CN103951968B - A kind of nanometer Fe (OH) 3 composite biological packing, preparation method and its usage - Google Patents
A kind of nanometer Fe (OH) 3 composite biological packing, preparation method and its usage Download PDFInfo
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Abstract
The invention discloses a kind of nanometer Fe (OH)3Composite biological packing, preparation method and its usage.Its preparation method is by Fe (OH)3Nano-particle preparation combines with polyurethane foam technology, first in situ preparation Fe (OH)3Nano-polyurethane performed polymer, then completes foaming, it is to avoid Fe (OH)3The problem that granule is easily reunited.Prepared composite biological packing specific surface area is big, and biological load performance is good, Fe (OH) in filler3Be uniformly dispersed, Stability Analysis of Structures, the metabolic activity of microorganism can be promoted, accelerate the biofilm of filling surface microorganism, avoid nano-particle due to the little toxic action that microorganism is produced of particle diameter simultaneously, and improve the frame strength of polyurethane foam filler, increase filler stability and impact resistance.The present invention is by regulation Fe (OH)3Content, the convenient density controlling prepared filler, it is ensured that filler is in suspended state in wastewater treatment process, improves packing specific area.
Description
Technical field
The invention belongs to the technology of field of waste water treatment, be specifically related to a kind of nanometer Fe (OH)3Composite biological packing, preparation method and its usage, it is high activity, high stability microorganism water process active carrier.
Background technology
Modern industry waste component is complicated, pollutant kind is many, and conventional biological treatment technology is difficult to solve.By adding biologic packing material in wastewater treatment process, increasing microbial activity and bio-diversity, the metabolic activity of raising microorganism and impact resistance are one of important means of wastewater biological intensive treatment.
Flexible polyurethane foam, owing to it is easy to make, machine-shaping simple, stable performance, is successfully used for preparing bio-carrier and being applied in waste water process.Owing to the hydrophilicity of conventional polyurethanes foam is relatively low, biological affinity is more weak, for improving the load of microorganisms activity of carrier, needs to be modified processing to flexible polyurethane foam by means of different.In all kinds of flexible polyurethane foam modification technologies, a class technology is by the organo-functional group modification (such as: cyanoethylation, amination and sulfonation) of polyurethane foam is improved the hydrophilic of polyurethane foam, permeability, specific surface area etc.；Another kind of technology is by adding activated carbon (CN1478891A), Nano-meter SiO_2 in the preparation process of polyurethane2(CN1631976A), carbon fiber, nano zine oxide, nano concavo-convex material isoreactivity component are to improve the stability of polyurethane foam, bioaffinity.By these modification technologies, enrich and developed the application of polyurethane biologic packing material greatly.
Iron oxides (Fe2O3、Fe(OH)3) there is high surface-active structure and good bioaffinity, Fe element is the essential elements of growth of microorganism simultaneously, it it is the important component part of cytochrome in biological oxidation enzyme system, Fe ion can play electron transmission and the effect of coenzyme activator, growth to numerous microorganisms has facilitation, synergistic catalyst conventional during therefore iron oxides is sewage disposal.After the yardstick of iron oxide particle is reduced to nanoscale, its surface atom number, specific surface area and surface energy etc. all sharply increase with the reduction of particle diameter, thus showing the features such as small-size effect, quantum size effect, skin effect and macro quanta tunnel effect, it has higher surface activity and catalysis activity.But free iron oxide nanoparticles is not only reunited in water body and lost nano effect, and microbial cell can be produced nanometer toxicity.Therefore suitable carrier must be selected to be fixed by nano-iron oxide, it is to avoid it is reunited and loss in water body, and prepare conveniently, to process simple polyurethane foam be preferable nanoparticle vector.
From the preparation technology of conventional polyurethane nano composite material, commonly used directly using the concentrated solution of nano-powder or nano-powder as the additive of polyurethane, then by mechanical means nano-particle disperseed and be prepared.Due to the preparation section of inorganic nanoparticles and the separation of the foamed process of polyurethane, the preparation process not only making composite polyurethane material is relatively cumbersome, increase the preparation cost of material, it is difficult to control the dispersibility of nano-particle, prevent particle agglomeration simultaneously in the preparation process of composite, thus is difficult to ensure that the performance of nano-polyurethane material.
Summary of the invention
Instant invention overcomes nanometer Fe (OH)3Reunion in waste water system and microorganism nanometer toxicity, it is provided that one prepares Fe (OH) at polyurethane foam preparation process situ3The method of nano-particle, improves Fe (OH)3Nano-particle stability in the treatment of waste water and biological activity.
