CN105664848A - Preparation method of lignin hierarchical porous carbon material with endellite as template - Google Patents
Preparation method of lignin hierarchical porous carbon material with endellite as template Download PDFInfo
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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Abstract
The invention relates to a preparation method of a lignin hierarchical porous carbon material with endellite as a template, and belongs to the technical field of environment function material preparation. The abundant natural mineral endellite nanotube which is cheap and easily available is used as a template; through a liquid impregnation method, sodium lignosulfonate and endellite are mixed; through calcination treatment, a template carbon material is preliminarily obtained and contains many mesopores and macropores; through activation of potassium hydroxide, lots of micropores are prepared, and the hierarchical porous carbon material is further obtained. The hierarchical porous carbon material prepared by the method is successively applied in efficient separation of tetracycline and chloramphenicol in a water environment, and has excellent regenerability.
Description
Technical field
The preparation method that the present invention relates to the lignin-base multi-stage porous carbon material that a kind of galapectite is template, belongs to technical field of environment function material preparation.
Background technology
At present, antibiotic is widely used in the treatment and prevention of disease in the fields such as agricultural, animal husbandry, disease treatment. But major part antibiotic is not owing to being transferred in environment directly with Excreta by organism metabolism, enables bacterial drug resistance to strengthen and ecosystem is had a negative impact. Nowadays, including many countries of China, antibiotic is detected continually in the water outlet of sewage treatment plant, surface water, subsoil water or even drinking water. Biological growth can be suppressed owing to organism is had serious toxic and side effects, long-term trace to take in accumulation in vivo by tetracycline, cause the imbalance of animal body normal flora, resistance reduction, the various disease of easy infection. Therefore, efficiently and effectively remove the antibiotic of residual in waste water, and then eliminate because resistant gene and resistant microorganism are evolved the crisis caused, be necessary and urgent.
Absorption method is for removing the antibiotic in water environment, oxidizing process, light solution, electrolysis and biological degradation method is included compared to other method for treating water, due to simple to operate, less costly, without destructive and toxic intermediates can be prevented effectively from, thus be considered as most suitable water technology. Being currently used for removing in water environment antibiotic adsorbent mainly has natural minerals, metal-oxide, material with carbon element and molecularly imprinted polymer, and wherein material with carbon element by extensive concern and is applied to sewage disposal owing to having the features such as the absorption property of high-specific surface area, abundant surface functional group, high chemical stability and excellence.
Material with carbon element mainly includes activated carbon, CNT, Graphene and carbon fiber etc., although material with carbon element is higher to antibiotic adsorbance relative to other adsorbents, but due to preparation process very complicated, relatively costly and adsorbance and the rate of adsorption can not meet the demand of present stage, thus design to prepare a kind of low cost, high efficiency material with carbon element necessary.
Multi-stage porous carbon material, owing to having different types of interconnective pore passage structure, so have the advantage of macropore, mesoporous and micropore simultaneously, and then demonstrates the absorption property of excellence. Macropore can form buffering reservoir and reduce the diffusion length to inner surface. Abundant mesoporous and micropore can provide relatively larger specific surface area and can reduce transport resistance, is conducive to adsorption process. At present, have the research work prepared in a large number about multi-stage porous carbon material, but the research being used in water environment by multi-stage porous carbon material antibiotic absorption almost without.
The preparation method of multi-stage porous carbon material mainly has template (hard template method and soft template method) and activation method (physical activation method and chemical activation method).Activation method is mainly for the manufacture of micropore and increases porosity, and conventional chemical activation reagent mainly has KOH, K2CO3With NaOH etc. and mainly have water vapour, CO for physical activation method2Deng. The Main Function of template be make mesoporous, but soft template method requires harshness due to experiment condition, the requirement of soft template structure is very accurate, largely limit the application of soft template method, for hard template, the selection of carbon source and hard mould agent is easier, and therefore relatively soft template method application is more extensive. But hard template method preparation process relates to a large amount of hard mould agent and (includes SBA-15, SBA-16 and KIT-6) removal, consider the synthesis cost of hard mould agent, therefore select a kind of environmental protection economy and the structure hard mould agent that meets demand is necessary.
