CN103623789B - Process multi-functional absorption agent and the preparation method of petrochemical wastewater for enhanced biodegradation - Google Patents
Process multi-functional absorption agent and the preparation method of petrochemical wastewater for enhanced biodegradation Download PDFInfo
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Abstract
The invention discloses the multi-functional absorption agent and the preparation method that process petrochemical wastewater for enhanced biodegradation. By NH4HCO3Solution, NH4H2PO4Solution, Ca (NO3)2Solution, NH4OH solution, hydrochloric acid solution, NH4The Cl aqueous solution and Ca-EDTA potassium solution are prepared into mixed liquor F. Urea and formalin are prepared into mixed liquor L. Styrene chloroformic solution, divinylbenzene chloroformic solution and azodiisobutyronitrile chloroformic solution are prepared into mixed liquor M. Mixed liquor L is added drop-wise to and in mixed liquor M, obtains mixed liquor N. Mixed liquor F is added drop-wise in mixed liquor N, obtains mixed liquor O; Mixed liquor O is added drop-wise to and in poly-vinyl alcohol solution, obtains mixed liquor P; Poly-vinyl alcohol solution is joined to centrifugation in mixed liquor P and obtains having the multi-functional absorption agent of nitrogen phosphorus slow-release function, take out cultivate 24h in petroleum hydrocarbon degradation bacteria culture fluid after air-dry. Manufacture craft of the present invention is simple, and the multi-functional absorption agent making has the function of slow-release nitrogen phosphorus function, absorption and biodegradation petroleum hydrocarbon.
Description
Technical field
The invention belongs to the processing technology field of petrochemical wastewater, particularly a kind of for enhanced biodegradation processing oilMulti-functional absorption agent and the preparation method of work waste water.
Background technology
Petrochemical wastewater relates to multiple industries such as the energy, mineral products, chemical industry, and Adsorption-Biodegradation is as a kind of associating water treatment skillArt is occupied important function in the processing of sewage. The most frequently used sorbing material of absorption organic pollution can be divided into physical absorption material at presentMaterial, chemisorbed material and biological adsorption material. Wherein, physisorption material has active carbon, molecular sieve, zeolite, active whiteSoil and clay minerals etc. have the solid of high-specific surface area, have advantages of that eliminating efficiency is high, enrichment function is strong, but also exist steadyQualitative poor, easily desorption, be subject to the deficiencies such as influence of temperature change. Chemisorbed material mainly comprises silica gel, synthetic fibers, treeFat, the molecularly imprinted polymer that utilizes biochemistry and Polymer Synthesizing etc. Conventional biological adsorption material has broad leaved plant,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 that petrochemical enterprise discharges under normal circumstances, the contained nutrient such as nitrogen and phosphorus cannot meet the requirement of microorganism,But the adsorbent with slow-release nitrogen and phosphorus function can meet this requirement. But, also lack at present for nitrogen and phosphorus disappearanceThe sorbing material of petrochemical wastewater processing.
Summary of the invention
The object of this invention is to provide a kind of multi-functional absorption agent and preparation side that processes petrochemical wastewater for enhanced biodegradationMethod. Its concrete steps are as follows:
(1) NH that is 0.35mol/L by 100mL concentration4HCO3The NH that solution and 100mL concentration are 0.62mol/L4H2PO4Mix, obtain mixed liquor A 1, the NH that is then 0.01mol/L by concentration4OH solution and concentration are the salt of 0.01mol/LIt is 9.0 that acid solution regulates the pH value of mixed liquor A 1, obtains 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/L3)2In solution, obtain mixed liquid B;
(3) in mixed liquid B, dropwise add dense HNO3To clarification, obtain mixed liquor C;
(4) hydrochloric acid solution that the NaOH solution that is 0.01mol/L by concentration and concentration are 0.01mol/L regulates the pH of mixed liquor CValue is 3.5, obtains mixed liquor D;
(5) be the NH of 1.1mol/L to adding 100mL concentration in mixed liquor D4The Cl aqueous solution, is mixed after mixingLiquid E;
(6) be the Ca-EDTA potassium solution of 0.15mol/L to adding 50mL concentration in mixed liquor E, after mixingTo mixed liquor F;
(7) aqueous solution of urea that is 47% by 60mL mass fraction is placed in 43 DEG C 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 DEG C of water-bath constant temperature and within 35 minutes, obtains mixed liquor H;
(8) to dripping NaOH solution and the concentration that concentration is 0.01mol/L in mixed liquor G under 1000r/min stirring condition beThe HCl solution of 0.005mol/L, 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 DEG C of water-baths and existUnder 1000r/min condition, stir 90～100 minutes, obtain mixed liquor J;
(10) in mixed liquor J, under 1000r/min stirring condition, drip NaOH solution and the concentration that concentration is 0.01mol/LFor the HCl solution of 0.005mol/L, the pH value that makes solution is 3.7～3.9, is then placed in 38 DEG C of water-baths at 1000r/min barUnder part, stir 90～100 minutes, obtain mixed liquor K;
