The preparation method of high strength high reactivity imbedded microbe carrier
Technical field
The present invention relates under the normal temperature aerobic conditions a kind of preparation and corresponding formula of simple and easy to do high strength high reactivity imbedded microbe.The imbedded microbe activity of this method and formula preparation is high, can efficiently remove the pollutent in ammonia nitrogen in high density and phenolic waste water, and the operation life in fluidized reactor can surpass more than 1.5 years.Because having under normal temperature, Actinochemical synthesis carries out, characteristics that operate under aerobic, and embedded material has the characteristics of biocompatibility, so method and formula can be widely used in the embedding of multiple-microorganism, enzyme, protein and non-microorganism kind material.But and heavy industrialization preparation.
Background technology
The imbedded microbe technology is high owing to having microbe density, and anti-external environment impact capacity is strong, and solid-liquid separation is simple, and therefore simple operation and other advantages has application prospect very widely in the fields such as industry such as wastewater treatments.But the current shortcoming that embedding bacterium ubiquity activity is low, the life-span is short, therefore, be difficult to realize industrial applications at present.How in guaranteeing the embedding carrier, on the basis of microorganism active, improve the life-span of carrier, making it long-term steady running in reactor is a current difficult problem.
Summary of the invention
The object of the invention is to overcome existing imbedded microbe activity not high, the shortcoming that support strength is lower.By adjusting the proportioning between acrylamide and polyvinyl alcohol, under the normal temperature aerobic conditions, by photochemistry, microorganism is carried out to embedding and fix.In microorganism is embedded in to carrier under approaching physiological condition, kept microbic activity; This carrier can surpass more than 1.5 years the working time in fluidized reactor.This method is simple, convenient, easy handling.
Formula of the present invention and preparation process are as follows:
Preparation process one:
1. appropriate acrylamide is dissolved in the water of a ml, adds a certain amount of methylene-bisacrylamide, be stirred to dissolving, obtain A solution; 2. add a certain amount of polyvinyl alcohol in the 60-a of 80-90 ° of C ml deionized water, be stirred to dissolving, obtain B solution;
3. A and B are mixed, then adding the PBS damping fluid to arrive is wherein neutrality to it; Then add the microorganism for the treatment of embedding, stir, obtain mixed solution C;
4. add dimethoxybenzoin solution 0.4ml in mixed solution C, Tetramethyl Ethylene Diamine 1.6ml, Potassium Persulphate saturated solution 4ml, rapid stirring is even;
5. the reaction solution in 4 is placed in to irradiation 2-8 minute under radiation source, is cured;
6. as required the embedding bacterium after solidifying is cut into to corresponding size and size.
Preparation process two:
1. add a certain amount of polyvinyl alcohol in the 60 ml deionized waters of 80-90 ℃, be stirred to dissolving, obtain A solution;
2. appropriate acrylamide is dissolved in A solution, adds a certain amount of methylene-bisacrylamide, be stirred to dissolving, obtain B solution; 3. adding the PBS damping fluid in B solution is neutrality to it; Then add the microorganism for the treatment of embedding, stir, obtain mixed solution C;
4. add dimethoxybenzoin solution 0.4ml in mixed solution C, Tetramethyl Ethylene Diamine 1.6ml, Potassium Persulphate saturated solution 4ml, rapid stirring is even;
5. the reaction solution in 4 is placed in to irradiation 2-8 minute under radiation source, is cured;
6. as required the embedding bacterium after solidifying is cut into to corresponding size and size.
This kind of embedding bacterium preparation method can by light source irradiation, reach transparent system under the normal temperature aerobic conditions, and opaque system and embedding system are carried out photochemistry and efficiently caused, and make it curing, and obtains high reactivity and long-life embedding bacterium.Be specially adapted to embedded immobilization microbial or other abiotic fixed packet embedding system.
This embedding is carried out the photochemistry initiation to transparent, opaque embedding system and is cured embedding, generally comprises following steps:
Step 1 adds 1.8 g-9g polyvinyl alcohol in the 60ml of 80-90 ° of C or a ml deionized water, is stirred to dissolving, obtains A solution;
Step 2, add the acrylamide monomer of 4.8 g-8.4 g and the linking agent of 0.12 g-0.6 g at the A solution of 60 ml of step 1, is stirred to dissolving, obtains solution B; Perhaps
Add the acrylamide of 4.8 g-8.4 g and the N of 0.12 g-0.6 g in the deionized water of b ml, N '-methylene-bisacrylamide, be stirred to dissolving, obtains solution A ', a+b=60 wherein;
Step 3, by the A solution of a ml of step 1 and the A ' solution blending of b ml, then add the PBS damping fluid, to its pH to neutral, obtains solution C; Perhaps
Add the PBS damping fluid in the B solution of the 60ml of step 2, to it to neutral, obtain solution C;
Step 4 adds 1-6 g to treat the embedding thing in solution C, stirs, and obtains mixed solution D;
Step 5 adds dimethoxybenzoin solution 0.2-0.6ml in mixed solution D, Tetramethyl Ethylene Diamine 0.8-2.8ml, and Potassium Persulphate saturated solution 2-8ml, rapid stirring is even;
Step 6, be placed in irradiation 2-8 minute under radiation source by the reaction solution obtained in step 5, is cured;
Step 7, cut into corresponding size and size by the embedding bacterium after solidifying as required.
