CN102603083A - Biological nanocomposite materials for removing organic matter out of water - Google Patents
Biological nanocomposite materials for removing organic matter out of water Download PDFInfo
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- CN102603083A CN102603083A CN2012101015448A CN201210101544A CN102603083A CN 102603083 A CN102603083 A CN 102603083A CN 2012101015448 A CN2012101015448 A CN 2012101015448A CN 201210101544 A CN201210101544 A CN 201210101544A CN 102603083 A CN102603083 A CN 102603083A
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Abstract
The invention belongs to the technical field of water purification, and particularly relates to a series of biological nanocomposite materials which use fungi as the continuous phase matrix and nano materials as the dispersed phase and are capable of effectively removing organic matter out of water. By organic integration of active groups on the surfaces of microbes with nano materials, the biological nanocomposite materials which are capable of effectively removing organic matter out of water and easy to recycle are obtained. The nano materials involved in the invention can be metallic oxide nano materials or metal hydroxide nano materials, specifically TiO2 nanotube, Al2O3 nanofiber, AIOOH nanofiber and CuO nanorod, and involved strains can be aspergillus niger, mucor mucedo, penicillium, etc..
Description
Technical field
The invention belongs to the water treatment technology field, be specifically related to a series of be the external phase matrix with the fungi, with the nano material be disperse phase and can efficiently remove organic biological nano matrix material in the water.
Background technology
The environmental problem that China reaches in significant period of time from now at present mainly is a water environmental problems, and water environmental problems mainly is again the pollution problem of organic waste water.Therefore, the improvement of organic waste water is extremely important one side in the efforts at environmental protection.Food, ferment, butcher, to reclaim town domestic sewage be the main source of organic waste water for trade effluent such as leather, papermaking, sugaring, rubber, weaving, printing and dyeing, agricultural chemicals, coking, petrochemical complex and useless household electrical appliances, the exhausted big major part in the organic waste water can have direct or indirect, acute or chronic intoxicating effect to human body.
At present, organic water treatment method mainly contains in the removal waste water: air stripping method, sterilization and disinfection technology, carbon filter technology, ion exchange technique, membrane separation technique, " coagulation-deposition-filtration " technology etc.These water technologies can effectively be controlled the organic content in the water, have that efficient is low, cost is high, a problem such as regeneration difficulty, though the photocatalytic degradation technology efficient of nano material is high, pollute lowly, but nano-grain is too little, is difficult to recovery.
Summary of the invention
The purpose of this invention is to provide a kind of with mikrobes such as fungi be external phase matrix, nano material be disperse phase can effectively remove organic biological nano matrix material in the water.The present invention utilizes reactive group and the nano material on mikrobe surface organically to integrate, thus the biological nano matrix material that acquisition can effectively be removed organism in the water and is easy to reclaim.
Biological nano matrix material of the present invention, it is prepared by following steps:
1) 0.5~0.7g peptone, 0.7~0.9g glucose are joined in the triangular flask that fills 40ml zero(ppm) water, stir, in mixed solution, add 0.1~0.3g nano material again; Then triangular flask is placed the ultrasonic 15~20min of ultrasonic cleaner, be transferred to high-pressure steam sterilizing pan again, keeping temperature is 121 ℃, and sterilization 20~30min is dissolved in the zero(ppm) water peptone and glucose fully, and reaches the disinfectant purpose; When liquid to be mixed is cooled to 70~80 ℃, in sterilisable chamber,, prepare liquid nutrient medium after the vibration evenly toward wherein adding 0.1~0.2g glycerine;
2) get bacterial classification and the rifle head is put in the aforesaid liquid substratum in that aseptic indoor 10 μ l rifle heads are sticking, triangular flask is sealed be placed on the constant-temperature shaking culture case and cultivate 48~72h, culture temperature is 30~38 ℃, and the incubator rotating speed is 150~200rpm;
3) mixed aqueous solution of preparation Hydrocerol A and Trisodium Citrate, wherein the massfraction of Hydrocerol A is 0.05~0.1%, the massfraction of Trisodium Citrate is 1~2%;
4) with step 2) the thalline solution that obtains isolates the thalline matrix material with 200 order stainless steel sieves; Clarify with mixed aqueous solution cleaning this matrix material to the washings of Hydrocerol A and Trisodium Citrate again, then this matrix material is placed sterilization 20~30min in the high-pressure steam sterilizing pan; Can obtain organic biological nano matrix material in the removal water of the present invention through post-processed at last.
