CN109351330A - C/SiO for VOCs absorption2The preparation method and applications of compound adsorbent - Google Patents

C/SiO for VOCs absorption2The preparation method and applications of compound adsorbent Download PDF

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CN109351330A
CN109351330A CN201811332224.7A CN201811332224A CN109351330A CN 109351330 A CN109351330 A CN 109351330A CN 201811332224 A CN201811332224 A CN 201811332224A CN 109351330 A CN109351330 A CN 109351330A
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sio
adsorbent
preparation
kit
vocs
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周桂林
雷冰漫
谢红梅
杨婉佳
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Chongqing Technology and Business University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/324—Inorganic material layers containing free carbon, e.g. activated carbon
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Abstract

The invention discloses a kind of C/SiO for VOCs absorption2The preparation method and applications of compound adsorbent.The present invention is first using ethyl orthosilicate as silicon source, P123 is that surfactant utilizes hydrothermal synthesis method synthesizing mesoporous silicon dioxide material KIT-6 that C is highly dispersed to the surface KIT-6 using infusion process then using sucrose as carbon source, its surface nonpolarity is improved, its adsorption capacity to VOCs is improved.The preparation method of the adsorbent is simple and has good absorption property, the C/SiO being prepared2Adsorbent has reusability, can effectively reduce operating cost.

Description

C/SiO for VOCs absorption2The preparation method and applications of compound adsorbent
Technical field
The present invention relates to a kind of support type mesoporous silicon oxide adsorbents for adsorbing VOCs, and in particular to one kind is for adsorbing The compound C/SiO of VOCs2Adsorbent and its preparation method and application.
Background technique
The source volatile organic matter (VOCs) is very extensive, can be divided into natural source and artificial source two major classes.Artificial source includes Industrial production, rural activity, traffic emission and other sources.The discharge amount of China industrial source VOCs accounts for 55% left side of artificial source The right side, and the huge number of the VOCs of industrial source emission.VOCs has carcinogenic, teratogenesis and mutagenic " three cause " effect to human body, And the environmental problems such as greenhouse effects, ozone hole and photochemical pollution can be led to.Coating industry is China VOCs Rich and influential family is discharged, the VOCs huge number of coating industry, discharge amount is big, emission source dispersion, and purified treatment is difficult.Currently, at VOCs Science and engineering skill is using more universal including condensation method, liquid absorption method, bioanalysis, Production by Catalytic Combustion Process, membrane separation process and absorption method. Condensation method need to increase pressure to reduce temperature, and processing cost is larger with difficulty.Liquid absorption method is generally only used for one pack system VOCs Processing, and absorbing liquid need to be handled, this improves operating costs.Bioanalysis need to cultivate high-quality microorganism, and microorganism The construction difficulty of suitable living environment is larger.Production by Catalytic Combustion Process apply in the industry it is very extensive, but be limited to catalyst mistake The factors such as living or activity is not high, and process object has selectivity and catalyst is expensive.Membrane separation technique investment cost Height, is generally only used for the pretreatment of high-concentration organic waste gas, and is dfficult to apply to the exhaust-gas treatment of atm number.Under comparing, Adsorption treatment technology has many advantages, such as that equipment is simple, easily operated, cost of investment is low, environmentally friendly, especially suitable for low concentration, strong wind The purification of the VOCs of amount, and the adsorbent after processing can be used under certain condition with regeneration cycle, be it is a kind of it is economical, Meet the selection of clean manufacturing theory and domestic economy truth.It therefore, is the VOCs removing sulfuldioxide being most widely used at present, entirely Ball occupation rate of market is about 25%.According to statistics, adsorption technology is VOCs processing technique popular at present, in American-European countries Occupation rate of market ranked third position, and the occupation rate of market in China ranked first position.Meanwhile adsorption treatment technology is to various VOCs' Absorption shows certain generality and popularity.It is environmental-friendly and economical and efficient in adsorption treatment technical research Adsorbent material has become new research hotspot.KIT-6 has biggish mesoporous pore volume and uniform mesoporous pore size, makes it have To the specificity and high-adsorption-capacity of organic matter absorption.But KIT-6 surface polarity is stronger, is unfavorable for nonpolarity and low pole C is distributed to the surface KIT-6 by the absorption of molecule, is conducive to improve its surface nonpolarity, enhancing is to nonpolarity and low pole substance Suction-operated.Therefore, the adsorption capacity of KIT-6 can be improved to a certain extent.