Wherein, in a preferred embodiment, described linking agent is N, N '-methylene-bisacrylamide.
Wherein, in a preferred embodiment, in step 1, the concentration of polyvinyl alcohol in solution is: the content of the polyvinyl alcohol contained in every 100 ml solution is 3-15 g.
In a preferred embodiment, in step 2, the concentration of described monomer in solution is: the content of the acrylamide monomer contained in every 100 ml solution is 8~14 g; N, the quality percent by volume of N '-methylene-bisacrylamide in solution is 0.2~1% (m/v, g/ml).
In a preferred embodiment, in step 3, enter the PBS damping fluid in being dissolved with the reaction solution of reactant, to its pH to neutral.
In a preferred embodiment, in step 4, the embedding thing for the treatment of added in reaction solution is active sludge, microorganism or other embedding object, describedly treats that the quality percent by volume of embedding thing in solution is 3.2~20%(m/v).
In a preferred embodiment, in step 5, described Potassium Persulphate, dimethoxybenzoin and the Tetramethyl Ethylene Diamine content in the solution of step 5 gained is respectively 0.03-0.67% (m/v, g/ml), 0.1-1.2% (m/v, g/ml), 1-5%(v/v, ml/ml).
In a preferred embodiment, in step 6, described irradiation is 2-8 minute.
In the present invention, described term " transparent system " refers to optically transparent system, includes but not limited to transparent, as can to absorb the photon that light source launches system, as clear solution etc.
In the present invention, described term " opaque system " refers to the opaque system of optics, includes but not limited to, opaque, the system that can not absorb in a large number the photon energy that light source launches.
In the present invention, described term " linking agent " refers to the chemical cross-linking agent that contains unsaturated double-bond, includes but not limited to N, N '-methylene-bisacrylamide.
In the present invention, described term " is treated the embedding thing " and is referred to microorganism, bacterium, enzyme etc., includes but not limited to active sludge, microorganism (such as nitrifier), enzyme etc.These treat that embedding substance is from wastewater treatment or other chemical biochemical industry field production treating processes.
In the present invention, described term " radiating light source " includes but not limited to ultraviolet source (such as 500W high voltage mercury lamp or other similar irradiation source) etc.
Compared with prior art, the present invention has following beneficial effect:
Embedding bacterium formula of the present invention, not only can be used for microorganism or the non-microorganism embedding of transparent system, also applicable to the microorganism of nontransparent system or the embedding of non-microorganism system.And the embedding bacterium carrier activity of gained is high, and the life-span is long, surpass more than 1.5 years the work-ing life in fluidized reactor.And the photochemical initiators in the present invention is efficient, the photochemical solidification Simple fast, the time is generally in 4 minutes, and polymerization system is simple, and cost is lower, is suitable for large-scale embedding bacterium preparation.
Specific embodiments
The present embodiment is implemented take technical solution of the present invention under prerequisite, provided detailed embodiment and process, but protection scope of the present invention is not limited to following embodiment.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.
Embodiment 1
Step 1 adds the polyvinyl alcohol of 3g in the 60 ml deionized waters of 80-90 ℃, is stirred to dissolving, obtains A solution;
Step 2, A solution is cooled to room temperature, adds therein the 6.5g acrylamide, 0.36g N, N '-methylene-bisacrylamide, be stirred to dissolving, obtains solution B;
Step 3, join the PBS damping fluid in solution B, adjusts its pH for neutral; Then add 4g active sludge (Minxing, Shanghai City sewage work provides), stir;
Step 4, add dimethoxybenzoin solution 0.4 ml in the mixed solution obtained in step 3, Tetramethyl Ethylene Diamine 1.6ml,, Potassium Persulphate saturated solution 4ml, rapid stirring is even;
Step 5, be placed under radiation source irradiation 4 minutes by the reaction solution obtained in step 4, is cured;
Step 6, cut into corresponding size and size by the embedding bacterium after solidifying as required.
Embodiment 2
Step 1, acrylamide 6g is dissolved in 20ml water, adds N, and N '-methylene-bisacrylamide 0.24 g, be stirred to dissolving, obtains solution A;
Step 2 adds the polyvinyl alcohol of 4g in the 40 ml deionized waters of 80-90 ° of C, is stirred to dissolving, obtains B solution;
Step 3, by A and B blend, stir;
Step 4, join the PBS damping fluid in the blend solution that step 3 obtains, and adjusts its pH for neutral, then add the 6g active sludge, stirs;
Step 4, add dimethoxybenzoin solution 0.4 ml in the mixed solution obtained in step 3, Tetramethyl Ethylene Diamine 1.6ml, and Potassium Persulphate saturated solution 4ml, rapid stirring is even;
Step 5, be placed under radiation source irradiation 5 minutes by the reaction solution obtained in step 4, is cured;
Step 6, cut into corresponding size and size by the embedding bacterium after solidifying as required.
