JPH02190186A - Continuous production of granular gel having immobilized microorganism and apparatus therefor - Google Patents

Abstract

PURPOSE:To easily obtain the subject granular gel by dropping a suspended aqueous solution composed of a water-soluble polymerizable compound, a polymerization agent, a microorganism, etc., into a mixed aqueous solution composed of sodium alginate and a polymerization agent different from the above agent and reacting the components with each other. CONSTITUTION:A suspended aqueous solution 1 is produced by mixing 5-30wt.% of a polymerizable compound such as monofunctional monomer, either one of 0.1-4wt.% of a polymerization initiator and 0.2-0.8wt.% of a polymerization accelerator among a redox polymerization agent, 1-20wt.% of colloidal silica, 0.3-6wt.% of gelling agent of >=2-valent metal salt and 0.5-3wt.% of microorganism. A mixed aqueous solution 2 is produced by mixing 0.2-2wt.% of sodium alginate and the remaining component of the above polymerization agent. The solution 1 is dropped from a nozzle 8 of an apparatus 3 into the dropping part 4 of the solution 2 to form particles 9' having a coating film of an alginic acid salt gel and the components are polymerized in a gel-forming part 5 by supplying air 10 thereto. The obtained granular gel 9 is separated in a separation part 6, the solution 2 is recycled to the dropping part 4 and the granular gel having immobilized microorganism is continuously recovered in a recovering vessel 13.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application) The present invention relates to a method for producing microorganism-immobilized granular gel useful for purifying wastewater.

(Prior Art) Encompassing methods are often used to immobilize microorganisms, and hydrophilic gels made from natural polymers and synthetic polymers are examples of entrapping solidification materials. When looking at the durability of the carrier, natural polymers are not sufficient, so synthetic polymers are considered to be the best choice. Examples of past applications include polyacrylamide gel,
Many carriers may be mentioned, such as polyvinyl alcohol gel, urethane prepolymer gel, photocrosslinked resin gel, and polyethylene glycol methacrylate gel.

When identifying microorganisms in these hydrophilic gels and using them as microorganism immobilization carriers, various shapes can be considered, such as spheres,
There are particle shapes such as cylinders and prisms, and relatively large plate shapes such as films and sheets. When treating wastewater by filling a reactor with these carriers, considering the reaction efficiency, the shape of the carrier should be one with a larger specific surface (CrA/c-gel), which is advantageous for boat fishing. For this reason, particulate carriers are preferred.

Although it is quite difficult to form hydrophilic synthetic polymer resin into granules, JP-A No. 59-11182 discloses a method for granulating photocured plum fat, and JP-A No. 63-24886 describes a method for granulating photocurable plum fat. Method for granulating gel, JP-A-60-1
Japanese Patent No. 53794 proposes a method for granulating a mixture of acrylamide and an alkinate.

The method described in JP-A-59-11182 is a means for gelling an aqueous suspended solution containing a photocurable resin phleformer, a photosensitizer, a natural polysaccharide such as sodium alginate, and oxygen. Since prepolymers alone cannot gel into particles, they rely on natural polysaccharides, which easily gel with metal salts.

That is, by utilizing the property that when sodium alkyne is dropped into an aqueous calcium chloride solution from a nozzle, an exchange between sodium and calcium ions occurs and a spherical gel body is easily formed. It is added dropwise to an aqueous calcium chloride solution to form spherical primary particles through gelation of the sodium alkyne, and the spherical particles are irradiated with ultraviolet rays, which are actinic rays. By excitation of the photosensitizer, a photocurable resin prepolymer is formed. to form secondary particles.

The method described in Tokushima Publication No. 63-24886 is to obtain a granular carrier in which microorganisms are immobilized on polyacrylamide gel. The liquid is dropped into an organic solvent from a nozzle in the form of droplets and gelled in the organic solvent. That is, a hydrophobic organic solvent is used to make the suspended aqueous solution into droplets, and the aqueous medium and the droplets are moved during continuous production, and when gelatinized, the granular gel is converted into an organic solvent. It is taken out from the solvent layer.

