CN107583612A - Charcoal preparation method and preparation system and mercury absorbent based on corncob - Google Patents
Charcoal preparation method and preparation system and mercury absorbent based on corncob Download PDFInfo
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Abstract
A kind of the charcoal preparation method based on corncob, preparation system and mercury absorbent are disclosed, shearing-crushing obtains corn cob granule after preparation method is washed including corncob；Corn cob granule addition is dried 45 hours in 80 DEG C 90 DEG C after being impregnated 34 hours in the aqueous solution containing stannous chloride and ferric trichloride and obtains mixture, and mixture is warming up to 350 450 DEG C with 8 10 DEG C/min speed under nitrogen in Muffle furnace and continues to obtain within 56 hours corncob charcoal particle；Corncob charcoal particle be passed through in the ethylene glycol solution containing frerrous chloride, zinc chloride and selenium powder under chlorine with 150 160 DEG C stirring 23 hours after, add aqueous slkali regulation pH value, then corncob charcoal is obtained within 67 hours with 40 50 DEG C of vacuum drying, corncob charcoal, dimethylformamide, TGA and anhydrous slufuric acid hydrogen sodium, which are put into after being stirred in container, to be sealed, 3 h are reacted at a temperature of 120 DEG C, adds in 95% ethanol solution containing nine hydrated sodium sulfides and obtains sulfhydrylation corncob charcoal.
Description
Technical field
The present invention relates to heavy metal process field, more particularly to a kind of charcoal preparation method and system based on corncob
Standby system and mercury absorbent.
Background technology
The modern industry develops and the raising of human living standard, causes to be discharged into the heavy metal wastewater thereby in environment and constantly increases
More, these are from smeltery, Electroplate Factory, mine, waste-rock yard, steel plant, and medicine, paint, electrolysis, agricultural chemicals, pigment etc.
The heavy metal wastewater thereby of industry has seriously affected the health or even life security of the mankind.Heavy metal is the one kind for causing water pollution
Poisonous and harmful substance, micro heavy metal can produce poisonous effect.Heavy metal ion in waste water can pass through food chain or
Food web builds up to slow poisoning by bio-absorbable, accumulation in human body, so as to injure bone, brain etc., seriously endangers human body
Health.World-shaking Japan's " minamata disease " and " pain disease " are exactly to be made respectively by mercury-containing waste water and cadmium wastewater pollution environment
Into.Mercury pollution also increasingly causes the very big concern of people naturally.Mercury, mercury is commonly called as, is unique a kind of in normal temperature and pressure state
It is in the metal of liquid down, does not burn, but there is volatility, heat volatilization is accelerated.Mercury and mercury compound in water can with element mercury,
Three kinds of states of monovalence mercury and bivalent mercury are present.Mercury has extremely strong persistence, migration and a bioconcentration, any shape in environment
The mercury of state can be converted into the methyl mercury of severe toxicity under certain condition.The seriousness and complexity of mercury pollution are considerably beyond conventional dirt
Thing is contaminated, or even exceedes persistence organic pollutant in some aspects.The mercury of different shape, its toxicity differ greatly, organic mercury and
Methyl mercury can invade human body by respiratory tract, alimentary canal, skin etc., and inorganic mercury is mainly kidney at the position that human body is accumulated,
Next to that spleen and liver.Methyl mercury can be also accumulated in brain tissue in addition to the internal organs such as liver, kidney are accumulated in by blood-brain barrier
It is interior.
Mercury source in environment is broadly divided into two parts of natural source and artificial source, come from coal-burning power plant, coal-burning boiler,
The every field such as non-ferrous metal metallurgy, manufacture of cement, mercurous product.According to UNEP2008 global atmosphere assessment reports, the whole world
Mercury In The Air total release is 7710 t, and natural source air mercury emission is 5207 t, the wherein t of ocean disposal 6282, and artificial source is arranged
It is high-volume 2503 t, wherein coal and oil discharges 1422 t.Since the industrial age, the mercury of anthropogenic discharge result in all over the world
The deposition of mercury is with average 0.5 to 3 times speed increase.
The method of processing Mercury in Wastewater pollution mainly has chemical precipitation method, light electrolysis-coagulant sedimentation, absorption method at present
Deng.Wherein absorption method is a kind of administering method being widely studied, and the active charcoal of conventional sorbing material, agriculture and forestry organic waste material, is glued
Soil, cellulose, silica etc..But these materials are relatively weak to the affinity of mercury in itself, and adsorption capacity is relatively low.
