CN103539252A - Biologic-photocatalytic composite degradation liquid system and preparation method thereof - Google Patents

Abstract

The invention discloses a biologic-photocatalytic composite degradation liquid system. The biologic-photocatalytic composite degradation liquid system comprises a mixed solution comprising a microbial degradation agent and a photocatalyst, wherein the microbial degradation agent is phanerochaete chrysosporium, and the photocatalyst is the oxalic acid produced by the metabolism of a Fe3O4 nanometer particle and the phanerochaete chrysosporium. The invention also discloses a preparation method of the biologic-photocatalytic composite degradation liquid system, and the preparation comprises the following steps: inoculating a phanerochaete chrysosporium spore suspension into a sterile mixed solution in a sterile condition, and carrying out shake cultivation on the sterile solution under illumination to obtain the biologic-photocatalytic composite degradation liquid system. The biologic-photocatalytic composite degradation liquid system disclosed by the invention can be used for effectively degrading phenol wastewater, and the preparation method has the advantages of scientific and reasonable raw material proportioning, simplicity in operation, low cost and the like.

Description

Bio combined photochemical catalysis composite degradation liquid system and preparation method thereof

Technical field

The present invention relates to the preparation field of degradation agents, be specifically related to a kind of bio combined photochemical catalysis composite degradation liquid system and preparation method thereof.

Background technology

Phenolic wastewater is mainly from production processes such as the industrial sectors such as coke-oven plant, producer gas plant, petroleum chemical plant, insulating material factory and petroleum cracking ethene processed, synthesizing phenol, tynex, synthol, organic pesticide and resol.In phenolic wastewater, mainly contain phenolic group compound as phenol, cresols, xylenol and nitrophenol cresols etc., it is one of important pollutent of water body.Phenolic compound is a kind of protoplasma poisonous substance, to all biologically active bodies, all can produce toxicity, can, by directly entering blood circulation with contacting without liver detoxification of skin, mucous membrane, cause cytoclasis and lose vigor, also can invade human body by oral cavity, cause cell injury.The phenol liquid of high density can make protein coagulating, and can continue to permeate in body, causes deep tissue damage, and necrosis and even whole body are poisoning, even the phenol liquid of lower concentration also can make protein denaturation.If the water that people's long-term drinking is polluted by phenol can cause chronic poisoning, there is anaemia, giddy, be losing one's memory and various neural disease, serious meeting causes death.Phenol and other objectionable impurities interact and produce synergistic effect, become more harmful, promote carcinogenicization.Phenolic wastewater not only brings serious threat to human health, also animals and plants is produced to harm, destroys the eubiosis.Phenols wastewater has a great impact our everyway of life, and the problem that phenols wastewater is processed becomes more complicated and urgent.

Phenol is one of typical organic pollutant in phenolic wastewater, phenol is the simplest phenol organic matter, poisonous, is corrosive, phenol is a kind of common chemical, is the important source material of producing some resin, sterilant, sanitas and medicine (as acetylsalicylic acid).Phenol has strong corrosive nature to skin, mucous membrane, also can suppress central nervous system or infringement liver, renal function.The standard about phenol that American National Environmental Protection Agency (EPA) formulates is pointed out, when the concentration of phenol surpasses 2.56mg/L, can produce chronic toxicity to fresh water hydrobiont; 3.5mg/L phenol content is that this compounds produces the minimum concentration of harm to human body.

