A kind of utilization feces of livestock and poultry prepares the method for carrying charcoal porous ceramics and slow-release compound fertilizer
Technical field
The invention belongs to field of environmental technology, and in particular to one kind is prepared using feces of livestock and poultry and carries charcoal porous ceramics and sustained release
The method of composite fertilizer.
Background technology
The feces of livestock and poultry of modern farming discharge causes very big pressure to environment.In traditional agriculture, feces of livestock and poultry
All it is that, by compost fermentation, preparing organic fertilizer is used for agricultural production, but modern aquaculture is in order to improve meat, eggs and milk or skin
The quality of hair, often adds the various additives such as iron copper zinc into feed, and these additives greatly can all be arranged with excrement
Go out in vitro, heavy metal can be contained in excrement, the harmful substances such as antibiotic are there is also sometimes because preventing and curing diseases, in excrement, these
Harmful substance, traditional fermented manure method is difficult to dispose, if directly fertilising can cause serious pollution to soil.Thus,
The method for needing to develop resource valuable in a kind of innoxious use feces of livestock and poultry, solve pollution problem.
At present, in water and air improvement, absorption method is a kind of method of the most frequently used Cheap highly effective, and this method is without secondary
Pollution, beneficial to utility is reclaimed, conventional adsorbent has much at present, there is resin, activated carbon, Nano titanate, diatomite
With zeolite etc., in these sorbing materials, some costs are high, and some adsorption capacities are not enough, and this limits its application.
The content of the invention
The side for carrying charcoal porous ceramics and slow-release compound fertilizer is prepared it is an object of the present invention to provide a kind of utilization feces of livestock and poultry
Method.The present invention is innoxious comprehensive utilization feces of livestock and poultry, prepares safe and efficient agricultural fertilizer and the cheap sorbing material of high-performance,
The present invention is raw material using phytophage feces of livestock and poultry, and amino acid and various elements system in excrement are extracted by catalysis oxidation and acid
Standby fertilizer, for agricultural production;Prepared by remaining solid carries charcoal porous ceramics, the processing available for waste water and waste gas, it is also possible to make
The functional filter material of biofilter.
The technical scheme of use is
A kind of utilization feces of livestock and poultry prepares the method for carrying charcoal porous ceramics and slow-release compound fertilizer, comprises the following steps:
1), take fresh feces of livestock and poultry, adjust moisture content 80-85%, add the 10-30% of stool quality diatomite,
1-2% nano barium titanate calcium and the hydrogen peroxide that 10-20% weight/mass percentage composition is 30%, stir, heating micro-boiling 10-
20min, then by stool quality and mixed acid volume ratio be 1Kg:1L ratios, it is respectively 0.3-0.8mol/L and 0.5- to add concentration
The mixed acid solution of 1mol/L phosphoric acid and nitric acid, stirs, and continues to heat holding micro-boiling 10-20min, separation of solid and liquid is obtained
Solid A and liquid A;
2), the solid A for obtaining step one with etc. quality, concentration is respectively 0.2-0.5mol/L and 1-3mol/L hydrogen-oxygens
Change the mixed ammonium/alkali solutions mixing of potassium and ammoniacal liquor, stir, closed, heating, 80-100 DEG C of heat-insulation soaking 12h, tune pH value is 11-
12, separation of solid and liquid obtains solid B and liquid B;
3), with the identical mixed alkali liquor used with step 2, the pH value of adjustment liquid A is 6-7, is staticly settled, solid-liquid
Separation, obtains solid C and liquid C;
4), solid B and solid C is mixed, 105-120 DEG C of drying adds the 10%- of solid B and solid C mixture qualities
60% adhesive, ball milling 1-8h is soaked, shaping, 60-90 DEG C of drying, in 950-1250 DEG C of temperature lower calcination 10-30min, is obtained
To porous ceramic film material, it is soaked in liquid B, heating is concentrated into Baume degrees and reaches 24-32, is cooled to room temperature, separates, inhaled
The porous ceramics and concentrated liquid D of attached saturation;
5), concentrated liquid D is mixed with liquid C, stirred, pH value 6-7 is adjusted with 0.1mol/L nitric acid acid solution, does
It is dry, obtain slow-release compound fertilizer.