For the present invention using ethyl orthosilicate as silicon source, P123 is that surfactant utilizes the synthesising mesoporous titanium dioxide of hydrothermal synthesis method Silicon materials KIT-6.Using sucrose as carbon source, C is highly dispersed to by the surface KIT-6 using infusion process, improves its surface nonpolarity, Improve its adsorption capacity to VOCs.
Summary of the invention
In view of this, the present invention provides a kind of for the compound C/SiO adsorbent of VOCs adsorption treatment and its preparation side Method, the sorbent preparation method is simple and has good absorption property.
For achieving the above object, C is distributed to the surface KIT-6 by infusion process and compound C/SiO is made by the present invention2It inhales Attached dose, make it have good absorption property.
The invention adopts the following technical scheme:
A kind of C/SiO for VOCs absorption2The preparation method of compound adsorbent, comprising the following steps:
(1) preparation of KIT-6
Using ethyl orthosilicate as silicon source, P123 is that surfactant utilizes hydrothermal synthesis method synthesizing mesoporous silicon dioxide material KIT-6。
(2) compound C/SiO2The preparation of adsorbent
Using sucrose as carbon source, the compound C/SiO of different carbon contents is prepared by infusion process2Material.It weighs sucrose and dissolves in In 5mL distilled water, it being added sample KIT-6 made from step (1) after being sufficiently stirred, the mass ratio of the sucrose and KIT-6 is 1~ 8:5 stirs solvent evaporated after 80kHz ultrasound 10min at room temperature, by the drying overnight in 120 DEG C of baking ovens of gained siccative, then will It is placed in 250~500 DEG C of carbonization 2h in the hyaline-quartz pipe under nitrogen atmosphere, and heating rate is 10 DEG C/min, obtains compound C/ SiO2Adsorbent.
The preparation method of step (1) the of the present invention KIT-6, the specific steps are as follows: weigh 16.0g P123 in polytetrafluoro In ethylene reaction kettle, 580.0mL distilled water and 27.6mL concentrated hydrochloric acid is added, stirring 4h becomes uniform molten under 35 DEG C of water-baths Liquid adds 36.8mL ethyl orthosilicate after 19.8mL n-butanol stirring 1h is added, continues stirring at 35 DEG C for 24 hours, then will be anti- Answering kettle to be placed in hydrothermal crystallizing in 100 DEG C of baking ovens, for 24 hours, taking-up is cooled to room temperature, and is filtered for multiple times and is washed to neutrality, is dried in 100 DEG C Drying overnight in case, then obtained white powder is placed in 550 DEG C of Muffle kiln roasting 6h to get product K IT-6.
The mass ratio of sucrose described in step (2) of the present invention and KIT-6 are 3:5.
Carburizing temperature described in step (2) of the present invention is 400 DEG C.
The present invention also provides the C/SiO2Application of the compound adsorbent in absorption VOCs.Further, described The type of VOCs is a variety of, toluene is exemplified as in the present invention, it is not limited to toluene.
Compared with prior art, the beneficial effects of the present invention are:
(1) C is highly dispersed to the surface KIT-6 using infusion process using sucrose as carbon source by the present invention, keeps its surface nonpolar It improves, improves its adsorption capacity to nonpolarity and low pole VOCs.
(2) preparation method of adsorbent of the present invention is simple and has good VOCs absorption property.
(3) C/SiO that the present invention is prepared2Adsorbent has reusability good, can effectively reduce cost.