Due to the difference of composition, acid-basicity and the concentration of phenolic wastewater, improvement method is also different, and the method for current industrial improvement phenolic wastewater is generally divided into the three major types such as physico-chemical process, chemical method, biochemical process.Biochemical process is to apply more general Treatment of Phenol Containing Water, it is mainly the metabolism that utilizes microorganism, phenolic compound in degradation water, is translated into inorganics to realize innoxious object, main better with the treatment effect of activated sludge process in biochemical process.Photocatalytic method in chemical method is the technology of domestic a kind of Phenol-Containing Wastewater Treatment newly developed, photocatalytic method is mainly to process the phenolic wastewater that copolycondensation method reclaims the lower concentration after resin, add therein photocatalyst, by rayed (UV-light or sunlight) heated and stirred blowing air sampling and measuring after two hours then, get final product stopped reaction after reaching emission standard containing phenol amount; Utilize TiO ₂deng semi-conductor, be the organism such as the thorough degradation of phenol of photocatalyst energy, but it to could produce OH oxidation of organic compounds with ultraviolet excitation, and use TiO ₂ultra-fine micropowder is made catalyzer, has brought great inconvenience to the separation and recovery of catalyst in sewage disposal later stage, thereby has limited the industrial applications of this technology.

Summary of the invention

For solving the deficiencies in the prior art, the invention provides a kind of preparation process simple, easy to operate, with low cost, effectively bio combined photochemical catalysis composite degradation liquid system of degradation of phenol waste water and preparation method thereof.

For solving the problems of the technologies described above, the present invention by the following technical solutions:

A photochemical catalysis composite degradation liquid system, described bio combined photochemical catalysis composite degradation liquid system comprises the mixed solution being comprised of microbiological deterioration agent and photocatalyst.

Described microbiological deterioration agent is Phanerochaete chrysosporium (Phanerochaete chrysosporium), and described photocatalyst is by Fe ₃o ₄the oxalic acid that nanoparticle and Phanerochaete chrysosporium metabolism produce forms.

The volumetric molar concentration of described oxalic acid is 24.45mmol/L～27.35mmol/L.

As a total technical conceive, the present invention also provides a kind of preparation method of above-mentioned bio combined photochemical catalysis composite degradation liquid system, comprises the following steps:

Under gnotobasis, Phanerochaete chrysosporium spore suspension is inoculated into by Fe ₃o ₄in the aseptic mixed solution that nano suspending liquid and liquid nutrient medium form, by aseptic mixed solution shaking culture under illumination, obtain bio combined photochemical catalysis composite degradation liquid system; The inoculum size of described Phanerochaete chrysosporium spore suspension is in the aseptic mixed solution of every 100ml, to inoculate Phanerochaete chrysosporium spore suspension 2ml～3ml.

As the present invention, further improve,

Described Fe ₃o ₄the preparation method of nano suspending liquid is, by FeCl ₃6H ₂o and FeSO ₄7H ₂after the concentrated hydrochloric acid that O is 38% with massfraction mixes, be added in deoxidation ultrapure water and obtain acidic iron salt solutions, wherein, Fe ³⁺, Fe ²⁺with the mol ratio of concentrated hydrochloric acid be 1.8～2: 1: 1, acidic iron salt solutions is dropwise dropped in the NaOH solution of 1.5mol/L, the volume ratio of acidic iron salt solutions and NaOH solution is 1: 5～6, natural subsidence after non magnetic stirring 30min～45min at 70 ℃～80 ℃, remove supernatant liquid and obtain throw out washing, throw out is scattered in 150ml～200ml deoxidation ultrapure water again, prepares Fe ₃o ₄nano suspending liquid.

The preparation method of described aseptic mixed solution is, by Fe ₃o ₄nano suspending liquid adds tween 80 to, in the liquid nutrient medium of pH=4.5～5.5, adds 0.359ml～5.667ml Fe in every 100ml liquid nutrient medium ₃o ₄nano suspending liquid, sterilizing 30min～45min at 105 ℃～115 ℃, then after cooling 30min～60min, make under aseptic condition; Described Fe ₃o ₄the concentration of nano suspending liquid is 20.97mg/ml～27.97mg/ml, and in described liquid nutrient medium, the volume fraction of tween 80 is 0.05%～1.0%.

The preparation method of described Phanerochaete chrysosporium spore suspension is, the Phanerochaete chrysosporium bacterial classification of cultivating 5d～7d in the potato sucrose slant medium of 4 ℃ will be stored in, standby in 28 ℃～30 ℃ activation 18h～24h, under aseptic condition, the Phanerochaete chrysosporium bacterial classification after activation is transferred in the ultrapure water after sterilizing and is mixed, obtain Phanerochaete chrysosporium spore suspension, regulate turbidity to 16%, described Phanerochaete chrysosporium spore suspension miospore concentration is 5.33 * 10 ⁵individual/ml.

