CN103374560B - A kind of preparation method of polyvinyl alcohol immobilized microorganism gel - Google Patents
A kind of preparation method of polyvinyl alcohol immobilized microorganism gel Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of polyvinyl alcohol immobilized microorganism gel.The method comprises following several step successively: (1) structure adaptability; (2) dissolving of solidifying agent; (3) conveying of solution and dropping; (4) step such as chemical crosslinking cure, washing.The inventive method adopts chemical crosslink technique, successfully achieve the batch preparation that particle diameter is the macrobead polyvinyl alcohol immobilized microorganism gel of 2 ~ 5mm, its gel-strength is higher, and by the design improvement to relative assembly, and no longer adopt droplet generator, greatly increase the level of automation that polyvinyl alcohol immobilized microorganism gel industry is produced, consume energy lower, technique is simpler.
Description
Technical field
The present invention relates to a kind of polyalcohol hydrogel, particularly relate to the preparation method of a kind of polyvinyl alcohol immobilized microorganism gel batch.
Background technology
Polyvinyl alcohol immobilized microorganism gel, because of its chemical property torpescence, nontoxicity, good biocompatibility, good mechanical performance, water regain is high, be easy to machine-shaping, and be widely used in the every field such as agricultural, medicine, daily-use chemical industry, environmental protection and desert control.
Crosslinked is water-soluble poval (PVA) material modification and the important step preparing PVA hydrogel.Cross-linking method can be divided into physical crosslinking, chemically crosslinked and radiation cross-linking process.Wherein, physical crosslinking is hydrogen bond and entanglement effect mainly, in practical application, take Kuraray as the commercial production technology that the technology of freeze-thaw repeatedly of representative has formed PVA hydrogel, but refrigerating apparatus is general larger in application, freeze-thaw needs repeatedly to carry out, so power consumption is comparatively large, preparation is complicated; Radiation crosslinking utilizes the direct radiation PVA solution such as gamma-rays, electron beam, X-ray, ultraviolet, PVA molecule is made to produce free radical and covalent cross-linking, because its cross-linking process does not need any additive can reach crosslinked object, therefore research is more in the biologically active substances such as immobilized enzyme, antibody, antigen, but because radiation crosslinking has sterilization and mutagenesis concurrently, it is few in the application of fixed microorganism carrier preparation field; Chemically crosslinked, namely make to carry out chemically crosslinked between PVA molecular chain under certain condition and form hydrogel, its crosslinking method is divided into again covalently cross-linked and coordination cross-linked, adopts chemical crosslink technique and form system to prepare PVA hydrogel practicable in practical application.
Wu Li state of Donghua University etc., Donghua University's journal (natural science edition), 2001, 27(6), the preparations and applicatio of polyvinyl alcohol hydrogel is studied, point out that Kuraray company has utilized circulating frozen freezing process to obtain containing a large amount of free water, good Oxygen permeability, the PVA hydrogel of suitable micro-organisms existence, and point out that the Synthesis and applications research of PVA hydrogel have been carried out for many years, Japan, the countries and regions such as Taiwan have started practical application in some field, but domesticly also rest on the experimental study stage so far, commercial production from mass-producing also has certain distance.In fact, Kuraray company has just achieved the commercial production of this kind of PVA hydrogel in calendar year 2001.
Application number is 01120095.2, and application people is the Chinese patent of Dalian Inst of Chemicophysics, Chinese Academy of Sciences, discloses a kind of system for preparing gel beads, drips three part compositions primarily of storage tank, conveying and microlayer model system; Its microlayer model system is dripped part and is made up of spray broom and droplet generator and gelation container.This preparation system can prepare the gel that particle diameter is 100 ~ 2000 μm well, and can be applied in the gel preparation of pharmaceutical industries.But, for preparing the PVA hydrogel that particle diameter is 2 ~ 5mm, this patent significant discomfort is closed, trace it to its cause: one, chemically crosslinked is prepared in PVA hydrogel process complicated chemical reaction environment, and formed by top layer to inner cross-linked network system, and mainly drop film forming formation microcapsule in solid solution in medicine; Its two, chemically crosslinked is prepared in the whole preparation process of PVA hydrogel more complicated, relates to the switching of high/low temperature, and solution system viscosity is higher, and technique is more complicated; Its three, PVA hydrogel particle is much bigger; Its four, the formation of drop needs droplet generator, its equipment and gel preparation become more complicated, energy consumption is also high, and operation easier strengthen.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of polyvinyl alcohol immobilized microorganism gel, the polyvinyl alcohol immobilized microorganism gel of the method energy batch processability excellence.