Charcoal is bio-organic materials（Also referred to as biomass）After low temperature thermal cracking under conditions of anaerobic or hypoxemia
Solid product, the % of usual carbon containing 40 % ~ 75, containing a small amount of mineral matter and volatile organic compound, in alkalescence, is not easy as microorganism point
Solution.Charcoal is added to the content that can increase soil organic matter in soil, improves the content of soil validity nutrient, so as to
Promote plant growth.Moreover, charcoal or good sorbing material, porous, huge surface area and the carboxyl base of charcoal
Group, which assigns it, has stronger adsorption capacity, while has substantial amounts of surface negative charge and high charge density, these properties
It is similar with activated carbon, there is preferably absorption is fixed to make to the polarity in water, soil or deposit or nonpolar organic pollutants
With, additionally it is possible to adsorb heavy metal.Therefore it can be used as a kind of adsorption agent, be played in terms of environmental pollution is controlled important
Effect.
A kind of charcoal base corn long-acting special composite fertilizer is by charcoal, chemical fertilizer, medical stone disclosed in patent document 1
Form with bentonite or be made up of charcoal, chemical fertilizer and bentonite, by weight percentage example meter charcoal, chemical fertilizer,
Medical stone and bentonite content are respectively 5~23.7%：71.3-82%：0~6%：5~8%, the charcoal powder be with
Agriculture waste biomass maize straw is raw material, passes through 350 DEG C to 400 DEG C temperature hot tearings under limit oxygen or anoxia condition after crushing
Solution, height aromatization, the solid matter of slightly solubility caused by 90 minutes are carbonized, by air-drying 24-48 hours or drying drying
30 minutes, obtain charcoal powder.The charcoal and medical stone of the patent can increase soil organic matter content, improved soil physics
Character, soil microbial activities are improved, but the ability of the processing heavy metal of the patent has much room for improvement, adsorbance deficiency.
A kind of preparation method of heavy metal wastewater thereby purification charcoal comprises the following steps disclosed in patent document 2：(1) will
After sludge semi-dry with the mixed compression forming of biological straw；(2) charcoal of compression forming is put into electric tube furnace
Row charing；(3) particle carries out chemical modification after carbonizing, and the charcoal with loose structure is made.The patent not only solves
The problem of cotton haulm raw material moisture content is low, the charcoal adsorption effect enhancing after chemical modification.But the stalk material of the patent
It is unfavorable for forming the big charcoal of specific surface area, and the specific surface area of charcoal and pore volume have much room for improvement.
Corncob is one kind common in numerous agriculture and forestry organic waste materials, and wide material sources are cheap.Rich in substantial amounts of fiber
Element, hemicellulose, lignin etc., are widely used in industrial production in recent years.
Prior art literature
Patent document
Patent document 1：Chinese patent discloses CN106916007 A
Patent document 2：Chinese patent discloses CN104289177 A.
The content of the invention
Problems to be solved by the invention
As described above, charcoal specific surface area and pore volume prepared by charcoal preparation method of the prior art have much room for improvement,
Adsorbance and adsorption rate are also required to lifting so as to improve the adsorption capacity of charcoal absorption heavy metal on the whole.
Solution to problem
The present inventor etc. have made intensive studies to reach above-mentioned purpose, specifically, in the first aspect of the present invention, sheet
Invention, which provides a kind of the step of charcoal preparation method based on corncob, to be included：
In first step, corncob cuts into 0.5-1.5 centimetres of segment after being washed, the segment is at 70 DEG C -80 DEG C
Middle drying, the segment after drying cross 60 mesh sieves after disintegrating apparatus crushes and obtain corn cob granule.
In second step, corn cob granule, which adds, impregnates 3-4 hours in the aqueous solution containing stannous chloride and ferric trichloride
Drying 4-5 hours in 80 DEG C -90 DEG C afterwards obtains mixture, corn cob granule, stannous chloride and three in the aqueous solution
The mass parts ratio of iron chloride is in 100:(5-8):(20-40).
In third step, the mixture is warming up to 350-450 under nitrogen in Muffle furnace with 8-10 DEG C/min speed
DEG C and continue 5-6 hours obtain corncob charcoal particle.