6), by the porous ceramics after immersion, 105 DEG C of drying, under isolation air conditionses, in carbonizing 30- at 400-500 DEG C
40min, is passed through with the vapor of the quality such as porous ceramics and to activate 20-30minh in 900 DEG C, obtain carrying charcoal porous ceramics.
Described feces of livestock and poultry is the excrement of Herbivore.
The adhesive that described step four is added is the one or more in kaolin, unselected clay, clay and bentonite.
Advantages of the present invention:While innoxious comprehensive utilization feces of livestock and poultry of the invention, cheap safe agriculture is prepared for
With slow-release compound fertilizer and available for waste water and the load charcoal porous ceramics of exhaust-gas treatment, non-secondary pollution, cost is low, technique letter
It is single, with good economic benefit and environmental benefit.
Brief description of the drawings
Fig. 1 is method process chart.
Embodiment
Nano barium titanate calcium powder body used is this laboratory by document (east, Hou Ping nano barium titanates in the embodiment of the present invention
The preparation of calcium powder body and its chemical journals of absorption behavior [J] to lead in water and cadmium, 2009, (12):1336-1342) method is closed
Into.
Embodiment 1
The cow dung 2Kg that fresh moisture content is 82% is taken, 500g diatomite, 30g nano barium titanate calcium and 300g is added
Weight/mass percentage composition be 30% hydrogen peroxide, stir, heat micro-boiling 10min, add 2L 0.5mol/L phosphoric acid
With 1mol/L nitric acid mixed acid solution, stir, continue to heat holding micro-boiling 10min, suction filtration obtains solid A and liquid
A;By solid A with etc. the potassium hydroxide containing 0.25mol/L of quality and the 2mol/L mixed alkali liquor of ammoniacal liquor mix, stirring is equal
Even, closed, heating after 80 DEG C of heat-insulation soaking 12h, adjusts pH value to be 11 with 0.1mol/L salpeter solutions, suction filtration, obtain solid B and
Liquid B;The pH value for adjusting liquid A with the mixed alkali liquor of the potassium hydroxide containing 0.25mol/L and 2mol/L ammoniacal liquor is 6, stirring
Uniformly, staticly settle, suction filtration, separation of solid and liquid, obtain solid C and liquid C;Solid B and solid C is mixed, 105 DEG C of drying, plus
Enter 40% kaolin of mixture gross mass, the bead that particle diameter is 3mm, 60 DEG C of bakings is made in mixing and ball milling 5h, wetting shaping
It is dry, it is placed in high temperature furnace, is calcined in 1000 DEG C in 20min, stove and be cooled to room temperature, obtained porous ceramics, be soaked in liquid B,
It is 27 that heating, which is concentrated into Baume degrees, and refrigerated separation obtains the porous ceramics and concentrated liquid D of adsorption saturation;By concentrated liquid D with
Liquid C is mixed, and adjusts pH value to be 7 with 0.1mol/L salpeter solutions, and spray drying obtains slow-release compound fertilizer 1;Will be porous after immersion
Ceramics, drying, are placed in retort, and 30min is carbonized in 450 DEG C under nitrogen protection, then are placed in activation furnace, are passed through porous ceramics
Vapor etc. quality activates 30min in 900 DEG C, obtains carrying charcoal porous ceramics 1.