The object of the present invention is achieved like this:
A preparation method for polyvinyl alcohol immobilized microorganism gel, is characterized in that, it comprises following several step successively:
(1) structure adaptability
Be 400 ~ 3000 by the polymerization degree, alcoholysis degree is the polyvinyl alcohol of 75 ~ 99%, be the amount of 30 ~ 90 according to parts by weight, add in the dissolution kettle with whipping appts, and add the sodium alginate that parts by weight are 0.1 ~ 50, and appropriate water, dissolve at 80 ~ 99 DEG C, after it dissolves, be cooled to less than 50 DEG C, then add biosolubilization dispersion, temperature preferably controls to be 20 ~ 40 DEG C.Wherein, the amount of the water of interpolation, energy is dissolve polyvinyl alcohol and sodium alginate fully; Add microorganism be generally living microorganism, its consumption is no more than 10% of gel particle, is specifically then selected according to practical use.
(2) dissolving of solidifying agent
Solidifying agent is added in the dissolution kettle with whipping appts, and add appropriate water, dissolve at 15 ~ 35 DEG C, preparation curing agent solution, described curing agent solution, select boronic acid containing mass percentage concentration be 3 ~ 5% and alkaline earth salt mass percentage concentration be the solution of 0.1 ~ 10%, send in solidification groove stand-by after obtained.Wherein, the selection of solidifying agent, can be selected according to concrete practical use: during PVA immobilized microorganism hydrogel for the preparation of wastewater treatment, then adopt the chemically crosslinked system of PVA-boric acid-alkaline-earth metal to be selected solidifying agent.
(3) conveying of solution and dropping
By the solution containing polymkeric substance and microorganism of gained in above-mentioned steps (1), be transported in solution Dropping feeder by toothed gear pump, surge pump or peristaltic pump, form through solution Dropping feeder the PVA solution drop that particle diameter is 2 ~ 5mm; Described solution Dropping feeder, be the sealing member with lid, it covers the feed pipe being connected with capstan, inlet channel and connection transferpump, for having a plate of multiple drip hole bottom it, and drip hole is connected with dropper outside casing.Too high at soltion viscosity, ooze at need, add suitable pressure to ooze by capstan; When dropping system does not temporarily use or solution impurity blocking needs to rinse, inlet channel can be opened and add process water flushing.
(4) chemical crosslinking cure, washing
By the PVA aqueous solution droplets of above-mentioned steps (3) gained, drop to and fill in the solidification groove of solidifying agent, solidification groove be arranged on solution Dropping feeder connect dropper below 10 ~ 50cm place, by the PVA aqueous solution droplets that Dropping feeder instills under whipped state, solidify 30min ~ 8h further and form polyvinyl alcohol immobilized microorganism gel particle.This process fully can realize the solidification of the microorganism to PVA hydrogel particle.
Above-mentioned dropper, its internal diameter is 1 ~ 4mm, and liquid outlet bottom dropper is carried out interior chamfered becomes inner concavity, so that relief pressure and form granular gel; Spacing between dropper is more than 5mm.
A plate in above-mentioned solution Dropping feeder, be set to the circle of flat smooth, and drip corresponding feed pipe in the middle of plate be set to non-through depressed area by liquid part, this depressed area is the middle dark region shoaled gradually to edge, and all drip hole are evenly arranged round this depressed area.
The drip hole that above-mentioned plate is arranged is provided with internal thread, and above-mentioned dropper is provided with outside screw, and the two is threaded by this.
