CN101817519B - Preparation method and use of millimetre-sized mesoporous carbon spheres - Google Patents
Preparation method and use of millimetre-sized mesoporous carbon spheres Download PDFInfo
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Abstract
The invention belongs to the field of inorganic nano material synthesis and particularly relates to a preparation method and use of millimetre-sized mesoporous carbon spheres. The preparation method comprises the following steps of: dissolving resorcinol in ethanol serving as a solvent; adding furfural and ethanol solution of hydrogen chloride, and stirring the mixture at 0 to 15 DEG C for 10 to 120 minutes; adding aqueous solution of hexamethylenetetramine and pore-forming material into the prepared solution to obtain solution of a precursor; adding the prepared solution of the precursor into liquid max containing an emulsifier, and stirring the solution to perform per-polymerization; volatilizing the solvent, filtering the remaining material, and washing and drying the product obtained by filtration; and carbonizing the product to obtain the millimetre-sized mesoporous carbon spheres. The preparation of the millimetre-sized mesoporous carbon spheres of the invention is performed under simple conditions and with easy operation. The millimetre-sized mesoporous carbon spheres prepared by the method have the characteristics of adjustable size, large specific surface area, large porevolume and the like, and can be used as adsorbent for hemoperfusion and the like.
Description
Technical field
The invention belongs to the synthetic field of inorganic nano material, relate to a kind of preparation method of millimetre-sized mesoporous carbon spheres.
Background technology
The intravital poisonous substance of people is divided into two types of exogenous poisonous substance and endogenous poisonous substances.The former is from the outer toxic substance (like agricultural chemicals) of human body, when this toxic substance is assembled the various pathologies that can cause health when too much at inside of human body; The latter then is the too much accumulation and can not effectively remove the time, the toxic substance of formation (like UCB, uric acid etc.) also can cause various pathologies of the caused metabolite of human body self health fault.
Under normal circumstances, human body can pass through autoprotection system such as liver detoxification system, and human body self immunity system and Excretory system etc. are detoxified the endogenous or exogenous poisonous substance of removing or neutralize.But for acute drugs poisoning, uremia, diseases such as liver failure when human body self has lost detoxification ability, only use general internal medicine Clinical Processing (comprise gastric lavage, antagonism medicine etc. is used in transfusion) often to be difficult to prove effective.Event is adopted medical sorbent material to carry out blood perfusion and is purified the blood, and removes wherein to reach clinical therapeutic efficacy behind some morbid substance.
The cardinal principle of blood perfusion is exactly adsorption.Blood perfusion has important effect with the development of sorbent material in the blood perfusion field, is the key factor of decision perfusion effect.Sorbent material commonly used at present mainly is activated carbon, resin and polysaccharide material.Mostly the aperture is big owing to above-mentioned materials, and pore size distribution is inhomogeneous, and specific surface area is low etc., make its in various degree exist adsorption rate low, adsorptive capacity is low wait not enough.Research and develop novel fast, high adsorption capacity with can realize that the sorbent material of perfusion device miniaturized is the actual requirement of blood purification treatment.
Our seminar is used for toxins in human body absorption (Chinese invention patent: CN101618869 and CN101274265 such as UCB, uric acid, cholic acid with mesoporous silicon oxide and mesoporous carbon recently; Chemical Communications, 2009,6071-6073).The result shows that mesoporous material has good adsorption property to it, and particularly mesoporous carbon still shows higher specific adsorption amount in UCB and Human Serum Albumin's PBS mixing solutions.In the clinical blood perfusing course, sorbent material is packed into after by high-temperature sterilization in the adsorption column, and blood externally passes through adsorption column under the effect of pressure.In order to make blood to pass through sorbent material smoothly, mostly medical perfusion level active carbon is the smooth bead of 1 millimeter, and cell that hemocyte in the blood etc. is big like this or albumen just can be smoothly result in blockage through being unlikely to from the accumulation gap of bead.If can synthesize the smooth mesoporous carbon spheres of 1 millimeter and be used for blood perfusion and use sorbent material; Not only help blood through mesoporous carbon spheres stacking gap; Brought into play the excellent absorption property of mesoporous material self simultaneously, with the application that promotes mesoporous material as medical sorbent material greatly.Content of the present invention is the synthetic of millimetre-sized mesoporous carbon spheres.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of millimetre-sized mesoporous carbon spheres, to overcome the deficiency of prior art.
