CN107487859B - A kind of method of fish-farming with sewage microalgae production livestock fodder additives - Google Patents
A kind of method of fish-farming with sewage microalgae production livestock fodder additives Download PDFInfo
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Abstract
The present invention provides a kind of method of fish-farming with sewage microalgae production livestock fodder additives, by isolating crude protein product and high protein product from algae, so that the protein content in poultry feed is higher than conventional feed, enough protein is provided for home poultry raising, simultaneously the protein from algae, thus corn and dregs of beans usage amount can be reduced.The present invention also describes a kind of method of sewage culture microalgae, using modification of chitosan, modified montmorillonite used it be prepared into the hollow adsorption column that adsorbed film assembles the metal ion in sewage is adsorbed, sewage is made to penetrate adsorption column by pumping suction function, sewage stops in adsorption column, it is contacted with immobilized microalgae, microalgae carries out growth and breeding using the organic nutrient substance in sewage.Carry out sewage disposal using this method, can effectively except substances such as metal ion, carbon, nitrogen, the phosphorus in decontaminated water, while can large-scale culturing micro-algae, reach sewage disposal and microdisk electrode dual purpose.
Description
Technical field
The invention belongs to Feed Production Technology and technical field of sewage, are more particularly to produced using fish-farming with sewage microalgae
The method of livestock fodder additives.
Background technology
Poultry feed one is to wheat, paddy or rice bran, wheat bran.General feeds form：Energy feed, rice bran, beanstalk chaff,
Bavin chaff and wheat bran etc., account for 50 ~ 60%；Vegetable protein feed, soya-bean cake, rape cake and cotton benevolence cake, accounts for 10 ~ 20%；Poultry property
Protein feed primary raw material comes from and cereal crops, is unfavorable for the long-term needs of human survival.
Microalgae is that have the protophyte of photosynthetic ability, and micro-algae propagation survival ability is extremely strong, can be from waste water
Various inorganic elements and organic matter are absorbed, microalgae contains multivitamin and protein and polysaccharide material, in the prior art, micro-
Algae cultivates many places in laboratory stage, and natural microalgae quantity is few, is not suitable for the production of extensive by-product.
With China's economic development, livestock and poultry cultivation sewage, municipal wastewater and increased become of trade effluent mainly pollute
Source, these discharges of sewage are big, and COD, carbon, the content of nitrogen and phosphorous are high, simultaneously containing various heavy metal substances.Traditional aerobic activity is dirty
Mud treatment technology input cost is high, and operation energy consumption is big, Treatment of Sludge trouble, and dirt cannot be fully utilized in the microorganism in activated sludge
Substance in water, in the nutriments such as most of carbon, nitrogen, phosphorus also residual water.It is supported using sewage as cheap culture medium scale
It is research hotspot both domestic and external to grow treated sewage.
A kind of methods of waste water microalgae processing feed of application for a patent for invention CN201510390515.1, this method is will be useless
After Aquaponic, collection, the microalgae of precipitation and maize peel, bacillus subtilis mixing, aerobic fermentation is accumulated on the ground, utilizes hair
The high temperature generated during ferment fully kills germ；The microalgae material of aerobic fermentation mixes again with live pig perfect compound feed after cooling
It closes, addition lactobacillus plantarum and long handle trichoderma in mixed process, adjusts moisture to 40-50%, carry out anaerobic fermentation to pH
Feeding live pig is taken out during 3.5-5.0.The present invention improves the utilization rate of waste water, reduces the drying expense of microalgae, kills waste water
In pathogen, improve the biological safety that microalgae utilizes, promote microalgae fodder utilize.Waste water microalgae processing
The beneficial bacterial content raising of feed, the production performance of live pig improve.Number of patent application CN201210448432.X, a kind of poultry are raised
Material and preparation method thereof, by isolating crude protein product and high protein product from algae so that the albumen in poultry feed
Content is higher than conventional feed, provides enough protein, while the source of the protein and algae for home poultry raising, thus can be with
Reduce corn and dregs of beans usage amount；It can be into other than producing poultry feed, in the polysaccharide solution after by-product pint albumen
Row decoloration obtains refined polysaccharide.Number of patent application CN201510996151.1 microalgaes feed addictive and feed improve eggs egg
The content of omega-3 polyunsaturated fatty acids and beta carotene in Huang, improves the immunity of organisms of birds, promotes to nutriment
Digest and assimilate, effectively improve the egg laying performance of egg birds.
In the prior art, using microdisk electrode also in laboratory stage, Chinese style stage and industrialization large-scale culture are few
It has been reported that, which kind of substance culture microalgae to be also the hot spot studied at this stage using；It is studied at present using microalgae treated sewage
Hot spot, microalgae utilize the organic substance amount reproduction in sewage, reach sewage disposal purpose, but the collection of microalgae becomes new again
The problem of, meanwhile, it is also less at present for the report of the research on utilization of microalgae idiotrophic value.