Embodiment 3
Step 1 adds the polyvinyl alcohol of 3g in the 60 ml deionized waters of 80-90 ° of C, is stirred to dissolving, obtains A solution;
Step 2, A solution is cooled to room temperature, adds therein the 4.5g acrylamide, 0.36g N, N '-methylene-bisacrylamide, be stirred to dissolving, obtains solution B;
Step 3, join the PBS damping fluid in solution B, adjusts its pH for neutral; Then (nitrifier mixes with the ratio of 1:1 with heterotrophic bacteria to add the 4g mixed bacterium.Wherein, the thickened sludge that nitrifier is Minxing, Shanghai sewage work is tamed and is obtained in the 40mg/l ammonia nitrogen waste water; The Aerobic Pond thickened sludge that heterotrophic bacteria is Minxing, Shanghai sewage work), stir;
Step 4, add dimethoxybenzoin solution 0.5 ml in the mixed solution obtained in step 3, Tetramethyl Ethylene Diamine 1.2ml, and Potassium Persulphate saturated solution 4ml, rapid stirring is even;
Step 5, be placed under radiation source irradiation 3 minutes by the reaction solution obtained in step 4, is cured;
Step 6, cut into corresponding size and size by the embedding bacterium after solidifying as required.
Embodiment 4
Step 1 adds the polyvinyl alcohol of 9g in the 60 ml deionized waters of 80-90 ° of C, is stirred to dissolving, obtains A solution;
Step 2, A solution is cooled to room temperature, adds therein the 2.5g acrylamide, 0.18g N, N '-methylene-bisacrylamide, be stirred to dissolving, obtains solution B;
Step 3, join the PBS damping fluid in solution B, adjusts its pH for neutral; Then add 4g nitrifier (Minxing, Shanghai sewage work thickened sludge obtains through the domestication of 40gm/l ammonia nitrogen waste water), stir;
Step 4, add dimethoxybenzoin solution 0.5 ml in the mixed solution obtained in step 3, Tetramethyl Ethylene Diamine 1.2ml, and Potassium Persulphate saturated solution 4ml, rapid stirring is even;
Step 5, be placed under radiation source irradiation 3 minutes by the reaction solution obtained in step 4, is cured;
Step 6, cut into corresponding size and size by the embedding bacterium after solidifying as required.
Embodiment 5
Step 1 adds the polyvinyl alcohol of 6g in the 60 ml deionized waters of 80-90 ° of C, is stirred to dissolving, obtains A solution;
Step 2, A solution is cooled to room temperature, adds therein the 3.5g acrylamide, 0.28g N, N '-methylene-bisacrylamide, be stirred to dissolving, obtains solution B;
Step 3, join the PBS damping fluid in solution B, adjusts its pH for neutral; Then add the 4g nitrifier, stir;
Step 4, add dimethoxybenzoin solution 0.5 ml in the mixed solution obtained in step 3, Tetramethyl Ethylene Diamine 1.2ml, and Potassium Persulphate saturated solution 4ml, rapid stirring is even;
Step 5, be placed under radiation source irradiation 3 minutes by the reaction solution obtained in step 4, is cured;
Step 6, cut into corresponding size and size by the embedding bacterium after solidifying as required.
The embodiment of the present invention 1,2, the embedding bacterium of preparation, have higher activity in 3,4,5.After of short duration domestication (in 2 week, be better than the embedding bacterium of other prior art, and the domestication of general embedding bacterium is 4-6 week), in the processing of high-concentration ammonia nitrogenous wastewater and micro-polluted water performance good, and have long work-ing life, generally can reach more than 1 year.Wherein the life-span of embodiment 5 and 3 prepared embedding bacterium can reach 1.5 years (other embedding bacterium life-span prepared generally is no more than 6 months at present).They are (filling ratio is 10%) in aerobic fluidized reactor, in 7 hours, to the ammonia nitrogen removal frank of 500mg/l concentration and following ammonia nitrogen waste water, can reach respectively 96%, 94%, 98%, 93% and 91%.Clearance to COD in micro-polluted water can reach respectively 75%, 68%, 72%, 65% and 74%, meets or exceeds other embedding bacterium at present.
Although the reference example embodiment is described the present invention, skilled person will appreciate that in the situation that do not depart from scope of the present invention and can carry out various variations and the alternative element corresponding with it of available equivalents.In addition, in the situation that do not depart from base region of the present invention, multiple modification can be carried out so that specific situation or material adapt to instruction of the present invention.
Although invention has been described by reference to various specific embodiments, will be appreciated that in the spirit and scope of the creative concept of describing and can carry out multiple variation.The intent of the present invention is not to be limited to described embodiment, but will have by the defined four corner of the language of appending claims.