CN108483680B - Handle heavy metal wastewater thereby biological adsorption device and preparation method thereof - Google Patents

Handle heavy metal wastewater thereby biological adsorption device and preparation method thereof Download PDF

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CN108483680B
CN108483680B CN201810591279.3A CN201810591279A CN108483680B CN 108483680 B CN108483680 B CN 108483680B CN 201810591279 A CN201810591279 A CN 201810591279A CN 108483680 B CN108483680 B CN 108483680B
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adsorption
rhizopus oryzae
heavy metal
preparation
starchy material
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CN108483680A (en
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高迅
刘德洋
陈哲
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Jiangsu Disaisi Automation Engineering Co ltd
Hohai University HHU
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Jiangsu Disaisi Automation Engineering Co Ltd
Hohai University HHU
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Abstract

The invention discloses a kind of processing heavy metal wastewater thereby biological adsorption devices and preparation method thereof, include the following steps, it 1) is shape in spherical, the internal immobilized cell ball in porous network structure by the pseudomonas pseudoalcaligenes collected after mixing fermentation culture and saccharomyces cerevisiae mixing thallus immobilization;2) using starchy material hydrolyzate as culture medium, Rhizopus oryzae spore suspension is accessed under conditions of pH=3-6, after shaken cultivation 24-48h, is collected by filtration to obtain diameter to be 50-100um Rhizopus oryzae pompon;3) immobilized cell ball and Rhizopus oryzae pompon are filled in biological adsorption device, which is concatenated by more adsorption columns;4) after the initial concentration of heavy metal ion≤800mg/L of heavy metal wastewater thereby adjustment, PH=5-7, biological adsorption device is flowed through, the hydraulic detention time 0.5-1h in every adsorption column.Using inhomogeneous microorganism live bacteria, under the action of different adsorption mechanisms, has to different heavy metals (Cd2+, Hg2+, Cu2+, Zn2+, Ni2+, Ag2+, Pb2+) and adsorb well.

Description

Handle heavy metal wastewater thereby biological adsorption device and preparation method thereof
Technical field
The present invention relates to sewage treatment field, in particular to a kind of processing heavy metal wastewater thereby biological adsorption device and its preparation Method.
Background technique
At present, process for treating heavy-metal waste water mainly has three classes: chemical reaction method, concentration and separation method and biological adsorption Method.The first kind be heavy metal ions in wastewater by the method that chemical reaction removes include neutralization precipitation method, sulphide precipitation, Ferrite coprecipitation, chemical reduction method, electrochemical reducing and high molecular heavy metals trapping agent method etc.;Second class is to make waste water In the heavy metal method that is concentrated, is separated under conditions of not changing its chemical form, including adsorbent absorption, ion hands over Change with UF membrane etc.;Third class biosorption process is a heavy metal-polluted method for treating water of new development in this year, by be micro- Biology and its derivative carry out the process of adsorbing heavy metal in water.
Compared with traditional adsorption method, 1) biosorption process has the advantage that at low concentrations, and metal can be selected The removal of property;2) energy conservation, treatment effeciency are high;3) it is easily isolated and recycled heavy metal 5) adsorbent is easy to regeneration.
The key of biosorption technology is to select suitable biological adsorption agent.Biological adsorption agent mostly uses living body and inactivation Two kinds of biological cell.Compared with inactivation biological cell, the adsorbance of living body biological cell absorption is more larger, adsorption process point 2 stages.1st stage is unrelated with metabolism, for biological adsorption process, carries out comparatively fast, in the process, metal ion can be by matching One or more of the effects of position, chelating are with ion exchange, physical absorption and microdeposit is compound to cell surface;2nd stage For biological cumulative process, progress is slower, and in the process, metal is transported into the cell.
But at present in document more will lose activity using single kind microorganism as biological adsorption agent, or mostly Microorganism and common adsorbent, such as active carbon, humic acid, sepiolite, polysaccharide resins are mixed with.Biological adsorption Mechanism is often different and different because of strain, and the source of biomaterial is very extensive, thus selects suitable strain as absorption Agent is particularly important.
