CN109603749A - A kind of preparation method and applications of modified straw straw biological charcoal - Google Patents
A kind of preparation method and applications of modified straw straw biological charcoal Download PDFInfo
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- CN109603749A CN109603749A CN201811599794.2A CN201811599794A CN109603749A CN 109603749 A CN109603749 A CN 109603749A CN 201811599794 A CN201811599794 A CN 201811599794A CN 109603749 A CN109603749 A CN 109603749A
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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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a kind of preparation method and applications of modified straw straw biological charcoal, belong to technical field of biological environmental protection, include the following steps: the preparation of 1) raw material: collecting power plant fly ash and farmland rice straw and be respectively dried, rice straw crushes；2) by the resulting flyash of step 1), roasting is after mixing with sodium hydroxide to get alkali fusion flyash；3) the alkali fusion flyash for obtaining step 2) is added in the rice straw that step 1) obtains, adds deionized water, shakes up, vibrates, dries, crushes, and obtains rice straw and alkali fusion mixture of fly ash；4) rice straw for obtaining step 3) and alkali fusion mixture of fly ash, pyrolysis crush to get modified straw straw biological charcoal；The raw material for preparing of the invention is agriculture and industry waste, and cheap and easy to get, preparation method is simple, and cost of manufacture is cheap, high to the removal rate of pollutant, and large amount of adsorption is without secondary pollution to environment, facilitates the control and improvement of environmental pollution.
Description
Technical field
The present invention relates to a kind of preparation methods of modification biological charcoal, more specifically more particularly to a kind of modified straw straw
The preparation method of stalk charcoal.Present invention simultaneously relates to the applications of the modification biological charcoal.
Background technique
The discharge amount of dyeing waste water is very big, counts according to Europe, and the weight ratio of fabric and waste discharge is 1:150~1:200,
China is about 1:200~1:400.China's textile waste is the 6th of national discharged volume of industrial waste water, wherein 80% belongs to
Dyeing waste water.There are many processing method of dyeing waste water, mainly there is absorption, oxidation, UF membrane, flocculation, biodegrade etc..Absorption method
There is special status in field of waste water treatment with the characteristic that it can selectively be enriched with certain compounds.Active carbon is current
One of most effective adsorbent, but since its regeneration is relatively difficult, processing cost is higher, and application surface is narrow.Therefore a kind of warp is found
The effective adsorbent that helps becomes the key of current technological development.
According to United Nations Environment Programme, the crops planted in the world can provide about 2,000,000,000 t of all kinds of stalks every year, I
State's agricultural crop straw annual output is 700,000,000 t or so, arranges first of the world, converts into 3.53 hundred million t of tandard coal amount, account for whole world stalk total amount
30% or so.The annual agricultural straw resource amount in China accounts for about the nearly half of biomass resource amount.Agricultural crop straw is a kind of
Valuable renewable resource, but for a long time due to being influenced by consumption idea and life style, China's straw from village resource
Be completely in high consumption, high pollution, low output situation, considerable a part of agricultural crop straw thrown aside or burnt
It burns, does not obtain rational exploitation and utilization.According to investigations, China's straw utilization rate is about 33% at present, and wherein most does not add processing,
What is utilized after technical treatment only accounts for about 2.6%.Therefore, comprehensive utilization agricultural straw resource is for economizing on resources, protecting
Environment increases farmers' income, the sustainable development of agricultural is promoted all to have important practical significance.Straw charring technology has been me
It is environmental-friendly, high in technological content to provide one for the solution of state's stalk comprehensive utilization problem, and great market-oriented prospect is easy to handle
Method.
Charcoal has large specific surface area, porosity height, is rich in surface function as a kind of novel environmentally friendly repair materials
Group and stronger ion-exchange capacity have stronger application potential in removal water pollutant.However traditional biological charcoal absorption effect
Rate is low, and charcoal density is light, particle is small, and it is difficult to be separated by solid-liquid separation after absorption, be easy to cause secondary pollution, nor is conducive to
The regeneration and recycling of charcoal.Studies have shown that general composite material is better than homogenous material to the adsorption effect of pollutant.Cause
This, has at present had some scholars concern charcoal and other materials be applied in combination, using physics, chemical method by charcoal
It is combined with other materials and is prepared into the material with new capability, new construction, comprehensive performance is better than former composition material, can meet each
The different requirement of kind.The preparation of biological carbon composite be usually in biomass raw material add other materials (magnetic material,
Nano material, inorganic salts etc.), then composite material is prepared by high temperature pyrolysis.Charcoal compares table after being prepared into composite material
Area and aperture increases, surface functional group increase significantly improves the removal ability of pollutant, and is easy to be separated by solid-liquid separation after adsorbing.
