CN104174358B - A kind of netted nitrogenous carbon adsorbent material and its preparation method and application - Google Patents
A kind of netted nitrogenous carbon adsorbent material and its preparation method and application Download PDFInfo
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- CN104174358B CN104174358B CN201410391402.9A CN201410391402A CN104174358B CN 104174358 B CN104174358 B CN 104174358B CN 201410391402 A CN201410391402 A CN 201410391402A CN 104174358 B CN104174358 B CN 104174358B
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Abstract
The invention provides a kind of netted nitrogenous carbon adsorbent material and its preparation method and application.The removal effect of the netted nitrogenous charcoal sorbing material of the present invention to Ciprofloxacin Hydrochloride is fine; This material feedstock is commercial polyurethane sponge, block copolymer, low molecule phenolic resins and melamine etc., and raw material is cheap, and production cost is lower, and wide material sources are easily produced, required production technology and production equipment simple; Compared with general sorbing material, this material, for being easily separated with sewage after block absorption, easily reclaiming and can not produce secondary pollution to environment.
Description
Technical field:
The present invention relates to a kind of for removing in water antibiotic netted nitrogenous carbon adsorbent materials such as Ciprofloxacin Hydrochloride and preparation method thereof.
Background technology:
In recent years, the appearance of antibiotic abuse, a large amount of drug resistance pathogenic bacteria causes people to antibiotic extensive concern.And Ciprofloxacin Hydrochloride is one of medicine that in third generation FQNS, antibacterial activity is stronger, be widely used in the clinical practice of people doctor and animal doctor, special in culture fishery, often by as fishing medicinal come the bacterial infective diseases of prevention and therapy aquatic animal, which results in this medicine and with original shape or metabolisable form entered environment, directly can threaten public health security and pollution of ecological environment.Present stage, the processing method of dirty organic pollutants mainly contains Physical, chemical method and bioanalysis.But the many factors such as such as sewage composition, organic concentration, pH value condition are vulnerable to chemical method and Biochemical method organic pollution, to space enrironment require high, especially some hazardous contaminant matter with common method be difficult to remove or treatment effect undesirable.And the material of this method synthesis is because cost is low, manufacture craft simple, may be used for industrial mass production; Meanwhile, adsorption effect is high, easily reclaim after materials adsorption, can put on a large scale in environment and carry out sewage disposal, can not produce secondary pollution to environment, so have good application prospect.
Acticarbon has larger specific area and abundant pore structure, effectively can adsorb organic pollution, prepare the absorbent charcoal material of supported metal phthalocyanine in printing and dyeing industry with containing Application comparison in the wastewater treatment of heavy metal is many as patent CN101215016B.But the particle of these adsorbents own is tiny, be difficult to after absorption be separated from water, and little for the patent of the acticarbon of the antibiotic aspects such as Ciprofloxacin Hydrochloride in removal water.From current research situation, netted nitrogenous Carbon Materials is fine to the adsorption effect of Ciprofloxacin Hydrochloride, and reaction condition is without the need to HTHP, and netted nitrogenous Carbon Materials is that blocks of solid easily reclaims.
Summary of the invention:
Main purpose of the present invention is to provide a kind of for removing in water the antibiotic netted nitrogenous carbon adsorbent materials such as Ciprofloxacin Hydrochloride.
Another object of the present invention is to provide the preparation method of above-mentioned nitrogenous solid adsorbent materials.
A present invention also object is to provide a kind of solid material of easily separated recovery in the application of removing large molecular acid organic pollution in water.
The present invention selects commercial polyurethane sponge to do the skeleton limbs of macroporous structure, commercial block copolymer is as soft template, low molecule phenolic resins is as presoma, melamine is nitrogenous source, adopts the method for solvent evaporation induced self-assembly to prepare the mesoporous carbon material having certain pattern with multi-stage artery structure.
