CN103623786B - What be applied to coal chemical industry enterprises wastewater treatment releases phosphorus adsorption plate and preparation method - Google Patents

What be applied to coal chemical industry enterprises wastewater treatment releases phosphorus adsorption plate and preparation method Download PDF

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CN103623786B
CN103623786B CN201310686383.8A CN201310686383A CN103623786B CN 103623786 B CN103623786 B CN 103623786B CN 201310686383 A CN201310686383 A CN 201310686383A CN 103623786 B CN103623786 B CN 103623786B
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mixed liquor
solution
adsorption plate
concentration
chemical industry
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CN103623786A (en
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丁爱中
谢恩
豆俊峰
程莉蓉
郑蕾
许新宜
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Beijing Normal University
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Beijing Normal University
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Abstract

The invention discloses be applied to coal chemical industry enterprises wastewater treatment release phosphorus adsorption plate and preparation method.By NH 4hCO 3solution, NH 4h 2pO 4solution, Ca (NO 3) 2solution, NH 4oH solution, hydrochloric acid solution, NH 4the Cl aqueous solution and Ca-EDTA potassium solution are prepared into mixed liquor F.Styrene chloroformic solution, divinylbenzene chloroformic solution and azodiisobutyronitrile chloroformic solution are prepared into mixed liquor M.Mixed liquor F is added drop-wise in mixed liquor M, obtains mixed liquor O; Spurted in the container that liquid nitrogen is housed by distilled water and make ice hockey particle, it is real that screening is placed on mould inner pressure; Mixed liquor O is poured in mould freeze settled, through the demoulding and freezing after obtain adsorption plate.Air-dry after this adsorption plate is cultivated 24h in petroleum hydrocarbon degradation bacterium liquid, can obtain.Manufacture craft of the present invention is simple, and obtained adsorption plate has the function of slowly-releasing phosphorus function, absorption and biodegradation coal chemical industry enterprises waste water Petroleum Hydrocarbon.

