CN106423052A - Method for preparing biochar balls through pyrolyzing farm ditch bottom mud and rice straws - Google Patents
Method for preparing biochar balls through pyrolyzing farm ditch bottom mud and rice straws Download PDFInfo
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Abstract
The invention relates to a method for preparing biochar balls through pyrolyzing farm ditch bottom mud and rice straws. The method comprises the following steps: 1, preparing ditch bottom mud powder for later use; 2, preparing rice straw powder, and preserving the rice straw powder in a wide-mouth bottle for later use; and 3, adding the ditch bottom mud powder to the rice straw powder, uniformly mixing the powders, adding a small amount of distilled water, preparing small pellets with a certain particle size by using a pelletizing machine, placing the small pellets in a quartz boat, placing the quartz boat in a vacuum tubular furnace, heating the furnace under nitrogen introducing anoxic keeping conditions for keeping the temperature unchanged for a certain time, naturally cooling the heated granular pellets in nitrogen atmosphere to room temperature, taking out the cooled granular pellets, carrying out ultrasonic cleaning on the granular pellets with deionized water until the pH value is 7, carrying out blast drying the cleaned pellets, and weighing the dried pellets in order to obtain the final biochar balls. The farm ditch bottom mud and the rice straws are convenient to draw and have low cost, and can be processed to form the biochar balls in order to realize changing of wastes into valuables and reach wide application prospect in the treatment of ammonia nitrogen in farmland drainage.
Description
Technical field
The present invention relates to a kind of preparation method of biology carbon ball, it is specifically related to a kind of farm ditch bed mud and rice straw pyrolysis
The method of the biological carbon ball of preparation.
Background technology
Ammonia nitrogen is the common contaminant of body eutrophication, and agricultural area source is its important pollution sources.China's agricultural production
During nitrogenous fertilizer usage amount larger, account for that world's nitrogenous fertilizer uses total amount 36.9%, and nitrogenous fertilizer apply absorbed by crops behind farmland,
Using the 40%-50% only accounting for its sowing amount.A large amount of nitrogen fertilizers, from Agricultural land loss, enter water body nearby through irrigation canals and ditches runoff and make
Become pollution.According to statistics, farmland nutrient loss is up to 27% to the contribution rate in periphery river, lake eutrophication, and ammonia nitrogen is farmland
The Main Morphology of the inorganic polluted by nitrogen of draining.During " 12 ", ammonia nitrogen is included contaminant transport model index body by China
System, in improvement water body of adopting an effective measure, ammonia and nitrogen pollution is of great practical significance.
Biological carbon is the biological material richness that low temperature (general ＜ 700 DEG C) pyrolysis is prepared under anoxic or oxygen free condition
Carbon solid, has larger specific surface area, porosity and extremely strong adsorption capacity.Research shows, biological carbon is preferable soil
Earth modifying agent, adds to soil, can improve soil nutrient, improve soil texture and microbial ecological.Research finds, adds
Promote the soil enzyme activities containing cinnamic acid after 2.5% and 5% corncob biological carbon, increased bacterial number in soil, subtract
Lack fungi.However, biological carbon is applied to water process aspect, focus primarily upon Organic Pollutants In Water and a huge sum of money at present
The Adsorption belonging to.
Irrigation canals and ditches are the important component parts of farmland sysrem, and farm ditch bed mud has " remittance " and " source " function of nutritive salt.Have
Research shows, farm ditch bed mud has significant suction-operated to ammonia nitrogen in agricultural drain.But, using farm ditch bed mud as former
Material pyrolysis preparation biological carbon, and at home and abroad there is not been reported as the sorbing material of water body ammonia nitrogen.It is therefore proposed that the present invention.
Content of the invention
For the above-mentioned technical problem of prior art, the invention provides a kind of farm ditch bed mud and rice straw pyrolysis preparation
The method of biological carbon ball, it utilizes rice straw to cover the obvious mitigation effect run off in naked field to farmland ammonia nitrogen, with farm ditch bed mud
Blending agriculture waste biomass water rice straw is raw material, the biological carbon ball sorbing material of anaerobic pyrolysis preparation at 600 DEG C, and passes through
Simulated experiment, studies its absorption property to water body ammonia nitrogen, builds kinetics model of biosorption and isotherm adsorption model, investigates temperature
Biological carbon ball is adsorbed with the impact of ammonia nitrogen effect, theoretical to providing for the improvement application of biological carbon ball ammonia nitrogen in agricultural drain
Reference.
