CN103623789A - Multifunctional adsorbent for reinforced biodegradation treatment of petrochemical wastewater and preparation method thereof - Google Patents

Multifunctional adsorbent for reinforced biodegradation treatment of petrochemical wastewater and preparation method thereof Download PDF

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CN103623789A
CN103623789A CN201310686406.5A CN201310686406A CN103623789A CN 103623789 A CN103623789 A CN 103623789A CN 201310686406 A CN201310686406 A CN 201310686406A CN 103623789 A CN103623789 A CN 103623789A
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CN103623789B (en
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豆俊峰
秦伟
丁爱中
许新宜
程莉蓉
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Beijing Normal University
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Beijing Normal University
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Abstract

The invention discloses a multifunctional adsorbent for reinforced biodegradation treatment of petrochemical wastewater and a preparation method thereof. The preparation method comprises the following steps: preparing a NH4HCO3 solution, a NH4H2PO4 solution, a Ca(NO3)2 solution, a NH4OH solution, a hydrochloric acid solution, a NH4Cl water solution and a calcium potassium ethylenediamine tetraacetate solution into a mixed solution F; preparing urea and formalin into a mixed solution L; preparing a styrene chloroformic solution, a divinylbenzene chloroformic solution and an azodiisobutyronitrile chloroformic solution into a mixed solution M; dropwisely adding the mixed solution L into the mixed solution M to obtain a mixed solution N; dropwisely adding the mixed solution F into the mixed solution N to obtain a mixed solution O; dropwisely adding the mixed solution O into a polyvinyl alcohol solution to obtain a mixed solution P; adding the polyvinyl alcohol solution into the mixed solution P, and centrifuging to obtain the multifunctional adsorbent with function of slowing release of nitrogen and phosphorus; and culturing in a petroleum hydrocarbon degrading bacterium culture solution for 24 hours, taking out, and drying in air. The manufacturing technique is simple; and the prepared multifunctional adsorbent has the functions of slowing release of nitrogen and phosphorus and adsorbing and biodegrading petroleum hydrocarbons.