Concrete technical scheme of the present invention is as follows:
A preparation method for netted nitrogenous carbon adsorbent material, the concrete steps of the method are as follows:
1) phenol 50 DEG C of meltings is added the NaOH aqueous solution of 20wt%, stir 10min, obtain solution A; Wherein the mass ratio of phenol and the NaOH aqueous solution is 5:1;
2) in solution A, drip 37wt% formalin, stir 10min.Room temperature is down to after being slowly warming up to 75 DEG C of maintenance 1h; Regulate pH to be 7 with the watery hydrochloric acid of 2mol/L, vacuum drying under 45 DEG C of conditions, obtains phenolic aldehyde performed polymer B; Wherein solution A and formalin mass ratio are 1:1.4;
3) in ethanol, polyethers F127 (molecular formula: EO is added
106pO
70eO
106, Aladdin Reagent Company), be stirred to polyethers F127 and dissolve, obtain solution C; Wherein the mass ratio of ethanol and F127 is 0.03:1.
4) add in solution C by above-mentioned phenolic aldehyde performed polymer B, wherein the mass ratio of B and C is 1:0.3; Mixed liquor constant temperature under 50 DEG C of conditions stirs after 5h, slow dropping carbamide mixed solution, the mol ratio of melamine and formaldehyde is 8:1, carbamide mixed solution and B, C mixture quality are than being 1:3, the hydrochloric acid solution reusing 2mol/L regulates pH to be that at about 5.5,50 DEG C, constant temperature stirs 2h; Obtaining glue is D;
5) getting glue D is injected in polyurethane sponge, and the volume ratio of glue D and polyurethane sponge is 1:2 (ml/cm
3); Constantly extrude bubble in polyurethane sponge with glass bar, so that macropore space filled by colloidal sol, populated polyurethane sponge is continuous rotation under draughty condition, makes glue D evenly be coated in the branch of polyurethane sponge; At room temperature sponge is placed in air and leaves standstill 20-40 hour, moisture in sponge is volatilized completely; Obtain sponge E;
6) sponge E is placed in the tube furnace of nitrogen atmosphere protection, with 2 DEG C/min ramp to 550 DEG C, sponge E is placed 3h under 550 DEG C of conditions, after naturally cooling to room temperature, obtain netted nitrogenous Carbon Materials.
Wherein, step 5) in get 2.5ml glue D to be injected into volume be 5cm
3polyurethane sponge in.
Step 6) in this step heat up and in temperature-fall period the constant flow of nitrogen at 70ml/min.
The netted nitrogenous carbon adsorbent material that above-mentioned preparation method obtains.
The application in water in antibiotic removed by this netted nitrogenous carbon adsorbent material, and wherein said antibiotic is Ciprofloxacin Hydrochloride.
The present invention has following beneficial effect:
The removal effect of the netted nitrogenous charcoal sorbing material of the present invention to Ciprofloxacin Hydrochloride is fine; This material feedstock is commercial polyurethane sponge, block copolymer, low molecule phenolic resins, ethyl orthosilicate and melamine etc., and raw material is cheap, and production cost is lower, and wide material sources are easily produced, required production technology and production equipment simple; Compared with general sorbing material, this material, for being easily separated with sewage after block absorption, easily reclaiming and can not produce secondary pollution to environment.
Experimental result is, Powdered Activated Carbon adsorbs one week the Ciprofloxacin Hydrochloride of 10mg/L under 25 DEG C of conditions, and clearance is 22.22%;
And be carbon source with phenolic resins, F127 be the Carbon Materials made of pore creating material under equal adsorption conditions, the clearance of Ciprofloxacin Hydrochloride reaches 89.94%;
When to taking phenolic resins as carbon source, F127 is pore creating material when making in the synthetic system of Carbon Materials that to add nitrogenous source be urea, and resulting materials is 90.11% to the clearance of Ciprofloxacin Hydrochloride under equal adsorption conditions;
When to taking phenolic resins as carbon source, F127 is pore creating material when making in the synthetic system of Carbon Materials that to add nitrogenous source be melamine, and resulting materials is 98.59% to the clearance of Ciprofloxacin Hydrochloride under equal adsorption conditions;
When with melamine be the obtained nitrogenous charcoal of nitrogenous source be made as Powdered time, be under equal conditions 92.67% to the clearance of Ciprofloxacin Hydrochloride.
