A kind of active carbon and preparation method thereof
Technical field
The present invention relates to Environmental Engineering Material technical fields, and in particular to a kind of active carbon and preparation method thereof.
Background technique
Marine oil spill accident occurs again and again, causes that also destructive calamity can be carried out to zoology after huge economic loss
It is difficult.There is expert's expression, this energy rich in aromatic compound of petroleum can convert in the organisms such as mammal or birds
For the stronger substance of toxicity, or even cause DNA mutation, so that the fecundity of organism is declined, serious person can suffer from cancer.More have
Expert indicates that greasy dirt can be trapped into deposit, endangers many decades even longer time.In addition, marine oil overflow is after the accident,
Petroleum can generate the soluble intermediate product such as aldehyde, ketone through photochemical catalytic oxidation, photochemical oxidation reaction or with oxygen effect, go forward side by side one
Step generates benzene class by redox reaction and contains toxicant, generates significant damage to organism.
Currently, marine oil overflow is handled mostly based on the methods of greasy dirt absorption felt absorption, but asphalt felt can only be to non-emulsified
The substances such as oil, other floatings and immiscible liquids are adsorbed, and intermediate product soluble for aldehyde, ketone etc. lacks adsorption energy
Power, effect is bad in terms of seawater cleaning.
Summary of the invention
The purpose of the present invention is to provide a kind of active carbons and preparation method thereof, are prepared into using method provided by the invention
To active carbon not only can effectively adsorb non-dairy carburetion, other floatings and the substances such as immiscible liquids, can also be to oil spilling
The solable matter for occurring to generate after oxidation reaction is effectively adsorbed, and has preferable purification effect to the seawater of oil spill
Fruit.
The present invention provides a kind of preparation methods of active carbon, comprising the following steps:
(1) the first coal and the second coal are mixed, obtains mixed coal, the ash content < 3wt% of first coal is waved
The content of hair point is 27wt%~29wt%, and caking index is 5~9;The ash content < 2wt% of second coal, volatile matter
Content be 30wt%~37wt%, and caking index be 10~20;
(2) mixed coal for obtaining the step (1) carries out the first sorting, obtains granularity as 4~8mm, and bulk density
For the first sorting material of 600~650g/L;
(3) the first sorting material for obtaining the step (2) carbonizes, and obtains carbonized material;
(4) carbonized material for obtaining the step (3) carries out the second sorting, obtains granularity as 3.3~8mm, and bulk density
For the second sorting material of 300~320g/L;
(5) the second sorting material for obtaining the step (4) activates, and obtains activated material;
(6) activated material for obtaining the step (5) carries out third sorting, and obtaining granularity is 2~8mm, and bulk density is
The active carbon of 210~260g/L.
Preferably, the mass ratio of the first coal and the second coal is (4~19) in the step (1): 1.
Preferably, charing includes preliminary charing and deep charring in the step (3).
Preferably, the temperature tentatively carbonized is 150~300 DEG C, and the time tentatively carbonized is 0.5~1h;It is warming up to
The heating rate of the temperature tentatively carbonized is 3~6 DEG C/min.
Preferably, the temperature of the deep charring is 450~550 DEG C, and the time of deep charring is 2~3h;It is warming up to institute
The heating rate for stating the temperature of deep charring is 5~10 DEG C/min.
Preferably, activation includes primary activation and deep activation in the step (5).
Preferably, the primary activation carries out in water vapour atmosphere, and the temperature of primary activation is 600~800 DEG C, tentatively
The time of activation is 3~5h.
Preferably, which is characterized in that the deep activation is mixed with flue gas in atmosphere in water vapour and carried out, deep activation
Temperature be 850~950 DEG C, time of deep activation is 65~70h.
Preferably, the volume ratio of water vapour and flue gas is 1:(2.3~9 in the mixed atmosphere).
The present invention provides the active carbon that the preparation method described in above-mentioned technical proposal is prepared, the heap of the active carbon
Specific gravity is 210~260g/L, and granularity is 2~8mm.