Invention content
To make up the vacancy of the prior art, fill up and study few lack using fish-farming with sewage microalgae production livestock fodder additives
It falls into, the present invention provides a kind of method of fish-farming with sewage microalgae production livestock fodder additives.
Using the present invention treated sewage, BOD ＜ 110mg/L, COD ＜ 380mg/L, suspended matter ＜ 20mg/L, ammonia nitrogen
＜ 40mg/L, total phosphorus ＜ 4mg/L.Treated, and sewage can be used for irrigating, cultivating, cleaning；Turn out the microalgae heavy metal come
Content is low, and protein, polysaccharide material and its vitamin substances content reach the standard of feed addictive, is feed addictive city
Field provides technical support.
The present invention is to realize in this way：
（1）Band stomata snake pipe is installed at sewage reaction tank bottom, downward, coiled pipe connects stomata with ozone generating-device
It connects；
（2）The preparation and installation of adsorption column：
A. 50 parts of chitosans are weighed, is added in the ethanol solution of 60ml 95% and impregnates, 60 DEG C of swelling 2h of constant temperature；（2）It will
150 parts of vanillic aldehydes are dissolved in the ethyl alcohol of 400ml 95%, and the soak for pouring into chitosan obtains mixed liquor；（3）Mixed liquor is placed
In microwave quick reaction device, 70 DEG C of heating temperature is set, reacts 10min, microwave power 300w, stirring；（4）It has reacted
Into cooled and filtered, ethyl alcohol is washed, and washing is dried under vacuum to constant weight, obtains modification of chitosan powder；
B. 20 parts of natural smectite is weighed, 5% sodium hydroxide of natural smectite quality is weighed, by solid-liquid mass ratio 1:
10 add in 200ml distilled water, and it is 5.6 to adjust pH, and 1h is stirred to react for 60 DEG C in water bath with thermostatic control, the freeze-day with constant temperature at 80 DEG C, carefully
Honed 100 mesh sieve, it is modified montmorillonite used to obtain sodium；
C. it is 10 to take cell concentration5The microalgae solution of/ml, aseptically, with sodium alginate soln, modification of chitosan
1:1:1 be uniformly mixed obtain mixed liquor；Mixed liquor is instilled into calcium chloride solution by syringe and carries out 20 ~ 30min of curing, is obtained
Calcium alginate coagulates pearl；Calcium alginate is coagulated pearl to be washed with distilled water 2 ~ 3 times, you can obtain immobilized microalgae glueballs；
The sodium alginate concentration is 20 ~ 25mg/ml；The calcium chloride solution concentration is 18 ~ 22mg/ml；
The mixed liquor is 1 with calcium chloride solution volume ratio：（1.5~2）；
D. 40 ~ 80 parts of Kynoar powder is taken, is dissolved in 25 ~ 50 parts of dibutyl phthalates, adds in 50 ~ 100 parts
Modification of chitosan powder, 50 ~ 100 parts of modified montmorillonite used powder, 2 ~ 10 parts of Geniposides, under nitrogen protection in 210 ~ 223 DEG C of oil
After 4 ~ 6h of stirring is mixed into uniform solution in bath, standing and defoaming obtains polymer；Polymer is passed through into the weightlessness of 5 ‰ measuring accuracies
Scale feeder feeds double screw extruder, under the mixing kneading effect of 250 ~ 300rpm and 2 ~ 5MPa, is sufficiently mixed material
Uniformly into the casting solution of stable homogeneous, casting solution enters spray by spinning pump with the speed accurate measurement of 90 ~ 100g/min
Head, inner cavity are entered using the nitrogen of 36 ~ 50ml/min flow velocitys as hollow supporting body after the air section evaporation of certain altitude
Phase separation and curing occur in the water-bath of 298K, is collected thick hollow-fibre membrane by collecting wheel with the speed of 25m/min；
E. thick hollow-fibre membrane d being prepared is immersed in 95% industrial alcohol 24 hours, extracts two fourth of phthalic acid
Ester diluent, during which needs to change ethyl alcohol 2 times, it is ensured that diluent extraction is clean, and the hollow-fibre membrane that extraction finishes is floated with clear water
Wash clean obtains hollow-fibre membrane.