In four steps, the corncob charcoal particle is molten in the ethylene glycol containing frerrous chloride, zinc chloride and selenium powder
It is passed through in liquid under chlorine after 150-160 DEG C of stirring 2-3 hour, to add aqueous slkali regulation pH value, then with 40-50 DEG C of vacuum
Dry 6-7 hours obtain corncob charcoal, wherein, corncob charcoal particle, ethylene glycol, chlorine in the ethylene glycol solution
The mass parts ratio for changing ferrous, zinc chloride and selenium powder is in 100:(600-800):(5-6) :(20-24) :(5-6).
In 5th step, corncob charcoal, dimethylformamide, TGA and anhydrous slufuric acid hydrogen sodium are put into container
Sealed after stirring, 3 h are reacted at a temperature of 120 DEG C, then add 95% ethanol solution containing nine hydrated sodium sulfides
In, and continue to react 1 h, it is 6-8 to be washed through deionized water to pH value, and being dried in vacuo 24 h at 60 DEG C obtains sulfhydrylation corn
Core charcoal.
In described preparation method, in second step, corn cob granule, stannous chloride and trichlorine in the aqueous solution
The mass parts ratio for changing iron is in 100:6:30.
In described preparation method, in four steps, the corncob charcoal particle in the ethylene glycol solution, second two
Alcohol, frerrous chloride, the mass parts ratio of zinc chloride and selenium powder are in 100:700:5.5:22 :5.5.
In described preparation method, in the 5th step, it is 7 to be washed through deionized water to pH value.
In described preparation method, in first step, corncob is first passed through after running water cleaned impurity, then via steaming
After distilled water is washed 2 times, 1 centimetre of segment is cut into, the segment is dried in 75 DEG C, and the segment after drying is through disintegrating apparatus
60 mesh sieves are crossed after crushing and obtain corn cob granule.
In described preparation method, in third step, the mixture is in Muffle furnace with 9 DEG C/min's under nitrogen
Speed is warming up to 380 DEG C and continues to obtain within 5.5 hours corncob charcoal particle.
According to another aspect of the present invention, a kind of mercury absorbent, the mercury absorbent include described preparation method and prepared
Sulfhydrylation corncob charcoal, calcium sulfide and sodium selenite, wherein, sulfhydrylation corncob charcoal, calcium sulfide and selenous acid
The mass parts ratio of sodium is in 100:(20-30): (40-60).
According to another aspect of the invention, the preparation system of the charcoal preparation method based on corncob described in a kind of implementation
Including pretreatment unit, mixing arrangement, carbonizing apparatus, processing unit and control device.
The pretreatment unit is including the cleaning equipment for cleaning corncob, drying plant and for crushing maize core
Disintegrating apparatus, the drying plant are provided with the first temperature sensor, and the disintegrating apparatus is provided with speed probe.
The mixing arrangement is provided with the fluid-delivery valve for quantitatively injecting the aqueous solution, the first concentration sensor and for drying the water
The irradiation modules of solution, the irradiation modules are provided with second temperature sensor.
The carbonizing apparatus includes Muffle furnace and three-temperature sensor.
The processing unit is provided with liquid-filling valve, the second concentration sensor, the acid-base value sensing for quantitatively injecting ethylene glycol solution
Device, the inlet for being quantitatively adding aqueous slkali, agitator, heating module and vacuum desiccator for stirring, wherein, heating
Module and vacuum desiccator are respectively equipped with the 4th temperature sensor and the 5th temperature sensor.
The control device connects the first, second, third, fourth and fifth temperature sensor, first, second concentration
Sensor, acidity-basicity sensor and speed probe simultaneously control the drying plant, irradiation modules, heating module and vacuum respectively
The temperature of drier, the rotating speed of disintegrating apparatus, the concentration of mixing arrangement and processing unit.
In described preparation system, control device include general processor, digital signal processor, PLC control panels, specially
With integrated circuit ASIC or on-site programmable gate array FPGA.
In described preparation system, control device includes memory, and the memory is one or more read-only
Memory ROM, random access memory ram, flash memory or Electrical Erasable programmable read only memory EEPROM.
