CN108435135A - A kind of preparation method of watermelon peel charcoal and its in removing waste water thallium application - Google Patents
A kind of preparation method of watermelon peel charcoal and its in removing waste water thallium application Download PDFInfo
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- CN108435135A CN108435135A CN201810520059.1A CN201810520059A CN108435135A CN 108435135 A CN108435135 A CN 108435135A CN 201810520059 A CN201810520059 A CN 201810520059A CN 108435135 A CN108435135 A CN 108435135A
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- watermelon peel
- charcoal
- waste water
- thallium
- thallium ion
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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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a kind of preparation methods of watermelon peel charcoal, comprise the steps of：(1), watermelon peel pre-processes：Watermelon peel is dried, watermelon peel powder is obtained；(2), it carbonizes：In a nitrogen atmosphere by the watermelon peel powder obtained by step (1), in the case where carbonization temperature is 400~600 DEG C, 0.5~1.5h is to get the watermelon peel charcoal for charing.Using watermelon peel charcoal made from preparation method of the present invention to the adsorption efficiency highest of sub- thallium ion, and it is simple for process, manufacturing cost is low.The invention also discloses a kind of minimizing technology of waste water Central Asia thallium ion, the sub- thallium ion removal efficiency of the minimizing technology of the waste water Central Asia of the present invention thallium ion is high, at low cost.
Description
Technical field
The present invention relates to a kind of preparation methods of Carbon Materials, and in particular to a kind of preparation method of watermelon peel charcoal and its
The application of thallium in removing waste water.
Background technology
China is industrial power, annual discharged volume of industrial waste water over ten billion ton, and management task is heavy.Wherein, about 65%
Industrial wastewater be not up to discharging standards, the heavy metal ion in waste water, which enters environment, must pollute the environment, influence people
Class health.
The heavy metal ion arrived involved in industrial wastewater common are Cd, Pb, Zn, Hg and Ni etc., but with sub- thallium ion
Industrial wastewater based on (Tl (I)), qualified discharge, the influence to environment be not the most severe.
Domestic processing industrial wastewater is method of chemical treatment using most methods at present, such as precipitation, flocculation.These can
It realizes discharged wastewater met the national standard, but a large amount of chemical reagent need to be used, cost great number and have secondary pollution.
Ion-exchange：Tl (I) is separated from aqueous solution, is not removed from environment really, resin regeneration
When will produce Tl (I) waste liquid of high concentration, need to carry out subsequent processing, it is expensive.In addition, due to Tl (I) and exchanger resin
Effect it is very strong, the Tl (I) that is adsorbed on resin is difficult to be come out by other ion exchanges, causes to regenerate extremely difficult.Except this it
Outside, in actual application process, can there are problems that and cationic competitive Adsorption coexists.These coexisting substances are trapped within friendship
It changes in column, causes final product that there is extremely strong corrosivity.
Membrane separation process：UF membrane includes reverse osmosis and micro-pore-film filtration.The membrane separation techniques such as nanofiltration, reverse osmosis, electrodialysis
Principle be to be detached solute and water by the selective penetrated property of film, it is preferable to the removal effect of ionic compound, and without pair
Effect.The waste water concentrated after processing is also required to be reprocessed or disposed as ion-exchange (such as with biological reducing method
Deng), and film process cost of equipment is high, film is cleaned and is replaced, and processing cost is relatively expensive.Therefore, in reality
It is very limited in the popularization of production.
There is also electrolysis, electrochemical reducing etc., all there are one common features for all these methods, exactly run into
This height, therefore it is very necessary and very significant to explore low-cost method.
Invention content
A kind of watermelon peel charcoal is provided it is an object of the invention to overcome in place of the shortcomings of the prior art
Preparation method and its in removing waste water thallium application.