Description

For enhanced biodegradation, process multi-functional absorption agent and the preparation method of petrochemical wastewater
Technical field
The invention belongs to the processing technology field of petrochemical wastewater, particularly a kind of multi-functional absorption agent and preparation method who processes petrochemical wastewater for enhanced biodegradation.
Background technology
Petrochemical wastewater relates to a plurality of industries such as the energy, mineral products, chemical industry, and Adsorption-Biodegradation occupies important function as a kind of water technology of combining in the processing of sewage.The most frequently used sorbing material of absorption organic pollution can be divided into physisorption material, chemisorbed material and biological adsorption material at present.Wherein, physisorption material has active carbon, molecular sieve, zeolite, atlapulgite and clay minerals etc. to have the solid of high-specific surface area, have advantages of that eliminating efficiency is high, enrichment function is strong, but also poor, the easy desorption of existence and stability, 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 of biochemistry and Polymer Synthesizing etc.Conventional biological adsorption material has broad leaved plant, the microorganism in fungi, soil and water etc.In the organic process of microbial degradation, need the participation of nitrogen and phosphorus nutrition element, in the waste water of generally petrochemical enterprise discharge, the nutrient such as contained nitrogen and phosphorus cannot meet the requirement of microorganism, yet the adsorbent with slow-release nitrogen and phosphorus function can meet this requirement.But, also lack the sorbing material of processing for the petrochemical wastewater of nitrogen and phosphorus disappearance at present.
Summary of the invention
The object of this invention is to provide a kind of multi-functional absorption agent and preparation method who processes petrochemical wastewater for enhanced biodegradation.Its concrete steps are as follows:
(1) NH that is 0.35mol/L by 100mL concentration 4hCO 3the NH that solution and 100mL concentration are 0.62mol/L 4h 2pO 4mix, obtain mixed liquor A 1, the NH that is then 0.01mol/L by concentration 4oH solution and concentration are that the pH value of the hydrochloric acid solution adjusting mixed liquor A 1 of 0.01mol/L is 9.0, obtain mixed liquor A;
(2) 200mL mixed liquor A is slowly added drop-wise under stirring condition to the Ca (NO that 300mL concentration is 0.025mol/L 3) 2in solution, obtain mixed liquid B;
(3) in mixed liquid B, dropwise add dense HNO 3to clarification, obtain mixed liquor C;
(4) it is 3.5 that the hydrochloric acid solution that the NaOH solution that is 0.01mol/L by concentration and concentration are 0.01mol/L regulates the pH value of mixed liquor C, obtains mixed liquor D;
(5) to adding 100mL concentration in mixed liquor D, be the NH of 1.1mol/L 4the Cl aqueous solution, obtains mixed liquor E after mixing;
(6) to adding 50mL concentration in mixed liquor E, be the Ca-EDTA potassium solution of 0.15mol/L, after mixing, obtain mixed liquor F;
(7) aqueous solution of urea that is 47% by 60mL mass fraction is placed in 43 ℃ of water-bath constant temperature and within 35 minutes, obtains mixed liquor G; The formalin that is 33% by 10mL mass fraction is placed in 43 ℃ of water-bath constant temperature and within 35 minutes, obtains mixed liquor H;
(8) to drip the HCl solution that NaOH solution that concentration is 0.01mol/L and concentration are 0.005mol/L in mixed liquor G under 1000r/min stirring condition, making the pH value of solution is 7.2～7.4, obtains mixed liquor I;
(9) mixed liquor H is joined in mixed liquor I under 1000r/min stirring condition, be then placed in 43 ℃ of water-baths and stir 90～100 minutes under 1000r/min condition, obtain mixed liquor J;
(10) to drip the HCl solution that NaOH solution that concentration is 0.01mol/L and concentration are 0.005mol/L in mixed liquor J under 1000r/min stirring condition, the pH value that makes solution is 3.7～3.9, then be placed in 38 ℃ of water-baths and under 1000r/min condition, stir 90～100 minutes, obtain mixed liquor K;
(11) 1600mL deionized water is added drop-wise in mixed liquor K under 1000r/min stirring condition, then under 1000r/min condition, stirs 8min, obtain mixed liquor L;
(12) the azodiisobutyronitrile chloroformic solution that the divinylbenzene chloroformic solution that the styrene chloroformic solution that is 11.5% by 200mL mass fraction, 40mL mass fraction are 9.5% and 40mL mass fraction are 1.5% fully mixes, and obtains mixed liquor M;
(13) 70mL mixed liquor L is added drop-wise in mixed liquor M under 1000r/min stirring condition, then under 1000r/min condition, stirs 8min, obtain mixed liquor N;
(14) 70mL mixed liquor F is added drop-wise in mixed liquor N under 1000r/min stirring condition, then under 1000r/min condition, stirs 8min, obtain mixed liquor O;
(15) 420mL mixed liquor O being added drop-wise under 1000r/min stirring condition to 210mL mass fraction is, in 5.5% poly-vinyl alcohol solution, then under 1000r/min condition, to stir 8min, obtains mixed liquor P;
(16) poly-vinyl alcohol solution that is 0.7% by 1380mL mass fraction joins in mixed liquor P, under 1000r/min condition, stir 7～8h, then at rotating speed, be under 6000r/min condition, to carry out centrifugation, then with deionized water washing 3 times, freeze drying obtains having the adsorbent of nitrogen phosphorus slow-release function;