The present invention provides a kind of preparation methods of active carbon, and the first coal and the second coal are mixed, Mixture Density Networks are obtained
Kind, the ash content < 3wt% of first coal, the content of volatile matter is 27wt%~29wt%, and caking index is 5~9;Institute
The ash content < 2wt% of the second coal is stated, the content of volatile matter is 30wt%~37wt%, and caking index is 10~20;Will
The mixed coal arrived carries out the first sorting, and obtaining granularity is 4~8mm, and bulk density is the first sorting material of 600~650g/L;
The first sorting material is carbonized;Obtained carbonized material is subjected to the second sorting, obtains granularity as 3.3~8mm, and heap ratio
The second sorting material that weight is 300~320g/L;The second sorting material is activated;Obtained activated material is subjected to third point
Choosing, obtaining granularity is 2~8mm, and bulk density is the active carbon of 210~260g/L.Hole is carried out to active carbon provided by the invention
Volume and specific surface area detection, the results showed that, the pore volume of the active carbon is 0.75~0.85cm3/ g, specific surface area are
1050m2/g.The active carbon being prepared using method provided by the invention not only can effectively adsorb non-dairy carburetion, other drifts
The substances such as floating and immiscible liquids oil spilling can also occur the soluble intermediate product such as aldehyde, ketone for generating after oxidation reaction
Effectively adsorbed.Oil spilling absorption test is carried out to active carbon provided by the invention, the experimental results showed that, through provided by the invention
After activated carbon adsorption, benzene homologues content is 2.36ppm in sample, lower than benzene homologues content 2.5ppm in the seawater of national regulation
It limits.In addition, dirt-removing power test experiments the result shows that, active carbon provided by the invention reaches 99% to the dirt-removing power of oil spilling
More than.
Detailed description of the invention
Fig. 1 is the desorption curve of 1# active carbon in the embodiment of the present invention 3;
Fig. 2 is the desorption curve of 2# active carbon in the embodiment of the present invention 3;
Fig. 3 is the desorption curve of 3# active carbon in the embodiment of the present invention 3.
Specific embodiment
The present invention provides a kind of preparation methods of active carbon, comprising the following steps:
(1) the first coal and the second coal are mixed, obtains mixed coal, the ash content < 3wt% of first coal is waved
The content of hair point is 27wt%~29wt%, and caking index is 5~9;The ash content < 2wt% of second coal, volatile matter
Content be 30wt%~37wt%, and caking index be 10~20;
(2) mixed coal for obtaining the step (1) carries out the first sorting, obtains granularity as 4~8mm, and bulk density
For the first sorting material of 600~650g/L;
(3) the first sorting material for obtaining the step (2) carbonizes, and obtains carbonized material;
(4) carbonized material for obtaining the step (3) carries out the second sorting, obtains granularity as 3.3~8mm, and bulk density
For the second sorting material of 300~320g/L;
(5) the second sorting material for obtaining the step (4) activates, and obtains activated material;
(6) activated material for obtaining the step (5) carries out third sorting, and obtaining granularity is 2~8mm, and bulk density is
The active carbon of 210~260g/L.
The active carbon being prepared using method provided by the invention not only can effectively adsorb non-dairy carburetion, other floatings
And the substances such as immiscible liquids, the solable matter that can also occur to generate after oxidation reaction to oil spilling are effectively adsorbed.
The present invention mixes the first coal and the second coal, obtains mixed coal, the ash content < of first coal
3wt%, the content of volatile matter is 27wt%~29wt%, and caking index is 5~9;The ash content < of second coal
2wt%, the content of volatile matter is 30wt%~37wt%, and caking index is 10~20.In the present invention, first coal
Mass ratio with the second coal is preferably (4~19): 1, more preferably (6~15): 1, most preferably (9~13): 1.
Before first coal and the second coal are mixed, the first coal and/or the second coal are preferably crushed by the present invention,
Obtain the first seed coal and/or the second seed coal;The granularity of the first seed coal and the second seed coal preferably stands alone as 4~8mm, more preferably
For 5~7mm.The present invention does not have special restriction for the broken mode, using well known to those skilled in the art broken
Technical solution.Present invention preferably employs this gyratory crushers of simon to be crushed first coal.