To achieve the above object, the technical solution that the present invention takes is：A kind of preparation method of watermelon peel charcoal, including
Following steps：
(1), watermelon peel pre-processes：Watermelon peel is dried, watermelon peel powder is obtained；
(2), it carbonizes：In a nitrogen atmosphere by the watermelon peel powder obtained by step (1), it is 400~600 DEG C in carbonization temperature
Under, 0.5~1.5h is to get the watermelon peel charcoal for charing.
Watermelon peel of the present invention is the pericarp of watermelon.The present invention uses raw material of the watermelon peel as biological carbon materials, especially
It is suitable for the absorption of the sub- thallium ion in absorption waste water, and are obtained by the multiple repetition test of inventor, using above-mentioned preparation
Watermelon peel charcoal made from method is high and simple for process to the adsorption efficiency of sub- thallium ion, manufacturing cost is low.
The preferred embodiment of preparation method as watermelon peel charcoal of the present invention, in step (2), the charing
Temperature is 450~550 DEG C, and the carbonization time is 1h.Using above-mentioned temperature, watermelon peel charcoal obtained to sub- thallium ion
Adsorption effect more preferably.
The more preferable embodiment of preparation method as watermelon peel charcoal of the present invention, the carbonization temperature are
500℃.At 500 DEG C, watermelon peel charcoal obtained is best to the adsorption effect of sub- thallium ion.
The preferred embodiment of preparation method as watermelon peel charcoal of the present invention, by watermelon obtained by step (2)
Skin charcoal acid or alkali are modified processing, obtain modified watermelon peel charcoal.The watermelon peel charcoal can pass through
Acid or alkali are modified processing.
The preferred embodiment of preparation method as watermelon peel charcoal of the present invention, the method for the modification
For：5 is mixed to watermelon peel charcoal with the hydrochloric acid of 0.1mol/L~for 24 hours, it is washed to pH value and is more than 5, fallen after stratification
Fall supernatant, it is dry, pickling material is obtained, then mixes pickling material with potassium hydroxide, the weight of the pickling material and potassium hydroxide
The ratio between be：Pickling material：Potassium hydroxide=1:2, it is added in deionized water, stirring 5~for 24 hours, supernatant is outwelled after stratification, then
8~12h is dried at 85 DEG C, then in vacuum tube furnace in a nitrogen atmosphere, with 5 DEG C/min of heating rate, 500 DEG C of constant temperature
1h, after be cooled to room temperature, finally grind, sieve with 100 mesh sieve the watermelon peel charcoal after can be obtained alkali modification.
The purpose of the present invention is to provide a kind of lifes of watermelon peel that the preparation method of the watermelon peel charcoal is prepared
Object charcoal.
The present invention also aims to provide application of the watermelon peel charcoal in the thallium ion of the removal waste water Central Asia.
It is still another object of the present invention to provide a kind of minimizing technology of waste water Central Asia thallium ion, waste water Central Asia thallium from
The minimizing technology of son comprises the steps of：It is added the watermelon peel charcoal in the waste water containing sub- thallium ion, reaction 0.5~
30min, the watermelon peel charcoal for having adsorbed sub- thallium ion is separated from waste water to get the waste water for removing sub- thallium ion and
The watermelon peel charcoal of sub- thallium ion is adsorbed；
In the waste water containing sub- thallium ion, the ratio between the content of the content and the watermelon peel charcoal of the Asia thallium ion
For：Thallium in waste water containing thallium：Watermelon peel charcoal=1:50~500.
Watermelon peel charcoal of the present invention is particularly suitable for the absorption of sub- thallium ion, and adsorption efficiency is high, and use is above-mentioned
The additive amount of watermelon peel charcoal, you can 95% or more absorption can be realized in a short time.It is repeatedly studied by inventor
Show that the increase of the additive amount with watermelon peel charcoal, the adsorbance of sub- thallium ion increase, but when watermelon peel charcoal
It is 1 that additive amount, which increases to the ratio between the content of sub- thallium ion and the content of watermelon peel charcoal,:When 200, it is further added by watermelon peel biology
The adsorbance of the content of charcoal, sub- thallium ion no longer increases with the increase of watermelon peel charcoal, occurs under adsorption effect instead
The phenomenon that drop, the reason is that absorption has been saturated, then adds more charcoals, adsorption effect meeting relative drop, therefore when sub- thallium
The content of ion and the ratio between the content of watermelon peel charcoal are：Thallium in waste water containing thallium：Watermelon peel charcoal=1:When 50~500,
With preferable adsorption effect.
