CN103755037B - Fixed adsorption tube reactor used for treating high-salinity phosphorus-deficient organic chemical waste water - Google Patents
Fixed adsorption tube reactor used for treating high-salinity phosphorus-deficient organic chemical waste water Download PDFInfo
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- CN103755037B CN103755037B CN201310686430.9A CN201310686430A CN103755037B CN 103755037 B CN103755037 B CN 103755037B CN 201310686430 A CN201310686430 A CN 201310686430A CN 103755037 B CN103755037 B CN 103755037B
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Abstract
The invention discloses a fixed adsorption tube reactor used for treating high-salinity phosphorus-deficient organic chemical waste water. The reactor is composed of a movable cover, a water inlet, air pressure valves, an installing plate, a fixed plate, a water outlet, a reactor main body, multifunctional adsorption tubes and a base, wherein the bottom of the water inlet is connected with the top of the movable cover, the air pressure valves are arranged on the top of the movable cover, the interior of the movable cover is provided with spiral threads connected with the reactor main body, the installing plate and the fixed plate are arranged at the upper part in the reactor main body, the installing plate is provided with hollow cylinders which are 5 cm long and can be connected with the adsorption tubes, the fixed plate is fixed on the reactor main body and provided with holes of a size same as that of the hollow cylinders, the water outlet is arranged at the outer side of the reactor main body, and the base is located at the lower part of the reactor main body. The invention has the following beneficial effects: when used for treating high-salinity phosphorus-deficient organic chemical waste water, the fixed adsorption tube reactor has the advantages of high treating efficiency, low cost and simple operation.
Description
Technical field
The invention belongs to the processing technology field of organic chemical waste water, be specifically related to process the fixed adsorption tube reactor that high salt lacks phosphorus organic chemical waste water.
Background technology
Organic chemical waste water relates to multiple industries such as the energy, mineral products, chemical industry, and the technology of current domestic process high concentrated organic wastewater mainly adopts biochemical process, and operational path is acted on substantially " physico-chemical pretreatment+A/O biochemical treatment+materialization advanced treatment ".Adsorption-Biodegradation occupies vital role 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 gac, 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, synthon, resin, utilizes the molecularly imprinted polymer etc. of biological chemistry and Polymer Synthesizing.Conventional biological adsorption material has broad leaved plant, the microorganism etc. in fungi, soil and water.
In the organic process of microbiological deterioration, need the participation of nitrogen and phosphorus nutrition element, in the waste water of enterprise's discharge under normal circumstances, the nutritive element such as contained nitrogen and phosphorus cannot meet the requirement of microorganism, but the sorbent material with slow-release nitrogen and phosphorus function can meet this requirement.But, also lack the sorbing material for nitrogen and the unbalance organic wastewater with difficult degradation thereby process of phosphorus nutrition at present.Meanwhile, for strengthening sorbent material to the effect of hardly degraded organic substance process in high concentrated organic wastewater, the adsorptive reactor of development of new is needed.Meanwhile, the exploitation of reactor and the sorbing material system that matches with it respectively are combined and carry out, it is one of emphasis of research at present that the adsorption efficiency of sorbing material is not fully exerted.At present, the research of the aspect that the exploitation of reactor and the sorbing material system that matches with it respectively to be combined also is lacked.
Summary of the invention
The object of this invention is to provide the fixed adsorption tube reactor that the high salt of process lacks phosphorus organic chemical waste water.Particular content of the present invention is as follows:
Process the fixed adsorption tube reactor that high salt lacks phosphorus organic chemical waste water to be made up of removable cover (1), water-in (2), air pressure valve (3), mounting plate (4), retaining plate (5), water outlet (6), reactor body (7), multi-functional adsorption tube (8), base (9).The bottom of water-in (2) is connected with the top of removable cover (1); Air pressure valve (3) is at the top of removable cover (1); The inside of removable cover (1), with spiricle, is connected with reactor body (7); Mounting plate (4) and retaining plate (5) are in the inner top of reactor body (7), mounting plate (4) is the hollow cylinder of 5cm with the length that can be connected with adsorption tube, retaining plate (5) is fixed on reactor body (7), and retaining plate (5) is distributed with the hole the same with mounting plate hollow cylinder size; Multi-functional adsorption tube (8) is installed on after on mounting plate (4), and downward through the hole on retaining plate (5), mounting plate (4) can be attached on retaining plate (5); Water outlet (6) is in the outside side of reactor body (7); Base is placed in reactor body (7) bottom.