F. hollow-fibre membrane is taken, is assembled into duplicature column, there are the space of 3 ~ 7cm wide, outermost tunic bottoms among duplicature
Portion is provided with dump valve, obtains adsorption column；
G. multiple adsorption columns are vertically fixed with brandreth, innermost layer hollow space parallel connection is connect with suction pump, is positioned over anti-
Ying Chizhong；
（3）Immobilized microalgae cell is filled in the intermediate space of adsorption column duplicature, seals adsorption column；
（4）It opens sewage pump and sewage is injected into reaction tank, when sewage is not to adsorption column 50 ~ 70%, stop pumping；It opens
Ozone generating-device, ozone aeration quantity are 15 ~ 40g/h, and action time is 10 ~ 20min/h, after ozonization 5h, open and take out
Water pump, adjusting flow are 1 ~ 1.4L/min, and 15 ~ 30min of working time, 40 ~ 60min of time of having a rest make sewage enter adsorption column
After being reacted with immobilized microalgae, the sewage after reaction is discharged into water purifying tank；
（5）After operation 4 ~ 7 days, stopping is filled with ozone, stops sewage pump, stop pumping pump, and immobilized microalgae is passed through suction
Attached column bottom-discharge valve is discharged, and is collected；Hollow-fibre membrane is cleaned 2 hours with 2 ~ 5wt%HCl, then with 2000 ~ 3000mg/L
NaClO+1000 ~ 2000mg/L NaOH are cleaned 2 hours, and every component cleaning flux is 15 ~ 30L/h, and 23 ~ 25 DEG C of temperature elutes
Liquid recycles after collecting for metal ion.
The conservation rate that the cleaning can improve tensile strength is 80% ~ 82.9%.
（6）It collects immobilized microalgae and carries out broken wall treatment, by microalgae drying and crushed using heated-air drying, take microalgae powder
100 ~ 200 parts, the cellulase and enzyme activity that 10 ~ 20 parts of enzyme activities of addition are 1400 ~ 1800U/g are 60000 ~ 70000U/g's
Neutral proteinase 1:1 combination, after mixing reacts 4 ~ 6h, centrifuges 10 ~ 20 minutes under 5000 ~ 6000rpm, obtains supernatant I and sinks
Shallow lake I；
（7）Supernatant I is added to after mixing 12 ~ 14h in 4 DEG C of isometric cold ethyl alcohol, filtering and concentrating to original volume
1/5 ~ 1/4, it is then freeze-dried, obtains microalgae powder i.e. livestock fodder additives；
（8）Microalgae powder is added in poultry feed, additive amount is 10% ~ 15%, feeding poultry.
As a further improvement on the present invention, the preparation method of the modification of chitosan is as follows：
（1）50 parts of chitosans are weighed, is added in the ethanol solution of 60ml 95% and impregnates, 60 DEG C of swelling 2h of constant temperature；（2）It will
150 parts of vanillic aldehydes are dissolved in the ethyl alcohol of 400ml 95%, and the soak for pouring into chitosan obtains mixed liquor；（3）Mixed liquor is placed
In microwave quick reaction device, 70 DEG C of heating temperature is set, reacts 10min, microwave power 300w, stirring；（4）It has reacted
Into cooled and filtered, ethyl alcohol is washed, and washing is dried under vacuum to constant weight, obtains modification of chitosan powder.
The chitosan of vanillic aldehyde graft modification has better filming performance, while can remove Cu very well2+、Zn2+, to having
The adsorption rate of machine object COD can reach 25mg/g；
As a further improvement on the present invention, the modified montmorillonite used preparation method is as follows：
20 parts of natural smectite is weighed, 5% sodium hydroxide of natural smectite quality is weighed, by solid-liquid mass ratio 1:10
200ml distilled water is added in, it is 5.6 to adjust pH, and 1h is stirred to react for 60 DEG C in water bath with thermostatic control, the freeze-day with constant temperature at 80 DEG C, fine grinding
Son is sieved with 100 mesh sieve, it is modified montmorillonite used to obtain sodium.
The raw material of specific proportioning carries out the property montmorillonite that sodium changes, to Cu2+、Pb2+、Zn2+、Cd2+Adsorption rate it is reachable respectively
99.2%th, 99.8%, 99.5% and 99.3%.
As a further improvement on the present invention, the immobilized microalgae preparation method is as follows：
It is 10 to take cell concentration3The microalgae solution of/ml, aseptically, with sodium alginate soln, modification of chitosan 1:
1:1 be uniformly mixed obtain mixed liquor；Mixed liquor is instilled into calcium chloride solution by syringe and carries out 20 ~ 30min of curing, obtains sea
Calcium alginate coagulates pearl；Calcium alginate is coagulated pearl to be washed with distilled water 2 ~ 3 times, you can obtain immobilized microalgae glueballs.The alginic acid
Na concn is 20 ~ 25mg/ml；The calcium chloride solution concentration is 18 ~ 22mg/ml；The mixed liquor and calcium chloride solution body
Product is than being 1：（1.5~2）.
As a further improvement on the present invention, the Kynoar ethylene molecule amount is 30KDa ~ 40Kda, gathers inclined fluorine
Ethylene concentration is 30 ~ 35wt%.
Polymer molecular weight size influences Kynoar system viscosity and membrane aperture size, and then influences pure water and pass through
Rate.When polymer molecular weight increases, system viscosity increases, and the growth of stingy drop and nucleus is limited, when polymer concentrated phase cures
Corresponding drop and spherulite size are smaller, and corresponding membrane aperture is smaller.
As a further improvement on the present invention, dibutyl phthalate, modification of chitosan, modified montmorillonite used powder weight
Score ratio is 1:2:2~2:2:5.