The preferred embodiment of minimizing technology as the waste water Central Asia of the present invention thallium ion, it is described containing sub- thallium ion
The pH of waste water is more than 4.Can be better achieved the absorption of sub- thallium ion in the pH value, the watermelon peel charcoal to sub- thallium from
The adsorption energy of son reaches 98% or more.
The more preferable embodiment of minimizing technology as the waste water Central Asia of the present invention thallium ion, it is described containing sub- thallium ion
Waste water in, the content and the ratio between the content of the watermelon peel charcoal of the Asia thallium ion are：Thallium in waste water containing thallium：Watermelon peel
Charcoal=1:200.It is obtained by the multiple repetition test of inventor, is somebody's turn to do when the content and watermelon peel charcoal of sub- thallium ion use
When proportioning, that is, there is preferable adsorption effect, and be unlikely to lead to the waste of charcoal, reached making full use of for charcoal
Rate, and in order to ensure that the absorption of sub- thallium ion is complete, the content of the content of sub- thallium ion and the watermelon peel charcoal is preferably
Said ratio.
The preferred embodiment of minimizing technology as the waste water Central Asia of the present invention thallium ion further includes sub- thallium ion
The recycling step of desorption and watermelon peel charcoal：0.01~1mol/L is added in the watermelon peel charcoal for having adsorbed sub- thallium ion
Acid solution vibrate 3~10min in the case where hunting speed is 150~300r/min, be then centrifuged for, watermelon peel after must be desorbed is given birth to
Object charcoal；The acid solution is HCl, H2SO4、H3PO4And HNO3At least one of solution.
Watermelon peel charcoal of the present invention may be implemented repeatedly to recycle in the removal of sub- thallium ion, by above-mentioned
99% or more desorption rate may be implemented in desorption manipulation, and watermelon peel charcoal is allow to reuse repeatedly.
The preferred embodiment of minimizing technology as the waste water Central Asia of the present invention thallium ion, the acid solution are
HNO3, a concentration of 0.1mol/L of the acid solution.It is obtained by the multiple repetition test of inventor, using the nitric acid of 0.1mol/L
When as desorption solution, desorption rate highest.
The beneficial effects of the present invention are：The present invention provides a kind of preparation method of watermelon peel charcoal and its removing
The application of thallium in waste water.Using watermelon peel charcoal made from preparation method of the present invention to the adsorption efficiency of sub- thallium ion most
Height, and it is simple for process, manufacturing cost is low.The present invention also provides a kind of minimizing technology of waste water Central Asia thallium ion, institute of the present invention
The sub- thallium ion removal efficiency for stating the minimizing technology of waste water Central Asia thallium ion is high, at low cost.
