CN115318257A - Preparation method of sauce-flavor wine vinasse-based porous carbon composite ionic liquid gas adsorbent - Google Patents
Preparation method of sauce-flavor wine vinasse-based porous carbon composite ionic liquid gas adsorbent Download PDFInfo
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Abstract
The invention discloses a preparation method of a sauce-flavor wine vinasse-based porous carbon composite ionic liquid gas adsorbent, which is characterized in that a large amount of solid waste sauce-flavor wine vinasse brewed by white spirit is used as a raw material, and the vinasse-based porous carbon with light specific gravity, developed microporous structure and high specific surface area is obtained through impurity removal pretreatment by hydrofluoric acid, high-temperature carbonization and secondary activation. Meanwhile, the proton type ionic liquid is innovatively used for modifying the porous carbon to create the sauce-flavor wine vinasse-based porous carbon composite ionic liquid gas adsorbent with higher thermal stability, so that the adsorption capacity and separation selectivity of the vinasse-based porous carbon to low-concentration gas are improved, and CO is absorbed by the porous carbon 2 The selective adsorption separation has excellent adsorption separation performance, has ultrahigh specific surface area, abundant pore structure properties and abundant active sites, has the advantages of simple preparation method, easy operation, low cost and the like, and can be used for gas such as natural gas, methane, low-concentration coal bed gas, coal-fired flue gas and the likeThe method has good industrial application prospect in the field of bulk adsorption separation.
Description
Technical Field
The invention relates to a preparation method of a sauce-flavor wine vinasse-based porous carbon composite ionic liquid gas adsorbent, and belongs to the field of new chemical materials and gas separation.
Background
Gas adsorption separation is an important step in various raw material gas purification sections, and is an effective method for relieving greenhouse gas emission. Typical examples include natural gas purification, hydrogen production, biogas purification, ethanol and ammonia production, and gas separation from industrial combustion emissions sources, among others. The main component of the natural gas comprises 70-95% of methane (CH) 4 ) The balance being carbon dioxide (CO) 2 ) Hydrogen sulfide (H) 2 S), sulfur dioxide (SO) 2 ) Isoacid gas and ethane (C) 2 H 6 ) Propane (C) 3 H 8 ) Light hydrocarbons, and the like. CO present in natural gas 2 、SO 2 、H 2 The acidic gases such as S and the like are not beneficial to storage and transportation, and should be separated and enriched, so that on one hand, pipeline corrosion is reduced, the heat value of natural gas is improved, and on the other hand, the acidic gas enrichment can provide basic resources for physical utilization, chemical utilization and biological utilization. In addition, CO 2 、SO 2 、H 2 S also widely exists in low-concentration coal bed gas, methane and industrial coal-fired flue gas, the direct discharge easily aggravates the greenhouse effect, and causes the waste of carbon resources, and the efficient realization of the selective capture of the gas is a necessary way for effectively utilizing the carbon resources in the face of the low-concentration gas. Industrially, the adsorption separation based on physical action has the advantages of low energy consumption, low equipment corrosivity, easy regeneration and the like, and has wide application prospect in gas separation. In common solid adsorbent, porous carbon material is used for separating CO through pressure swing physical adsorption 2 、H 2 S and other gases have obvious advantages of convenience and energy conservation, can be operated at normal temperature and normal pressure, and the porous carbon adsorbent can be regenerated and recycled under the condition of pressure reduction or temperature rise.