The effect of invention
According to the charcoal preparation method and preparation system and mercury absorbent based on corncob of the present invention, the present invention utilizes jade
The meter Xin material for being advantageous to be formed bigger specific surface area and pore volume in carbonization process, passes through tin particle and iron particle
It can be distributed in the micropore of corncob charcoal so that micropore swells, and further improves the specific surface area of corncob charcoal
And pore volume, corncob charcoal adsorbance of the invention is big, and adsorption capacity is significantly improved, and tin is adsorbed with corncob charcoal
The hydrophily of particle, iron particle and zinc particles enhancing charcoal, improves the specific surface area and pore volume of charcoal, significantly improves
The adsorption capacity of charcoal, the corncob charcoal that the present invention is obtained by sulfhydrylation corncob charcoal, after sulfhydryl modified
Sulfydryl and the heavy metal ion of charcoal produce complexing, mercapto functional group in adsorption process with mercury ion in solution
Affinity greatly enhances, and further increases its adsorbance to mercury, therefore, technical scheme overcomes prior art
Technological deficiency, achieve significant technique effect.
Described above is only the general introduction of technical solution of the present invention, in order to cause the technological means of the present invention clearer
Understand, reach the degree that those skilled in the art can be practiced according to the content of specification, and in order to allow the present invention
Above and other objects, features and advantages can become apparent, below with the present invention embodiment illustrated
Explanation.
Brief description of the drawings
[Fig. 1] shows that the step of charcoal preparation method based on corncob of one embodiment of the present of invention is illustrated
Figure.
[Fig. 2] shows that the corncob charcoal of one embodiment of the present of invention and existing charcoal dynamic absorption are bent
Line compares figure.
[Fig. 3] shows the corncob charcoal of one embodiment of the present of invention and existing charcoal adsorption isothermal curve
Compare figure.
[Fig. 4] shows the structural representation of the preparation system of one embodiment of the present of invention.
Embodiment
The specific embodiment of the present invention is more fully described below with reference to accompanying drawings.Although show the present invention's in accompanying drawing
Specific embodiment, it being understood, however, that may be realized in various forms the present invention without should be limited by embodiments set forth here
System.Conversely, there is provided these embodiments are to be able to be best understood from the present invention, and can be complete by the scope of the present invention
Be communicated to those skilled in the art.
It should be noted that some vocabulary has been used to censure specific components among specification and claim.Ability
Field technique personnel it would be appreciated that, technical staff may call same component with different nouns.This specification and right
It is required that not in a manner of the difference of noun is used as and distinguishes component, but differentiation is used as with the difference of component functionally
Criterion."comprising" or " comprising " as mentioned in working as in specification in the whole text and claim are an open language, therefore should be solved
It is interpreted into " include but be not limited to ".Specification subsequent descriptions for implement the present invention better embodiment, so it is described description be with
For the purpose of the rule of specification, the scope of the present invention is not limited to.Protection scope of the present invention is when regarding appended right
It is required that institute's defender is defined.
For ease of the understanding to the embodiment of the present invention, done further by taking several specific embodiments as an example below in conjunction with accompanying drawing
Explanation, and each accompanying drawing does not form the restriction to the embodiment of the present invention.
Specifically, the step schematic diagram of the charcoal preparation method of the invention based on corncob as shown in Figure 1, such as
Shown in Fig. 1, the charcoal preparation method step based on corncob includes：
In first step, corncob cuts into 0.5-1.5 centimetres of segment after being washed, the segment is at 70 DEG C -80 DEG C
Middle drying, the segment after drying cross 60 mesh sieves after disintegrating apparatus crushes and obtain corn cob granule.
Corncob includes lignin, cellulose, hemicellulose etc., present invention discover that corncob is as a kind of renewable money
Source, its material are advantageous to prepare charcoal, corncob by carbonization process can be formed than existing charcoal specific surface area and
The corncob charcoal that pore volume significantly increases, loose structure dramatically increase the adsorption site of charcoal.The present invention passes through cleaning
The impurity on corncob is removed, then corncob is cut into 0.5-1.5 centimetres of segment, this is advantageous to the completion of subsequent treatment
Rate, segment are dried in 70 DEG C -80 DEG C, and drying temperature is too high to be possible to cause damage to the material of corncob, reduce absorption
Site, drying temperature is too low, reduces drying efficiency, and the segment after drying crosses 60 mesh sieves after disintegrating apparatus crushes and obtains jade
Meter slug particle, further, the adjustable broken particle size range of disintegrating apparatus, the corn cob granule are less than 60 mesh, it is preferable that institute
It is 30-60 mesh to state corn cob granule, and further, the corn cob granule is 50 mesh.