The method described in Tokushima No. 60-153794 is to obtain a granular carrier in which microorganisms are immobilized on a polyacrylamide gel, and contains an acrylamide monomer, a crosslinking agent, a redox polymerization agent, an alkyne salt, and a microorganism. An aqueous suspension solution is dropped into a droplet of a calcium salt or aluminum salt, the primary particles formed are transferred into an organic solvent, and the polymerization of acrylamide is carried out to obtain a spherical gel.

(Invention or problem to be solved Section J11) The method described in JP-A-59-11182 requires the addition of a special substance, that is, a natural polysaccharide, to make the photocurable resin prepolymer into a spherical gel. is necessary. Furthermore, this method requires separate steps for particle formation and polymerization, making the process complicated.

The method described in JP-A-63-24886 requires the use of an organic solvent that is harmful to microorganisms. Is it possible to use edible oil in place of part or all of the organic starting line in order to reduce this drawback? In this case, the oil will adhere to the surface of the obtained carrier particles, and this will be completely removed. It is difficult to leave behind.

The method described in JP-A-60-153794 is as follows:
The difference is that sodium alginate is added to form paired particles from Japanese Patent Application Laid-Open No. 63-24886. That is, there is a primary particle formation process in which an alginate film is formed by replacing soda with calcium or aluminum, and then a secondary particle formation process in which acrylamide is gelled in an organic solvent. Thus, it is necessary to use organic solvents that are harmful to microorganisms. In addition, this method requires separate steps for particle formation and polymerization, making the process complicated.

In addition, as a method for granulating natural polymer gel, JP-A No. 62-1
No. 95284 discloses a method for granulating algin-brewed salt,
It describes a method that is different from conventional methods. That is, this is a granulation method in which a microorganism suspension containing calcium ions is added to an aqueous sodium alkinate solution to form a film of calcium alginate. According to this, it is easy to granulate it, or when used for wastewater treatment, there is a problem that calcium ions are released by one phosphate ion contained and the gel collapses.

In this way, conventional methods for obtaining microorganism-immobilized carriers in the form of particles require problems such as the need for organic solvents that are unfavorable for microorganism-immobilized carriers, complicated processes, and poor medical quality. there were.

The present invention provides a method and apparatus for easily producing granular gel with immobilized microorganisms continuously without such drawbacks.

(Means for Solving the Problems) The present invention provides a gelatinized compound comprising a water-soluble polymerizable compound, either a polymerization accelerator or a polymerization initiator thereof, colloidal silica, and a salt of a divalent or higher-valent metal. A suspended aqueous solution containing a mixture of the agent and the microorganism is dropped into a mixed aqueous solution containing sodium alginate and the remaining one of the polymerization accelerator and the polymerization initiator of the above polymerizable compound, and the above polymerization occurs within the formed droplets. This method is based on the polymerization of chemical compounds and has been further developed into continuous granulation.

That is, a suspension formed by mixing a water-soluble polymerizable compound, one of its polymerization accelerator and polymerization initiator, colloidal silica, a gelling agent consisting of a salt of a divalent or higher metal, and a microorganism. The aqueous solution is transformed into a mixed aqueous solution containing sodium alginate and the remaining one of the polymerization accelerator and polymerization initiator of the above-mentioned polymerizable compound, which circulates through the dropping part, the gel forming part, the gel separation part, and returns to the original dropping part. Dripping from the dripping part,
This is a method for continuously producing gelled particulate gel by causing a gelling reaction of a polymerizable compound within a droplet in a gel forming section.

Further, a suspension formed by mixing a water-soluble polymerizable compound, either one of its polymerization accelerator and polymerization initiator, colloidal silica, a gelling agent consisting of a salt of a divalent or higher metal, and a microorganism. A dropping site with a nozzle for dropping an aqueous solution, a mixed aqueous solution containing sodium alginate and the remaining one of the polymerization accelerator and polymerization initiator of the above-mentioned polymerizable compound are sequentially moved from the dropping site to a gel forming site and gel separation. part, and each constituent part that returns to the original dropping part and moves as a circulant, the suspended aqueous solution is dropped into the mixed aqueous solution from the dropping part, and the gelled particles are taken out from the gel separation part. This is a continuous production device for microorganism-immobilized granular gel.

Furthermore, this is a continuous production device for microorganism-immobilized granular gel in which the circulation of the mixed aqueous solution is carried out using an air lift method.