Post-processed described in the above-mentioned steps is in matrix material, progressively to add alcohol; At first making the volume(tric)fraction of alcohol in solution is 20~30%; Making volume(tric)fraction after 15~20 minutes is 40~50%, is 75~80% through making volume(tric)fraction after 15~20 minutes again; Then matrix material is put into the drying cupboard that has siccative, temperature remains on 40~50 ℃, continues 5~6 hours.
The nano material that relates in the above-mentioned steps can (concrete can be TiO for length 100~300nm, particle diameter 5~10nm) for metal oxide nano-material or metal hydroxides nano material
2Nanotube, Al
2O
3Nanofiber, AIOOH nanofiber, CuO nanometer rod etc., the bacterial classification that relates to can be black mold, mucor mucedo, penicillium spp etc.
Description of drawings
TiO described in Fig. 1: the embodiment 1
2The transmission electron microscope photo of the compound water-purifying material of/black mold;
Al described in Fig. 2: the embodiment 2
2O
3The stereoscan photograph of the compound water-purifying material of/mucor mucedo;
The stereoscan photograph of the compound water-purifying material of AIOOH/ penicillium spp described in Fig. 3: the embodiment 3.
From two figure, can find out TiO
2, Al
2O
3Reach the AIOOH nano material and can both be compounded in the thalline surface uniformly, almost do not have the existence of agglomeration.Make the heavy metal ion in nano material and the water that bigger contact rate arranged.
Embodiment
Embodiment 1: by TiO
2The biological nano matrix material of nanotube and black mold preparation.
0.5g peptone, 0.7g glucose are joined in the 50ml triangular flask that fills 40ml zero(ppm) water, stir; In mixed solution, add 0.1g TiO
2Nanotube, triangular flask place the ultrasonic 20min of ultrasonic cleaner; Triangular flask is transferred to and keeps 121 ℃ of sterilizations of temperature 20min in the high-pressure steam sterilizing pan, peptone and glucose is dissolved in the zero(ppm) water fully, and reaches the disinfectant purpose; To be cooled after 70 ℃, in sterilisable chamber,, promptly prepare liquid nutrient medium after the vibration evenly toward wherein adding 0.2g glycerine;
Get aspergillus niger strain and the rifle head is put in the liquid nutrient medium in that aseptic indoor 10 μ l rifle heads are sticking, triangular flask is sealed be placed on the constant-temperature shaking culture case and cultivate, culture cycle is 60h, and culture temperature is 30 ℃, and the incubator rotating speed is 150rpm;
To use massfraction be 0.05% Hydrocerol A and massfraction is that 2% sodium citrate aqueous solution constantly cleans to the washings clarification with the thalline matrix material of thalline solution after 200 mesh are separated, and places the 20min that sterilizes in the high-pressure steam sterilizing pan then;
In the thalline matrix material, progressively add alcohol, at first making the volume(tric)fraction of alcohol in solution is that to make volume(tric)fraction after 20%, 15 minute be 40%, is 75% through making volume(tric)fraction after 15 minutes again; Then matrix material is put into the drying cupboard that has siccative, temperature remains on 50 ℃, continues 6 hours, thereby obtains black mold nano composite material 0.15 gram.
The Biocomposite material of present embodiment preparation contains in the organic sewage experiment of polysaccharide (starch) (concentration is 1.0g/L) in processing, and the experimental data of table 1 shows through COD (COD) test, black mold TiO
2Nano water purifying material has very strong adsorptive power to organism, and the COD that the water quality after the absorption meets regulation in China's ground water environment quality standard (GB3838-88) goes out water quality standard (15mg/L).