After completing described be crushed, the present invention is preferably dried obtained the first seed coal and/or the second seed coal.The present invention
It is preferred that the first seed coal and/or the second seed coal are independently dried to moisture content is 4.8wt%~5.2wt%.The present invention couple
There is no special restriction in the mode of the drying, using the technical solution of drying well known to those skilled in the art.This
Invention preferably uses the converter of φ 1.5m, long 15m that the first seed coal and/or the second seed coal is dried.
It obtains after mixing matchmaker's kind, the present invention, which plants the mixing matchmaker, carries out the first sorting, obtains granularity as 4~8mm, and heap
The first sorting material that specific gravity is 600~650g/L.The present invention does not have special restriction for the mode of first sorting, uses
The technical solution of sorting well known to those skilled in the art.In the present invention, first sorting preferably includes the first sieve
Divide and first is classified.The present invention does not have the mode sieved and be classified special restriction, using known to those skilled in the art
Screening and classification technical solution.The mixed material is preferably carried out the first screening by vibrating screen by the present invention, is obtained
To the first screening material that granularity is 4~8mm;Then TQSF stone removing machine by use of principle is utilized, it will the first screening material progress the
One classification, obtaining granularity is 4~8mm, and the first sorting that bulk density is 600~650g/L is expected.
After obtaining the first sorting material, the present invention carbonizes the first sorting material, obtains carbonized material.In the present invention
In, the charing preferably carries out in the absence of air conditions.In the present invention, the charing preferably includes tentatively charing and depth
Degree charing.In the present invention, the temperature tentatively carbonized is preferably 150~300 DEG C, and more preferably 200~250 DEG C;It is described
The time tentatively carbonized is preferably 0.5~1h;The heating rate for being warming up to the temperature tentatively carbonized is preferably 3~6 DEG C/
Min, more preferably 4~5 DEG C/min.
In the present invention, the temperature of the deep charring is preferably 450~550 DEG C, and more preferably 480~520 DEG C;It is described
The time of deep charring is preferably 2~3h;The heating rate for being warming up to the temperature of the deep charring is preferably 5~10 DEG C/
Min, more preferably 6~8 DEG C/min.
After obtaining carbonized material, the carbonized material is carried out the second sorting by the present invention, obtains granularity as 3.3~8mm, and heap ratio
The second sorting material that weight is 300~320g/L.The present invention does not have special restriction for the mode of second sorting, using this
The technical solution sorted known to the technical staff of field.In the present invention, second sorting preferably includes the second screening
With the second classification.The present invention does not have the mode sieved and be classified special restriction, and use is well known to those skilled in the art
The technical solution of screening and classification.The carbonized material is preferably carried out the second screening by vibrating screen by the present invention, obtains grain
The second screening material that degree is 3.3~8mm;Then 5TZX-50 gravity selector is utilized, the second screening material is carried out second point
Grade, obtaining granularity is 3.3~8mm, and the second sorting that bulk density is 300~320g/L is expected.
After obtaining the second sorting material, the present invention activates the second sorting material.In the present invention, the activation is excellent
Choosing includes primary activation and deep activation.In the present invention, the primary activation carries out preferably in water vapour atmosphere.In this hair
In bright, the temperature of the primary activation is preferably 600~800 DEG C, and more preferably 650~750 DEG C;The time of the primary activation
Preferably 3~5h, more preferably 3.5~4.5h.
In the present invention, the deep activation is preferably mixed with flue gas in atmosphere in water vapour and is carried out;The gaseous mixture
The volume ratio of water vapour and flue gas is preferably 1:(2.3~9 in atmosphere), more preferably 1:(4~7).The present invention is for the flue gas
There is no special restriction, using the flue gas well known to those skilled in the art for being activated to active carbon.In this hair
In bright embodiment, the flue gas specifically includes 2% SO2, 15% N2, 2% O2, 13% CO, 28% CO2And carbon
Hydrogen compound and 40% oxynitrides.In the present invention, the temperature of the deep activation is preferably 850~950 DEG C, more excellent
It is selected as 880~920 DEG C;The time of the deep activation is preferably 65~70h, more preferably 67~69h.The present invention is for described
Equipment used by activating does not have special restriction, using activation equipment well known to those skilled in the art.In the present invention
Embodiment in, the activation is specifically carried out using Si Lipu activation furnace.
