chart of removing the plant bionic high efficient adsorbent of persistent organic pollutants in the water.
The specific embodiment
According to the principle of plant surface wax strong absorption persistence organic pollutant, the cuticular waxy component of plant is loaded to the natural clay mineral surfaces form the plant bionic organic matter, remove persistent organic pollutants in the water; Organic pollution in the organic wastewater is naphthalene, pyrene, phenanthrene, naphthols.
Embodiment 1
1) utilizes discarded plant epidermis, behind the removal pulp wherein, obtain plant epidermis,, obtain natural wax extract through the Soxhlet extracting method;
2) the wax extract is mixed with the natural clay mineral, natural clay mineral and wax extract mass volume ratio 1: 3, normal temperature vibrated 1 hour down, filtered;
3) filter cake is air-dry under normal temperature, and dries 1 hour down at 80 ℃, grinds, and 40 orders that sieve obtain plant bionic high efficient adsorbent; Filtrate recovery is reused.
Embodiment 2
1) utilizes discarded plant epidermis, behind the removal pulp wherein, obtain plant epidermis,, obtain natural wax extract through the Soxhlet extracting method;
2) the wax extract is mixed with the natural clay mineral, natural clay mineral and wax extract mass volume ratio 1: 80, normal temperature vibrated 6 hours down, filtered;
3) filter cake is air-dry under normal temperature, and dries 2 hours down at 90 ℃, grinds, and 200 orders that sieve obtain plant bionic high efficient adsorbent; Filtrate recovery is reused.
Embodiment 3
Manually peel off the fresh apple pericarp, pericarp is boiled 1h in water after, artificial removal's pulp as much as possible.Clean with distilled water then, remove all residual pulp, obtain a large amount of epidermises.This epidermis by apparatus,Soxhlet's, under 70 ℃, is extracted 6h with 1: 1 chloroform methanol organic solvent, obtain waxy component.After the rotary evaporator evaporation, dry naturally again.Add 0～1.5g plant epicuticular wax quality sample, 30mL methyl alcohol successively in the 40mL sample bottle, add a certain amount of ca-montmorillonite simultaneously, after hand the mixing, place the constant temperature oscillator 6h that vibrates, temperature is 25 ℃ ± 0.5 ℃.Blot supernatant as far as possible, under the normal temperature sample is positioned in the fume hood and dries, at 80-90 ℃ of oven dry 2h down, it is standby to grind 100 mesh sieves.Obtain plant bionic high efficient adsorbent, its wax load capacity is 0.1%-60%.
Embodiment 4
The naphthalene solution (the Tu Shui ratio is about 1: 1000) of getting 10mg plant bionic high efficient adsorbent (wax content is 40%) and 10ml adds in the sample bottle of 10ml, 25 ℃ of 24 hours (absorption reach balance) of vibrating down.The concentration range of naphthalene: 0.02-28 μ g/mL.Experiment records the clearance 60% of naphthalene.Wherein the high adsorption capacity of naphthalene can reach 21mg/g.When the Tu Shui ratio was 1: 100, clearance was greater than 90%.
Embodiment 5
The luxuriant and rich with fragrance solution (the Tu Shui ratio is about 1: 1000) of getting 10mg plant bionic high efficient adsorbent (wax content is 40%) 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 95%.The high adsorption capacity of its China and Philippines can reach 7 mg/g, and promptly 1g plant bionic high efficient adsorbent (wax content is 40%) can be used for adsorption treatment 7 L and contains pyrene organic wastewater (1 μ g/mL).
Embodiment 6
The pyrene solution (the Tu Shui ratio is about 1: 10000) of getting 1mg plant bionic high efficient adsorbent (wax content is 40%) 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: 0.001-0.1 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 1g plant bionic high efficient adsorbent (wax content is 40%) can be used for adsorption treatment 50L and contains pyrene organic wastewater (0.1 μ g/mL).