Summary of the invention
The present invention provides a kind of processing heavy metal wastewater thereby biological adsorption device and preparation method thereof, utilizes inhomogeneous micro- life Object viable bacteria, under the action of different adsorption mechanisms, to different heavy metal (Cd2+, Hg2+, Cu2+, Zn2+, Ni2+, Ag2+, Pb2+ it) is adsorbed.
To solve the above-mentioned problems, the technical solution adopted by the present invention is that such: a kind of side handling heavy metal wastewater thereby Method includes the following steps,
1) preparation of immobilized cell ball: A) by polyvinyl alcohol, calcium alginate, acryloyl and water in mass ratio 6~15: After 0.5~1.5:3~5:100 ratio is mixed, the polyvinyl alcohol hydrosol is obtained, the class collected after mixing fermentation culture is produced into alkali Pseudomonad and saccharomyces cerevisiae thallus, which are added, forms mixed solution into the polyvinyl alcohol hydrosol, wherein Pseudomonas alcaligenes and The additive amount of saccharomyces cerevisiae thallus meet the Pseudomonas alcaligenes that 4-6g weight in wet base is added in the polyvinyl alcohol hydrosol of every 100mL and Saccharomyces cerevisiae Mixed Microbes;B) mixed solution is added to peristaltic pump containing 3~5w/v%N '-methylene-bisacrylamide and 1- In the saturation boric acid solution of 2w/v%CaSO4, gel ball is formed, cooling 5-10h, thaws, so at room temperature under the conditions of placing -20 DEG C Gel ball investment mass concentration is 0.2~0.5g/L phosphorus after thawing at room temperature by cooling 1-2h under the conditions of being placed in -10 DEG C again afterwards In hydrochlorate, shape is obtained in spherical, the internal immobilized cell ball in porous network structure;
2) preparation of Rhizopus oryzae pompon: A) commercially available starchy material is crushed, obtaining average grain diameter is that 500-1000 is micro- Micro- starchy material of rice;B after micro- starchy material and water) are mixed into paste with the ratio of 150-200%, it is heated to 40- 70 DEG C, amylase is added and plant rennet, amylase enzyme concentration are not the micro- starchy material of 1200-1500U/g, vegetable protein The dosage of enzyme is the 0.1-0.2wt% of micro- starchy material, then passes through the silk screen filter of 800-1000 mesh while hot, obtains uniform Filtrate adds water sugar addition after filtrate is cooling, and it is 20-30g/L starchy material hydrolyzate, gained starchy material that total reducing sugar, which is made, Hydrolyzate with starchiness hydrolysis clear liquid with starchiness hydrolytic residue particle by forming, the starchiness hydrolysis clear liquid and starchiness water The weight ratio for solving particle is 90-95:5-10;C it) using starchy material hydrolyzate as culture medium, is accessed under conditions of pH=3-6 Rhizopus oryzae spore suspension, concentration is 105-106/mL to spore in the medium after inoculation, in 25-30 DEG C, 200-250rpm Revolving speed under, after shaken cultivation 24-48h, being collected by filtration to obtain diameter is 50-100um Rhizopus oryzae pompon;
3) preparation of biological adsorption device: the biological adsorption device is concatenated by more adsorption columns, the adsorption column It is provided with water inlet on lower sides, overfall is provided in adsorption column upper portion side wall, upper screen cloth is provided in adsorption column under Sieve, upper screen cloth position are higher than the position where water inlet, and lower screen cloth position is lower than the position where overfall, institute It is filled with immobilized cell ball and Rhizopus oryzae pompon in the adsorption space that the adsorption column side wall and upper and lower sieve stated are surrounded, The volume packing ratio of immobilized cell ball and Rhizopus oryzae pompon is 60-90:10-40, and the two is in the total filling rate of adsorption space 50-80% also sets up in the adsorption space and is equipped with annular guide shell, the top and bottom of the annular guide shell respectively with it is upper Sieve and lower screen cloth do not contact, and absorption column bottom is provided with aerator, which is located at below annular guide shell;
4) processing of heavy metal wastewater thereby: by concentration of heavy metal ion adjustment≤800mg/L initial in heavy metal wastewater thereby, PH tune It is whole for after 5-7, the hydraulic detention time 0.5-1h followed by biological adsorption device, in every adsorption column.