Embodiment 2
The cow dung 2Kg that fresh moisture content is 85% is taken, 200g diatomite, 20g nano barium titanate calcium and 200g is added
Weight/mass percentage composition be 30% hydrogen peroxide, stir, heat micro-boiling 20min, add 2L 0.3mol/L phosphoric acid
With 1mol/L nitric acid mixed acid solution, stir, continue to heat holding micro-boiling 20min, suction filtration obtains solid A and liquid
A;By solid A with etc. the potassium hydroxide containing 0.5mol/L of quality and the 3mol/L mixed alkali liquor of ammoniacal liquor mix, stir,
It is closed, heat, after 100 DEG C of heat-insulation soaking 12h, adjust pH value to be 12 with 0.1mol/L salpeter solutions, suction filtration obtains solid B and liquid
Body B;The pH value for adjusting liquid A with the mixed alkali liquor of the potassium hydroxide containing 0.5mol/L and 3mol/L ammoniacal liquor is 7, and stirring is quiet
Precipitation is put, suction filtration, separation of solid and liquid obtains solid C and liquid C;Solid B and solid C is mixed, 120 DEG C of drying add mixture
The bead that particle diameter is 8mm is made in 30% kaolin of gross mass, mixing and ball milling 1h, wetting shaping, and 90 DEG C of drying are placed in height
In warm stove, calcined in 1100 DEG C in 20min, stove and be cooled to room temperature, obtained porous ceramics, be soaked in liquid B, heating is concentrated into
Baume degrees is 24, refrigerated separation, obtains the porous ceramics and concentrated liquid D of adsorption saturation;Concentrated liquid D is mixed with liquid C,
PH value is adjusted to be 6 with 0.1mol/L salpeter solutions, evaporation drying obtains slow-release compound fertilizer 2;By the porous ceramics after immersion, 105 DEG C
Drying, is placed in retort, and 40min is carbonized in 450 DEG C under nitrogen protection, then is placed in activation furnace, is passed through the matter such as porous ceramics
The vapor of amount activates 20min in 900 DEG C, obtains carrying charcoal porous ceramics 2.
Embodiment 3
Take the sheep manure 2Kg that fresh adjustment moisture content is 80%, add 600g diatomite, 40g nano barium titanate calcium and
400g weight/mass percentage composition is 30% hydrogen peroxide, is stirred, and heats micro-boiling 15min, adds 2L 0.8mol/L's
The nitric acid mixed acid solution of phosphoric acid and 0.5mol/L, stirs, and continues to heat holding micro-boiling 15min, suction filtration obtains solid A
And liquid A;By solid A with etc. the potassium hydroxide containing 0.25mol/L of quality and the 2mol/L mixed solution of ammoniacal liquor mix, stir
Mix uniformly, airtight heating, after 90 DEG C of heat-insulation soaking 12h, adjust pH value to be 11 with 0.1mol/L salpeter solutions, suction filtration obtains solid B
And liquid B;The pH values that liquid A is adjusted with the mixed alkali liquor of the potassium hydroxide containing 0.25mol/L and 2mol/L ammoniacal liquor are 7, are stirred
Mix, staticly settle, suction filtration, separation of solid and liquid obtains solid C and liquid C;Solid B and solid C is mixed, 110 DEG C of drying are added
The bead that particle diameter is 5mm, 80 DEG C of bakings is made in 60% unselected clay of mixture gross mass, mixing and ball milling 6h, wetting shaping
It is dry, it is placed in high temperature furnace, is calcined in 950 DEG C in 30min, stove and be cooled to room temperature, obtained porous ceramics, be soaked in liquid B, plus
It is 32 that heat, which is concentrated into Baume degrees, and refrigerated separation obtains the porous ceramics and concentrated liquid D of adsorption saturation;By concentrated liquid D with
Liquid C is mixed, and is 6 with 0.1mol/L salpeter solutions adjustment pH value, evaporation drying obtains slow-release compound fertilizer 3;Will be many after immersion
Hole ceramics, 105 DEG C of drying, are placed in retort, and 40min is carbonized in 400 DEG C under nitrogen protection, then are placed in activation furnace, are passed through
The vapor of the quality such as porous ceramics activates 20min in 900 DEG C, obtains carrying charcoal porous ceramics 3.
