A kind of activated carbon and preparation method thereof
Technical field
The present invention relates to Environmental Engineering Material technical field, and in particular to a kind of activated carbon and preparation method thereof.
Background technology
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 oil can be in the biological conversion in the body such as mammal or birds
For the stronger material of toxicity, or even cause DNA mutation, the fecundity of organism is declined, severe patient can suffer from cancer.More have
Expert represents that greasy dirt can be trapped into deposit, endangers many decades even longer time.In addition, after marine oil overflow accident occurs,
Oil 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, and significant damage is produced to organism.
At present, marine oil overflow is handled more based on the methods of greasy dirt absorption felt absorption, but asphalt felt can only be to non-emulsified
The materials such as oil, other floatings and immiscible liquids are adsorbed, and lack energy of adsorption for the soluble intermediate product such as aldehyde, ketone
Power, effect is bad in terms of seawater cleaning.
The content of the invention
It is an object of the invention to provide a kind of activated carbon and preparation method thereof, is prepared into using method provided by the invention
To activated carbon not only can effectively adsorb non-emulsified oil, other floatings and the material such as immiscible liquids, can also be to oil spilling
The solable matter for occurring to generate after oxidation reaction is effectively adsorbed, and there is preferably purification to imitate the seawater of oil spill
Fruit.
The invention provides a kind of preparation method of activated carbon, comprise the following steps:
(1) the first coal and the second coal are mixed, obtains mixed coal, the ash content < 3wt% of first coal, wave
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 is 10~20;
(2) mixed coal obtained the step (1) carries out the first sorting, and it is 4~8mm to obtain granularity, and bulk density
For 600~650g/L the first sorting material;
(3) the first sorting material for obtaining the step (2) is carbonized, and obtains carbonized material;
(4) carbonized material obtained the step (3) carries out the second sorting, and it is 3.3~8mm to obtain granularity, and bulk density
For 300~320g/L the second sorting material;
(5) the second sorting material for obtaining the step (4) is activated, and obtains activated material;
(6) activated material for obtaining the step (5) carries out the 3rd sorting, and it is 2~8mm to obtain granularity, and bulk density is
210~260g/L activated carbon.
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 is carried 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, it is characterised in that the deep activation is carried out in the mixed atmosphere of water vapour and flue gas, deep activation
Temperature be 850~950 DEG C, the time of deep activation is 65~70h.
Preferably, the volume ratio of water vapour and flue gas is 1 in the mixed atmosphere:(2.3~9).
The invention provides the activated carbon that the preparation method described in above-mentioned technical proposal is prepared, the heap of the activated carbon
Proportion is 210~260g/L, and granularity is 2~8mm.
The invention provides a kind of preparation method of activated carbon, and the first coal and the second coal are mixed, obtain Mixture Density Networks
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 are 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 it is 4~8mm to obtain granularity, and the first sorting that bulk density is 600~650g/L is expected;
Described first sorting material is carbonized;Obtained carbonized material is subjected to the second sorting, it is 3.3~8mm to obtain granularity, and heap ratio
The second sorting material that weight is 300~320g/L;Described second sorting material is activated;Obtained activated material is carried out the 3rd point
Choosing, it is 2~8mm to obtain granularity, and bulk density is 210~260g/L activated carbon.Hole is carried out to activated carbon provided by the invention
Volume and specific surface area detection, the results showed that, the pore volume of the activated carbon is 0.75~0.85cm3/ g, specific surface area are
1050m2/g.The activated carbon being prepared using method provided by the invention not only can effectively adsorb non-emulsified oil, other drifts
The materials such as floating and immiscible liquids, the soluble intermediate products such as the aldehyde, the ketone that are generated after oxidation reaction oil spilling can also occur
Effectively adsorbed.Oil spilling absorption test is carried out to activated carbon provided by the invention, test result indicates that, through provided by the invention
After charcoal absorption, benzene homologues content is 2.36ppm in sample, less than benzene homologues content 2.5ppm in the seawater of national regulation
Limit.In addition, dirt-removing power test experiments result shows that activated carbon provided by the invention reaches 99% to the dirt-removing power of oil spilling
More than.
Brief description of the drawings
Fig. 1 is the desorption curve of 1# activated carbons in the embodiment of the present invention 3;
Fig. 2 is the desorption curve of 2# activated carbons in the embodiment of the present invention 3;
Fig. 3 is the desorption curve of 3# activated carbons in the embodiment of the present invention 3.