Experimental result represents, under the same conditions, is that the removal effect of nitrogenous charcoal to Ciprofloxacin Hydrochloride of carbon source is best with melamine, and when this material is block, adsorption effect is better.So netted nitrogenous charcoal of the present invention can effectively remove Ciprofloxacin Hydrochloride in water, easily reclaiming after absorption, and can not produce secondary pollution to environment, is environmental friendliness shaped material.
Accompanying drawing illustrates:
Fig. 1 is netted nitrogenous Carbon Materials schematic diagram prepared by the embodiment of the present invention 1.
Fig. 2 is the nitrogenous Carbon Materials schematic diagram of powdery prepared by comparative example 2.
Fig. 3 is the solution state figure of test examples 2.
Fig. 4 is the solution state figure of test examples 3.
Detailed description of the invention:
In order to make the object of the invention, technical scheme and effect be easy to understand, below in conjunction with accompanying drawing and instantiation, set forth the present invention further.
Embodiment 1
The present invention prepares the method for netted nitrogenous Carbon Materials, and described preparation method comprises the following steps:
Netted nitrogenous Carbon Materials in this example selects commercial polyurethane sponge to do the skeleton limbs of macroporous structure, commercial block copolymer is as soft template, low molecule phenolic resins (phenolic aldehyde performed polymer) is as presoma, the method of solvent evaporation induced self-assembly is adopted to prepare the ordered mesoporous carbon material with multi-stage artery structure, concrete preparation method is as follows: polyethers F127 in following instance, molecular formula: EO
106pO
70eO
106, Aladdin Reagent Company of manufacturer.
(1) phenol 50 DEG C of meltings is added the NaOH aqueous solution of 20wt%, stir 10min, obtain solution A; Wherein the mass ratio of phenol and the NaOH aqueous solution is 5:1.
(2) in solution A, drip 37wt% formalin, stir 10min.Room temperature is down to after being slowly warming up to 75 DEG C of maintenance 1h; Regulate pH to be 7 with the watery hydrochloric acid of 2mol/L, vacuum drying under 45 DEG C of conditions, obtains phenolic aldehyde performed polymer B; Wherein solution A and formalin mass ratio are 1:1.4.
(3) in ethanol, add polyethers F127, be stirred to polyethers F127 and dissolve, obtain solution C; Wherein the mass ratio of ethanol and polyethers F127 is 0.03:1.
(4) add in solution C by B, wherein the mass ratio of B and C is 1:0.3; Mixed liquor constant temperature under 50 DEG C of conditions stirs after 5h, slow dropping carbamide mixed solution, the mol ratio of melamine and formaldehyde is 8:1, carbamide mixed solution and B, C mixed liquor mass ratio are 1:3, the hydrochloric acid solution reusing 2mol/L regulates pH to be that at about 5.5,50 DEG C, constant temperature stirs 2h.Obtaining glue is D;
(5) getting 2.5ml glue D, to be injected into volume be 5cm
3polyurethane sponge in.Constantly squeeze out the bubble of sweeping along wherein so that macropore space filled by colloidal sol with glass bar, populated polyurethane sponge is continuous rotation under draughty condition, makes glue D evenly be coated in the branch of polyurethane sponge.At normal temperatures sponge being placed in air makes sponge moisture volatilize completely; Obtain sponge E;
(6) sponge E is placed in the tube furnace of nitrogen atmosphere protection, with 2 DEG C/min ramp to 550 DEG C, E is placed 3h under 550 DEG C of conditions, after naturally cooling to room temperature, obtain netted nitrogenous Carbon Materials; The constant flow of this step nitrogen in intensification and temperature-fall period is at 70ml/min.