But these composite materials are often expensive, the too small easy reunion of particle, and have certain toxicity, can reduce environmental microorganism
Type and quantity, these disadvantages limit the popularization and application of these composite materials.Currently, charcoal and its composite material are main
It is used to adsorb inorganic pollution in environment (such as heavy metal, fluorine) and organic pollutant (such as dyestuff, petroleum hydrocarbon, pesticide, antibiosis
Element etc.), study its adsorption effect and the mechanism of action.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and applications of modified straw straw biological charcoal.System of the invention
Standby raw material is agriculture and industry waste, and cheap and easy to get, preparation method is simple, and cost of manufacture is cheap, high to the removal rate of pollutant,
Large amount of adsorption, it is without secondary pollution to environment, facilitate environmental pollution and is managed and administered.
The technical scheme of the present invention is realized as follows: a kind of preparation method of modified straw straw biological charcoal, including such as
Lower step:
1) flyash and rice straw, flyash drying the preparation of raw material: are collected；Rice straw drying crushes；
2) preparation of alkali fusion flyash: roasting is after the resulting flyash of step 1) is mixed with sodium hydroxide to get alkali fusion
Flyash；
3) mixing of rice straw and alkali fusion flyash: the alkali fusion flyash that step 2) obtains is added to step 1) and is obtained
Rice straw in, add the deionized water of certain volume, sequentially by shaking up, vibrate, dry and crush, obtain straw straw
Stalk and alkali fusion mixture of fly ash；
4) preparation of modified straw straw biological charcoal: rice straw that step 3) is obtained and alkali fusion mixture of fly ash according to
Sequence is by pyrolysis and crushes to get modified straw straw biological charcoal.
A kind of preparation method of above-mentioned modified straw straw biological charcoal, flyash described in step 1) are coal-burning power plant
Flyash, partial size are less than 0.045mm, dry under 100~110 DEG C of environment；
The rice straw is farmland rice straw, is dried under 70~90 DEG C of environment, and partial size is less than 1.00mm after crushing.
A kind of preparation method of above-mentioned modified straw straw biological charcoal, step 2) specifically: by the resulting powder of step 1)
Coal ash and sodium hydroxide be in mass ratio 1:1~1.5 after mixing, roast 0.5 under 600~700 DEG C of temperature environment~
2h, product of roasting are crushed to partial size less than 1.00mm, obtain by alkali fusion treated flyash, i.e. alkali fusion flyash.
A kind of preparation method of above-mentioned modified straw straw biological charcoal, the step 2) sodium hydroxide are analysis pure chemistry
Reagent.
A kind of preparation method of above-mentioned modified straw straw biological charcoal, rice straw described in step 3) and alkali fusion powder
The mixed proportion of coal ash is mass ratio 1:0.1~0.5；The matter of the alkali fusion flyash and rice straw mixture and deionized water
Amount volume ratio is 1:10g/ml；The duration of oscillation is 2~6h；The drying temperature is 70~90 DEG C；Partial size after the crushing
Less than 1.00mm.
A kind of preparation method of above-mentioned modified straw straw biological charcoal, described in step 4) be pyrolyzed specifically: with 10 DEG C/
For the heating rate of min by room temperature to 650~750 DEG C, heat preservation is pyrolyzed 1~2h, natural cooling after the completion of pyrolysis；The crushing
Partial size is less than 1.00mm afterwards.
Modified straw straw biological charcoal as described in claim 1 of the invention is for removing water body methylene in sewage
Blue and cationic red application.
Above-mentioned modified straw straw biological charcoal is for removing the application of water body Methylene Blue and cationic red in sewage
In, obtained modified straw straw biological charcoal can handle methylene blue waste water in the range of 7≤pH≤13,1≤pH≤
Cationic red waste water is handled in 13 ranges.
