CN104445193A - Branch and leaf porous carbon with function of removing degradation-resistant organic pollutant effluent 2,4,6-trichlorophenol as well as preparation method and application thereof - Google Patents
Branch and leaf porous carbon with function of removing degradation-resistant organic pollutant effluent 2,4,6-trichlorophenol as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses branch and leaf porous carbon with a function of removing degradation-resistant organic pollutant effluent 2,4,6-trichlorophenol as well as a preparation method and an application thereof. The preparation method comprises the following steps: preparing branch and leaf biomass carbon, carrying out grinding and screening, activating by a KOH solution at a temperature of 800 DEG C under the condition of nitrogen protection, and carbonizing at a constant temperature for 2 hours to obtain the branch and leaf porous carbon. A large amount of tests are carried out to screen the preparation method of the branch and leaf porous carbon, and the test results show that the branch and leaf porous carbon has a removal effect above 95% for the degradation-resistant organic pollutant effluents, especially the 2,4,6-trichlorophenol effluent, has important application value to treat the degradation-resistant organic pollutant effluents, is capable of promoting the recycle of the agricultural waste and is significant for the environment protection.
Description
Technical field
The present invention relates to a kind of porous charcoal, there is branches and leaves porous charcoal removing the trichlorophenol effect of difficult degradation organic polluting water 2,4,6 and preparation method thereof and application
Background technology
The object of the invention is the pollution in order to solve Organic Chemicals In Groundwater.The preliminary investigation of the Chinese Academy of Sciences to Beijing-tianjin-tangshan Area Organic Contamination of Groundwater thing shows, in this area's underground water, organism kinds reaches 133 kinds.Organic pollutant content in underground water is very micro-, but much organism toxicity is very large, is enough to cause various health problem.After organic pollutant enters aeration zone and waterbearing stratum, not only its residue can maintain tens of and even upper a century, chronic pollution environment, and its intermediates also pollutes the environment, and some intermediate product even has larger toxicity.The Organic Contamination of Groundwater things such as arene, halogenated hydrocarbon, agricultural chemicals, quite a few is " three cause thing ".For this reason, in external drinking water standard, organic constituent index is considerably beyond inorganic component index.Such as, in the compulsory index of U.S.'s standard in 1996, organic constituent accounts for 64, and inorganic component only accounts for 24.China's drinking water standard organic constituent index of 1985 only has 5, far less than developed country.
2,4,6 trichlorophenols are Typical Representatives of difficult degradation toxic compounds, one of reason being into environmental pollution, and the U.S., European Union and China etc. are all classified as priority pollutants.2,4,6 trichlorophenols are a kind of sterilant, are widely used in agricultural chemicals manufacture, papermaking, dyeing, and its toxicity is large, and difficult for biological degradation, has three and cause effect and genetoxic.2,4,6 trichlorophenols solubleness in water surrounding is higher, easily remains in the environment.The ordinary method of process chlorophenol pollutant has biological process, chemical method and Physical.Wherein, active carbon adsorption has economy, effectively and the advantage such as no coupling product problem.
The preparation of gac is the carbonaceous material based on charcoal in consisting of activating element, makes it become porous material to carry out.Raw material prepared by early activity charcoal generally adopts timber but enriches cheap coal preparation because transferring to again after its limited source, welding by storage, and replaces wood activated charcoal gradually.At present, along with energy problem is more and more serious, people start to find coal alternative materials, and the exploitation of the activated carbon raw material that low cost, source are extensively, performance is high receives the concern of people gradually.Resource-based cycling and reutilization theory is in recent years increasingly extensive with the research that agroforestry rejected material and polymeric scrap material etc. prepare gac for raw material.
Therefore, necessaryly on the basis of prior art, make full use of agricultural wastes, turn waste into wealth, exploitation one has removes difficult degradation organic polluting water 2,4, and 6 trichlorophenols, have the novel porous charcoal of vital role to environment protection.
Summary of the invention
Goal of the invention: the object of the invention is to make full use of agricultural wastes branches and leaves, turn waste into wealth, one is provided can effectively to remove difficult degradation organic polluting water, especially effectively 2 can be removed, 4, the branches and leaves porous charcoal of 6 trichlorophenols, another object of the present invention is to provide the preparation method of branches and leaves porous charcoal, and process 2,4, the method for 6 trichlorophenols.
