CN105668804A - Spongy high-efficient biological treatment material for dyeing waste water and preparation technology of spongy high-efficient biological treatment material - Google Patents

Spongy high-efficient biological treatment material for dyeing waste water and preparation technology of spongy high-efficient biological treatment material Download PDF

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Publication number
CN105668804A
CN105668804A CN201410666825.7A CN201410666825A CN105668804A CN 105668804 A CN105668804 A CN 105668804A CN 201410666825 A CN201410666825 A CN 201410666825A CN 105668804 A CN105668804 A CN 105668804A
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CN
China
Prior art keywords
spongy
gac
dimensional network
treatment
organic composite
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CN201410666825.7A
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Chinese (zh)
Inventor
陈永
马伟
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海南大学
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Priority to CN201410666825.7A priority Critical patent/CN105668804A/en
Publication of CN105668804A publication Critical patent/CN105668804A/en

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Abstract

The invention discloses a preparation technology of a spongy high-efficient activated carbon/organic composite biological treatment material which can be recycled and has a three-dimensional network hole structure, for dyeing waste water. In order to solve the problem that sewage including dyeing waste water and the like is difficult to treat, and overcome the defects that activated carbon is easy to deposit and difficult to recycle, and free paint enzymes have harsh requirements for environmental conditions; in the preparation technology disclosed by the invention, polyvinyl alcohol and methanal are subjected to a reaction, a foaming hole-forming method is combined, starch is added to be used as a foaming agent and is composited with the activated carbon, and then vibration and fixation are performed through a paint enzyme solution, so that the flexible high-efficient spongy activated carbon /organic composite biological carrier material which can suspend in water, can be recycled and has the three-dimensional network hole structure is prepared. According to the material, the strong adsorptivity of the activated carbon and the high efficiency of the enzymes are combined, so that the problem that the dyeing waste water is incomplete to treat through a treatment agent at present is solved, the treatment efficiency can be further improved, the application range is enlarged, and a high-efficient broad-spectrum environmentally-friendly way is provided for sewage treatment.

Description

A kind of spongy efficient Dyeing and Printing Wastewater Biological Treatment material and preparation technology thereof

Technical field

The invention belongs to environmental engineering material field, it is specifically related to a kind of spongy efficient, the gac with the three-dimensional network pore structure/organic composite biological wastewater treatment material that can be recycled and preparation technology thereof.

Background technology

China discharges the waste water of enormous amount every year, and water pollution control is very urgent. Trade effluent is the main source of water pollutions, and wherein dye printing and dyeing wastewater is the most difficult. China produces the dyestuff of hundreds of thousands of ton every year, accounts for more than the 30% of Gross World Product, has again 10-15% to enter into environment with the form of waste water, environment causes very big destruction. Waste water from dyestuff colourity is dark, concentration height, and pollutant component complexity, difficult degradation, most of poisonous and harmful, traditional treatment process does not often reach desirable effect. Therefore, the decolouring of waste water from dyestuff and degraded have become a difficult problem maximum in Industrial Wastewater Treatment, and finding more effective treatment process is each national common target.

Water pollutions is the problem that people pay close attention to always, along with pollutant kind increase, composition become more complicated, its advanced treatment be it is also proposed higher requirement. Gac (AC) has very strong adsorption catalysis ability, redox property, wide material sources, renewable, acid and alkali-resistance; Organic pollutant, dyestuff, heavy metal being had good removal effect, and can clarify, deodorizing, remove peculiar smell etc., application is widely. But gac is in the process of process pollutant effluents, it is easy to deposit to the bottom, on the one hand that the pollutent absorption in water body is less, and bigger pollution load can not be born; Recycling difficulty on the other hand, particularly in the river of ocean, pollution and reservoir governance process.

Laccase is a kind of polyphenoloxidase containing copper, it is possible to the multiple phenolic of catalysis and non-phenolic compound generation oxidizing reaction, multiple organic pollutant of degrading, and is widely used in Industrial Wastewater Treatment and the aspect such as dye decolored. As a kind of biological catalyst, laccase has efficient, single-minded and gentle enzymic catalytic reaction characteristic. But free laccase is very responsive to environment, the factor such as temperature, pH easily makes its active reduction or loses, thus limits its application.

Summary of the invention

The present invention is directed to the problem of the sewage disposal difficulties such as dyeing waste water, simultaneously synthetic activity charcoal easily deposits, is difficult to recycle and envrionment conditions is required the defects such as harsh by free laccase, it provides a kind of spongy efficient and preparation technology of the gac with three-dimensional network pore structure/organic composite biological wastewater treatment material that can be recycled.