For reaching above-mentioned purpose, the present invention is achieved by the following technical solutions：
A kind of farm ditch bed mud and the method for the biological carbon ball of rice straw pyrolysis preparation, comprise the following steps：
(1) irrigation canals and ditches bed mud is fetched air blast under uniform temperature and is dried, and picks debris therein, grinds, sieves, and is obtained
Irrigation canals and ditches bed mud powder, standby；
(2) remove surface impurity through water washing from the beginning after rice straw is fetched, dry, cut short, air blast under uniform temperature
Fully dry, with microphyte pulverizer grinding and sieving, prepared rice straw powder, and it is stored in wide-mouth bottle, standby；
(3) irrigation canals and ditches bed mud powder is mixed rice straw powder, mix, prepared using pellet processing machine after adding a small amount of distilled water
Become the pellets of certain particle diameter, place in quartz boat, be placed in vacuum tube furnace, logical nitrogen keeps under anoxia condition,
600 DEG C -800 DEG C constant temperature certain times are heated to certain heating rate, then proceed to treat natural cooling in nitrogen atmosphere
Take out to room temperature, deionized water is cleaned by ultrasonic to pH neutrality, is finally dried with air blast, weighs, make biological carbon ball finished product.
Irrigation canals and ditches bed mud in described step (1) dries 20-24h at 100-105 DEG C.3rd, farm ditch as claimed in claim 1
The method of bed mud and the biological carbon ball of rice straw pyrolysis preparation it is characterised in that：Irrigation canals and ditches bed mud in described step (1) grinds
Afterwards, cross 80-100 mesh sieve.
The air blast at 80-90 DEG C of rice straw in described step (2) is fully dry.
Rice straw in described step (2) crosses 80-90 mesh sieve after pulverizing.
The weight of the irrigation canals and ditches bed mud in described step (3) and rice straw powder is than for 5-20:1.
The particle diameter of the pellets in described step (3) is 4-5mm.
Nitrogen 200-300mL min is led in described step (3)-1Keep under anoxia condition, with 8-9 DEG C of min-1Intensification
Speed is heated to 500-600 DEG C of constant temperature 3-4h.
24h is dried in 100-105 DEG C of air blast in described step (3).
The method of farm ditch bed mud of the present invention and the biological carbon ball of rice straw pyrolysis preparation has the advantages that：
1st, the interpolation of appropriate rice straw, increased the skeleton structure supporting biological carbon ball inner space, is conducive to improving
The porosity of biological carbon ball, increases permeability, thus improving its mass-transfer performance.
2nd, the interpolation of rice straw, makes biological carbon ball introduce more hydroxyls and aromatic ring structure, improves it hydrophilic
Property, and stability is higher, in addition, biological carbon ball surface acidity oxygen-containing functional group quantity also has increase after adding rice straw.
3rd, adsorption dynamics adsorption kinetics research shows, the biological carbon ball that the present invention is obtained relatively meets pseudo-first-order to the adsorption reaction of ammonia nitrogen
Kinetics equation and pseudo-second order kinetic equation, can preferably describe it and adsorb ammonia nitrogen process, and it is mainly subject to chemical absorption of surface
, in addition to interior diffusion, also there is the speed that other process co- controlling biology carbon balls adsorb ammonia nitrogen in process control.
4th, Tellurium determination research shows, Langmuir equation can preferably describe the absorption to ammonia nitrogen for the biological carbon ball
Journey, and this adsorption process belongs to the uniform mono layer adsorption in surface, and biological carbon ball is to absorb heat to the adsorption process of ammonia nitrogen
Journey, high temperature is conducive to adsorbing.
5th, farm ditch bed mud and rice straw are drawn materials conveniently, with low cost, be prepared into biological carbon ball can not only become give up into
Treasured, and have broad application prospects in terms of the improvement of ammonia nitrogen in agricultural drain.
