Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of low-ash briquetted coal-based activated carbon.
The purpose of the invention is realized by adopting the following technical scheme:
a preparation method of low-ash briquetted coal-based activated carbon comprises the following steps:
s1, pretreatment of coal material
Drying raw material coal of non-caking coal and long flame coal by hot air, and simultaneously carrying out micro-oxidation, wherein the temperature of the hot air is 160 ℃ plus 120 ℃, the heat treatment time is 30-50min, and after cooling, the raw material coal is respectively ground, wherein the volatile contents of the non-caking coal and the long flame coal are 25-35 wt.%, the caking index of the non-caking coal is 0.8-2.6, the grinding granularity is 400 meshes of 300 plus, and the grinding granularity of the long flame coal is 600 meshes of 400 plus 400;
s2, coal blending and forming
The non-caking coal and the long flame coal are mixed according to the weight part ratio of 10: (1-3) mixing, mechanically stirring or air stirring to be uniform; adding a modified phenolic resin binder accounting for 1-3% of the weight of the mixed coal material, and stirring uniformly again to obtain a mixture A; adding the mixture A into a forming device, pressing the mixture A out of the forming device, feeding the mixture A into a sieving machine, and re-forming the dust sieved out of the forming material and the ground raw material;
s3 carbonization
Heating the molded material to 600-700 ℃ under the protection of nitrogen or argon, carrying out thermal pyrolysis for 3h at the heating rate of 2 ℃/min to obtain a calcined product A, adding the calcined product A into a hydrochloric acid solution, soaking to remove redundant impurities, washing with deionized water to obtain a carbonized product, wherein the volatile content of the carbonized product is 3-8%, and the strength of the carbonized product is more than 94%;
s4, activation treatment
Sending the carbonized product into drying equipment to be dried until the moisture content is less than 4%, screening the dried carbonized product, and enabling the carbonized product with the particle size of 2-8mm to enter an activation section; the activation section is activated by adopting a gas activation method, the activation temperature is 900 ℃, the activation furnace pressure is 100Pa, and the activation time is 30-72h, so that an activated product is obtained, and the loss on ignition of the activated product is 45-55%;
s5, post-processing
And (2) screening the activated product by adopting two-stage crushing to obtain a finished product, dissolving sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium hexametaphosphate in water to prepare a treatment solution, adding the finished product into the treatment solution, wherein the liquid-solid ratio is 60-100ml/g, stirring and reacting for 1-5h under the condition of 70 ℃ water bath, filtering, rinsing with clear water, and drying for multiple times by using drying equipment to obtain the low-ash briquette coal-based activated carbon.
Preferably, the forming pressure of the forming equipment is 24-25MPa, and the compression ratio is 2-2.5.
Preferably, the concentrations of the sodium hydroxide, the potassium hydroxide, the sodium bicarbonate and the sodium hexametaphosphate in the treatment solution are 2mol/L, 0.5mol/L and 0.4mol/L, respectively.
Preferably, the ash content of the low-ash pressed coal activated carbon is less than 3%, the iodine adsorption value is greater than 950mg/g, the methylene blue adsorption value is greater than 200mg/g, and the strength is greater than 90%.
Preferably, the modified phenolic resin consists of water-soluble phenolic resin, modified filler and diluent, wherein the weight ratio of the water-soluble phenolic resin to the modified filler to the diluent is (10-20): (1-3): 100, the modified filler is a composition of modified bryophyte fibers and carboxymethyl chitosan hydrogel.