Description of the drawings
Fig. 1 is after watermelon peel charcoal adsorbed sub- thallium ion described in embodiment 1, respectively 1mol/L, 0.1mol/L,
HCl, H of 0.01mol/L2SO4、H3PO4And HNO3In desorption rate comparison result；
Fig. 2 is the SEM figures under 1~3 charcoal difference enlargement ratio of test group, wherein Fig. 2 a are described in test group 3
Watermelon peel charcoal, enlargement ratio be 500 times；Fig. 2 b are watermelon peel charcoal described in test group 1, and enlargement ratio is 500 times；
Fig. 2 c are watermelon peel charcoal described in test group 2, and enlargement ratio is 500 times；Fig. 2 d are the watermelon peel under 400 DEG C of carbonization temperatures
Charcoal, enlargement ratio are 500 times；Fig. 2 e are the watermelon peel charcoal under 500 DEG C of carbonization temperatures, and enlargement ratio is 500 times；
Fig. 2 f are the watermelon peel charcoal under 600 DEG C of carbonization temperatures, and enlargement ratio is 500 times；Fig. 2 g are to be adopted under 500 DEG C of carbonization temperatures
Watermelon peel charcoal made from the preparation method described in embodiment 1, enlargement ratio are 1000 times；Fig. 2 h are 500 DEG C of carbonization temperatures
After watermelon peel charcoal absorption thallium made from preparation method described in lower use embodiment 1, enlargement ratio is 5000 times；Fig. 2 i are
After adsorbing thallium using watermelon peel charcoal made from preparation method described in embodiment 1 under 500 DEG C of carbonization temperatures, enlargement ratio is
5000 times；Fig. 2 j are under 400 DEG C of carbonization temperatures using watermelon peel charcoal, times magnification made from preparation method described in embodiment 1
Rate is 1000 times；Fig. 2 k are to be put using watermelon peel charcoal made from preparation method described in embodiment 1 under 600 DEG C of carbonization temperatures
Big multiplying power is 1000 times；
Fig. 3 is Fourier's infrared test figure of the watermelon peel charcoal of the test group 1~3 in embodiment 7；
Fig. 4 is the sub- thallium removal rate of the different dosages of the watermelon peel charcoal of test group 1~3.
Specific implementation mode
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention
It is described further.
Embodiment 1
A kind of embodiment of the preparation method of watermelon peel charcoal of the present invention, comprises the steps of：
(1), watermelon peel pre-processes：Watermelon peel is dried, is crushed, is sieved with 100 mesh sieve, obtain watermelon peel powder；
(2), it carbonizes：Watermelon peel powder obtained by step (1) is placed in vacuum tube furnace, in a nitrogen atmosphere, heating
Rate is 5 DEG C/min, and in the case where carbonization temperature is 500 DEG C, constant temperature carbonizes 1h, and grinding is sieved with 100 mesh sieve and given birth to get the watermelon peel
Object charcoal.
The watermelon peel charcoal that the preparation method of watermelon peel charcoal described in the present embodiment is prepared.
A kind of embodiment of the minimizing technology of the waste water Central Asia of the present invention thallium ion, waste water Central Asia thallium described in the present embodiment
The minimizing technology of ion comprises the steps of：
(a), watermelon peel charcoal described in the present embodiment, reaction are added in the waste water containing sub- thallium ion that pH is 8
10min, the watermelon peel charcoal for having adsorbed sub- thallium ion is separated from waste water to get the waste water for removing sub- thallium ion and
The watermelon peel charcoal of sub- thallium ion is adsorbed；
(b), the recycling of the desorption and watermelon peel charcoal of sub- thallium ion：In the watermelon peel charcoal for having adsorbed sub- thallium ion
The middle salpeter solution that 0.1mol/L is added vibrates 5min, is then centrifuged for, after must being desorbed in the case where hunting speed is 200r/min
Watermelon peel charcoal；
(c), the watermelon peel charcoal after desorption that step (b) obtains is recycled and reused for step (a).
Embodiment 2
A kind of embodiment of the preparation method of watermelon peel charcoal of the present invention, comprises the steps of：
(1), watermelon peel pre-processes：Watermelon peel is dried, is crushed, is sieved with 100 mesh sieve, obtain watermelon peel powder；
(2), it carbonizes：Watermelon peel powder obtained by step (1) is placed in vacuum tube furnace, in a nitrogen atmosphere, heating
Rate is 5 DEG C/min, in the case where carbonization temperature is 400 DEG C, carbonizes 1.5h, grinding sieves with 100 mesh sieve to get watermelon peel biology
Charcoal.
The watermelon peel charcoal that the preparation method of watermelon peel charcoal described in the present embodiment is prepared.
