CN106501131A - A kind of method of on-line checking hydrargyrum in charcoal intra-particle diffusion - Google Patents
A kind of method of on-line checking hydrargyrum in charcoal intra-particle diffusion Download PDFInfo
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- CN106501131A CN106501131A CN201611006593.8A CN201611006593A CN106501131A CN 106501131 A CN106501131 A CN 106501131A CN 201611006593 A CN201611006593 A CN 201611006593A CN 106501131 A CN106501131 A CN 106501131A
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- charcoal
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- hydrargyrum
- particle diffusion
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N13/00—Investigating surface or boundary effects, e.g. wetting power; Investigating diffusion effects; Analysing materials by determining surface, boundary, or diffusion effects
- G01N2013/003—Diffusion; diffusivity between liquids
Abstract
The present invention relates to a kind of method of on-line checking hydrargyrum in charcoal intra-particle diffusion, the method passes through to be pyrolyzed cotton stalk under the manual control condition of anaerobic, goes the removal of impurity to obtain charcoal with hydrochloric acid；Then charcoal will be dried to be suspended in sodium chloride solution；Application isothermal titration calorimeter, with mercury solution titrate charcoal suspension, by on-line checking reaction system in micro- thermal change, characterize hydrargyrum in charcoal intra-particle diffusion effect.The invention belongs to adsorption process detection method, with easy to operate compared with similar technique, sensitivity is high, the advantage such as results expression is directly perceived, can be with on-line checking contents of many kinds of heavy metal ion in charcoal intra-particle diffusion effect.
Description
Technical field
The present invention relates to a kind of on-line checking hydrargyrum belongs to environmental monitoring online in the method for charcoal intra-particle diffusion
Detection technique field.
Background technology
Charcoal (biochar) is by biological residuum etc. under the manual control condition of anaerobism or anaerobic, through high warm
Solution generates CO2, imflammable gas, outside volatility oils and tar-like substance, also produced is a class indissoluble, stable, highly
Solid matter aromatization, being rich in carbon, component are mainly carbon, hydrogen, oxygen, nitrogen etc., and phosphorus content, more than 70%, is category
One kind in black wood charcoal category.According to the difference of charcoal preparing raw material, it is also possible to containing units such as potassium, calcium, ferrum, magnesium, sodium, zinc, copper
Element.Charcoal has loose porous structure, and specific surface area is huge, and surface carries a large amount of negative charges and higher charge density,
And containing the functional group such as nitrogenous, oxygen-containing, sulfur-bearing, with very big cation exchange capacity (CEC) (CEC), can absorbing copper, lead, chromium, hydrargyrum,
The heavy metals such as cadmium, zinc；It also has low production cost, ecological safety, the distinguishing feature such as pollution-free.These features make which as one
Plant efficient, cheap adsorbent significant role is played in soil improvement, improvement water body and heavy metal pollution of soil problem.Raw
The absorption behavior of thing charcoal can affect heavy metal ion Transport And Transformation in the environment, ecological effect and contaminated environment medium
Control and the process such as reparation.Therefore, the adsorption of research charcoal heavy metal ion becomes environmental worker in recent years
The problem in science that extremely pays close attention to.
At present, following 4 kinds can be summarized as with regard to charcoal heavy metal absorption mechanism：(1) after adding charcoal, soil
PH is raised, and heavy metal in soil ion forms metal hydroxidess, carbonate or phosphate and precipitates or increased soil table
Face avtive spot.(2) ion exchange and cation-π effects.The essence of ion exchange is the negatively charged group in charcoal surface
With the electrostatic interaction of the heavy metal ion of positive charge in solution, belong to non-obligate absorption, energy of adsorption is relatively low.The intensity of electrostatic interaction
Depend on surface negative charge group produce variable surface electric charge, exchange capacity affected by pH more notable, with obvious
Reversibility.And the essence of cation-π effects is more complicated, wherein there is the composition of certain electrostatic interaction.Cation-π effects are depended on
In the aromaricity of biological carbon surface, pi-conjugated aromatic structure is more, and electron donation is stronger, then this kind of effect is more obvious.The suction
Attached do not affected by charcoal surface charge, affected by pH less.(3) metal ion defines spy with charcoal surface functional group
Fixed metal complex, fixation of this reaction for the heavy metal ion for having very strong affinity with specific ligand in soil
It is very important.The absorption behavior of charcoal heavy metal ion has close relationship with charcoal surface oxygen functional group.