Preferably, the mixing fermentation culture process of pseudomonas pseudoalcaligenes and saccharomyces cerevisiae are as follows:
A) the culture of saccharomyces cerevisiae seed liquor
Saccharomyces cerevisiae strain on inclined-plane is inoculated in primary-seed medium and carries out shaking flask culture, at 27-30 DEG C, revolving speed After 260rmp culture for 24 hours, it is inoculated in secondary seed medium and carries out fermentation tank culture, at 30-32 DEG C, revolving speed 260-280rmp, 2.5~3m of ventilatory capacity3The seed liquor that saccharomyces cerevisiae is obtained after/h culture 24-36h, wherein the primary-seed medium are as follows: ferment Female cream 5g/L, peptone 6g/L, glucose 20g/L;Secondary seed medium are as follows: glucose 40-50g/L, yeast extract 5-8g/ L, peptone 5-8g/L, (NH4) 2SO42-3g/L, MgSO47H2O0.25-0.3g/L, NaCl0.15-0.2g/L, KH2PO42.8-3g/L;
B) the culture of Pseudomonas alcaligenes seed liquor
Pseudomonas alcaligenes strain on inclined-plane is inoculated in primary-seed medium and carries out shaking flask culture, at 27-30 DEG C, is turned After fast 160-180rmp culture for 24 hours, it is inoculated in secondary seed medium and carries out fermentation tank culture, at 27-30 DEG C, revolving speed 160- 180rmp, 2.5~3m of ventilatory capacity3/ h cultivates 24-36h, obtains the seed liquor of Pseudomonas alcaligenes, wherein the first order seed Culture medium are as follows: glucose 20-30g/L, yeast extract 5-8g/L, peptone 6-8g/L;The secondary seed medium are as follows: grape Sugared 20-30g/L, beancake powder 10-12g/L, KNO31-1.2g/L, KH2PO41-1.2g/L, FeCl26H2O0.05-0.08g/ L, CaCl27H2O0.02-0.04g/L, MgSO47H2O1-1.2g/L;
C) mixed fermentation
By volume by the resulting saccharomyces cerevisiae seed liquor of step 1) and the resulting Pseudomonas alcaligenes seed liquor of step 2) 1-3:1-3 is mixed, and is transferred in fermentation medium with the inoculum concentration of 10-20% and is carried out High Density Cultivation, at 30 DEG C, revolving speed 220-260rmp, 5~10m of ventilatory capacity3/ h cultivates 36-48h, and the culture solution after fermenting is stood, centrifugal enrichment thallus, as Pseudomonas pseudoalcaligenes and saccharomyces cerevisiae thallus, wherein the fermentation medium are as follows: glucose sugar 80-100g/L, yeast extract 5- 10g/L, peptone 5-10g/L, beancake powder 10-12g/L, KNO31-1.2g/L, KH2PO42-2.5g/L, FeCl2 6H2O0.05-0.08g/L CaCl27H2O0.02-0.04g/L, MgSO47H2O1.5-1.8g/L, NaCl0.15- 0.18g/L;
Preferably, the starchy material is corn flour, de- embryo corn flour or tapioca starch.
It is further preferred that the starchy material is corn flour.
Present invention employs common fixation support-polyvinyl alcohol, and Pseudomonas alcaligenes and saccharomyces cerevisiae are fixed, It has that intensity is high, chemical stability is good, Resistance to microbes performance is strong, nontoxic to microorganism, cheap etc. a series of excellent Point, the middle agglomeration problem for introducing calcium alginate and solving particle, enhances the balling-up ability of polyvinyl alcohol gel on this basis, In addition, the addition of calcium alginate and CaSO4 strengthen gel particle intensity, while also introducing acrylamide polymerization reaction, it is allowed to Inside polyvinyl alcohol gel particle and surface forms polyacrylamide reticular structure, effectively improves polyvinyl alcohol gel Water-soluble dilatancy makes polyvinyl alcohol immobilized microorganism have comparatively ideal physics (particle size) and mechanical performance, significantly Pseudomonas alcaligenes and saccharomyces cerevisiae are increased to the tolerance of toxic metal ions, has achieved the effect that recycle.