Above-mentioned solidification groove, be provided with lower agitating device, solidify after fixing liquid and be sent back to solidifying agent dissolution kettle by pump, again to utilize, and add water to the PVA hydrogel particle of gained washing 1 ~ 3 time, fully can clean residual solidified agent, and obtained purer polyvinyl alcohol immobilized microorganism gel particle, further discharging obtains product.Can be in parallel by multiple solidification groove, be convenient to switch and carry out chemically crosslinked and washing discharging process fast.
The present invention has following beneficial effect:
The inventive method adopts chemical crosslink technique, successfully achieve the batch preparation that particle diameter is the macrobead polyvinyl alcohol immobilized microorganism gel of 2 ~ 5mm, its gel-strength is higher, and by the design improvement to relative assembly, and no longer adopt droplet generator, greatly increase the level of automation that polyvinyl alcohol immobilized microorganism gel industry is produced, consume energy lower, technique is simpler.
Accompanying drawing explanation
Fig. 1 is the structural representation not connecting the sealing member of dropper in the solution Dropping feeder adopted in the embodiment of the present invention 1.
Fig. 2 is the structural representation dripping plate in the solution Dropping feeder adopted in the embodiment of the present invention 1.
Fig. 3 is the structural representation of the dropper in the solution Dropping feeder adopted in the embodiment of the present invention 1.
Embodiment
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that the present embodiment is only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above to the present invention.
Embodiment 1
A preparation method for polyvinyl alcohol immobilized microorganism gel, it comprises following several step successively:
(1) structure adaptability
Be 400 by the polymerization degree, alcoholysis degree is the polyvinyl alcohol of 75%, according to the amount of 90kg, add in the dissolution kettle with agitator, and add the water of sodium alginate 50kg and 500kg, dissolve at 80 DEG C, after it dissolves, be cooled to 50 DEG C, then the microorganism adding 10kg dissolves dispersion at 20 DEG C;
(2) dissolving of solidifying agent
By 5kg boric acid and 10kg calcium chloride, add in the dissolution kettle with agitator, and add 85kg water, dissolve at 15 DEG C, send in solidification groove stand-by after it dissolves;
(3) conveying of solution and dropping
By the solution containing polymkeric substance and microorganism of gained in step (1), be transported in solution Dropping feeder by toothed gear pump, form through solution Dropping feeder the PVA aqueous solution droplets that particle diameter is 2 ~ 5mm; This solution Dropping feeder, as shown in Figure of description 1-3, it is the sealing member 1 with lid, it covers the feed pipe 2 being connected with capstan 3, inlet channel 4 and being connected transferpump, for having a plate 6 of multiple drip hole 5 bottom it, and drip hole 5 is connected with outside casing the dropper 10 that internal diameter is 4mm, and the bottom liquid outlet of dropper 10 is inner concavity, the spacing between adjacent two droppers 10 is 5mm; Drip plate 6 and be set to the circle of flat smooth, and drip corresponding feed pipe 2 in the middle of plate 6 be set to non-through depressed area 7 by liquid part, this depressed area 7 be the dark region shoaled gradually to edge, centre, and all drip hole 5 are evenly arranged round this depressed area 7; Drip hole 5 is provided with internal thread 8, and dropper is provided with outside screw 9, and the two is threaded by this;
4) chemical crosslinking cure, washing
By the PVA aqueous solution droplets of step (3) gained, drop to and fill in the solidification groove of solidifying agent, solidification groove be arranged on solution Dropping feeder connect dropper below 10cm place, solidification 30min is stirred with the lower agitating device arranged in solidification groove, solidify after fixing liquid and be sent back to solidifying agent dissolution kettle by pump, again to utilize, clean 2 times with process water more afterwards, namely obtain polyvinyl alcohol immobilized microorganism gel particle product.