(4) charcoal heavy metal ion relies primarily on surface adsorption.Charcoal has larger specific surface area, have with reference to heavy metal from
The strong tendency of son, therefore can preferably remove the heavy metal ion in solution and soil.Above adsorption process is primarily present in
Biological carbon surface, achievement in research are more.But for the research of intra-particle diffusion is mainly by the adsorption kinetic data, using granule
Internal diffusion model (Qt=kipt1/2+ C, QtRepresent adsorbance (mg g during t-1),kipFor intra-particle diffusion speed constant (mg
g·min-0.5), C is constant) indirect analog intra-particle diffusion process；But the sampling during the adsorption kinetic data, test
Large effect can be produced to the precision that tests etc. link.It is little for a kind of artificial, environmental factorss interference of this urgent demand research and development,
Can online, the new method of real-time detection intra-particle diffusion process.
In the last few years, isothermal titration calorimetric (ITC) technology play the role of key in calorimetric and heat analysis research, it
It is the most direct method of thermodynamic driving force sign in intermolecular interaction, has become identification intermolecular weak interaction not
The laboratory facilities that can lack, are widely used in the research and development of colloidal interface thermodynamics, biological and bionical system thermodynamics and medicine
In field.The ITC adaptability of technology is strong, equally effective to macromole and small molecule, substantially compatible any buffering or additive,
The isothermal reaction in 2-80 DEG C of temperature range can be carried out, and the complete thermodynamics of molecule association reaction are given in an experiment
Sensitivity and repeatability of the distribution (comprising enthalpy-Δ H, entropy-Δ S, binding constant-Ka, stoichiometric proportion-n etc.), with maximum.
For this purpose, intuitively reflecting micro- thermal change during internal diffusion by ITC technology under constant temperature, simulation obtains more smart
Accurate intra-particle diffusion model.
Content of the invention
It is an object of the invention to provide a kind of method of on-line checking hydrargyrum in charcoal intra-particle diffusion, the method passes through
Cotton stalk is pyrolyzed under the manual control condition of anaerobic, goes the removal of impurity to obtain charcoal with hydrochloric acid；Then charcoal will be dried to hang
Float in sodium chloride solution；Application isothermal titration calorimeter, is titrated charcoal suspension with mercury solution, is reacted by on-line checking
Micro- thermal change in system, characterizes hydrargyrum in charcoal intra-particle diffusion effect.The invention belongs to adsorption process detection method, with
Similar technique is compared with easy to operate, and sensitivity is high, the advantage such as results expression is directly perceived, can with on-line checking various heavy from
Son is in charcoal intra-particle diffusion effect.
A kind of method of the on-line checking hydrargyrum of the present invention in charcoal intra-particle diffusion, the method utilize cotton stalk
Prepare charcoal, apply isothermal titration calorimeter, titrate charcoal suspension with mercury solution, by on-line checking reaction system in
Micro- thermal change, characterize hydrargyrum in charcoal intra-particle diffusion effect, concrete operations follow these steps to carry out：
A, charcoal source and preparation：Cotton stalk is reclaimed in farmland, in the artificial control that temperature is 500-700 DEG C of anaerobic
Under the conditions of pyrolysis obtain charcoal, with disintegrating machine by charcoal grinding be crushed to fine particle, be 0.5-2mol/L's with concentration
2-24 hours are processed under hydrochloric acid room temperature, is filtered after going removal of impurity interference, and deionized water balance purge remnants hydrochloric acid, it is placed in temperature
60 DEG C of drying baker of degree are dried, and after 100 mesh sieves, are obtained charcoal, are stored for future use；
B, isothermal calorimetric titration：0.05-0.2 gram of the charcoal that step a is obtained is weighed, and volume is suspended in for 100ml, concentration
For in the sodium chloride solution of 0.01-0.03mol/L, used as titrate, volumetric solution is the mercury bichloride that concentration is 50-100mg/L
Solution, by volumetric solution and after titrate vacuum outgass 5-20 minutes, then the titrate injection calorimeter reaction by 1-1.2ml
Chi Zhong, volumetric solution 100-250 μ l mercury bichlorides solution is injected in burette, and temperature is 25-30 DEG C, 300 rpms of rotating speed,
Baseline time is the 300-500 seconds, and titration time is the 2500-3600 seconds, by hydrargyrum and the drop reaction of charcoal suspension, obtains
Micro- thermal change curve of adsorption process and constant temperature titration curve, obtain the ginseng for characterizing intra-particle diffusion effect by matched curve
Number.
A kind of method of the on-line checking hydrargyrum of the present invention in charcoal intra-particle diffusion, first with cotton in the method
Chopped straw stalk prepares charcoal, then applies isothermal titration Calorimetric Techniques, titrates charcoal suspension with mercury solution；By online note
In record titration process, micro- thermal change of reaction system to be characterizing adsorption process, so as to realize expanding in charcoal granule with regard to hydrargyrum
The detection of scattered higher sensitivity.