The Maotai liquor in Guizhou is well-known, and the annual production value of the Maotai liquor is over billion. However, the bulk solid waste vinasse generated in the brewing process of the sauce-flavor white spirit is mainly used for feed or organic fertilizer at present, the utilization rate is low, and the large-scale utilization is limited due to poor safety and reliability of the product environment, small treatment capacity and the like. The distiller's grains solid waste is rich in biomass, low in biomass cost and environment-friendly, and is a renewable resourceAnd the preparation method has wide prospect for preparing the biomass charcoal porous adsorbent. At present, patent CN109835897B discloses a metal/heteroatom modified spirit vinasse-based activated carbon and a preparation method thereof, wherein vinasse, a nitrogen-containing compound and a transition metal compound are ground and mixed uniformly in a mortar, then the mixture is carbonized at 600-900 ℃ for 1-3 h, the carbonized activated carbon is soaked in acid for 5-15 h, and then the acid is treated by CO 2 Or activating the gas atmosphere with water vapor at 700-900 ℃ for 2-5 h to obtain the metal/heteroatom modified distiller's grains based activated carbon, and using the metal/heteroatom modified distiller's grains based activated carbon to catalyze persulfate to oxidize and degrade organic pollutants such as acid red, methyl orange and the like in water at normal temperature and normal pressure. The patent CN108975333A discloses a preparation method of modified distillers ' grains based activated carbon, which comprises adding distillers ' grains raw materials into phosphoric acid solution, performing ultrasonic treatment for 25-35 min, drying, activating at 510-530 ℃ for 2-3 h, soaking in NaOH solution for 4-6 h, washing, drying, grinding to obtain distillers ' grains activated carbon, and adding Fe (NO) 3 ) 3 And (3) dropwise adding NaOH solution into the solution until the pH value is 8.1-8.3, sealing and standing for 71-73h to obtain the hydroxyl iron modified vinasse-based activated carbon for removing Congo red in water. The patent CN109928391A discloses a modified white spirit vinasse-based activated carbon and a preparation method thereof, which comprises the steps of carbonizing a white spirit vinasse for 3-5 h at 700-900 ℃, then ultrasonically mixing the white spirit vinasse with activators such as potassium hydroxide, potassium nitrate, potassium carbonate or sodium hydroxide and the like to carry out hydrothermal reaction at 100-200 ℃ to obtain activated carbon, and then putting the activated carbon into a dicyandiamide, melamine, ammonium chloride or urea solution to carbonize for 3-5 h at 850-950 ℃ to obtain the modified white spirit vinasse-based activated carbon which is used for catalyzing persulfate oxidative degradation of organic pollutants in organic wastewater. Patent CN11210447A discloses a preparation method of yellow wine lees-based activated carbon, which comprises the steps of mixing lees with hydrochloric acid solution to obtain slurry, hydrolyzing the slurry in a water bath at 100 ℃, carbonizing the slurry for 1 to 5 hours at 400 to 600 ℃, and impregnating the slurry in activating agent solution such as potassium hydroxide, potassium chloride, potassium carbonate, zinc chloride and the like to obtain the yellow wine lees-based activated carbon. Patent CN113479879A discloses an activated carbon material based on secondary fermentation vinasse and a preparation method and application thereof, wherein a low-temperature pre-carbonized material obtained by fermenting biomass twice is directly mixed with an alkaline inorganic substance, and then the activated carbon material based on the secondary fermentation vinasse is prepared by calcining and is used as a super capacitorAnd (3) a device electrode material.
In the prior patent, vinasse is mainly prepared into biomass-based activated carbon and a catalyst carrier by hydrolysis, pyrolysis, physical activation, chemical activation or heteroatom modification and the like, and the biomass-based activated carbon and the catalyst carrier are mainly used for removing and degrading organic pollutants in dye and organic wastewater or super capacitor materials. At present, no clear technical route for preparing the vinasse-based microporous-structure porous carbon material applied to gas adsorption separation by adopting sauce wine vinasse exists.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method technology of a sauce-flavor wine vinasse-based porous carbon composite ionic liquid gas adsorbent, the technical route recycles sauce-flavor wine vinasse to prepare the porous carbon gas adsorbent with excellent performance, and the ionic liquid is adopted to modify the adsorbent, so that the prepared material is applied to normal-temperature and normal-pressure trapping of low-partial-pressure gas recovery and has great development value.