The details of the present invention will be described below, but first, the gel material to which the present invention can be applied, the material and principle for granulation will be explained.

The above polymerizable compound may be one that undergoes radical polymerization with a redox polymerization agent to form a hydrophilic gel (
, monofunctional heptamer-1 polyfunctional heptamer-1 unsaturated prepolymers, and the like.

Examples of monofunctional monomers include acrylamide, methacrylamide, hydrodiethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol acrylate, and glycerol monomethacrylate. Examples of the polyfunctional seven-mer include ethylene glycol dimethacrylate, ethylene glycol diacrylate, butanediol dimethacrylate, butanediol diacrylate, glycerol dimethacrylate, N%N-methylenebisacrylamide,
Examples include N,N-diallyl-L-tartaric acid diamide and triacryl formal. Unsaturated prepolymers include polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polyesters of acrylic or methacrylic acid of polyvinyl alcohol, xylylene diisocyanate, polyethylene glycol and 2- There are those obtained by subjecting hydroxyethyl methacrylate to a urethane reaction.

In the above-mentioned water-soluble polymerizable compounds having unsaturated groups, even if monofunctional monomers are made into polymers alone, three-dimensional figures cannot be applied, so that gels have poor shape retention. Therefore, monofunctional septamers are used in conjunction with polyfunctional hexamers.

Multifunctional monomer prepolymers consist only of these single substances,
Alternatively, a mixture of several types may be used.

The polymerization agent is a redox polymerization agent consisting of a polymerization initiator and a polymerization accelerator. Redox polymerization agents include calcium persulfate-dimethylaminopropionitrile, potassium persulfate-sodium hydrogen sulfite, ammonium persulfate-sodium hydrogen sulfite, ammonium persulfate-sodium thiosulfate, hydrogen peroxide-ferrous chloride, and There are combinations such as hydrogen-ascorbic acid and potassium persulfate-hydrazine.

Examples of the microorganisms include bacteria, fungi, protozoa, and activated sludge made of a mixture of these, such as blue-green algae. It may be a sex bacteria.

Examples of gelling agents made of salts of divalent or higher-valent metals include calcium chloride, calcium nitrate, aluminum chloride, aluminum sulfate, and a/I/miniram nitrate, which may also be used in the form of hydrates. These serve as gelling agents for colloidal silica and sodium alginate. Calcium chloride is preferred as the gelling agent in view of its low inhibitory effect on microorganisms.

A monovalent metal salt such as sodium chloride or potassium chloride may be used in combination with the above divalent or higher metal salt. However, −
The Kintsuru salt only functions as a gelling agent for colloidal silica.

Td: Colloidal silicate is added to solidify the droplets of a suspended aqueous solution dropped into a mixed aqueous solution containing sodium alginate so that they do not disperse and break, and to gel them into particles (particularly into spherical shapes). It is something to do. That is, colloidal silica instantaneously gels with divalent or higher valence metal salts to form a viscous precipitated gel. Therefore, the aqueous suspension solution becomes a viscous suspension.

When the suspension aqueous solution is dropped into a mixed aqueous solution containing sodium alginate and the remaining one of the polymerization agents of the polymerizable compound, it forms droplets that are strong enough not to disperse or become irregularly shaped, and to form droplets on the surface of the droplets. At the same time as forming an insoluble gel film of alkyne salt, one of the polymerizing agents in the mixed aqueous solution diffuses into the solution, and the polymerizable compound is polymerized inside the droplet together with the other polymerizing agent. It is something. Colloidal silica can also be expected to have the following effects:

When forming a hydrophilic synthetic polymer gel, if the concentration of the polymerizable compound in the suspended aqueous solution is too low, the mechanical strength of the gel will be low, and conversely, if the concentration is too high, the gel will have a dense matrix. It tends to decrease due to substance permeability. For this purpose, the concentration of polymerizable monomers has to be determined in such a way as to adjust the mechanical strength and material permeability of the gel, or by the presence of a precipitated gel from colloidal silica in the gel, this - can be easily adjusted.