Main advantages of the present invention：The invention belongs to adsorption process detection method, with operation letter compared with similar technique
Just, sensitivity is high, the advantage such as results expression is directly perceived, and contents of many kinds of heavy metal ion can be detected in charcoal intra-particle diffusion effect.
Description of the drawings
Fig. 1 is that mercury solution of the present invention titrates charcoal volumetric solution heat release rate figure；
Fig. 2 is isothermal calorimetric titration matched curve figure of the present invention.
Specific embodiment
Embodiment 1
A, charcoal source and preparation：Cotton stalk is reclaimed in farmland, in the manual control condition that temperature is 500 DEG C of anaerobics
Lower pyrolysis obtains charcoal, charcoal grinding is crushed to fine particle with disintegrating machine, with the salt sour room that concentration is 0.5mol/L
Temperature is lower to be processed 2 hours, filters after going removal of impurity interference, and deionized water balance purge remnants hydrochloric acid, is placed in temperature 60 C and does
Dry case is dried, and after 100 mesh sieves, is obtained charcoal, is stored for future use；
B, isothermal calorimetric titration：0.05 gram of the charcoal that step a is obtained being weighed, volume being suspended in for 100ml, concentration is
As titrate in the sodium chloride solution of 0.01mol/L, volumetric solution is that concentration is the mercury bichloride solution of 50mg/L, will titrate
After liquid and titrate vacuum outgass 5 minutes, then by the titrate injection calorimeter reaction tank of 1ml, by 100 μ l of volumetric solution
In mercury bichloride solution injection burette, temperature is 25 DEG C, 300 rpms of rotating speed, and baseline time is 300 seconds, titration time
For 2500 seconds, by hydrargyrum and the drop reaction of charcoal suspension, the micro- thermal change curve and constant temperature drop of adsorption process is obtained
Determine curve (Fig. 1), the parameter (Fig. 2) for characterizing intra-particle diffusion effect is obtained by matched curve.
Embodiment 2
A, charcoal source and preparation：Cotton stalk is reclaimed in farmland, in the manual control condition that temperature is 600 DEG C of anaerobics
Lower pyrolysis obtains charcoal, charcoal grinding is crushed to fine particle with disintegrating machine, with the salt sour room that concentration is 1.0mol/L
Temperature is lower to be processed 12 hours, filters after going removal of impurity interference, and deionized water balance purge remnants hydrochloric acid, is placed in temperature 60 C and does
Dry case is dried, and after 100 mesh sieves, is obtained charcoal, is stored for future use；
B, isothermal calorimetric titration：0.1 gram of the charcoal that step a is obtained being weighed, volume being suspended in for 100ml, concentration is
As titrate in the sodium chloride solution of 0.02mol/L, volumetric solution is that concentration is the mercury bichloride solution of 80mg/L, will titrate
After liquid and titrate vacuum outgass 10 minutes, then by the titrate injection calorimeter reaction tank of 1.1ml, by volumetric solution
In 180 μ l mercury bichlorides solution injection burette, temperature is 28 DEG C, 300 rpms of rotating speed, and baseline time is 400 seconds, titration
Time is 3000 seconds, by hydrargyrum and the drop reaction of charcoal suspension, obtains micro- thermal change curve and the perseverance of adsorption process
Warm titration curve, obtains the parameter for characterizing intra-particle diffusion effect by matched curve.
Embodiment 3
A, charcoal source and preparation：Cotton stalk is reclaimed in farmland, in the manual control condition that temperature is 700 DEG C of anaerobics
Lower pyrolysis obtains charcoal, charcoal grinding is crushed to fine particle with disintegrating machine, with the hydrochloric acid room temperature that concentration is 2mol/L
Lower process 24 hours, filters after going removal of impurity interference, and deionized water balance purge remnants hydrochloric acid, is placed in temperature 60 C drying
Case is dried, and after 100 mesh sieves, is obtained charcoal, is stored for future use；
B, isothermal calorimetric titration：0.2 gram of the charcoal that step a is obtained being weighed, volume being suspended in for 100ml, concentration is
As titrate in the sodium chloride solution of 0.03mol/L, volumetric solution is that concentration is the mercury bichloride solution of 100mg/L, will drip
After determining liquid and titrate vacuum outgass 20 minutes, then by the titrate injection calorimeter reaction tank of 1.2ml, by volumetric solution
In 250 μ l mercury bichlorides solution injection burette, temperature is 30 DEG C, 300 rpms of rotating speed, and baseline time is 500 seconds, titration
Time is 3600 seconds, by hydrargyrum and the drop reaction of charcoal suspension, obtains micro- thermal change curve and the perseverance of adsorption process
Warm titration curve, obtains the parameter for characterizing intra-particle diffusion effect by matched curve.