A kind of embodiment of the minimizing technology of the waste water Central Asia of the present invention thallium ion, waste water Central Asia thallium described in the present embodiment
The minimizing technology of ion comprises the steps of：
(a), watermelon peel charcoal described in the present embodiment, reaction are added in the waste water containing sub- thallium ion that pH is 10
10min, the watermelon peel charcoal for having adsorbed sub- thallium ion is separated from waste water to get the waste water for removing sub- thallium ion and
The watermelon peel charcoal of sub- thallium ion is adsorbed；
(b), the recycling of the desorption and watermelon peel charcoal of sub- thallium ion：In the watermelon peel charcoal for having adsorbed sub- thallium ion
The middle salpeter solution that 1mol/L is added vibrates 5min, is then centrifuged for, the west after must being desorbed in the case where hunting speed is 200r/min
Melon skin charcoal；
(c), the watermelon peel charcoal after desorption that step (b) obtains is recycled and reused for step (a).
Embodiment 3
A kind of embodiment of the preparation method of watermelon peel charcoal of the present invention, comprises the steps of：
(1), watermelon peel pre-processes：Watermelon peel is dried, is crushed, is sieved with 100 mesh sieve, obtain watermelon peel powder；
(2), it carbonizes：Watermelon peel powder obtained by step (1) is placed in vacuum tube furnace, in a nitrogen atmosphere, heating
Rate is 5 DEG C/min, in the case where carbonization temperature is 600 DEG C, carbonizes 0.5h, grinding sieves with 100 mesh sieve to get watermelon peel biology
Charcoal.
The watermelon peel charcoal that the preparation method of watermelon peel charcoal described in the present embodiment is prepared.
A kind of embodiment of the minimizing technology of the waste water Central Asia of the present invention thallium ion, waste water Central Asia thallium described in the present embodiment
The minimizing technology of ion comprises the steps of：
(a), watermelon peel charcoal described in the present embodiment, reaction are added in the waste water containing sub- thallium ion that pH is 11
10min, the watermelon peel charcoal for having adsorbed sub- thallium ion is separated from waste water to get the waste water for removing sub- thallium ion and
The watermelon peel charcoal of sub- thallium ion is adsorbed；
(b), the recycling of the desorption and watermelon peel charcoal of sub- thallium ion：In the watermelon peel charcoal for having adsorbed sub- thallium ion
The middle salpeter solution that 0.01mol/L is added vibrates 5min, is then centrifuged for, after must being desorbed in the case where hunting speed is 200r/min
Watermelon peel charcoal；
(c), the watermelon peel charcoal after desorption that step (b) obtains is recycled and reused for step (a).
Embodiment 4
In order to probe into removal effect of the additive amount to sub- thallium ion of watermelon peel charcoal, in the initial concentration containing Tl (I)
For in the solution of 10.25mg/L, the watermelon peel being prepared using the preparation method of watermelon peel charcoal described in embodiment 1 is added
Charcoal, the dosage of the watermelon peel charcoal are respectively 0.25g/L, 0.5g/L, 1g/L, 2g/L, 3g/L, 4g/L, 5g/L,
And changing the temperature in embodiment 1, the watermelon peel charcoal being prepared at 400 DEG C, 500 DEG C and 600 DEG C of test is mixed
30min is stirred, then supernatant liquid filtering is taken respectively, adds 20%1 by volume fraction:1HNO3Supernatant to be measured (sample) is preserved,
Finally Tl (I) concentration in sample, the dosage and different charcoals of different watermelon peel charcoals are measured with atomic absorption spectrophotometer
Tl (I) removal effect of watermelon peel charcoal obtained is shown in Table 2 at a temperature of change.
The Tl (I) of watermelon peel charcoal obtained under the dosage and different carbonization temperatures of the different watermelon peel charcoals of table 2
Removal rate
From the results shown in Table 2, with the increase of the dosage of watermelon peel charcoal, the removal rate of Tl (I) increases,
When additive amount increases to 0.5g/L, the Tl's (I) of the watermelon peel charcoal obtained using 500 DEG C of carbonization temperatures is big in removal rate
In 95%, in order to ensure removal rate and cost, the preferably dosage of watermelon peel charcoal is 2g/L, the i.e. waste water containing sub- thallium ion
In, the content of the Asia thallium ion and the ratio between the content of the watermelon peel charcoal are：Thallium in waste water containing thallium：Watermelon peel charcoal
=1:200.In addition, from table 2 it can be seen that compared with 400 DEG C and 600 DEG C, Tl (I) removal rate under 500 DEG C of carbonization temperature
It is relatively high in identical dosage.