Embodiment 2 (comparison example)
Prepare the method for the nitrogenous Carbon Materials of powdery, described preparation method comprises the following steps:
(1) phenol 50 DEG C of meltings is added the NaOH aqueous solution of 20wt%, stir 10min, obtain solution A; Wherein the mass ratio of phenol and the NaOH aqueous solution is 5:1.
(2) in solution A, drip 37wt% formalin, stir 10min.Room temperature is down to after being slowly warming up to 75 DEG C of maintenance 1h; Regulate pH to be 7 with the watery hydrochloric acid of 2mol/L, vacuum drying under 45 DEG C of conditions, obtains phenolic aldehyde performed polymer B; Wherein solution A and formalin mass ratio are 1:1.4.
(3) in ethanol, add polyethers F127, be stirred to polyethers F127 and dissolve, obtain solution C; Wherein the mass ratio of ethanol and polyethers F127 is 0.03:1.
(4) add in solution C by B, wherein the mass ratio of B and C is 1:0.3; Mixed liquor constant temperature under 50 DEG C of conditions stirs after 5h, slow dropping carbamide mixed solution, the mol ratio of melamine and formaldehyde is 8:1, carbamide mixed solution and B, C mixed liquor mass ratio are 1:3, the hydrochloric acid solution reusing 2mol/L regulates pH to be that at about 5.5,50 DEG C, constant temperature stirs 2h.Get glue after reacting completely and put into baking oven in 100 degrees Celsius of placement 24h, after dry, grinding, obtains powder D.
(5) powder D is placed in the tube furnace of nitrogen atmosphere protection, at 550 DEG C, heats 3h, after cool to room temperature, obtain the nitrogenous Carbon Materials of powdery as Fig. 2.In heat treatment process, heating rate is 2 DEG C/min, and in intensification and Temperature fall process, the constant flow of nitrogen is at 70ml/min.
Embodiment 3 (comparison example)
Prepare the method for powdery carbon material, described preparation method comprises the following steps:
(1) phenol 50 DEG C of meltings is added the NaOH aqueous solution of 20wt%, stir 10min, obtain solution A; Wherein the mass ratio of phenol and the NaOH aqueous solution is 5:1.
(2) in solution A, drip 37wt% formalin, stir 10min.Room temperature is down to after being slowly warming up to 75 DEG C of maintenance 1h; Regulate pH to be 7 with the watery hydrochloric acid of 2mol/L, vacuum drying under 45 DEG C of conditions, obtains phenolic aldehyde performed polymer B; Wherein solution A and formalin mass ratio are 1:1.4.
(3) in ethanol, add polyethers F127, be stirred to F127 and dissolve, obtain solution C; Wherein the mass ratio of ethanol and polyethers F127 is 0.03:1.
(4) add in solution C by B, wherein the mass ratio of B and C is 1:0.3; Mixed liquor constant temperature under 50 DEG C of conditions stirs 5h, and get glue after reacting completely and put into baking oven in 100 degrees Celsius of placement 24h, after dry, grinding, obtains powder D.
(5) powder D is placed in the tube furnace of nitrogen atmosphere protection, at 550 DEG C, heats 3h, after cool to room temperature, obtain the nitrogenous Carbon Materials of powdery as Fig. 2.In heat treatment process, heating rate is 2 DEG C/min, and in intensification and Temperature fall process, the constant flow of nitrogen is at 70ml/min.
Embodiment 4 (comparison example)
Preparation take urea as the method for the netted nitrogenous Carbon Materials of nitrogenous source, and described preparation method comprises the following steps:
(1) phenol 50 DEG C of meltings is added the NaOH aqueous solution of 20wt%, stir 10min, obtain solution A; Wherein the mass ratio of phenol and the NaOH aqueous solution is 5:1.