A kind of method of the on-line checking hydrargyrum of the present invention in charcoal intra-particle diffusion, the method pass through in anaerobic
Cotton stalk is pyrolyzed under manual control condition, goes the removal of impurity to obtain charcoal with hydrochloric acid；Then charcoal will be dried and is suspended in chlorine
Change in sodium solution；Application isothermal titration calorimeter, with mercury solution titrate charcoal suspension, by on-line checking reaction system in
Micro- thermal change, characterize hydrargyrum in charcoal intra-particle diffusion effect.Biological carbon surface has loose porous structure, specific surface
Product is huge, the feature such as functional group is abundant.The complete thermodynamics that molecule association reaction is provided using isothermal titration calorimetric (ITC) instrument
Distribution, these heat distributions can occur the change of heat, slight fever amount with mercury ion during charcoal granule diffusion inside
Change can be online show in real time.There is chemical reaction in charcoal surface group and mercury ion, biological carbon surface from
Exchange adsorption effect between son and mercury ion, mercury ion deposit physisorption of generation etc. and have in biological carbon surface
The change of heat.After charcoal surface adsorption mercury ion saturation, mercury ion can enter charcoal internal void, diffusion inside mistake
Journey also has the change of slight fever amount, and this heat also intuitively can be reflected by isothermal titration calorimeter in real time.
Claims (1)
1. method of a kind of on-line checking hydrargyrum in charcoal intra-particle diffusion, it is characterised in that the method is prepared using cotton stalk
Charcoal, apply isothermal titration calorimeter, with mercury solution titrate charcoal suspension, by on-line checking reaction system in micro-
Thermal change, characterizes hydrargyrum in charcoal intra-particle diffusion effect, and concrete operations follow these steps to carry out：
A, charcoal source and preparation：Cotton stalk is reclaimed in farmland, in the manual control condition that temperature is 500-700 DEG C of anaerobic
Lower pyrolysis obtains charcoal, charcoal grinding is crushed to fine particle with disintegrating machine, with the hydrochloric acid that concentration is 0.5-2mol/L
2-24 hours are processed under room temperature, is filtered after going removal of impurity interference, and deionized water balance purge remnants hydrochloric acid, it is placed in temperature 60
DEG C drying baker is dried, and after 100 mesh sieves, is obtained charcoal, is stored for future use；
B, isothermal calorimetric titration：0.05-0.2 gram of the charcoal that step a is obtained being weighed, volume being suspended in for 100ml, concentration is
As titrate in the sodium chloride solution of 0.01-0.03mol/L, volumetric solution is that concentration is molten for the mercury bichloride of 50-100mg/L
Liquid, by volumetric solution and after titrate vacuum outgass 5-20 minutes, then the titrate injection calorimeter reaction tank by 1-1.2ml
In, volumetric solution 100-250 l mercury bichlorides solution to be injected in burette, temperature is 25-30 DEG C, 300 rpms of rotating speed,
Baseline time is the 300-500 seconds, and titration time is the 2500-3600 seconds, by hydrargyrum and the drop reaction of charcoal suspension, obtains
Micro- thermal change curve of adsorption process and constant temperature titration curve, obtain the ginseng for characterizing intra-particle diffusion effect by matched curve
Number.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611006593.8A CN106501131A (en) | 2016-11-16 | 2016-11-16 | A kind of method of on-line checking hydrargyrum in charcoal intra-particle diffusion |
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| CN201611006593.8A CN106501131A (en) | 2016-11-16 | 2016-11-16 | A kind of method of on-line checking hydrargyrum in charcoal intra-particle diffusion |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014152291A1 (en) * | 2013-03-14 | 2014-09-25 | Old Dominion University Research Foundation | Carboxylated biochar compositions and methods of making and using the same |
| CN104941575A (en) * | 2014-03-25 | 2015-09-30 | 南京农业大学 | Multi-amino carbon composite material for selectively fixing mercury, chromium and lead in polluted soil and preparation method |
-
2016
- 2016-11-16 CN CN201611006593.8A patent/CN106501131A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014152291A1 (en) * | 2013-03-14 | 2014-09-25 | Old Dominion University Research Foundation | Carboxylated biochar compositions and methods of making and using the same |
| CN104941575A (en) * | 2014-03-25 | 2015-09-30 | 南京农业大学 | Multi-amino carbon composite material for selectively fixing mercury, chromium and lead in polluted soil and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| YUN Z J ET.AL: "Characterization of mercury-containing protein in human plasma", 《METALLOMICS》 * |
| 赵凌宇 等: "木屑和稻杆基生物质炭对汞的吸附特性比较", 《农业环境科学学报》 * |
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Application publication date: 20170315 |