CN103951968A - Nano Fe(OH)3 composite biological filler as well as preparation method and application thereof - Google Patents

Nano Fe(OH)3 composite biological filler as well as preparation method and application thereof Download PDF

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CN103951968A
CN103951968A CN201410183640.0A CN201410183640A CN103951968A CN 103951968 A CN103951968 A CN 103951968A CN 201410183640 A CN201410183640 A CN 201410183640A CN 103951968 A CN103951968 A CN 103951968A
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composite biological
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CN103951968B (en
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盛宇星
曹宏斌
李玉平
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Institute of Process Engineering of CAS
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Abstract

The invention discloses a nano Fe(OH)3 composite biological filler as well as a preparation method and application thereof. The method is characterized by combining Fe(OH)3 nanoparticle preparation with the polyurethane (PU) foaming technique, firstly preparing a Fe(OH)3 nano PU prepolymer in situ and then completing foaming, thus avoiding the problem that Fe(OH)3 particles are easy to aggregate. The nano Fe(OH)3 composite biological filler and the preparation method have the beneficial effects that the prepared composite biological filler has large specific surface area and good biological load performance; Fe(OH)3 in the filler is uniformly dispersed, has a stable structure and can accelerate the metabolic activity of microorganisms, accelerate the biofilm formation of the microorganisms on the surface of the filler, simultaneously avoid the toxic effects of nanoparticles on the microorganisms due to small particle sizes, improve the skeleton strength of the PU foam filler and improve the stability and impact resistance of the filler; by adjusting the content of Fe(OH)3, the density of the prepared filler is convenient to control, thus ensuring the filler to be in a state of suspension in a wastewater treatment process and increasing the specific surface area of the filler.