Embodiment
The invention provides a kind of preparation method of activated carbon, comprise the following steps:
(1) the first coal and the second coal are mixed, obtains mixed coal, the ash content < 3wt% of first coal, wave
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 is 10~20;
(2) mixed coal obtained the step (1) carries out the first sorting, and it is 4~8mm to obtain granularity, and bulk density
For 600~650g/L the first sorting material;
(3) the first sorting material for obtaining the step (2) is carbonized, and obtains carbonized material;
(4) carbonized material obtained the step (3) carries out the second sorting, and it is 3.3~8mm to obtain granularity, and bulk density
For 300~320g/L the second sorting material;
(5) the second sorting material for obtaining the step (4) is activated, and obtains activated material;
(6) activated material for obtaining the step (5) carries out the 3rd sorting, and it is 2~8mm to obtain granularity, and bulk density is
210~260g/L activated carbon.
The activated carbon being prepared using method provided by the invention not only can effectively adsorb non-emulsified oil, other floatings
And the material 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, be most preferably (9~13):1.
Before first coal and the second coal are mixed, the present invention is preferably crushed the first coal and/or the second coal,
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 scheme.First coal is crushed present invention preferably employs this gyratory crusher of simon.
After completing described crush, the first seed coal and/or the second seed coal that preferred pair of the present invention obtains are dried.The present invention
It is preferred that it is 4.8wt%~5.2wt% that the first seed coal and/or the second seed coal, which are independently dried to moisture,.The present invention is right
There is no special restriction in the mode of the drying, using the technical scheme of drying well known to those skilled in the art.This
Preferably the first seed coal and/or the second seed coal are dried using φ 1.5m, long 15m converter for invention.
Obtain after mixing matchmaker's kind, the mixing matchmaker is planted and carries out the first sorting by the present invention, and it is 4~8mm to obtain granularity, and heap
The first sorting material that proportion is 600~650g/L.The present invention does not have special restriction for the mode of the described first sorting, uses
The technical scheme 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 special restriction for the mode sieved and be classified, using known to those skilled in the art
Screening and classification technical scheme.The mixed material is preferably carried out the first screening by the present invention by vibratory sieve, is obtained
To the first screening material that granularity is 4~8mm;Then TQSF stone removing machine by use of principle is utilized, the described first screening material is carried out the
One classification, it is 4~8mm to obtain granularity, and the first sorting that bulk density is 600~650g/L is expected.
After obtaining the first sorting material, the present invention is carbonized the described first sorting material, obtains carbonized material.In the present invention
In, the charing is preferably carried out under conditions of air is completely cut off.In the present invention, the charing preferably includes preliminary charing and depth
Degree charing.In the present invention, the temperature tentatively carbonized is preferably 150~300 DEG C, 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, 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, and it is 3.3~8mm to obtain granularity, 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 the described second sorting, using this
The technical scheme of sorting known to art personnel.In the present invention, second sorting preferably includes the second screening
With the second classification.The present invention does not have a special restriction for the mode sieving and be classified, and use is well known to those skilled in the art
Screening and the technical scheme of classification.The carbonized material is preferably carried out the second screening by the present invention by vibratory sieve, obtains grain
Spend the second screening material for 3.3~8mm;Then 5TZX-50 gravity selectors are utilized, the described second screening material is carried out second point
Level, it is 3.3~8mm to obtain granularity, and the second sorting that bulk density is 300~320g/L is expected.
After obtaining the second sorting material, the present invention is activated the described 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 is carried out preferably in water vapour atmosphere.In this hair
In bright, the temperature of the primary activation is preferably 600~800 DEG C, 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 carried out in the mixed atmosphere of water vapour and flue gas;The gaseous mixture
The volume ratio of water vapour and flue gas is preferably 1 in atmosphere:(2.3~9), 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 activated 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
Elect 880~920 DEG C as;The time of the deep activation is preferably 65~70h, more preferably 67~69h.The present invention is for described
Equipment does not have special restriction used by activation, 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 furnaces.
After obtaining activated material, the activated material is carried out the 3rd sorting by the present invention, and it is 2~8mm to obtain granularity, and bulk density
For 210~260g/L activated carbon.The present invention does not have special restriction for the mode of the described 3rd sorting, using this area skill
The technical scheme of sorting known to art personnel.In the present invention, the 3rd sorting preferably includes the 3rd screening and the 3rd
Classification.The present invention does not have special restriction for the mode sieving and be classified, using screening well known to those skilled in the art and
The technical scheme of classification.The activated material is preferably carried out the 3rd screening by the present invention by vibratory sieve, obtain granularity for 2~
8mm the 3rd screening material;Then 5TZX-50 gravity selectors are utilized, the described 3rd screening material is subjected to the 3rd classification, obtains grain
Spend for 2~8mm, and bulk density is 210~260g/L activated carbon.
The invention provides the activated carbon that the preparation method described in above-mentioned technical proposal is prepared, the heap of the activated carbon
Proportion is 210~260g/L, and granularity is 2~8mm.