The technical scheme adopted by the invention for preparing the sauce-flavor wine vinasse-based porous carbon composite ionic liquid gas adsorbent comprises the following three steps of (1) firstly using 0.5-2 mol.L of sauce-flavor wine vinasse -1 Removing impurities with hydrofluoric acid for pretreatment for 12-24 h, washing with a large amount of deionized water, drying, crushing to 50-200 meshes, and then introducing nitrogen gas at a flow rate of 100-200 ml/min -1 Under the nitrogen atmosphere at 5-10 ℃ for min -1 Heating to 500 ℃ for pre-carbonization for 1-3 h to obtain a porous carbon precursor; (2) The porous carbon precursor and the activating agent are mixed by mechanical ball milling according to a specific mass ratio, and then the nitrogen flow is 50-100 ml.min -1 Under the nitrogen atmosphere at 5-10 ℃ for min -1 Heating to 600-800 deg.C, secondary carbonizing for 1-3 h, and passing through 0.1-0.5 mol.L -1 Washing the mixture with hydrochloric acid and deionized water to be neutral, filtering and drying to obtain the sauce-flavor wine vinasse-based porous carbon; (3) Adding the sauce fragrant wine vinasse-based porous carbon and the ionic liquid into a solvent according to a specific mass ratio, washing by hexane, toluene or acetone, separating, and drying to obtain the sauce fragrant wine vinasse-based porous carbon composite ionic liquid gas adsorbent.
In the step (1), the main components of the sauce-flavor wine lees include, but are not limited to, fermented sorghum, rice hulls, wheat and corn.
In the step (2), the mass ratio of the porous carbon precursor to the activating agent is 1.
In the step (2), the activating agent includes but is not limited to KOH and K 2 CO 3 、KHCO 3 、 K 3 PO 4 、NaOH、H 3 PO 4 、ZnCl 2 And NaNH 2 。
In the step (2), the mechanical ball milling time is 5-15 min.
In the step (3), the mass ratio of the sauce fragrant wine lees-based porous carbon to the ionic liquid is 1.
In the step (3), the ionic liquid is a carboxylate proton type ionic liquid.
In the step (3), the organic amine structure required for synthesizing the carboxylate proton type ionic liquid includes, but is not limited to, diethylenetriamine, tetraethylenepentamine, and polyethyleneimine, and the polycarboxylic acid structure required for synthesizing the carboxylate proton type ionic liquid includes, but is not limited to, iminodiacetic acid, ethylenediamine-N, N' -diacetic acid, and nitrilotriacetic acid.
The invention has the advantages that:
(1) The invention 'treats waste with waste', can realize resource utilization of the sauce flavor vinasse solid waste, and the prepared porous carbon composite ionic liquid gas adsorbent can realize efficient collection and recovery of low-concentration gas in various gas source fields (natural gas, methane, coal bed gas and coal-fired flue gas), and is easy to regenerate and recycle.
(2) The preparation method is simple and beneficial to industrial operation, and the prepared porous carbon composite ion liquid gas adsorbent has the advantages of high specific surface area, light specific gravity, developed microporous structure and rich active sites.
(3) The porous carbon gas adsorbent prepared by the invention has good performance in gas adsorption separation, and can adsorb CO at normal pressure 2 、CH 4 、H 2 S、SO 2 Etc. has good adsorption performance and adsorption capacity5.20～10.7 mmol/g。
(4) The method comprises the steps of adopting liquor brewing bulk solid waste, namely sauce flavor liquor vinasse as a raw material, pretreating, pre-carbonizing and secondarily activating the vinasse to obtain vinasse-based porous carbon which is used for CO 2 And (4) adsorption research. The vinasse is pretreated by hydrofluoric acid to remove ash such as metal oxide, silicon dioxide and the like in the raw materials. The pre-carbonization selection of 500 ℃/2h can effectively remove moisture, organic impurities, volatile matters and the like in the lees raw materials, and provide a good-quality porous carbon precursor for secondary activation. The mechanical ball milling method is favorable for controlling the mechanical ball milling strength, the solid-solid mixing uniformity and the ball milling time in the physical mixing process.