Description

A kind of nanometer Fe (OH) 3composite biological packing, preparation method and its usage
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 reactivity, high stability microorganism water treatment active carrier.
Background technology
Modern industry waste water complicated component, pollutant kind are many, and conventional biologic treating technique is difficult to solve.By add biologic packing material in wastewater treatment process, increase microorganism active and species diversity, the metabolic activity and the shock resistance that improve microorganism are one of important means of wastewater biological intensive treatment.
Soft polyurethane ester foam because it is easy to make, simple, the stable performance of machine-shaping, success is for the preparation of bio-carrier and be applied in wastewater treatment.Because the hydrophilicity of conventional polyurethanes foam is lower, biological affinity a little less than, active for improving the load of microorganisms of carrier, need to soft polyurethane ester foam, carry out modification by means of different.In all kinds of soft polyurethane ester foam modification technologies, a class technology is by the wetting ability of the organo-functional group modification to polyurethane foam (as: cyanoethylation, amination and sulfonation) raising polyurethane foam, permeability, specific surface area etc.; Another kind of technology by adding gac (CN1478891A), nanometer SiO in the preparation process of urethane 2(CN1631976A), carbon fiber, nano zine oxide, nano concavo-convex material isoreactivity component are to improve stability, the bioaffinity of polyurethane foam.By these modification technologies, greatly enrich with develop the application of urethane biologic packing material.
Ferriferous oxide (Fe 2o 3, Fe (OH) 3) there is high surface-active structure and good bioaffinity, Fe element is the bioelement of microorganism growth simultaneously, it is the important component part of cytopigment in bio-oxidation enzyme system, Fe ion can play the effect of electronics transmission and coenzyme activator, numerous microbial growths are had to promoter action, so ferriferous oxide is synergistic catalyst conventional in sewage disposal.When the yardstick of iron oxide particle is reduced to after nanoscale, its surface atom number, specific surface area and surface can etc. all with particle diameter reduce and sharply increase, thereby the features such as the small-size effect of showing, quantum size effect, surface effects and macro quanta tunnel effect, it has higher surfactivity and catalytic activity.Yet free iron oxide nanoparticles is not only reunited and is lost nano effect in water body, and can produce nanometer toxicity to microorganism cells.Therefore must select suitable carrier that nano-iron oxide is fixed, avoid its reunion and the loss in water body, and easy to prepare, to process simple polyurethane foam be desirable nanoparticle vector.
From the preparation technology of polyurethane nano composite material in the past, generally adopt and directly using the concentrated solution of nano-powder or nano-powder as the additive of urethane, then by mechanical means, nano particle disperseed and be prepared.Separated due to the preparation section of inorganic nanoparticles and the foamed process of urethane, not only make the preparation process of composite polyurethane material relatively loaded down with trivial details, increase the preparation cost of material, simultaneously in the preparation process of matrix material, be difficult to control nano particle dispersiveness, prevent particle agglomeration, thereby be difficult to guarantee the performance of nano-polyurethane material.
Summary of the invention
The present invention has overcome nanometer Fe (OH) 3reunion in waste water system and microorganism nanometer toxicity, provide a kind of and prepared Fe (OH) at polyurethane foam preparation process situ 3the method of nano particle, has improved Fe (OH) 3stability and the biological activity of nano particle in wastewater treatment.
In order to achieve the above object, the present invention has adopted the method for being prepared as follows:
A kind of nanometer Fe (OH) 3the preparation method of composite biological packing, this composite biological packing is Fe (OH) 3nano particle composite polyurethane porous plastics, its preparation method comprises 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) mixing solutions step (1) being obtained hybrid reaction 1.5～2 hours under sonic oscillation is fully disperseed base polyurethane prepolymer for use as, and is made inorganic aqueous solution in Oil solvent, be dispersed into nanoscale small droplets in Oil solvent;
(3) mixing solutions step (2) being obtained continues reaction 0.5～1 hour under mechanical stirring, make to be in contact with one another at the base polyurethane prepolymer for use as and the inorganic aqueous solution small droplets that disperse, under the effect of cosurfactant, form reverse micelle, formed reverse micelle forms W/O Microemulsion be dispersed in oil solution under mechanical stirring in, control mechanical stirring velocity lower than 10rpm, to guarantee the generation of water-in-oil particulate in microemulsion system;
(4) mixing solutions evaporation concentration step (3) being obtained, obtains Fe (OH) 3nano compound polyurethane performed polymer;
Above-mentioned inorganic aqueous solution is FeCl 3solution and ammonia soln.
The time of hybrid reaction described in step (1) is 1.5～2 hours, for example 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.
The time of the described continuation reaction of step (2) is 0.5～1 hour, for example 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.
Preferably, 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, 1:0.22:8.2:0.2 for example, 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 with retarder and is made by diphenylmethanediisocyanate (being called for short MDI), polyvalent alcohol at 80～85 ℃, preferably at 80 ℃, reacts 2.5h.
Described temperature of reaction is 80～85 ℃, for example 80.3 ℃, 80.6 ℃, 80.9 ℃, 81.2 ℃, 81.5 ℃, 81.8 ℃, 82.1 ℃, 82.4 ℃, 82.7 ℃, 83 ℃, 83.3 ℃, 83.6 ℃, 84 ℃, 84.3 ℃, 84.6 ℃ or 84.9 ℃.
The described reaction times is 2.5～3.5h, for example 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 base polyurethane prepolymer for use as preparation process, the optional spent glycol of described polyvalent alcohol is or/and BDO, preferably ethylene glycol.
Preferably, in base polyurethane prepolymer for use as preparation process, described retarder is organic molecule letones, and preferably acetone is or/and cyclopentanone.