Above-mentioned modified straw straw biological charcoal is for removing the application of water body Methylene Blue and cationic red in sewage
In, obtained modified straw straw biological charcoal to the time of equilibrium adsorption of methylene blue and cationic red be 2~for 24 hours, to Asia
The time of equilibrium adsorption of methyl blue is preferably 4~for 24 hours.
The present invention after adopting the above method, compared with prior art, has the following advantages that and effect:
1) flyash that uses of the present invention contains a large amount of porous vitreums, is in porosity cellular tissue, specific surface area compared with
Greatly, while its surface also has a large amount of Si-O-Si keys, Al-O-Al key isoreactivity group, and adsorption activity is higher.But fine coal
Ash has open hole in forming process, since portion gas escapes, and surface is in honeycomb；Portion gas does not escape quilt
It is rolled in particle and forms closure hole, internal is also in honeycomb.The former has absorption property since hole is exposed to surface；
The absorption property of the latter then very little, need to be with closed hole be either physically or chemically opened, to improve its porosity and specific surface
Product.Alkali fusion processing can not only open hole, moreover it is possible to be allowed to generate a large amount of new microscopic pinholes by the effect of alkali, increase specific surface
Long-pending and porosity, the effect for handling waste water will also greatly improve.
2) present invention prepares adsorbent material charcoal to including this agricultural wastes of rice straw progress resource utilization,
And by flyash modified its adsorption efficiency of raising of alkali fusion, modified straw straw biological charcoal high-efficiency adsorbent is obtained.
3) present invention uses agriculture and industry waste cheap and easy to get for raw material, and it is solid can to control industrial or agricultural to a certain extent
Body waste pollution alleviates the processing pressure of agriculture and industry waste, realizes the higher value application of agriculture and industry waste, change give up into
Treasured is expected to merchandized handling.
4) modified straw straw biological charcoal produced by the present invention, in dyeing waste water it is generally existing go methylene blue and
Cationic red has significant adsorption effectiveness, improves treatment effeciency, is conducive to water pollution control, before having preferable application
Scape.
Detailed description of the invention
Fig. 1 is the SEM figure of flyash, alkali fusion flyash, charcoal and modified straw straw biological charcoal of the present invention, wherein scheming
1 (a) schemes for the SEM of flyash, the SEM figure of Fig. 1 (b) alkali fusion flyash, and Fig. 1 (c) is that the SEM of rice straw charcoal schemes, Fig. 1
(d) the SEM figure of modified straw straw biological charcoal.
Fig. 2 is Fourier's phenogram of rice straw charcoal and modified straw straw biological charcoal of the present invention.
Fig. 3 is the EDS energy spectrum diagram of rice straw charcoal and modified straw straw biological charcoal of the present invention.
Fig. 4 is that modified straw straw biological charcoal is real to methylene blue and cationic red adsorption equilibrium in the embodiment of the present invention 4
Test result figure.
Fig. 5 is modified straw straw biological charcoal in the embodiment of the present invention 5 to methylene blue and cationic red adsorption dynamics adsorption kinetics
Experimental result picture.
Fig. 6 is for modified straw straw biological charcoal in the embodiment of the present invention 6 to methylene blue under different solutions initial pH value
With cationic red Adsorption experimental results figure.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below, but does not constitute to of the invention any
Limitation.
A kind of preparation method of modified straw straw biological charcoal of the invention, includes the following steps:
1) preparation of raw material: collection cut size is less than the coal-burning power plant's flyash and farmland rice straw of 0.045mm, fine coal
Ash is dried under 100~110 DEG C of environment；Rice straw is dried under 70~90 DEG C of environment, is then crushed to partial size and is less than
1.00mm。
Wherein, the chemical component of coal-burning power plant's flyash is shown in Table 1,
Chemical component (mass fraction) unit of 1 flyash of table: %
2) preparation of alkali fusion flyash: being 1:1~1.5 by the resulting flyash of step 1) and sodium hydroxide in mass ratio,
After mixing, 0.5~2h is roasted under 600~700 DEG C of temperature environment, product of roasting is crushed to partial size and is less than 1.00mm,
By alkali fusion treated flyash, i.e. alkali fusion flyash.The sodium hydroxide is analysis pure chemistry reagent.