After obtaining activated material, the activated material is carried out third sorting by the present invention, obtains granularity as 2~8mm, and bulk density
For the active carbon of 210~260g/L.The mode that the present invention sorts the third does not have special restriction, using this field skill
The technical solution sorted known to art personnel.In the present invention, the third sorting preferably includes third screening and third
Classification.The present invention does not have the mode sieved and be classified special restriction, using it is well known to those skilled in the art screening and
The technical solution of classification.The present invention preferably by the activated material by vibrating screen carry out third screening, obtain granularity be 2~
The third of 8mm sieves material;Then 5TZX-50 gravity selector is utilized, the third is sieved into material and carries out third classification, obtains grain
Degree is 2~8mm, and bulk density is the active carbon of 210~260g/L.
The present invention provides the active carbon that the preparation method described in above-mentioned technical proposal is prepared, the heap of the active carbon
Specific gravity is 210~260g/L, and granularity is 2~8mm.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
(1) the first coal of 80kg and the second coal of 20kg are crushed using this gyratory crusher of simon respectively, are obtained
Granularity is the first seed coal and the second seed coal of 4~8mm;Using the converter of φ 1.5m, long 15m to the first seed coal and the second seed
Coal it is dry to moisture content be 5.0wt%, by after drying the first seed coal and the second seed coal mix, obtain mixed coal;Wherein,
The ash content of first coal is 2wt%, and volatilization is divided into 28wt%, and caking index is 8;The ash content of second coal is
1wt%, volatilization is divided into 30wt%, and caking index is 12;
(2) mixed coal for obtaining step (1) carries out the first screening by 2 mesh and 4 mesh vibrating screens, and obtaining granularity is
The first screening material of 4.7~8mm;Then TQSF stone removing machine by use of principle is utilized, the first screening material is subjected to the first classification,
It removes bulk density and is greater than the material of 650g/L and bulk density less than 600, obtaining granularity is 4.7~8mm, and bulk density is 620g/L
First sorting material;
(3) in the absence of air conditions, it is risen with the first sorting material that the heating rate of 5 DEG C/min obtains step (2)
Temperature carries out preliminary charing 1h to 200 DEG C at 200 DEG C, is then warming up to resulting material with the heating rate of 10 DEG C/min
500 DEG C, and deep charring 2.5h is carried out at 500 DEG C, obtain carbonized material;
(4) carbonized material for obtaining step (3) carries out the second screening by 2 mesh and 4 mesh vibrating screens, and obtaining granularity is 4.7
The second screening material of~8mm;Then 5TZX-50 gravity selector is utilized, the second screening material is subjected to the second classification, removal
Bulk density is greater than 320g/L and bulk density is less than the material of 300g/L, and obtaining granularity is 4.7~8mm, and bulk density is 310g/L
Second sorting material;
(5) the second sorting material for obtaining step (4) is placed in using in Si Lipu activation furnace, in water vapour atmosphere in
Primary activation 3h at a temperature of 600 DEG C, then deep activation 67h at a temperature of water vapour mixes with flue gas in atmosphere in 900 DEG C,
Obtain activated material;Wherein, the volume ratio of water vapour and flue gas is 15:85 in the mixed atmosphere, and the flue gas includes 2%
SO2, 15% N2, 2% O2, 13% CO, 28% CO2And hydrocarbon and 40% oxynitrides;
(6) activated material for obtaining step (5) carries out third screening by 2 mesh and 4 mesh vibrating screens, and obtaining granularity is 4.7
The third of~8mm sieves material;Then 5TZX-50 gravity selector is utilized, the third is sieved into material and carries out third classification, removal
Bulk density is greater than 260g/L and bulk density is less than the material of 210g/L, and obtaining granularity is 4.7~8mm, and bulk density is 230g/L
Active carbon.
