CN104689788A - Biochar modification method for improving ammonium nitrogen adsorption capability in soil/water - Google Patents
Biochar modification method for improving ammonium nitrogen adsorption capability in soil/water Download PDFInfo
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- CN104689788A CN104689788A CN201510107212.4A CN201510107212A CN104689788A CN 104689788 A CN104689788 A CN 104689788A CN 201510107212 A CN201510107212 A CN 201510107212A CN 104689788 A CN104689788 A CN 104689788A
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Abstract
The invention discloses a biochar modification method for improving ammonium nitrogen adsorption capability in soil/water. The biochar modification method comprises the following steps: (1) putting biomass in a muffle furnace, cracking to prepare biochar at an anaerobic or anoxic condition by using an argon purging manner; (2) grinding the biochar in a mortar, and sieving; (3) mixing the sieved biochar with hydrogen peroxide, putting the mixture in a culture room being 28-35 DEG C and carrying out modification treatment; (4) filtering the hydrogen peroxide from the modified biochar; (5) flushing the biochar with deionized water; (6) regulating the biochar to be a neutral pH value; (7) filtering and drying the biochar. According to the biochar modification method disclosed by the invention, the operation is simple, the cost is low and industrial production can be easily achieved, compared with the non-modified biochar, the prepared modified biochar has the advantages that adsorption capability of the ammonium nitrogen in an aqueous solution is greatly improved, and the stability is good.
Description
Technical field
The present invention relates to a kind of charcoal method of modifying improving ammonium nitrogen adsorption capacity in soil/water body, belong to charcoal technical field of modification.
Background technology
Since 20 century 70s, in China's agricultural production, the amount of application of nitrogenous fertilizer increases sharply, at some prolific areas more so.But from historical variations, no matter be nitrogenous fertilizer, phosphate fertilizer, or potash fertilizer, the utilization rate of fertilizer of China chief crop is all in downward trend gradually.China's utilization rate of nitrogen fertilizer only has 30% ~ 35%, lower than the utilization rate of nitrogen fertilizer of developed country 10 ~ 20 percentage points.The one economy worry of peasant is not only in the loss of this nitrogen, all causes pollution to a certain degree to surface water and groundwater environment and even marine ecosystems simultaneously.Therefore, amount of application of nitrogen fertilizer is large, nitrogen utilization efficiency is low is the outstanding problem perplexing China's agricultural production always.How to strengthen the nitrogen management in agricultural production, both the facilitation of nitrogen application to agricultural production had been ensured, ensure again the sustainable development of agricultural and environment, finally realize the unification of the economic benefit of nitrogen application, ecological benefits and social benefit, be the focus that environmental science is paid close attention to, be also the significant problem concerning modern agriculture High-efficient Production and sustainable development always.
In recent years, charcoal starts the concern causing people.Charcoal is by the rich carbon organic substance of living beings (as agricultural crop straw, forestry waste etc.) or derivatives thereof pyrolysis and obtained one under the condition of high temperature anaerobic.Charcoal be applied to soil can not only consolidate carbon increase converge, improve soil quality, increase crop yield, to reduce poisonous and harmful heavy metallic active etc., and in raising Soil Nitrogen utilization ratio, reduce nitrogen loss aspect and also have a remarkable effect.Its larger specific area of charcoal and stronger adsorption capacity, by improving Cation Exchange Capacity in Soils and regulating soil pH value, improve the holding capabilities of soil ammonium, reduce the number of dropouts of Soil Nitrogen.Therefore, charcoal is considered to a kind of effective soil conditioner, is widely used in agricultural soil, to reach the utilization rate improving nitrogenous fertilizer, the object reducing nitrogen loss.