Embodiment 5
In order to probe into the removal effect of watermelon peel charcoal in the case of different pH to sub- thallium ion, containing the initial of Tl (I)
In the solution of a concentration of 10.25mg/L, watermelon peel charcoal described in embodiment 1, the dosage of the watermelon peel charcoal is added
For 2g/L, pH=2,4,6,8,9,10,11,12 are adjusted, stirring 30min is mixed, then takes supernatant liquid filtering respectively, by body
Fraction adds 20%1:1HNO3Supernatant to be measured (sample) is preserved, is finally measured in sample with atomic absorption spectrophotometer
Tl (I) concentration, watermelon peel charcoal is shown in Table 3 to the removal effect of sub- thallium ion in the case of different pH.
Removal rate of the table 3 in the different initial pH watermelon peel charcoals of Tl (I) solution
From table 3 it can be seen that when pH is more than or equal to 4, the watermelon peel charcoal reaches the adsorption energy of sub- thallium ion
98% or more.
Embodiment 6
It is initial containing Tl (I) in 25mL in order to probe into the influence of the type and concentration of acid to the desorption effect of sub- thallium ion
Watermelon peel charcoal described in embodiment 1 is added in the solution of a concentration of 10.25mg/L, the dosage of the watermelon peel charcoal is
2g/L, the pH for adjusting solution are 11, so prepare 12 Duplicate Samples, take supernatant liquid filtering after stirring 30min at room temperature, by volume
Score adds 2%1:1HNO3It preserves；It keeps and takes out supernatant with syringe after sample, be separately added into 25mL HCl, H2SO4、
H3PO4And HNO3, test desorption effect when a concentration of 1mol/L, 0.1mol/L, 0.01mol/L of each acid：Desorption process exists
It is carried out in shaking table, it is 25 DEG C, hunting speed 200r/min, duration of oscillation 5min that temperature, which is arranged, in shaking table, is put after desorption
Enter centrifugation aggregation biological carbon materials in centrifuge, and take supernatant, adds volume 2% plus 1:1HNO3Sample is preserved, atom is finally used
Absorption spectrophotometer measures Tl (I) concentration in sample (desorption concentration).Test result is shown in Fig. 1.It will be seen from figure 1 that
The HNO of 0.1mol/L3Desorption effect is best, and desorption rate is close to 90%.
Test uses the HNO of 0.1mol/L3Be continuing with after desorption adsorbance and desorption rate (adsorbance in table 4 and
The test of desorption rate is the quality of the Carbon Materials before being adsorbed using first time as initial calculation standard), test result is shown in Table 4,
From table 4, it can be seen that therefore using the HNO of 0.1mol/L3Repeatedly elution absorption after material, Carbon Materials can be recycled 5 times and
More than.