(5) The invention provides a method for preparing a porous carbon gas adsorbent by utilizing bulk solid waste sauce-flavor wine vinasse, which promotes the resource utilization of the vinasse solid waste, and simultaneously, in order to improve the adsorption capacity and separation selectivity of the traditional porous carbon, the invention utilizes characteristic functional groups such as hydroxyl, carboxyl, C-O bond and the like contained in a vinasse-based porous carbon structure as the action site of ionic liquid modified porous carbon, so that the ionic liquid modified porous carbon adsorbent has better CO 2 、H 2 S、 SO 2 The polycarboxylate proton type ionic liquid with equal acidic gas adsorption capacity and high thermal stability and rich hydrogen bond sites is immobilized on the vinasse-based porous carbon so as to promote the adsorption performance of the vinasse-based porous carbon on low-concentration greenhouse gases and realize efficient selective capture and separation of basic carbon resources.
(6) The invention mainly considers the influence of the following factors on the preparation and adsorption performance of the vinasse porous carbon. First, the effect of the amount of activator on the pot-ale-based porous carbon was examined when the KOH amount was small (<1 g) Ultramicropores in distiller's grains based porous carbon (<1 nm), especially more micropore structures within the range of 0.45-0.65 nm, corresponding to CO under normal pressure 2 The adsorption capacity is increased; in contrast, the amount of KOH used (>1g) The specific surface area of the porous carbon is obviously increased, the quantity of medium pores and large pores is increased, and the corresponding CO is in normal pressure 2 The adsorption capacity decreases. Then, the influence of the kind of the activating agent on the lees-based porous carbon was examined, and when the lees-based porous carbon was prepared by using the same amount (0.5 g) of the activating agent and using different activating agents, the porous carbon had a large amountThe microporous structure has a low specific surface area, and compared with the KOH activating effect, the KOH activating effect has remarkable advantage, and the specific surface area reaches 1059m 2 G, corresponding to CO at atmospheric pressure 2 The adsorption capacity is maximum; finally, the influence of the secondary activation temperature on the vinasse-based porous carbon is considered, the factor investigation is mainly carried out at 600-800 ℃, the specific surface area is increased along with the increase of the temperature, but the number of micropores is increased and then reduced, and when the activation temperature is 700 ℃, the vinasse-based porous carbon has the largest micropores (wherein the number of the micropores is the maximum of the microporous carbon) ((the activation temperature is the maximum of the microporous carbon in the vinasse-based porous carbon in the case of the activation temperature is the maximum of the microporous carbon in the case of the activation temperature of 700 ℃) (<1 nm) amount, corresponding to CO at atmospheric pressure 2 The adsorption capacity is maximized.
Drawings
FIG. 1 is a SEM representation of the gas adsorbent prepared in various examples: FIG. 1a is example 1; FIG. 1b shows example 2.
FIG. 2 is a TEM representation of the gas adsorbent prepared in example 1.
FIG. 3 is a graph showing a pore structure of the gas adsorbent prepared in example 1, wherein FIG. 3a is a nitrogen adsorption/desorption isotherm; figure 3b is a pore size distribution curve.
FIG. 4 is a schematic synthesis scheme of the ionic liquid of example 3, salt of [ TEPAH ] [ IDA ] carboxylic acid in proton form.
FIG. 5 is a schematic diagram of modification of a vinasse-based porous carbon chemically grafted [ SCA-2H ] [ OOCR ] carboxylate proton type ionic liquid in example 4.
FIG. 6 shows CO as a gas adsorbent prepared in example 1 2 、CH 4 、N 2 Gas adsorption curve.
FIG. 7 shows SO obtained as a gas adsorbent in example 2 2 、H 2 S、CO 2 Gas adsorption curve.