Further preferably, the preparation method of the modified filler comprises the following steps:
s1 modified bryophyte fiber
Washing moss with clear water for several times to remove soil impurities on the surface, drying the cleaned moss until the moisture content is less than 10%, weighing 1 part by weight of the dried moss, adding 100 parts by weight of deionized water, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite, heating in a 75 ℃ water bath for 1h under stirring, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite again, continuing to stir and heat for 1h, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite again, stirring, filtering out precipitates, leaching with an acetic acid solution, soaking the precipitates in a mixed water solution of hydrogen peroxide and acetic acid according to a liquid-material ratio of 50ml/g for 20-30min, transferring into a reaction kettle with a polytetrafluoroethylene substrate, heating in a 140 ℃ water bath for 12-24h, cooling to room temperature, centrifuging the suspension, and freeze-drying at-60 ℃, mechanically pulverizing, micronizing, and sieving to obtain micropowder with particle size of 40-70 μm to obtain modified bryophyte fiber;
s2 preparation of hydrogel
Weighing 1 part by weight of polyvinyl alcohol, dissolving the polyvinyl alcohol in deionized water, wherein the mass part of the polyvinyl alcohol is 2-5%, adjusting the pH value of the solution to 5 with glacial acetic acid, adding 12-15 parts of carboxymethyl chitosan, mixing and stirring, introducing nitrogen into the mixed solution to obtain a uniform and transparent precursor solution, adding deionized water with the same volume as the precursor solution, stirring to obtain a viscous solution, standing for 24 hours, soaking for 72-120 hours with the deionized water, changing water once every 12 hours, performing forced air drying at 80 ℃ for 12 hours after soaking is completed, performing vacuum drying at 60 ℃ for 24 hours, mechanically crushing for micronization, and screening to obtain micro powder with the particle size of 40-70 mu m, thereby preparing the carboxymethyl chitosan hydrogel;
s3, proportioning
And mixing the modified bryophyte fibers with the carboxymethyl chitosan hydrogel according to a ratio to prepare the modified filler.
Preferably, in the mixed aqueous solution of hydrogen peroxide and acetic acid, the mass fractions of hydrogen peroxide and acetic acid are 10 wt.% and 10 wt.%, respectively.
Preferably, the mass mixing ratio of the modified bryophyte fibers to the hydrogel micropowder (3-6): 1.
the invention has the beneficial effects that:
(1) according to the invention, through grinding of different coal raw materials, weakly caking coal with limited reserves is avoided, the particle size and the proportion of the pulverized coal are adjusted, so that pulverized coal particles can be fully dispersed and filled, and the molding compactness of the briquetted activated carbon is improved, thereby improving the strength, reducing the using amount of the binder and reducing the adverse effect of the binder on pores of the activated carbon.
(2) Part of metal oxide components can be dissolved through hydrochloric acid treatment, acid-insoluble metal oxide and silicon oxide can be further removed through post-treatment of an alkali solution, and meanwhile, on the basis of good metal complexing performance of sodium hexametaphosphate, the metal content in the coal-based activated carbon can be further reduced by adding the sodium hexametaphosphate into the treatment solution, so that the ash content is reduced.
(3) The modified phenolic resin is used as the binder, the carbon content is high, the binding property is good, the coking rate is high in the pyrolysis process, a part of the activated carbon is formed after pyrolysis, the adsorption capacity is good, the influence on a pore structure is small, and the forming mechanical strength is high.
Detailed Description
The invention is further described with reference to the following examples.