Current research shows, charcoal is applied to after in soil by certain way, by changing the pH value of soil and soil conductivity, cation exchange capacity (CEC), the rhizospheric environment of plant and soil respiration, thus affects the suction-operated of soil to ammonium nitrogen.The same with other the soil organism, charcoal itself does not have anion exchange capacity, so can not adsorb nitrate nitrogen, but can adsorb ammonium nitrogen.This suction-operated can be interpreted as the electrostatic adsorption of charcoal surface band negative electrical charge functional group.Under normal circumstances, the adsorption capacity of freshly prepd primitive organism charcoal to ammonium nitrogen is relatively low.Therefore, want the holding capabilities improving ammonium nitrogen in soil and water, reduce the loss of ammonium nitrogen, must solve and how improve charcoal to this key scientific problems of the adsorption capacity of ammonium nitrogen.Namely charcoal modification technology is a very potential approach.
Research report at present about charcoal is relatively many, but what the charcoal used in major part research adopted is by traditional processing technology, the i.e. freshly prepd primitive organism charcoal of non-modified or modified, this primitive organism charcoal preparation process is rough, raw material sources otherness is larger, surface oxygen functional group and negative electrical charge quantity not high, less to the cation adsorbing capabilities in soil, to the ammonium nitrogen in soil and water and other cation holding capabilities relatively limited.Therefore, need to carry out modification to it, improve its adsorption capacity to ammonium nitrogen with this.Modified charcoal, its surface negative charge quantity and oxygen-containing functional group significantly increase, and cation exchange capacity (CEC) strengthens, and substantially increases the fixing effect to ammonium nitrogen.Current existing charcoal modification technology mainly concentrates on and carries out the modification of chemical functional group to charcoal surface, and on the absorption being mainly used in heavy metal (Cu, Cd, Pb, Zn) and waste water treatment.And the weak point such as these modification technologies exist complex process, course of reaction is loaded down with trivial details, cost is higher, operability is not strong.Desirable charcoal modification technology should be low cost, workable, technique carries out mass modification to charcoal simply.
Summary of the invention
The technical problem to be solved in the present invention is: provide a kind of charcoal method of modifying improving ammonium nitrogen adsorption capacity in soil/water body, there is method simple to operate, cheap for manufacturing cost, be easy to suitability for industrialized production, effectively can improve charcoal in soil/water body to advantages such as the adsorption capacities of ammonium nitrogen, effectively can solve nitrogen loss in current nitrogen application process serious, the problems such as fertilizer utilization efficiency is low, body eutrophication, and existing modification technology complex process, the problem such as course of reaction is loaded down with trivial details, cost is higher.
Technical scheme of the present invention: a kind of charcoal method of modifying improving ammonium nitrogen adsorption capacity in soil/water body, comprises the following steps:
(1) living beings are put into Muffle furnace, adopt the mode of argon purge, cracking charcoal under the condition of anaerobism or anoxic; Adopt argon purge can ensure anaerobism needed for biomass cracking or anaerobic environment in this step.
(2) sieve after charcoal being put into mortar grinding; The primitive organism charcoal shape size just prepared differs, and in this step, grinding is to sieve better, makes it even, contributes to like this improving the modified effect in subsequent step.
(3) charcoal after sieving is mixed with hydrogen peroxide in the culturing room being placed on 28 ° of C-35 ° of C and carry out modification; Adopt hydrogen peroxide to carry out modification in this step, owing to only having H and O two kinds of elements in hydrogen peroxide, other too much elements or impurity interference can not be introduced; The temperature controlling culturing room is mainly arranged to cultivate the needs of microorganism, and being placed in culturing room is in order to avoid temperature fluctuation is excessive, affects experimental result.
(4) filtration is carried out to modified charcoal and remove hydrogen peroxide; Because hydrogen peroxide itself has very strong oxidisability, after modification flushing is carried out to charcoal and remove hydrogen peroxide, hydrogen peroxide can be avoided to continue to be oxidized charcoal in drying course, and to Influence on test result during subsequent adjustment pH value.
(5) by deionized water, charcoal is rinsed;
(6) regulate the pH value of charcoal to neutral;
(7) charcoal is filtered, drying and processing.Conveniently can store after oven dry, and prepare for follow-up adsorption experiment.
The cracking condition of aforementioned biological matter in Muffle furnace is: the heating gradient in Muffle furnace is 2.5 ° of C min
-1, after cracking temperature reaches 500 ° of C, stop 30 min.Find through inventor Experimental comparison, its absorption property of the charcoal prepared under this condition is best.Because when temperature is too low, living beings can not thoroughly carbonization, and when temperature is too high, can cause again charcoal height aromatization.Also there is impact to the physical-chemical parameters such as productive rate, specific area, pH of charcoal simultaneously.