Embodiment 4
Take the horsehit 2Kg that fresh adjustment moisture content is 80%, add 400g diatomite, 30g nano barium titanate calcium and
300g weight/mass percentage composition is 30% hydrogen peroxide, is stirred, and heats micro-boiling 13min, adds 2L 0.5mol/L's
The nitric acid mixed acid solution of phosphoric acid and 0.8mol/L, stirs, and continues to heat holding micro-boiling 13min, suction filtration obtains solid A
And liquid A;By solid A with etc. the potassium hydroxide containing 0.2mol/L of quality and the 3mol/L mixed alkali liquor of ammoniacal liquor mix, stir
Mix uniformly, airtight heating, after 84 DEG C of heat-insulation soaking 12h, adjust pH value to be 11 with 0.1mol/L salpeter solutions, suction filtration obtains solid B
And liquid B;The pH values that liquid A is adjusted with the mixed alkali liquor of the potassium hydroxide containing 0.2mol/L and 3mol/L ammoniacal liquor are 6, are stirred
Mix, staticly settle, suction filtration, separation of solid and liquid obtains solid C and liquid C;Solid B and solid C is mixed, 105 DEG C of drying are added
The bead that particle diameter is 7mm is made in 50% kaolin of mixture gross mass, mixing and ball milling 8h, wetting shaping, and 90 DEG C dry,
It is placed in high temperature furnace, is calcined in 1200 DEG C in 10min, stove and be cooled to room temperature, obtained porous ceramics, be soaked in liquid B, heated
It is 30 to be concentrated into Baume degrees, and refrigerated separation obtains the porous ceramics and concentrated liquid D of adsorption saturation;By concentrated liquid D and liquid
Body C is mixed, and pH value 7 is adjusted with 0.1mol/L salpeter solutions, and evaporation drying obtains slow-release compound fertilizer 4;By the porous pottery after immersion
Porcelain, 105 DEG C of drying, is placed in retort, and 30min is carbonized in 500 DEG C under nitrogen protection, then is placed in activation furnace, is passed through porous
The vapor of the quality such as ceramics activates 20min in 900 DEG C, obtains carrying charcoal porous ceramics 4.
Embodiment 5
The deer excrement 2Kg that fresh moisture content is 80% is taken, 400g diatomite, 30g nano barium titanate calcium and 400g is added
Weight/mass percentage composition be 30% hydrogen peroxide, stir, heat micro-boiling 18min, add 2L 0.8mol/L phosphoric acid
With 1mol/L nitric acid mixed acid solution, stir, continue to heat holding micro-boiling 18min, suction filtration obtains solid A and liquid
A;By solid A with etc. the potassium hydroxide containing 0.5mol/L of quality and the 1mol/L mixed alkali liquor of ammoniacal liquor mix, stir,
After airtight heating, 100 DEG C of heat-insulation soaking 12h, pH value is adjusted to be 11 with 0.1mol/L salpeter solutions, suction filtration obtains solid B and liquid
B;The pH value for adjusting liquid A with the mixed alkali liquor of the potassium hydroxide containing 0.5mol/L and 1mol/L ammoniacal liquor is 6, is stirred, and is stood
Precipitation, suction filtration, separation of solid and liquid obtains solid C and liquid C;Solid B and solid C is mixed, 120 DEG C of drying add mixture total
The bead that particle diameter is 6mm, 80 DEG C of bakings is made in 10% clay and 10% bentonite of quality, mixing and ball milling 4h, wetting shaping
It is dry, it is placed in high temperature furnace, is calcined in 1250 DEG C in 20min, stove and be cooled to room temperature, obtained porous ceramics, be soaked in liquid B,
It is 26 that heating, which is concentrated into Baume degrees, and refrigerated separation obtains the porous ceramics and concentrated liquid D of adsorption saturation;By concentrated liquid D with
Liquid C is mixed, and pH value 7 is adjusted with 0.1mol/L salpeter solutions, and spray drying obtains slow-release compound fertilizer 5;By the porous pottery after immersion
Porcelain, 105 DEG C of drying, is placed in retort, and 30min is carbonized in 450 DEG C under nitrogen protection, then is placed in activation furnace, is passed through porous
The vapor of the quality such as ceramics activates 20min in 900 DEG C, obtains carrying charcoal porous ceramics 5.