Brief description
Fig. 1 is the biological carbon ball outside drawing of the present invention；
Fig. 2-7 is the SEM figure of straw biological carbon and biological carbon ball；
Fig. 8 is the infrared spectrum of biological carbon ball；
Fig. 9 be defined first _ order kinetics equation biology carbon ball adsorb ammonia nitrogen kinetic curve；
Figure 10 be defined second-order kinetic equation biology carbon ball adsorb ammonia nitrogen kinetic curve；
Figure 11 is the kinetic curve that modified intra-particle diffusion model biology carbon ball adsorbs ammonia nitrogen；
Figure 12-16 is the biological adsorption isothermal curve to ammonia nitrogen for the carbon ball；
Figure 17 is the impact to ammonia nitrogen absorption effect for the temperature.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
Embodiment
The present embodiment adopts farmland ditch bed mud to blend a certain proportion of rice straw as the biological carbon ball of raw material preparation,
Irrigation canals and ditches bed mud and rice straw are taken from Shaoxin City Yuecheng District farmland, and concrete grammar is：
(1) irrigation canals and ditches bed mud is fetched and is dried 24h after 105 DEG C of air blast, and picks the wherein debris such as weeds, grinds, and crosses 100 mesh
Sieve, prepared irrigation canals and ditches bed mud powder, standby；
(2) remove surface impurity through water washing from the beginning after rice straw is fetched, dry, cut short, fully dry in 80 DEG C of air blast
Dry, cross 80 mesh sieves, prepared rice straw powder after being pulverized with microphyte pulverizer, and be stored in wide-mouth bottle, standby；This reality
Apply chemical reagent used in example be analysis pure.
(3) the irrigation canals and ditches bed mud powder sample of 5 parts of each 1kg is mixed the paddy rice straw of 0g, 50g, 100g, 150g, 200g respectively
Stalk powder sample, mixes, and is prepared into, using LD-88A pellet processing machine, the pellets that particle diameter is 5mm after adding a small amount of distilled water, then
Put in quartz boat, be placed in BTF-1200C vacuum tube furnace, logical nitrogen 300mL min-1Keep under anoxia condition, with 9
℃·min-1Heating rate be heated to 600 DEG C of constant temperature 4h, then proceed in nitrogen atmosphere to take after after naturally cool to room temperature
Go out, deionized water is cleaned by ultrasonic to pH neutrality, dries 24h after 105 DEG C of air blast, weighs, make biological carbon ball finished product, such as
Shown in Fig. 1, and it is numbered respectively is SS-0, SS-50, SS-100, SS-150, SS-200.
Performance test
First, the physicochemical characterization analysis of biological carbon
In biological carbon, C, H, N, O constituent content is entered using EA3000 elemental analyser (Italian Euro vector company)
Row measures；Specific surface area and distribution of pores adopt Empyrean specific surface area and lacunarity analysis instrument (U.S. Micromeritics
Company) test；Surface topography adopts JSM-6360LV SEM (NEC JEOL) to analyze；Transmission INFRARED SPECTRUM exists
NEXUS FTIS (U.S. Buddhist nun high-tensile strength) is upper to be tested；The surface acidity oxygen-containing functional group quantity of biological carbon ball
Using Boehm titration measuring, experiment is repeated 3 times averages；
Mass transfer performances measure：Add 1mL0.1% methylene blue solution to be made into test fluid in 50mL deionized water, and put into
10 biological carbon balls, after standing 24h, with deionized water as reference, measure biological carbon ball place methylene blue at 665nm respectively
The absorbance of test fluid and the absorbance of former test fluid, calculate the methylene blue percentage of biological carbon ball absorption, experiment weight with this
Average for 3 times again；
Mechanical strength coefficient determination：10 biological carbon balls are put into 100mL conical flask, adds 50mL deionized water, with
120r·min-1Constant temperature oscillation, observes the percentage accounting of intact biology carbon ball quantity after 24h, represents the machinery of biological carbon ball with this
Strength factor.
2nd, the ammonia nitrogen absorption performance measurement of biological carbon ball
1st, ammonia nitrogen absorption kinetic determination
By 30mg L-1Ammonium chloride solution as ammonia nitrogen simulated wastewater, take 200mL to put in the conical flask of 250mL, plus
Enter 4 biological carbon balls weighed as adsorbent, seal, with 120r min under 25 DEG C of constant temperature-1Constantly vibration waste water is molten
Liquid, takes its ammonia nitrogen of useless water determination when 5min, 10min, 30min, 50min, 70min, 1.5h, 2h, 6h, 12h and 24h
Concentration, and be compared with the ammonia-nitrogen content of former simulated wastewater, thus calculating the ammonia nitrogen absorption amount of biological carbon ball.By accurate one
Level, pseudo-second order kinetic equation and modified intra-particle diffusion model are fitted to experiment the data obtained, dynamic to determine optimal absorption
Mechanical model.