The embodiment of the invention relates to a preparation method of low-ash briquetted coal activated carbon, which comprises the following steps:
s1, pretreatment of coal material
Drying raw material coal of non-caking coal and long flame coal by hot air, and simultaneously carrying out micro-oxidation, wherein the temperature of the hot air is 160 ℃ plus 120 ℃, the heat treatment time is 30-50min, and after cooling, the raw material coal is respectively ground, wherein the volatile contents of the non-caking coal and the long flame coal are 25-35 wt.%, the caking index of the non-caking coal is 0.8-2.6, the grinding granularity is 400 meshes of 300 plus, and the grinding granularity of the long flame coal is 600 meshes of 400 plus 400;
s2, coal blending and forming
The non-caking coal and the long flame coal are mixed according to the weight part ratio of 10: (1-3) mixing, mechanically stirring or air stirring to be uniform; adding a modified phenolic resin binder accounting for 1-3% of the weight of the mixed coal material, and stirring uniformly again to obtain a mixture A; adding the mixture A into a forming device, pressing the mixture A out of the forming device, feeding the mixture A into a sieving machine, and re-forming the dust sieved out of the forming material and the ground raw material;
s3 carbonization
Heating the molded material to 600-700 ℃ under the protection of nitrogen or argon, carrying out thermal pyrolysis for 3h at the heating rate of 2 ℃/min to obtain a calcined product A, adding the calcined product A into a hydrochloric acid solution, soaking to remove redundant impurities, washing with deionized water to obtain a carbonized product, wherein the volatile content of the carbonized product is 3-8%, and the strength of the carbonized product is more than 94%;
s4, activation treatment
Sending the carbonized product into drying equipment to be dried until the moisture content is less than 4%, screening the dried carbonized product, and enabling the carbonized product with the particle size of 2-8mm to enter an activation section; the activation section is activated by adopting a gas activation method, the activation temperature is 900 ℃, the activation furnace pressure is 100Pa, and the activation time is 30-72h, so that an activated product is obtained, and the loss on ignition of the activated product is 45-55%;
s5, post-processing
And (2) screening the activated product by adopting two-stage crushing to obtain a finished product, dissolving sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium hexametaphosphate in water to prepare a treatment solution, adding the finished product into the treatment solution, wherein the liquid-solid ratio is 60-100ml/g, stirring and reacting for 1-5h under the condition of 70 ℃ water bath, filtering, rinsing with clear water, and drying for multiple times by using drying equipment to obtain the low-ash briquette coal-based activated carbon.
According to the invention, through grinding of different coal raw materials, weakly caking coal with limited reserves is avoided, the particle size and the proportion of the pulverized coal are adjusted, so that pulverized coal particles can be fully dispersed and filled, and the molding compactness of the briquetted activated carbon is improved, thus the strength is improved, the using amount of a binder can be reduced, and the adverse effect of the binder on the pores of the activated carbon is reduced;
the ash content of the non-sticky coal is high, the ash production requirement of the briquetted activated carbon is difficult to meet, the main component of the ash of the non-sticky coal is metal or silicon oxide, part of metal oxide components can be dissolved through hydrochloric acid treatment, acid-insoluble metal oxide and silicon oxide can be further removed through post-treatment of alkali solution, and meanwhile, the metal content in the coal-based activated carbon can be further reduced by adding the non-sticky coal into the treatment solution based on good metal complexing performance of sodium hexametaphosphate, so that the ash content is further reduced;
the binder used in the prior art is generally an asphalt binder, mainly coal tar pitch, is suitable for producing binders of coal-based columnar activated carbon and honeycomb activated carbon, but can be melted and volatilized after being heated, so that the strength of a final product is not high, and in the production of the activated carbon, residues of the asphalt can block pores of the activated carbon and are not beneficial to improving the quality of the activated carbon; the modified phenolic resin is used as the binder, the carbon content is high, the binding property is good, the coking rate is high in the pyrolysis process, a part of the active carbon is formed after pyrolysis, the adsorption capacity is good, the influence on a pore structure is small, and the forming mechanical strength is high;
preferably, the forming pressure of the forming equipment is 24-25MPa, and the compression ratio is 2-2.5.
Preferably, the concentrations of the sodium hydroxide, the potassium hydroxide, the sodium bicarbonate and the sodium hexametaphosphate in the treatment solution are 2mol/L, 0.5mol/L and 0.4mol/L, respectively.
Preferably, the ash content of the low-ash pressed coal activated carbon is less than 3%, the iodine adsorption value is greater than 950mg/g, the methylene blue adsorption value is greater than 200mg/g, and the strength is greater than 90%.
Preferably, the modified phenolic resin consists of water-soluble phenolic resin, modified filler and diluent, wherein the weight ratio of the water-soluble phenolic resin to the modified filler to the diluent is (10-20): (1-3): 100, the modified filler is a composition of modified bryophyte fibers and carboxymethyl chitosan hydrogel.