Because of Rhizopus oryzae because itself has the characteristics that balling-up, it is not necessarily to immobilization, the present invention directly has chosen starchy material Hydrolyzate cultivates it, and the starchy material hydrolyzate is by 5-15wt% starchiness hydrolytic residue particle and 70- 80wt% starchiness hydrolysis clear liquid composition, wherein starchiness hydrolysis clear liquid can be provided for the production of Rhizopus oryzae carbon source, nitrogen source and Other microelements, and starchiness hydrolytic residue particle provides carrier for the growth of spore, forms with control Rhizopus oryzae is commonly used to Calcium carbonate etc. compare, have innate advantage, it is uniform and stable to be dispersed in starchiness liquefaction clear liquid so that rice root Mould spore is constantly wrapped in starchy material hydrolyzate in residue particles after developing for mycelium, and then formation densification, And have the mycelium pellet of certain mechanical strength, through lot of experiment validation, using starchy material hydrolyzate, without adding any object In the case where matter, Rhizopus oryzae spore liquid can balling-up well, and spherical size uniform (ball 50-100um), have it is good Mechanical performance, biomass are big, and chitin content is high, big to heavy metal ion adsorbed ability in fillable adsorption column.
With prior art ratio, the present invention has chosen the viable bacteria of Pseudomonas alcaligenes, saccharomyces cerevisiae and Rhizopus oryzae as life Object adsorbent, it is the generally acknowledged fungi that most metal ions are all had with stronger adsorption capacity that wherein saccharomyces cerevisiae, which is because of it, Rhizopus oryzae because in its cell wall chitin and chitosan content it is higher, functional group-COOH of cell surface ,-NH2 ,- OH can and metal ion combination, thus by cell surface adsorb or be complexed reach to adsorption of metal ions purpose;It is false to produce alkali For zygosaccharomyces in bacterium class, it is the complexing of cell surface first, followed by into bacterium that adsorption mechanism, which is mainly absorption intracellular, The slow diffusion process in portion, these three bacterium whiles, are applied, can be under the action of different adsorption mechanisms, to different heavy metals (Cd2+, Hg2+, Cu2+, Zn2+, Ni2+, Ag2+, Pb2+) all has suction-operated well.As immobilized cell ball and meter Gen Mould pompon is filled in when being adsorbed in bioreactor, due to the effect of aerator, immobilized cell ball and Rhizopus oryzae Mycelium pellet is suspended in the adsorption space that upper screen cloth, lower screen cloth and adsorption column side wall are surrounded, and in annular stream guiding barrel shape At circulation, enhance the contact of immobilized cell ball and Rhizopus oryzae pompon with waste water, so both strengthen to heavy metal from Son absorption.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of biological absorber.
Specific embodiment
In order to deepen the understanding of the present invention, the present invention will be described in further detail with reference to the examples below, these implementations Example for explaining only the invention, is not intended to limit the scope of the present invention..
In following embodiment, the method for Yield of chitin are as follows: drying to constant weight by mycelium, takes 40g, and 0.5mol/L is added Hydrochloric acid solution, boiling water bath 1h, is washed to neutrality, and solid is collected by centrifugation;15% sodium hydroxide solution is added, boiling water bath 30min takes off Protein out is washed till neutrality, and solid is collected by centrifugation, and adds appropriate oxalic acid solution in 70 DEG C of warm bath 30min, is washed to neutrality, Solid, as chitin is collected by centrifugation;50% sodium hydroxide solution, 121 DEG C of processing 2.5h deacetylations are added, are washed to neutrality, It is collected by centrifugation solid, is added 0.1mol/L hydrochloric acid solution, boiling water bath 2h, then with sodium hydroxide solution tune pH10, it is heavy to be collected by centrifugation It forms sediment, obtains chitosan after dry.