2nd, ammonia nitrogen absorption thermoisopleth measures
Take the conical flask of 8 250mL, be separately added into the ammonia nitrogen simulation that 100mL prepares by variable concentrations ammonium chloride solution useless
Water, respectively adds 4 biological carbon balls weighed as adsorbent, with 120r min under 25 DEG C of constant temperature-1Constantly vibration waste water is molten
Liquid, takes its ammonia nitrogen concentration of useless water determination after balance to be adsorbed, and is compared with the ammonia-nitrogen content of former simulated wastewater, thus counting
Calculate the ammonia nitrogen absorption amount of biological carbon ball.Computing formula is as follows：
In formula：qtFor the adsorbance to ammonia nitrogen for the biological carbon ball t, mg g-1；C0、CtIt is respectively initial, t waste water
The concentration of sample ammonia nitrogen, mg L-1；V is the volume of waste water sample, mL；M is the dosage of biological carbon ball, g.
3rd, assay method
Reference《Water and effluent monitoring analysis method (fourth edition)》Middle relevant regulations, ammonia nitrogen adopts Nessler's reagent photometer to survey
Fixed, nessler reagent is prepared with mercuric chloride-KI-potassium hydroxide solution, before water determination, adds ZnSO4Solution simultaneously adjusts pH value
To 10.5, flocculation sediment hypsokinesis takes supernatant to make sample, under 420nm wavelength, measures absorbance with 10mm cuvette.Analyzer
Device is UV-2102PCS type ultraviolet-uisible spectrophotometer (You Nike Shanghai Instrument Ltd., wavelength accuracy is ± 0.3nm),
Experiment is repeated 3 times averages.
The performance test results and analysis
First, the physicochemical property of biological carbon and phenetic analysis
Water intaking rice straw powder sample puts into quartz boat, is placed in vacuum tube furnace, and logical nitrogen is simultaneously pyrolyzed at 600 DEG C
4h, prepared rice straw biological carbon.The physicochemical properties of rice straw biological carbon and biological carbon ball are shown in Table 1.
Table 1 rice straw biological carbon and the physicochemical properties of biological carbon ball
As it can be seen from table 1 the content of rice straw biological carbon C, H, N and O will apparently higher than farm ditch bed mud biological carbon (i.e.
SS-0), but itself H/C and O/C atomic ratio is relatively low, only 0.03 and 0.15, illustrate rice straw in the preparation life of 600 DEG C of anaerobic pyrolysises
More aromatic ring structure is defined during thing carbon, this is because the phosphorus content of pyrolysis product is higher, H/C ratio and O/C
Ratio is lower, then its armaticity improves, and polarity declines.In conjunction with ESEM result (Fig. 2-7) it is also found that rice straw is biological
Carbon appearance structure surfaces externally and internally relative smooth, aperture is larger, meets measured BET pore size, is 74.59nm, and farm ditch
Bed mud biology carbon surface is then more coarse, forms a small amount of pore structure, and aperture is less, is 15.88nm, this has resulted in farm ditch bottom
The specific surface area of mud biological carbon compares the larger of rice straw biological carbon.However, pyrolysis system after with the addition of a certain amount of rice straw
Standby biological carbon ball compares the biological carbon ball (SS-0) of pure farm ditch bed mud preparation, and its mass-transfer performance improves much, wherein, SS-50
The mass transfer performances of biological carbon ball are up to 52%, and this illustrates the interpolation of appropriate rice straw, increased the biological carbon ball inner space of support
Skeleton structure, be conducive to improving the porosity of biological carbon ball, increase its permeability.Additionally, being pyrolyzed the biological carbon of preparation herein
Ball mechanical strength is higher, and water resistant impulsive force is strong, 120r min in deionized water-1After constant temperature oscillation 24h, its serviceability rate all reaches
100%.
With infrared spectrum analysis biology carbon ball, obtain the result of Fig. 8.According to Fig. 8,3000-3665cm-1Wide absorption
Peak is that the stretching vibration of the O-H of hydroxyl causes, and with the increase of rice straw addition in biological carbon ball, this absorption peak strength is bright
Aobvious strengthen, and intermolecular hydrogen bonding is to polymolecular associated forms (3400-3200cm-1) i.e. polymer change, reflect biological carbon
In ball, the content of organic matter such as cellulose is increasing.In 2356cm-1Near, SS-50, SS-100, SS-150 and SS-200 all occur
On phenyl ring=C-H stretching vibration absworption peak, and SS-0 does not have this phenomenon, and the interpolation of rice straw is described, make biological carbon ball
Introduce aromatic cyclic structure, and this structure is difficult to be destroyed in the reaction, therefore with the addition of the biological carbon ball of rice straw
Stability is higher.Additionally, 5 kinds of biological carbon balls are in 1005cm-1Nearby all occur in that the C-O stretching vibration absworption peak of alcohol, and inhale
Receipts intensity is larger, and wherein, SS-0 there is likely to be C-O-C group (1031cm-1).763-787cm-1It is to become outside the C-H face of phenyl ring
Shape vibration absorption peak is it may be determined that the replacement type that the present invention is pyrolyzed phenyl ring in the biological carbon ball of preparation is 1,3 two replacements.