3) mixing of rice straw and alkali fusion flyash: the alkali fusion flyash that step 2) obtains is added to step 1) and is obtained
Rice straw in, the mixed proportion of rice straw and alkali fusion flyash is mass ratio 1:0.1~0.5, add deionized water,
Alkali fusion flyash and rice straw mixture and the mass volume ratio of deionized water are 1:10g/ml, are then shaken up, and 2~6h is vibrated
Afterwards, it is dried under 70~90 DEG C of environment, then is crushed to partial size less than 1.00mm, obtained rice straw and mixed with alkali fusion flyash
Object；
4) preparation of modified straw straw biological charcoal: rice straw and alkali fusion mixture of fly ash that step 3) obtains are put
In corundum crucible, cover tightly crucible lid, be put into Muffle furnace, with the heating rate of 10 DEG C/min by room temperature to 650~
750 DEG C, heat preservation pyrolysis 1~2h, after the completion of pyrolysis in Muffle furnace natural cooling, further take out sample, be crushed to partial size and be less than
1.00mm is to get modified straw straw biological charcoal.
The specific surface area of 650~750 DEG C of rice straw charcoals is 76.25-84.69m2/ g, modified charcoal ratio
Surface area is significantly increased, and improves to 311.6-352.4m2/ g, diameter is less than increased significantly for 1nm micropore.By Fig. 1 (a) and (b)
Compare flyash and alkali fusion flyash, it can be seen that sodium hydroxide not only opens the closed hole of flyash, is also allowed to generate
A large amount of new microscopic pinholes increase specific surface area and porosity.By Fig. 1 (c) and (d) comparison charcoal before modified after, can be with
Finding out can make rice straw biology carbon surface become rougher by the method for the invention, increase micropore quantity and volume, and
One layer of alkali fusion flyash " velvet-like " overlay film is formed well in biological carbon surface, specific surface area is increased, so as to enhance its suction
Attached performance.As shown in Figure 2, wave-length coverage is clearly enhanced by the method for the invention is located at 1100~450cm-1Si-in section
The absorbance of O-Si key, Al-O-Al key isoreactivity group, while by Fig. 3 (a) and (b) it is found that the method for the present invention obviously increases
The content of essential element O, Si and Al contained by modified straw straw biological carbon surface alkali fusion flyash are added, it is possible to determine that modified
Biological carbon surface on successfully load upper alkali fusion flyash, can achieve modified effect by the above method.
Embodiment 1
The flyash that will be collected in power plant is dried at 105 DEG C, and the flyash and sodium hydroxide after drying are with mass ratio
It is uniformly mixed, is fitted into corundum crucible for 1:1.2, after roasting 1h at 650 DEG C with Muffle furnace, taken out after cooling in burner hearth,
Partial size is less than 1.00mm to get alkali fusion flyash after crushing.Farmland rice straw is dried under 80 DEG C of environment, rice straw powder
Partial size is less than 1.00mm after broken.By after dries pulverizing rice straw and alkali fusion flyash with mass ratio be 10:3, i.e. alkali fusion powder
The addition quality of coal ash is the 30% of rice straw quality to be uniformly mixed, then deionized water is added in mixture, mixture with
The mass volume ratio of deionized water is 1:10g/ml, vibrates 2h, dries under 80 DEG C of environment, is crushed to partial size less than 1.00mm.
By the mixture of rice straw and alkali fusion flyash after drying, it is put in corundum crucible, covers tightly crucible lid, put
Enter in Muffle furnace, pyrolysis temperature is risen to 650 DEG C respectively with 10 DEG C/min heating rate, heat preservation pyrolysis 1.5h, after the completion of pyrolysis
The natural cooling in Muffle furnace, further takes out sample, is crushed to partial size less than 1.00mm to get modified straw straw biological charcoal.
Application effect: it by the above-mentioned modified straw straw biological charcoal being prepared, is added to containing 10mg/L methylene
In blue or cationic red aqueous solution, for pH in 6~8 ranges, adding concentration is 0.25g/L, is placed on constant-temperature table, in 25 ±
2h is vibrated with 150r/min in 1 DEG C of temperature range.Modified straw straw biological charcoal can be effectively in adsorbed water body as the result is shown
Methylene blue and cationic red.Prepared modified straw straw biological charcoal is 22.7mg/g to the adsorbance of methylene blue, is inhaled
Attached amount improves more than 5 times compared with the pure rice straw charcoal prepared under the same terms；Adsorbance to cationic red is 27.8mg/
G, adsorbance improve about 65% compared with the pure rice straw charcoal prepared under the same terms.