The mixing fermentation culture process of 1 pseudomonas pseudoalcaligenes of embodiment and saccharomyces cerevisiae, includes the following steps:
1) culture of saccharomyces cerevisiae seed liquor
Saccharomyces cerevisiae slant strains are inoculated in primary-seed medium and carry out shaking flask culture, at 27-30 DEG C, revolving speed After 260rmp culture for 24 hours, it is inoculated in secondary seed medium and carries out fermentation tank culture, at 30 DEG C, revolving speed 260rmp, ventilatory capacity 2.5~3m3/ h culture obtains the seed liquor of saccharomyces cerevisiae afterwards for 24 hours, wherein the primary-seed medium are as follows: yeast extract 5g/L, Peptone 6g/L, glucose 20g/L;Secondary seed medium are as follows: glucose 40g/L, yeast extract 5g/L, peptone 5g/L, (NH4) 2SO42g/L, MgSO47H2O0.25g/L, NaCl0.15g/L, KH2PO42.8g/L.
2) culture of Pseudomonas alcaligenes seed liquor
Monad slant strains are inoculated in primary-seed medium and carry out shaking flask culture, and at 27-30 DEG C, revolving speed 160rmp is trained After supporting for 24 hours, it is inoculated in secondary seed medium and carries out fermentation tank culture, at 30 DEG C, revolving speed 160rmp, 2.5~3m of ventilatory capacity3/h Culture for 24 hours, obtains the seed liquor of saccharomyces cerevisiae, wherein the primary-seed medium are as follows: glucose 20g/L, yeast extract 5g/ L, peptone 6g/L;The secondary seed medium are as follows: glucose 20g/L, beancake powder 10g/L, KNO31g/L, KH2PO41g/L, FeCl26H2O0.05g/L, CaCl27H2O0.02g/L, MgSO47H2O1g/L;
3) mixed fermentation
By volume by the resulting saccharomyces cerevisiae seed liquor of step 1) and the resulting Pseudomonas alcaligenes seed liquor of step 2) 1-3:1-3 is mixed, and is transferred in fermentation medium with 20% inoculum concentration and is carried out High Density Cultivation, at 30 DEG C, revolving speed 260rmp, 5~10m of ventilatory capacity3/ h cultivates 36-48h, and the culture solution after fermenting is stood, centrifugal enrichment thallus, the hair Ferment culture medium are as follows: glucose sugar 80g/L, yeast extract 5g/L, peptone 5g/L, beancake powder 10g/L, KNO31g/L, KH2PO42g/L, FeCl26H2O0.05g/L, CaCl27H2O0.02g/L, MgSO47H2O1.5g/L, NaCl0.15g/L.
A kind of preparation method of the immobilized cell ball of embodiment 2, includes the following steps:
A) polyvinyl alcohol, calcium alginate, acryloyl and water after 12:1:4:100 ratio is mixed in mass ratio, are obtained poly- The pseudomonas pseudoalcaligenes collected after mixing fermentation culture and saccharomyces cerevisiae thallus are added to polyvinyl alcohol the vinyl alcohol hydrosol Mixed solution is formed in the hydrosol, wherein the additive amount of Pseudomonas alcaligenes and saccharomyces cerevisiae thallus meets the poly- second of every 100mL The Pseudomonas alcaligenes and saccharomyces cerevisiae Mixed Microbes of 5g weight in wet base are added in the enol hydrosol;B) mixed solution is added with peristaltic pump Into the saturation boric acid solution containing 4w/v%N '-methylene-bisacrylamide and 1.5w/v%CaSO4, gel ball is formed, place- Cooling 5-10h, thaws at room temperature under the conditions of 20 DEG C, and cooling 1-2h will after thawing at room temperature under the conditions of being then placed in -10 DEG C again It is to obtain shape in spherical, the internal immobilization in porous network structure in 0.3g/L phosphate that gel ball, which puts into mass concentration, Cell ball A.
A kind of preparation method of the immobilized cell ball of embodiment 3, includes the following steps:
A) polyvinyl alcohol, calcium alginate, acryloyl and water after 6:0.5:3:100 ratio is mixed in mass ratio, are obtained The pseudomonas pseudoalcaligenes collected after mixing fermentation culture and saccharomyces cerevisiae thallus are added to polyethylene the polyvinyl alcohol hydrosol Mixed solution is formed in the alcohol hydrosol, and the additive amount for controlling Pseudomonas alcaligenes and saccharomyces cerevisiae thallus meets every 100mL's The Pseudomonas alcaligenes and saccharomyces cerevisiae Mixed Microbes of 4g weight in wet base are added in the polyvinyl alcohol hydrosol;Again by mixed solution peristaltic pump It is added in the saturation boric acid solution containing 3w/v%N '-methylene-bisacrylamide and 1w/v%CaSO4, forms gel ball, put Cooling 5-10h, thaws at room temperature under the conditions of setting -20 DEG C, cooling 1-2h under the conditions of being then placed in -10 DEG C again, after thawing at room temperature, It is to obtain shape in spherical, the internal fixation in porous network structure in 0.2g/L phosphate by gel ball investment mass concentration Change cell ball B.