(2) in solution A, drip 37wt% formalin, stir 10min.Room temperature is down to after being slowly warming up to 75 DEG C of maintenance 1h; Regulate pH to be 7 with the watery hydrochloric acid of 2mol/L, vacuum drying under 45 DEG C of conditions, obtains phenolic aldehyde performed polymer B; Wherein solution A and formalin mass ratio are 1:1.4.
(3) in ethanol, add polyethers F127, be stirred to F127 and dissolve, obtain solution C; Wherein the mass ratio of ethanol and F127 is 0.03:1.
(4) add in solution C by B, wherein the mass ratio of B and C is 1:0.3; In mixed liquor, add urea, urea and B, C mixed liquor mass ratio are 1:2, after constant temperature stirs 5h under 50 DEG C of conditions, use the hydrochloric acid solution of 2mol/L to regulate pH to be that at about 5.5,50 DEG C, constant temperature stirs 2h.Obtaining glue is D;
(5) getting 2.5ml glue D, to be injected into volume be 5cm
3polyurethane sponge in.Constantly squeeze out the bubble of sweeping along wherein so that macropore space filled by colloidal sol with glass bar, populated polyurethane sponge is continuous rotation under draughty condition, makes glue D evenly be coated in the branch of polyurethane sponge.At normal temperatures sponge being placed in air makes sponge moisture volatilize completely; Obtain sponge E;
(6) sponge E is placed in the tube furnace of nitrogen atmosphere protection, with 2 DEG C/min ramp to 550 DEG C, E is placed 3h under 550 DEG C of conditions, after naturally cooling to room temperature, obtain netted nitrogenous Carbon Materials; The constant flow of this step nitrogen in intensification and temperature-fall period is at 70ml/min.
Application example
Material 1 is the netted nitrogenous Carbon Materials (taking melamine as nitrogenous source) that the embodiment of the present invention 1 obtains;
Material 2 is the nitrogenous Carbon Materials of powdery (taking melamine as nitrogenous source) that embodiment 2 obtains;
Material 3 is the powdery carbon material that embodiment 3 obtains;
Material 4 is the netted nitrogenous Carbon Materials (taking urea as nitrogenous source) that embodiment 4 obtains;
Material 5 is Powdered Activated Carbon.
The Ciprofloxacin Hydrochloride removal capacity test of material 1, material 2, material 3, material 4 and material 5 is as follows:
Test examples 1
The specific area, pore structure etc. of nitrogenous Carbon Materials (taking melamine as nitrogenous source) is obtained by nitrogen adsorption desorption instrument.According to absorption result, table 1 is listed in the specific area of material, pore volume and aperture.The specific area 310.99m of netted nitrogenous Carbon Materials
2/ g, and the specific area of Powdered nitrogenous Carbon Materials only has 6.11m
2/ g.Netted nitrogenous Carbon Materials not only has certain microcellular structure and also has certain mesoporous pore volume, has multistage pore passage structure.
The structural parameters of table 1 sample
Note: D, average pore diameter; S
bETby BJH model according to N
2absorption/desorption isotherm calculates; V
t, total pore volume; V
micmicropore volume.
Test examples 2
(1) take netted nitrogenous Carbon Materials (taking melamine as the nitrogenous source) 0.1040g that embodiment 1 is obtained, being added to 200mL initial concentration is in the Ciloxan of 10mg/L, and solution state, as Fig. 3, obtains mixed liquor A.
(2) mixed liquor A is put into biochemical cultivation case, temperature is set to 25 DEG C, leaves standstill seven days, obtains mixed liquid B.
(3) get solution B, after filtering with 0.45 μm of filter, enter high performance liquid chromatography and survey its concentration, its clearance and adsorbance are as table 2.
Test examples 3
(1) take the nitrogenous Carbon Materials of powdery (taking melamine as the nitrogenous source) 0.1006g that embodiment 2 is obtained, being added to 200mL initial concentration is in the Ciloxan of 10mg/L, and solution state, as Fig. 4, obtains mixed liquor C.