Aforementioned argon purge speed is 1 L min
-1.
The aperture of aforementioned sieve is 149-850 μm; Select the object of this pore diameter range to be comparatively simultaneously uniform in guarantee particle size in the present invention, the recovery productive rate of charcoal can be improved substantially.
Charcoal is placed in the time of culturing room in abovementioned steps (3) is more than 350 h or 2 weeks, is convenient to charcoal and hydrogen peroxide thoroughly reacts.
Charcoal is 1:10(w:v with the solid-to-liquid ratio of hydrogen peroxide in abovementioned steps (3)), this solid-to-liquid ratio can make charcoal in hydrogen peroxide by abundant modification, has taken into account the balance of modified effect and saving material cost.Aforementioned hydrogen peroxide concentration is 30%.
Adopt Whatman No. 1 qualitative filter paper and Buchner funnel to carry out filtration treatment to modification biological charcoal in abovementioned steps (4), this kind of mode is convenient to carry out filtration treatment.
The aforementioned employing hydrochloric acid of 1mol and the NaOH of 1mol regulate charcoal pH value, and too high or too low hydrochloric acid or naoh concentration can cause the pH of charcoal to regulate fluctuating range excessive or too small, thus affect equilibration time.
Adopt constant temperature oven to carry out drying and processing to modified charcoal in abovementioned steps (7), temperature is 60 ° of C, and this kind of drying mode had both had good drying effect and speed, and too high baking temperature can be avoided again to affect the attribute of modification biological charcoal.
Beneficial effect of the present invention:
Compared with prior art, charcoal method of modifying of the present invention is simple to operate, with low cost, be easy to suitability for industrialized production, obtained modification biological charcoal, compared with the charcoal absorption property before modification, greatly improves the absorption property of ammonium nitrogen in the aqueous solution, and has good stability.Adopt the present invention can carry out mass modification to charcoal, there are good market prospects.
accompanying drawing illustrates:
Fig. 1 is the graph of a relation of the forward and backward ammonium nitrogen maximal absorptive capacity of modification, surface negative charge amount and modification time;
Fig. 2 is that charcoal is before modified to ammonium nitrogen adsorption isotherm;
Fig. 3 is that modified charcoal is to ammonium nitrogen adsorption isotherm.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment 1:
1, the preparation and modification of charcoal
(1), select maple charcoal (the red maple of 20% sugar maple+80%) at argon purge (1 L min
-1) condition under in Muffle furnace, carry out Pintsch process produce charcoal, the heating gradient of charcoal in Muffle furnace is 2.5 ° of C min
-1, be 30min when cracking in Muffle furnace reaches the time of staying after maximum temperature 500 ° of C.
(2) 149 ~ 850 μm of sieves are crossed after, obtained charcoal grinds in mortar.
(3), for optimize modified condition better, contrast verification before modified artifact charcoal to the adsorption capacity of ammonium nitrogen and stability thereof, the modification of charcoal adopt respectively deionized water, 15% and 30% hydrogen peroxide under 28 ° of C-35 ° of C, place different time (15 min by solid-to-liquid ratio 1:10 (w/v), 45 min, 6 h, 110 h, 350 h).
(4), then adopt Whatman No. 1 qualitative filter paper and Buchner funnel to carry out filtration and remove hydrogen peroxide.
(5), rinse by deionized water.
(6), adopt the NaOH of the hydrochloric acid of 1 mol and 1 mol to regulate charcoal pH value, make it reach neutral (pH=7).Because charcoal itself has very strong cushioning effect, so need every 24h to regulate once, until its pH value reaches balance.
(7), again filter with Whatman No. 1 qualitative filter paper, then put into the constant temperature oven dry for standby that temperature is 60 ° of C.