Molecular weight is 30KDa ~ 40Kda, the Kynoar ethylene of a concentration of 30 ~ 35wt%, with two fourth of phthalic acid
Ester, modification of chitosan, modified montmorillonite used powder ratio of weight and number are 1:2:2~2:2:5, the performance of the film prepared is：Pure water
580 ~ 800Lm of flux-2h-1（298K）, 0.101 ~ 0.115 μm, 15.2 ~ 20.4N of tensile strength of average pore size, porosity 70 ~
80%。
As a further improvement on the present invention, adsorption column hollow space is not communicated with two membranes intermediate space part.
As a further improvement on the present invention, immobilized microalgae loading 50 ~ 70% in the adsorption column.
As a further improvement on the present invention, the ozonization time is 5h/ days.
Then the present invention is mixed and made into adsorption column film by being modified to chitosan and montmorillonite with Kynoar,
Using the adsorption column that is assembled into of immobilized microalgae filling duplicature, sewage passes through the suction-operated of adsorption column outer membrane, and 98% or so
Heavy metal ion adsorbed, the sewage after absorption is entered inside adsorption column to be reacted with immobilized microalgae, and microalgae can be sharp
Growth and breeding is carried out with the Organic Carbon And Total Nitrogen phosphorus substance in sewage, further except the carbon nitrogen phosphorus substance in decontaminated water.After microalgae processing
Sewage again pass by adsorption column inner layer film after discharge, be almost free of the polluters such as heavy metal, carbon, nitrogen, phosphorus.
Advantages of the present invention：
1. using the sewage culture microalgae after adsorption column absorption heavy metal ion, heavy metal ion is reduced in microalgae
Enrichment recycles microalgae production livestock fodder additives, and the micro algae growth amount cultivated by the present invention is big, is easy to collect, and poisons
Property it is low, composite green environmental protection, sustainable development requirement.
2. the present invention by being modified to chitosan and montmorillonite is used as membrane material, can adsorb well heavy metal from
Son can effectively adsorb Pb In Exhausted Water, every, heavy metal ion such as nickel, molybdenum, while montmorillonite also has except malicious function, further net
Change sewage.
3. the present invention carries out both culturing microalgae using sewage, sewage can be purified and large-scale culturing micro-algae is used
In feed additive production, the sustainable development requirement of resource reutilization is reached.
4. adsorption column prepared by the present invention is hybrid organic-inorganic film, the advantages of having concentrated polyvinylidene fluoride separation membrane with
And the absorption property of chitosan, montmorillonite, film stable physical property, pure water flux and hydrophily are improved to some extent.
5. the adsorption column of the present invention has good pressure-resistant performance, arbitrary size can be made without supporter, membrane module and shape,
The advantages that loading density is big in membrane module, unit volume membrane area and flux is big.
Description of the drawings
Fig. 1 is the schematic diagram of adsorption column of the present invention.Wherein 1 is outer layer hollow membrane, and 2 be inner layer hollow membrane, and 3 be filling microalgae
Middle layer segment, 4 be hollow space.
Specific embodiment
The following examples can make those skilled in the art that the present invention be more fully understood, but not limit in any way
The present invention.
Embodiment 1
The present embodiment is for Pig farm wastewater processing.
The preparation of adsorption column and installation method are as follows in the present embodiment：
A. 80 parts of the Kynoar powder of 40Kda, 30wt% are taken, is dissolved in 25 parts of dibutyl phthalates, adds in 50
Part modification of chitosan powder, 50 parts of modified montmorillonite used powder, 2 parts of Geniposides stir 4h in 210 DEG C of oil baths under nitrogen protection
After being mixed into uniform solution, standing and defoaming obtains polymer；Polymer is fed by the Weightlessness balance feeder of 5 ‰ measuring accuracies
Double screw extruder under the mixing kneading effect of 250rpm and 2MPa, makes material be sufficiently mixed uniformly into the casting of stable homogeneous
Film liquid, casting solution enter nozzle by spinning pump with the speed accurate measurement of 90g/min, and inner cavity is with 36ml/min flow velocitys
Nitrogen is as hollow supporting body, into generation phase separation in 25 DEG C of water-bath and admittedly after the air section evaporation of certain altitude
Change, collected thick hollow-fibre membrane by collecting wheel with the speed of 25m/min；
B. thick hollow-fibre membrane d being prepared is immersed in 95% industrial alcohol 24 hours, extracts two fourth of phthalic acid
Ester diluent, during which needs to change ethyl alcohol 2 times, it is ensured that diluent extraction is clean, and the hollow-fibre membrane that extraction finishes is floated with clear water
Wash clean obtains hollow-fibre membrane.