Adopt the product sample in the present embodiment 1, carry out certain experiment to obtain: as can be seen from surface and the section SEM photo of products obtained therefrom, its surface and inside have obvious pore space structure, thus UNICOM microorganism newly becomes the passage of mass transfer in metabolic process, exchange, has a good permeability.Under 50 DEG C of comparative high temperature, carry out impact experiment, the ability that product sample is disposed of sewage declines to some extent, but temperature influence is little, and can recover normal after 8 ~ 16h greatly.PVA hydrogel all better can carry out sewage disposal from 17.1 DEG C to 50 DEG C, and after process, COD of sewage value is mostly at below 100mg/l.Products obtained therefrom sample, after the high strong sewage of 649mg/l impacts 96 hours, still can be disposed of sewage preferably, and energy qualified discharge (being less than 100mkg/l), its processing efficiency is 2 times of activated sludge process; PH be 6 acidic conditions PVA Gel Treatment sewage effect is not affected, and be under the condition of 9 settings in PH, carry out alkali impact experiment, appropriate alkali impacts the sewage disposal being even conducive to bacterium, and before and after alkali impacts, the change of PVA Gel Treatment COD of sewage value is little.
Embodiment 2
A preparation method for polyvinyl alcohol immobilized microorganism gel, it comprises following several step successively:
(1) structure adaptability
Be 3000 by the polymerization degree, alcoholysis degree is the polyvinyl alcohol of 99%, according to the amount of 30kg, add in the dissolution kettle with whipping appts, and add sodium alginate 0.1kg and 500kg water, dissolve at 99 DEG C, after it dissolves, be cooled to 45 DEG C, add the dispersion of 3kg biosolubilization again, it is 40 DEG C that temperature controls;
(2) dissolving of solidifying agent
By 3kg boric acid and 0.1kg aluminum chloride, add in the dissolution kettle with whipping appts, and add 96.9kg water, dissolve at 35 DEG C, send in solidification groove stand-by after it dissolves;
(3) conveying of solution and dropping
By the solution containing polymkeric substance and microorganism of gained in above-mentioned steps (1), be transported in solution Dropping feeder by surge pump, form through solution Dropping feeder the PVA aqueous solution droplets that particle diameter is 2 ~ 5mm; In this solution Dropping feeder, the internal diameter of dropper is 1mm; Spacing between adjacent two droppers is 7mm, and other structures are all identical with the solution Dropping feeder structure in embodiment 1;
4) chemical crosslinking cure, washing
By the PVA aqueous solution droplets of step (3) gained, drop to and fill in the solidification groove of solidifying agent, solidification groove be arranged on solution Dropping feeder connect dropper below 50cm place, 8h is solidified under the stirring action of the lower agitating device be provided with in solidification groove, solid solution is sent back to solidifying agent dissolution kettle by pump afterwards, again to utilize, clean 1 time with water water more thereafter, polyvinyl alcohol immobilized microorganism gel particle product can be obtained.
Embodiment 3
A preparation method for polyvinyl alcohol immobilized microorganism gel, it comprises following several step successively:
(1) structure adaptability
Be 2500 by the polymerization degree, alcoholysis degree is the polyvinyl alcohol of 89%, according to the amount of 60kg, add in the dissolution kettle with agitator, and add 10kg sodium alginate, 500kg water, dissolve at 89 DEG C, after it dissolves, be cooled to 35 DEG C, then add the dispersion of 5kg biosolubilization, it is 30 DEG C that temperature controls;
(2) dissolving of solidifying agent
By 4kg boric acid and 1kg calcium chloride, add in the dissolution kettle with agitator, and add 95kg water, dissolve at 25 DEG C, send in solidification groove stand-by after it dissolves;
(3) conveying of solution and dropping
By the solution containing polymkeric substance and microorganism of gained in step (1), be transported in solution Dropping feeder by peristaltic pump, form through solution Dropping feeder the PVA aqueous solution droplets that particle diameter is 2 ~ 5mm; In the solution Dropping feeder adopted, the internal diameter of dropper is 3mm; Spacing between adjacent two droppers is 8mm, and other structures are all identical with the solution Dropping feeder structure in embodiment 1;
4) chemical crosslinking cure, washing
By the PVA aqueous solution droplets of step (3) gained, drop to be arranged in parallel fill in multiple solidification grooves of solidifying agent, solidification groove be arranged on solution Dropping feeder connect dropper below 30cm place, 3h is solidified under whipped state, solidify after fixing liquid and be sent back to solidifying agent dissolution kettle by pump, again to utilize, clean 3 times with water more afterwards, polyvinyl alcohol immobilized microorganism gel particle product can be obtained.