2, adsorption experiment
The modification biological charcoal taking 0.5 g joins in the centrifuge tube of 50 mL, adds the ammonium sulfate (0,5,10,50,100 mg NH of 40 mL variable concentrations
4-N L
1), earthquake device shakes 16 h with the speed of 400 rpm, and then carries out centrifugal, leave standstill.Finally measure the concentration of ammonium nitrogen in solution.
3, desorption experiment
After adsorption test terminates, the solution in centrifuge tube is outwelled.Join in centrifuge tube with the ultra-pure water of 40 ml again, vibrate.Measure the concentration of ammonium nitrogen in solution again.Verify that how many ammonium nitrogens are resolved out with this, thus assessed modification biological charcoal better to the sorption potential of ammonium nitrogen.
4, results and analysis
Table 1 charcoal modification time and physico-chemical properties thereof
Table 1 is charcoal modification time and physico-chemical properties thereof, as known from Table 1, along with the increase of oxidization time in modifying process, the pH value of charcoal reduces gradually, and show as O content and add twice on element composition, H content slightly reduces, and C content then decreases about 20%.Show by after the oxidation processes in modifying process, charcoal surface introduces more acid oxygen-containing functional group.
Fig. 1 is the graph of a relation of the forward and backward ammonium nitrogen maximal absorptive capacity of modification, surface negative charge amount and modification time, as can be seen from Figure 1, through the charcoal that the present invention is modified, all has greatly improved in ammonium nitrogen maximal absorptive capacity and surface negative charge amount.
Fig. 2 is the adsorption isotherm of charcoal before modified to ammonium nitrogen, and as shown in Figure 2, before modified, when without pH adjustment process, the adsorbance of charcoal to ammonium nitrogen of different pH value is relatively low and difference is little.
Fig. 3 be modified charcoal to the adsorption isotherm of ammonium nitrogen, as shown in Figure 3, compared with unmodified charcoal, the adsorption capacity of modified charcoal to ammonium nitrogen improves 3-4 doubly.Wherein, modification time is longer, and pH value is less, and surface acidity oxygen-containing functional group is more, after regulating process by pH value, stronger to the adsorption capacity of ammonium nitrogen.
Claims (10)
1. improve a charcoal method of modifying for ammonium nitrogen adsorption capacity in soil/water body, it is characterized in that: comprise the following steps:
(1) living beings are put into Muffle furnace, adopt the mode of argon purge, cracking charcoal under the condition of anaerobism or anoxic;
(2) sieve after charcoal being put into mortar grinding;
(3) charcoal after sieving is mixed with hydrogen peroxide in the culturing room being placed on 28 ° of C-35 ° of C and carry out modification;
(4) filtration is carried out to modified charcoal and remove hydrogen peroxide;
(5) by deionized water, charcoal is rinsed;
(6) regulate the pH value of charcoal to neutral;
(7) charcoal is filtered, drying and processing.
2. the charcoal method of modifying of ammonium nitrogen adsorption capacity in raising soil/water body according to claim 1, is characterized in that: the cracking condition of living beings in Muffle furnace is: the heating gradient in Muffle furnace is 2.5 ° of C min
-1, after cracking temperature reaches 500 ° of C, stop 30 min.
3. the charcoal method of modifying of ammonium nitrogen adsorption capacity in raising soil/water body according to claim 1, is characterized in that: argon purge speed is 1 L min
-1.
4. the charcoal method of modifying of ammonium nitrogen adsorption capacity in raising soil/water body according to claim 1, is characterized in that: the aperture of described sieve is 149-850 μm.
5. the charcoal method of modifying of ammonium nitrogen adsorption capacity in raising soil/water body according to claim 1, is characterized in that: in described step (3), charcoal is placed in the time of culturing room is more than 350 h or 2 weeks.
6. the charcoal method of modifying of ammonium nitrogen adsorption capacity in raising soil/water body according to claim 1, is characterized in that: in described step (3), the solid-to-liquid ratio of charcoal and hydrogen peroxide is 1:10.
7. the charcoal method of modifying of ammonium nitrogen adsorption capacity in raising soil/water body according to claim 1, is characterized in that: described hydrogen peroxide concentration is 30%.