Technical scheme: for realizing above object, the technical scheme that the present invention takes is:
One has the branches and leaves porous charcoal removing the trichlorophenol effect of difficult degradation organic polluting water 2,4,6, and it prepares by the following method:
First dry branches and leaves are shattered, then under the protection of nitrogen, under 450 ° of C conditions, constant temperature carbonizes 3 hours, obtain branches and leaves biomass charcoal, again branches and leaves biomass charcoal is ground, cross 200 ~ 300 mesh sieves, then branches and leaves biomass charcoal is immersed in KOH solution and activates 24 ~ 48 hours, taking-up is placed in baking oven and dries, then at 700 ~ 900 ° of C and under having the condition of nitrogen protection, the biomass charcoal activated through KOH is placed on tube furnace constant temperature charing 1 ~ 3h, first rinse with rare HCl after charing, clean with distilled water again, finally place and dry in an oven, grinding, obtain branches and leaves porous charcoal.
Preferably, above-described have the branches and leaves porous charcoal removing the trichlorophenol effect of difficult degradation organic polluting water 2,4,6, and it prepares by the following method:
First shattered by dry branches and leaves, then under the protection of nitrogen, under 450 ° of C conditions, constant temperature carbonizes 3 hours, obtains branches and leaves biomass charcoal, then is ground by branches and leaves biomass charcoal, crosses 200 mesh sieves, then biomass charcoal is immersed in 5molL
-1activate 24 hours in KOH solution, take out and be placed in 105 ° of C baking ovens and dry, then under having the condition of nitrogen protection at 800 ° of C, the branches and leaves biomass charcoal activated is placed on tube furnace constant temperature carbonizes 2 h through KOH, after charing, first use 0.1 mol L
-1hCl rinses, then with distilled water cleaning, is finally placed in 105 ° of C baking ovens and dries, and grinding, obtains branches and leaves porous charcoal; Described biomass charcoal and 5molL
-1the mass volume ratio of KOH solution is 1:2 ~ 5.
The shaker test of branches and leaves charcoal carbonization condition:
(1) branches and leaves biomass charcoal and 5molL
-1the screening of the different impregnating ratio of KOH solution
Get branches and leaves biomass charcoal and 5molL respectively
-1kOH solution is 1:1,2:1,3:1,4:1,5:1 in impregnating ratio; carry out activation 24 hours; taking-up is placed in 105 ° of C baking ovens and dries; then at 800 ° of C and under having the condition of nitrogen protection; the branches and leaves biomass charcoal activated through KOH is placed on tube furnace constant temperature and carbonizes 2 h, after charing, first use 0.1 mol L
-1hCl rinses, then with distilled water cleaning, is finally placed in 105 ° of C baking ovens and dries, and grinding, obtains 4 kinds of branches and leaves porous charcoal; Taking 0.2g branches and leaves porous charcoal respectively adds in 2,4, the 6 trichlorophenol 250mL solution that concentration is 80 mg/L respectively, the pH of regulator solution is about 5.2, is in 25 ° of C isothermal vibration devices in water temperature, concussion process 2h, centrifugal membrane filtration, 2,4 are surveyed in supernatant liquor by liquid chromatography (PE, USA), 6 trichlorophenol concentration, branches and leaves porous charcoal obtained under different impregnating ratio condition is to 2, and the adsorption effect of 4,6 trichlorophenols as shown in Figure 1.Result shows, when impregnating ratio is 3:1, and 2,4, the clearance of 6 trichlorophenols is the highest.Therefore, the impregnating ratio that the present invention selects is 3:1.