Table 1: black mold TiO
2Nano composite material is to putting organic absorption result
OCD (mg/L) before the absorption | Absorption back OCD (mg/L) | Adsorption rate |
101 | 1.1 | 99% |
Embodiment 2: by Al
2O
3The biological nano matrix material of nanofiber mucor mucedo preparation
0.7g peptone, 0.9g glucose are joined in the 50ml triangular flask that fills 40ml zero(ppm) water, stir; In mixed solution, add 0.1g Al
2O
3Nanofiber, triangular flask place the ultrasonic 20min of ultrasonic cleaner; Triangular flask is transferred to and keeps 121 ℃ of sterilizations of temperature 20min in the high-pressure steam sterilizing pan, peptone and glucose is dissolved in the zero(ppm) water fully, and reaches the disinfectant purpose; To be cooled after 80 ℃, in sterilisable chamber,, promptly prepare liquid nutrient medium after the vibration evenly toward wherein adding 0.2g glycerine;
Get the mucor mucedo bacterial classification and the rifle head is put in the liquid nutrient medium in that aseptic indoor 10 μ l rifle heads are sticking, triangular flask is sealed be placed on the constant-temperature shaking culture case and cultivate, culture cycle is 48h, and culture temperature is 38 ℃, and the incubator rotating speed is 150rpm;
To use massfraction be 0.1% Hydrocerol A and massfraction is that 1% sodium citrate aqueous solution constantly cleans to the washings clarification with the thalline matrix material of thalline solution after 200 mesh are separated, and places the 25min that sterilizes in the high-pressure steam sterilizing pan then;
In matrix material, progressively add alcohol, at first making the volume(tric)fraction of alcohol in solution is that to make volume(tric)fraction after 30%, 20 minute be 50%, is 80% through making volume(tric)fraction after 20 minutes again; Then matrix material is put into the drying cupboard that has siccative, temperature remains on 50 ℃, continues 5 hours.Thereby obtain black mold nano composite material 0.25 gram.
The Biocomposite material of present embodiment preparation contains in the organic sewage experiment of polysaccharide (starch) (concentration is 1.0g/L) in processing, and the experimental data of table 2 shows through COD (COD) test, black mold TiO
2Nano water purifying material has very strong adsorptive power to organism, and the COD that the water quality after the absorption meets regulation in China's ground water environment quality standard (GB3838-88) goes out water quality standard (15mg/L).
Table 2: mucor mucedo Al
2O
3Nano composite material is to putting organic absorption result
OCD (mg/L) before the absorption | Absorption back OCD (mg/L) | Adsorption rate |
105 | 1.5 | 98% |
Embodiment 3: by the biological nano matrix material of AIOOH nanofiber penicillium spp preparation
0.6g peptone, 0.8g glucose are joined in the 50ml triangular flask that fills 40ml zero(ppm) water, stir; In mixed solution, add 0.3g AIOOH nanofiber, triangular flask places the ultrasonic 15min of ultrasonic cleaner; Triangular flask is transferred to and keeps 121 ℃ of sterilizations of temperature 25min in the high-pressure steam sterilizing pan, peptone and glucose is dissolved in the zero(ppm) water fully, and reaches the disinfectant purpose; To be cooled after 70 ℃, in sterilisable chamber,, promptly prepare liquid nutrient medium after the vibration evenly toward wherein adding 0.1g glycerine;
Get the penicillium spp bacterial classification and the rifle head is put in the liquid nutrient medium in that aseptic indoor 10 μ l rifle heads are sticking, triangular flask is sealed be placed on the constant-temperature shaking culture case and cultivate, culture cycle is 72h, and culture temperature is 30 ℃, and the incubator rotating speed is 150rpm;
To use massfraction be 0.05% Hydrocerol A and massfraction is that 2% sodium citrate aqueous solution constantly cleans to the washings clarification with the thalline matrix material of thalline solution after 200 mesh are separated, and places the 30min that sterilizes in the high-pressure steam sterilizing pan then;
In matrix material, progressively add alcohol, at first making the volume(tric)fraction of alcohol in solution is that to make volume(tric)fraction after 20%, 15 minute be 40%, is 75% through making volume(tric)fraction after 15 minutes again; Then matrix material is put into the drying cupboard that has siccative, temperature remains on 40 ℃, continues 6 hours.Thereby obtain black mold nano composite material 0.18 gram.
The Biocomposite material of present embodiment preparation contains in the organic sewage experiment of polysaccharide (starch) (concentration is 1.0g/L) in processing, and the experimental data of table 3 shows through COD (COD) test, black mold TiO
2Nano water purifying material has very strong adsorptive power to organism, and the COD that the water quality after the absorption meets regulation in China's ground water environment quality standard (GB3838-88) goes out water quality standard (15mg/L).