FIG. 8 shows CO produced as gas adsorbents in examples 2,3,4 and 5 2 Gas adsorption profile, example 2: KOH-C-1; example 3: KOH-C-1/[ TEPAH ]][IDA] 0.2 (ii) a Example 4: KOH-C-1/[ SCA-2H ]][OOCR] 0.2 (ii) a Example 5: KOH-C-1/[ TEPAH][IDA] 0.5 。
Detailed Description
In the aspect of specific implementation process, the invention focuses on the consideration of the following factors on the increase of the vinassePreparation of the porous carbon and influence of adsorption performance. First, the effect of the amount of activator on the lees-based porous carbon was examined when the amount of KOH was small (<1g) Ultramicropores in distiller's grains-based porous carbon: (<1 nm), especially more micropore structures within the range of 0.45-0.65 nm, corresponding to CO under normal pressure 2 The adsorption capacity is increased; in contrast, the amount of KOH used (>1g) The specific surface area of the porous carbon is obviously increased, the number of medium pores and large pores is increased, and the corresponding CO is generated at normal pressure 2 The adsorption capacity decreases. Then, the influence of the variety of the activating agent on the vinasse-based porous carbon is examined, when the vinasse-based porous carbon is prepared under the conditions of the same using amount (0.5 g) and different activating agents, the porous carbon has a large number of microporous structures and a low specific surface area, and compared with the porous carbon, the KOH has a remarkable activating effect and the specific surface area reaches 1059m 2 G, corresponding to CO at atmospheric pressure 2 The adsorption capacity is maximum; finally, the influence of the secondary activation temperature on the vinasse-based porous carbon is considered, the factor investigation is mainly carried out at 600-800 ℃, the specific surface area is increased along with the increase of the temperature, but the number of micropores is increased and then reduced, and when the activation temperature is 700 ℃, the vinasse-based porous carbon has the largest micropores (wherein the number of the micropores is the maximum of the microporous carbon) ((the activation temperature is the maximum of the microporous carbon in the vinasse-based porous carbon in the case of the activation temperature is the maximum of the microporous carbon in the case of the activation temperature of 700 ℃) (<1 nm) amount, corresponding to CO at atmospheric pressure 2 The adsorption capacity is maximized.
Example 1
A preparation method of a sauce-flavor wine vinasse-based porous carbon gas adsorbent. The dried vinasse is added at 2 mol.L -1 Stirring and pretreating in hydrofluoric acid solution for 24h, washing with deionized water, drying at 105 ℃, pulverizing to 50-200 meshes, and then stirring in nitrogen flow of 100 ml/min -1 Maintaining inert atmosphere at 5 deg.C/min -1 Heating to 500 ℃ for pre-carbonization for 2h to obtain a porous carbon precursor; mechanically ball-milling the porous carbon precursor and the KOH activating agent for 10min according to the mass ratio of 1.5, and then carrying out nitrogen flow at 50 ml-min -1 Maintaining inert atmosphere at 5 deg.C/min -1 Heating to 700 ℃ for secondary carbonization for 2h, and carrying out 0.1 mol.L -1 Washing with hydrochloric acid, washing with deionized water to neutrality, filtering, and oven drying at 105 deg.C to obtain sauce-flavored wine lees-based porous carbon gas adsorbent (KOH-C-0.5).
Micro-morphology of porous carbon gas adsorbentBy performing characterization, as can be seen from the SEM image 1a, irregular pores are formed on the surface of the porous carbon, and as can be seen from the TEM image 2, a large number of micro-pore structures similar to wormholes are formed in the adsorbent and are randomly distributed in the carbon skeleton. Meanwhile, the specific surface area and pore structure of the porous carbon gas adsorbent are characterized, and the result is shown in fig. 3. Wherein FIG. 3a is a nitrogen adsorption/desorption isotherm, and classification of the adsorption isotherm by IUPAC shows that the curve is of type I and at a lower relative pressure (P/P) 0 <0.1)，N 2 Has large adsorption capacity and a wide relative pressure range (0.1) after the inflection point<P/P 0 <1.0 Maintained at a relative level, indicating that the adsorbent has a largely microporous structure, it can also be seen from the pore size distribution curve of fig. 3b that the adsorbent has a pore size distribution mainly between 0.45 and 1nm. The analysis shows that the specific surface area of the prepared sauce-flavor wine vinasse-based adsorbent is 1059m 2 Per g, total pore volume 0.57cm 3 G, micropore volume of 0.50cm 3 /g。