Halloysite nanotubes is as the nanotube-shaped silicate clay mineral of many walls of a kind of abundance, there is the hollow tubular structure similar to CNT, high specific surface area, abundant mesoporous and micropore, excellent chemistry and thermally-stabilised, be desirable hard mould agent. The selecting of carbon source prepares no less important for multi-stage porous carbon material. Sodium lignin sulfonate, it is a large amount of a kind of side-products produced in paper industry, compared with including furfural, DVB with other carbon source, sodium lignin sulfonate possesses the advantages such as renewable, economy, environmental protection, has been widely studied for preparing activated carbon, carbon fiber and CNT etc.
Summary of the invention
The preparation method that it is an object of the invention to provide the lignin-base multi-stage porous carbon material that a kind of galapectite is template, and the lignin-base multi-stage porous carbon material prepared by the method is realized to tetracycline in water environment and chloromycetin quick, high efficiency separation.
The preparation method of lignin-base multi-stage porous carbon material of the present invention, be by purification process after natural minerals galapectite dipping with finite concentration lignin sulfonic acid sodium solution in, process and after high speed centrifugation through condition of negative pressure, reclaim overstory quality sodium sulfonate solution to recycle, after lower floor's solid is dried, under nitrogen atmosphere is protected, high-temperature calcination in tube furnace, product after calcining is soaked with HF to remove template galapectite, remove after completely until galapectite, repeatedly clean with the mixed solution of ethanol and distilled water, dry to constant weight, obtain the template material with carbon element being template with galapectite. by template material with carbon element and KOH with different mass ratio mixed grindings to after uniformly, high-temperature calcination under nitrogen atmosphere is protected in tube furnace, after being cooled to room temperature, add dilute hydrochloric acid and remove impurity, repeatedly clean with the mixed solution of ethanol and distilled water again, drying to constant weight obtains the lignin-base multi-stage porous carbon material being template with galapectite, by multiple characterization method, disclose the physicochemical characteristics of the lignin-base multi-stage porous carbon material being template with galapectite, utilize gained with galapectite be template lignin-base multi-stage porous carbon material carry out the Study on adsorption properties to tetracycline in water environment and chloromycetin.
The technical solution used in the present invention is specific as follows:
A kind of galapectite is the preparation method of the lignin-base multi-stage porous carbon material of template, carries out as steps described below:
(1) preparation of lignin-base template material with carbon element:
Liquid-phase impregnation process is utilized to prepare lignin-base template material with carbon element:
Weighing galapectite, join in hydrochloric acid solution, after reacting by heating, sucking filtration, a large amount of distilled water flushings, to neutral, dried, can be obtained the galapectite after purification process.
Wherein, the ratio of described galapectite and hydrochloric acid solution is 2-5g:10mL, and wherein the concentration of hydrochloric acid solution is 1-4mol/L;
Described reacting by heating condition is 40-80 DEG C of reaction 1-6h.
Galapectite after purification process is mixed with lignin sulfonic acid sodium solution; after mixture is stood under condition of negative pressure; high speed centrifugation is to reach closelypacked effect; then lower floor's solid is dried to constant weight to understand the mass loss in calcination process; after weighing, put into porcelain boat, be placed in tube furnace, under the protection of nitrogen atmosphere; after calcining, naturally cool to room temperature. Solid hydrofluoric acid dips after calcining is to remove hard template galapectite, to be removed completely after, with the mixed solution of a large amount of deionized waters and ethanol, (volume ratio of deionized water and ethanol is: 1:1-3:1) repeatedly clean, dry to constant weight, obtain the template material with carbon element (LTC) being template with galapectite.
By whether infrared test detection template is removed completely, if not finding inorganic constituents in collection of illustrative plates, namely it is believed that galapectite is removed completely.