The different adsorbances and desorption rate for recycling number of table 4
| Number is desorbed | Adsorbance (mg/g) | Desorption rate (mg/g) |
| 1 | 5.16 | 3.83 |
| 2 | 5.08 | 4.39 |
| 3 | 5.09 | 4.18 |
| 4 | 5.01 | 3.96 |
| 5 | 5.01 | 3.90 |
Embodiment 7
For influence of the modified condition to adsorption effect for the watermelon peel charcoal probed into, three test groups are set：
Test group 1：Watermelon peel charcoal described in embodiment 1, is denoted as not deliming material；
Test group 2：Watermelon peel charcoal described in 5g embodiments 1 is added in 200mL 0.1mol/L HCl, 12h is stirred,
It is washed to pH>5), water lotion is layered after standing, and water lotion is layered after standing, then outwells supernatant, 85 DEG C of drying 12h, finally
It grinds, sieve with 100 mesh sieve the watermelon peel charcoal that can be obtained and be modified described in test group 2, be denoted as deliming material；
Test group 3：Test group 2 is mixed with potassium hydroxide, the weight ratio of the test group 2 and potassium hydroxide is：Acid
Wash material：Potassium hydroxide=1:2, it is added in deionized water, stirs 10h, outwell supernatant after stratification, dried at 85 DEG C
12h, then in vacuum tube furnace with 5 DEG C/min of heating rate, under nitrogen atmosphere, constant temperature 1h at 500 DEG C, after be cooled to
Room temperature finally grinds, sieves with 100 mesh sieve and can be obtained the modified watermelon peel charcoal of test group 3, is denoted as KOH modified materials.
Fig. 2 is the SEM figures under 1~3 charcoal difference enlargement ratio of test group, wherein Fig. 2 a are described in test group 3
Watermelon peel charcoal, enlargement ratio be 500 times；Fig. 2 b are watermelon peel charcoal described in test group 1, and enlargement ratio is 500 times；
Fig. 2 c are watermelon peel charcoal described in test group 2, and enlargement ratio is 500 times；Fig. 2 d are that embodiment is used under 400 DEG C of carbonization temperatures
Watermelon peel charcoal made from 1 preparation method, enlargement ratio are 500 times；Fig. 2 e are under 500 DEG C of carbonization temperatures using implementation
The watermelon peel charcoal made from preparation method described in example 1, enlargement ratio are 500 times；Fig. 2 f are to be adopted under 600 DEG C of carbonization temperatures
The watermelon peel charcoal made from the preparation method described in embodiment 1, enlargement ratio are 500 times；Fig. 2 g are 500 DEG C of charing temperature
Degree is lower using watermelon peel charcoal made from preparation method described in embodiment 1, and enlargement ratio is 1000 times；Fig. 2 h are 500 DEG C of charcoals
After adsorbing thallium using watermelon peel charcoal made from preparation method described in embodiment 1 at a temperature of change, enlargement ratio is 5000 times；
Fig. 2 i are amplification after adsorbing thallium using watermelon peel charcoal made from preparation method described in embodiment 1 under 500 DEG C of carbonization temperatures
Multiplying power is 5000 times；Fig. 2 j are that watermelon peel charcoal made from preparation method described in embodiment 1 is used under 400 DEG C of carbonization temperatures,
Enlargement ratio is 1000 times；Fig. 2 k are under 600 DEG C of carbonization temperatures using watermelon peel biology made from preparation method described in embodiment 1
Charcoal, enlargement ratio are 1000 times.
Figure it is seen that the pattern of three kinds of materials of test group 1~3 is not quite similar, the carbon of test group 1 and test group 2
Constructor closes general porous structure, and wherein test group 1 becomes apparent from；Compare the biological carbon materials under different temperatures again, from figure
The SEM figures of 2d~2f not only have poroid, also lamellar structure, this may as can be seen that 500 DEG C of material pore structure is more rich
It is 500 DEG C of materials one of advantageous reason in the structure of functional material.From the SEM of Fig. 2 g~2k figures as can be seen that charcoal
It is at 500 DEG C for compared to 400 DEG C and 600 DEG C of charcoal obtained (without apparent pore structure) to change temperature, and pore structure is richer
Rich (trepanning on hole), specific surface area is also relatively large, and adsorption site is more, is conducive to adsorb.