Testing CO of adsorbent by BSD-PM2 physical adsorption instrument 2 、CH 4 、N 2 The gas adsorption performance and the adsorption curve are shown in FIG. 6, under the same conditions, the adsorption capacities are greatly different according to different gases, and the sequence is CO 2 >CH 4 >N 2 . CO at 273.15K under 1bar 2 The adsorption capacity is 6.34 mmol/g, and CO is obtained by calculation of IAST competitive adsorption 2 The selectivity was 24.1% (1 bar, CO respectively) 2 :N 2 ＝15％:85％)，5.6％(1bar,CO 2 :CH 4 ＝40％:60％)。
Example 2
A preparation method of a sauce-flavor wine lees-based porous carbon gas adsorbent. Adding dried distiller's grains at 2 mol. L -1 Stirring and pretreating the hydrofluoric acid solution for 24 hours, washing the hydrofluoric acid solution by deionized water, drying the hydrofluoric acid solution at 105 ℃, crushing the hydrofluoric acid solution to 50 to 200 meshes, and then placing the hydrofluoric acid solution in nitrogen with the flow rate of 100 ml/min -1 Maintaining inert atmosphere at 5 deg.C/min -1 Heating to 500 ℃ for pre-carbonization for 2h to obtain a porous carbon precursor; mechanically ball-milling the porous carbon precursor and a KOH activating agent for 15min according to a mass ratio of 1 -1 Maintained inertiaIn a neutral atmosphere, at 5 ℃ min -1 Heating to 700 ℃ for secondary carbonization for 2h, and carrying out 0.1 mol.L -1 Washing with hydrochloric acid, washing with deionized water to neutral, filtering, and oven drying at 105 deg.C to obtain sauce-flavored wine lees-based porous carbon adsorbent (KOH-C-1).
The microstructure of the porous carbon gas adsorbent is characterized, and analysis shows that the pore diameter of the gas adsorbent is mainly distributed at 0.45-3.5 nm, and the specific surface area is 2079m 2 G, total pore volume 1.14cm 3 ·g -1 Pore volume of the micropores is 0.94cm 3 ·g -1 。
Testing H of adsorbent by BSD-PM2 physical adsorption instrument 2 S、SO 2 、CO 2 The gas adsorption performance, adsorption curve is shown in fig. 7. As can be seen from the figure, under the conditions of 273.15K and 1bar, H 2 S adsorption capacity of 6.68 mmol/g -1 ，SO 2 The adsorption capacity was 9.52 mmol/g -1 ，CO 2 The adsorption capacity was 5.96 mmol/g -1 。
Example 3
A preparation method of a sauce-flavor wine lees-based porous carbon composite ionic liquid gas adsorbent. The dried vinasse is added at 2 mol.L -1 Stirring and pretreating in hydrofluoric acid solution for 24h, washing with deionized water, drying at 105 ℃, crushing to 50-200 meshes, and then introducing nitrogen gas at 100 ml/min -1 Maintaining inert atmosphere at 5 deg.C/min -1 Heating to 500 ℃ for pre-carbonization for 2h to obtain a porous carbon precursor; mechanically ball-milling the porous carbon precursor and a KOH activating agent for 15min according to the mass ratio of 1 -1 Maintaining inert atmosphere at 5 deg.C/min -1 Heating to 700 ℃ for secondary carbonization for 2h, and carrying out 0.1 mol.L -1 Washing with hydrochloric acid, washing with deionized water to neutrality, filtering, and oven drying at 105 deg.C to obtain sauce-flavored wine lees-based porous carbon adsorbent (KOH-C-1). Simultaneously, organic amine and carboxylic acid are reacted in ethanol according to the molar ratio of 1An ionic liquid. For example: [ TEPAH][IDA]The synthetic route of the carboxylate protonic ionic liquid is shown in figure 4. Then, the distiller's grains-based porous carbon is reacted with [ TEPAH ]][IDA]Adding the carboxylate proton type ionic liquid into acetone according to the mass ratio of 1.2, fully stirring and dipping, filtering and drying to obtain the vinasse-based porous carbon composite ionic liquid gas adsorbent (KOH-C-1/[ TEPAH ]][IDA] 0.2 )。