C. hollow-fibre membrane is taken, is assembled into duplicature column, there are the space of 7cm wide, outermost tunic bottoms among duplicature
Dump valve is provided with, obtains adsorption column；
D. multiple adsorption columns are vertically fixed with brandreth, innermost layer hollow space parallel connection is connect with suction pump, is positioned over anti-
Ying Chizhong；
The present embodiment concrete operation step is as follows：
Immobilized microalgae is filled into adsorption column, seals adsorption column, opens sewage pump by the processing of pig farm level-one grid
Sewage injection reaction tank afterwards, when sewage is not to adsorption column 70%, stops pumping；Open ozone generating-device, ozone aeration quantity
For 40g/h, action time 20min/h, after ozonization 5h, suction pump is opened, adjustings flow is 1.4L/min, during work
Between 30min, time of having a rest 60min, sewage is made to enter after adsorption column reacted with immobilized microalgae, the sewage after reaction is arranged
Enter water purifying tank；After operation 7 days, stopping is filled with ozone, stops sewage pump, stop pumping pump, and immobilized microalgae is passed through adsorption column
Bottom-discharge valve is discharged, and is collected；Hollow-fibre membrane is cleaned 2 hours with 2wt%HCl, then with 2000mg/L NaClO+1000mg/
L NaOH are cleaned 2 hours, 23 DEG C of temperature.The conservation rate that the cleaning can improve tensile strength is 80%；
It collects immobilized microalgae and carries out broken wall treatment, by microalgae drying and crushed using heated-air drying, take microalgae powder 100
Part, add in the cellulase that 10 parts of enzyme activities are 1400U/g and the neutral proteinase 1 that enzyme activity is 60000U/g:1 combination, is mixed
After even reaction 4h, centrifuged 10 minutes under 5000rpm, obtain supernatant I and precipitation I；
Supernatant I is added to after mixing 12h in 4 DEG C of isometric cold ethyl alcohol, the 1/5 of filtering and concentrating to original volume, so
After be freeze-dried, obtain microalgae powder i.e. livestock fodder additives；
Microalgae powder is added in poultry feed, additive amount 10%, feeding poultry.
In the present embodiment, immobilized microalgae loading 70% in adsorption column.A concentration of 4.2g/L of microalgae after culture.
Embodiment 2
The present embodiment is used for sanitary sewage disposal.
Adsorption column is prepared as follows with installation method in the present embodiment：
A. 40 parts of 30Kda, 35wt% Kynoar powder is taken, is dissolved in 30 parts of dibutyl phthalates, adds in 30 parts
Modification of chitosan powder, 75 parts of modified montmorillonite used powder, 5 parts of Geniposides stir 5h under nitrogen protection in 215 DEG C of oil baths and mix
After synthesizing uniform solution, standing and defoaming obtains polymer；Polymer is double by the Weightlessness balance feeder feeding of 5 ‰ measuring accuracies
Screw extruder under the mixing kneading effect of 280rpm and 4MPa, makes material be sufficiently mixed uniformly into the casting film of stable homogeneous
Liquid, casting solution enter nozzle by spinning pump with the speed accurate measurement of 100g/min, and inner cavity is with 45ml/min flow velocitys
Nitrogen is as hollow supporting body, into generation phase separation in the water-bath of 298K and admittedly after the air section evaporation of certain altitude
Change, collected thick hollow-fibre membrane by collecting wheel with the speed of 25m/min；
B. thick hollow-fibre membrane d being prepared is immersed in 95% industrial alcohol 24 hours, extracts two fourth of phthalic acid
Ester diluent, during which needs to change ethyl alcohol 2 times, it is ensured that diluent extraction is clean, and the hollow-fibre membrane that extraction finishes is floated with clear water
Wash clean obtains hollow-fibre membrane.
C. hollow-fibre membrane is taken, is assembled into duplicature column, there are the space of 3cm wide, outermost tunic bottoms among duplicature
Dump valve is provided with, obtains adsorption column；
D. multiple adsorption columns are vertically fixed with brandreth, innermost layer hollow space parallel connection is connect with suction pump, is positioned over anti-
Ying Chizhong；
The present embodiment concrete operation step is as follows：
It opens sewage pump and sanitary sewage is injected into reaction tank, when sewage is not to adsorption column 50%, stop pumping；It opens smelly
Oxygengenerating plant, ozone aeration quantity is 15g/h, action time 10min/h, after ozonization 5h, opens suction pump, adjusts
Flow is 1L/min, working time 15min, time of having a rest 40min, and sewage is made to enter adsorption column and is reacted with immobilized microalgae
Afterwards, the sewage after reaction is discharged into water purifying tank；
After operation 4 days, stopping is filled with ozone, stops sewage pump, stop pumping pump, and immobilized microalgae is passed through adsorption column bottom
Portion's dump valve discharge, is collected, hollow-fibre membrane is cleaned 2 hours with 4wt%HCl, then with 2500mg/L NaClO+1500mg/L
NaOH is cleaned 2 hours, and every component cleans flux as 22L/h, 24 DEG C of temperature.The cleaning can improve the holding of tensile strength
Rate is 81.6%；
It collects immobilized microalgae and carries out broken wall treatment, by microalgae drying and crushed using heated-air drying, take microalgae powder 200
Part, add in the cellulase that 20 parts of enzyme activities are 1800U/g and the neutral proteinase 1 that enzyme activity is 70000U/g:1 combination, is mixed
After even reaction 6h, centrifuged 20 minutes under 6000rpm, obtain supernatant I and precipitation I；
Supernatant I is added to after mixing 14h in 4 DEG C of isometric cold ethyl alcohol, the 1/4 of filtering and concentrating to original volume, so
After be freeze-dried, obtain microalgae powder i.e. livestock fodder additives；
Microalgae powder is added in poultry feed, additive amount 15%, feeding poultry.