The temperature of described shaking culture is 30 ℃～37 ℃, and rotating speed is 120r/min～150r/min, and the time is 2d～3d, and the condition of described illumination is fluorescent lamp.

Described liquid nutrient medium is Kirk liquid nutrient medium.

Bio combined photochemical catalysis composite degradation liquid system of the present invention can be applicable to the degraded of phenolic waste water, specifically comprise the following steps: initial phenolic waste water is added in bio combined photochemical catalysis composite degradation liquid system, under illumination condition, constant temperature oscillation is processed, and completes the degraded to phenolic waste water in system.

Described oscillation treatment rotating speed is 120r/min～150r/min, and temperature is 30 ℃～37 ℃, and the time is 1d～5d.

The time of described oscillation treatment is preferably 3d.

The light source of described illumination condition is common fluorescent lamp.

The concentration that described initial phenolic waste water is added to the phenolic waste water in system after bio combined photochemical catalysis composite degradation liquid system is 20mg/L～120mg/L.

Oxalic acid volumetric molar concentration of the present invention is can form yellow title complex according to oxalate and trivalent titanium ion, and color is deepened with the increase of concentration of oxalic acid, absorbance is the linear principle increasing with the increase of concentration of oxalic acid, with ultraviolet-visible spectrophotometer determine oxalic acid with after titanous chloride colour developing in the absorbancy at 400nm place, and by calculating.

Kirk liquid nutrient medium component of the present invention is: medium base solution (L ^-1) be: KH ₂pO ₄2.0 _g, MgSO ₄7H ₂o 0.71g, VITMAIN B1 0.01g, ammonium tartrate 0.2g, glucose 10g, liquid microelement 100ml, the sodium tartrate damping fluid that buffered soln is 20mmol/L; Liquid microelement composition (L ^-1) be: NaCl 1.0g, CoCl ₂6H ₂o 0.18g, Na ₂moO ₄2H ₂o 0.01g, ZnSO ₄7H ₂o 0.1g, CaCl ₂0.1g, CuSO ₄5H ₂o 0.01g, MnSO ₄h ₂o 0.5g, FeSO ₄7H ₂o 0.1g, AlK (SO ₄) ₂12H ₂o 0.01g, MgSO ₄7H ₂o 3.0g, H ₃bO ₃0.01g, glycine 1.5g.

Compared with prior art, beneficial effect of the present invention is:

Bio combined photochemical catalysis composite degradation liquid system of the present invention comprises mixed solution when being comprised of microbiological deterioration agent and photocatalyst with biological degradation and photocatalytic Degradation, and microbiological deterioration agent is Phanerochaete chrysosporium, and photocatalyst is by Fe ₃o ₄the oxalic acid that nanoparticle and Phanerochaete chrysosporium metabolism produce forms, Fe ₃o ₄nanoparticle is not only free in system, is also wrapped in Phanerochaete chrysosporium outside surface, and structure is special, energy stable existence.

The preparation method of bio combined photochemical catalysis composite degradation liquid system of the present invention is simple, and proportioning raw materials is scientific and reasonable, with low cost, equipment is simple, less investment, treatment process is easy, easy to operate, working cost is low.Oxalic acid in bio combined photochemical catalysis composite degradation liquid system is secreted generation in Phanerochaete chrysosporium metabolic process, oxalic acid volumetric molar concentration is 24.45mmol/L～27.35mmol/L, the present invention has utilized the meta-bolites oxalic acid of microorganism in system, has reduced preparation cost.And in preparation process, shaking culture process time is short under illumination, only needs 2d～3d, and preparation process Raw consumption is few, in the aseptic mixed solution of every 100ml, only need inoculation Phanerochaete chrysosporium spore suspension 2ml～3ml.