Below in conjunction with the embodiment in the present invention, the technical scheme in the present invention is clearly and completely described.It is aobvious
So, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Based on the reality in the present invention
Example is applied, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, is all belonged to
In the scope of protection of the invention.
Embodiment 1
(1) coals of 80kg first and the coals of 20kg second are crushed respectively using this gyratory crusher of simon, obtained
Granularity is 4~8mm the first seed coal and the second seed coal;Using φ 1.5m, long 15m converter to the first seed coal and the second seed
Coal drying to moisture is 5.0wt%, and dried first seed coal and the second seed coal are mixed, 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 that step (1) obtains is subjected to the first screening by 2 mesh and 4 mesh vibratory sieves, obtaining granularity is
4.7~8mm the first screening material;Then TQSF stone removing machine by use of principle is utilized, the described first screening material is subjected to the first classification,
Remove bulk density and be more than the material of 650g/L and bulk density less than 600, it is 4.7~8mm to obtain granularity, and bulk density is 620g/L
First sorting material;
(3) under conditions of air is completely cut off, risen with the first sorting material that 5 DEG C/min heating rate 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 10 DEG C/min heating rate
500 DEG C, and deep charring 2.5h is carried out at 500 DEG C, obtain carbonized material;
(4) carbonized material that step (3) obtains is subjected to the second screening by 2 mesh and 4 mesh vibratory sieves, obtains granularity as 4.7
~8mm the second screening material;Then 5TZX-50 gravity selectors are utilized, the described second screening material is subjected to the second classification, removed
Bulk density is more than 320g/L and bulk density is less than 300g/L material, and it is 4.7~8mm to obtain granularity, 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 furnaces, in water vapour atmosphere in
Primary activation 3h at a temperature of 600 DEG C, then in the mixed atmosphere of water vapour and flue gas at a temperature of 900 DEG C deep activation 67h,
Obtain activated material;Wherein, the volume ratio of water vapour and flue gas is 15 in the mixed atmosphere:85, the flue gas includes 2%
SO2, 15% N2, 2% O2, 13% CO, 28% CO2And hydrocarbon and 40% oxynitrides;
(6) activated material that step (5) obtains is subjected to the 3rd screening by 2 mesh and 4 mesh vibratory sieves, obtains granularity as 4.7
~8mm the 3rd screening material;Then 5TZX-50 gravity selectors are utilized, the described 3rd screening material is subjected to the 3rd classification, removed
Bulk density is more than 260g/L and bulk density is less than 210g/L material, and it is 4.7~8mm to obtain granularity, and bulk density is 230g/L
Activated carbon.
Embodiment 2
(1) coals of 85kg first and the coals of 15kg second are crushed respectively using this gyratory crusher of simon, obtained
Granularity is 5~7mm the first seed coal and the second seed coal;Using φ 1.5m, long 15m converter to the first seed coal and the second seed
Coal drying to moisture is 4.8wt%, and dried first seed coal and the second seed coal are mixed, obtain mixed coal;Wherein, it is 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 that step (1) obtains is subjected to the first screening by 2 mesh and 5 mesh vibratory sieves, obtains granularity as 4
~8mm the first screening material;Then TQSF stone removing machine by use of principle is utilized, the described first screening material is subjected to the first classification, gone
Except bulk density is more than the material that 650g/L and bulk density be less than 610, it be 4~8mm to obtain granularity, and bulk density is the of 630g/L
One sorting material;
(3) under conditions of air is completely cut off, risen with the first sorting material that 6 DEG C/min heating rate 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 7 DEG C/min heating rate
550 DEG C, and deep charring 3h is carried out at 550 DEG C, obtain carbonized material;
(4) carbonized material that step (3) obtains is subjected to the second screening by 2 mesh and 5 mesh vibratory sieves, obtain granularity for 4~
8mm the second screening material;Then 5TZX-50 gravity selectors are utilized, the described second screening material is subjected to the second classification, removes heap
Proportion is more than the material that 320g/L and bulk density are less than 270g/L, and it be 4~8mm to obtain granularity, 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 furnaces, in water vapour atmosphere in
Primary activation 4h at a temperature of 800 DEG C, then in the mixed atmosphere of water vapour and flue gas at a temperature of 850 DEG C deep activation 69h,
Obtain activated material;Wherein, the volume ratio of water vapour and flue gas is 20 in the mixed atmosphere:80, the flue gas includes 2%
SO2, 15% N2, 2% O2, 13% CO, 28% CO2And hydrocarbon and 40% oxynitrides;
(6) activated material that step (5) obtains is subjected to the 3rd screening by 2 mesh and 5 mesh vibratory sieves, obtain granularity for 4~
8mm the 3rd screening material;Then 5TZX-50 gravity selectors are utilized, the described 3rd screening material is subjected to the 3rd classification, removes heap
Proportion is more than 260g/L and bulk density is less than 230g/L material, and it is 4~8mm to obtain granularity, and bulk density is 250g/L work
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 activated carbon prepared by example 1 is detected:Accurately weigh respectively embodiment 1 preparation activated carbon 2.2000g,
2.2001g and 2.2000g, numbering is that A#, B# and C# are tested respectively, the results are shown in Table 1.