(11) 1600mL deionized water is added drop-wise in mixed liquor K, then at 1000r/min under 1000r/min stirring conditionUnder condition, stir 8min, obtain mixed liquor L;
(12) divinyl that the styrene chloroformic solution that is 11.5% by 200mL mass fraction, 40mL mass fraction are 9.5%The azodiisobutyronitrile chloroformic solution that benzene chloroform solution 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, then at 1000r/min under 1000r/min stirring conditionUnder condition, stir 8min, obtain mixed liquor N;
(14) 70mL mixed liquor F is added drop-wise in mixed liquor N, then at 1000r/min under 1000r/min stirring conditionUnder condition, stir 8min, obtain mixed liquor O;
(15) 420mL mixed liquor O is added drop-wise under 1000r/min stirring condition 210mL mass fraction be 5.5% poly-In vinyl alcohol solution, then under 1000r/min condition, stir 8min, obtain mixed liquor P;
(16) poly-vinyl alcohol solution that is 0.7% by 1380mL mass fraction joins in mixed liquor P, at 1000r/min barUnder part, stirring 7～8h, is then under 6000r/min condition, to carry out centrifugation at rotating speed, 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, makes petroleum hydrocarbon degradation bacteriumBe absorbed and fixed on adsorbent, wherein the bacteria containing amount of petroleum hydrocarbon degradation bacteria culture fluid is 5 × 1010CFU/ml, the consisting of of nutrient solution:NH4N03：2.0g·L-1，NaCl：10.5g·L-1，KH2PO4：2.5g·L-1，FeCl3：0.10g·L-1，MgSO4：3.5g·L-1，CaCl2·2H2O：0.15g·L-1；
(18) adsorbent step (17) being obtained takes out air-dry, can obtain processing petrochemical industry for enhanced biodegradationThe multi-functional absorption agent of waste water.
The invention has the beneficial effects as follows, manufacture craft is simple, the multi-functional absorption agent making have slow-release nitrogen phosphorus function, absorption andThe function of biodegradation petrochemical wastewater Petroleum Hydrocarbon.
Detailed description of the invention
The invention provides a kind of multi-functional absorption agent and preparation method who processes petrochemical wastewater for enhanced biodegradation, belowWith an embodiment, the present invention is described.
Embodiment 1.
The NH that is 0.35mol/L by 100mL concentration4HCO3The NH that solution and 100mL concentration are 0.62mol/L4H2PO4Mix, obtain mixed liquor A 1, the NH that is then 0.01mol/L by concentration4OH solution and concentration are the salt of 0.01mol/LIt is 9.0 that acid solution regulates the pH value of mixed liquor A 1, obtains mixed liquor A; 200mL mixed liquor A is slow under stirring conditionBeing added drop-wise to 300mL concentration is the Ca (NO of 0.025mol/L3)2In solution, obtain mixed liquid B; In mixed liquid B, dropwise addEnter dense HNO3To clarification, obtain mixed liquor C; The NaOH solution that is 0.01mol/L by concentration and concentration are 0.01mol/LIt is 3.5 that hydrochloric acid solution regulates the pH value of mixed liquor C, obtains mixed liquor D; In mixed liquor D, add 100mL concentration to beThe NH of 1.1mol/L4The Cl aqueous solution, obtains mixed liquor E after mixing; In mixed liquor E, add 50mL concentration to beThe Ca-EDTA potassium solution of 0.15mol/L, obtains mixed liquor F after mixing;
The aqueous solution of urea that is 47% by 60mL mass fraction is placed in 43 DEG C of water-bath constant temperature and within 35 minutes, obtains mixed liquor G; Will10mL mass fraction is that 33% formalin is placed in 43 DEG C of water-bath constant temperature and within 35 minutes, obtains mixed liquor H; To mixed liquorIn G, under 1000r/min stirring condition, drip the HCl that NaOH solution that concentration is 0.01mol/L and concentration are 0.005mol/LSolution, making the pH value of solution is 7.2～7.4, obtains mixed liquor I; Mixed liquor H is joined under 1000r/min stirring conditionIn mixed liquor I, be then placed in 43 DEG C of water-baths and under 1000r/min condition, stir 90～100 minutes, obtain mixed liquor J; ToIn mixed liquor J, under 1000r/min stirring condition, dripping NaOH solution and the concentration that concentration is 0.01mol/L is 0.005mol/LHCl solution, the pH value that makes solution is 3.7～3.9, is then placed in 38 DEG C of water-baths and stirs 90～100 under 1000r/min conditionMinute, obtain mixed liquor K; 1600mL deionized water is added drop-wise under 1000r/min stirring condition in mixed liquor K, soAfter under 1000r/min condition, stir 8min, obtain mixed liquor L;
The divinylbenzene chloroform that the styrene chloroformic solution that is 11.5% by 200mL mass fraction, 40mL mass fraction are 9.5%The azodiisobutyronitrile chloroformic solution that solution 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 conditionStir 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 conditionStir 8min, obtain mixed liquor O;
It is 5.5% polyvinyl alcohol that 420mL mixed liquor O is added drop-wise to 210mL mass fraction under 1000r/min stirring conditionIn solution, then under 1000r/min condition, stir 8min, obtain 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, stirsMixing 7～8h, is then under 6000r/min condition, to carry out centrifugation at rotating speed, then with deionized water washing 3 times, coldThe dry adsorbent that obtains having nitrogen phosphorus slow-release function of freeze-drying;
By the adsorbent with nitrogen phosphorus slow-release function in petroleum hydrocarbon degradation bacteria culture fluid, cultivate 24h take out air-dry, can be usedProcess the multi-functional absorption agent of petrochemical wastewater in enhanced biodegradation.