The problem low for the adsorption rate that solves that existing blood perfusion is big with the sorbent material aperture, pore size distribution is inhomogeneous, specific surface area is low etc. and cause, that adsorptive capacity is low etc. the invention discloses a kind of preparation method of millimetre-sized mesoporous carbon spheres.
The preparation method of a kind of millimetre-sized mesoporous carbon spheres of the present invention comprises the steps:
1, the configuration of precursor solution: a, Resorcinol is dissolved in the ethanol, add furfural and ethanol solution of hydrogen chloride then, between 0-15 ℃, stir 10-120min; Add the hexamethylenetetramine aqueous solution and pore-forming material in b, the solution that in step a, makes and continue to stir 30-180min, obtain precursor solution.
In the said step (1), F
127, Resorcinol, furfural, hydrogenchloride, hexamethylenetetramine and alcoholic acid mol ratio be 0.005-0.025: 1: 1-2: 0.003-0.01: 0.05-0.2: 15-40: 0.5-1.0;
Preferably, the mol ratio of pore-forming material, Resorcinol, furfural, hydrogenchloride, hexamethylenetetramine, second alcohol and water is 0.015: 1: 1.5: 0.005: 0.1: 20: 0.75;
Described ethanol solution of hydrogen chloride is for formulated with conventional concentrated hydrochloric acid-ethanol;
Said pore-forming material is for gathering oxyethylene-gather propylene oxide-gather oxyethylene segmented copolymer;
Its triblock copolymer F
127, molecular formula is EO
106PO
70EO
106, EO represents OCH
2CH
2Block, PO represents OCH
2CH
2CH
2Block.
2, precursor prepolymerization: the precursor solution that configures is joined in the whiteruss solution that contains emulsifying agent, stir prepolymerization 60-240min down at 45-70 ℃ then and obtain the prepolymerization product.
The precursor solution that wherein configures is 0.05-0.5 with the volume ratio that contains the whiteruss solution of emulsifying agent: 1.
Described emulsifying agent is sorbitol anhydride oleate Span-80, and the weight percentage of emulsifying agent is 0.3wt%-4wt% in the described whiteruss solution that contains emulsifying agent.
3, the volatilization of etoh solvent: the prepolymerization product of step 2 is heated 120-600min under 95-125 ℃ of stirring, vapor away the ethanol in the precursor solution, obtain intermediate product.This intermediate product is millimeter level black or dark-brown phenolic resin balls.
Ethanol evaporable temperature can be 115 ℃, and the time is 240min;
4, filter, wash and drying: the intermediate product in the filtered and recycled step 3, the washing after drying obtains the exsiccant phenolic resin balls.
Described drying temperature is 100 ℃, and the time is 12h.
5, remove pore-forming material and carbonized phenolic resin ball: the high temperature cabonization under inert atmosphere of the exsiccant phenolic resin balls in the step 4 is obtained millimetre-sized mesoporous carbon spheres.
Preferably, the carbonization temperature that obtains millimetre-sized mesoporous carbon spheres is 600-900 ℃, and carbonization time is 60-600min;
Preferably, the carbonization temperature that obtains millimetre-sized mesoporous carbon spheres is 600-800 ℃, and the time is 60-240min;
The ball smooth surface of the said millimetre-sized mesoporous carbon that makes, the diameter of ball are 0.9-1.8mm, and the aperture of mesoporous carbon spheres is 5.0-10.0nm, and specific surface area is 450-650m
2/ g, pore volume are 0.40-0.65cm
3/ g.
In addition, carbonization temperature is 350-450 ℃, when carbonization time is 60-240min, can obtain millimetre-sized mesoporous resol.
Described inert atmosphere is selected from nitrogen;
Described carbonization heat-up rate is 2 ℃/min.
The invention provides a kind of preparation method of millimetre-sized mesoporous carbon spheres, this method prepares mesoporous carbon with soft template method and is the basis, utilizes microemulsion method to add volatilization and induces self-assembly process successfully to make millimetre-sized mesoporous carbon spheres first.
In addition, this preparation method can regulate and control the size of mesoporous carbon spheres through the preparation temperature of change precursor solution and the addition of precursor solution, but the key of this technology is the preparation of millimetre-sized mesoporous carbon spheres.