Table 1 implements the pore volume volume data of 1 activated carbon prepared
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 test sample product 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 activated carbon provided by the invention is
0.75~0.85cm3/g。
The specific surface area of the activated carbon prepared using dynamic N2 adsorption specific-surface area detection instrument to embodiment 1 is detected,
Specifically use using helium as carrier gas, nitrogen as adsorbate (testing gas) dual gas supply dynamic method of testing to institute
The specific surface area for stating activated carbon is analyzed and processed.The pre-treatment of testing sample comprises the following steps:Work prepared by embodiment 1
Property charcoal in 150 DEG C of baking oven dry 120min, take out cooling after grind powdering (ensure 90% activated carbon can pass through
325 mesh sieves), accurately weigh respectively gained active carbon powder 0.0984g, 0.0645g and 0.0645g, respectively numbering 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: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 activated carbon provided by the invention is 1050m2/
g。
According to ASTM F726-12 standards《Sorbing material absorption property standard method of test》Defined method is to the present invention
The dirt-removing power of activated carbon prepared by embodiment 1 is tested, the results showed that, the dirt-removing power of activated carbon provided by the invention reaches
To more than 99%.
By activated carbon prepared by the embodiment of the present invention 1 to oil carry out adsorption experiment, and with common greasy dirt in the prior art
Absorption felt is contrasted, and specifically includes following steps:
Under ordinary light conditions, in the diameter 19cm of borosilicate glass, depth 10cm, with surface plate or sheet glass
(volume ratio of seawater and oil is 85 for addition seawater and oil mixed liquor in the crystallising dish of lid:15) 2L, 65g embodiments are added
1 activated carbon prepared, after 5min is stirred under conditions of stir speed (S.S.) is 150rpm, water oil stain is adsorbed completely;Drag for
After taking the activated carbon for being adsorbed with greasy dirt, the water surface is clean, the small oil droplet and other hypostasis not disperseed in water.
Under equal conditions, dirt-removing power survey is carried out using four pieces of 6cm × 6cm, thickness 2.5cm common greasy dirt absorption felt
Examination, after 5min is stirred under conditions of stir speed (S.S.) is 150rpm, the water surface still suffers from most of greasy dirt;Continue stir 5min after it is quiet
1h is put, water oil stain about 90% is adsorbed, and oil slick not to be adsorbed is left on the water surface, and with the presence of the small oil droplet that sinks.
Under illumination condition, oil can generate the soluble intermediate product such as aldehyde, ketone through chemical reaction, and further rapid logical
Oxidization-reduction reaction generation benzene class contains toxicant.Therefore, the present invention contains toxicant by detecting benzene class in seawater sample
Content, judge activated 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 charcoal absorption provided by the invention is numbered as a#, using the absorption felt absorption of common greasy dirt
Seawater sample numbering be b#.Because light application time is longer, the soluble intermediate product such as the aldehyde that is generated in seawater sample, ketone is got over
It is more, and then cause the benzene class of generation more containing toxicant.In order to ensure a# seawater samples with b# seawater samples since absorption
To absorption terminate receive illumination time it is identical, by a# seawater samples absorption terminate after stand, to b# seawater samples absorption terminate
Afterwards, gained a# seawater samples and b# seawater samples are together subjected to benzene homologues content detection, specifically use GB11895-89 acetyl
Change worry paper chromatography-fluorescence spectrophotometry to detect gained a# seawater samples and b# seawater samples.As a result show, gained a#
Benzene homologues are 2.36ppm in seawater sample, less 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 activated carbon being prepared using method provided by the invention not only can be effective
Non-emulsified oil, other floatings and the material such as immiscible liquids are adsorbed, the aldehyde that oil spilling can also occur generate after oxidation reaction,
The soluble intermediate product such as ketone is effectively adsorbed, and after charcoal absorption provided by the invention, benzene homologues content is in sample
2.36ppm, less than the restriction of benzene homologues content 2.5ppm in the seawater of national regulation.In addition, dirt-removing power test experiments result
Show, activated carbon provided by the invention reaches more than 99% to the dirt-removing power of oil spilling.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.