Detailed description of the invention
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with attached drawing to the present invention make into The detailed description of one step, in which:
Fig. 1 is the TG spectrogram of CS03 adsorbent；
Fig. 2 is the DSC spectrogram of CS03 adsorbent；
Fig. 3 is KIT-6 and compound C/SiO2The N of adsorbent2Adsorption/desorption isothermal curve and pore size distribution curve；
Fig. 4 is KIT-6 and compound C/SiO2Adsorbent toluene breakthrough curve；
Fig. 5 is KIT-6 and compound C/SiO2Adsorbent toluene desorption curve；
Fig. 6 is influence of the carburizing temperature to Adsorption of Toluene；
Fig. 7 is C/SiO2To toluene sorption cycle curve.
Specific embodiment
Hereinafter reference will be made to the drawings, and a preferred embodiment of the present invention will be described in detail.
Embodiment 1
The compound C/SiO of the present embodiment2The preparation method of adsorbent, comprising the following steps:
(1) preparation of KIT-6
16.0g P123 is weighed in ptfe autoclave, 580.0mL distilled water and 27.6mL concentrated hydrochloric acid is added, in 4h is stirred under 35 DEG C of water-baths and becomes uniform solution, adds the positive silicic acid second of 36.8mL after 19.8mL n-butanol stirring 1h is added Ester continues stirring at 35 DEG C for 24 hours.Then reaction kettle being placed in hydrothermal crystallizing in 100 DEG C of baking ovens, for 24 hours, taking-up is cooled to room temperature, more Secondary filtering is simultaneously washed to neutrality, the drying overnight in 100 DEG C of baking ovens, then obtained white powder is placed in 550 DEG C of Muffle furnace Middle roasting 6h, up to product K IT-6.
(2) compound C/SiO2The preparation of adsorbent
Using sucrose as carbon source, the compound C/SiO of different carbon contents is prepared by infusion process2Material.Specifically: weigh 0.1g Sucrose dissolves in 5mL distilled water, and the KIT-6 of 0.500g is added after being sufficiently stirred, and stirs steam after 80kHz ultrasound 10min at room temperature Dry solvent.By the drying overnight in 120 DEG C of baking ovens of gained siccative, then place it in 400 in the hyaline-quartz pipe under nitrogen atmosphere DEG C carbonization 2h, heating rate be 10 DEG C/min.Obtain compound C/SiO2Adsorbent is named as CS01.
Embodiment 2
It weighs 0.2g sucrose and dissolves in 5mL distilled water, the KIT-6 of 0.500g is added after being sufficiently stirred.Remaining step all with reality As applying example 1, sample CS02 is obtained.
Embodiment 3
It weighs 0.3g sucrose and dissolves in 5mL distilled water, the KIT-6 of 0.500g is added after being sufficiently stirred.Remaining step all with reality As applying example 1, sample CS03 is obtained.
Embodiment 4
It weighs 0.5g sucrose and dissolves in 5mL distilled water, the KIT-6 of 0.500g is added after being sufficiently stirred.Remaining step all with reality As applying example 1, sample CS05 is obtained.
Embodiment 5
It weighs 0.8g sucrose and dissolves in 5mL distilled water, the KIT-6 of 0.500g is added after being sufficiently stirred.Remaining step all with reality As applying example 1, sample CS08 is obtained.
Comparative example 1
It weighs 0.0g sucrose and dissolves in 5mL distilled water, the KIT-6 of 0.500g is added after being sufficiently stirred.Remaining step all with reality As applying example 1, sample CS00 is obtained.
By the compound C/SiO of Examples 1 to 5 and comparative example 12Adsorbent carries out adsorption desorption to toluene, is then adsorbed The adsorption desorption performance evaluation of agent:
The adsorption desorption performance evaluation of adsorbent carries out in 20 DEG C of thermostatic absorption pipes under normal pressure.The adsorption experiment of toluene When, the concentration of toluene are as follows: 33803mg/m3；When the detachment assays of toluene, the flow of air are as follows: 20ml/min.
Specific steps are as follows:
Weigh the compound C/SiO of 50mg2Adsorbent is in 20 DEG C of isothermal reaction pipes, and reaction temperature is by water bath with thermostatic control system control System.It is passed through toluene, in the reaction temperature and the concentration of toluene are as follows: 33803mg/m3Under the conditions of thermostatic absorption toluene (toluene flux Controlled by flowmeter), (air mass flow is by flowing for constant temperature desorption toluene under the conditions of the reaction temperature and air mass flow are 20ml/min Meter control), by residual toluene content in the II type gas-chromatography on-line checking tail gas of GC-7890 with fid detector, detector bar Part are as follows: 220 DEG C of detector temperature, 160 DEG C of temperature of vaporization chamber, 140 DEG C of post case temperature.