In order to achieve the above object, present invention employs following preparation method:
A kind of nanometer Fe (OH)3The preparation method of composite biological packing, this composite biological packing is Fe (OH)3Nano-particles reinforcement polyurethane foam plastics, its preparation method includes Fe (OH)3The preparation of nano compound polyurethane performed polymer and Fe (OH)3The foaming of nano compound polyurethane performed polymer.
Preferably, described Fe (OH)3Nano compound polyurethane performed polymer completes preparation in microemulsion system, and its preparation method comprises the steps:
(1) base polyurethane prepolymer for use as, cosurfactant, oil solvent and inorganic aqueous solution are mixed；
(2) mixed solution step (1) obtained hybrid reaction 1.5～2 hours under sonic oscillation, make base polyurethane prepolymer for use as fully dispersed in oil solvent, and make inorganic aqueous solution be dispersed into nanoscale droplet in oil solvent；
(3) continue under mechanical stirring to react 0.5～1 hour by the mixed solution that step (2) obtains, make to contact with each other with inorganic aqueous solution droplet at scattered base polyurethane prepolymer for use as, reverse micelle is formed under the effect of cosurfactant, the reverse micelle formed is dispersed in oil solution formation W/O Microemulsion under mechanical stirring, control mechanical agitation speed less than 10rpm, to guarantee the generation of Water-In-Oil microgranule in microemulsion system；
(4) mixed solution evaporation and concentration step (3) obtained, obtains Fe (OH)3Nano compound polyurethane performed polymer；
Above-mentioned inorganic aqueous solution is FeCl3Solution and ammonia spirit.
The time of hybrid reaction described in step (1) is 1.5～2 hours, such as 1.53 hours, 1.56 hours, 1.59 hours, 1.62 hours, 1.65 hours, 1.68 hours, 1.71 hours, 1.74 hours, 1.77 hours, 1.8 hours, 1.83 hours, 1.86 hours, 1.89 hours, 1.92 hours, 1.95 hours or 1.98 hours.
Step (2) the described time continuing reaction is 0.5～1 hour, such as 0.53 hour, 0.56 hour, 0.59 hour, 0.62 hour, 0.65 hour, 0.68 hour, 0.71 hour, 0.74 hour, 0.77 hour, 0.8 hour, 0.83 hour, 0.86 hour, 0.89 hour, 0.92 hour, 0.95 hour or 0.98 hour.
nullPreferably，Base polyurethane prepolymer for use as in step (1)、Cosurfactant、The volume ratio that adds of oil solvent and inorganic aqueous solution is 1:0.2～0.5:8～12:0.2，Such as 1:0.22:8.2:0.2、1:0.24:8.4:0.2、1:0.26:8.6:0.2、1:0.28:8.8:0.2、1:0.3:9:0.2、1:0.32:9.2:0.2、1:0.34:9.4:0.2、1:0.36:9.6:0.2、1:0.38:9.8:0.2、1:0.4:10:0.2、1:0.42:10.2:0.2、1:0.44:10.4:0.2、1:0.44:10.6:0.2、1:0.46:10.8:0.2、1:0.48:11:0.2、1:0.25:11.2:0.2、1:0.35:11.4:0.2、1:0.37:11.6:0.2 or 1:0.45:11.8:0.2.
Preferably, described base polyurethane prepolymer for use as is reacted 2.5～3.5h at 80～85 DEG C with retarder prepared by methyl diphenylene diisocyanate (being called for short MDI), polyhydric alcohol, preferably reacts 2.5h at 80 DEG C.
Described reaction temperature is 80～85 DEG C, such as 80.3 DEG C, 80.6 DEG C, 80.9 DEG C, 81.2 DEG C, 81.5 DEG C, 81.8 DEG C, 82.1 DEG C, 82.4 DEG C, 82.7 DEG C, 83 DEG C, 83.3 DEG C, 83.6 DEG C, 84 DEG C, 84.3 DEG C, 84.6 DEG C or 84.9 DEG C.
The described response time is 2.5～3.5h, such as 2.55h, 2.6h, 2.65h, 2.7h, 2.75h, 2.8h, 2.85h, 2.9h, 2.95h, 3h, 3.05h, 3.1h, 3.15h, 3.2h, 3.25h, 3.3h, 3.35h, 3.4h or 3.45h.
Preferably, in polyurethane prepolymer production procedure, described polyhydric alcohol can be selected for ethylene glycol or/and BDO, preferably ethylene glycol.