FTIR spectrum figure, adsorption rate and the desorption rate of testing experiment group 1~3.Test result is shown in Fig. 3,4.From Fig. 3
In as can be seen that in 3600-3200cm-1, hydroxyl (- OH, 3250) most notably KOH modified materials (test group 3) is secondly examination
Test group 1, test group 2 it is least apparent；The Carbon Materials of test group 1 are in 1800-1200cm-1, the functional group of performance is esterifying carboxyl group
(1625、1375cm-1), wherein 1375cm-1It is particularly evident；The material of test group 1 is in 1006cm-1On position, performance another
Functional group is the C-O stretching vibrations in carboxylic acid, all more significantly compared to other two kinds of materials.The presence of these functional groups is exactly
Illustrate that the Carbon Materials not being modified are more suitable for the sorbing material of removal thallium, and the machine of Carbon Materials Adsorption thallium
System also forms complex compound with these functional groups, final that precipitation occurs or is adsorbed on related on Carbon Materials.
From fig. 4, it can be seen that under the different dosages of the watermelon peel charcoal of test group 1~3, unmodified charcoal
It remains to reach preferable adsorption effect.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than is protected to the present invention
The limitation of range is protected, although being explained in detail to the present invention with reference to preferred embodiment, those skilled in the art should
Understand, technical scheme of the present invention can be modified or replaced equivalently, without departing from the essence of technical solution of the present invention
And range.
Claims (10)
1. a kind of preparation method of watermelon peel charcoal, which is characterized in that comprise the steps of：
(1), watermelon peel pre-processes：Watermelon peel is dried, watermelon peel powder is obtained；
(2), it carbonizes：In a nitrogen atmosphere by the watermelon peel powder obtained by step (1), in the case where carbonization temperature is 400~600 DEG C,
0.5~1.5h is carbonized to get the watermelon peel charcoal.
2. the preparation method of watermelon peel charcoal as described in claim 1, which is characterized in that in step (2), the carbonization temperature
It it is 450~550 DEG C, the carbonization time is 1h；Preferably, the carbonization temperature is 500 DEG C.
3. the preparation method of watermelon peel charcoal as claimed in claim 2, which is characterized in that further include step after step (2)
(3)：Watermelon peel charcoal acid or alkali obtained by step (2) are modified processing, obtain modified watermelon peel charcoal.
4. the watermelon peel that a kind of preparation method using any one of claims 1 to 3 watermelon peel charcoal is prepared
Charcoal.
5. application of the watermelon peel charcoal as claimed in claim 4 in the thallium ion of the removal waste water Central Asia.
6. a kind of minimizing technology of waste water Central Asia thallium ion, which is characterized in that comprise the steps of：In the waste water containing sub- thallium ion
Watermelon peel charcoal described in middle addition claim 4 reacts 0.5~30min, will adsorb the watermelon peel charcoal of sub- thallium ion
It is separated from waste water to get removing the waste water of sub- thallium ion and having adsorbed the watermelon peel charcoal of sub- thallium ion；
In the waste water containing sub- thallium ion, the content of the Asia thallium ion and the ratio between the content of the watermelon peel charcoal are：
Thallium in waste water containing thallium：Watermelon peel charcoal=1:50~500.
7. the minimizing technology of the waste water Central Asia as claimed in claim 6 thallium ion, which is characterized in that the waste water containing sub- thallium ion
PH be more than or equal to 4.
8. the minimizing technology of the waste water Central Asia as claimed in claim 6 thallium ion, which is characterized in that the waste water containing sub- thallium ion
In, the content of the Asia thallium ion and the ratio between the content of the watermelon peel charcoal are：Thallium in waste water containing thallium：Watermelon peel charcoal
=1:200.
9. the minimizing technology of the waste water Central Asia as claimed in claim 6 thallium ion, which is characterized in that further include the desorption of sub- thallium ion
With the recycling step of watermelon peel charcoal：The acid of 0.01~1mol/L is added in the watermelon peel charcoal for having adsorbed sub- thallium ion
Solution vibrates 3~10min, is then centrifuged in the case where hunting speed is 150~300r/min, the watermelon peel biology after must being desorbed
Charcoal；The acid solution is HCl, H2SO4、H3PO4And HNO3At least one of solution.
10. the minimizing technology of the waste water Central Asia as claimed in claim 9 thallium ion, which is characterized in that the acid solution is HNO3, institute
State a concentration of 0.1mol/L of acid solution.
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