Table 1 KIT-6 and compound C/SiO2The physical parameter of adsorbent
aIs obtained according to BET equation calculation
bDesorption pore volume is obtained according to BJH method
cIs obtained by isothermal curve desorption line computation according to BJH method
Table 2 KIT-6 and compound C/SiO2Adsorbent is to toluene adsorption desorption performance evaluation
The CS03 adsorbent of embodiment 3 is subjected to TG-DSC analysis, test condition on NETZSCH instrument are as follows: with 10 DEG C/ The heating rate of min rises to 700 DEG C, air velocity 60mL/min from room temperature, as depicted in figs. 1 and 2.
By Fig. 1 TG curve it is found that CS03 adsorbent occur respectively in 50-250 DEG C and 250-550 DEG C of two temperature ranges it is bright Aobvious mass loss peak, in static atmosphere of air, CS03 adsorbent starts to thermally decompose at 50 DEG C, as temperature increases, 50- 150 DEG C of sections, weight loss rate is smaller, and curve is gentle.Temperature continues to increase, and weight loss rate becomes larger, and weight loss significantly increases, When temperature rises to 250 DEG C, weight-loss ratio is about 20%, this can be attributed to the de- of the crystallization water and free liquid water in sample It removes.As constant temperature increases, the weight loss rate of sample is significantly increased, and an apparent zero-g period occurs, into quick Weightless area.In quick weight loss area: 250 DEG C of -550 DEG C of sections, TG curve become precipitous, and mass fraction becomes 35% from 85%, lose Rate is 50% again.There is apparent highly endothermic peak in 50-250 DEG C and 250-550 DEG C of two temperature ranges in Fig. 2 DSC curve, Sucrose is attributed to be thermally decomposed.Therefore, significant weightless feature is reflected on TG curve.When temperature is higher than 550 DEG C, TG curve It tends towards stability again, weight loss rate is smaller, and DSC curve also occurs without strong peak, illustrates that no component is thermally decomposed.CS03 adsorbent is in warm Occurs maximum weight loss rate in decomposable process when 280 DEG C, it can thus be appreciated that CS03 adsorbent has maximum thermal decomposition at 280 DEG C Rate.
By the KIT-6 (i.e. sample CS00) of comparative example 1 and compound C/SiO2Adsorbent carries out N2Adsorption-desorption analysis, N2It inhales Attached-desorption isothermal curve is measured at -196 DEG C by 3020 type of TriStarII (Merck & Co., Inc, the U.S.) fully-automatic analyzer. Sample is in 250 DEG C of pretreatments degassing 6h before testing.Sample specific surface uses Brunauer-Emmett-Te-ller (BET) equation It calculates, pore-size distribution is calculated using Barrrtt-Joyner-Halenda (BIH) desorption isotherm, testing result such as Fig. 3 and table 1 It is shown.