Wherein, the mass ratio of the galapectite after described purification process and lignin sulfonic acid sodium solution is 1:3-5, and wherein sodium lignin sulfonate liquid quality fraction is 20%-40%;
Described being statically placed in when condition of negative pressure is-0.1-(-0.3) Mpa stands 2h-4h;
Described high speed centrifugation condition is the centrifugal 1.5h-2.5h of the rotating speed with 2000-4000r/min;
Described calcining concrete operations are that the programming rate with 3-7 DEG C/min is raised to 400-600 DEG C from room temperature and calcines 1h-3h at such a temperature;
The mass fraction of described Fluohydric acid. is 10%-20%.
(2) activation of template material with carbon element
After extremely uniform to the template material with carbon element after drying and solid potassium hydroxide mixed grinding; it is placed in nickel pot after cover lid; in tube furnace under nitrogen protection; after calcining; after naturally cooling to room temperature; the impurity such as the potassium carbonate generated in addition dilute hydrochloric acid removal course of reaction; then with the mixed solution of a large amount of deionized waters and ethanol, (deionized water with the volume ratio of ethanol is: 1:1-3:1) repeatedly clean to neutral; dry to constant weight, obtain lignin-base multi-stage porous carbon material (LTCA) being template with galapectite.
Wherein, described template material with carbon element and solid potassium hydroxide mass ratio are 1:3-1:4;
Described calcining concrete operations are that the programming rate with 3-7 DEG C/min is raised to 700 DEG C-900 DEG C from room temperature and calcines 1h-2h at such a temperature;
The concentration of described dilute hydrochloric acid is 2mol/L.
The technological merit of the present invention:
The present invention is with rich reserves, natural minerals halloysite nanotubes cheap and easy to get for template; Using industry byproduct sodium lignin sulfonate as carbon source, environmental protection, cheap, renewable; The method that hard template method combines with KOH activation method is utilized to prepare multi-stage porous carbon material, obtained product replicates the hollow tubular structure of galapectite, thus there is a large amount of macropore and meso-hole structure, a large amount of micropore is created again through KOH chemical activation method, thus preparing the multi-stage porous carbon material being interconnected, not only there is the specific surface area (2320m that comparison is high2/ g) and pore volume (1.342mL/g), and there is good heat stability and chemical stability, existence due to hierarchical porous structure, macropore can form buffering reservoir to reduce the diffusion length to interior surface, abundant micropore and mesoporous can provide relatively larger specific surface area and less transport resistance, cause that absorbability is excellent, it is successfully realized the efficient quick adsorption to tetracycline in water environment and chloromycetin, adsorbance is relatively big (during 298K, adsorbance to tetracycline is 1226.4mg/g, adsorbance to chloromycetin is 1022.8mg/g) rate of adsorption is very fast, regenerability is excellent simultaneously.
Accompanying drawing explanation
, LTCA(b Fig. 1: LTC(a)) scanning electron microscope (SEM) photograph;
Fig. 2: LTC (a), LTCA(b) transmission electron microscope picture;
Fig. 3: SLS, the infrared spectrogram of LTC, LTCA;
The N of Fig. 4: LTC and LTCA2Adsorption-desorption figure (a) and graph of pore diameter distribution (b, c), (b) and (c) is the graph of pore diameter distribution of LTC and LTCA respectively;
Fig. 5: under 298K, the impact on LTCA tetracycline adsorption (a) He chloromycetin (b) of the pH value of solution;
Fig. 6: the LTCA adsorption isotherm matched curve figure to tetracycline (a) in water environment He chloromycetin (b);
Fig. 7: LTCA to the adsorption dynamics adsorption kinetics figure of tetracycline in water environment;
Fig. 8: LTCA to the adsorption dynamics adsorption kinetics figure of chloromycetin in water environment.
Detailed description of the invention
Below in conjunction with being embodied as example, the present invention will be further described.