Preferably, in polyurethane prepolymer production procedure, described retarder is organic molecule letones, preferably acetone or/and Ketocyclopentane.
Preferably, in polyurethane prepolymer production procedure, the volume ratio of described methyl diphenylene diisocyanate (MDI), polyhydric alcohol and retarder three is 2.2～2.4:1:5, such as 2.22:1:5,2.24:1:5,2.26:1:5,2.28:1:5,2.3:1:5,2.32:1:5,2.34:1:5,2.36:1:5 or 2.38:1:5, preferably 2.4:1:5.
Described cosurfactant can be selected for any one or the mixture of at least two in n-butyl alcohol, isoamyl alcohol or hexanol.The mixture of described mixture such as n-butyl alcohol and isoamyl alcohol, n-butyl alcohol and the mixture of the mixture of hexanol, isoamyl alcohol and hexanol, the mixture of n-butyl alcohol, isoamyl alcohol and hexanol.
Described oil solvent is Pentamethylene..
Described FeCl3The concentration of solution is 0.05～0.1mol/L, such as 0.055mol/L, 0.06mol/L, 0.065mol/L, 0.07mol/L, 0.075mol/L, 0.08mol/L, 0.085mol/L, 0.09mol/L or 0.095mol/L, preferably 0.05mol/L.
The concentration of described ammonia spirit is 0.1～0.2mol/L, such as 0.11mol/L, 0.12mol/L, 0.13mol/L, 0.14mol/L, 0.15mol/L, 0.16mol/L, 0.17mol/L, 0.18mol/L or 0.19 mol/L, preferably 0.2mol/L.
Step (4) described evaporating temperature is 60～75 DEG C, such as 61 DEG C, 62 DEG C, 63 DEG C, 64 DEG C, 65 DEG C, 66 DEG C, 67 DEG C, 68 DEG C, 69 DEG C, 70 DEG C, 71 DEG C, 72 DEG C, 73 DEG C or 74 DEG C, preferably 60 DEG C.
Described Fe (OH)3The foaming of nano compound polyurethane performed polymer is by Fe (OH)3Nano compound polyurethane performed polymer, polyisocyanates, polyether polyol and catalyst 1:40～50:30 by volume～50:0.2 has mixed, such as 1:40:30:0.2,1:40:45:0.2,1:40:50:0.2,1:45:50:0.2 or 1:50:50:0.2.
Preferably, described polyisocyanates can be selected for methyl diphenylene diisocyanate (MDI) or/and toluene di-isocyanate(TDI) (TDI).
Described catalyst comprises two class materials, respectively organic tin material or/and organic amine material.
The two of the purpose of the present invention are to provide a kind of nanometer Fe (OH) prepared by method as defined above3Composite biological packing, described nanometer Fe (OH)3The density of composite biological packing is 1.05～1.1g/L, makes composite biological packing keep suspended state in the treatment of waste water, improves the contact area of filler and waste water.Described density such as 1.055g/L, 1.06g/L, 1.065g/L, 1.07g/L, 1.075g/L, 1.08g/L, 1.085g/L, 1.09g/L or 1.095g/L.
The three of the purpose of the present invention are to provide a kind of nanometer Fe (OH) as above3Composite biological packing, it processes active carrier for microorganism water.
Compared with the prior art, there is advantages that
The present invention is by Fe (OH)3Nano-particle preparation combines with polyurethane foam technology, completes the preparation in situ of the inorganic nanoparticles during polyurethane foam, simplifies the preparation process of nano compound polyurethane material, reduce preparation difficulty.Described method first passes through preparation Fe (OH) in situ3Nano-particles reinforcement base polyurethane prepolymer for use as, then completes foaming, it is to avoid Fe (OH)3The problem that nano-particle is easily reunited.Prepared composite biological packing specific surface area is big, and biological load performance is good, Fe (OH) in filler3Nano-particle is uniformly dispersed, Stability Analysis of Structures, the metabolic activity of microorganism can be promoted, accelerate the biofilm of filling surface microorganism, avoid nano-particle due to the little toxic action that microorganism is produced of particle diameter simultaneously, and improve the frame strength of polyurethane foam filler, increase filler stability and impact resistance.
The present invention is by regulation Fe (OH)3Content in filler, the convenient density controlling prepared filler, it is ensured that filler is in suspended state in wastewater treatment process, improves packing specific area.