In the present embodiment, immobilized microalgae loading 50% in adsorption column, the microalgae density after culture is 5.0g/L.
Embodiment 3
The present embodiment is used for municipal sewage treatment.
Adsorption column is prepared as follows with installation method in the present embodiment：
A. 80 parts of 35Kda, 30wt% Kynoar powder is taken, is dissolved in 50 parts of dibutyl phthalates, adds in 100
Part modification of chitosan powder, 100 parts of modified montmorillonite used powder, 10 parts of Geniposides stir in 223 DEG C of oil baths under nitrogen protection
After 6h is mixed into uniform solution, standing and defoaming obtains polymer；Polymer is fed by the Weightlessness balance feeder of 5 ‰ measuring accuracies
Enter double screw extruder, under the mixing kneading effect of 300rpm and 5MPa, material is made to be sufficiently mixed uniformly into stable homogeneous
Casting solution, casting solution enter nozzle by spinning pump with the speed accurate measurement of 100g/min, and inner cavity is flowed with 50ml/min
The nitrogen of speed as hollow supporting body, after the air section evaporation of certain altitude into occur in the water-bath of 298K phase separation with
Curing is collected thick hollow-fibre membrane by collecting wheel with the speed of 25m/min；
B. thick hollow-fibre membrane d being prepared is immersed in 95% industrial alcohol 24 hours, extracts two fourth of phthalic acid
Ester diluent, during which needs to change ethyl alcohol 2 times, it is ensured that diluent extraction is clean, and the hollow-fibre membrane that extraction finishes is floated with clear water
Wash clean obtains hollow-fibre membrane.
C. hollow-fibre membrane is taken, is assembled into duplicature column, there are the space of 5cm wide, outermost tunic bottoms among duplicature
Dump valve is provided with, obtains adsorption column；
D. multiple adsorption columns are vertically fixed with brandreth, innermost layer hollow space parallel connection is connect with suction pump, is positioned over anti-
Ying Chizhong；
The present embodiment concrete operation step is as follows：
It opens sewage pump and sanitary sewage is injected into reaction tank, when sewage is not to adsorption column 60%, stop pumping；It opens smelly
Oxygengenerating plant, ozone aeration quantity is 25g/h, action time 20min/h, after ozonization 5h, opens suction pump, adjusts
Flow is 1.2L/min, working time 20min, time of having a rest 50min, and sewage is made to enter adsorption column and is carried out instead with immobilized microalgae
Sewage after reaction is discharged into water purifying tank by Ying Hou；
After operation 6 days, stopping is filled with ozone, stops sewage pump, stop pumping pump, and immobilized microalgae is passed through adsorption column bottom
Portion's dump valve discharge, is collected；Hollow-fibre membrane is cleaned 2 hours with 5wt%HCl, then with 3000mg/L NaClO+2000mg/L
NaOH is cleaned 2 hours, and every component cleans flux as 30L/h, 25 DEG C of temperature.The cleaning can improve the holding of tensile strength
Rate is 82.9%；
（6）It collects immobilized microalgae and carries out broken wall treatment, by microalgae drying and crushed using heated-air drying, take microalgae powder
150 parts, add in the cellulase that 15 parts of enzyme activities are 1600U/g and the neutral proteinase 1 that enzyme activity is 65000U/g:1 combination,
After mixing reaction 5h, centrifuged 20 minutes under 6000rpm, obtain supernatant I and precipitation I；
（7）Supernatant I is added to after mixing 14h in 4 DEG C of isometric cold ethyl alcohol, the 1/4 of filtering and concentrating to original volume,
Then it is freeze-dried, obtains microalgae powder i.e. livestock fodder additives；
（8）Microalgae powder is added in poultry feed, additive amount 13%, feeding poultry.
In the present embodiment, immobilized microalgae loading 60% in adsorption column；Microalgae density after culture is 4.0g/L.