Embodiment 2
The flyash that will be collected in power plant is dried at 100 DEG C, and the flyash and sodium hydroxide after drying are with mass ratio
It is uniformly mixed, is fitted into corundum crucible for 1:1, after roasting 2h at 600 DEG C with Muffle furnace, taken out after cooling in burner hearth, powder
Partial size is less than 1.00mm to get alkali fusion flyash after broken.Farmland rice straw is dried under 70 DEG C of environment, rice straw crushes
Partial size is less than 1.00mm afterwards.By after dries pulverizing rice straw and alkali fusion flyash with mass ratio be 10:1, i.e. alkali fusion fine coal
The addition quality of ash is uniformly mixed for the 10% of rice straw quality, then a certain amount of deionized water is added in mixture, mixes
The mass volume ratio for closing object and deionized water is 1:10g/ml, vibrates 4h, then dries under 70 DEG C of environment, it is small to be crushed to partial size
In 1.00mm.
By the mixture of rice straw and alkali fusion flyash after drying, it is put in corundum crucible, covers tightly crucible lid, put
Enter in Muffle furnace, pyrolysis temperature is risen to 700 DEG C with 10 DEG C/min heating rate, 1h is pyrolyzed at this temperature, after the completion of pyrolysis
The natural cooling in Muffle furnace, further takes out sample, is crushed to partial size less than 1.00mm to get modified straw straw biological charcoal.
Application effect: it by the above-mentioned modified straw straw biological charcoal being prepared, is added to containing 10mg/L methylene
In blue or cationic red aqueous solution, for pH in 6~8 ranges, adding concentration is 0.25g/L, is placed on constant-temperature table, in 25 ±
4h is vibrated with 150r/min in 1 DEG C of temperature range.Modified straw straw biological charcoal can be effectively in adsorbed water body as the result is shown
Methylene blue and cationic red.Prepared modified straw straw biological charcoal is respectively 21.5mg/ to the adsorbance of methylene blue
g；Adsorbance to cationic red is 25.1mg/g.
Embodiment 3
The flyash that will be collected in power plant is dried at 110 DEG C, and the flyash and sodium hydroxide after drying are with mass ratio
It is uniformly mixed, is fitted into corundum crucible for 1:1.5, after roasting 0.5h at 700 DEG C with Muffle furnace, taken after cooling in burner hearth
Out, partial size is less than 1.00mm to get alkali fusion flyash after crushing.Farmland rice straw is dried under 90 DEG C of environment, straw straw
Partial size is less than 1.00mm after stalk crushes.Rice straw after dries pulverizing is mixed with alkali fusion flyash with quality and 10:5
Even, i.e. the addition quality of alkali fusion flyash is respectively the 50% of rice straw quality, then deionized water is added in mixture, is mixed
The mass volume ratio for closing object and deionized water is 1:10g/ml, and oscillation for 24 hours, dries under 90 DEG C of environment, is crushed to partial size and is less than
1.00mm。
By the mixture of rice straw and alkali fusion flyash after drying, it is put in corundum crucible, covers tightly crucible lid, put
Enter in Muffle furnace, with 10 DEG C/min heating rate pyrolysis temperature is risen to 750 DEG C respectively, be pyrolyzed 2h respectively at this temperature, heat
After the completion of solution in Muffle furnace natural cooling, further take out sample, it is raw to get modified straw stalk less than 1.00mm to be crushed to partial size
Object charcoal.
Application effect: it by the above-mentioned modified straw straw biological charcoal being prepared, is added to containing 10mg/L methylene
In blue or cationic red aqueous solution, for pH in 6~8 ranges, adding concentration is 0.25g/L, is placed on constant-temperature table, in 25 ±
6h is vibrated with 150r/min in 1 DEG C of temperature range.Modified straw straw biological charcoal can be effectively in adsorbed water body as the result is shown
Methylene blue and cationic red.Prepared modified straw straw biological charcoal is 24.3mg/g to the adsorbance of methylene blue；It is right
The adsorbance of cationic red is 30.8mg/g.