Additionally, without adding extra non-polyurethane foam raw material in whole preparation process, it is to avoid Fe (OH)3The destruction of nano grain surface active group.
Detailed description of the invention
Technical scheme is further illustrated below by detailed description of the invention.
Embodiment 1
(1) by volume 2.4 parts of MDI, 1 part of 1,4-butanediol and 5 parts of acetone are reacted at 80 DEG C 2.5h and prepare base polyurethane prepolymer for use as；
(2) by volume by 0.2 part of isoamyl alcohol, 8 parts of Pentamethylene., FeCl of 0.1 part of 0.05mol/L3Solution and 0.1 part of 0.2mol/L ammonia spirit mixing；
(3) mixed solution that above-mentioned 1 part of base polyurethane prepolymer for use as obtains with step (2) is mixed, first hybrid reaction 1.5 hours under sonic oscillation, (mixing speed is less than 10rpm) continues reaction 0.5 hour the most under mechanical stirring, then by mixed solution evaporation and concentration, evaporating temperature is 60 DEG C, obtains Fe (OH)3Nano compound polyurethane performed polymer；
(4) by volume by 40 parts of MDI, 50 parts of ethylene glycol, 0.2 part of dibutyl tin cinnamic acid base and 1 part of Fe (OH)3Nano compound polyurethane performed polymer has mixed polyurethane foam and has prepared nanometer Fe (OH)3Composite biological packing.
Embodiment 2
(1) by volume 2.3 parts of MDI, 1 part of ethylene glycol and 5 parts of acetone are reacted at 85 DEG C 3.5h and prepare base polyurethane prepolymer for use as；
(2) by volume by 0.5 part of n-butyl alcohol, 12 parts of Pentamethylene., FeCl of 0.1 part of 0.05mol/L3Solution and 0.1 part of 0.2mol/L ammonia spirit mixing；
(3) mixed solution that above-mentioned 1 part of base polyurethane prepolymer for use as obtains with step (2) is mixed, first hybrid reaction 2 hours under sonic oscillation, (mixing speed is less than 10rpm) continues reaction 1 hour the most under mechanical stirring, then by mixed solution evaporation and concentration, evaporating temperature is 75 DEG C, obtains Fe (OH)3Nano compound polyurethane performed polymer；
(4) by volume by 40 parts of TDI, 30 parts of ethylene glycol, 0.2 part of dibutyl tin cinnamic acid base and 1 part of Fe (OH)3Nano compound polyurethane performed polymer has mixed polyurethane foam and has prepared nanometer Fe (OH)3Composite biological packing.
Embodiment 3
(1) by volume 2.2 parts of MDI, 1 part of 1,4-butanediol and 5 parts of Ketocyclopentane are reacted at 80 DEG C 2.5h and prepare base polyurethane prepolymer for use as；
(2) by volume by 0.5 part of hexanol, 12 parts of Pentamethylene., FeCl of 0.1 part of 0.05mol/L3Solution and 0.1 part of 0.2mol/L ammonia spirit mixing；
(3) mixed solution that above-mentioned 1 part of base polyurethane prepolymer for use as obtains with step (1) is mixed, first hybrid reaction 1.5 hours under sonic oscillation, (mixing speed is less than 10rpm) continues reaction 0.5 hour the most under mechanical stirring, then by mixed solution evaporation and concentration, evaporating temperature is 60 DEG C, obtains Fe (OH)3Nano compound polyurethane performed polymer；
(4) by volume by 50 parts of MDI, 50 parts of ethylene glycol, 0.2 part of dibutyl tin cinnamic acid base and 1 part of Fe (OH)3Nano compound polyurethane performed polymer has mixed polyurethane foam and has prepared nanometer Fe (OH)3Composite biological packing.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the invention is not limited in above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (23)
1. a nanometer Fe (OH)3The preparation method of composite biological packing, it is characterised in that described method bag
Include Fe (OH)3The preparation of nano compound polyurethane performed polymer and Fe (OH)3Nano compound polyurethane performed polymer
Foaming；
Described Fe (OH)3Nano compound polyurethane performed polymer completes preparation, its preparation side in microemulsion system
Method comprises the steps:
(1) base polyurethane prepolymer for use as, cosurfactant, oil solvent and inorganic aqueous solution are mixed；
(2) mixed solution that step (1) is obtained hybrid reaction 1.5～2 hours under sonic oscillation；
(3) continue under mechanical stirring to react 0.5～1 hour by the mixed solution that step (2) obtains, control
Mechanical agitation speed processed is less than 10rpm；
(4) mixed solution evaporation and concentration step (3) obtained, obtains Fe (OH)3Nano combined poly-ammonia
Ester performed polymer；
Wherein, step (1) described inorganic aqueous solution is FeCl3Solution and ammonia spirit.