When a polymerization accelerator and a polymerization initiator are simultaneously present in a suspended aqueous solution containing a reviredox-based polymerizing agent organism, radical polymerization is immediately initiated, resulting in gelation or ILn. Therefore, it gels during the step of dropping it into an aqueous sodium alkinate solution, making it difficult to form droplets.

To counter this pot life, it is possible to solve this by adding either a polymerization accelerator or a polymerization initiator to the suspended aqueous solution containing microorganisms, and adding the remaining one because it is water-soluble and contains sodium alginate. can.

Next, the composition ratio of the suspension aqueous solution will be explained.

When using monofunctional heptamer as a polymerizable compound,
This is generally 5 to 30'l for the aqueous suspension.
hM96 is used, in which case the multifunctional monomer used as crosslinking agent is generally used in an amount of 0.5 to 51 LjL%. If both of these are too small, the gel strength tends to decrease, making it difficult to maintain the shape as a carrier. Furthermore, if these amounts are too large, the gel strength will increase, but the permeability of substances within the gel will decrease, so the reaction efficiency (processing) will tend to decrease. If a monofunctional monomer is not used, the polyfunctional monomer is generally
30 heavy J! %, and as mentioned above, too little tends to weaken the gel strength, while too much tends to reduce substance permeability. Unsaturated prepolymers are also often used in similar composition proportions as polyfunctional monomers.

The amount of the redox polymerization agent is appropriately determined in consideration of the type of monomer, gel initiation time, etc. One of the components of the redox polymerization agent, a polymerization initiator and a polymerization accelerator, is contained in the suspension aqueous solution, and the amount of the polymerization initiator is 0.1 to 0. It is preferable that the aqueous suspension solution contains 4-fold i96 and a polymerization accelerator in an amount of 0.2 to 0.8-fold i95.

With respect to the component of the redox polymerization agent contained in the aqueous suspension solution, the other component is contained in the mixed aqueous solution containing sodium alginate, or the polymerization initiator is 0.1 to 51% by weight based on the mixed aqueous solution. It is preferable to include the polymerization accelerator in the mixed aqueous solution in an amount of 0.2 to 5% by weight.

The microorganisms are used in an appropriate amount, preferably 0.5 to 3% by weight (9F) (in the case of activated sludge, expressed as ML8B) for the suspended aqueous solution.

Colloidal silica is used in an amount of 1 to 2 ON kg6 for a suspended aqueous solution with a silicon content, and when this amount is small, droplets may be dispersed in a mixed aqueous solution containing sodium alginate, or even if not dispersed, droplets may be formed. The shape of the gel becomes amorphous and the shape of the gel is similarly amorphous and difficult to form into clean particles. In terms of shape, a spherical shape is the best shape considering its wear resistance. If the amount of colloidal silica is too large, the polymerization reaction of the polymerizable compound may be suppressed, and the strength of the resulting gel may be reduced. If this amount is too small, the alginate gel film will not be formed sufficiently on the surface of the droplet dropped into the mixed aqueous solution containing sodium alginate, resulting in the droplet being dispersed, gelling in an irregular shape, or becoming granular. In some cases, a gel may not be obtained.

Sodium alginate is commercially available with various properties ranging from low viscosity to high viscosity, but it is preferably used in an amount of 0.2 to 211%. If the amount is too low, the formation of a gel film of alginic salt on the surface of the droplet of the suspended waterline will be weak (
The gel shape of the microorganism-immobilized gel formed is non-stoichiometric, or the droplets are dispersed. If the amount is too high, the viscosity of the mixed aqueous solution will increase, the droplets will stick to each other, the gel film of alginate will become thicker, and when the microorganism-immobilized gel is taken out, a large amount of alginic acid will be carried out, resulting in wasted water. The amount is large.

The gelling agent of the present invention has a metal content of 0.3 to 61 AJl in the case of a divalent metal salt, and a trivalent In the case of metal salts, the metal content is preferably 0.1 to 3% by weight. The gelling agent of the present invention is added in sufficient amount to gel the colloidal silica in the suspended aqueous solution to produce a precipitated gel;
In this case, when the aqueous suspension solution is dropped into a mixed aqueous solution containing sodium alginate, a gel film of alginate is effectively formed on the surface of the droplet.