Claims (5)
1. a preparation method for polyvinyl alcohol immobilized microorganism gel, is characterized in that, it comprises following several step successively:
(1) structure adaptability
Be 400 ~ 3000 by the polymerization degree, alcoholysis degree is the polyvinyl alcohol of 75 ~ 99%, be the amount of 30 ~ 90 according to parts by weight, add in the dissolution kettle with whipping appts, and add the sodium alginate that parts by weight are 0.1 ~ 50, and appropriate water, dissolve at 80 ~ 99 DEG C, after it dissolves, be cooled to less than 50 DEG C, then add biosolubilization dispersion, it is 20 ~ 40 DEG C that temperature controls;
(2) dissolving of solidifying agent
Solidifying agent is added in the dissolution kettle with whipping appts, and add appropriate water, dissolve at 15 ~ 35 DEG C, preparation curing agent solution, described curing agent solution, select boronic acid containing mass percentage concentration be 3 ~ 5% and alkaline earth salt mass percentage concentration be the solution of 0.1 ~ 10%, send in solidification groove stand-by after obtained;
(3) conveying of solution and dropping
By the solution containing polymkeric substance and microorganism of gained in described step (1), be transported in solution Dropping feeder by toothed gear pump, surge pump or peristaltic pump, form through solution Dropping feeder the PVA solution drop that particle diameter is 2 ~ 5mm; Described solution Dropping feeder, for the sealing member (1) with lid, it covers the feed pipe (2) being connected with capstan (3), inlet channel (4) and being connected transferpump, for having a plate (6) of multiple drip hole (5) bottom it, and drip hole (5) is connected with dropper (10) outside casing; Described dropper (10), its internal diameter is 1 ~ 4mm, and dropper (10) bottom liquid outlet becomes inner concavity; Spacing between dropper (10) is more than 5mm;
(4) chemical crosslinking cure, washing
By the PVA aqueous solution droplets of described step (3) gained, drop to and fill in the solidification groove of solidifying agent, solidification groove is arranged on 10 ~ 50cm place, dropper (10) below that solution Dropping feeder connects, by the PVA aqueous solution droplets that Dropping feeder instills under whipped state, solidify 30min ~ 8h further and form polyvinyl alcohol immobilized microorganism gel particle.
2. the preparation method of polyvinyl alcohol immobilized microorganism gel according to claim 1, it is characterized in that: described plate (6), be set to the circle of flat smooth, and drip corresponding feed pipe (2) in the middle of plate (6) be set to non-through depressed area (7) by liquid part, this depressed area (7) be the dark region shoaled gradually to edge, centre.
3. the preparation method of polyvinyl alcohol immobilized microorganism gel according to claim 1 and 2, is characterized in that: the described upper drip hole (5) arranged of plate (6) is provided with internal thread (8), and described dropper (10) is provided with outside screw (9).
4. the preparation method of polyvinyl alcohol immobilized microorganism gel according to claim 1 and 2, is characterized in that: described solidification groove, is provided with lower agitating device; Solidified after fixing liquid and be sent back to solidifying agent dissolution kettle by pump, after add water to the PVA hydrogel particle of gained washing 1 ~ 3 time, namely obtain product.
5. the preparation method of polyvinyl alcohol immobilized microorganism gel according to claim 3, is characterized in that: described solidification groove, is provided with lower agitating device; Solidified after fixing liquid and be sent back to solidifying agent dissolution kettle by pump, after add water to the PVA hydrogel particle of gained washing 1 ~ 3 time, namely obtain product.
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| CN104758976A (en) * | 2014-01-08 | 2015-07-08 | 上海高科生物工程有限公司 | Dual-network hydrogel loaded with thermo-sensitive particle protide medicines and preparation method |
| CN105441418A (en) * | 2015-12-11 | 2016-03-30 | 华南理工大学 | Polyvinyl alcohol immobilized microorganism gel beads and preparation method and use thereof |
| TWI726377B (en) * | 2019-08-02 | 2021-05-01 | 國立清華大學 | Boric acid-containing polyvinyl alcohol nanoparticle and preparation method thereof |
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