In second step S2, it is small that corn cob granule adds dipping 3-4 in the aqueous solution containing stannous chloride and ferric trichloride
When after dry 4-5 hours in 80 DEG C -90 DEG C and obtain mixture, corn cob granule, stannous chloride in the aqueous solution and
The mass parts ratio of ferric trichloride is in 100:(5-8):(20-40).The present invention is by studying discovery, tin particle and iron particle energy
Enough be distributed in the micropore of corncob charcoal so that micropore swells, further improve corncob charcoal specific surface area and
Pore volume.Will line rod particle add the aqueous solution containing stannous chloride and ferric trichloride in impregnate 3-4 hours after at 80 DEG C -90
Dry 4-5 hours obtain mixture in DEG C, and this dipping can cause tin particle and iron particle to be fast and effeciently attached to corn
On slug particle.In order to improve the specific surface area and pore volume of tack and corncob charcoal, the present invention has found institute by research
The mass parts ratio for stating the corn cob granule in the aqueous solution, stannous chloride and ferric trichloride is in 100:(5-8):(20-40) can
To obtain optimum performance.
In third step S3, the mixture is warming up to 350- under nitrogen in Muffle furnace with 8-10 DEG C/min speed
450 DEG C and continue 5-6 hours obtain corncob charcoal particle.
In four steps S4, the corncob charcoal particle is in the ethylene glycol containing frerrous chloride, zinc chloride and selenium powder
It is passed through in solution under chlorine after 150-160 DEG C of stirring 2-3 hour, to add aqueous slkali regulation pH value, it is then true with 40-50 DEG C
Sky dries 6-7 hours and obtains corncob charcoal, wherein, corncob charcoal particle, ethylene glycol in the ethylene glycol solution,
The mass parts ratio of frerrous chloride, zinc chloride and selenium powder is in 100:(600-800):(5-6) :(20-24) :(5-6).Pass through
Four steps S4 processing, corncob charcoal adsorbance of the invention is big, and adsorption capacity significantly improves, and is inhaled on corncob charcoal
Strengthen the hydrophily of charcoal with tin particle, iron particle and zinc particles, improve the specific surface area and pore volume of charcoal, significantly
Improve the adsorption capacity of charcoal.
In 5th step S5, corncob charcoal, dimethylformamide, TGA and anhydrous slufuric acid hydrogen sodium are put into container
In stir after seal, 3 h are reacted at a temperature of 120 DEG C, it is molten then to add 95% ethanol containing nine hydrated sodium sulfides
In liquid, and continue to react 1 h, it is 6-8 to wash to pH value through deionized water, and 24 h are dried in vacuo at 60 DEG C and obtain sulfhydrylation jade
Rice core charcoal.The sulfydryl of charcoal after sulfhydryl modified produces complexing with heavy metal ion, and mercapto functional group is being inhaled
Affinity during attached with mercury ion in solution greatly enhances, and further increases its adsorbance to mercury.
In order to further illustrate the significant performance of the sulfhydrylation corncob charcoal of the preparation method of present invention preparation, it incite somebody to action this
Invent the sulfhydrylation corncob charcoal prepared and existing charcoal carries out dynamic absorption contrast, existing charcoal refers to existing
Charcoal in technology, for example, in the market adsorption capacity is the charcoal product of average level.Set mercury ion initial mass dense
Spend for 40 mg/L, solid-to-liquid ratio 1: 400.Make supporting electrolyte with 0.01 mol/L sour sodium, using batch balancing method.It is accurate to claim
Take the corncob of a certain amount of different disposal to be put into 100 mL triangular flasks, be separately added into the mercury Standard Reserving Solution of certain volume.
Then it is 0.01 mol/L to adjust background ions concentration, is settled to 40 mL with distilled water, regulating thermostatic water bath chader water temperature is extremely
25 DEG C, triangular flask is put into and wherein shaken with 120 r/min rotating speed, corresponding time point (5 min, 10 min, 30
Min, 60 min, 120 min, 240 min, 360 min, 480 min, 720 min) take supernatant determine its mercury from
Sub- concentration.Measure obtains sulfhydrylation corncob charcoal as shown in Figure 2 and relatively schemed with existing charcoal dynamic absorption curve ratio.