Although a monovalent metal salt may be used in combination with the gelling agent of the present invention,
The gelling agent of the present invention may be used in sufficient amount to form the above-mentioned alkyne-temperature gel film, and may optionally be used in a reduced amount compared to when only the gelling agent of the present invention is used. can.

Next, the procedure of the continuous manufacturing method of the present invention will be explained.

The aqueous suspension solution may be prepared by mixing the components in any order, but first dissolve the polymerizable compound in water, add colloidal silica, and stir well. Colloidal silica is alkaline, so it is preferable for microorganisms. If not, add a pn buffer to adjust the pH to around neutrality in advance), then add one of the polymerization accelerators (or polymerization initiator), and add microorganisms (in activated sludge) to this. (preferably use the condensed liquid) and suspend well.
Further, it is preferable to add a divalent or higher valent metal salt and, if necessary, further a monovalent metal salt (these may be used in the form of a water solution) and stir well. At this time, coroital silica immediately gels, and the entire liquid becomes a viscous suspended aqueous solution containing microorganisms.

Prick R with a mixed aqueous solution of alginic soda and the remaining polymerization initiator (or polymerization accelerator). Next, a circuit for circulating and moving this mixed aqueous solution, that is, a circuit consisting of a dropping section for the suspended aqueous solution, a gel forming section communicating with this, and a gel separating section is filled. Note that here, in the gel forming part, since the polymerization reaction of the polymerizable compound is performed inside the droplet surrounded by the insoluble gel film of alginate, it is necessary to ensure time for the polymerization reaction to complete. The polymerization reaction time is approximately 10 minutes or less if the polymerization is carried out at the above-mentioned polymerization speed and the polymerization promoter is used at a certain degree.

When the suspension aqueous solution is dripped from the dropping part, it is preferable to drop it one drop at a time from a nozzle.If the nozzle diameter is set to 1 to 1.5 fl11, the diameter of the granular gel obtained is 2 to 4 mm. In addition, the number of nozzles may be single or plural.The gel separating section should be able to cut the granular gel with a mesh or the like, and the mixed aqueous solution that has passed through the mesh should return to the original dripping section.

From the above, when the aqueous suspension solution is dropped from the nozzle into the mixed port liquid from the nozzle at a time in the dripping section, particles wrapped in a gel film of γ Lugin and salt are instantly formed. Both the particles and the mixed aqueous solution move through the gel forming part, but the polymerizable compound within the particles starts a polymerization reaction by diffusion and penetration of the polymerization accelerator or polymerization initiator on the mixed aqueous solution side, and gelation occurs in a few minutes. do. The particulate gel that has reached the gel separating part from the gel forming part is separated by a mesh or the like, and the particulate gel is taken out of the system, and the mixed aqueous solution that has passed through the mesh returns to the original dripping part.

Microorganism-immobilized granular gel can be continuously produced by the above method. The obtained granular gel has an alginic gel film, and this film is easily absorbed by the phosphate ions in the U1 water and mixed into the waste water during wastewater treatment. It is better to remove it from the beginning with a buffer solution.

Next, the continuous manufacturing apparatus of the present invention will be explained with reference to FIG.

As described in the continuous production method, the suspended aqueous solution 1 containing microorganisms is semi-distributed into a container. Also, the mixed aqueous solution @2 is filled into the main body 3 of the apparatus. The continuous production device consists of a dropping section 4, a gel forming section 5, and a gel separating section 6. The suspended aqueous solution 1 is fed from the pump 7 to the nozzle 8, and the droplets dropped drop by drop into the mixed aqueous solution in the dripping section 4 instantly become particles 9 wrapped in an alginate gel film.

The particles 9 move together with the mixed aqueous solution through the conduit of the gel forming section 5 due to the air lift action of air 10 introduced from within itself or from the outside, and reach the air 10 discharge section 11 . During this time (
At d) in the figure, the polymerization reaction of the polymerizable compound in the particles 9 is completed. Therefore, it is necessary to set the particle movement time in the gel forming section 5 in such a way that the time required for the reaction to be completed is limited. Since the polymerization reaction time is about 4 to 5 minutes in this case, the migration distance &d of the gel forming section 5 is a residence time of 4 to 5 minutes. The setting of this residence time can be determined by the discharge rate of the air 10, that is, the transfer rate of the particles 9 and the mixed aqueous solution 2 in the air 10, and the rate of transfer of the mixed bath liquid 2 of the entire apparatus. You can adjust eI@speed.