(2) screening of the carbonization temperature of branches and leaves porous charcoal
Get branches and leaves biomass charcoal and 5molL
-1kOH solution is when impregnating ratio 3:1; carry out activation 24 hours, taking-up is placed in 105 ° of C baking ovens dries, then under the protection of nitrogen; under the condition of 650 ° of C, 700 ° of C, 750 ° of C, 800 ° of C, 900 ° of C, 1000 ° of C, constant temperature carbonizes 1 to 3 hour respectively, first uses 0.1 mol L after charing
-1hCl rinses, then with distilled water cleaning, is finally placed in 105 ° of C baking ovens and dries, and grinding, obtains 5 kinds of branches and leaves porous charcoal; Take each 0.2g of branches and leaves biomass charcoal sample carbonized at 650 ° of C, 700 ° of C, 750 ° of C, 800 ° of C, 900 ° of C and 1000 ° of C temperature respectively, add that concentration is 80 mg/L respectively to 2,4, in 6 trichlorophenol 250mL solution, the pH of regulator solution is about 5.2, be in 25 ° of C isothermal vibration devices in water temperature, concussion process 2h, centrifugal membrane filtration, with liquid chromatography (PE, USA) 2 are surveyed in supernatant liquor, 4,6 trichlorophenol concentration, branches and leaves porous charcoal obtained under different carbonization temperature condition is to 2, the adsorption effect of 4,6 trichlorophenols as shown in Figure 2.Result shows.Under the carbonization temperature of 800 ° of C, the clearance of 2,4,6 trichlorophenols is the highest.Therefore, the carbonization temperature that the present invention selects is 800 ° of C.
(3) screening of the different carbonization time (preferred result 800 ° of C) of branches and leaves porous charcoal
Get branches and leaves biomass charcoal and 5molL
-1kOH solution is when impregnating ratio 3:1; carry out activation 24 hours; taking-up is placed in 105 ° of C baking ovens and dries; then under the protection of nitrogen; then at 800 ° of C and under having the condition of nitrogen protection; the branches and leaves biomass charcoal activated through KOH is placed on tube furnace constant temperature charing 30min, 60min, 90min, 2h respectively, after charing, first uses 0.1 mol L
-1hCl rinses, then with distilled water cleaning, is finally placed in 105 ° of C baking ovens and dries, and grinding, obtains 4 kinds of branches and leaves porous charcoal; The 0.2g branches and leaves porous charcoal taking constant temperature charing 30min, 60min, 90min, 2h is respectively added in 2,4, the 6 trichlorophenol 250mL solution that concentration is 80 mg/L respectively, the pH of regulator solution is about 5.2, is in 25 ° of C isothermal vibration devices in water temperature, concussion process 2h, centrifugal membrane filtration, 2,4 are surveyed in supernatant liquor by liquid chromatography (PE, USA), 6 trichlorophenol concentration, the branches and leaves porous charcoal that different carbonization time obtains is to 2, and the adsorption effect of 4,6 trichlorophenols as shown in Figure 3.Result shows, when carbonization time is 2h, and 2,4, the clearance of 6 trichlorophenols is the highest.Therefore, the carbonization time that the present invention selects is 2h.
The preparation method with the branches and leaves porous charcoal removing the trichlorophenol effect of difficult degradation organic polluting water 2,4,6 of the present invention, it comprises the following steps:
First dry branches and leaves shatter, and then under the protection of nitrogen, under 450 ° of C conditions, constant temperature carbonizes 3 hours, obtains branches and leaves biomass charcoal.Again branches and leaves biomass charcoal is ground, cross 200 mesh sieves, then biomass charcoal is immersed in 5molL
-124 hours are activated in KOH solution; and every 8 h stir 1min, take out and are placed in 105 ° of C baking ovens and dry, then at 800 ° of C and under having the condition of nitrogen protection; the branches and leaves biomass charcoal activated through KOH is placed on tube furnace constant temperature and carbonizes 2 h, after charing, first use 0.1 mol L
-1hCl rinses, then with distilled water cleaning, is finally placed in 105 ° of C baking ovens and dries, and grinding, obtains branches and leaves porous charcoal; Described biomass charcoal and 5molL
-1the mass volume ratio of KOH solution is 1:2 ~ 5.
Provided by the invention have the application of branches and leaves porous charcoal in preparation removal organic waste water 2,4,6 trichlorophenol preparation of removing the trichlorophenol effect of difficult degradation organic polluting water 2,4,6.