(2) mixed liquor C is put into biochemical cultivation case, temperature is set to 25 DEG C, leaves standstill seven days, obtains mixed liquor D.
(3) get solution D, after filtering with 0.45 μm of filter, enter high performance liquid chromatography and survey its concentration, its clearance and adsorbance are as table 2.
Test examples 4
(1) take the powdery carbon material 0.1003g that embodiment 3 is obtained, being added to 200mL initial concentration is in the Ciloxan of 10mg/L, and solution state, as Fig. 4, obtains mixed liquor E.
(2) mixed liquor E is put into biochemical cultivation case, temperature is set to 25 DEG C, leaves standstill seven days, obtains mixed liquor F.
(3) get solution F, after filtering with 0.45 μm of filter, enter high performance liquid chromatography and survey its concentration, its clearance and adsorbance are as table 2.
Test examples 5
(1) take netted nitrogenous Carbon Materials (taking urea as the nitrogenous source) 0.0998g that embodiment 4 is obtained, being added to 200mL initial concentration is in the Ciloxan of 10mg/L, and solution state, as Fig. 4, obtains mixed liquor G.
(2) mixed liquor G is put into biochemical cultivation case, temperature is set to 25 DEG C, leaves standstill seven days, obtains mixed liquor H.
(3) get Solution H, after filtering with 0.45 μm of filter, enter high performance liquid chromatography and survey its concentration, its clearance and adsorbance are as table 2.
Test examples 6
(1) take the powdered activated Carbon Materials 0.1104g of material 5, being added to 200mL initial concentration is in the Ciloxan of 10mg/L, obtains mixed liquor I.
(2) mixed liquor I is put into biochemical cultivation case, temperature is set to 25 DEG C, leaves standstill seven days, obtains mixed liquor J.
(3) get solution J, after filtering with 0.45 μm of filter, enter high performance liquid chromatography and survey its concentration, its clearance and adsorbance are as table 2.
The clearance of table 2 sample and adsorbance
Conclusion: netted nitrogenous Carbon Materials prepared by the embodiment of the present invention 1 is the highest to Ciprofloxacin Hydrochloride clearance, adsorbance might as well.Other reference material difference.
Test examples 7
(1) take netted nitrogenous Carbon Materials (taking melamine as the nitrogenous source) 0.1189g that embodiment 1 is obtained, being added to 200mL initial concentration is in the Ciloxan of 50mg/L, obtains mixed liquor K.
(2) mixed liquor K is put into biochemical cultivation case, temperature is set to 25 DEG C, leaves standstill seven days, obtains mixed liquor L.
(3) get solution L, after filtering with 0.45 μm of filter, enter high performance liquid chromatography and survey its concentration, its clearance and adsorbance are as table 3.
Test examples 8
(1) take the nitrogenous Carbon Materials of powdery (taking melamine as the nitrogenous source) 0.1020g that embodiment 2 is obtained, being added to 200mL initial concentration is in the Ciloxan of 50mg/L, obtains mixed liquor M.
(2) mixed liquor M is put into biochemical cultivation case, temperature is set to 25 DEG C, leaves standstill seven days, obtains mixed liquor N.
(3) get solution N, after filtering with 0.45 μm of filter, enter high performance liquid chromatography and survey its concentration, its clearance and adsorbance are as table 3.
Test examples 9
(1) take the powdery carbon material 0.1055g that embodiment 3 is obtained, being added to 200mL initial concentration is in the Ciloxan of 50mg/L, obtains mixed liquor O.
(2) mixed liquor O is put into biochemical cultivation case, temperature is set to 25 DEG C, leaves standstill seven days, obtains mixed liquor P.
(3) get solution P, after filtering with 0.45 μm of filter, enter high performance liquid chromatography and survey its clearance of its concentration and adsorbance as table 3.