Bio combined photochemical catalysis composite degradation liquid system of the present invention can be applicable in the degradation process of phenolic waste water, and effective degradation of phenol waste water, specifically phenolic waste water is added in bio combined photochemical catalysis composite degradation liquid system, by biological degradation and photocatalytic degradation combined degradation phenolic waste water, treating processes is simple to operate, and processing cost is low.Phanerochaete chrysosporium can rely on the catalysis of its Medium peroxidase activity (lignin peroxidase LiP and manganese peroxidase MnP) to carry out degradation of contaminant; Fe under illumination ₃o ₄when the oxalic acid of secreting in nanoparticle and Phanerochaete chrysosporium process of growth coexists, can set up class light Fenton system, form a kind of photocatalyst, compare traditional photochemical catalysis technique, at common fluorescent lamp, irradiate, do not add H ₂o ₂situation under can produce hydroxyl radical free radical (OH) oxidative degradation phenol organism, hydroxyl radical free radical has higher redox potential, can be without being selectively H by the pollutant oxidation of difficult degradation in water ₂o, CO ₂and N ₂deng inorganic molecules.Meanwhile, in the catalytic oxidation process of phenol, also can produce oxalic acid, improve Pyrogentisinic Acid's clearance, effectively remove the phenol in waste water, Pyrogentisinic Acid's clearance reaches more than 90%, in Phenol-Containing Wastewater Treatment, has broad application prospects.

The reaction equation that in Photocatalytic Degradation Process, OH produces is as follows:

$\mathrm{Iron\; oxide}+n{H}_2{C}_2{O}_4\↔{[\≡\mathrm{Fe}{\left(C_2{O}_4\right)}_n]}^{(2n-3)-}---\left(1\right)$

${[\≡\mathrm{Fe}{\left(C_2{O}_4\right)}_n]}^{(2n-3)-}+\mathrm{hv}\→\mathrm{Fe}{\left(C_2{O}_4\right)}_2^{2-}(\mathrm{or}\≡\mathrm{Fe}{\left(C_2{O}_4\right)}_2^{2-})+{\mathrm{CO}}_2{\·}^{-}---\left(2\right)$

${\mathrm{Fe}}^{\mathrm{III}}{\left(C_2{O}_4\right)}_n^{3-2n}+\mathrm{hv}\→{\left[{\mathrm{Fe}}^{\mathrm{II}}{\left(C_2{O}_4\right)}_{n-1}\right]}^{4-2n}+C_2{O}_4{\·}^{-}---\left(3\right)$

C ₂O ₄· ^-→CO ₂+CO ₂· ^- (4)

CO ₂· ^-+O ₂→CO ₂+O ₂· ^- (5)

O ₂· ^-+Fe ³⁺→Fe ²⁺+O ₂ (6)

O ₂· ^-+nH ⁺+Fe ²⁺→Fe ³⁺+H ₂O ₂ (7)

Fe ²⁺+H ₂O ₂→Fe ³⁺+OH ^-+·OH (8)

Phanerochaete chrysosporium in the present invention (BKMF-1767) is purchased from Chinese Typical Representative culture collection center (CCTCC), and preserving number is: CCTCC AF96007, the strain transfer of Phanerochaete chrysosporium is deposited on potato sucrose slant medium.

Accompanying drawing explanation

Fig. 1 is the bio combined photochemical catalysis composite degradation liquid system photo of the present embodiment 1 preparation.

Fig. 2 is the present embodiment 1 load Fe ₃o ₄the photo of Phanerochaete chrysosporium after nanoparticle.

Fig. 3 is the bio combined photochemical catalysis composite degradation liquid system schematic diagram of the present embodiment 1 preparation.

Fig. 4 is without Fe ₃o ₄the photo of the substratum of nanoparticle.

Embodiment

Below in conjunction with Figure of description and specific embodiment, the invention will be further described, but protection domain not thereby limiting the invention.