Embodiment 1:
(1) preparation of lignin-base template material with carbon element
The present invention utilizes liquid-phase impregnation process to prepare lignin-base template material with carbon element, weigh 2g galapectite, join in the hydrochloric acid solution that 100mL concentration is 1mol/L, heating is to 40 DEG C, reaction 1h, sucking filtration, a large amount of distilled water flushings are to neutral, dry, obtain the galapectite after purification, galapectite after 2g purification process is mixed with the lignin sulfonic acid sodium solution that 6g mass fraction is 20%, mixture is statically placed under condition of negative pressure (-0.1Mpa) after 2h, with the rotating speed high speed centrifugation 1.5h of 2000r/min to reach closelypacked effect, then lower floor's solid is dried to constant weight, porcelain boat is put into after weighing, it is placed in tube furnace, under the protection of nitrogen atmosphere, after being raised to 400 DEG C with the programming rate of 3 DEG C/min from room temperature and calcine 1h at such a temperature, naturally cool to room temperature. at 400 DEG C, the solid mass fraction after calcining is that 10% hydrofluoric acid dips is to remove hard template galapectite, to be removed completely after, repeatedly clean with the mixed solution of the deionized water that a large amount of volume ratios are 1:1 and ethanol, dry to constant weight, obtain the template material with carbon element (LTC) being template with galapectite.
(2) activation of template material with carbon element
After extremely uniform with solid potassium hydroxide 3g mixed grinding for the template material with carbon element 1g after drying; it is placed in nickel pot after cover lid; in tube furnace under nitrogen protection; after being raised to 700 DEG C with the programming rate of 3 DEG C/min from room temperature and calcine 1h at such a temperature; after naturally cooling to room temperature; the impurity such as the potassium carbonate generated in the dilute hydrochloric acid removal course of reaction of addition 2mol/L; then repeatedly clean to neutrality with the mixed solution of a large amount of deionized waters and ethanol; dry to constant weight, obtain lignin-base multi-stage porous carbon material (LTCA) being template with galapectite.
Embodiment 2:
(1) preparation of lignin-base template material with carbon element
Liquid-phase impregnation process is utilized to prepare lignin-base template material with carbon element, weigh 5g galapectite, join in the hydrochloric acid solution that 100mL concentration is 4mol/L, heating is to 80 DEG C, reaction 6h, sucking filtration, a large amount of distilled water flushings are to neutral, dry, obtain the galapectite after purification, galapectite after 2g purification process is mixed with the lignin sulfonic acid sodium solution that 10g mass fraction is 40%, mixture is statically placed under condition of negative pressure (-0.3Mpa) after 4h, with the rotating speed high speed centrifugation 2.5h of 4000r/min to reach closelypacked effect, then lower floor's solid is dried to constant weight, porcelain boat is put into after weighing, it is placed in tube furnace, under the protection of nitrogen atmosphere, with 7oThe programming rate of C/min is raised to 600 from room temperatureoAfter C at such a temperature calcining 3h, naturally cool to room temperature.600oUnder C, the solid mass fraction after calcining is that 20% hydrofluoric acid dips is to remove hard template galapectite, band is removed after completely, repeatedly clean with the mixed solution of a large amount of deionized waters and ethanol, dry to constant weight, obtain the template material with carbon element (LTC) being template with galapectite.
(2) activation of template material with carbon element
By the template material with carbon element after drying with the mass ratio of 1:4 and solid potassium hydroxide mixed grinding to after uniformly, being placed in nickel pot after cover lid, with 7 in tube furnace under nitrogen protectionoThe programming rate of C/min is raised to 900 from room temperatureoAfter C at such a temperature calcining 2h, after naturally cooling to room temperature, the impurity such as the potassium carbonate generated in the dilute hydrochloric acid removal course of reaction of addition 2mol/L, then repeatedly clean to neutrality with the mixed solution of a large amount of deionized waters and ethanol, dry to constant weight, obtain lignin-base multi-stage porous carbon material (LTCA) being template with galapectite.