466cm-1It to be the vibration absorption peak of Si-O-Si that neighbouring absworption peak is corresponding, and in biological carbon ball, the peak of Si-O-Si then represents
Ash content.
By Boehm titration, the content of biological carbon ball surface acidity oxygen-containing functional group is determined.Result shows,
SS-0, SS-50, SS-100, SS-150 and SS-200 biological carbon ball surface acidity oxygen-containing functional group content is respectively
2.74mmol·L-1、2.88mmol·L-1、3.71mmol·L-1、3.36mmol·L-1With 3.03mmol L-1.Contrast SS-0
Biological carbon ball, it can be found that the interpolation of rice straw, increased the content of biological carbon ball surface acidity oxygen-containing functional group, and acid
The increase of oxygen-containing functional group content then can improve the hydrophily of biological carbon, increases the cation exchange capacity (CEC) of biological carbon, favorably
In the absorption to ammonia nitrogen.
2nd, the ammonia nitrogen absorption experiment of biological carbon ball
1st, adsorption dynamics adsorption kinetics analysis
Fig. 4 reflects the relation of the adsorbance to ammonia nitrogen for the biological carbon ball and adsorption time, from Fig. 9-11, biological carbon ball
To ammonia nitrogen all in positive absorption, adsorbance extend in time first in rising trend, after gradually tend to balance.Before 2h, ammonia nitrogen absorption increases
Substantially, after 6h, adsorbance is basicly stable, therefore it is ammonia nitrogen absorption equilibration time that subsequent experimental takes 6h for amount.
With reference to pseudo-first-order kinetics equation, pseudo-second order kinetic equation and modified intra-particle diffusion model, soft using Origin8.6
The experimental data that part adsorbs ammonia nitrogen to biological carbon ball is fitted analyzing.
Pseudo-first-order kinetics equation expression formula is：
Pseudo-second order kinetic equation expression formula is：
Modified intra-particle diffusion model expression formula is：
qt=kit0.5+C (4)
In formula：qtAnd qeIt is respectively during elapsed time t and the biological adsorbance to ammonia nitrogen for the carbon ball, mg g during adsorption equilibrium-1；T is adsorption time, h；k1、k2And kiIt is respectively the speed of pseudo-first-order dynamics, pseudo-second order kinetic and modified intra-particle diffusion model
Constant, its unit is respectively h-1、g·(mg·h)-1With mg (g h0.5)-1；C is constant.
Fitting experimental data result is listed in table 2.By fitting parameter (table 2), the equal energy of pseudo-first-order, pseudo-second order kinetic
Preferably describe the SS-0 biology absorption behavior to ammonia nitrogen for the carbon ball, but adsorption reaction more meets pseudo-first-order kinetics equation, may
Affected larger in its adsorption process by particle inner transmission matter resistance.However, for SS-50, SS-100, SS-150 and SS-200 life
Thing carbon ball, the ideal of the calibrated first _ order kinetics equation of result of pseudo-second order kinetic equation model, the theoretical adsorption capacity of ammonia nitrogen
Basically identical with the data that experiment records, show that it is mainly subject to chemical absorption of surface process control, meet agriculture drainage ditch bottom
Mud adsorbs the ammonia nitrogen mainly feature based on chemisorbed and ion exchange.Additionally, the relative coefficient R from equation model2Value
From the point of view of modified intra-particle diffusion model be not appropriate for the description biological adsorption process to ammonia nitrogen for the carbon ball herein, if but the curve of its matching lead to
Cross initial point, then rate constants are intra-particle diffusion, if not passing through initial point then it represents that also having other process co- controllings reaction speed
Rate.Can be seen that constant C in modified intra-particle diffusion model by table 2 and Figure 11 is not 0, and that is, curve, all without initial point, illustrates to give birth to
The speed that thing carbon ball adsorbs ammonia nitrogen is probably by chemical absorption of surface and intra-particle diffusion co- controlling.