Preparing method of the present invention has following characteristics:
1, simple, the easy handling of preparing method's condition;
2, prepared ball smooth surface, diameter help blood through mesoporous carbon spheres stacking gap at 0.9-1.8mm, satisfy the pattern requirement of blood perfusion with sorbent material;
3, the aperture of the mesoporous carbon spheres of gained is 5-10nm, and specific surface area is 450-650m
2/ g, pore volume are 0.40-0.65cm
3/ g;
4, the carbon ball that makes of this method has characteristics such as adjustable size, specific surface area and pore volume are big, and absorption property is excellent.
5, this millimetre-sized mesoporous carbon spheres combines perfusion and requires the constructional feature with mesoporous material with the pattern of sorbent material, with the sorbent material field good application prospects is arranged at perfusion, uses sorbent material like the blood perfusion of uremic patient.
The prepared millimetre-sized mesoporous carbon spheres of this preparation method can be used as blood perfusion with sorbent material or other sorbent materials.
Description of drawings
Fig. 1: diameter is at the digital photograph of the mesoporous carbon spheres of 0.9-1.5mm
Fig. 2: the SEM photo on millimetre-sized mesoporous carbon spheres surface
Fig. 3: millimetre-sized mesoporous carbon spheres grinds the TEM photo of back fragment
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, should be understood that these embodiment only are used to the present invention is described and are not used in restriction protection scope of the present invention.
Embodiment 1
At first the 4.6g Resorcinol is dissolved in the 40g ethanol; Add 6g furfural and 0.75g 1wt% ethanol solution of hydrogen chloride subsequently.Stir 30min down at 10 ℃ subsequently.Adding volumetric molar concentration then is the aqueous solution 1.8mL and the 8g F of the hexamethylenetetramine of 2.54mol/L
127Stir 60min, the mol ratio of its composition, F
127: Resorcinol: furfural: HCl: hexamethylenetetramine: ethanol: water=0.015: 1: 1.5: 0.005: 0.1: 20: 0.75.Above-mentioned solution is put into the 500mL whiteruss solution that contains 8gSpan-80, then under 60 ℃ of stirrings, and prepolymerization 120min.Under 115 ℃ of stirrings, heat 240min subsequently.Filter and the washing and recycling resultant, behind 100 ℃ of dry 12h, the gained bead is put into atmosphere furnace, be raised to 800 ℃ of insulation 4h with the speed among the 2 ℃/min, whole carbonization process carries out under nitrogen atmosphere, obtains millimetre-sized mesoporous carbon spheres.Accompanying drawing 1 is a gained mesoporous carbon spheres digital photograph intuitively, and can detect gained mesoporous carbon spheres diameter is 0.9-1.5mm.Scanning electron microscopic observation can know that the microcosmic surface of gained mesoporous carbon spheres is very smooth in the accompanying drawing 2.Accompanying drawing 3 is observed this mesoporous carbon spheres and is had unordered mesoporous for the gained mesoporous carbon spheres being ground the TEM collection of illustrative plates of back fragment.Through detecting, the specific surface area of this mesoporous carbon spheres is 577.5m
2/ g, most probable pore size are 7.6nm, and pore volume is 0.60cm
3/ g.
Embodiment 2
Consistent like embodiment 1 said building-up process, just whipping temp is 0 ℃ in precursor formulations prepared from solutions process, and churning time is 120min.The diameter of gained mesoporous carbon spheres is 1.1-1.8mm, and the specific surface area of ball is 590.2m
2/ g, most probable pore size are 6.1nm, and pore volume is 0.45cm
3/ g.
Embodiment 3
Consistent like embodiment 1 said building-up process, just whipping temp is 15 ℃ in precursor formulations prepared from solutions process, and churning time is 10min.The diameter of gained mesoporous carbon spheres is 0.8-1.3mm, and the specific surface area of ball is: 650.0m
2/ g, most probable pore size are 9.8nm, and pore volume is 0.50cm
3/ g.
Embodiment 4
Consistent like embodiment 1 said building-up process, be 45 ℃ just in the prepolymerized temperature of precursor solution stirring, churning time is 240min.The diameter of gained mesoporous carbon spheres is 0.8-1.5mm, and the specific surface area of ball is: 550.0m
2/ g, most probable pore size are 5.8nm, and pore volume is 0.40cm
3/ g.
Embodiment 5
Consistent like embodiment 1 said building-up process, be 45 ℃ just in the prepolymerized temperature of precursor solution stirring, churning time is 240min.The diameter of gained mesoporous carbon spheres is 0.8-1.5mm, and the specific surface area of ball is: 550.0m
2/ g, most probable pore size are 5.8nm, and pore volume is 0.40cm
3/ g.