Embodiment 3:
(1) preparation of lignin-base template material with carbon element
Liquid-phase impregnation process is utilized to prepare lignin-base template material with carbon element, weigh 3g galapectite, join in the hydrochloric acid solution that 100mL concentration is 3mol/L, heating is to 60 DEG C, reaction 4h, sucking filtration, a large amount of distilled water flushings are to neutral, dry, obtain the galapectite after purification, galapectite after 2g purification process is mixed with the lignin sulfonic acid sodium solution that 8g mass fraction is 30%, mixture is statically placed under condition of negative pressure (-0.2Mpa) after 3h, with the rotating speed high speed centrifugation 2h of 3000r/min to reach closelypacked effect, then lower floor's solid is dried to constant weight, porcelain boat is put into after weighing, it is placed in tube furnace, under the protection of nitrogen atmosphere, with 5oThe programming rate of C/min is raised to 500 from room temperatureoAfter C at such a temperature calcining 2h, naturally cool to room temperature. 500oUnder C, the solid mass fraction after calcining is that 15% hydrofluoric acid dips is to remove hard template galapectite, band is removed after completely, repeatedly clean with the mixed solution of a large amount of deionized waters and ethanol, dry to constant weight, obtain the template material with carbon element (LTC) being template with galapectite.
(2) activation of template material with carbon element
By the template material with carbon element after drying with the mass ratio of 1:4 and solid potassium hydroxide mixed grinding to after uniformly, being placed in nickel pot after cover lid, with 5 in tube furnace under nitrogen protectionoThe programming rate of C/min is raised to 800 from room temperatureoAfter C at such a temperature calcining 2h, after naturally cooling to room temperature, the impurity such as the potassium carbonate generated in the dilute hydrochloric acid removal course of reaction of addition 2mol/L, then repeatedly clean to neutrality with the mixed solution of a large amount of deionized waters and ethanol, dry to constant weight, obtain lignin-base multi-stage porous carbon material (LTCA) being template with galapectite.
Fig. 1 is LTC(a prepared by the present invention), LTCA(b) scanning electron microscope (SEM) photograph; As can be seen from Figure 1: the scanning electron microscope (SEM) photograph of LTC clearly shows many intensive tubular conduit structures, these tubular conduit structures stay after removing HNTs; Novel is that the LTCA after overactivation alters a great deal on surface topography, occur in that interconnective carbon nanosheet is probably and with KOH, priming reaction is at high temperature occurred by the tube wall of LTC, progressively making tube wall thinning, meanwhile, pipeline still exists for connecting carbon nanosheet. Thus infer that the shape characteristic of material with carbon element is produced considerable influence by use and the activation of potassium hydroxide of galapectite.
Fig. 2 is LTC (a), LTCA(b prepared by the present invention) transmission electron microscope picture;As can be seen from Figure 2: galapectite presents nanoscale hollow tubular structure well; Obviously, intensive tubular conduit structure being can be observed in the transmission electron microscope picture of LTC, mainly the structure of HNTs is replicated and causes, and this is consistent with the scanning electron microscope (SEM) photograph of LTC; As for LTCA, after overactivation pipeline shrink, the thinning formation carbon nanosheet of tube wall, in powerful transmission electron microscope picture it is observed that due to activation formed a large amount of micropores, with N2The result of adsorption experiment is consistent.