The fitting parameter of table 2 kinetics equation
2nd, adsorption isotherm line analysis
Preparing ammonium chloride concentration respectively is 50,35,30,25,20,15,10 and 5mg L-1Ammonia nitrogen simulated wastewater, research
Biological carbon ball reaches the relation between ammonia nitrogen absorption amount during adsorption equilibrium and ammonia nitrogen in solution concentration.Figure 12-16 is biological carbon
The adsorption isothermal curve to ammonia nitrogen for the ball, by Figure 12-16 it is found that biological carbon ball is initial with solution to the equilibrium adsorption capacity of ammonia nitrogen
The increase of concentration and increase.
Ammonia nitrogen absorption amount during adsorption equilibrium that biological carbon ball is reached is used with the now experimental data such as ammonia nitrogen concentration of solution
Langmuir and Freundlich Tellurium determination is fitted.
Langmuir equation expression formula is：
Freundlich equation expression formula is：
In formula：qeFor equilibrium adsorption capacity, mg g-1；qmFor saturated extent of adsorption, mg g-1；KLAnd KFIt is respectively Langmuir
With the constant of Freundlich equation at constant temperature, its unit respectively L mg-1(mg g-1)(L·mg-1)1/n；CeFlat for absorption
NH in solution during weighing apparatus4 +Concentration, mg L-1；N is the constant relevant with biological carbon ball adsorption strength.
With Origin8.6 software analysis, equation model parameter is shown in Table 3.Two kinds of Tellurium determination matchings in comparison sheet 3
Relative coefficient R2Value, it can be found that Langmuir equation can preferably describe the adsorption process to ammonia nitrogen for the biological carbon ball, and
And real balance adsorbance qeIt is respectively less than theoretical saturated extent of adsorption qm, illustrate that this adsorption process belongs to the uniform monolayer in surface
Absorption.With the increase of rice straw addition, biological carbon ball is continuously increased to the saturated extent of adsorption of ammonia nitrogen, wherein SS-200
Saturated extent of adsorption is maximum, reaches 6.038mg g-1.Additionally, literature research shows, the numerical value energy of 1/n in Freundlich equation
The reflection complexity to ammonia nitrogen absorption for the biological carbon, shows that as 0.1 ＜ 1/n ＜ 1 it is easy to adsorb, 1/n value is less, absorption effect
Fruit is better.As shown in Table 3, the 1/n value of this paper Freundlich equation is respectively less than 1, and adsorption isothermal curve is all in convex
Shape, by BDDT classification, belongs to type I, illustrates that biological carbon ball has preferable adsorption capacity to ammonia nitrogen.
The fitting parameter of table 3 Largmuir and Freundlich Tellurium determination
3rd, the impact to adsorption effect for the temperature
Take 100mL 30mg L-1Ammonium chloride solution put in the conical flask of 250mL, add 4 biological carbon balls, with
120r·min-1Constantly vibrate solution, and be placed on 10,15,20,25,30,35,40 DEG C of constant temperatures respectively, to simulate
The water temperature of agricultural drain, measures the adsorbance of its ammonia nitrogen when biological carbon ball reaches adsorption equilibrium, and experimental result is as shown in figure 17.
As shown in Figure 17, between 10-40 DEG C, temperature is higher for water temperature, and biological carbon ball is also bigger to the adsorbance of ammonia nitrogen, this
Illustrate that this adsorption process is endothermic process, high temperature is conducive to the absorption to ammonia nitrogen for the biological carbon ball.Additionally, contrast with SS-0 finding,
Its ammonia nitrogen absorption amount of biological carbon ball that with the addition of rice straw substantially rises, and this also indicates that biological carbon ball relies primarily on chemical behavior
Absorption ammonia nitrogen, the interpolation of rice straw makes biological carbon ball introduce more hydrophilic radicals, enhances the energy of its absorption ammonia nitrogen
Power, this is consistent with the FTIR pattern analysis results of Fig. 8 biology carbon ball in literary composition.
The present invention blends rice straw as raw material with farm ditch bed mud, the biological carbon ball of anaerobic pyrolysis preparation, analysis at 600 DEG C
Its physicochemical characterization characteristic, has investigated its absorption behavior to ammonia nitrogen, and have studied the impact to adsorption effect for the temperature, draw with
Draw a conclusion：
1st, the interpolation of appropriate rice straw, increased the skeleton structure supporting biological carbon ball inner space, is conducive to improving
The porosity of biological carbon ball, increases permeability, thus improving its mass-transfer performance.
2nd, infrared spectrum analysis finds, the interpolation of rice straw makes biological carbon ball introduce more hydroxyls and aromatic rings
Structure, improves its hydrophily, and stability is higher, in addition, adding the acid oxygen-containing official of biological carbon ball surface after rice straw
Quantity can be rolled into a ball also increase, and SS-0, SS-50, SS-100, SS-150 and SS-200 biological carbon ball surface acidity oxygen-containing functional group contains
Amount is respectively 2.74mmol L-1, 2.88mmol L-1, 3.71mmol L-1, 3.36mmol L-1With 3.03mmol L-1.