Embodiment 6
The cow dung 2Kg that fresh moisture content is 81% is taken, 400g diatomite, 20g nano barium titanate calcium and 300g is added
Weight/mass percentage composition be 30% hydrogen peroxide, stir, heat micro-boiling 12min, add 2L 0.8mol/L phosphoric acid
With 1mol/L nitric acid mixed acid solution, stir, continue to heat holding micro-boiling 12min, suction filtration obtains solid A and liquid
A;By solid A with etc. the potassium hydroxide containing 0.25mol/L of quality and the 2mol/L mixed alkali liquor of ammoniacal liquor mix, stirring is equal
Even, airtight heating after 95 DEG C of heat-insulation soaking 12h, adjusts pH value to be 12, suction filtration obtains solid B and liquid with 0.1mol/L salpeter solutions
Body B;The pH value for adjusting liquid A with the mixed alkali liquor of the potassium hydroxide containing 0.25mol/L and 2mol/L ammoniacal liquor is 7, and stirring is quiet
Precipitation is put, suction filtration, separation of solid and liquid obtains solid C and liquid C;Solid B and solid C is mixed, 105 DEG C of drying add mixture
The bead that particle diameter is 4mm is made in 40% kaolin of gross mass, mixing and ball milling 8h, wetting shaping, and 85 DEG C of drying are placed in height
In warm stove, calcined in 1050 DEG C in 20min, stove and be cooled to room temperature, obtained porous ceramics, be soaked in liquid B, heating is concentrated into
Baume degrees is 28, refrigerated separation, obtains the porous ceramics and concentrated liquid D of adsorption saturation;Concentrated liquid D is mixed with liquid C,
PH value 7 is adjusted with 0.1mol/L salpeter solutions, evaporation drying obtains slow-release compound fertilizer 6;By the porous ceramics after immersion, 105 DEG C of bakings
It is dry, it is placed in retort, 40min is carbonized in 450 DEG C under nitrogen protection, then be placed in activation furnace, it is passed through the quality such as porous ceramics
Vapor activate 30min in 900 DEG C, obtain carrying charcoal porous ceramics 6.
Embodiment 7:The performance indications parameter of slow-release compound fertilizer
By the composite fertilizer obtained by embodiment 1-6 according to National Standard of the People's Republic of China " organic-inorganic complex fertilizer "
(GB18877-2009) require and the fertile performance of method test and safety index;By " slow release fertilizer " (GB/T 23348-2009),
Test sustained release performance.Indices are shown in Table 1:
The index (weight/mass percentage composition) of the compound fertilizer of table 1
Embodiment 8:Carry charcoal porous ceramics performance
The load charcoal porous ceramics 1-6 that embodiment 1-6 is obtained is by " CJ/T 299-2008 water process manually ceramic grain filter "
The method detection of regulation, every testing result is shown in Table 2
Table 2 carries charcoal porous ceramics performance indications
Embodiment 9:Carry purifying property of the charcoal porous ceramics to water
In order to investigate the absorption property for carrying charcoal porous ceramics 1-6 heavy metals and organic matter obtained in embodiment 1-6, take
2L is leaded and methylenum careuleum be respectively 200mg/L and 5mg/L mixed standard solution, adjust the pH value of solution to 6, be separately added into 200g
The load charcoal porous ceramics obtained in embodiment 1-6, is stirred frequently, soaks 1h, and heavy metal lead in supernatant is surveyed with Atomic absorption
Content, with the content of spectrophotometric determination methylenum careuleum, clearance is calculated by formula (1).It the results are shown in Table 3.
In formula:η is clearance (%);C0For initial concentration (mg/L);CeFor equilibrium concentration (mg/L).
Table 3 carries the absorption property of charcoal porous ceramics
Embodiment 10:Carry removal capacity of the charcoal porous ceramics to formaldehyde in air
The load charcoal porous ceramics 500g obtained in Example 1-6 is placed in 500 × 300mm pallet, is placed in long × wide
In × a height of 1250mm × 800mm × 1000mm full glass air chamber, the initial concentration of formaldehyde is 5mg/ in adjusting tank
m3, under the conditions of indoor natural light, air in fan, disturbance case is opened, 12h is placed, according to GB/T18204.26-2000, used
Concentration of formaldehyde in phenol reagent method mensure case, calculates adsorbance and clearance, while doing blank assay.It the results are shown in Table 4:
Removal capacity of the table 4 to formaldehyde in air
|
Concentration of formaldehyde (mg/m3) after absorption |
Clearance (%) |
Carry charcoal porous ceramics 1 |
0 |
100 |
Carry charcoal porous ceramics 2 |
0 |
100 |
Carry charcoal porous ceramics 3 |
0 |
100 |
Carry charcoal porous ceramics 4 |
0 |
100 |
Carry charcoal porous ceramics 5 |
0 |
100 |
Carry charcoal porous ceramics 6 |
0 |
100 |
Blank assay |
4.91 |
1.8 |