A kind of preparation method of the immobilized cell ball of embodiment 4, includes the following steps:
A) polyvinyl alcohol, calcium alginate, acryloyl and water after 15:1.5:5:100 ratio is mixed in mass ratio, are obtained The pseudomonas pseudoalcaligenes collected after mixing fermentation culture and saccharomyces cerevisiae thallus are added to polyethylene the polyvinyl alcohol hydrosol Mixed solution is formed in the alcohol hydrosol, wherein the additive amount of Pseudomonas alcaligenes and saccharomyces cerevisiae thallus meets the poly- of every 100mL The Pseudomonas alcaligenes and saccharomyces cerevisiae Mixed Microbes of 6g weight in wet base are added in the vinyl alcohol hydrosol;B) mixed solution peristaltic pump is added Enter into the saturation boric acid solution containing 5w/v%N '-methylene-bisacrylamide and 2w/v%CaSO4, forms gel ball, place- Cooling 5-10h, thaws at room temperature under the conditions of 20 DEG C, and cooling 1-2h will after thawing at room temperature under the conditions of being then placed in -10 DEG C again It is to obtain shape in spherical, the internal immobilization in porous network structure in 0.5g/L phosphate that gel ball, which puts into mass concentration, Cell ball C.
A kind of preparation method of the Rhizopus oryzae pompon of embodiment 5, includes the following steps:
A) commercially available corn flour is crushed, obtains micro- corn flour that average grain diameter is 800 microns;B) by micro- corn flour and water with After 180% ratio is mixed into paste, it is heated to 40-70 DEG C, amylase is added and plant rennet, amylase enzyme concentration are The micro- corn flour of 1300U/g, the dosage of plant rennet are the 0.15wt% of micro- corn flour, then pass through 800-1000 purpose while hot Silk screen filter obtains uniform filtrate, adds water sugar addition after filtrate is cooling, and it is 30g/L corn flour hydrolyzate, gained that total reducing sugar, which is made, Corn flour hydrolyzate is made of corn flour hydrolysis clear liquid with corn flour hydrolytic residue particle, the corn flour hydrolysis clear liquid and corn The weight ratio that powder hydrolyzes particle is 90-95:5-10;C) it using corn flour hydrolyzate as culture medium, is accessed under conditions of pH=3-6 Rhizopus oryzae spore suspension, concentration is 105-106/mL to spore in the medium after inoculation, in 25-30 DEG C, 200-250rpm Revolving speed under, after shaken cultivation 24-48h, be collected by filtration to obtain 50-100um Rhizopus oryzae pompon A, dry cell weight 5.7g/L, Extracted and measurement, chitin content reach 25.6% (g/g dry mycelium).
A kind of preparation method of the Rhizopus oryzae pompon of embodiment 6, includes the following steps:
1) preparation of embryo corn flour hydrolyzate: A is taken off) commercially available de- embryo corn flour is crushed, obtaining average grain diameter is 500 microns Micro- de- embryo corn flour;B after micro- de- embryo corn flour and water) are mixed into paste with 150% ratio, it is heated to 40-70 DEG C, is added Enter amylase and plant rennet, amylase enzyme concentration is the micro- de- embryo corn flour of 1200U/g, and the dosage of plant rennet is micro- de- Then the 0.1wt% of embryo corn flour passes through the silk screen filter of 800-1000 mesh while hot, obtain uniform filtrate, add after filtrate is cooling Water sugar addition, it is 30g/L corn flour hydrolyzate that total reducing sugar, which is made, and it is clear by de- embryo corn flour hydrolysis that gained takes off embryo corn flour hydrolyzate Liquid and de- embryo corn flour hydrolytic residue particle form, the weight of the de- embryo corn flour hydrolysis clear liquid and de- embryo corn flour hydrolysis particle Amount is than being 90-95:5-10;C) using de- embryo corn flour hydrolyzate as culture medium, Rhizopus oryzae spore is accessed under conditions of pH=3-6 Suspension, concentration is 105-106/mL to spore in the medium after inoculation, under 25-30 DEG C, the revolving speed of 200-250rpm, vibration After swinging culture 24-48h, it is collected by filtration to obtain 50-100um Rhizopus oryzae pompon B, dry cell weight 5.3g/L, extracted and survey Fixed, chitin content reaches 22.6% (g/g dry mycelium).