From the figure 3, it may be seen that the N of each adsorbent2Adsorption-desorption isothermal is IV type thermoisopleth, p/p0It is for the region 0-0.4 Mono layer adsorption in adsorbent duct；p/p0H1 type hysteresis loop is formd for the jumping area in the region 0.4-0.8.H1 type lag The formation of ring can be attributed to N2Capillary condensation phenomenon has occurred in molecule in adsorbent meso-hole structure；In p/p0For the area 0.8-1.0 Domain is the multi-molecular absorption that table is formed outside adsorbent, and the N of each adsorbent2Adsorbance with the increase of relative pressure and Slowly it is incremented by, i.e., adsorbent reaches saturation ADSORPTION STATE.From the figure 3, it may be seen that the Adsorption and desorption isotherms of each adsorbent have been respectively formed on H1 Type hysteresis loop shows that the series adsorbent has typical mesopore orbit structure, and pore-size distribution is concentrated, this and each adsorbent Pore-size distribution test result is consistent.Obtained compound C/SiO2The lag style type of adsorbent is not with the increase of C dosage And change, i.e., each compound C/SiO2Adsorbent maintains meso-hole structure possessed by KIT-6, and the variation of C dosage does not destroy The type of KIT-6 meso-hole structure.With the increase of C dosage, compound C/SiO2The height of the H1 type hysteresis loop of adsorbent gradually drops It is low, and jumping point is mobile to the low direction of relative pressure, i.e., adsorbent is to N2Adsorbance reduce, illustrate C dosage increase drop Low adsorbent is to N2Adsorption capacity, this can be attributed to excessive C and form multilayer load on the surface KIT-6, and C can adhere to In duct, inner wall or even blocking portion cellular structure port and internal gutter, reduce pore size.Such as table 1, CS00, The specific surface area of CS01, CS02, CS03, CS05, CS08 are respectively 633.7,523.7,524.89,490.1,483.7 and 493.2m2/ g, KIT-6 have biggish specific surface area, provide material base in the high degree of dispersion of activated carbon surface for C, For compound C/SiO2Adsorbent provides suitable specific surface area.Ensure compound C/SiO2The more adsorption activities of adsorbent surface Therefore the formation in site can improve compound C/SiO to a certain extent2The adsorption capacity of adsorbent.Not with dosage of sucrose It is disconnected to increase, compound C/SiO2The Kong Rong of adsorbent and aperture reduce, this can be attributed to the C meeting for being highly dispersed in the surface KIT-6 It is attached to duct inner wall or even blocking portion cellular structure port and internal gutter；Preparing compound C/SiO2Adsorbent In roasting process, more C, which easily assembles, forms C aggregation, this may also cause compound C/SiO2The aperture of adsorbent and Kong Rong Reduce, therefore, high dosage of sucrose is unfavorable for maintaining the good cellular structure of active carbon.The introducing of C has significantly affected KIT-6 material The structural behaviour of material, this will will have a direct impact on obtained corresponding compound C/SiO2The absorption property of adsorbent material.
By the KIT-6 of embodiment and compound C/SiO2Adsorbent carries out toluene adsorption desorption in 20 DEG C of thermostatic absorption pipe, The entrance concentration of toluene is 33803mg/m by turning the control of finger flowmeter3, by the II type gas-chromatography of GC-7890 with fid detector Residual toluene content in on-line checking tail gas.As shown in Figure 4 and Figure 5.
By Fig. 4 and Fig. 5 it is found that C is distributed to the surface KIT-6, toluene can be extended to its time of break-through, increase it to toluene Equilibrium adsorption capacity, and shorten the desorption equilibrium time to toluene.CS01, CS02, CS03, CS05, CS08 compared with CS00, It has increased separately 8.8%, 21.0%, 24.7%, 27.0%, 11.3% to the saturated extent of adsorption of toluene.Therefore, modified through C KIT-6 afterwards increases the saturated extent of adsorption of toluene, and improves the utilization rate of KIT-6.As it can be seen that C dosage prepared by the present invention The respectively compound C/SiO of 0.1g, 0.2g, 0.3g, 0.5g and 0.8g2Adsorbent has VOCs adsorptivity more better than KIT-6 Can, it is efficient VOCs adsorbent.And every kind of adsorbent shows different performances to the adsorption desorption of VOCs, reason may be The C dosage of KIT-6 Dispersion on surface is different, this species diversity results in them and is not quite similar to the adsorption desorption performance of VOCs.