Bio combined photochemical catalysis composite degradation liquid system of the present invention has the mixed solution of biological degradation and photocatalytic Degradation when being comprised of microbiological deterioration agent and photocatalyst, microbiological deterioration agent is Phanerochaete chrysosporium, and photocatalyst is by Fe ₃o ₄the oxalic acid that nanoparticle and Phanerochaete chrysosporium metabolism produce forms, and the volumetric molar concentration of oxalic acid is 24.45mmol/L～27.35mmol/L.Phanerochaete chrysosporium in the present invention (BKMF-1767) is purchased from Chinese Typical Representative culture collection center (CCTCC), and preserving number is: CCTCC AF96007, the strain transfer of Phanerochaete chrysosporium is deposited on potato sucrose slant medium.Bio combined photochemical catalysis composite degradation liquid system of the present invention can be effectively by microbiological deterioration and photocatalytic Degradation combined degradation phenolic waste water.

Embodiment 1: the preparation method of bio combined photochemical catalysis composite degradation liquid system.

(1), Fe ₃o ₄the preparation of nano suspending liquid: by 9.7936g FeCl ₃6H ₂o and 5.5980g FeSO ₄7H ₂after the concentrated hydrochloric acid that O is 12mol/L with 1.6775ml concentration mixes, be added in 50ml deoxidation ultrapure water and obtain acidic iron salt solutions, taking 18g solid NaOH is dissolved in 300ml deoxidation ultrapure water, above-mentioned acidic iron salt solutions is dropwise dropped in NaOH solution, natural subsidence after non magnetic stirring 30min at 70 ℃, remove supernatant liquid and obtain throw out, throw out again after deoxidation ultrapure water washing, is scattered in 150ml deoxidation ultrapure water again, obtains the Fe that concentration is 27.97mg/ml ₃o ₄nano suspending liquid;

(2), the preparation of Phanerochaete chrysosporium spore suspension: be transferred to by being stored in the Phanerochaete chrysosporium bacterial classification of cultivating 7d in 4 ℃ of potato sucrose slant mediums that to activate 24h in 30 ℃ of fixed temperature and humidity incubators standby, ultrapure water is cooled to normal temperature after 115 ℃ of sterilizing 30min under ultra violet lamp, then under aseptic condition, with the cotton swab of sterilizing, picking Phanerochaete chrysosporium bacterial classification after activation is transferred in the ultrapure water after sterilizing and mixes, obtain Phanerochaete chrysosporium spore suspension, regulate turbidity to 16%, the spore concentration of Phanerochaete chrysosporium spore suspension is 5.33 * 10 ⁵individual/ml,

(3), Fe ₃o ₄the preparation of the aseptic mixed solution that nano suspending liquid and Kirk liquid nutrient medium form: the Fe that is 27.97mg/ml by 5.667ml concentration ₃o ₄nano suspending liquid adds 100ml to, pH=4.5, and containing in the Kirk liquid nutrient medium of 0.05ml tween 80, sterilizing 30min at 115 ℃, then after cooling 60min, obtain Fe under aseptic condition ₃o ₄the aseptic mixed solution of nano suspending liquid and Kirk liquid nutrient medium;

(4), the preparation of bio combined photochemical catalysis composite degradation liquid system: under gnotobasis, be 5.33 * 10 by 3ml spore concentration ⁵the Phanerochaete chrysosporium spore suspension of individual/ml is inoculated into 100ml Fe ₃o ₄the aseptic mixed solution of nano suspending liquid and Kirk liquid nutrient medium, then under the YZ08-T5 of 8W three primary colours fluorescent tube light irradiation, in 30 ℃, constant-temperature shaking culture 3d under 150r/min condition, obtain bio combined photochemical catalysis composite degradation liquid system, as shown in Figure 1 and Figure 2, Fig. 3 is the schematic diagram of bio combined photochemical catalysis composite degradation liquid system.

Result shows, from Fig. 1, Fig. 2 and Fig. 3, the bio combined photochemical catalysis composite degradation liquid system that the present embodiment makes comprises mixed solution when being comprised of microbiological deterioration agent and photocatalyst with microbiological deterioration and photocatalytic Degradation, microbiological deterioration agent is Phanerochaete chrysosporium, and photocatalyst is by Fe ₃o ₄the oxalic acid that nanoparticle and Phanerochaete chrysosporium metabolism produce forms, and oxalic acid volumetric molar concentration is 24.45mmol/L～27.35mmol/L.