Fig. 3 is SLS(sodium lignin sulfonate), the infrared spectrogram of LTC, LTCA; As can be seen from Figure 3: in the spectrogram of SLS, 3410cm-1 place's broad peak is-OH stretching vibration peak; 2942cm-1And 1461cm-1The peak at place is stretching vibration peak and the bending vibration peak of C-H in methyl respectively; 1600cm-1、1518cm-1、1426cm-1The peak at place is owing to the skeletal vibration of aromatic structure; In carboxylic acid, alcohols, phenols and esters, the stretching vibration peak of C-O is positioned at 1220cm-1Place; Additionally the peak value of β-O-4 ehter bond is at 1118cm-1Place, the vibration peak of sulfonic acid is positioned at 1043cm-1Place; Infrared spectrum for LTC, it is found that after carbonization, with O-H (3410cm-1),C-O(1220cm-1),-SO3H(1043cm-1),C-H(2942cm-1),C=O(1600cm-1) and C-C/C=C (1518cm-1) relevant peak intensity weakens or disappear; But the LTCA after activation only shows more weak O-H (3441cm-1),C=O,C=C(1633cm-1) and C-O (1050cm-1) peak, prove that carbonization and activation process make the functional group of sodium lignin sulfonate that large change occur.
Fig. 4 is the N of LTC and LTCA2Adsorption-desorption figure (a) and graph of pore diameter distribution (b, c), (b) and (c) is the graph of pore diameter distribution of LTC and LTCA respectively; Figure 4, it is seen that classify according to IUPAC, LTC demonstrates typical IV type curve, is mainly characterized by high P/PoTime, there is obvious hysteresis loop, imply the presence of substantial amounts of mesoporous and macropore, consistent with the pore passage structure presented in SEM and TEM image. LTCA shows I and IV type composite adsorption behavior, and the hole disclosing LTCA is mainly made up of the pore system of two different structures and demonstrates huge N under low relative pressure2Absorbability is primarily due to the existence of a large amount of micropore. Meanwhile, slight delayed of desorption curve discloses the existence at LTCA intermediary hole. The graph of pore diameter distribution of LTC and LTCA is calculate according to BJH method and DFT method to obtain respectively, as shown in figure (b) and (c). Can clearly observe the effect due to hard template HNTs, the pore-size distribution of LTC between 2 to 100nm, wider distribution. The pore-size distribution of LTCA is narrower, by KOH priming reaction, produces a large amount of micropore (< 2nm) along the HNTs duct stayed and mesoporous (2-6nm) on a small quantity on carbon wall. Table 1 lists the detailed Pore genesis of LTC, LTCA. Be can be seen that by data in table, be obtained for through the activation of KOH, specific surface area and pore volume and clearly improve, for instance, activate specific surface area and the pore volume respectively 389.9m of front LTC2/ g, 0.770mL/g, the specific surface area of the LTCA after activation and pore volume respectively 2320m2/ g, 1.342mL/g. From the above result that can draw, the use of HNTs template and KOH activation are for promoting that the development of porosity is very important to obtain multi-stage artery structure.
In the present invention, in specific embodiments, absorption property evaluation carries out by the following method: utilize Staticadsorption experiment to complete. Respectively the tetracycline of 10mL variable concentrations and chloromycetin solution are joined in centrifuge tube, be added thereto to 2.0mgLTCA respectively, water bath with thermostatic control stands, investigated solution ph, time of contact, the temperature impact on tetracycline and chloromycetin absorption.Absorption is collected by centrifugation, is obtained clear liquid at the middle and upper levels after reaching capacity, and records chloromycetin molecular concentration not adsorbed in test solution with ultraviolet-visible photometer, calculates and obtains adsorption capacity (Qe)。
Wherein CoAnd C (mg/L)e(mg/L) being initial and equilibrium concentration respectively, m (mg) is adsorbent amount, and V (mL) is liquor capacity.