3rd, adsorption dynamics adsorption kinetics research shows, SS-0 biology carbon ball relatively meets pseudo-first-order dynamics side to the adsorption reaction of ammonia nitrogen
Journey, and for SS-50, SS-100, SS-150 and SS-200 biology carbon ball, pseudo-second order kinetic equation can preferably describe its suction
Attached ammonia nitrogen process, it is mainly subject to chemical absorption of surface process control.Modified intra-particle diffusion model shows, in addition to interior diffusion, also deposits
Adsorb the speed of ammonia nitrogen in other process co- controlling biology carbon balls.
4th, Tellurium determination research shows, Langmuir equation can preferably describe the absorption to ammonia nitrogen for the biological carbon ball
Journey, and this adsorption process belongs to the uniform mono layer adsorption in surface.The impact to adsorption effect for the temperature shows, biological carbon ball
Adsorption process to ammonia nitrogen is endothermic process, and high temperature is conducive to adsorbing.
5th, farm ditch bed mud and rice straw are drawn materials conveniently, with low cost, be prepared into biological carbon ball can not only become give up into
Treasured, and have broad application prospects in terms of the improvement of ammonia nitrogen in agricultural drain.
With farm ditch bed mud as base-material, rice straw is auxiliary material to the present invention, is blended according to both mass ratioes, by farm ditch bed mud sample
Product and to press bed mud and stalk mass ratio be 20:1、10:1、20:3、5:Particle diameter all made by the 14 kinds of samples being blended is 5mm's
Pellets, and anaerobic pyrolysis 4h becomes biological carbon ball at 600 DEG C, be respectively labeled as SS-0, SS-50, SS-100, SS-150,
SS-200.By elementary analysis, specific surface area and lacunarity analysis, ESEM, infrared spectrum analysis and Boehm titration etc.
Means characterize composition and the structure of biological carbon ball.Using simulated experiment, have studied the absorption property to ammonia nitrogen for the biological carbon ball, structure
Build adsorption dynamics adsorption kinetics and isotherm adsorption model, and investigate the impact to ammonia nitrogen absorption effect for the temperature.Result shows, adds water
Rice straw, is conducive to increasing biological carbon ball permeability and hydrophily, improves its mass-transfer performance.The acid oxygen-containing official of biological carbon ball surface
2.74mmol L can be respectively by mass contg-1、2.88mmol·L-1、3.71mmol·L-1、3.36mmol·L-1With
3.03mmol·L-1.Dynamics research shows, SS-0 meets pseudo-first-order kinetics equation to the absorption of ammonia nitrogen, and quasi- second motive force
Learn equation and can preferably describe SS-50, SS-100, SS-150 and SS-200 absorption ammonia nitrogen process, in addition to interior diffusion, also exist
Other process co- controlling biology carbon balls adsorb the speed of ammonia nitrogen.Biological carbon ball adsorption isothermal curve meets Langmuir equation,
And the 1/n exponential quantity of Freundlich equation is respectively less than 1, belongs to endothermic process, high temperature is conducive to it to adsorb ammonia nitrogen.Biological carbon ball
There is to ammonia nitrogen preferable adsorption capacity, have broad application prospects in terms of the improvement of ammonia nitrogen in agricultural drain.
Above-described embodiment is only used for illustrating the inventive concept of the present invention, rather than the restriction to rights protection of the present invention,
All changes that using this design, the present invention is carried out with unsubstantiality, all should fall into protection scope of the present invention.
Claims (9)
1. a kind of method of farm ditch bed mud and the biological carbon ball of rice straw pyrolysis preparation is it is characterised in that comprise the following steps：
（1）Irrigation canals and ditches bed mud fetches air blast under uniform temperature dries, and picks debris therein, grinds, sieves, prepared irrigation canals and ditches
Bed mud powder, standby；
（2）Rice straw removes surface impurity through water washing from the beginning after fetching, and dries, cuts short, air blast is abundant under uniform temperature
It is dried, with microphyte pulverizer grinding and sieving, prepared rice straw powder, and be stored in wide-mouth bottle, standby；
（3）Irrigation canals and ditches bed mud powder is mixed rice straw powder, mixes, after adding a small amount of distilled water, be prepared into one using pellet processing machine
Determine the pellets of particle diameter, place in quartz boat, be placed in vacuum tube furnace, logical nitrogen keeps under anoxia condition, with one
Fixed heating rate is heated to 600 DEG C -800 DEG C constant temperature certain times, then proceedes in nitrogen atmosphere after naturally cool to room
Take out after temperature, deionized water is cleaned by ultrasonic to pH neutrality, is finally dried with air blast, weighs, make biological carbon ball finished product.