Preferably, in base polyurethane prepolymer for use as preparation process, described diphenylmethanediisocyanate (MDI), polyvalent alcohol and retarder three's volume ratio is 2.2～2.4:1:5, for example 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, be preferably 2.4:1:5.
Described cosurfactant can be selected the mixture of any one or at least two kinds in propyl carbinol, primary isoamyl alcohol or n-hexyl alcohol.Described mixture is the mixture of propyl carbinol and primary isoamyl alcohol for example, the mixture of propyl carbinol and n-hexyl alcohol, the mixture of primary isoamyl alcohol and n-hexyl alcohol, the mixture of propyl carbinol, primary isoamyl alcohol and n-hexyl alcohol.
Described Oil solvent is pentamethylene.
Described FeCl 3the concentration of solution is 0.05～0.1mol/L, and for example 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, be preferably 0.05mol/L.
The concentration of described ammonia soln is 0.1～0.2mol/L, and for example 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 0.19mol/L, be preferably 0.2mol/L.
The described vaporization temperature of step (4) is 60～75 ℃, for example 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃ or 74 ℃, is preferably 60 ℃.
Described Fe (OH) 3the foaming of nano compound polyurethane performed polymer is by Fe (OH) 3nano compound polyurethane performed polymer, polyisocyanates, polyether glycol and catalyzer by volume 1:40～50:30～50:0.2 have mixed, for example 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 diphenylmethanediisocyanate (MDI) or/and tolylene diisocyanate (TDI).
Described catalyzer comprises two class materials, is respectively organic tin material or/and organic amine material.
It is a kind of by method prepares as mentioned above nanometer Fe (OH) that two of object of the present invention is to provide 3composite biological packing, described nanometer Fe (OH) 3the density of composite biological packing is 1.05～1.1g/L, makes composite biological packing in wastewater treatment, keep suspended state, improves the contact area of filler and waste water.Described density is 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 for example.
Three of object of the present invention is to provide a kind of nanometer Fe as above (OH) 3composite biological packing, it is for microorganism water treatment active carrier.
Compared with the prior art, the present invention has following beneficial effect:
The present invention is by Fe (OH) 3nano particle preparation combines with polyurethane foam technology, completes the inorganic nanoparticles original position preparation in polyurethane foam process, has simplified the preparation process of nano compound polyurethane material, has reduced preparation difficulty.First described method prepares Fe (OH) by original position 3nano particle composite polyurethane performed polymer, then completes foaming, has avoided Fe (OH) 3the problem that nano particle is easily reunited.Prepared composite biological packing specific surface area is large, and biological load performance is good, Fe in filler (OH) 3nanoparticulate dispersed is even, Stability Analysis of Structures, can promote the metabolic activity of microorganism, accelerate the biofilm of filling surface microorganism, avoid nano particle due to the little toxic action to microorganisms of particle diameter simultaneously, and improved the frame strength of polyurethane foam filler, increase filler stability and impact resistance.
The present invention is by regulating Fe (OH) 3content in filler, the convenient density of controlling prepared filler, assurance filler in suspended state, improves packing specific area in wastewater treatment process.
In addition, in whole preparation process, without adding extra non-polyurethane foam raw material, avoided Fe (OH) 3the destruction of nano grain surface active group.
Embodiment
Below by embodiment, further illustrate technical scheme of the present invention.
Embodiment 1
(1) by volume 2.4 parts of MDI, 1 part of BDO and 5 parts of acetone are reacted to 2.5h at 80 ℃ and prepare base polyurethane prepolymer for use as;
(2) by volume by the FeCl of 0.2 part of primary isoamyl alcohol, 8 parts of pentamethylene, 0.1 part of 0.05mol/L 3solution and 0.1 part of 0.2mol/L ammonia soln mix;
(3) above-mentioned 1 part of base polyurethane prepolymer for use as is mixed with the mixing solutions that step (2) obtains, first hybrid reaction 1.5 hours under sonic oscillation, then under mechanical stirring, (stirring velocity is lower than 10rpm) continues reaction 0.5 hour, then by mixing solutions evaporation concentration, vaporization temperature is 60 ℃, 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 two lauric acid base and 1 part of Fe (OH) 3nano compound polyurethane performed polymer has mixed polyurethane foam and has made 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 to 3.5h at 85 ℃ and prepare base polyurethane prepolymer for use as;
(2) by volume by the FeCl of 0.5 part of propyl carbinol, 12 parts of pentamethylene, 0.1 part of 0.05mol/L 3solution and 0.1 part of 0.2mol/L ammonia soln mix;
(3) above-mentioned 1 part of base polyurethane prepolymer for use as is mixed with the mixing solutions that step (2) obtains, first hybrid reaction 2 hours under sonic oscillation, then under mechanical stirring, (stirring velocity is lower than 10rpm) continues reaction 1 hour, then by mixing solutions evaporation concentration, vaporization temperature is 75 ℃, 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 two lauric acid base and 1 part of Fe (OH) 3nano compound polyurethane performed polymer has mixed polyurethane foam and has made nanometer Fe (OH) 3composite biological packing.
Embodiment 3
(1) by volume 2.2 parts of MDI, 1 part of BDO and 5 parts of cyclopentanone are reacted to 2.5h at 80 ℃ and prepare base polyurethane prepolymer for use as;
(2) by volume by the FeCl of 0.5 part of n-hexyl alcohol, 12 parts of pentamethylene, 0.1 part of 0.05mol/L 3solution and 0.1 part of 0.2mol/L ammonia soln mix;
(3) above-mentioned 1 part of base polyurethane prepolymer for use as is mixed with the mixing solutions that step (1) obtains, first hybrid reaction 1.5 hours under sonic oscillation, then under mechanical stirring, (stirring velocity is lower than 10rpm) continues reaction 0.5 hour, then by mixing solutions evaporation concentration, vaporization temperature is 60 ℃, 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 two lauric acid base and 1 part of Fe (OH) 3nano compound polyurethane performed polymer has mixed polyurethane foam and has made nanometer Fe (OH) 3composite biological packing.
Applicant's statement, the present invention illustrates detailed method of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed method, does not mean that the present invention must rely on above-mentioned detailed method and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.