To use the multi-functional absorption agent that the inventive method makes to carry out absorption and biodegradation examination to petrochemical wastewater belowTest, 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, result to petrochemical wastewaterShow that this multi-functional absorption agent can effectively adsorb and biodegradation the pollutant in petrochemical wastewater: work as water inletWhen COD is 684mg/L, the COD after processing in water outlet can be reduced to below 47mg/L.
Claims (1)
1. process a multi-functional absorption agent for petrochemical wastewater for enhanced biodegradation, it is characterized in that, prepare this many meritsThe concrete steps of energy adsorbent are as follows:
(1) NH that is 0.35mol/L by 100mL concentration4HCO3Solution and 100mL concentration are 0.62mol/LNH4H2PO4Mix, obtain mixed liquor A l, the NH that is then 0.01mol/L by concentration4OH solution and concentration areIt is 9.0 that the hydrochloric acid solution of 0.01mol/L regulates the pH value of mixed liquor A l, obtains 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/L3)2In solution, obtain mixed liquid B;
(3) in mixed liquid B, dropwise add dense HNO3To clarification, obtain mixed liquor C;
(4) hydrochloric acid solution that the NaOH solution that is 0.01mol/L by concentration and concentration are 0.01mol/L regulates the pH of mixed liquor CValue is 3.5, obtains mixed liquor D;
(5) be the NH of 1.1mol/L to adding 100mL concentration in mixed liquor D4The Cl aqueous solution, is mixed after mixingLiquid E;
(6) be the Ca-EDTA potassium solution of 0.15mol/L to adding 50mL concentration in mixed liquor E, after mixingTo mixed liquor F;
(7) aqueous solution of urea that is 47% by 60mL mass fraction is placed in 43 DEG C 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 DEG C of water-bath constant temperature and within 35 minutes, obtains mixed liquor H;
(8) to dripping NaOH solution and the concentration that concentration is 0.01mol/L in mixed liquor G under 1000r/min stirring condition beThe HCl solution of 0.005mol/L, 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 DEG C of water-baths and existUnder 1000r/min condition, stir 90～100 minutes, obtain mixed liquor J;
(10) in mixed liquor J, under 1000r/min stirring condition, drip NaOH solution and the concentration that concentration is 0.01mol/LFor the HCl solution of 0.005mol/L, the pH value that makes solution is 3.7～3.9, is then placed in 38 DEG C of water-baths at 1000r/min barUnder part, stir 90～100 minutes, obtain mixed liquor K;
(11) 1600mL deionized water is added drop-wise in mixed liquor K, then at 1000r/min under 1000r/min stirring conditionUnder condition, stir 8min, obtain mixed liquor L;
(12) divinyl that the styrene chloroformic solution that is 11.5% by 200mL mass fraction, 40mL mass fraction are 9.5%The azodiisobutyronitrile chloroformic solution that benzene chloroform solution 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, then at 1000r/min under 1000r/min stirring conditionUnder condition, stir 8min, obtain mixed liquor N;
(14) 70mL mixed liquor F is added drop-wise in mixed liquor N, then at 1000r/min under 1000r/min stirring conditionUnder condition, stir 8min, obtain mixed liquor O;
(15) 420mL mixed liquor O is added drop-wise under 1000r/min stirring condition 210mL mass fraction be 5.5% poly-In vinyl alcohol solution, then under 1000r/min condition, stir 8min, obtain mixed liquor P;
(16) poly-vinyl alcohol solution that is 0.7% by 1380mL mass fraction joins in mixed liquor P, at 1000r/min barUnder part, stirring 7～8h, is then under 6000r/min condition, to carry out centrifugation at rotating speed, 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, makes petroleum hydrocarbon degradation bacteriumBe absorbed and fixed on adsorbent, wherein the bacteria containing amount of petroleum hydrocarbon degradation bacteria culture fluid is 5 × 1010CFU/ml, the consisting of of nutrient solution:NH4NO3：2.0g·Ｌ-1，NaCl：10.5g·L-1，KH2PO4：2.5g·L-1，FeCl3：0.10g·L-1，MgSO4：3.5g.L-1，CaCl2·2H2O：0.15g·L-1；
(18) adsorbent step (17) being obtained takes out air-dry, can obtain processing petrochemical industry for enhanced biodegradationThe multi-functional absorption agent of waste water.
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