Wherein, described multi-functional adsorption tube is prepared by the following method:
(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 soln 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 solution C;
(4) regulate the pH value of mixed solution C to be 3.5 with the hydrochloric acid soln of concentration to be the NaOH solution of 0.01mol/L and concentration be 0.01mol/L, obtain mixed solution D;
(5) in mixed solution D, the NH that 100mL concentration is 1.1mol/L is added
4the Cl aqueous solution, obtains mixed solution E after mixing;
(6) in mixed solution E, add the Ca-EDTA potassium solution that 50mL concentration is 0.15mol/L, after mixing, obtain mixed solution F;
(7) by 200mL massfraction be 11.5% vinylbenzene chloroformic solution, 40mL massfraction be 9.5% divinylbenzene chloroformic solution and 40mL massfraction be 1.5% Diisopropyl azodicarboxylate chloroformic solution fully mix, obtain mixed solution M;
(8) 60mL mixed solution F is added drop-wise in mixed solution M under 1000r/min agitation condition, then under 1000r/min condition, stirs 8min, obtain mixed solution O;
(9) distilled water being spurted in the container that liquid nitrogen is housed quick freezing 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 tubing die die cavity;
(11) mixed solution 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 lyophilization is removed chloroform and ice hockey particle can the adsorption tube of slow releasing phosphoric;
(12) adsorption tube 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 tube, 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 tube step (12) obtained takes out air-dry, can obtain multi-functional adsorption tube.
The invention has the beneficial effects as follows, to high salt, this fixed adsorption tube reactor lacks when phosphorus organic chemical waste water processes that efficiency is high, cost is low, simple to operate.
Accompanying drawing explanation
Accompanying drawing 1 is the skeleton view that the high salt of process lacks the fixed adsorption tube reactor of phosphorus organic chemical waste water.In accompanying drawing 1,1 is removable cover, and 2 is water-in, and 3 is air pressure valve, and 4 is mounting plate, and 5 is retaining plate, and 6 is water outlet, and 7 is reactor body, and 8 is multi-functional adsorption tube, and 9 is base.
Accompanying drawing 2 is schematic diagram of mounting plate.In accompanying drawing 2,1 is mounting plate, and 2 is hollow cylinder.
Embodiment
Embodiment
(1) processing high salt, to lack the preparation process of the fixed adsorption tube reactor of phosphorus organic chemical waste water as follows:
Fixed adsorption tube reactor is made by poly (methyl methacrylate) plate, and the diameter of reactor body is 50cm, and height is 100cm, and top 5cm diameter is 49cm, outside with spiricle.Removable cover diameter is 50cm height is the inner spiricle with matching with reactor body of 20cm, bottom 5cm.The diameter of water-in is 8cm, and height is 10mm, is positioned at removable cover central authorities.Distance water-in outer rim 15cm place, is symmetrical arranged the air pressure valve of 2 diameter 8cm.Mounting plate diameter 49cm, the hollow cylinder it being evenly distributed with diameter 5cm is protruding and downward, cylinder height 5cm.Multi-functional adsorption tube is the hollow circular-tube of both ends open, and interior diameter is 5cm, and length is 80cm, is connected with cylindrical projection on mounting plate.Retaining plate is positioned at the downward 6cm in reactor body top, and diameter is 50cm, it is evenly arranged the circular opening of diameter 6cm, and the center of circle of each circular opening overlaps with mounting plate.Water outlet is positioned at reactor body top, the distance downward 25cm in top, diameter 4cm.Base is positioned at reactor body bottom, is solid cylinder, diameter 55cm, height 10cm.