Claims (10)

1. a nanometer Fe (OH) 3the preparation method of composite biological packing, is characterized in that, described method comprises Fe (OH) 3the preparation of nano compound polyurethane performed polymer and Fe (OH) 3the foaming of nano compound polyurethane performed polymer.
2. the method for claim 1, is characterized in that, 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) mixing solutions step (1) being obtained hybrid reaction 1.5～2 hours under sonic oscillation;
(3) mixing solutions step (2) being obtained continues reaction 0.5～1 hour under mechanical stirring, controls mechanical stirring velocity lower than 10rpm;
(4) mixing solutions evaporation concentration step (3) being obtained, obtains Fe (OH) 3nano compound polyurethane performed polymer;
Wherein, the described inorganic aqueous solution of step (1) is FeCl 3solution and ammonia soln;
Preferably, to add ratio be 1:0.2～0.5:8～12:0.2 to the volume of base polyurethane prepolymer for use as, cosurfactant, Oil solvent and inorganic aqueous solution.
3. method as claimed in claim 2, is characterized in that, described base polyurethane prepolymer for use as reacts 2.5～3.5h with retarder by diphenylmethanediisocyanate, polyvalent alcohol and makes at 80～85 ℃, preferably at 80 ℃, reacts 2.5h and makes.
4. method as claimed in claim 3, is characterized in that, ethylene glycol selected by described polyvalent alcohol or/and BDO, preferably ethylene glycol;
Preferably, described retarder is organic molecule letones, and preferably acetone is or/and cyclopentanone;
Preferably, described diphenylmethanediisocyanate, polyvalent alcohol and retarder three's volume ratio is 2.2～2.4:1:5, preferably 2.4:1:5.
5. the method as described in one of claim 2-4, is characterized in that, described cosurfactant is selected the mixture of any one or at least two kinds in propyl carbinol, primary isoamyl alcohol or n-hexyl alcohol;
Preferably, described Oil solvent is pentamethylene.
6. the method as described in one of claim 2-5, is characterized in that, described FeCl 3the concentration of solution is 0.05～0.1mol/L, is preferably 0.05mol/L;
Preferably, the concentration of described ammonia soln is 0.1～0.2mol/L, is preferably 0.2mol/L.
7. the method as described in one of claim 2-6, is characterized in that, the described vaporization temperature of step (4) is 60～75 ℃, is preferably 60 ℃.
8. the method as described in one of claim 1-7, is characterized in that, described Fe (OH) 3the foaming of nano compound polyurethane performed polymer is by Fe (OH) 3nano compound polyurethane performed polymer, polyisocyanates, polyether glycol and catalyzer by volume 1:40～50:30～50:0.2 have mixed;
Preferably, described polyisocyanates is selected diphenylmethanediisocyanate or/and tolylene diisocyanate;
Preferably, described catalyzer is that organic tin material is or/and organic amine material.
9. the nanometer Fe (OH) being prepared by the described method of one of claim 1-8 3composite biological packing, is characterized in that, described nanometer Fe (OH) 3the density of composite biological packing is 1.05～1.1g/L.
10. a nanometer Fe as claimed in claim 9 (OH) 3the purposes of composite biological packing, is characterized in that, it is for microorganism water treatment active carrier.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104342431A (en) * 2014-11-03 2015-02-11 遵义医学院 Preparation method of magnetic nanometer carrier for immobilized enzyme
CN105060467A (en) * 2015-08-25 2015-11-18 桂琪 Porous biological stuffing, preparing method thereof and application thereof
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
CN112591888A (en) * 2020-11-25 2021-04-02 南京神克隆环保科技有限公司 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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CN1704157A (en) * 2004-05-05 2005-12-07 兰克赛斯德国有限公司 Foam material for removing pollutants and/or heavy metal from floating medium
CN101070425A (en) * 2007-06-15 2007-11-14 中国科学院广州地球化学研究所 Method for preparing composite magnetic polyurethane foam carrier and use thereof

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CN1704157A (en) * 2004-05-05 2005-12-07 兰克赛斯德国有限公司 Foam material for removing pollutants and/or heavy metal from floating medium
CN101070425A (en) * 2007-06-15 2007-11-14 中国科学院广州地球化学研究所 Method for preparing composite magnetic polyurethane foam carrier and use thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104342431A (en) * 2014-11-03 2015-02-11 遵义医学院 Preparation method of magnetic nanometer carrier for immobilized enzyme
CN105060467A (en) * 2015-08-25 2015-11-18 桂琪 Porous biological stuffing, preparing method thereof and application thereof
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
CN112591888A (en) * 2020-11-25 2021-04-02 南京神克隆环保科技有限公司 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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