Table 3: penicillium spp AIOOH nano composite material is to putting organic absorption result
OCD (mg/L) before the absorption | Absorption back OCD (mg/L) | Adsorption rate |
98 | 1.0 | 99% |
Claims (5)
1. remove organic biological nano matrix material in the water for one kind, it is by following method preparation:
1) 0.5~0.7g peptone, 0.7~0.9g glucose are joined in the triangular flask that fills 40ml zero(ppm) water, stir, in mixed solution, add 0.1~0.3g nano material again; Then triangular flask is placed the ultrasonic 15~20min of ultrasonic cleaner, be transferred to high-pressure steam sterilizing pan again, keeping temperature is 121 ℃, and sterilization 20~30min is dissolved in the zero(ppm) water peptone and glucose fully, and reaches the disinfectant purpose; When liquid to be mixed is cooled to 70~80 ℃, in sterilisable chamber,, prepare liquid nutrient medium after the vibration evenly toward wherein adding 0.1~0.2g glycerine;
2) get bacterial classification and the rifle head is put in the aforesaid liquid substratum in that aseptic indoor 10 μ l rifle heads are sticking, triangular flask is sealed be placed on the constant-temperature shaking culture case and cultivate 48~72h, culture temperature is 30~38 ℃, and the incubator rotating speed is 150~200rpm;
3) mixed aqueous solution of preparation Hydrocerol A and Trisodium Citrate, wherein the massfraction of Hydrocerol A is 0.05~0.1%, the massfraction of Trisodium Citrate is 1~2%;
4) with step 2) the thalline solution that obtains isolates the thalline matrix material with 200 order stainless steel sieves; Clarify with mixed aqueous solution cleaning this matrix material to the washings of Hydrocerol A and Trisodium Citrate again, then this matrix material is placed sterilization 20~30min in the high-pressure steam sterilizing pan; Can obtain removing organic biological nano matrix material in the water through post-processed at last.
2. organic biological nano matrix material in a kind of removal water as claimed in claim 1 is characterized in that: bacterial classification is black mold, mucor mucedo or penicillium spp.
3. organic biological nano matrix material in a kind of removal water as claimed in claim 1; It is characterized in that: the post-processed in the step 4) is in matrix material, progressively to add alcohol; At first making the volume(tric)fraction of alcohol in solution is 20~30%; Making volume(tric)fraction after 15~20 minutes is 40~50%, is 75~80% through making volume(tric)fraction after 15~20 minutes again; Then matrix material is put into the drying cupboard that has siccative, temperature remains on 40~50 ℃, continues 5~6 hours.
4. organic biological nano matrix material in a kind of removal water as claimed in claim 1 is characterized in that: nano material is metal oxide nano-material or metal hydroxides nano material, length 100~300nm, particle diameter 5~10nm.
5. organic biological nano matrix material in a kind of removal water as claimed in claim 4 is characterized in that: nano material is TiO
2Nanotube, Al
2O
3Nanofiber, AIOOH nanofiber or CuO nanometer rod.
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Cited By (1)
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CN104609574A (en) * | 2015-02-05 | 2015-05-13 | 苏州大学 | Preparation method of microorganism-nano particle composite system used for degrading phenol |
Citations (4)
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US6416668B1 (en) * | 1999-09-01 | 2002-07-09 | Riad A. Al-Samadi | Water treatment process for membranes |
US20030010712A1 (en) * | 2001-04-18 | 2003-01-16 | Minghua Gao | Process for biochemical treatment of waste water using nano materials |
CN1544343A (en) * | 2003-11-19 | 2004-11-10 | 吉林大学 | Nanometer water purifying material for organic removal, its preparation method and uses |
CN101700925A (en) * | 2009-11-18 | 2010-05-05 | 吉林大学 | Method for preparing biological composite nano-water-purifying materials for removing radioactive substances in water |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6416668B1 (en) * | 1999-09-01 | 2002-07-09 | Riad A. Al-Samadi | Water treatment process for membranes |
US20030010712A1 (en) * | 2001-04-18 | 2003-01-16 | Minghua Gao | Process for biochemical treatment of waste water using nano materials |
CN1544343A (en) * | 2003-11-19 | 2004-11-10 | 吉林大学 | Nanometer water purifying material for organic removal, its preparation method and uses |
CN101700925A (en) * | 2009-11-18 | 2010-05-05 | 吉林大学 | Method for preparing biological composite nano-water-purifying materials for removing radioactive substances in water |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104609574A (en) * | 2015-02-05 | 2015-05-13 | 苏州大学 | Preparation method of microorganism-nano particle composite system used for degrading phenol |
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