Carburizing temperature is to porous C/SiO2The influence of composite material Adsorption of Toluene
It is research carburizing temperature to porous C/SiO2Influence of the composite material to Adsorption of Toluene is provided with carburizing temperature Respectively 250 DEG C, 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C and 500 DEG C of control group, dosage of sucrose is constant for 0.3g, investigation The performance of adsorbent obtained absorption toluene, the removal rate of toluene and the relationship of carburizing temperature, are shown in Fig. 6 under different carburizing temperatures. As shown in fig. 6, the sample without high-temperature roasting processing shows poor Adsorption of Toluene, absorption property starts in absorption It occurs as soon as in 2-3 minute afterwards and sharply declines, curve is steeper, and toluene removal rate decrease speed is fast, shows toluene gas molecule Enter adsorbent quickly and penetrates；And with by porous C/SiO made from carbonization treatment2Composite material is compared, and the adsorbent is very Reach adsorption saturation, toluene adsorbance very little fastly.When carburizing temperature is 250 DEG C, 300 DEG C and 350 DEG C, the suction of corresponding adsorbent Attached performance is more close, and with the raising of carburizing temperature, corresponding C/SiO2The absorption property of adsorbent gradually increases, when penetrating Between be respectively 5.7min, 8.7min, 12.8min.When carburizing temperature reaches 400 DEG C, C/SiO2The absorption property of adsorbent reaches To best, time of break-through 23.1min, the downward trend of adsorption curve is also the gentlest.With the further liter of carburizing temperature Height, when reaching 450 DEG C and 500 DEG C, C/SiO2The absorption property of adsorbent is gradually reduced, adsorbent of the time of break-through compared with 400 DEG C It is short, but still better than above mentioned carburizing temperature be respectively 250 DEG C, 300 DEG C, 350 DEG C of C/SiO2Adsorbent.
It follows that carburizing temperature is to C/SiO2The Adsorption of Toluene of adsorbent, which has, to be significantly affected, at 250-400 DEG C Carburizing temperature section in, Adsorption of Toluene enhances with the raising of carburizing temperature；In 400-500 DEG C of carburizing temperature In section, Adsorption of Toluene is reduced with the raising of carburizing temperature, and 400 DEG C are preparation C/SiO2The best carbon of adsorbent Change temperature.In desorption stage, by the C/SiO of carbonization treatment2The desorption rate of adsorbent, which is greater than, does not pass through N2The absorption of roasting Agent, and the absorption property difference of the adsorbent by the processing of different carburizing temperatures is little.Carburizing temperature is increased, is promoted mesoporous SiO2Surface sucrose is carbonized to form carbon film, thus changes adsorbent to the absorption property of toluene molecule.
Porous C/SiO2The circular regeneration performance study of composite material
Select the C/SiO under optimum experimental condition2Adsorbent (i.e. dosage of sucrose is 0.3g, and carburizing temperature is 400 DEG C), into Row circulation absorption/detachment assays.After first time absorption/desorption, without any processing, continues second and third time is followed Ring experiment, after circulation experiment three times, sample is placed in 60,80 or 100 DEG C of environment and carries out desorption processing, until reaching de- Hereafter attached balance continues absorption/detachment assays.By multiple absorption/detachment assays, C/SiO is investigated2Adsorbent can Performance is recycled, as a result such as Fig. 7.
As shown in fig. 7, first time absorption/detachment assays time of break-through longest, is 29.9min, first at the time point Benzene removal rate is 99.2%；With second, the progress of third time absorption/detachment assays, the time of break-through of toluene shortens, respectively For 14.7min, 11.9min, and toluene removal rate at the time point is respectively 97.1%, 96.9%, and relatively first time penetrates The toluene removal rate at time point is substantially reduced.This shows with C/SiO2The reuse of adsorbent, the sample is to toluene Absorption property decline；And with C/SiO2The increase of adsorbent access times, time of break-through are also gradually shortened, the suction to toluene Attached performance also decreases.
After carrying out the processing of 60 DEG C of desorptions, the time of break-through of toluene is gone up, and is 15.6min, with second and the Absorption/detachment assays are compared three times, and absorption property is enhanced, this shows C/SiO2Adsorbent can be de- by simply heating up Attached processing is used for multiple times to realize.After carrying out 80 DEG C of desorption processing, the time of break-through of toluene continues to extend, at 60 DEG C of desorptions Time after reason is more close, but its subsequent curve is more smooth, and adsorbable toluene level is higher.It is warming up to 100 DEG C of desorptions After processing, the time of break-through of toluene is 23.6min, and toluene removal rate at the time point is 99.4%, with first time absorption/ The data of desorption are closest, show the C/SiO through being recycled2Adsorbent is after 100 DEG C of thermal desorptions are handled, C/SiO2It inhales The attached dose of absorption property to toluene can be restored to the performance of fresh sample substantially.