Embodiment 4
The flyash that will be collected in power plant is dried at 105 DEG C, and the flyash and sodium hydroxide after drying are with mass ratio
It is uniformly mixed, is fitted into corundum crucible for 1:1.2, after roasting 1h at 650 DEG C with Muffle furnace, taken out after cooling in burner hearth,
Partial size is less than 1.00mm to get alkali fusion flyash after crushing.Farmland rice straw is dried under 80 DEG C of environment, rice straw powder
Partial size is less than 1.00mm after broken.Rice straw after dries pulverizing is uniformly mixed with alkali fusion flyash with mass ratio for 10:1,
I.e. the addition quality of alkali fusion flyash is the 10% of rice straw quality, then a certain amount of deionized water is added in mixture,
Mixture and the mass volume ratio of deionized water are 1:10g/ml, vibrate 2h, dry under 80 DEG C of environment, be crushed to partial size and be less than
1.00mm。
By the mixture of rice straw and alkali fusion flyash after drying, it is put in corundum crucible, covers tightly crucible lid, put
Enter in Muffle furnace, pyrolysis temperature is risen to 700 DEG C with 10 DEG C/min heating rate, 2h is pyrolyzed at this temperature, after the completion of pyrolysis
The natural cooling in Muffle furnace, further takes out sample, is crushed to partial size less than 1.00mm to get modified straw straw biological charcoal.
Application effect: by the above-mentioned modified straw straw biological charcoal being prepared, be added to respectively containing 5,10,15,
20,30,40,60, in the aqueous solution of 80mg/L methylene blue or cationic red, in 6~8 ranges, add concentration is pH
0.25g/L is placed on constant-temperature table, interior with 150r/min oscillation 3h in 25 ± 1 DEG C of temperature ranges.Experimental result as shown in figure 4,
Show that modified straw straw biological charcoal can effectively adsorbed water body Methylene Blue and cationic red by Fig. 4.It is hot at 700 DEG C
2h is solved, under the conditions of the addition quality of alkali fusion flyash is the 10% of rice straw quality, the modified straw straw biological charcoal of preparation
40.8mg/g can reach to the maximal absorptive capacity of methylene blue；63.1mg/g can reach to the maximal absorptive capacity of cationic red.
Embodiment 5
The modified straw straw biological charcoal being prepared in 4 through the embodiment of the present invention, is added to containing 10mg/L methylene
In the aqueous solution of base indigo plant or cationic red, for pH in 6~8 ranges, adding concentration is 0.25g/L, is placed on constant-temperature table, in 25
In ± 1 DEG C of temperature range with 150r/min oscillation 10min, 30min, 1,2,4,8,16, for 24 hours.Experimental result as shown in figure 5, by
Fig. 5 shows that modified straw straw biological charcoal can effectively adsorbed water body Methylene Blue and cationic red.It is pyrolyzed at 700 DEG C
2h, under the conditions of the addition quality of alkali fusion flyash is the 10% of rice straw quality, the modified straw straw biological charcoal pair of preparation
The maximal absorptive capacity of methylene blue can reach 34.9mg/g；36.7mg/g can reach to the maximal absorptive capacity of cationic red.
Embodiment 6
The flyash modified pig manure charcoal of alkali fusion being prepared in 4 through the embodiment of the present invention, is added to containing 10mg/
In the aqueous solution of L methylene blue or cationic red, the initial pH value of the aqueous solution is adjusted to 1,3,5,7,9,11,13 respectively, throws
Adding concentration is 0.25g/L, is placed on constant-temperature table, interior with 150r/min oscillation 2h in 25 ± 1 DEG C of temperature ranges.Experimental result is such as
Shown in Fig. 6, show that the flyash modified pig manure charcoal of alkali fusion can effectively adsorbed water body Methylene Blue and cation by Fig. 6
It is red.2h is pyrolyzed at 700 DEG C, under the conditions of the addition quality of alkali fusion flyash is the 10% of pig manure quality, the alkali fusion fine coal of preparation
The modified pig manure charcoal of ash has preferable adsorption effect, to the maximal absorptive capacity (pH of methylene blue in solution initial pH value > 5
=13) it can reach 32.2mg/g；38.7mg/g can reach to the maximal absorptive capacity (pH=11) of cationic red.
Embodiment provided above is better embodiment of the invention, only is used to facilitate to illustrate the present invention, not to this hair
It is bright to make any form of restriction, any those of ordinary skill in the art, if not departing from the proposed skill of the present invention
In the range of art feature, using the equivalent embodiment for locally changing or modifying made by disclosed technology contents, and
Without departing from technical feature content of the invention, in the range of still falling within the technology of the present invention feature.