By Fig. 2 it should be apparent that whether sulfhydrylation corncob charcoal of the invention or existing charcoal, in preceding 30 min
Linear increased trend, subsequent adsorbance continue to increase, and reach adsorption equilibrium in 240 min or so.Sulfhydrylation corncob is given birth to
The mg/kg of adsorbance 14563 of thing charcoal, the mg/kg of adsorbance 6701 of existing charcoal, therefore, sulfhydrylation corncob charcoal
Adsorption capacity significantly improved than existing charcoal.
In order to further illustrate the significant performance of the sulfhydrylation corncob charcoal of the preparation method of present invention preparation, it incite somebody to action this
Invent the sulfhydrylation corncob charcoal prepared and existing charcoal carries out isothermal adsorption contrast, set mercury ion initial mass dense
Spend for 5,10,20,40,80,120,200 mg/L, solid-to-liquid ratio 1: 400.Make supporting electrolyte with 0.01 mol/L sour sodium, adopt
With batch balancing method.The corncob for accurately weighing a certain amount of different disposal is put into 100 mL triangular flasks, is separately added into certain
The mercury Standard Reserving Solution of volume.Then it is 0.01 mol/L to adjust background ions concentration, and 40 mL are settled to distilled water, is adjusted
Triangular flask is put into 25 DEG C and wherein shakes 6 h with 120 r/min rotating speed, stood after taking-up by thermostatic control oscillator vibration water temperature
2 h, filtering supernatant obtain filtrate and are used to determine its ion concentration of mercury.Sulfhydrylation as shown in Figure 3 will be made after result treatment
Corncob charcoal figure compared with existing charcoal adsorption isothermal curve, the sulfhydrylation corncob charcoal it can be seen from the Fig. 3
The mg/kg of maximal absorptive capacity 44684, the mg/kg of maximal absorptive capacity 27260 of existing charcoal, corncob charcoal with it is existing
Charcoal all increases the adsorbance of mercury in solution with the rise of equilibrium concentration.
Above comparative illustration sulfhydrylation corncob charcoal is than mercury ion in existing charcoal significantly more adsorbent solution.
In the preferred embodiment of the described preparation method of the present invention, in second step S2, the jade in the aqueous solution
The mass parts ratio of meter slug particle, stannous chloride and ferric trichloride is in 100:6:30.
In the preferred embodiment of the described preparation method of the present invention, in four steps S4, in the ethylene glycol solution
Corncob charcoal particle, ethylene glycol, frerrous chloride, the mass parts ratio of zinc chloride and selenium powder be in 100:700:5.5:
22 :5.5。
The present invention described preparation method preferred embodiment in, in the 5th step S5, through deionized water wash to
PH value is 7.
In the preferred embodiment of the described preparation method of the present invention, in first step S1, corncob first passes through originally
After water has cleaned impurity, then after being washed 2 times via distilled water, 1 centimetre of segment is cut into, the segment is dried in 75 DEG C,
Segment after drying crosses 60 mesh sieves after disintegrating apparatus crushes and obtains corn cob granule.
In the preferred embodiment of the described preparation method of the present invention, in third step S3, the mixture is in Muffle
380 DEG C are warming up under nitrogen with 9 DEG C/min speed and continue to obtain within 5.5 hours corncob charcoal particle in stove.
Present invention also offers a kind of mercury absorbent, the mercury absorbent includes sulfhydrylation prepared by described preparation method
Corncob charcoal, calcium sulfide and sodium selenite, wherein, the quality of sulfhydrylation corncob charcoal, calcium sulfide and sodium selenite
Part ratio is in 100:(20-30): (40-60).The mercury absorbent is handled especially suitable for the heavy metal of soil, mercury absorption
Agent is closed and is applied in soil very much, can be effectively improved soil environment, the specific surface area that sulfhydrylation corncob charcoal significantly increases and
Loose structure and the particle of attachment significantly absorb the mercury in soil, and calcium sulfide further promotes the mineralising of mercury, sodium selenite
The biological effectiveness of mercury is weakened using the antagonistic effect of selenium and mercury, significantly reduces the mercury content of crops.The mercury absorption of the present invention
Agent has good soil environment friendly, will not produce secondary pollution, and cost is low and easy to operate.
Present invention also offers a kind of preparation system of the charcoal preparation method based on corncob described in implementation, such as Fig. 4
The structural representation of the preparation system of charcoal preparation method based on corncob described in shown implementation, preparation system include pre-
Processing unit 1, mixing arrangement 2, carbonizing apparatus 3, processing unit 4 and control device 5.