Of the present invention have removal difficult degradation organic polluting water 2,4, the branches and leaves porous charcoal of 6 trichlorophenol effects removes organic waste water 2 in preparation, application in 4,6 trichlorophenol preparations, method during concrete process process waste water is, the consumption of branches and leaves porous charcoal is 0.8 ~ 1.0 g/L, during process, the pH value of regulator solution is 3 to 9, and during process, temperature is 25 to 45 ° of C, and the treatment time is 2 ~ 3 h.
branches and leaves porous charcoal removes 2,4,6 trichlorophenol processing parameter screening experiments
(1) pH value of different solutions is to 2, the screening of the clearance of 4,6 trichlorophenols
Take 0.2g 800 ° of C respectively and carbonize the branches and leaves porous charcoal prepared, add that concentration is 80 mg/L respectively to 2,4, in 6 trichlorophenol 250mL solution, the pH of regulator solution is 3,5.2,7,9, is in 25 ° of C isothermal vibration devices in water temperature, concussion process 2h, centrifugal membrane filtration, with liquid chromatography (PE, USA) 2 are surveyed in supernatant liquor, 4,6 trichlorophenol concentration, the branches and leaves porous charcoal that different carbonization time obtains is to 2, the adsorption effect of 4,6 trichlorophenols as shown in Figure 4.Result shows, when pH value is 5.2, and 2,4, the clearance of 6 trichlorophenols is best.Therefore, the optimum pH of the solution of the present invention's selection is 5.2.
(2) different concns 2, the screening of the clearance of 4,6 trichlorophenols
Take 0.2g 800 ° of C respectively and carbonize the branches and leaves porous charcoal prepared, add to respectively concentration be 50,80,100,150mg/L 2,4, in 6 trichlorophenol 250mL solution, the pH of regulator solution is 5.2, is in 25 ° of C isothermal vibration devices in water temperature, concussion process 2h, centrifugal membrane filtration, with liquid chromatography (PE, USA) 2 are surveyed in supernatant liquor, 4,6 trichlorophenol concentration, the branches and leaves porous charcoal that different carbonization time obtains is to 2, the adsorption effect of 4,6 trichlorophenols as shown in Figure 5.Result shows, when 2, when 4,6 trichlorophenol concentration are 80mg/L, and 2,4, the clearance of 6 trichlorophenols is best.Therefore, the present invention selects the optimal concentration for the treatment of soln to be 80mg/L.
(3) different treatment temperature is to 2, the screening of the clearance of 4,6 trichlorophenols
Taking 0.2g 800 ° of C respectively and carbonize the branches and leaves porous charcoal prepared, is 2,4 of 80 mg/L to concentration, in 6 trichlorophenol 250mL solution, the pH of regulator solution is 5.2, regulates water temperature to be 25 ° of C, 35 ° of C, 45 ° of C in isothermal vibration device respectively, concussion process 2h, centrifugal membrane filtration, with liquid chromatography (PE, USA) 2 are surveyed in supernatant liquor, 4,6 trichlorophenol concentration, different treatment temperature is to 2, the adsorption effect of 4,6 trichlorophenols as shown in Figure 6.Result shows, the treatment effect of three kinds of temperature is close, all reaches more than 90%, and consider easy to operate and reduce energy consumption consideration, the present invention selects the Optimal Temperature for the treatment of soln to be 25 ° of C.
As preferred method, method when the present invention disposes of sewage is: the consumption of branches and leaves porous charcoal is 0.8g/L, and during process, the pH value of regulator solution is 5.2, and during process, temperature is 25 ° of C, and the treatment time is 2 h.
Accompanying drawing explanation
Fig. 1 branches and leaves biomass charcoal and 5molL
-1the screening broken line graph of the different impregnating ratio of KOH solution.
Fig. 2 is the screening broken line graph of the carbonization temperature of branches and leaves porous charcoal.
Fig. 3 is branches and leaves porous charcoal different carbonization time screening broken line graph.
Fig. 4 be the pH value of different solutions to 2, the clearance experimental curve diagram of 4,6 trichlorophenols.
Fig. 5 is branches and leaves porous charcoal process different concns 2,4, the clearance experimental curve diagram of 6 trichlorophenols.