By being analyzed above it is known that C/SiO2Adsorbent has good reusability.Without thermal desorption When processing, with C/SiO2The Adsorption of Toluene of the reuse of adsorbent, the adsorbent gradually declines, and decrease speed compared with Fastly.This toluene molecule for being attributable to be adsorbed in adsorbent surface fails to be desorbed completely, to cover in adsorption activity The heart, so as to cause the decline of corresponding adsorbent absorption property.After 60 DEG C, 80 DEG C and 100 DEG C of desorption processing, C/SiO2Absorption The absorption property of agent gradually enhances again, even up to the Adsorption of Toluene of fresh adsorbent.This, which is attributable to heat treatment, to have The toluene molecule of effect removing adsorbent surface absorption, makes its adsorption activated centre sufficiently be exposed and restore its adsorptivity Energy.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, protection model of the invention It encloses without being limited thereto.Those skilled in the art's made equivalent substitute or transformation on the basis of the present invention, in the present invention Protection scope within.Protection scope of the present invention is subject to claims.

Claims (7)

1. a kind of C/SiO for VOCs absorption2The preparation method of compound adsorbent, comprising the following steps:
(1) preparation of KIT-6
It is surfactant by silicon source, P123 of ethyl orthosilicate, utilizes hydrothermal synthesis method synthesizing mesoporous silicon dioxide material KIT-6；
(2)C/SiO2The preparation of compound adsorbent
Weigh sucrose and dissolve in 5mL distilled water, after being sufficiently stirred be added step (1) made from sample KIT-6, the sucrose with The mass ratio of KIT-6 is 1~8:5, solvent evaporated is stirred after 80kHz ultrasound 10min at room temperature, by gained siccative in 120 DEG C Drying overnight in baking oven, then place it in 250~500 DEG C of carbonization 2h, heating rate in the hyaline-quartz pipe under nitrogen atmosphere and be 10 DEG C/min, obtain C/SiO2Compound adsorbent.
2. preparation method according to claim 1, which is characterized in that the preparation of step (1) described KIT-6, specific steps It is as follows: to weigh 16.0g P123 in ptfe autoclave, 580.0mL distilled water and 27.6mL concentrated hydrochloric acid is added, in 35 Stirring 4h becomes uniform solution under DEG C water-bath, adds the positive silicic acid second of 36.8mL after 19.8mL n-butanol stirring 1h is added Ester continues stirring at 35 DEG C for 24 hours, and reaction kettle is then placed in hydrothermal crystallizing in 100 DEG C of baking ovens, and for 24 hours, taking-up is cooled to room temperature, more Secondary filtering is simultaneously washed to neutrality, the drying overnight in 100 DEG C of baking ovens, then obtained white powder is placed in 550 DEG C of Muffle furnace Middle roasting 6h is to get product K IT-6.
3. preparation method according to claim 1, which is characterized in that the mass ratio of sucrose and KIT-6 described in step (2) For 3:5.
4. preparation method according to claim 1, which is characterized in that carburizing temperature described in step (2) is 400 DEG C.
5. the C/SiO that any one of Claims 1 to 4 preparation method obtains2Compound adsorbent.
6. C/SiO described in claim 52Application of the compound adsorbent in absorption VOCs.
7. application according to claim 6, which is characterized in that the VOCs is toluene.
CN201811332224.7A 2018-11-09 2018-11-09 C/SiO for VOCs absorption2The preparation method and applications of compound adsorbent Pending CN109351330A (en)

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CN113713768A (en) * 2021-09-07 2021-11-30 盐城工学院 High-temperature-resistant activated carbon composite adsorbent and preparation method and application thereof
CN114210307A (en) * 2022-01-05 2022-03-22 上海恒业微晶材料科技股份有限公司 Preparation method and application of novel carbon-silicon material

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CN113713768A (en) * 2021-09-07 2021-11-30 盐城工学院 High-temperature-resistant activated carbon composite adsorbent and preparation method and application thereof
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