First the present invention adopts polyvinyl alcohol and formaldehyde reaction, in conjunction with foaming pore method, add starch as whipping agent, and with gac compound, spongy gac/organic composite biological solid support material that single stage method is prepared into flexibility, may float on the water surface, has three-dimensional network vesicular structure; Again carrier is placed in laccase solution, under certain condition, vibrate in shaking table certain time can obtain a kind of can high-activity treatment of textile dye waste, the spongy biological sewage treatment material of the gac/organic composite with three-dimensional network pore structure that simultaneously can recycle.

In the present invention, spongy Dyeing and Printing Wastewater Biological Treatment material adopts following technical scheme:

Main raw materials in proportion and processing parameter are as follows:

Polyvinyl alcohol: 10g

Dilute sulphuric acid (9%): 10 ~ 32mL

Formaldehyde (40%): 8 ~ 12mL

Zulkovsky starch: 8 ~ 12mL

Gac: 5 ~ 15g

Water: 80 ~ 200mL

Acetalation temperature: 50 ~ 85 DEG C

The envrionment temperature of laccase fixation reaction: 10 ~ 35 DEG C

Laccase fixation reaction environmental PH value: 1 ~ 6

Its preparation technology is:

(1) first the polyvinyl alcohol of about 10g is added water swelling.

(2) the heat collecting type constant temperature blender with magnetic force that (1) be placed in 95 DEG C is slowly stirred to it and dissolves completely.

(3) (2) are cooled to 70 DEG C, add the Zulkovsky starch after a certain amount of dissolving and gac, fully mix.

(4) add the formaldehyde solution of a certain amount of 9% dilution heat of sulfuric acid and 40%, stir evenly.

(5) thermostat water bath being placed in certain temperature carries out acetalation, obtains gac/organic composite three-dimensional network pore structure material.

(6) (5) are placed in organic solvent and carry out solvent displacement.

(7) (6) are taken out from organic solvent, carry out abundant drying, obtain gac/organic composite three-dimensional network pore structure finished material.

(8) (7) are placed in the laccase solution of finite concentration and certain pH, at a certain temperature, being placed in shaking table certain time of vibrating can obtain the gac/organic composite biological wastewater treatment material of a kind of spongy three-dimensional network pore structure that can be recycled, has.

Enzyme, by the high efficiency of the strong adsorptivity of gac and enzyme being combined, is fixed on spongy gac porous material by the present invention, develops the product of a kind of efficient, reusable edible, to solve the problems such as treatment of dyeing wastewater is difficult. Not only overcome above shortcoming by fixation techniques for enzyme, and show stability height, easily separated recovery, the series of advantages such as can reuse, it is to increase the utilising efficiency of enzyme, reduce cost; Gac as the strong sorbent material of one, can the multiple pollutant such as absorbing dye, heavy metal, can be used for the advanced treatment of waste water. In addition, obtained compound wastewater Biological treatment material is spongy, has softness, can be suspended in the medium advantage of water body, can more lastingly, the pollutent in adsorbed water body effectively. By certain simple reclaiming, compound wastewater Biological treatment material can realize recycling, and effectively prevent secondary pollution problem. In a word, the present invention can solve the problems such as current treatment of dyeing wastewater agent process is incomplete, and can further improve processing efficiency, expands range of application, for sewage disposal provides the approach of efficient a, wide spectrum and environmental protection.

Embodiment

Embodiment 1:

(1) 120mL that first added water by the polyvinyl alcohol of about 10g is swelling.

(2) the heat collecting type constant temperature blender with magnetic force that (1) be placed in 95 DEG C is slowly stirred to it and dissolves completely.

(3) (2) are cooled to 70 DEG C, add Zulkovsky starch and the 15g gac of the 9g being dissolved in 20mL water, fully mix.

(4) add 9% dilution heat of sulfuric acid of 32mL and the formaldehyde solution of the 40% of 12mL, stir evenly.

(5) thermostat water bath being placed in certain 70 DEG C carries out acetalation, obtains gac/organic composite three-dimensional network pore structure material.

(6) (5) are placed in normal hexane and carry out solvent displacement.

(7) (6) are taken out from normal hexane, carry out abundant drying, obtain gac/organic composite three-dimensional network pore structure bio-carrier.

(8) laccase solution that (7) are placed in 1.5g/L and pH=3, at 30 DEG C, is placed in the shaking table 12h that vibrates and can obtain spongy efficient, the treatment of dyeing wastewater material that can be recycled.

Embodiment 2:

(1) 140mL that first added water by the polyvinyl alcohol of about 10g is swelling.

(2) the heat collecting type constant temperature blender with magnetic force that (1) be placed in 95 DEG C is slowly stirred to it and dissolves completely.

(3) (2) are cooled to 70 DEG C, add Zulkovsky starch and the 10g gac of the 10g being dissolved in 20mL water, fully mix.

(4) add 9% dilution heat of sulfuric acid of 32mL and the formaldehyde solution of the 40% of 8mL, stir evenly.