Embodiment 2: the preparation method of bio combined photochemical catalysis composite degradation liquid system.

(1), Fe ₃o ₄the preparation of nano suspending liquid is consistent with embodiment 1 step (1);

(2), the preparation of Phanerochaete chrysosporium spore suspension is consistent with embodiment 1 step (2);

(3), Fe ₃o ₄the preparation of the aseptic mixed solution that nano suspending liquid and Kirk liquid nutrient medium form: by 1.820ml, the Fe that concentration is 27.97mg/ml ₃o ₄nano suspending liquid adds 100ml to, pH=4.5, and containing in the Kirk liquid nutrient medium of 0.05ml tween 80, sterilizing 30min at 115 ℃, then after cooling 60min, obtain Fe under aseptic condition ₃o ₄the aseptic mixed solution of nano suspending liquid and Kirk liquid nutrient medium;

(4), the preparation of bio combined photochemical catalysis composite degradation liquid system: under gnotobasis, be 5.33 * 10 by 2ml spore concentration ⁵the Phanerochaete chrysosporium spore suspension of individual/ml is inoculated into 100ml Fe ₃o ₄the aseptic mixed solution that nano suspending liquid and Kirk liquid nutrient medium form, then, under the YZ08-T5 of 8W three primary colours fluorescent tube light irradiation, in 30 ℃, constant-temperature shaking culture 3d under 150r/min condition, obtains bio combined photochemical catalysis composite degradation liquid system.

Embodiment 3: the application of the preparation method of bio combined photochemical catalysis composite degradation liquid system and processing phenolic waste water.

Fe ₃o ₄in the preparation process of the aseptic mixed solution that nano suspending liquid and Kirk liquid nutrient medium form, to adding concentration in six groups of 100mlKirk liquid nutrient mediums, be the Fe of 27.97mg/ml respectively ₃o ₄nano suspending liquid 0.359ml, 1.084ml, 1.820ml, 2.567ml, 3.708ml, 5.667ml, i.e. Fe ₃o ₄nanoparticle is respectively 0.1g/L, 0.3g/L, 0.5g/L, 0.7g/L, 1.0g/L, 1.5g/L with respect to the concentration of aseptic mixed solution, and other preparation processes are consistent with embodiment 1.To the different Fe that prepare ₃o ₄in the bio combined photochemical catalysis composite degradation liquid system of nanoparticle concentration, add 6.383ml, concentration is the initial phenolic waste water of 1000mg/L, in six groups of bio combined photochemical catalysis composite degradation liquid systems, phenol concentration is 60mg/L, and in 30 ℃, 150r/min, under illumination and dark condition, difference shaking culture 3d, completes degraded.Then sampling, utilizes ultraviolet spectrophotometer to measure remaining phenol content in solution, and calculates the clearance of phenol, the results are shown in following table 1.

Result shows, as shown in Table 1, under illumination, Fe in bio combined photochemical catalysis composite degradation liquid system ₃o ₄when nanoparticle concentration is 0.5g/L, the clearance of phenol is the highest, is 93.41%, Fe ₃o ₄nanoparticle excessive concentration or the too low removal that is all unfavorable for phenol.In addition, in table 1 under illumination condition the clearance of phenol apparently higher than the clearance under dark condition, this is mainly because compound system under dark condition is mainly to utilize biological adsorption and biological degradation to process phenolic waste water, and under illumination condition, this compound system also can effectively utilize Fe ₃o ₄nanoparticle-oxalic acid carries out photocatalytic degradation processing in conjunction with the photocatalyst forming, and illustrates that under illumination condition, bio combined photochemical catalysis composite degradation liquid system is mainly by microbiological deterioration and photocatalytic Degradation associated treatment phenolic waste water.