Embodiment 4
The embodiment directly carries out scenedesmus cultivation not utilize the present invention using Wastewater from Pig Farm, is the comparison of embodiment 1
Example.Specific method is as follows：
Using the waste water culture scenedesmus on pig farm, start to collect when scenedesmus concentration is more than 2.1g/L, precipitate, it is small after precipitation
The dry matter content of ball algae is 15%.By scenedesmus and the maize peel that crushed 40 mesh sieve by weight 1:3 mixings, in blending process
It according to dosage adds bacillus subtilis (2.0 × 1010cfu/g) for 150g/ tons, aerobic fermentation is accumulated on ground after mixing, accumulation is high
It spends for 100cm, in cone, bottom surface diameter of a circle is 2.0 meters.Environment temperature during fermentation is 25 DEG C.It ferments the 60th hour and examines
The height of ranging ground 2/3, (temperature of charge reaches 72 at deep 25cm when reaching 60 DEG C away from surface of material 20cm depths fermentation temperature
DEG C), heap fermentation again after material is opened from inside to outside at this time, piling height is trapezoidal to be still 100cm, bottom surface circle it is straight
Diameter is 2.0 meters.The fermentation temperature at the 6th day (the 3rd day of second of heap fermentation) stacking material 20cm that ferments reaches 60 DEG C again
Stop when (temperature of charge reaches 74 DEG C at depth 25cm at this time), then material is spread out and is cooled to 25 DEG C.
25 DEG C of scenedesmus material will be cooled to again with complete compound feed for fattening pig by weight 1:3 mixing, mixed process
Middle addition lactobacillus plantarum (content 2.0 × 1010Cfu/g, 200g/ tons of additive amount), long handle trichoderma (content 1.5 × 109cfu/
G, 200g/ tons of additive amount), moisture is adjusted to 50%, and the material mixed is packed into fermentation bag, anaerobism is carried out after compacting
It ferments, ferments 3 days at 25 DEG C, detection pH (5% aqueous solution) 3.5 takes out feeding growing and fattening pigs.
Each content of material such as table 1 in treated in above example sewage, microalgae dry weight such as table 2 after sewage disposal, in
Empty fiber membrane performance such as table 3, protein content such as table 4 in microalgae after culture.
Each content of material in sewage after the processing of 1 each embodiment of table
Microalgae dry weight after 2 each embodiment sewage disposal of table
3 each embodiment doughnut film properties of table
Protein content in microalgae after 4 each embodiment culture of table
By the data of embodiment 1 and embodiment 4 in table 1 ~ 4 as a comparison it is found that compared to the side without using the present invention
Method carries out sewage feed addictive prepared by processing culture microalgae, and protein content will in feed addition prepared by the present invention
Height, while, processing after microalgae amount concentration higher stronger to the detergent power of sewage.
The above embodiment of the present invention scheme is only the description of the invention and cannot limit the present invention, in the power with the present invention
Any change in the sharp comparable meaning and scope of claim, is all considered to be and is included within the scope of the claims.
Claims (5)
- A kind of 1. method of fish-farming with sewage microalgae production livestock fodder additives, which is characterized in that include the following steps：（1）Band stomata snake pipe is installed at sewage reaction tank bottom, downward, coiled pipe is connect stomata with ozone generating-device；（2）The preparation and installation of adsorption column：A. 50 parts of chitosans are weighed, is added in the ethanol solution of 60mL 95% and impregnates, 60 DEG C of swelling 2h of constant temperature；By 150 parts of perfume (or spice) Oxalaldehyde is dissolved in the ethyl alcohol of 400mL 95%, and the soak for pouring into chitosan obtains mixed liquor；It is quick that mixed liquor is positioned over microwave In reaction unit, 70 DEG C of heating temperature is set, reacts 10min, microwave power 300w, stirring；Reaction is completed, cooled and filtered, Ethyl alcohol is washed, and washing is dried under vacuum to constant weight, obtains modification of chitosan powder；B. 20 parts of natural smectite is weighed, 5% sodium hydroxide of natural smectite quality is weighed, by solid-liquid mass ratio 1:10 add Enter 200mL distilled water, it is 5.6 to adjust pH, and 1h is stirred to react for 60 DEG C in water bath with thermostatic control, the freeze-day with constant temperature at 80 DEG C, fine grinding 100 mesh sieve, it is modified montmorillonite used to obtain sodium；C. it is 10 to take cell concentration5The microalgae solution of/mL, aseptically, with sodium alginate soln, modification of chitosan 1:1:1 It is uniformly mixed and obtains mixed liquor；Mixed liquor is instilled into calcium chloride solution by syringe and carries out 20 ~ 30min of curing, obtains seaweed Sour calcium coagulates pearl；Calcium alginate is coagulated pearl to be washed with distilled water 2 ~ 3 times, you can obtain immobilized microalgae glueballs；The sodium alginate concentration is 20 ~ 25mg/mL；The calcium chloride solution concentration is 18 ~ 22mg/mL；The mixed liquor and calcium chloride solution volume that the microalgae