Embodiment 2
(1) the first coal of 85kg and the second coal of 15kg are crushed using this gyratory crusher of simon respectively, are obtained
Granularity is the first seed coal and the second seed coal of 5~7mm;Using the converter of φ 1.5m, long 15m to the first seed coal and the second seed
Coal it is dry to moisture be 4.8wt%, by after drying the first seed coal and the second seed coal mix, obtain mixed coal;Wherein, described
The ash content of first coal is 2wt%, and volatilization is divided into 29wt%, and caking index is 9;The ash content of second coal is 1wt%,
Volatilization is divided into 37wt%, and caking index is 20;
(2) mixed material for obtaining step (1) carries out the first screening by 2 mesh and 5 mesh vibrating screens, and obtaining granularity is 4
The first screening material of~8mm;Then TQSF stone removing machine by use of principle is utilized, the first screening material is subjected to the first classification, is gone
Except bulk density is greater than the material of 650g/L and bulk density less than 610, obtaining granularity is 4~8mm, and bulk density is the of 630g/L
One sorting material;
(3) in the absence of air conditions, it is risen with the first sorting material that the heating rate of 6 DEG C/min obtains step (2)
Temperature carries out preliminary charing 0.5h to 300 DEG C at 300 DEG C, is then warming up to resulting material with the heating rate of 7 DEG C/min
550 DEG C, and deep charring 3h is carried out at 550 DEG C, obtain carbonized material;
(4) carbonized material for obtaining step (3) carries out the second screening by 2 mesh and 5 mesh vibrating screens, obtain granularity be 4~
The second screening material of 8mm;Then 5TZX-50 gravity selector is utilized, the second screening material is subjected to the second classification, removes heap
Specific gravity is greater than the material that 320g/L and bulk density are less than 270g/L, and obtaining granularity is 4~8mm, and bulk density is the of 300g/L
Two sorting material;
(5) the second sorting material for obtaining step (4) is placed in using in Si Lipu activation furnace, in water vapour atmosphere in
Primary activation 4h at a temperature of 800 DEG C, then deep activation 69h at a temperature of water vapour mixes with flue gas in atmosphere in 850 DEG C,
Obtain activated material;Wherein, the volume ratio of water vapour and flue gas is 20:80 in the mixed atmosphere, and the flue gas includes 2%
SO2, 15% N2, 2% O2, 13% CO, 28% CO2And hydrocarbon and 40% oxynitrides;
(6) activated material for obtaining step (5) carries out third screening by 2 mesh and 5 mesh vibrating screens, obtain granularity be 4~
The third of 8mm sieves material;Then 5TZX-50 gravity selector is utilized, the third is sieved into material and carries out third classification, removes heap
Specific gravity is greater than 260g/L and bulk density is less than the material of 230g/L, and obtaining granularity is 4~8mm, and bulk density is the work of 250g/L
Property charcoal.
Embodiment 3
According to method as defined in GB/T 7702.20-1997, the present invention is implemented using mercury replacement and helium set of permutations are legal
The pore volume of active carbon prepared by example 1 is detected: accurately weigh respectively the preparation of embodiment 1 active carbon 2.2000g,
2.2001g and 2.2000g, number is that A#, B# and C# are tested respectively, the results are shown in Table 1.
Table 1 implements the pore volume data of the active carbon of 1 preparation
Sample number into spectrum |
A# |
B# |
C# |
Real density d1 (g/cm3) |
0.3136 |
0.3128 |
0.3123 |
Grain density d2 (g/cm3) |
0.2501 |
0.2502 |
0.2499 |
Pore volume v (cm3/g) |
0.81 |
0.80 |
0.80 |
As shown in Table 1, the pore volume of institute's sample is respectively 0.81cm3/g、0.80cm3/ g and 0.80cm3/ g, pore volume
Average value be 0.80cm3/g.Above-mentioned experiment is repeated several times, the results showed that, the pore volume of active carbon provided by the invention is
0.75~0.85cm3/g。
It is detected using specific surface area of the dynamic N2 adsorption specific-surface area detection instrument to active carbon prepared by embodiment 1,
Specifically use using helium as carrier gas, nitrogen as adsorbate (i.e. test gas) dual gas supply dynamic method of testing to institute
The specific surface area for stating active carbon is analyzed and processed.The pre-treatment of sample to be tested is the following steps are included: work prepared by embodiment 1
Property charcoal dry 120min in 150 DEG C of baking oven, take out it is cooling after grind powdering and (guarantee that 90% active carbon can pass through
325 meshes), accurately weigh respectively gained active carbon powder 0.0984g, 0.0645g and 0.0645g, respectively number be 1#, 2# and
3#, carries out single-spot testing under 25 DEG C of environment temperature, and the desorption curve of 1#, 2# and 3# sample is shown in Fig. 1~3.Test result table
Bright, the specific surface area of 1#, 2# and 3# sample is respectively as follows: 1050m2/g、1053m2/ g and 1046m2/ g, specific surface area average value are
1050m2/g.Above-mentioned experiment is repeated several times, the results showed that, the specific surface area average value of active carbon provided by the invention is 1050m2/
g。
According to method as defined in ASTM F726-12 standard " adsorbent material absorption property standard method of test " to the present invention
The dirt-removing power of active carbon prepared by embodiment 1 is tested, the results showed that, the dirt-removing power of active carbon provided by the invention reaches
To 99% or more.