(17) adsorbent step (16) being obtained is cultivated 24h in petroleum hydrocarbon degradation bacteria culture fluid, and petroleum hydrocarbon degradation bacterium is absorbed and fixed on adsorbent, and wherein the bacteria containing amount of petroleum hydrocarbon degradation bacteria culture fluid is 5 * 10 10cFU/ml, the consisting of of nutrient solution: NH 4n0 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;
(18) adsorbent step (17) being obtained takes out air-dry, can obtain processing for enhanced biodegradation the multi-functional absorption agent of petrochemical wastewater.
The invention has the beneficial effects as follows, manufacture craft is simple, and the multi-functional absorption agent making has the function of slow-release nitrogen phosphorus function, absorption and biodegradation petrochemical wastewater Petroleum Hydrocarbon.
The specific embodiment
The invention provides a kind of multi-functional absorption agent and preparation method who processes petrochemical wastewater for enhanced biodegradation, with an embodiment, the present invention is described below.
Embodiment 1.
The NH that is 0.35mol/L by 100mL concentration 4hCO 3the NH that solution and 100mL concentration are 0.62mol/L 4h 2pO 4mix, obtain mixed liquor A 1, the NH that is then 0.01mol/L by concentration 4oH solution and concentration are that the pH value of the hydrochloric acid solution adjusting mixed liquor A 1 of 0.01mol/L is 9.0, obtain mixed liquor A; 200mL mixed liquor A is slowly added drop-wise under stirring condition to the Ca (NO that 300mL concentration is 0.025mol/L 3) 2in solution, obtain mixed liquid B; In mixed liquid B, dropwise add dense HNO 3to clarification, obtain mixed liquor C; It is 3.5 that the hydrochloric acid solution that the NaOH solution that is 0.01mol/L by concentration and concentration are 0.01mol/L regulates the pH value of mixed liquor C, obtains mixed liquor D; To adding 100mL concentration in mixed liquor D, be the NH of 1.1mol/L 4the Cl aqueous solution, obtains mixed liquor E after mixing; To adding 50mL concentration in mixed liquor E, be the Ca-EDTA potassium solution of 0.15mol/L, after mixing, obtain mixed liquor F;
The aqueous solution of urea that is 47% by 60mL mass fraction is placed in 43 ℃ of water-bath constant temperature and within 35 minutes, obtains mixed liquor G; The formalin that is 33% by 10mL mass fraction is placed in 43 ℃ of water-bath constant temperature and within 35 minutes, obtains mixed liquor H; To drip the HCl solution that NaOH solution that concentration is 0.01mol/L and concentration are 0.005mol/L in mixed liquor G under 1000r/min stirring condition, making the pH value of solution is 7.2～7.4, obtains mixed liquor I; Mixed liquor H is joined in mixed liquor I under 1000r/min stirring condition, be then placed in 43 ℃ of water-baths and under 1000r/min condition, stir 90～100 minutes, obtain mixed liquor J; To drip the HCl solution that NaOH solution that concentration is 0.01mol/L and concentration are 0.005mol/L in mixed liquor J under 1000r/min stirring condition, the pH value that makes solution is 3.7～3.9, then be placed in 38 ℃ of water-baths and under 1000r/min condition, stir 90～100 minutes, obtain mixed liquor K; 1600mL deionized water is added drop-wise in mixed liquor K under 1000r/min stirring condition, then under 1000r/min condition, stirs 8min, obtain mixed liquor L;
The azodiisobutyronitrile chloroformic solution that the divinylbenzene chloroformic solution that the styrene chloroformic solution that is 11.5% by 200mL mass fraction, 40mL mass fraction are 9.5% and 40mL mass fraction are 1.5% fully mixes, and obtains mixed liquor M;
60mL mixed liquor L is added drop-wise in mixed liquor M under 1000r/min stirring condition, then under 1000r/min condition, stirs 8min, obtain mixed liquor N;
60mL mixed liquor F is added drop-wise in mixed liquor N under 1000r/min stirring condition, then under 1000r/min condition, stirs 8min, obtain mixed liquor O;
It is in 5.5% poly-vinyl alcohol solution that 420mL mixed liquor O is added drop-wise to 210mL mass fraction under 1000r/min stirring condition, then under 1000r/min condition, stirs 8min, obtains mixed liquor P;
The poly-vinyl alcohol solution that is 0.7% by 1380mL mass fraction joins in mixed liquor P, under 1000r/min condition, stir 7～8h, then at rotating speed, be under 6000r/min condition, to carry out centrifugation, then with deionized water washing 3 times, freeze drying obtains having the adsorbent of nitrogen phosphorus slow-release function;
The adsorbent with nitrogen phosphorus slow-release function is cultivated to 24h in petroleum hydrocarbon degradation bacteria culture fluid and take out air-dryly, can obtain processing for enhanced biodegradation the multi-functional absorption agent of petrochemical wastewater.
Be that the multi-functional absorption agent of using the inventive method to make has been carried out absorption and biodegradation test to petrochemical wastewater below, further illustrate the present invention.
The multi-functional absorption agent of using the inventive method to make has been carried out absorption and biodegradation test to petrochemical wastewater, result shows that this multi-functional absorption agent can effectively adsorb and biodegradation the pollutant in petrochemical wastewater: when influent COD is 684mg/L, the COD after processing in water outlet can be reduced to below 47mg/L.