Table 1 is different Fe under illumination and dark condition ₃o ₄the impact of the bio combined photochemical catalysis composite degradation liquid system Pyrogentisinic Acid waste water clearance of nanoparticle concentration

Fe 3O 4Nanoparticle concentration (g/L)	Clearance under illumination (%)	Dark lower clearance (%)
			0.1	65.78	12.82
0.3	67.00	27.58
			0.5	93.41	30.61
0.7	43.26	40.36
			1.0	32.16	28.45
1.5	35.80	23.75

Embodiment 4: utilize the application of bio combined photochemical catalysis composite degradation liquid system degradation of phenol waste water.

Respectively to 100ml Fe ₃o ₄the aqueous solution of nanoparticle, without Fe ₃o ₄the substratum of nanoparticle, Fe ₃o ₄in the mixed solution of nanoparticle-oxalic acid and four groups of systems of bio combined photochemical catalysis composite degradation liquid system, add 6.383ml, the initial phenolic waste water that concentration is 1000mg/L, in four groups of systems, phenol degree is 60mg/L.Fe ₃o ₄fe in the aqueous solution of nanoparticle ₃o ₄the concentration of nanoparticle is 0.5g/L; Without Fe ₃o ₄as shown in Figure 4, this substratum is 5.33 * 10 for having inoculated 2ml spore concentration to the substratum of nanoparticle ⁵the Kirk liquid nutrient medium of the Phanerochaete chrysosporium spore suspension of individual/ml; Fe ₃o ₄fe in nanoparticle-oxalic acid mixed solution ₃o ₄the concentration of nanoparticle is that 0.5g/L, oxalic acid volumetric molar concentration are 4.545mmol/L; Bio combined photochemical catalysis composite degradation liquid system is prepared gained by embodiment 2.To add above four groups of systems of phenolic waste water in illumination, 30 ℃, the 3d that vibrates under the condition of 150r/min, completes the processing of phenolic waste water.And then utilize ultraviolet spectrophotometer to measure the content of processing rear Phenol in Aqueous Solution, and calculate the clearance of phenol, result is as described in Table 2.

Result shows, as shown in Table 2, and Fe ₃o ₄nanoparticle-oxalic acid blended liquid phase compares Fe ₃o ₄the clearance of nanoparticle Pyrogentisinic Acid waste water is higher, and oxalic acid and Fe are described ₃o ₄nanoparticle is the phenol in can better degraded system in conjunction with the photocatalyst of rear formation.During bio combined photochemical catalysis composite degradation liquid system degradation of phenol waste water, clearance has reached 93.41%, obviously more higher than other three groups of system Pyrogentisinic Acids' clearance, illustrate that bio combined photochemical catalysis composite degradation liquid system is by microbiological deterioration and photocatalytic degradation associated treatment phenolic waste water, obviously be better than single microbiological deterioration or photocatalytic degradation, the phenol in effectively removal system.

Shown in Fig. 4 without Fe ₃o ₄phanerochaete chrysosporium in the substratum of nanoparticle is white.So from Fig. 1 and Fig. 2, the Fe in bio combined photochemical catalysis composite degradation liquid system ₃o ₄a nanoparticle part is wrapped in Phanerochaete chrysosporium outside surface, remaining Fe ₃o ₄nanoparticle is free in system.

The impact of the different system Pyrogentisinic Acid's clearances of table 2

System	Clearance (%)
		Fe 3O 4The aqueous solution of nanoparticle	4.40
Without Fe 3O 4The substratum of nanoparticle	41.20
		Fe 3O 4Nanoparticle-oxalic acid mixed solution	14.33
Bio combined photochemical catalysis composite degradation liquid system	93.41

Claims (9)

1. a bio combined photochemical catalysis composite degradation liquid system, is characterized in that: described bio combined photochemical catalysis composite degradation liquid system comprises the mixed solution being comprised of microbiological deterioration agent and photocatalyst.