A kind of preparation method of the Rhizopus oryzae pompon of embodiment 7, includes the following steps:
1) preparation of tapioca starch hydrolyzate: A) commercially available tapioca starch is crushed, obtain micro- tapioca starch that average grain diameter is 1000; B after tapioca starch and water) are mixed into paste with 200% ratio, it is heated to 40-70 DEG C, amylase and plant rennet is added, Amylase enzyme concentration is the micro- tapioca starch of 1500U/g, and the dosage of plant rennet is the 0.2wt% of micro- tapioca starch, is then passed through while hot The silk screen filter for crossing 800-1000 mesh obtains uniform filtrate, adds water sugar addition after filtrate is cooling, and it is 30g/L wood that total reducing sugar, which is made, Potato powder hydrolyzate, gained tapioca starch hydrolyzate are made of tapioca starch hydrolysis clear liquid with corn flour hydrolytic residue particle, the cassava It is 90-95:5-10 that powder, which hydrolyzes clear liquid and the weight ratio of tapioca starch hydrolysis particle,;C) using tapioca starch hydrolyzate as culture medium, in pH Rhizopus oryzae spore suspension is accessed under conditions of=3-6, concentration is 105-106/mL to spore in the medium after inoculation, in It 25-30 DEG C, under the revolving speed of 200-250rpm, after shaken cultivation 24-48h, is collected by filtration to obtain 50-100um Rhizopus oryzae pompon C, dry cell weight 5.35g/L, extracted and measurement, chitin content reach 23.2% (g/g dry mycelium).
Application Example 2,3 or 4 gained immobilized cell balls and embodiment 5,6 or 7 resulting Rhizopus oryzae pompons carry out The processing method of heavy metal wastewater thereby, includes the following steps:
1) preparation of biological adsorption device: as shown in Figure 1, the biological adsorption device is concatenated by 2 adsorption columns 1, institute It is provided with water inlet on the adsorption column lower sides stated, overfall is provided in adsorption column upper portion side wall, is provided in adsorption column 1 Upper screen cloth 2 and lower screen cloth 3,2 position of upper screen cloth are higher than the position where water inlet, and 3 position of lower screen cloth is lower than spilling Filled with immobilized cell ball in the adsorption space that position where mouthful, the adsorption column side wall and upper and lower sieve are surrounded With Rhizopus oryzae pompon, the volume packing ratio of immobilized cell ball and Rhizopus oryzae pompon is 60-90:10-40, and the two is being adsorbed The total filling rate in space is 60%, also sets up in the adsorption space and is equipped with annular guide shell 4, the upper end of the annular guide shell 4 It is not contacted with upper screen cloth and lower screen cloth respectively with lower end, absorption column bottom is provided with aerator 5, which is located at ring 4 lower section of shape guide shell.
2) processing of heavy metal wastewater thereby: by concentration of heavy metal ion adjustment≤800mg/L initial in heavy metal wastewater thereby, PH tune It is whole for after 5-7, the hydraulic detention time 0.5-1h followed by biological adsorption device, in every adsorption column.