The granular gel 9, which has undergone the polymerization reaction, moves up the pipe by an air lift and reaches the gel separation section 6, where the granular gel 9 and the mixed aqueous solution 2 are separated by the mesh 12. The mixed aqueous solution 2 that has passed through the mesh 12 returns to the dripping section 4. The granular gel 9 is uniformly distributed from the mesh 12 into a collection container 13.

As described above, microorganism-immobilized granular gel made of polymer gel can be continuously produced.

(Example) Example 1 A granular gel in which activated sludge was fixed on a polyacrylamide gel was manufactured. The suspension aqueous solution is as follows. The activated sludge concentrate was added to an aqueous solution in which acrylamide monomer and N,N-methylenebisacrylamide were dissolved and mixed well. To this, a polymerization accelerator, dimethylaminoprobionitrile (hereinafter abbreviated as DMAPN, 511jl) was added.
aqueous solution) was added. Colloidal silica (Snowtex-40, trade name, Nichicho Kagaku Kogyo Co., Ltd.) was added and mixed, and further calcium chloride trihydrate was added and mixed. The mixed aqueous solution to be filled into the manufacturing equipment is as follows. Sodium alginate (manufactured by 81GM, NDA-21
58, low viscosity) and polymerization initiator potassium persulfate (hereinafter K
A mixed aqueous solution consisting of 1810s) was prepared. However, for the suspension aqueous solution obtained above, the acrylamide monomer was 18! [96, N% N-methylenebisacrylamide 1% by weight, activated sludge 21'h%, DMAP No. 5% by weight. Colloidal silica has a proportion of silicon dioxide of 7.
6fti96, calcium chloride dihydrate has a calcium content of 5 to the total I of silicon dioxide and calcium content.
It was added to make the weight percentage. In addition, 96 tons of sodium alginate was added to the resulting mixed aqueous solution, and 5 tons of K mushrooms were added to the resulting mixed aqueous solution.
O- was set to double j196.

The continuous manufacturing apparatus shown in FIG. 1 was used.

The IIMltu water flood solution was supplied by a microphone to a dropping container (50, , t) equipped with one nozzle (diameter 1f [l) so that it was dripped from the nozzle once every 10 seconds. In the circuit in which the mixed aqueous solution circulated and moved, the dripping part was a cylindrical container with a diameter of 5 ann and a volume of 10 Qmz, and the bottom part was a hopper. A silicone tube (inner diameter 5 m) was used as the gel forming part communicating with this, and the length to the air discharge part was set to ensure a residence time of 5 minutes. The air volume of the airsoft tube was adjusted using a glass tube (inner &51 [1) so that the rising strayness inside the tube was 420 crA/'cf·min. The gel separation part installed at the top of the airsoft tube is made of nylon mesh (approximately 10 meshes) at an angle of 45
The mixed aqueous solution that passed through this was returned to the original dripping section. In addition, the granular gel was made to fall down the mesh and into the container.

Under these conditions, the aqueous solution described in 1'iI was continuously dropped from the nozzle, and as a result, granular gel could be continuously obtained from the gel separation section. Since this granular gel was covered with a gel film of calcium alkinate, it was placed in a phosphorus buffer aqueous solution and stirred for 10 minutes to dissolve the film. The size of the finally obtained activated sludge fixed granular gel of polyacrylamide was about 3.5 thresholds in diameter.

Example 2 A granular gel in which activated sludge was fixed to polyethylene glycol dimethacrylate gel was produced.

The suspension aqueous solution is as follows. Polyethylene glycol dimethacrylate [23o, Shin-Nakayaku Chemical Industry Co., Ltd.]
, trade name] was added to the aqueous solution and mixed well. This is added to the polymerization accelerator buApN (53k
19b aqueous solution) was added. This is combined with colloidal silica (
Snowtex-40) was removed and mixed, and then calcium chloride dihydrate was added and mixed well. The mixed aqueous solution was an aqueous solution of sodium alginate and polymerization initiator KtStOs.