Fig. 6 be different treatment temperature to 2, the clearance experimental curve diagram of 4,6 trichlorophenols.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, concrete material proportion, processing condition and result thereof described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
Embodiment 1
Have the branches and leaves porous charcoal removing the trichlorophenol effect of difficult degradation organic polluting water 2,4,6, it prepares by the following method:
First dry branches and leaves shatter, and then under the protection of nitrogen, under 450 ° of C conditions, constant temperature carbonizes 3 hours, obtains branches and leaves biomass charcoal, then are ground by branches and leaves biomass charcoal, cross 200 mesh sieves, get branches and leaves biomass charcoal and 5molL
-1the mass volume ratio of KOH solution is 1:3, by branches and leaves biomass charcoal at 5molL
-1soak 24 h in KOH solution and carry out activation treatment, and every 8 h stir 1min, are then placed in 105 ° of C baking ovens and dry, then at 800 ° of C and under having the condition of nitrogen protection, tube furnace constant temperature carbonizes 2 h, with 0.1 mol L after charing
-1hCl washes 5 times, and distilled water cleans, and dries in 105 ° of C baking ovens, and grinding, obtains branches and leaves porous charcoal.
Embodiment 2
Have the branches and leaves porous charcoal removing the trichlorophenol effect of difficult degradation organic polluting water 2,4,6, it prepares by the following method:
First shattered by dry branches and leaves, then under the protection of nitrogen, under 450 ° of C conditions, constant temperature carbonizes 3 hours, obtains branches and leaves biomass charcoal.Again branches and leaves biomass charcoal is ground, cross 300 mesh sieves, get branches and leaves biomass charcoal and 5molL
-1the mass volume ratio of KOH solution is 1:2, by branches and leaves biomass charcoal at 5molL
-1soak 48 h in KOH solution and carry out activation treatment, and every 8 h stir 1min, are then placed in 105 ° of C baking ovens and dry, then at 1000 ° of C and under having the condition of nitrogen protection, tube furnace constant temperature carbonizes 3 h, with 0.1 mol L after charing
-1hCl washes 5 times, and distilled water cleans, and dries in 105 ° of C baking ovens, and grinding, obtains branches and leaves porous charcoal.
Embodiment 32,4,6 trichlorophenols remove test
To take more than 0.4g be embodiment 1 and implement the 2 branches and leaves porous charcoal prepared, be added to that concentration is 80 mg/L respectively 2,4, in 6 trichlorophenol 500mL solution, the pH of regulator solution is about 5.2, is in 25 ° of C isothermal vibration devices in water temperature, concussion process 2h, centrifugal membrane filtration, with liquid chromatography (PE, USA) 2,4,6 trichlorophenol concentration in supernatant liquor are surveyed, test-results shows, 2,4,6 trichlorophenol clearances are respectively 99.72% and 95.08%.
Shown that by above experimental result the porous carbon material that the branches and leaves that the present invention uses are produced is conducive to agricultural wastes of dissolving; promote the recycle of resource, and 2 in organic polluting water can be removed, 4; 6 trichlorophenols, significant to environment protection, there is good application value.
Above embodiment is only for illustrating technical conceive of the present invention and feature; its object is to allow person skilled in the art understand content of the present invention and to be implemented; can not limit the scope of the invention with this; all equivalences done according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention.
Claims (6)
1. one kind has the branches and leaves porous charcoal removing the trichlorophenol effect of difficult degradation organic polluting water 2,4,6, and it is characterized in that, it prepares by the following method:
First dry branches and leaves are shattered, then under the protection of nitrogen, under 450 ° of C conditions, constant temperature carbonizes 3 hours, obtain branches and leaves biomass charcoal, the grinding of branches and leaves biomass charcoal will be got again, cross 200 ~ 300 mesh sieves, then branches and leaves biomass charcoal is immersed in KOH solution and activates 24 ~ 48 hours, taking-up is placed in baking oven and dries, then at 800 ~ 1000 ° of C and under having the condition of nitrogen protection, the branches and leaves biomass charcoal activated through KOH is placed on tube furnace constant temperature charing 2 ~ 3h, first rinse with HCl after charing, clean with distilled water again, finally place and dry in an oven, grinding, obtain branches and leaves porous charcoal.
2. according to claim 1 have the branches and leaves porous charcoal removing the trichlorophenol effect of difficult degradation organic polluting water 2,4,6, and it is characterized in that, it prepares by the following method:
First shattered by dry branches and leaves, then under the protection of nitrogen, under 450 ° of C conditions, constant temperature carbonizes 3 hours, obtains branches and leaves biomass charcoal, then is ground by branches and leaves biomass charcoal, crosses 200 mesh sieves, then biomass charcoal is immersed in 5molL
-1activate 24 hours in KOH solution, take out and be placed in 105 ° of C baking ovens and dry, then under having the condition of nitrogen protection at 800 ° of C, the branches and leaves biomass charcoal activated is placed on tube furnace constant temperature carbonizes 2 h through KOH, after charing, first use 0.1 mol L
-1hCl rinses, then with distilled water cleaning, is finally placed in 105 ° of C baking ovens and dries, and grinding, obtains branches and leaves porous charcoal; Described biomass charcoal and 5molL
-1the mass volume ratio of KOH solution is 1:2 ~ 5.