2. bio combined photochemical catalysis composite degradation liquid system according to claim 1, is characterized in that: described microbiological deterioration agent is Phanerochaete chrysosporium (Phanerochaete chrysosporium), and described photocatalyst is by Fe ₃o ₄the oxalic acid that nanoparticle and Phanerochaete chrysosporium metabolism produce forms.

3. bio combined photochemical catalysis composite degradation liquid system according to claim 2, is characterized in that: the volumetric molar concentration of described oxalic acid is 24.45mmol/L～27.35mmol/L.

4. a preparation method for the bio combined photochemical catalysis composite degradation liquid system as described in claim 1～3 any one, is characterized in that comprising the following steps: under gnotobasis, Phanerochaete chrysosporium spore suspension is inoculated into by Fe ₃o ₄in the aseptic mixed solution that nano suspending liquid and liquid nutrient medium form, by aseptic mixed solution shaking culture under illumination, obtain bio combined photochemical catalysis composite degradation liquid system; The inoculum size of described Phanerochaete chrysosporium spore suspension is in the aseptic mixed solution of every 100ml, to inoculate Phanerochaete chrysosporium spore suspension 2ml～3ml.

5. the preparation method of bio combined photochemical catalysis composite degradation liquid system according to claim 4, is characterized in that: described Fe ₃o ₄the preparation method of nano suspending liquid is, by FeCl ₃6H ₂o and FeSO ₄7H ₂after the concentrated hydrochloric acid that O is 38% with massfraction mixes, be added in deoxidation ultrapure water and obtain acidic iron salt solutions, wherein, Fe ³⁺, Fe ²⁺with the mol ratio of concentrated hydrochloric acid be 1.8～2: 1: 1, acidic iron salt solutions is dropwise dropped in the NaOH solution of 1.5mol/L, the volume ratio of acidic iron salt solutions and NaOH solution is 1: 5～6, natural subsidence after non magnetic stirring 30min～45min at 70 ℃～80 ℃, remove supernatant liquid and obtain throw out washing, throw out is scattered in 150ml～200ml deoxidation ultrapure water again, prepares Fe ₃o ₄nano suspending liquid.

6. according to the preparation method of the bio combined photochemical catalysis composite degradation liquid system described in claim 4 or 5, it is characterized in that: the preparation method of described aseptic mixed solution is, by Fe ₃o ₄nano suspending liquid adds tween 80 to, in the liquid nutrient medium of pH=4.5～5.5, adds 0.359ml～5.667ml Fe in every 100ml liquid nutrient medium ₃o ₄nano suspending liquid, sterilizing 30min～45min at 105 ℃～115 ℃, then after cooling 30min～60min, make under aseptic condition; Described Fe ₃o ₄the concentration of nano suspending liquid is 20.97mg/ml～27.97mg/ml, and in described liquid nutrient medium, the volume fraction of tween 80 is 0.05%～1.0%.

7. the preparation method of bio combined photochemical catalysis composite degradation liquid system according to claim 4, it is characterized in that: the preparation method of described Phanerochaete chrysosporium spore suspension is, the Phanerochaete chrysosporium bacterial classification of cultivating 5d～7d in the potato sucrose slant medium of 4 ℃ will be stored in, standby in 28 ℃～30 ℃ activation 18h～24h, under aseptic condition, the Phanerochaete chrysosporium bacterial classification after activation is transferred in the ultrapure water after sterilizing and is mixed, obtain Phanerochaete chrysosporium spore suspension, regulate turbidity to 16%, described Phanerochaete chrysosporium spore suspension miospore concentration is 5.33 * 10 ⁵individual/ml.

8. according to the preparation method of the bio combined photochemical catalysis composite degradation liquid system described in claim 4 or 5 or 7, it is characterized in that: the temperature of described shaking culture is 30 ℃～37 ℃, rotating speed is 120r/min～150r/min, and the time is 2d～3d, and the condition of described illumination is fluorescent lamp.

9. according to the preparation method of the bio combined photochemical catalysis composite degradation liquid system described in claim 4 or 5 or 7, it is characterized in that: described liquid nutrient medium is Kirk liquid nutrient medium.

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