Active carbon prepared by the embodiment of the present invention 1 to petroleum carry out adsorption experiment, and with common greasy dirt in the prior art
Absorption felt compares, specifically includes the following steps:
Under ordinary light conditions, in the diameter 19cm of borosilicate glass, depth 10cm, have surface plate or sheet glass
Seawater and petroleum mixed liquor (volume ratio of seawater and petroleum is 85:15) 2L are added in the crystallising dish of lid, 65g embodiment is added
The active carbon of 1 preparation, under conditions of stirring rate is 150rpm after stirring 5min, water oil stain is adsorbed completely;Fishing
After taking the active carbon for being adsorbed with greasy dirt, the water surface is clean, does not have the small oil droplet and other hypostasis of dispersion in water.
Under equal conditions, dirt-removing power survey is carried out using the common greasy dirt absorption felt of four pieces of 6cm × 6cm, thickness 2.5cm
Examination, under conditions of stirring rate is 150rpm after stirring 5min, there are still most of greasy dirts for the water surface;Continue stir 5min after it is quiet
1h is set, water oil stain about 90% is adsorbed, and there are unadsorbed oil slick on the water surface, and with the presence of the small oil droplet that sinks.
Under illumination condition, petroleum can generate the soluble intermediate product such as aldehyde, ketone through chemical reaction, and further logical rapidly
Oxidization-reduction reaction generates benzene class and contains toxicant.Therefore, the present invention contains toxicant by benzene class in detection seawater sample
Content, judge active carbon provided by the invention and common greasy dirt absorption felt to the absorption feelings of the soluble intermediate product such as aldehyde, ketone
Condition.
The seawater sample for using activated carbon adsorption provided by the invention is numbered as a#, using the absorption felt absorption of common greasy dirt
Seawater sample number be b#.Since light application time is longer, the solubility intermediate product such as aldehyde, ketone for generating in seawater sample is got over
It is more, and then cause the benzene class generated more containing toxicant.In order to guarantee a# seawater sample with b# seawater sample since absorption
The time for terminating to receive illumination to absorption is identical, will stand after the absorption of a# seawater sample, until the absorption of b# seawater sample terminates
Afterwards, gained a# seawater sample is subjected to together with b# seawater sample benzene homologues content detection, specifically uses GB11895-89 acetyl
Change worry paper chromatography-fluorescence spectrophotometry to detect gained a# seawater sample and b# seawater sample.The result shows that gained a#
Benzene homologues are 2.36ppm in seawater sample, lower than the restriction of benzene homologues content 2.5ppm in the seawater of national regulation, and gained b#
Benzene homologues are 3.81ppm in seawater sample, hence it is evident that higher than benzene homologues content limit value in the seawater of national regulation.
As can be seen from the above embodiments, the active carbon being prepared using method provided by the invention not only can be effective
Adsorb non-dairy carburetion, other floatings and the substances such as immiscible liquids, oil spilling can also be occurred the aldehyde generated after oxidation reaction,
The solubility intermediate product such as ketone is effectively adsorbed, and after activated carbon adsorption provided by the invention, benzene homologues content is in sample
2.36ppm, lower than the restriction of benzene homologues content 2.5ppm in the seawater of national regulation.In addition, dirt-removing power test experiments result
Show that active carbon provided by the invention reaches 99% or more to the dirt-removing power of oil spilling.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.