The pretreatment unit 1 is including the cleaning equipment 6 for cleaning corncob, drying plant 7 and for crushing maize
The disintegrating apparatus 8 of core, the drying plant 7 are provided with the first temperature sensor 9, and the disintegrating apparatus 8 is provided with speed probe 10.
The mixing arrangement 2 is provided with the fluid-delivery valve 11 for quantitatively injecting the aqueous solution, the first concentration sensor 12 and for drying
The irradiation modules 13 of the aqueous solution, the irradiation modules 13 are provided with second temperature sensor 14.
The carbonizing apparatus 3 includes Muffle furnace 15 and three-temperature sensor 16.
The processing unit 4 is provided with the liquid-filling valve 17, the second concentration sensor 18, acid-base value for quantitatively injecting ethylene glycol solution
Sensor 19, the inlet 20 for being quantitatively adding aqueous slkali, the agitator 21 for stirring, heating module 22 and vacuum drying
Device 23, wherein, heating module 22 and vacuum desiccator 23 are respectively equipped with the 4th temperature sensor 24 and the 5th temperature sensor 25.
The control device 5 connect the first, second, third, fourth and fifth temperature sensor 9,14,16,24,
25th, first, second concentration sensor 12,18, acidity-basicity sensor 19 and speed probe 10 and the drying is controlled to set respectively
Standby 7, irradiation modules 13, heating module 22 and the temperature of vacuum desiccator 23, the rotating speed of disintegrating apparatus 8 and the and of mixing arrangement 2
The concentration of processing unit 4.
In the preferred embodiment of described preparation system, control device 5 includes general processor, Digital Signal Processing
Device, PLC control panels, application-specific integrated circuit ASIC or on-site programmable gate array FPGA.
In the preferred embodiment of described preparation system, control device 5 includes memory, the memory be one or
Multiple read only memory ROMs, random access memory ram, flash memory or Electrical Erasable programmable read only memory
EEPROM。
In one embodiment, the preparation system is additionally provided with remote controllers, and the remote controllers pass through wireless
Communication equipment connects preparation system and sends and receives control signal.The Wireless Telecom Equipment includes bluetooth, ZigBee or Wi-
Fi modules.
Industrial applicibility
The charcoal preparation method based on corncob, preparation system and the mercury absorbent of the present invention can be in charcoal field system
Make and use.
Although embodiment of the present invention is described above in association with accompanying drawing, the invention is not limited in above-mentioned
Specific embodiments and applications field, above-mentioned specific embodiment are only schematical, directiveness, rather than restricted
's.One of ordinary skill in the art is under the enlightenment of this specification and in the scope for not departing from the claims in the present invention and being protected
In the case of, the form of many kinds can also be made, these belong to the row of protection of the invention.
Claims (10)
1. a kind of charcoal preparation method based on corncob, its step include：
First step（S1）In, corncob cuts into 0.5-1.5 centimetres of segment after being washed, the segment is at 70 DEG C -80
Dried in DEG C, the segment after drying crosses 60 mesh sieves after disintegrating apparatus crushes and obtains corn cob granule；
Second step（S2）In, corn cob granule, which adds, impregnates 3-4 hours in the aqueous solution containing stannous chloride and ferric trichloride
Drying 4-5 hours in 80 DEG C -90 DEG C afterwards obtains mixture, corn cob granule, stannous chloride and three in the aqueous solution
The mass parts ratio of iron chloride is in 100:(5-8):(20-40)；
Third step（S3）In, the mixture is warming up to 350-450 under nitrogen in Muffle furnace with 8-10 DEG C/min speed
DEG C and continue 5-6 hours obtain corncob charcoal particle；
Four steps（S4）In, the corncob charcoal particle is molten in the ethylene glycol containing frerrous chloride, zinc chloride and selenium powder
It is passed through in liquid under chlorine after 150-160 DEG C of stirring 2-3 hour, to add aqueous slkali regulation pH value, then with 40-50 DEG C of vacuum
Dry 6-7 hours obtain corncob charcoal, wherein, corncob charcoal particle, ethylene glycol, chlorine in the ethylene glycol solution
The mass parts ratio for changing ferrous, zinc chloride and selenium powder is in 100:(600-800):(5-6) :(20-24) :(5-6)；
5th step（S5）In, corncob charcoal, dimethylformamide, TGA and anhydrous slufuric acid hydrogen sodium are put into container
Sealed after stirring, 3 h are reacted at a temperature of 120 DEG C, then add 95% ethanol solution containing nine hydrated sodium sulfides
In, and continue to react 1 h, it is 6-8 to be washed through deionized water to pH value, and being dried in vacuo 24 h at 60 DEG C obtains sulfhydrylation corn
Core charcoal.