Embodiment 6
Consistent like embodiment 1 said building-up process, be 70 ℃ just in the prepolymerized temperature of precursor solution stirring, churning time is 60min.The diameter of gained mesoporous carbon spheres is 1.4-1.8mm, and the specific surface area of ball is: 558.0m
2/ g, most probable pore size are 8.8nm, and pore volume is 0.58cm
3/ g.
Embodiment 7
Consistent like the said building-up process of embodiment 1, just the addition of emulsifying agent is 2.12g (the emulsifying agent weight percentage that contains in the whiteruss of emulsifying agent is 0.3wt%) in whiteruss.The diameter of gained mesoporous carbon spheres is 1.0-1.4mm, and the specific surface area of ball is: 640.0m
2/ g, most probable pore size are 5.8nm, and pore volume is 0.58cm
3/ g.
Embodiment 8
Consistent like the said building-up process of embodiment 1, just the addition of emulsifying agent is 16g ((the emulsifying agent weight percentage that contains in the whiteruss of emulsifying agent is 4wt%) in whiteruss.The diameter of gained mesoporous carbon spheres is 1.0-1.5mm, and the specific surface area of ball is: 610.0m
2/ g, most probable pore size are 5.5nm, and pore volume is 0.54cm
3/ g.
Embodiment 9
Consistent like embodiment 1 said building-up process, be 600 ℃ just in carbonization temperature, carbonization time is 60min.The diameter of gained mesoporous carbon spheres is 1.0-1.6mm, and the specific surface area of ball is 600.2m
2/ g, most probable pore size are 6.7nm, and pore volume is 0.55cm
3/ g.
Comparative Examples 1
At first the 4.6g Resorcinol is dissolved in the 40g ethanol; Add 6g furfural and 0.75g 1wt% ethanol solution of hydrogen chloride subsequently.Stir 30min down at 10 ℃ subsequently.The aqueous solution 1.8mL and the 8g F that add the hexamethylenetetramine of 2.54mol/L then
127Stir 60min.Above-mentioned solution is put into the 500mL whiteruss solution that contains 8g Span-80, then under 60 ℃ of stirrings, and prepolymerization 120min.Under 90 ℃ of stirrings, heat 240min subsequently.Filter and the washing and recycling resultant, behind 100 ℃ of dry 12h, the gained bead is put into atmosphere furnace, be raised to 800 ℃ of insulation 4h with the speed among the 2 ℃/min, whole carbonization process carries out under nitrogen atmosphere, obtains millimetre-sized mesoporous carbon spheres.The diameter of gained mesoporous carbon spheres is 0.8-1.2mm, and the microcosmic surface of ball is coarse.The specific surface area of this mesoporous carbon spheres is: 530.3m2/g, most probable pore size are 7.2nm, and pore volume is 0.48cm
3/ g.
Comparative Examples 2
At first the 9.2g Resorcinol is dissolved in the 80g ethanol; Add 12g furfural and 1.5g 1wt% ethanol solution of hydrogen chloride subsequently.Stir 30min down at 10 ℃ subsequently.Adding volumetric molar concentration then is the aqueous solution 3.6mL and the 16g F of the hexamethylenetetramine of 2.54mol/L
127Stir 60min.Above-mentioned solution is put into the 500mL whiteruss solution that contains 8g Span-80, then under 60 ℃ of stirrings, and prepolymerization 120min.Under 115 ℃ of stirrings, heat 240min subsequently.Filter and the washing and recycling resultant, behind 100 ℃ of dry 12h, the gained bead is put into atmosphere furnace, be raised to 800 ℃ of insulation 4h with the speed among the 2 ℃/min, whole carbonization process carries out under nitrogen atmosphere.The diameter of gained mesoporous carbon spheres is 0.3-0.8mm, and the specific surface area of ball is: 550.0m
2/ g, most probable pore size are 7.4nm, and pore volume is 0.55cm
3/ g.