Claims (1)

1. for enhanced biodegradation, process multi-functional absorption agent and the preparation method of petrochemical wastewater, it is characterized in that, the concrete steps of this technique are as follows:
(1) NH that is 0.35mol/L by 100mL concentration 4hCO 3the NH that solution and 100mL concentration are 0.62mol/L 4h 2pO 4mix, obtain mixed liquor A 1, the NH that is then 0.01mol/L by concentration 4oH solution and concentration are that the pH value of the hydrochloric acid solution adjusting mixed liquor A 1 of 0.01mol/L is 9.0, obtain mixed liquor A;
(2) 200mL mixed liquor A is slowly added drop-wise under stirring condition to the Ca (NO that 300mL concentration is 0.025mol/L 3) 2in solution, obtain mixed liquid B;
(3) in mixed liquid B, dropwise add dense HNO 3to clarification, obtain mixed liquor C;
(4) it is 3.5 that the hydrochloric acid solution that the NaOH solution that is 0.01mol/L by concentration and concentration are 0.01mol/L regulates the pH value of mixed liquor C, obtains mixed liquor D;
(5) to adding 100mL concentration in mixed liquor D, be the NH of 1.1mol/L 4the Cl aqueous solution, obtains mixed liquor E after mixing;
(6) to adding 50mL concentration in mixed liquor E, be the Ca-EDTA potassium solution of 0.15mol/L, after mixing, obtain mixed liquor F;
(7) aqueous solution of urea that is 47% by 60mL mass fraction is placed in 43 ℃ of water-bath constant temperature and within 35 minutes, obtains mixed liquor G; The formalin that is 33% by 10mL mass fraction is placed in 43 ℃ of water-bath constant temperature and within 35 minutes, obtains mixed liquor H;
(8) to drip the HCl solution that NaOH solution that concentration is 0.01mol/L and concentration are 0.005mol/L in mixed liquor G under 1000r/min stirring condition, making the pH value of solution is 7.2～7.4, obtains mixed liquor I;
(9) mixed liquor H is joined in mixed liquor I under 1000r/min stirring condition, be then placed in 43 ℃ of water-baths and stir 90～100 minutes under 1000r/min condition, obtain mixed liquor J;
(10) to drip the HCl solution that NaOH solution that concentration is 0.01mol/L and concentration are 0.005mol/L in mixed liquor J under 1000r/min stirring condition, the pH value that makes solution is 3.7～3.9, then be placed in 38 ℃ of water-baths and under 1000r/min condition, stir 90～100 minutes, obtain mixed liquor K;
(11) 1600mL deionized water is added drop-wise in mixed liquor K under 1000r/min stirring condition, then under 1000r/min condition, stirs 8min, obtain mixed liquor L;
(12) the azodiisobutyronitrile chloroformic solution that the divinylbenzene chloroformic solution that the styrene chloroformic solution that is 11.5% by 200mL mass fraction, 40mL mass fraction are 9.5% and 40mL mass fraction are 1.5% fully mixes, and obtains mixed liquor M;
(13) 70mL mixed liquor L is added drop-wise in mixed liquor M under 1000r/min stirring condition, then under 1000r/min condition, stirs 8min, obtain mixed liquor N;
(14) 70mL mixed liquor F is added drop-wise in mixed liquor N under 1000r/min stirring condition, then under 1000r/min condition, stirs 8min, obtain mixed liquor O;
(15) 420mL mixed liquor O being added drop-wise under 1000r/min stirring condition to 210mL mass fraction is, in 5.5% poly-vinyl alcohol solution, then under 1000r/min condition, to stir 8min, obtains mixed liquor P;
(16) poly-vinyl alcohol solution that is 0.7% by 1380mL mass fraction joins in mixed liquor P, under 1000r/min condition, stir 7～8h, then at rotating speed, be under 6000r/min condition, to carry out centrifugation, then with deionized water washing 3 times, freeze drying obtains having the adsorbent of nitrogen phosphorus slow-release function;
(17) adsorbent step (16) being obtained is cultivated 24h in petroleum hydrocarbon degradation bacteria culture fluid, and petroleum hydrocarbon degradation bacterium is absorbed and fixed on adsorbent, and wherein the bacteria containing amount of petroleum hydrocarbon degradation bacteria culture fluid is 5 * 10 10cFU/ml, the 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;
(18) adsorbent step (17) being obtained takes out air-dry, can obtain processing for enhanced biodegradation the multi-functional absorption agent of petrochemical wastewater.
CN201310686406.5A 2013-12-12 2013-12-12 Process multi-functional absorption agent and the preparation method of petrochemical wastewater for enhanced biodegradation Expired - Fee Related CN103623789B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106693921A (en) * 2015-07-28 2017-05-24 江苏吉华化工有限公司 High polymer adsorbing material for organic chemical wastewater

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JPS51138060A (en) * 1975-05-23 1976-11-29 Kuraray Co Ltd Treating method of waste containing branched polyvalent alcohols
CN102941071A (en) * 2012-12-03 2013-02-27 北京师范大学 Preparation method of biodegradable oil absorption microsphere with nitrogen nutrient element slow release function
CN102963959A (en) * 2012-12-03 2013-03-13 北京师范大学 Preparation method of microsphere particles capable of slowly releasing nitrogen and adsorbing-biologically degrading petroleum hydrocarbon
CN103011380A (en) * 2012-12-03 2013-04-03 北京师范大学 Preparation method of biodegradable oil absorption plate capable of slowly releasing nitrogen element

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51138060A (en) * 1975-05-23 1976-11-29 Kuraray Co Ltd Treating method of waste containing branched polyvalent alcohols
CN102941071A (en) * 2012-12-03 2013-02-27 北京师范大学 Preparation method of biodegradable oil absorption microsphere with nitrogen nutrient element slow release function
CN102963959A (en) * 2012-12-03 2013-03-13 北京师范大学 Preparation method of microsphere particles capable of slowly releasing nitrogen and adsorbing-biologically degrading petroleum hydrocarbon
CN103011380A (en) * 2012-12-03 2013-04-03 北京师范大学 Preparation method of biodegradable oil absorption plate capable of slowly releasing nitrogen element

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106693921A (en) * 2015-07-28 2017-05-24 江苏吉华化工有限公司 High polymer adsorbing material for organic chemical wastewater

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