Further preferably, the preparation method of the modified filler comprises the following steps:
s1 modified bryophyte fiber
Washing moss with clear water for several times to remove soil impurities on the surface, drying the cleaned moss until the moisture content is less than 10%, weighing 1 part by weight of the dried moss, adding 100 parts by weight of deionized water, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite, heating in a 75 ℃ water bath for 1h under stirring, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite again, continuing to stir and heat for 1h, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite again, stirring, filtering out precipitates, leaching with an acetic acid solution, soaking the precipitates in a mixed water solution of hydrogen peroxide and acetic acid according to a liquid-material ratio of 50ml/g for 20-30min, transferring into a reaction kettle with a polytetrafluoroethylene substrate, heating in a 140 ℃ water bath for 12-24h, cooling to room temperature, centrifuging the suspension, and freeze-drying at-60 ℃, mechanically pulverizing, micronizing, and sieving to obtain micropowder with particle size of 40-70 μm to obtain modified bryophyte fiber;
s2 preparation of hydrogel
Weighing 1 part by weight of polyvinyl alcohol, dissolving the polyvinyl alcohol in deionized water, wherein the mass part of the polyvinyl alcohol is 2-5%, adjusting the pH value of the solution to 5 with glacial acetic acid, adding 12-15 parts of carboxymethyl chitosan, mixing and stirring, introducing nitrogen into the mixed solution to obtain a uniform and transparent precursor solution, adding deionized water with the same volume as the precursor solution, stirring to obtain a viscous solution, standing for 24 hours, soaking for 72-120 hours with the deionized water, changing water once every 12 hours, performing forced air drying at 80 ℃ for 12 hours after soaking is completed, performing vacuum drying at 60 ℃ for 24 hours, mechanically crushing for micronization, and screening to obtain micro powder with the particle size of 40-70 mu m, thereby preparing the carboxymethyl chitosan hydrogel;
s3, proportioning
And mixing the modified bryophyte fibers with the carboxymethyl chitosan hydrogel according to a ratio to prepare the modified filler.
The bonding strength of the resin can be further improved by adding the modified filler, on one hand, the modified moss plant fibers and the carboxymethyl chitosan hydrogel can provide partial bonding force, the water holding capacity of the modified moss plant fibers and the carboxymethyl chitosan hydrogel is strong, the permeation of the binder in the microporous structure of the activated carbon can be reduced, and the influence of the permeation of the binder on the quality of the activated carbon is reduced.
Preferably, in the mixed aqueous solution of hydrogen peroxide and acetic acid, the mass fractions of hydrogen peroxide and acetic acid are 10 wt.% and 10 wt.%, respectively.
Preferably, the mass mixing ratio of the modified bryophyte fibers to the hydrogel micropowder (3-6): 1.
example 1
A preparation method of low-ash briquetted coal-based activated carbon comprises the following steps:
s1, pretreatment of coal material
Drying raw material coal of non-caking coal and long flame coal by hot air, carrying out micro-oxidation at the same time, wherein the temperature of the hot air is 150 ℃, the heat treatment time is 30-50min, and grinding is respectively carried out after cooling, wherein the volatile content of the non-caking coal and the long flame coal is 25-35 wt.%, the caking index of the non-caking coal is 0.8-2.6, the grinding granularity is 300-400 meshes, and the grinding granularity of the long flame coal is 400-600 meshes;
s2, coal blending and forming
And (3) mixing the non-caking coal and the long flame coal according to the weight part ratio of 5: 1, mixing, mechanically stirring or stirring with air until the mixture is uniform; adding a modified phenolic resin binder accounting for 2% of the weight of the mixed coal material, and stirring uniformly again to obtain a mixture A; adding the mixture A into a forming device, wherein the forming pressure of the forming device is 24MPa, the compression ratio is 2.2, pressing the formed material out, then feeding the formed material into a sieving machine, and re-forming the dust sieved out of the formed material and the ground raw material;
s3 carbonization
Heating the molded material to 600-700 ℃ under the protection of nitrogen or argon, carrying out thermal pyrolysis for 3h at the heating rate of 2 ℃/min to obtain a calcined product A, adding the calcined product A into a hydrochloric acid solution, soaking to remove redundant impurities, washing with deionized water to obtain a carbonized product, wherein the volatile content of the carbonized product is 3-8%, and the strength of the carbonized product is more than 94%;