2. the method for claim 1, it is characterised in that base polyurethane prepolymer for use as, help surface activity
It is 1:0.2～0.5:8～12:0.2 that the volume of agent, oil solvent and inorganic aqueous solution adds ratio.
3. the method for claim 1, it is characterised in that described base polyurethane prepolymer for use as is by diphenyl
Methane diisocyanate, polyhydric alcohol and retarder react 2.5～3.5h at 80～85 DEG C and prepare.
4. the method for claim 1, it is characterised in that described base polyurethane prepolymer for use as is by diphenylmethyl
Alkane diisocyanate, polyhydric alcohol and retarder react 2.5h at 80 DEG C and prepare.
5. method as claimed in claim 3, it is characterised in that described polyhydric alcohol select ethylene glycol or/and
1,4-butanediol.
6. method as claimed in claim 3, it is characterised in that ethylene glycol selected by described polyhydric alcohol.
7. method as claimed in claim 3, it is characterised in that described retarder is organic molecule ketone
Material.
8. method as claimed in claim 3, it is characterised in that described retarder is acetone or/and ring penta
Ketone.
9. method as claimed in claim 3, it is characterised in that described methyl diphenylene diisocyanate,
The volume ratio of polyhydric alcohol and retarder three is 2.2～2.4:1:5.
10. method as claimed in claim 3, it is characterised in that described methyl diphenylene diisocyanate,
The volume ratio of polyhydric alcohol and retarder three is 2.4:1:5.
11. methods as described in one of claim 1-10, it is characterised in that described cosurfactant selects
With any one in n-butyl alcohol, isoamyl alcohol or hexanol or the mixture of at least two.
12. methods as described in one of claim 1-10, it is characterised in that described oil solvent is Pentamethylene..
13. methods as described in one of claim 1-10, it is characterised in that described FeCl3Solution dense
Degree is 0.05～0.1mol/L.
14. methods as described in one of claim 1-10, it is characterised in that described FeCl3Solution dense
Degree is 0.05mol/L.
15. methods as described in one of claim 1-10, it is characterised in that the concentration of described ammonia spirit
It is 0.1～0.2mol/L.
16. methods as described in one of claim 1-10, it is characterised in that the concentration of described ammonia spirit
For 0.2mol/L.
17. methods as described in one of claim 1-10, it is characterised in that step (4) described evaporation
Temperature is 60～75 DEG C.
18. methods as described in one of claim 1-10, it is characterised in that step (4) described evaporation
Temperature is 60 DEG C.
19. methods as described in one of claim 1-10, it is characterised in that described Fe (OH)3Nanometer is multiple
The foaming closing base polyurethane prepolymer for use as is by Fe (OH)3Nano compound polyurethane performed polymer, polyisocyanates, poly-
Ethoxylated polyhydric alcohol and catalyst 1:40～50:30 by volume～50:0.2 has mixed.
20. methods as claimed in claim 19, it is characterised in that described polyisocyanates selects diphenyl
Methane diisocyanate is or/and toluene di-isocyanate(TDI).
21. methods as claimed in claim 19, it is characterised in that described catalyst is organic tin material
Or/and organic amine material.
The nanometer Fe (OH) that 22. 1 kinds are prepared by the described method of one of claim 1-213Compound bio
Filler, it is characterised in that described nanometer Fe (OH)3The density of composite biological packing is 1.05～1.1g/L.
23. 1 kinds of nanometer Fe as claimed in claim 22 (OH)3The purposes of composite biological packing, its feature
Being, it processes active carrier for microorganism water.
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| CN105060467B (en) * | 2015-08-25 | 2018-05-18 | 桂琪 | A kind of multiporous biological filler and its preparation method and application |
| CN110280127A (en) * | 2019-06-21 | 2019-09-27 | 深圳职业技术学院 | A kind of method of biologic packing material and preparation method thereof and processing VOCs |
| CN112591888B (en) * | 2020-11-25 | 2022-10-25 | 南京神克隆科技有限公司 | MBBR filler for enhancing denitrification performance and preparation method thereof |
| CN113336312A (en) * | 2021-06-04 | 2021-09-03 | 中国科学院重庆绿色智能技术研究院 | Microbial filler and application thereof in ammonia nitrogen removal |
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