Comparative Examples 3
At first the 4.6g Resorcinol is dissolved in the 40g ethanol; Add 6g furfural and 0.75g 1wt% ethanol solution of hydrogen chloride subsequently.Stir 30min down at 30 ℃ subsequently.The aqueous solution 1.8mL and the 8g F that add the hexamethylenetetramine of 2.54mol/L then
127Stir 60min.Above-mentioned solution is put into the 500mL whiteruss solution that contains 8g Span-80, then under 60 ℃ of stirrings, and prepolymerization 120min.Under 115 ℃ of stirrings, heat 240min subsequently.Filter and the washing and recycling resultant, behind 100 ℃ of dry 12h, the gained bead is put into atmosphere furnace, be raised to 800 ℃ of insulation 4h with the speed among the 2 ℃/min, whole carbonization process carries out under nitrogen atmosphere.The diameter of gained mesoporous carbon spheres is 0.1-0.4mm, and the specific surface area of ball is: 560.7m
2/ g, most probable pore size are 7.8nm, and pore volume is 0.49cm
3/ g.
Comparative Examples 4
At first the 4.6g Resorcinol is dissolved in the 40g ethanol; Add 6g furfural and 0.75g 1wt% ethanol solution of hydrogen chloride subsequently.Stir 30min down at 30 ℃ subsequently.Add 0.64g hexamethylenetetramine and 8g F then
127Stir 60min.Above-mentioned solution is put into the 500mL whiteruss solution that contains 8g Span-80, then under 60 ℃ of stirrings, and prepolymerization 120min.Under 115 ℃ of stirrings, heat 240min subsequently.Resultant does not have balling-up, all forms with dung and is bonded at wall of container and at the end.
Comparative Examples 5
At first the 4.6g Resorcinol is dissolved in the 40g ethanol; Add 6g furfural and 0.75g 1wt% ethanol solution of hydrogen chloride subsequently.Stir 30min down at 30 ℃ subsequently.Add then 2.54mol/L the aqueous solution 1.8mL and the 8g F of hexamethylenetetramine
127Stir 60min.Above-mentioned solution is put into the 500mL whiteruss solution that contains 8g Span-80, then under 60 ℃ of stirrings, and prepolymerization 300min.Under 115 ℃ of stirrings, heat 240min subsequently.The resultant caking does not form bead.
Claims (4)
1. the preparation method of a millimetre-sized mesoporous carbon spheres comprises the steps:
(1) configuration precursor solution: a, Resorcinol is dissolved in the etoh solvent, add furfural and ethanol solution of hydrogen chloride then, stir 10-120min at 0-15 ℃; Add the aqueous solution and the pore-forming material of hexamethylenetetramine in b, the solution that in step a, makes and continue to stir 30-180min, obtain precursor solution;
(2) precursor prepolymerization: the precursor solution for preparing is joined in the whiteruss that contains emulsifying agent, stir prepolymerization then and obtain the prepolymerization product;
(3) volatilization of solvent: heating 120-600min vapors away the etoh solvent in the prepolymerization product under 95-125 ℃ of stirring;
(4) filtration, washing, drying obtain millimeter level phenolic resin balls;
(5) the carbonized phenolic resin ball obtains millimetre-sized mesoporous carbon spheres;
In the said step (1), the mol ratio of pore-forming material, Resorcinol, furfural, hydrogenchloride, hexamethylenetetramine, second alcohol and water is 0.005-0.025: 1: 1-2: 0.003-0.01: 0.05-0.2: 15-40: 0.5-1.0;
In the said step (2), described precursor solution is 0.05-0.5 with the volume ratio that contains the whiteruss of emulsifying agent: 1;
Stirring prepolymerization in the said step (2) is to stir prepolymerization 60-240min down at 45-70 ℃;
Pore-forming material is for gathering oxyethylene-gather propylene oxide-gather oxyethylene segmented copolymer in the described step (1);
Emulsifying agent is selected from sorbitol anhydride oleate in the said step (2), and the weight percentage of emulsifying agent is 0.3wt%-4wt% in the said whiteruss solution that contains emulsifying agent.
2. the preparation method of a kind of millimetre-sized mesoporous carbon spheres as claimed in claim 1 is characterized in that: the condition of carbonized phenolic resin ball is under inert atmosphere in the said step (5), and carbonization temperature is 600-900 ℃, and carbonization time is 60-600min.
3. millimetre-sized mesoporous carbon spheres; For the preparation method according to the arbitrary described millimetre-sized mesoporous carbon spheres of claim 1-2 makes, described millimetre-sized mesoporous carbon spheres ball smooth surface, the spherical diameter size is 0.9-1.8mm; Mesoporous aperture is 5.0-10.0nm, and specific surface area is 450-650m
2/ g, pore volume are 0.40-0.65cm
3/ g.
4. millimetre-sized mesoporous carbon spheres as claimed in claim 3 is applied to blood perfusion and uses sorbent material.
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