Claims (7)
1. a preparation method who removes the plant bionic high efficient adsorbent of persistent organic pollutants in the water is characterized in that, comprises the steps:
1) utilizes discarded plant epidermis, behind the removal pulp wherein, obtain plant epidermis, extract, obtain natural wax extract with the Soxhlet method;
2) the wax extract is mixed natural clay mineral and wax extract mass volume ratio 1: 3-1 with the natural clay mineral: 80, normal temperature vibrated 1～6 hour down, filtered;
3) filter cake is air-dry under normal temperature, and dries 1～2 hour down at 80～90 ℃, grinds, and the 40-200 order that sieves obtains plant bionic high efficient adsorbent; Filtrate recovery is reused.
2. a kind of preparation method who removes the plant bionic high efficient adsorbent of persistent organic pollutants in the water according to claim 1 is characterized in that described natural clay mineral are calcium-base bentonite original soil or sodium bentonite original soil.
3. a kind of preparation method who removes the plant bionic high efficient adsorbent of persistent organic pollutants in the water according to claim 1, the granularity that it is characterized in that described natural clay mineral is 40～200 orders.
4. a kind of preparation method who removes the plant bionic high efficient adsorbent of persistent organic pollutants in the water according to claim 1 is characterized in that plant cuticular wax content is 0.1%～60% in the described plant bionic high efficient adsorbent.
5. a kind of preparation method who removes the plant bionic high efficient adsorbent of persistent organic pollutants in the water according to claim 1, the described discarded plant epidermis of its feature is the epidermis of tomato, apple, green pepper, orange, potato or wax gourd.
6. using method of the plant bionic high efficient adsorbent of persistent organic pollutants in the removal water of method preparation according to claim 1, it is characterized in that adsorbent is added in the organic wastewater pond, stir, precipitate, the ratio of the consumption of adsorbent and pending organic wastewater amount is 1: 1000～1: 10000.
7. a kind of using method of removing the plant bionic high efficient adsorbent of persistent organic pollutants in the water according to claim 6 is characterized in that the persistent organic pollutants in the described organic wastewater are naphthalene, pyrene, phenanthrene and naphthols.
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| CNB2007100677820A CN100446851C (en) | 2007-03-26 | 2007-03-26 | Preparation and using method of plant bionic high efficient adsorbent for removing difficult degradation organic pollutant |
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| CN102211795A (en) * | 2011-04-20 | 2011-10-12 | 华中科技大学 | Method for regenerating eluant in organic polluted soil eluent |
| CN106180168A (en) * | 2016-09-22 | 2016-12-07 | 北京新源环境有限公司 | The method that plant bionic repairs place soil with chemical leaching, microbial association |
| CN106520288A (en) * | 2016-10-29 | 2017-03-22 | 常州亚环环保科技有限公司 | Preparation method of low temperature resistant automobile brake fluid |
| CN108704620B (en) * | 2018-07-02 | 2021-04-20 | 大连理工大学 | Preparation method and application of chitosan/hydrophobic montmorillonite adsorbing material for treating anions in wastewater |
| CN108910971A (en) * | 2018-07-10 | 2018-11-30 | 奚永乐 | A kind of purifying domestic sewage agent and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5492881A (en) * | 1994-03-25 | 1996-02-20 | Diamond; Charles M. | Sorbent system |
| WO1999043446A1 (en) * | 1998-02-27 | 1999-09-02 | Cri Recycling Service, Inc. | Removal of contaminants from materials |
| CN1187272C (en) * | 2003-04-07 | 2005-02-02 | 浙江大学 | Method for treating organic wastewater by using microwave cooperated with bentonite |
| CN1253077C (en) * | 2004-02-09 | 2006-04-26 | 许盛英 | Non-birdnesting type concavo-convex rod colorful cat sand |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5492881A (en) * | 1994-03-25 | 1996-02-20 | Diamond; Charles M. | Sorbent system |
| WO1999043446A1 (en) * | 1998-02-27 | 1999-09-02 | Cri Recycling Service, Inc. | Removal of contaminants from materials |
| CN1187272C (en) * | 2003-04-07 | 2005-02-02 | 浙江大学 | Method for treating organic wastewater by using microwave cooperated with bentonite |
| CN1253077C (en) * | 2004-02-09 | 2006-04-26 | 许盛英 | Non-birdnesting type concavo-convex rod colorful cat sand |
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