solution is uniformly mixed with sodium alginate soln, modification of chitosan Than being 1：（1.5~2）；D. 40 ~ 80 parts of Kynoar powder is taken, is dissolved in 25 ~ 50 parts of dibutyl phthalates, adds in 50 ~ 100 parts of modifications Chitosan powder, 50 ~ 100 parts of modified montmorillonite used powder of sodium, 2 ~ 10 parts of Geniposides, under nitrogen protection in 210 ~ 223 DEG C of oil baths After 4 ~ 6h of middle stirring is mixed into uniform solution, standing and defoaming obtains polymer；Polymer is passed through into the Weightlessness balance of 5 ‰ measuring accuracies Feeder feeds double screw extruder, under the mixing kneading effect of 250 ~ 300rpm and 2 ~ 5MPa, material is made to be sufficiently mixed The even casting solution into stable homogeneous, casting solution enter nozzle by spinning pump with the speed accurate measurement of 90 ~ 100g/min, Inner cavity enters 298K using the nitrogen of 36 ~ 50mL/min flow velocitys as hollow supporting body after the air section evaporation of certain altitude Water-bath in occur phase separation and curing, with the speed of 25m/min by collect wheel thick hollow-fibre membrane is collected；E. thick hollow-fibre membrane d being prepared is immersed in 95% industrial alcohol 24 hours, and extraction dibutyl phthalate is dilute Agent is released, during which needs to change ethyl alcohol 2 times, it is ensured that diluent extraction is clean, and it is dry with clear water rinsing will to extract the hollow-fibre membrane finished It is net to obtain hollow-fibre membrane；F. hollow-fibre membrane is taken, is assembled into duplicature column, there are the space of 3 ~ 7cm wide among duplicature, outermost tunic bottom is set Dump valve is equipped with, obtains adsorption column；G. multiple adsorption columns are vertically fixed with brandreth, innermost layer hollow space parallel connection is connect with suction pump, is positioned over reaction tank In；（3）Immobilized microalgae glueballs is filled in the intermediate space of adsorption column duplicature, seals adsorption column；（4）It opens sewage pump and sewage is injected into reaction tank, when sewage is not to adsorption column 50 ~ 70%, stop pumping；Open ozone Generating means, ozone aeration quantity are 15 ~ 40g/h, and action time is 10 ~ 20min/h, after ozonization 5h, open suction pump, Adjusting flow is 1 ~ 1.4L/min, and 15 ~ 30min of working time, 40 ~ 60min of time of having a rest make sewage enter adsorption column and fixation After change microalgae glueballs is reacted, the sewage after reaction is discharged into water purifying tank；（5）After operation 4 ~ 7 days, stopping is filled with ozone, stops sewage pump, stop pumping pump, and immobilized microalgae glueballs is passed through suction Attached column bottom-discharge valve is discharged, and is collected；Hollow-fibre membrane is cleaned 2 hours with 2 ~ 5wt%HCl, then with 2000 ~ 3000mg/L NaClO+1000 ~ 2000mg/L NaOH are cleaned 2 hours, and every component cleaning flux is 15 ~ 30L/h, and 23 ~ 25 DEG C of temperature elutes Liquid recycles after collecting for metal ion；（6）It collects immobilized microalgae glueballs and carries out broken wall treatment, by microalgae drying and crushed using heated-air drying, take microalgae powder 100 ~ 200 parts, the cellulase and enzyme activity that 10 ~ 20 parts of enzyme activities of addition are 1400 ~ 1800U/g are 60000 ~ 70000U/g's Neutral proteinase 1:1 combination, after mixing reacts 4 ~ 6h, centrifuges 10 ~ 20 minutes under 5000 ~ 6000rpm, obtains supernatant I and sinks Shallow lake I；（7）Supernatant I is added in 4 DEG C of isometric cold ethyl alcohol mix 12 ~ 14h after, filtering and concentrating to original volume 1/5 ~ 1/4, it is then freeze-dried, obtains microalgae powder i.e. livestock fodder additives.
- 2. a kind of method of fish-farming with sewage microalgae production livestock fodder additives according to claim 1, it is characterised in that： Solar energy LED lamp is provided with outside adsorption column, power supply is provided using solar energy power accumulating plate, is provided in rainy weather for micro algae growth Light source, the intensity of light source are 6000 ~ 10000lux.
- 3. a kind of method of fish-farming with sewage microalgae production livestock fodder additives according to claim 1, it is characterised in that： Immobilized microalgae glueballs loading 50 ~ 70% in adsorption column, adsorption column hollow space are not communicated with duplicature intermediate space part.
- 4. a kind of method of fish-farming with sewage microalgae production livestock fodder additives according to claim 1, it is characterised in that： The ozonization time is 5h/ days.
- 5. a kind of method of fish-farming with sewage microalgae production livestock fodder additives according to claim 1, it is characterised in that： The Kynoar molecular weight is 30KDa ~ 40KDa, a concentration of 30 ~ 35wt% of Kynoar.
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| CN101525576B (en) * | 2009-04-14 | 2013-03-13 | 普罗米绿色能源(深圳)有限公司 | Method for producing microalgae with domestic sewage and industrial sewage |
| CN102161550B (en) * | 2011-01-13 | 2012-11-21 | 蔡志武 | Method for producing feed additive from livestock and poultry breeding wastewater and purifying breeding wastewater to reclaimed water |
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