The clearance of table 3 sample and adsorbance
Conclusion: netted nitrogenous Carbon Materials prepared by the embodiment of the present invention 1 is the highest to Ciprofloxacin Hydrochloride clearance, adsorbance might as well.Other reference material difference.
Claims (6)
1. a preparation method for netted nitrogenous carbon adsorbent material, the concrete steps of the method are as follows:
1) phenol 50 DEG C of meltings is added the NaOH aqueous solution of 20wt%, stir 10min, obtain solution A; Wherein the mass ratio of phenol and the NaOH aqueous solution is 5:1;
2) in solution A, drip 37wt% formalin, stir 10min;
Room temperature is down to after being slowly warming up to 75 DEG C of maintenance 1h; Regulate pH to be 7 with the watery hydrochloric acid of 2mol/L, vacuum drying under 45 DEG C of conditions, obtains phenolic aldehyde performed polymer B; Wherein solution A and formalin mass ratio are 1:1.4;
3) in ethanol, add polyethers F127, be stirred to polyethers F127 and dissolve, obtain solution C; Wherein the mass ratio of ethanol and polyethers F127 is 0.03:1;
4) add in solution C by above-mentioned phenolic aldehyde performed polymer B, wherein the mass ratio of B and C is 1:0.3; Mixed liquor constant temperature under 50 DEG C of conditions stirs after 5h, slow dropping carbamide mixed solution, the mol ratio of melamine and formaldehyde is 8:1, carbamide mixed solution and B, C mixture quality are than being 1:3, the hydrochloric acid solution reusing 2mol/L regulates pH to be that at 5.5,50 DEG C, constant temperature stirs 2h; Obtaining glue is D;
5) getting glue D is injected in polyurethane sponge, and the volume ratio of glue D and polyurethane sponge is 1:2(ml/cm
3); With glass bar extruding polyurethane sponge in bubble, glue is filled macropore space, after filling at room temperature by sponge in air 20-40 hour, obtain sponge E;
6) sponge E is placed in the tube furnace of nitrogen atmosphere protection, with 2 DEG C/min ramp to 550 DEG C, sponge E is placed 3h under 550 DEG C of conditions, after naturally cooling to room temperature, obtain netted nitrogenous Carbon Materials.
2. the preparation method of netted nitrogenous carbon adsorbent material according to claim 1, wherein, getting 2.5ml glue D in step 5), to be injected into volume be 5cm
3polyurethane sponge in.
3. the preparation method of netted nitrogenous carbon adsorbent material according to claim 1, wherein, in step 6) this step heat up and in temperature-fall period the constant flow of nitrogen at 70ml/min.
4. the netted nitrogenous carbon adsorbent material that obtains of preparation method described in claim 1.
5. the application in water in antibiotic removed by netted nitrogenous carbon adsorbent material described in claim 4.
6. apply according to claim 5, wherein said antibiotic is Ciprofloxacin Hydrochloride.
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| CN108240923A (en) * | 2016-12-27 | 2018-07-03 | 中国科学院宁波城市环境观测研究站 | A kind of air sampling sponge and preparation method thereof |
| CN107597143A (en) * | 2017-09-25 | 2018-01-19 | 东华大学 | A kind of metal nanoparticle is uniformly embedded into the controllable method for preparing of the elctro-catalyst of mesoporous carbon spheres internal structure |
| CN111774033B (en) * | 2020-06-08 | 2023-03-21 | 天津科技大学 | Preparation method and application of easily-recycled adsorption material with waste polyurethane as base material |
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| CN101497019A (en) * | 2009-01-19 | 2009-08-05 | 中国科学院山西煤炭化学研究所 | Carbon dioxide adsorption material in high-temperature flue gas as well as production method and use |
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| CN101497019A (en) * | 2009-01-19 | 2009-08-05 | 中国科学院山西煤炭化学研究所 | Carbon dioxide adsorption material in high-temperature flue gas as well as production method and use |
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