(5) thermostat water bath being placed in certain 55 DEG C carries out acetalation, obtains gac/organic composite three-dimensional network pore structure material.

(6) (5) are placed in normal hexane and carry out solvent displacement.

(7) (6) are taken out from normal hexane, carry out abundant drying, obtain gac/organic composite three-dimensional network pore structure bio-carrier.

(8) laccase solution that (7) are placed in 1.5g/L and pH=2, at 25 DEG C, is placed in the shaking table 12h that vibrates and can obtain spongy efficient, the treatment of dyeing wastewater material that can be recycled.

Claims (2)

1. the gac of the one kind spongy three-dimensional network pore structure that can be recycled, has/organic composite biological wastewater treatment material, it is characterised in that, main raw materials in proportion and processing parameter are as follows:
Polyvinyl alcohol: 10g
Dilute sulphuric acid (9%): 10 ~ 32mL
Formaldehyde (40%): 8 ~ 12mL
Zulkovsky starch: 8 ~ 12mL
Gac: 5 ~ 15g
Water: 80 ~ 200mL
Acetalation temperature: 50 ~ 85 DEG C
The envrionment temperature of laccase fixation reaction: 10 ~ 35 DEG C
Laccase fixation reaction environment pH value: 1 ~ 6.
2. spongy efficient, the preparation technology of compound wastewater Biological treatment material that can be recycled as claimed in claim 1 realizes as follows:
(1) first the polyvinyl alcohol of about 10g is added water swelling;
(2) the heat collecting type constant temperature blender with magnetic force that (1) be placed in 95 DEG C is slowly stirred to it and dissolves completely;
(3) (2) are cooled to 70 DEG C, add the Zulkovsky starch after a certain amount of dissolving and gac, fully mix;
(4) add the formaldehyde solution of a certain amount of 9% dilution heat of sulfuric acid and 40%, stir evenly;
(5) thermostat water bath being placed in certain temperature carries out acetalation, obtains gac/organic composite three-dimensional network pore structure material;
(6) (5) are placed in organic solvent and carry out solvent displacement;
(7) (6) are taken out from organic solvent, carry out abundant drying, obtain gac/organic composite three-dimensional network pore structure finished material;
(8) (7) are placed in the laccase solution of finite concentration and certain pH, at a certain temperature, being placed in shaking table certain time of vibrating can obtain the gac/organic composite biological wastewater treatment material of the spongy three-dimensional network pore structure that can be recycled, has.
CN201410666825.7A 2014-11-20 2014-11-20 Spongy high-efficient biological treatment material for dyeing waste water and preparation technology of spongy high-efficient biological treatment material CN105668804A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105903451A (en) * 2016-05-09 2016-08-31 李迎春 Heavy metal adsorption sponge as well as preparation method and use thereof
CN106047854A (en) * 2016-07-20 2016-10-26 申昱环保科技股份有限公司 Preparation method of sewage treatment bactericide with rod-shaped activated carbon

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Publication number Priority date Publication date Assignee Title
CN1986789A (en) * 2006-12-20 2007-06-27 福州晨翔环保工程有限公司 Composite immobilized enzyme material for repairing polluted water source and its preparing process
CN101055105A (en) * 2007-02-06 2007-10-17 彭泽福 Adsorption disinfection filtering machine for circumfluence space
CN101462816A (en) * 2009-01-12 2009-06-24 浙江大学 Apparatus for integrated treatment and comprehensive utilization of wastewater and use thereof
CN103723725A (en) * 2013-12-31 2014-04-16 海南大学 Preparation method of silanized active carbon and preparation method of immobilized enzyme

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1986789A (en) * 2006-12-20 2007-06-27 福州晨翔环保工程有限公司 Composite immobilized enzyme material for repairing polluted water source and its preparing process
CN101055105A (en) * 2007-02-06 2007-10-17 彭泽福 Adsorption disinfection filtering machine for circumfluence space
CN101462816A (en) * 2009-01-12 2009-06-24 浙江大学 Apparatus for integrated treatment and comprehensive utilization of wastewater and use thereof
CN103723725A (en) * 2013-12-31 2014-04-16 海南大学 Preparation method of silanized active carbon and preparation method of immobilized enzyme

Non-Patent Citations (1)

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Title
李国朝等: "聚乙烯醇/活性炭多孔复合材料处理印染废水研究", 《安徽农业科学》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105903451A (en) * 2016-05-09 2016-08-31 李迎春 Heavy metal adsorption sponge as well as preparation method and use thereof
CN106047854A (en) * 2016-07-20 2016-10-26 申昱环保科技股份有限公司 Preparation method of sewage treatment bactericide with rod-shaped activated carbon

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Inventor after: Chen Yong

Inventor after: Chen Daming

Inventor after: Ma Wei

Inventor after: Li De

Inventor before: Chen Yong

Inventor before: Ma Wei

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