s4, activation treatment
Sending the carbonized product into drying equipment to be dried until the moisture content is less than 4%, screening the dried carbonized product, and enabling the carbonized product with the particle size of 2-8mm to enter an activation section; the activation section is activated by adopting a gas activation method, the activation temperature is 900 ℃, the activation furnace pressure is 100Pa, and the activation time is 60 hours, so that an activated product is obtained, and the loss on ignition of the activated product is 45-55%;
s5, post-processing
Screening an activated product by adopting two-stage crushing to obtain a finished product, dissolving sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium hexametaphosphate in water to prepare a treatment solution, wherein the concentrations of the sodium hydroxide, the potassium hydroxide, the sodium bicarbonate and the sodium hexametaphosphate in the treatment solution are respectively 2mol/L, 0.5mol/L and 0.4mol/L, adding the finished product into the treatment solution, the liquid-solid ratio is 80ml/g, stirring and reacting for 1-5h under the condition of 70 ℃ water bath, filtering out, rinsing with clear water, and drying by using drying equipment for multiple times to obtain the low-ash briquette coal-based activated carbon;
the modified phenolic resin consists of water-soluble phenolic resin, modified filler and diluent, wherein the weight ratio of the water-soluble phenolic resin to the modified filler to the diluent is 12: 3: 100, the preparation method of the modified filler comprises the following steps:
s1 modified bryophyte fiber
Washing moss for a plurality of times by using clean water, removing soil impurities on the surface, drying the cleaned moss until the moisture content is less than 10%, weighing 1 part by weight of the dried moss, adding 100 parts by weight of deionized water, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite, heating in a 75 ℃ water bath for 1h under the stirring condition, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite again, continuing to stir and heat for 1h, adding 1 part by weight of glacial acetic acid and 1 part by weight of sodium sulfite again, stirring, filtering out precipitates, leaching by using an acetic acid solution, soaking the precipitates into a mixed aqueous solution of hydrogen peroxide and acetic acid according to the liquid-material ratio of 50ml/g, wherein the mass fractions of the hydrogen peroxide and the acetic acid in the mixed aqueous solution of the hydrogen peroxide and the acetic acid are respectively 10 wt.%, and the soaking time is 20-30min, then transferring the mixture into a reaction kettle with a polytetrafluoroethylene substrate, heating the mixture in water bath at 140 ℃ for 16h, cooling the mixture to room temperature, centrifuging the suspension, freeze-drying the suspension at-60 ℃, mechanically crushing the suspension into micropowder, and screening the micropowder to obtain micropowder with the particle size of 40-70 mu m, thereby obtaining the modified bryophyte fiber;
s2 preparation of hydrogel
Weighing 1 part by weight of polyvinyl alcohol, dissolving the polyvinyl alcohol in deionized water, wherein the mass part of the polyvinyl alcohol is 4%, adjusting the pH value of the solution to 5 with glacial acetic acid, adding 14 parts of carboxymethyl chitosan, mixing and stirring, introducing nitrogen into the mixed solution to obtain a uniform and transparent precursor solution, adding deionized water with the same volume as that of the precursor solution, stirring to obtain a viscous solution, standing for 24h, soaking for 96h with the deionized water, changing water once every 12h, performing forced air drying at 80 ℃ for 12h after soaking is completed, performing vacuum drying at 60 ℃ for 24h, mechanically crushing and micronizing, and screening to obtain micro powder with the particle size of 40-70 mu m, thereby preparing the carboxymethyl chitosan hydrogel;
s3, proportioning
Mixing the modified bryophyte fibers with the carboxymethyl chitosan hydrogel according to a mass ratio of 4: 1, mixing to obtain the modified filler.
Example 2
The preparation is the same as example 1, and the weight ratio of the water-soluble phenolic resin, the modified filler and the diluent is 10: 2: 100, the mass ratio of the modified bryophyte fibers to the carboxymethyl chitosan hydrogel is 6: 1.
example 3
The same preparation as example 1 was carried out, wherein the treatment solution was a mixed solution of sodium hydroxide, potassium hydroxide and sodium bicarbonate, and the concentrations of sodium hydroxide, potassium hydroxide and sodium bicarbonate were 2mol/L, 0.5mol/L and 0.5mol/L, respectively.