Experimental example 1: regulate the pH respectively 3,4,5,6,7,8 of the tetracycline of 250mg/L with the hydrochloric acid of low concentration and ammonia, the pH regulating 200mg/L chloromycetin solution with the hydrochloric acid of low concentration and ammonia is 3,4,5,6,7,8,9,10,11. the tetracycline and the chloromycetin solution that take the above-mentioned different pH of 10mL are respectively put in different centrifuge tubes, it is separately added into 2mgLTCA more wherein, all test fluid are put in 298K water-bath stand after 24.0h, the supernatant is collected in centrifugation, not adsorbed tetracycline and chloromycetin molecular concentration can measure with ultraviolet-uisible spectrophotometer respectively, adsorption capacity is calculated according to result, by comparing the pH value that can draw solution to the impact of adsorbance, as shown in Figure 5, test result indicate that: when the pH value of solution is increased to 8 by 3, the absorption removal rate (Removal%) of TC is reduced to 81% by 92%, when pH is 3, adsorbance is maximum, reach 1151.65mg/g, being primarily due in the solution of different pH value TC molecule mainly has four kinds of existence form: TCH3 +,TCH2 ±,TCH-And TC2-, when pH is relatively low be 3.0 time, mostly with positively charged TCH3 +And TCH2 ±Two kinds of forms exist, such that it is able to the negative charge on LTCA surface by electrostatic interaction to improve the adsorbance of TC; Along with the increase of pH, with the TCH of negative charge-And TC2-Content increases, and due to electrostatic repulsion, the adsorbance of tetracycline is gradually decreased by LTCA, but adsorbance is still very considerable reaches 1031.35mg/g; The change of pH is little for the Adsorption Effect of chloromycetin, and adsorbance remains at higher level (higher than 1000mg/g), shows absorbability stronger for LTCA and environmental suitability, illustrates that this material is applicable to multiple environment as adsorbent.
Experimental example 2: take 10mL initial concentration respectively 20, 60, 100, 150, 200, 250, 280, 300, 320 and the tetracycline of 350mg/L and initial concentration respectively 20, 50, 80, 100, 120, 150, 180, 200, 220, 250 and the chloromycetin solution of 280mg/L be added separately in different centrifuge tubes, it is separately added into 2mgLTCA, test fluid is put in respectively 298K, after 308K and 318K water-bath stands 24.0h, the supernatant is collected in centrifugation, not adsorbed tetracycline and chloromycetin molecular concentration measure with ultraviolet-uisible spectrophotometer respectively, and calculate adsorption capacity according to result:
To tetracycline adsorption capacity: during 298K, adsorbance is 1226.4mg/g;
To chloromycetin adsorption capacity: during 298K, adsorbance is 1022.8mg/g.
As shown in Figure 6, test result indicate that: along with the rising of concentration and temperature, the adsorbance of tetracycline and chloromycetin is increased by LTCA therewith, it is finally reached balance, the maximum equilibrium adsorption capacity of tetracycline is increased along with the rising of temperature, during 298K, the maximum equilibrium adsorption capacity of tetracycline is 1297.0mg/g by LTCA, and in document, the maximum equilibrium adsorption capacity of other adsorbents is 672mg/g; During 298K, the maximum equilibrium adsorption capacity of chloromycetin is 1067.2mg/g by LTCA, and in document, the maximum equilibrium adsorption capacity of other adsorbents is 2.5mg/g.It will thus be seen that the maximum equilibrium adsorption capacity of LTCA is far above other adsorbents, show very excellent absorption property.
Experimental example 3: take tetracycline that 10mL initial concentration is 150mg/L and chloromycetin solution is added separately in centrifuge tube, it is separately added into 2.0mgLTCA, test fluid is individually placed in the water-bath of 298K, 308K and 318K to stand 10,30,60,180,360,540 and 720 minutes respectively. After standing completes, the supernatant is collected in centrifugation, and not adsorbed chloromycetin molecular concentration ultraviolet-uisible spectrophotometer measures, and calculates adsorption capacity according to result. As shown in Figure 7 and Figure 8, test result indicate that: along with the increase of time of contact, adsorbance increases sharply, reaching balance after 6h, in whole time range, the absorption of tetracycline and chloromycetin solution is all shown quick adsorption equilibrium by LTCA.