Description

What be applied to coal chemical industry enterprises wastewater treatment releases phosphorus adsorption plate and preparation method
Technical field
The invention belongs to the processing technology field of coal chemical industrial waste water, particularly a kind of be applied to coal chemical industry enterprises wastewater treatment release phosphorus adsorption plate and preparation method.
Background technology
Adsorption-Biodegradation occupies important function as a kind of water technology of combining in the process of sewage.Be adsorbed with the most frequently used sorbing material of organic pollutants at present and can be divided into physisorption material, chemisorbed material and biological adsorption material.Wherein, physisorption material has active carbon, molecular sieve, zeolite, atlapulgite and clay minerals etc. to have the solid of high-specific surface area, there is the advantage that eliminating efficiency is high, enrichment function is strong, but also existence and stability poor, easily desorption, be subject to the deficiencies such as influence of temperature change.Chemisorbed material mainly comprises silica gel, synthetic fibers, resin, utilizes the molecularly imprinted polymer etc. of biochemistry and Polymer Synthesizing.Conventional biological adsorption material has broad leaved plant, the microorganism etc. in fungi, soil and water.In the organic process of microbial degradation, need the participation of phosphorus nutrition element, the nutrients such as phosphorus contained in the waste water that coal chemical industry enterprises is discharged under normal circumstances cannot meet the requirement of microorganism, but the adsorbent with slowly-releasing phosphorus function can meet this requirement.But, also lack the sorbing material for Coal Chemical Industry treatment of Organic Wastewater at present.
Summary of the invention
The object of this invention is to provide a kind of be applied to coal chemical industry enterprises wastewater treatment release phosphorus adsorption plate and preparation method.Its concrete steps are as follows:
(1) be the NH of 0.35mol/L by 100mL concentration 4hCO 3solution and 100mL concentration are the NH of 0.62mol/L 4h 2pO 4mixing, obtain mixed liquor A 1, is then the NH of 0.01mol/L by concentration 4oH solution and concentration are that the hydrochloric acid solution of 0.01mol/L regulates the pH value of mixed liquor A 1 to be 9.0, obtain mixed liquor A;
(2) 200mL mixed liquor A is slowly added drop-wise under agitation the Ca (NO that 300mL concentration is 0.025mol/L 3) 2in solution, obtain mixed liquid B;
(3) in mixed liquid B, dense HNO is dropwise added 3to clarification, obtain mixed liquor C;
(4) regulate the pH value of mixed liquor C to be 3.5 with the hydrochloric acid solution of concentration to be the NaOH solution of 0.01mol/L and concentration be 0.01mol/L, obtain mixed liquor D;
(5) in mixed liquor D, the NH that 100mL concentration is 1.1mol/L is added 4the Cl aqueous solution, obtains mixed liquor E after mixing;
(6) in mixed liquor E, add the Ca-EDTA potassium solution that 50mL concentration is 0.15mol/L, after mixing, obtain mixed liquor F;
(7) by 200mL mass fraction be 11.5% styrene chloroformic solution, 40mL mass fraction be 9.5% divinylbenzene chloroformic solution and 40mL mass fraction be 1.5% azodiisobutyronitrile chloroformic solution fully mix, obtain mixed liquor M;
(8) 60mL mixed liquor F is added drop-wise in mixed liquor M under 1000r/min stirring condition, then under 1000r/min condition, stirs 8min, obtain mixed liquor O;
(9) distilled water being spurted in the container that liquid nitrogen is housed snap frozen and make ice hockey particle, is that the ice hockey particle of 50 ~ 100 μm is stand-by with choosing grain size scope after sieved through sieve;
(10) ice hockey particle garbled in step (9) is placed in also compacting in mould cavity;
(11) mixed liquor O is poured in the mould that step (10) obtains, and together puts into liquid nitrogen freeze settled 6 hours, after taking out the demoulding, obtain solid mixt; Obtaining after this solid mixt vacuum freeze drying is removed chloroform and ice hockey particle can the adsorption plate of slow releasing P elements;
(12) adsorption plate that step (11) obtains is cultivated 24h in petroleum hydrocarbon degradation bacteria culture fluid, be absorbed and fixed at by petroleum hydrocarbon degradation bacterium on this adsorption plate, wherein the bacteria containing amount of petroleum hydrocarbon degradation bacteria culture fluid is 5 × 10 10cFU/ml, consisting of of nutrient solution: NH 4nO 3: 2.0gL -1, NaCl:10.5gL -1, KH 2pO 4: 2.5gL -1, FeCl 3: 0.10gL -1, MgSO 4: 3.5gL -1, CaCl 22H 2o:0.15gL -1;
(13) adsorption plate that step (12) obtained takes out air-dry, and what can obtain being applied to coal chemical industry enterprises wastewater treatment releases phosphorus adsorption plate.
The invention has the beneficial effects as follows, manufacture craft is simple, and obtained adsorption plate has the function of slowly-releasing phosphorus function, absorption and biodegradation coal chemical industry enterprises waste water Petroleum Hydrocarbon.
Detailed description of the invention
The invention provides a kind of be applied to coal chemical industry enterprises wastewater treatment release phosphorus adsorption plate and preparation method, with an embodiment, the present invention is described below.
Embodiment 1.
Be the NH of 0.35mol/L by 100mL concentration 4hCO 3solution and 100mL concentration are the NH of 0.62mol/L 4h 2pO 4mixing, obtain mixed liquor A 1, is then the NH of 0.01mol/L by concentration 4oH solution and concentration are that the hydrochloric acid solution of 0.01mol/L regulates the pH value of mixed liquor A 1 to be 9.0, obtain mixed liquor A; 200mL mixed liquor A is slowly added drop-wise under agitation the Ca (NO that 300mL concentration is 0.025mol/L 3) 2in solution, obtain mixed liquid B; Dense HNO is dropwise added in mixed liquid B 3to clarification, obtain mixed liquor C; Regulate the pH value of mixed liquor C to be 3.5 with the hydrochloric acid solution of concentration to be the NaOH solution of 0.01mol/L and concentration be 0.01mol/L, obtain mixed liquor D; The NH that 100mL concentration is 1.1mol/L is added in mixed liquor D 4the Cl aqueous solution, obtains mixed liquor E after mixing; In mixed liquor E, add the Ca-EDTA potassium solution that 50mL concentration is 0.15mol/L, after mixing, obtain mixed liquor F;
Be the styrene chloroformic solution of 11.5% by 200mL mass fraction, 40mL mass fraction be 9.5% divinylbenzene chloroformic solution and 40mL mass fraction be 1.5% azodiisobutyronitrile chloroformic solution fully mix, obtain mixed liquor M;
60mL mixed liquor F is added drop-wise in mixed liquor M under 1000r/min stirring condition, then under 1000r/min condition, stirs 8min, obtain mixed liquor O;
Distilled water being spurted in the container that liquid nitrogen is housed snap frozen and make ice hockey particle, is that the ice hockey particle of 50 ~ 100 μm to be placed in mould cavity and compacting with choosing grain size scope after sieved through sieve; Mixed liquor O is poured in mould, and together puts into liquid nitrogen freeze settled 6 hours, after taking out the demoulding, obtain solid mixt; Obtaining after this solid mixt vacuum freeze drying is removed chloroform and ice hockey particle can the adsorption plate of slow releasing P elements;
Adsorption plate being cultivated in petroleum hydrocarbon degradation bacteria culture fluid 24h takes out air-dry, and what can obtain being applied to coal chemical industry enterprises wastewater treatment releases phosphorus adsorption plate.
Here uses the obtained adsorption plate of the inventive method to carry out absorption and biodegradation test to coal chemical industrial waste water, further illustrates the present invention.
The obtained adsorption plate of the inventive method is used to carry out absorption and biodegradation test to petrochemical wastewater, result shows that this adsorption plate effectively can adsorb and biodegradation the pollutant in coal chemical industrial waste water: when influent COD is 883mg/L, and the COD after process in water outlet can be reduced to below 62mg/L.