(2) multi-functional adsorption tube is prepared by following process:
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 soln 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 solution C; Regulate the pH value of mixed solution C to be 3.5 with the hydrochloric acid soln of concentration to be the NaOH solution of 0.01mol/L and concentration be 0.01mol/L, obtain mixed solution D; The NH that 100mL concentration is 1.1mol/L is added in mixed solution D
4the Cl aqueous solution, obtains mixed solution E after mixing; In mixed solution E, add the Ca-EDTA potassium solution that 50mL concentration is 0.15mol/L, after mixing, obtain mixed solution F;
Be the vinylbenzene chloroformic solution of 11.5% by 200mL massfraction, 40mL massfraction be 9.5% divinylbenzene chloroformic solution and 40mL massfraction be 1.5% Diisopropyl azodicarboxylate chloroformic solution fully mix, obtain mixed solution M;
60mL mixed solution F is added drop-wise in mixed solution M under 1000r/min agitation condition, then under 1000r/min condition, stirs 8min, obtain mixed solution O;
Distilled water being spurted in the container that liquid nitrogen is housed quick freezing and make ice hockey particle, is that the ice hockey particle of 50 ~ 100 μm to be placed in tubing die die cavity and compacting with choosing grain size scope after sieved through sieve; Mixed solution 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 lyophilization is removed chloroform and ice hockey particle can the adsorption tube of slow releasing phosphoric;
Adsorption plate being cultivated in petroleum hydrocarbon degradation bacteria culture fluid 24h takes out air-dry, can obtain multi-functional adsorption tube.
(3) degradation experiment
The fixed adsorption tube reactor using the present invention to obtain lacks phosphorus organic chemical waste water to high salt to have carried out processing test, result shows that this fixed adsorption tube reactor efficiently can remove the multiple biodegradable organic compounds in waste water, when influent COD is 766mg/L, the COD after process in water outlet can be reduced to below 56mg/L.
Claims (1)
1. process the fixed adsorption tube reactor that high salt lacks phosphorus organic chemical waste water, it is characterized in that, this reactor is made up of removable cover, water-in, air pressure valve, mounting plate, retaining plate, water outlet, reactor body, multi-functional adsorption tube and base; The bottom of water-in is connected with the top of removable cover; Air pressure valve is at the top of removable cover; The inside of removable cover, with spiricle, is connected with reactor body; Mounting plate and retaining plate are above reactor body inside, be the hollow cylinder of 5cm with the length that can be connected with adsorption tube on a mounting board, retaining plate is fixed on reactor body, and retaining plate is distributed with the hole the same with mounting plate hollow cylinder size; Water outlet is in the outside side of reactor body; Base is placed in reactor body bottom; Wherein, described multi-functional adsorption tube is prepared by the following method:
(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 soln 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 solution C;
(4) regulate the pH value of mixed solution C to be 3.5 with the hydrochloric acid soln of concentration to be the NaOH solution of 0.01mol/L and concentration be 0.01mol/L, obtain mixed solution D;
(5) in mixed solution D, the NH that 100mL concentration is 1.1mol/L is added
4the Cl aqueous solution, obtains mixed solution E after mixing;
(6) in mixed solution E, add the Ca-EDTA potassium solution that 50mL concentration is 0.15mol/L, after mixing, obtain mixed solution F;
(7) by 200mL massfraction be 11.5% vinylbenzene chloroformic solution, 40mL massfraction be 9.5% divinylbenzene chloroformic solution and 40mL massfraction be 1.5% Diisopropyl azodicarboxylate chloroformic solution fully mix, obtain mixed solution M;
(8) 60mL mixed solution F is added drop-wise in mixed solution M under 1000r/min agitation condition, then under 1000r/min condition, stirs 8min, obtain mixed solution O;
(9) distilled water being spurted in the container that liquid nitrogen is housed quick freezing 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 tubing die die cavity;
(11) mixed solution 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 lyophilization is removed chloroform and ice hockey particle can the adsorption tube of slow releasing phosphoric;
(12) adsorption tube 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 tube, 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 tube step (12) obtained takes out air-dry, can obtain multi-functional adsorption tube.
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CN1384065A (en) * | 2001-04-28 | 2002-12-11 | 沈阳碧水蓝天环境科技有限公司 | Biological treating process of high-concentration organic waste water |
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 |
CN102976499A (en) * | 2012-12-03 | 2013-03-20 | 北京师范大学 | Method for preparing composite board capable of simultaneously slowly releasing nitrogen and adsorbing/biologically degrading petroleum hydrocarbons |
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CN1384065A (en) * | 2001-04-28 | 2002-12-11 | 沈阳碧水蓝天环境科技有限公司 | Biological treating process of high-concentration organic waste water |
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 |
CN102976499A (en) * | 2012-12-03 | 2013-03-20 | 北京师范大学 | Method for preparing composite board capable of simultaneously slowly releasing nitrogen and adsorbing/biologically degrading petroleum hydrocarbons |
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