Claims (9)
1. a galapectite is the preparation method of the lignin-base multi-stage porous carbon material of template, it is characterised in that carry out as steps described below:
(1) preparation of lignin-base template material with carbon element:
Liquid-phase impregnation process is utilized to prepare lignin-base template material with carbon element:
Weigh galapectite, join in hydrochloric acid solution, after reacting by heating, sucking filtration, a large amount of distilled water flushings, to neutral, dried, can be obtained the galapectite after purification process;
Galapectite after purification process is mixed with lignin sulfonic acid sodium solution, after mixture is stood under condition of negative pressure, high speed centrifugation is to reach closelypacked effect, then lower floor's solid is dried to constant weight, put into porcelain boat after weighing, be placed in tube furnace, under the protection of nitrogen atmosphere, after calcining, naturally cool to room temperature; Solid hydrofluoric acid dips after calcining to remove hard template galapectite, to be removed completely after, repeatedly clean with the mixed solution of a large amount of deionized waters and ethanol, dry to constant weight, obtain the template material with carbon element (LTC) being template with galapectite;
(2) activation of template material with carbon element
After extremely uniform to the template material with carbon element after drying and solid potassium hydroxide mixed grinding; it is placed in nickel pot after cover lid; in tube furnace under nitrogen protection; after calcining; after naturally cooling to room temperature, add dilute hydrochloric acid and remove the impurity such as the potassium carbonate that generates in course of reaction, then repeatedly clean to neutrality with the mixed solution of a large amount of deionized waters and ethanol; dry to constant weight, obtain lignin-base multi-stage porous carbon material (LTCA) being template with galapectite.
2. a kind of galapectite according to claim 1 is the preparation method of the lignin-base multi-stage porous carbon material of template, it is characterized in that, the ratio of the galapectite described in step (1) and hydrochloric acid solution is 2-5g:10mL, and wherein the concentration of hydrochloric acid solution is 1-4mol/L; Described reacting by heating condition is 40-80 DEG C of reaction 1-6h.
3. a kind of galapectite according to claim 1 is the preparation method of the lignin-base multi-stage porous carbon material of template, it is characterized in that, the mass ratio of the galapectite after purification process described in step (1) and lignin sulfonic acid sodium solution is 1:3-5, and wherein sodium lignin sulfonate liquid quality fraction is 20%-40%.
4. a kind of galapectite according to claim 1 is the preparation method of the lignin-base multi-stage porous carbon material of template, it is characterised in that stand 2h-4h when being statically placed in condition of negative pressure described in step (1) for-0.1-(-0.3) Mpa; Described high speed centrifugation condition is the centrifugal 1.5h-2.5h of the rotating speed with 2000-4000r/min.
5. a kind of galapectite according to claim 1 is the preparation method of the lignin-base multi-stage porous carbon material of template, it is characterized in that, calcining concrete operations described in step (1) is that the programming rate with 3-7 DEG C/min is raised to 400-600 DEG C from room temperature and calcines 1h-3h at such a temperature; The mass fraction of described Fluohydric acid. is 10%-20%.
6. a kind of galapectite according to claim 1 is the preparation method of the lignin-base multi-stage porous carbon material of template, it is characterised in that template material with carbon element described in step (2) and solid potassium hydroxide mass ratio are 1:3-1:4.
7. a kind of galapectite according to claim 1 is the preparation method of the lignin-base multi-stage porous carbon material of template, it is characterized in that, calcining concrete operations described in step (2) is that the programming rate with 3-7 DEG C/min is raised to 700 DEG C-900 DEG C from room temperature and calcines 1h-2h at such a temperature; The concentration of described dilute hydrochloric acid is 2mol/L.
8. the lignin-base multi-stage porous carbon material described in claim 1-7 Arbitrary Term, it is characterised in that described lignin-base multi-stage porous carbon material has a large amount of macropore, meso-hole structure and microcellular structure, for the multi-stage porous carbon material being interconnected.
9. the application to tetracycline in water environment and the adsorbing separation of chloromycetin of the lignin-base multi-stage porous carbon material described in any one of claim 1-8.
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