Claims (1)

1. be applied to the preparation method releasing phosphorus adsorption plate of coal chemical industry enterprises wastewater treatment, it is characterized in that, the concrete steps of the method are as follows:
(1) be the NH of 0.35mol/L by 100mL concentration 4hCO 3solution and 100mL concentration are the NH of 0.62mol/L 4h 2pO 4mixing, obtain mixed liquor A 1, is then the NH of 0.01mol/L by concentration 4oH solution and concentration are that the hydrochloric acid solution of 0.01mol/L regulates the pH value of mixed liquor A 1 to be 9.0, obtain mixed liquor A;
(2) 200mL mixed liquor A is slowly added drop-wise under agitation the Ca (NO that 300mL concentration is 0.025mol/L 3) 2in solution, obtain mixed liquid B;
(3) in mixed liquid B, dense HNO is dropwise added 3to clarification, obtain mixed liquor C;
(4) regulate the pH value of mixed liquor C to be 3.5 with the hydrochloric acid solution of concentration to be the NaOH solution of 0.01mol/L and concentration be 0.01mol/L, obtain mixed liquor D;
(5) in mixed liquor D, the NH that 100mL concentration is 1.1mol/L is added 4the Cl aqueous solution, obtains mixed liquor E after mixing;
(6) in mixed liquor E, add the Ca-EDTA potassium solution that 50mL concentration is 0.15mol/L, after mixing, obtain mixed liquor F;
(7) by 200mL mass fraction be 11.5% styrene chloroformic solution, 40mL mass fraction be 9.5% divinylbenzene chloroformic solution and 40mL mass fraction be 1.5% azodiisobutyronitrile chloroformic solution fully mix, obtain mixed liquor M;
(8) 60mL mixed liquor F is added drop-wise in mixed liquor M under 1000r/min stirring condition, then under 1000r/min condition, stirs 8min, obtain mixed liquor O;
(9) distilled water being spurted in the container that liquid nitrogen is housed snap frozen and make ice hockey particle, is that the ice hockey particle of 50 ~ 100 μm is stand-by with choosing grain size scope after sieved through sieve;
(10) ice hockey particle garbled in step (9) is placed in also compacting in mould cavity;
(11) mixed liquor O is poured in the mould that step (10) obtains, and together puts into liquid nitrogen freeze settled 6 hours, after taking out the demoulding, obtain solid mixt; Obtaining after this solid mixt vacuum freeze drying is removed chloroform and ice hockey particle can the adsorption plate of slow releasing P elements;
(12) adsorption plate that step (11) obtains is cultivated 24h in petroleum hydrocarbon degradation bacteria culture fluid, be absorbed and fixed at by petroleum hydrocarbon degradation bacterium on this adsorption plate, wherein the bacteria containing amount of petroleum hydrocarbon degradation bacteria culture fluid is 5 × 10 10cFU/mL, consisting of of nutrient solution: NH 4nO 3: 2.0gL -1, NaCl:10.5gL -1, KH 2pO 4: 2.5gL -1, FeCl 3: 0.10gL -1, MgSO 4: 3.5gL -1, CaCl 22H 2o:0.15gL -1;
(13) adsorption plate that step (12) obtained takes out air-dry, and what can obtain being applied to coal chemical industry enterprises wastewater treatment releases phosphorus adsorption plate.
CN201310686383.8A 2013-12-12 2013-12-12 What be applied to coal chemical industry enterprises wastewater treatment releases phosphorus adsorption plate and preparation method Expired - Fee Related CN103623786B (en)

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AU2003289540A1 (en) * 2002-12-31 2004-07-22 Ku-Su Kim Wastewater disposal agent and process for preparing thereof
CN102500340B (en) * 2011-09-30 2013-05-01 北京师范大学 Porous particle with functions of adsorbing and biodegrading petroleum hydrocarbon and preparation method of porous particle
CN102408160B (en) * 2011-09-30 2013-01-02 北京师范大学 Biodegradable perforated plate for adsorption and biodegradation of petroleum hydrocarbon pollutants as well as preparation method thereof
FR2985200B1 (en) * 2012-01-03 2015-01-23 Cie Financiere Et De Participations Roullier PHOSPHATE - BASED GRANULAR MATERIAL, METHOD FOR MANUFACTURING THE SAME AND USE THEREOF IN A DEVICE FOR DEPHOSPHATION OF WASTEWATER.
CN102963959B (en) * 2012-12-03 2013-11-13 北京师范大学 Preparation method of microsphere particles capable of slowly releasing nitrogen and adsorbing-biologically degrading petroleum hydrocarbon
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