3. the preparation method with the branches and leaves porous charcoal removing the trichlorophenol effect of difficult degradation organic polluting water 2,4,6 according to claim 2, is characterized in that, comprise the following steps:
First shattered by dry branches and leaves, then under the protection of nitrogen, under 450 ° of C conditions, constant temperature carbonizes 3 hours, obtains branches and leaves biomass charcoal, then is ground by branches and leaves biomass charcoal, crosses 200 mesh sieves, then biomass charcoal is immersed in 5molL
-124 hours are activated in KOH solution; and every 8 h stir 1min, take out and are placed in 105 ° of C baking ovens and dry, then at 800 ° of C and under having the condition of nitrogen protection; the branches and leaves biomass charcoal activated through KOH is placed on tube furnace constant temperature and carbonizes 2 h, after charing, first use 0.1 mol L
-1hCl rinses, then with distilled water cleaning, is finally placed in 105 ° of C baking ovens and dries, and grinding, obtains branches and leaves porous charcoal; Described biomass charcoal and 5molL
-1the mass volume ratio of KOH solution is 1:3.
4. having described in claim 1 or 2 removes the application of branches and leaves porous charcoal in preparation removal organic waste water 2,4,6 trichlorophenol preparation of difficult degradation organic polluting water 2,4,6 trichlorophenol effect.
5. according to claim 4 have removal difficult degradation organic polluting water 2,4, the branches and leaves porous charcoal of 6 trichlorophenol effects removes the application in organic waste water 2,4,6 trichlorophenol preparation in preparation, it is characterized in that, during process waste water, the consumption of branches and leaves porous charcoal is 0.8 ~ 1.0 g/L, and during process, the pH value of regulator solution is 3 to 9, during process, temperature is 25 to 45 ° of C, and the treatment time is 2 ~ 3 h.
6. according to claim 5 have removal difficult degradation organic polluting water 2,4, the branches and leaves porous charcoal of 6 trichlorophenol effects removes organic waste water 2 in preparation, application in 4,6 trichlorophenol preparations, is characterized in that, the consumption of branches and leaves porous charcoal is 0.8g/L, during process, the pH value of regulator solution is 5.2, and during process, temperature is 25 to 45 ° of C, and the treatment time is 2 h.
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| CN201410728552.4A CN104445193A (en) | 2014-12-03 | 2014-12-03 | Branch and leaf porous carbon with function of removing degradation-resistant organic pollutant effluent 2,4,6-trichlorophenol as well as preparation method and application thereof |
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| CN201410728552.4A CN104445193A (en) | 2014-12-03 | 2014-12-03 | Branch and leaf porous carbon with function of removing degradation-resistant organic pollutant effluent 2,4,6-trichlorophenol as well as preparation method and application thereof |
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| CN111841497A (en) * | 2020-07-30 | 2020-10-30 | 盐城工学院 | Modified loofah sponge-based biomass charcoal and preparation method and application thereof |
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| CN102050444A (en) * | 2009-10-28 | 2011-05-11 | 周军 | Method for producing active carbon by using withered grass and fallen leaves |
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| US20030230194A1 (en) * | 2002-06-17 | 2003-12-18 | Michael Heine | Activated carbon fibers and related methods for the use and production thereof and of making protective clothing and a filter module |
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| CN104888708A (en) * | 2015-07-02 | 2015-09-09 | 黑龙江大学 | Corn bran-based three-dimensional multi-level pore structure carbon material and preparation method thereof |
| CN104888708B (en) * | 2015-07-02 | 2017-06-27 | 黑龙江大学 | Corn scytoblastema three-dimensional multistage pore structure carbon material and preparation method thereof |
| CN111841497A (en) * | 2020-07-30 | 2020-10-30 | 盐城工学院 | Modified loofah sponge-based biomass charcoal and preparation method and application thereof |
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Application publication date: 20150325 |