8. the charcoal method of modifying of ammonium nitrogen adsorption capacity in raising soil/water body according to claim 1, is characterized in that: adopt Whatman No. 1 qualitative filter paper and Buchner funnel to carry out filtration treatment to modification biological charcoal in described step (4).
9. the charcoal method of modifying of ammonium nitrogen adsorption capacity in raising soil/water body according to claim 1, is characterized in that: adopt the hydrochloric acid of 1mol and the NaOH of 1mol to regulate charcoal pH value.
10. the charcoal method of modifying of ammonium nitrogen adsorption capacity in raising soil/water body according to claim 1, is characterized in that: adopt constant temperature oven to carry out drying and processing to modified charcoal in described step (7), temperature is 60 ° of C.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105561925A (en) * | 2016-03-08 | 2016-05-11 | 湖南大学 | Method for removing metformin HCL (metformin hydrochloride) in water by utilizing alternanthera philoxeroides charcoal modified by hydrogen peroxide |
| CN105617988A (en) * | 2016-01-14 | 2016-06-01 | 南开大学 | Preparation method of charcoal type adsorbent and application of charcoal type adsorbent in ammonia-nitrogen adsorption |
| CN105766491A (en) * | 2016-02-29 | 2016-07-20 | 上海交通大学 | Method for controlling atmospheric emission loss of fumigant on basis of animal dung biochar |
| CN106083331A (en) * | 2016-06-14 | 2016-11-09 | 华南农业大学 | A kind of modification biological charcoal preparation and application that can reduce compost noxious gas emission |
| CN108940203A (en) * | 2018-08-09 | 2018-12-07 | 重庆三峡学院 | A kind of Three Gorges adaptability vegetation charcoal preparation method and applications |
| CN113231031A (en) * | 2021-06-29 | 2021-08-10 | 东北农业大学 | Method for preparing high-adsorption-performance biochar from urban garden waste, product and application thereof |
| CN114702351A (en) * | 2022-04-18 | 2022-07-05 | 香港科技大学 | Modified biochar and preparation method and application thereof |
| CN115025758A (en) * | 2022-06-13 | 2022-09-09 | 江苏省环境科学研究院 | Application of chemically aged biochar in copper ion adsorption |
-
2015
- 2015-03-12 CN CN201510107212.4A patent/CN104689788A/en active Pending
Non-Patent Citations (1)
| Title |
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| 张扬等: "改性玉米芯生物碳对氨氮的吸附特性", 《化工学报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105617988A (en) * | 2016-01-14 | 2016-06-01 | 南开大学 | Preparation method of charcoal type adsorbent and application of charcoal type adsorbent in ammonia-nitrogen adsorption |
| CN105766491A (en) * | 2016-02-29 | 2016-07-20 | 上海交通大学 | Method for controlling atmospheric emission loss of fumigant on basis of animal dung biochar |
| CN105561925A (en) * | 2016-03-08 | 2016-05-11 | 湖南大学 | Method for removing metformin HCL (metformin hydrochloride) in water by utilizing alternanthera philoxeroides charcoal modified by hydrogen peroxide |
| CN106083331A (en) * | 2016-06-14 | 2016-11-09 | 华南农业大学 | A kind of modification biological charcoal preparation and application that can reduce compost noxious gas emission |
| CN106083331B (en) * | 2016-06-14 | 2019-11-08 | 华南农业大学 | A kind of modification biological charcoal preparation and application can be reduced compost noxious gas emission |
| CN108940203A (en) * | 2018-08-09 | 2018-12-07 | 重庆三峡学院 | A kind of Three Gorges adaptability vegetation charcoal preparation method and applications |
| CN113231031A (en) * | 2021-06-29 | 2021-08-10 | 东北农业大学 | Method for preparing high-adsorption-performance biochar from urban garden waste, product and application thereof |
| CN114702351A (en) * | 2022-04-18 | 2022-07-05 | 香港科技大学 | Modified biochar and preparation method and application thereof |
| CN115025758A (en) * | 2022-06-13 | 2022-09-09 | 江苏省环境科学研究院 | Application of chemically aged biochar in copper ion adsorption |
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Application publication date: 20150610 |