However, for the suspension aqueous solution obtained above, polyethylene glycol dimethacrylate 10 weight i9b, activated sludge 2 weight %, nMApNO, 5i fish porridge were added. Colloidal silica is 7.61% based on the proportion of silicon dioxide, and calcium chloride dihydrate is the sum of silicon dioxide and calcium.
Calcium was added so that 5 times M96 was added to k.

In addition, the mixed aqueous solution obtained above was chopped to give 0.81% by weight of alkyne soda and 21% by weight of K-Ss On.

The continuous manufacturing equipment used is the one shown in Figure 1, and each condition is the same as Example 1.
I made it exactly the same. As a result of continuously dropping the aqueous suspension solution from the nozzle, it was possible to continuously produce granular gel.

After removing the calcium alkinate gel film, the activated sludge-fixed granular gel consisting of polyethylene glycol dimethacrylate gel and silica precipitate gel had a diameter of about 2.8 min.

Example 3 An activated sludge fixed granular gel was produced in the same manner as in Example 1 or Example 2. However, instead of the polymerization accelerator DMAPN, *8 tO· as a polymerization initiator was added to the aqueous suspension. Therefore, the polymerization accelerator DMAPN was added to the mixed aqueous solution instead of the polymerization initiator Kl 810m. in the suspension aqueous solution *
Ss O- was 0.25 irtm%, and the other compositions were the same as in Example 1 or Example 2. The concentration of alkyne-brewing soda in the mixed aqueous solution described in 11 is 0.8 times 9b, D
MAPN was set to 21kg6. The manufacturing apparatus shown in FIG. 1 was used, and each condition was exactly the same as in Example 1 or Example 2.

As a result, it was possible to continuously produce a good granular gel with fixed activated sludge, both when using an acrylamide monomer and when using a polyethylene glycol dimethacrylate monomer. After forming a gel film of calcium alkinate with an aqueous phosphate buffer solution, the granular gel has a diameter of about 3 in the case of acrylamide gel (about 2 in the case of I[l polyethylene glycol dimethacrylate gel).
It was 51m1.

(Effects of the Invention) According to the present invention, spherical microorganism-immobilized granular gel can be continuously produced using a simple method and apparatus without using thick IN and solvents that inhibit microorganisms.

[Brief explanation of the drawing]

FIG. 1 is a sectional view of a continuous manufacturing apparatus showing one embodiment of the present invention. Explanation of symbols 1... Suspended aqueous solution 2... Mixed aqueous solution 3.
・Device body 4... Lower chest 5... Gel forming part 6... Gel separation part 7... Supply Honda 8... Nozzle 9... Granular gel
1o...Air 11...Air discharge part 12.
...Metshu 13...Collection container

Claims (1)

[Claims] 1. A water-soluble polymerizable compound, either one of its polymerization accelerator and polymerization initiator, colloidal silica, a gelling agent consisting of a salt of a divalent or higher metal, and a microorganism are mixed together. The suspension aqueous solution formed by
Then, it is dropped from the dropping part into the mixed aqueous solution containing the remaining one of the polymerization accelerator and polymerization initiator of sodium alginate and the polymerizable compound, which circulates back to the original dropping part, and polymerization within the droplet occurs in the gel forming part. 1. A continuous production method for microorganism-immobilized granular gel, which is characterized by performing a gelation reaction of a chemical compound and removing gelled particles from a gel separation section. 2. A suspension formed by mixing a water-soluble polymerizable compound, one of its polymerization accelerator and polymerization initiator, colloidal silica, a gelling agent consisting of a salt of a divalent or higher metal, and a microorganism. A dropping site with a nozzle for dropping an aqueous solution, a gel forming site and a gel separation site where a mixed aqueous solution containing sodium alginate and the remaining one of the polymerization accelerator and polymerization initiator of the above polymerizable compound is sequentially applied from the dropping site. , and each constituent part that returns to the original dropping site and circulates, the suspended aqueous solution is dropped into the mixed aqueous solution from the dropping site, and the gelled particles are removed from the gel separation site. A continuous manufacturing device for microorganism-immobilized granular gel that can be taken out. 3. The continuous production apparatus for microorganism-immobilized granular gel according to claim 2, wherein the circulating movement of the mixed aqueous solution is an air lift method.