Comparative example 1
A preparation method of low-ash briquetted coal-based activated carbon comprises the following steps:
s1, pretreatment of coal material
Drying raw material coal of non-caking coal and long flame coal by hot air, carrying out micro-oxidation at the same time, wherein the temperature of the hot air is 150 ℃, the heat treatment time is 30-50min, and grinding is respectively carried out after cooling, wherein the volatile content of the non-caking coal and the long flame coal is 25-35 wt.%, the caking index of the non-caking coal is 0.8-2.6, the grinding granularity is 300-400 meshes, and the grinding granularity of the long flame coal is 400-600 meshes;
s2, coal blending and forming
The non-caking coal and the long flame coal are mixed according to the weight part ratio of 10: 2, mixing, mechanically stirring or stirring with air to be uniform; adding a coal tar binder accounting for 2% of the weight of the mixed coal material, and stirring uniformly again to obtain a mixture A; adding the mixture A into a forming device, wherein the forming pressure of the forming device is 24MPa, the compression ratio is 2.2, pressing the formed material out, then feeding the formed material into a sieving machine, and re-forming the dust sieved out of the formed material and the ground raw material;
s3 carbonization
Heating the molded material to 600-700 ℃ under the protection of nitrogen or argon, carrying out thermal pyrolysis for 3h at the heating rate of 2 ℃/min to obtain a calcined product A, adding the calcined product A into a hydrochloric acid solution, soaking to remove redundant impurities, washing with deionized water to obtain a carbonized product, wherein the volatile content of the carbonized product is 3-8%, and the strength of the carbonized product is more than 94%;
s4, activation treatment
Sending the carbonized product into drying equipment to be dried until the moisture content is less than 4%, screening the dried carbonized product, and enabling the carbonized product with the particle size of 2-8mm to enter an activation section; the activation section is activated by adopting a gas activation method, the activation temperature is 900 ℃, the activation furnace pressure is 100Pa, and the activation time is 60 hours, so that an activated product is obtained, and the loss on ignition of the activated product is 45-55%;
s5, post-processing
The activated product is screened by adopting two-stage crushing to obtain a finished product, sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium hexametaphosphate are dissolved in water to prepare a treatment solution, the concentrations of the sodium hydroxide, the potassium hydroxide, the sodium bicarbonate and the sodium hexametaphosphate in the treatment solution are respectively 2mol/L, 0.5mol/L and 0.4mol/L, the finished product is added into the treatment solution, the liquid-solid ratio is 80ml/g, the mixture is stirred and reacted for 1 to 5 hours under the condition of water bath at 70 ℃, the mixture is filtered and rinsed by clear water, and drying equipment is used for drying for multiple times to obtain the low-ash briquette coal-based activated carbon.
Examples of the experiments
The basic performance indexes of the activated carbon prepared in the examples 1 to 3 and the comparative example 1 are measured, and the measurement results are as follows:
performance index
|
Measurement method
|
Example 1
|
Example 2
|
Example 3
|
Comparative example 1
|
Ash content
|
GB/T7702.15-2008
|
2.9%
|
2.8%
|
3.9%
|
2.7%
|
Iodine adsorption number
|
GB/T7702.7-2008
|
986mg/g
|
993mg/g
|
1010mg/g
|
1105mg/g
|
Methylene blue adsorption number
|
GB/T7702.6-2008
|
209mg/g
|
216mg/g
|
223mg/g
|
231mg/g
|
Mechanical strength
|
GB/T7702.3-2008
|
98.1%
|
97.7%
|
97.9%
|
83.4%
|
Specific surface area
|
GB/T7702.20-2008
|
975m2/g
|
982m2/g
|
1022m2/g
|
1128m2/g
|
Hardness of ball
|
Standard ASTM
|
93.8%
|
93.0%
|
92.9%
|
80.5%
|
Abrasion resistance value
|
Standard ASTM
|
87.6%
|
87.4%
|
87.3%
|
78.0% |
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.