Immobilized cell ball A and Rhizopus oryzae pompon A, immobilized cell ball B and Rhizopus oryzae pompon B, immobilized cell Ball C is filled in above-mentioned different bioreactor from Rhizopus oryzae pompon C, immobilized cell ball A and Rhizopus oryzae pompon C respectively Adsorption column in, be respectively designated as the first biological adsorption device, the second biological adsorption device, third biological adsorption device, the 4th biology inhale Adnexa, wherein the packing ratio of immobilized cell ball A and Rhizopus oryzae pompon A are 80:20 in the first biological adsorption device, the The packing ratio of immobilized cell ball B and Rhizopus oryzae pompon B is 60:40 in two biological adsorption devices, in third biological adsorption device The packing ratio of immobilized cell ball C and Rhizopus oryzae pompon C is 90:10, and immobilized cell ball A is filled out with Rhizopus oryzae pompon C's It fills than for 70:30, preparing respectively containing the mixed solution of 30mg/LCu2+, Zn2+, Ni2+, Cd2+, Cr2+, Hg2+, Pb2+, adjustment After pH=5-7, the concentration variation such as table 1 of each biological adsorption device are passed in and out:
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, it is all according to the present invention Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.

Claims (1)

1. a kind of preparation method for the biological adsorption device for handling heavy metal wastewater thereby, which is characterized in that include the following steps,
1) preparation of immobilized cell ball: A) by polyvinyl alcohol, calcium alginate, acryloyl and water 12:1:4:100 in mass ratio After ratio is mixed, the polyvinyl alcohol hydrosol is obtained, by the pseudomonas pseudoalcaligenes collected after mixing fermentation culture and wine brewing ferment Female thallus, which is added, forms mixed solution into the polyvinyl alcohol hydrosol, wherein Pseudomonas alcaligenes and saccharomyces cerevisiae thallus add Dosage meets the Pseudomonas alcaligenes and saccharomyces cerevisiae Mixed Microbes that 5g weight in wet base is added in the polyvinyl alcohol hydrosol of every 100mL;B) Mixed solution is added to the saturation boric acid containing 4w/v%N '-methylene-bisacrylamide and 1.5w/v%CaSO4 with peristaltic pump In solution, gel ball is formed, cooling 5-10h, thaws at room temperature under the conditions of placing -20 DEG C, cold under the conditions of being then placed in -10 DEG C again Gel ball investment mass concentration is to obtain shape in spherical, inside in 0.3g/L phosphate after thawing at room temperature by but 1-2h In the immobilized cell ball of porous network structure;
2) preparation of Rhizopus oryzae pompon: A) commercially available corn flour is crushed, it is former to obtain micro- starchiness that average grain diameter is 800 microns Material;B after micro- starchy material and water) are mixed into paste with 180% ratio, it is heated to 40-70 DEG C, amylase and plant is added Object protease, amylase enzyme concentration are the micro- starchy material of 1300U/g, and the dosage of plant rennet is micro- starchy material Then 0.15wt% passes through the silk screen filter of 800-1000 mesh while hot, obtain uniform filtrate, add water sugar addition after filtrate is cooling, It is 30g/L starchy material hydrolyzate that total reducing sugar, which is made, and gained starchy material hydrolyzate hydrolyzes clear liquid and starchiness by starchiness The weight ratio of hydrolytic residue particle composition, the starchiness hydrolysis clear liquid and starchiness hydrolysis particle is 90-95:5-10;C) with Starchy material hydrolyzate is culture medium, Rhizopus oryzae spore suspension is accessed under conditions of pH=3-6, spore is being trained after inoculation Supporting concentration in base is 105-106/mL, and under 25-30 DEG C, the revolving speed of 200-250rpm, after shaken cultivation 24-48h, filtering is received Integrate and obtains diameter as 50-100 μm of Rhizopus oryzae pompon;
3) preparation of biological adsorption device: the biological adsorption device is concatenated by more adsorption columns, the adsorption column lower part It is provided with water inlet on side wall, overfall is provided in adsorption column upper portion side wall, is provided with upper screen cloth and lower screen cloth in adsorption column, Upper screen cloth position is higher than the position where water inlet, and lower screen cloth position is lower than the position where overfall, described It is fixed filled with immobilized cell ball and Rhizopus oryzae pompon in the adsorption space that adsorption column side wall and upper and lower sieve are surrounded The volume packing ratio for changing cell ball and Rhizopus oryzae pompon is 60-90:10-40, and the two is 60% in the total filling rate of adsorption space, Also set up in the adsorption space and be equipped with annular guide shell, the top and bottom of the annular guide shell respectively with upper screen cloth and under Sieve does not contact, and absorption column bottom is provided with aerator, which is located at below annular guide shell.
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