2. preparation method according to claim 1, it is characterised in that second step（S2）In, the jade in the aqueous solution
The mass parts ratio of meter slug particle, stannous chloride and ferric trichloride is in 100:6:30.
3. preparation method according to claim 1 or 2, it is characterised in that four steps（S4）In, the ethylene glycol is molten
The mass parts ratio of corncob charcoal particle, ethylene glycol, frerrous chloride, zinc chloride and selenium powder in liquid is in 100:700:
5.5:22 :5.5。
4. preparation method according to claim 1, it is characterised in that the 5th step（S5）In, through deionized water wash to
PH value is 7.
5. preparation method according to claim 1, it is characterised in that first step（S1）In, corncob first passes through originally
After water has cleaned impurity, then after being washed 2 times via distilled water, 1 centimetre of segment is cut into, the segment is dried in 75 DEG C,
Segment after drying crosses 60 mesh sieves after disintegrating apparatus crushes and obtains corn cob granule.
6. according to the preparation method any one of claim 1-5, it is characterised in that third step（S3）In, it is described mixed
Compound is warming up to 380 DEG C with 9 DEG C/min speed under nitrogen in Muffle furnace and continues to obtain corncob charcoal in 5.5 hours
Particle.
7. a kind of mercury absorbent, prepared by the preparation method that the mercury absorbent is included according to any one of claim 1-6
Sulfhydrylation corncob charcoal, calcium sulfide and sodium selenite, wherein, sulfhydrylation corncob charcoal, calcium sulfide and selenous acid
The mass parts ratio of sodium is in 100:(20-30): (40-60).
8. a kind of preparation system for implementing the charcoal preparation method based on corncob any one of claim 1-6, its
Including pretreatment unit（1）, mixing arrangement（2）, carbonizing apparatus（3）, processing unit（4）And control device（5）, its feature exists
In,
The pretreatment unit（1）Including the cleaning equipment for cleaning corncob（6）, drying plant（7）With for crushing jade
Meter Xin disintegrating apparatus（8）, the drying plant（7）Provided with the first temperature sensor（9）, the disintegrating apparatus（8）Provided with turn
Fast sensor（10）；
The mixing arrangement（2）Fluid-delivery valve provided with the quantitative injection aqueous solution（11）, the first concentration sensor（12）With for doing
The irradiation modules of the dry aqueous solution（13）, the irradiation modules（13）Provided with second temperature sensor（14）；
The carbonizing apparatus（3）Including Muffle furnace（15）With three-temperature sensor（16）；
The processing unit（4）Liquid-filling valve provided with quantitative injection ethylene glycol solution（17）, the second concentration sensor（18）, soda acid
Spend sensor（19）, inlet for being quantitatively adding aqueous slkali（20）, agitator for stirring（21）, heating module（22）
And vacuum desiccator（23）, wherein, heating module（22）And vacuum desiccator（23）It is respectively equipped with the 4th temperature sensor（24）
With the 5th temperature sensor（25）；
The control device（5）Connect the first, second, third, fourth and fifth temperature sensor（9、14、16、24、
25）, first, second concentration sensor（12、18）, acidity-basicity sensor（19）And speed probe（10）And respectively described in control
Drying plant（7）, irradiation modules（13）, heating module（22）And vacuum desiccator（23）Temperature, disintegrating apparatus（8）Rotating speed
And mixing arrangement（2）And processing unit（4）Concentration.
9. preparation system according to claim 8, wherein,
Control device（5）Including general processor, digital signal processor, PLC control panels, application-specific integrated circuit ASIC or scene
Programmable gate array FPGA.
10. harvester according to claim 8 or claim 9, it is characterised in that：Control device（5）It is described to deposit including memory
Reservoir is that one or more read only memory ROMs, random access memory ram, flash memory or Electrical Erasable may be programmed
Read-only storage EEPROM.
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| CN110369486B (en) * | 2019-07-17 | 2023-04-14 | 中国科学院城市环境研究所 | Preparation and application of sulfhydrylation biochar for repairing heavy metal polluted water and soil |
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