Claims (9)
1. a kind of preparation method of modified straw straw biological charcoal, which comprises the steps of:
1) flyash and rice straw, flyash drying the preparation of raw material: are collected；Rice straw drying crushes；
2) preparation of alkali fusion flyash: roasting is after the resulting flyash of step 1) is mixed with sodium hydroxide to get alkali fusion fine coal
Ash；
3) the alkali fusion flyash that step 2) obtains the mixing of rice straw and alkali fusion flyash: is added to the rice that step 1) obtains
In careless stalk, add the deionized water of certain volume, sequentially by shaking up, vibrate, dry and crush, obtain rice straw with
Alkali fusion mixture of fly ash；
4) preparation of modified straw straw biological charcoal: rice straw and alkali fusion mixture of fly ash that step 3) obtains sequentially are passed through
It crosses pyrolysis and crushes to get modified straw straw biological charcoal.
2. a kind of preparation method of modified straw straw biological charcoal according to claim 1, it is characterised in that: in step 1)
The flyash is coal-burning power plant's flyash, and partial size is less than 0.045mm, dries under 100~110 DEG C of environment；The straw
Stalk is farmland rice straw, is dried under 70~90 DEG C of environment, and partial size is less than 1.00mm after crushing.
3. a kind of preparation method of modified straw straw biological charcoal according to claim 1, it is characterised in that: step 2) tool
Body are as follows: by the resulting flyash of step 1) and sodium hydroxide be in mass ratio 1:1~1.5 after mixing, at 600~700 DEG C
Temperature environment under roast 0.5~2h, product of roasting is crushed to partial size less than 1.00mm, obtains by alkali fusion treated fine coal
Ash, i.e. alkali fusion flyash.
4. a kind of preparation method of modified straw straw biological charcoal according to claim 1 or 3, it is characterised in that: step
2) sodium hydroxide is analysis pure chemistry reagent.
5. a kind of preparation method of modified straw straw biological charcoal according to claim 1, it is characterised in that: in step 3)
The mixed proportion of the rice straw and alkali fusion flyash is mass ratio 1:0.1~0.5；The alkali fusion flyash and straw straw
Stalk mixture and the mass volume ratio of deionized water are 1:10g/ml；The duration of oscillation is 2~6h；The drying temperature is 70
~90 DEG C；Partial size is less than 1.00mm after the crushing.
6. a kind of preparation method of modified straw straw biological charcoal according to claim 1, it is characterised in that: in step 4)
The pyrolysis specifically: with the heating rate of 10 DEG C/min by room temperature to 650~750 DEG C, heat preservation 1~2h of pyrolysis, pyrolysis
Natural cooling after the completion；Partial size is less than 1.00mm after the crushing.
7. modified straw straw biological charcoal as described in claim 1 is for removing water body Methylene Blue and cation in sewage
Red application.
8. modified straw straw biological charcoal according to claim 7 for remove in sewage water body Methylene Blue and sun from
The red application of son, which is characterized in that obtained modified straw straw biological charcoal handles methylene blue in the range of 7≤pH≤13
Waste water handles cationic red waste water in the range of 1≤pH≤13.
9. modified straw straw biological charcoal according to claim 7 or 8 for remove in sewage water body Methylene Blue and
The application of cationic red, which is characterized in that suction of the obtained modified straw straw biological charcoal to methylene blue and cationic red
Attached equilibration time is 2~for 24 hours, the time of equilibrium adsorption to methylene blue is preferably 4~and for 24 hours.
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| CN112717881A (en) * | 2020-11-20 | 2021-04-30 | 南方科技大学 | Straw modified biochar and preparation method and application thereof |
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| CN114405473A (en) * | 2022-02-17 | 2022-04-29 | 广东石油化工学院 | Preparation method and application of calcium hydroxide modified straw stalk biochar |
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| CN115254018A (en) * | 2022-07-18 | 2022-11-01 | 宁夏大学 | Biochar prepared from industrial solid waste and wetland biomass and preparation method thereof |
| CN115957718A (en) * | 2022-12-21 | 2023-04-14 | 安徽大学 | Fly ash biochar composite material as well as preparation method and application thereof |
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