2. farm ditch bed mud as claimed in claim 1 and the biological carbon ball of rice straw pyrolysis preparation method it is characterised in that：Described
Step（1）In irrigation canals and ditches bed mud dry 20-24h at 100-105 DEG C.
3. farm ditch bed mud as claimed in claim 1 and the biological carbon ball of rice straw pyrolysis preparation method it is characterised in that：Described
Step（1）In irrigation canals and ditches bed mud grind after, cross 80-100 mesh sieve.
4. farm ditch bed mud as claimed in claim 1 and the biological carbon ball of rice straw pyrolysis preparation method it is characterised in that：Described
Step（2）In rice straw at 80-90 DEG C air blast fully dry.
5. farm ditch bed mud as claimed in claim 1 and the biological carbon ball of rice straw pyrolysis preparation method it is characterised in that：Described
Step（2）In rice straw pulverize after cross 80-90 mesh sieve.
6. farm ditch bed mud as claimed in claim 1 and the biological carbon ball of rice straw pyrolysis preparation method it is characterised in that：Described
Step（3）In irrigation canals and ditches bed mud and rice straw powder weight than for 5-20:1.
7. farm ditch bed mud as claimed in claim 1 and the biological carbon ball of rice straw pyrolysis preparation method it is characterised in that：Described
Step（3）In pellets particle diameter be 4-5mm.
8. farm ditch bed mud as claimed in claim 1 and the biological carbon ball of rice straw pyrolysis preparation method it is characterised in that：Described
Step（3）In logical nitrogen 200-300mL min-1Keep under anoxia condition, with 8-9 DEG C of min-1Heating rate be heated to
500-600 DEG C of constant temperature 3-4h.
9. farm ditch bed mud as claimed in claim 1 and the biological carbon ball of rice straw pyrolysis preparation method it is characterised in that：Described
Step（3）In dry 24h in 100-105 DEG C of air blast.
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| CN201610712580.6A CN106423052A (en) | 2016-08-23 | 2016-08-23 | Method for preparing biochar balls through pyrolyzing farm ditch bottom mud and rice straws |
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| CN201610712580.6A CN106423052A (en) | 2016-08-23 | 2016-08-23 | Method for preparing biochar balls through pyrolyzing farm ditch bottom mud and rice straws |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108236918A (en) * | 2016-12-27 | 2018-07-03 | 海门市源美美术图案设计有限公司 | Efficient absorption charcoal prepared by a kind of rice straw and preparation method thereof |
| CN111533263A (en) * | 2020-05-12 | 2020-08-14 | 浙江伊诺环保科技股份有限公司 | Movable microecological treatment device and method for nitrogen and phosphorus removal of wastewater |
| CN111533262A (en) * | 2020-05-12 | 2020-08-14 | 浙江伊诺环保科技股份有限公司 | Preparation method of denitrification dephosphorization microecosystem filler |
| CN112121762A (en) * | 2020-09-21 | 2020-12-25 | 迪天环境技术南京股份有限公司 | Preparation method of biomass charcoal-based filter material loaded with nano zero-valent iron |
-
2016
- 2016-08-23 CN CN201610712580.6A patent/CN106423052A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 王潋等: ""底泥基生物炭对水中二价铅的吸附性能"", 《净水技术》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108236918A (en) * | 2016-12-27 | 2018-07-03 | 海门市源美美术图案设计有限公司 | Efficient absorption charcoal prepared by a kind of rice straw and preparation method thereof |
| CN111533263A (en) * | 2020-05-12 | 2020-08-14 | 浙江伊诺环保科技股份有限公司 | Movable microecological treatment device and method for nitrogen and phosphorus removal of wastewater |
| CN111533262A (en) * | 2020-05-12 | 2020-08-14 | 浙江伊诺环保科技股份有限公司 | Preparation method of denitrification dephosphorization microecosystem filler |
| CN112121762A (en) * | 2020-09-21 | 2020-12-25 | 迪天环境技术南京股份有限公司 | Preparation method of biomass charcoal-based filter material loaded with nano zero-valent iron |
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Application publication date: 20170222 |