Example 4
A preparation method of a sauce-flavor wine vinasse-based porous carbon composite ionic liquid gas adsorbent. The dried vinasse is added at 2 mol.L -1 Stirring and pretreating in hydrofluoric acid solution for 24h, washing with deionized water, drying at 105 deg.C, pulverizing to 50-200 meshes, and introducing nitrogen gas at 100 ml/min -1 Maintaining inert atmosphere at 5 deg.C/min -1 Heating to 500 ℃ for pre-carbonization for 2h to obtain a porous carbon precursor; mechanically ball-milling the porous carbon precursor and a KOH activating agent for 15min according to the mass ratio of 1 -1 Maintaining inert atmosphere at 5 deg.C/min -1 Heating to 700 ℃ for secondary carbonization for 2h, and carrying out 0.1 mol.L -1 Washing with hydrochloric acid, washing with deionized water to neutrality, filtering, and oven drying at 105 deg.C to obtain sauce-flavored wine lees-based porous carbon adsorbent (KOH-C-1). Meanwhile, organic amine and carboxylic acid are mixed according to the molar ratio of 1 to 2 through acid-base neutralization reaction to synthesize various primary amine, tertiary amine, silane coupling agents and carboxylate proton type ionic liquids containing hydroxyl or ether bonds with characteristic structures. Then adding the vinasse-based porous carbon and the ionic liquid into toluene according to the mass ratio of 1.2 for reflux, and preparing the vinasse-based porous carbon composite ionic liquid gas adsorbent by a chemical grafting method. For example: vinasse-based porous carbon chemical grafting [ SCA-2H ]][OOCR]Carboxylate proton type ionic liquid modification, KOH-C-1/[ SCA-2H ]][OOCR] 0.2 The synthetic route is shown in FIG. 5.
Example 5
A preparation method of a sauce-flavor wine vinasse-based porous carbon composite ionic liquid gas adsorbent. Adding dried distiller's grains at 2 mol. L -1 Stirring and pretreating in hydrofluoric acid solution for 24h, washing with deionized water, drying at 105 deg.C, pulverizing to 50-200 meshes, and introducing nitrogen gas at 100 ml/min -1 Maintained under inert atmosphere at 5 deg.C/min -1 Heating to 500 ℃ for pre-carbonization for 2h to obtain a porous carbon precursor; mechanically ball-milling the porous carbon precursor and a KOH activating agent for 15min according to the mass ratio of 1 -1 Maintained under inert atmosphere at 5 deg.C/min -1 Heating to 700 ℃, carbonizing for 2h for the second time, and processing by 0.1 mol.L -1 Washing with hydrochloric acid, washing with deionized water to neutrality, filtering, and oven drying at 105 deg.C to obtain sauce-flavored wine lees-based porous carbon adsorbent (KOH-C-1). And simultaneously, reacting organic amine and carboxylic acid in ethanol according to the molar ratio of 1. Then, the distiller's grains-based porous carbon is reacted with [ TEPAH ]][IDA]Adding carboxylate proton type ionic liquid into acetone according to the mass ratio of 1.5][IDA] 0.5 )。
Example 6
The gas adsorbents obtained in examples 2,3,4 and 5 were tested for CO using a BSD-PM2 physical adsorption apparatus 2 The adsorption performance, adsorption curve, is shown in fig. 8. As can be seen from the graph, the adsorption capacity of KOH-C-1 was 5.96 mmol/g at 273.15K and 1bar -1 ， KOH-C-1/[TEPAH][IDA] 0.2 The adsorption capacity was 8.85 mmol/g -1 ，KOH-C-1/[SCA-2H][OOCR] 0.2 The adsorption capacity was 7.79 mmol/g -1 After the solid loading of the ionic liquid is increased, KOH-C-1/[ TEPAH][IDA] 0.5 The adsorption capacity is as high as 10.7 mmol/g -1 。
The method of the invention takes solid waste resource utilization as a starting point, takes the large amount of solid waste, namely sauce-flavor wine lees, brewed by white spirit as a raw material, and obtains the product with light specific gravity, developed micropore structure and specific surface area as high as 3657.6m by hydrofluoric acid impurity removal pretreatment, high-temperature carbonization and secondary activation 2 ·g -1 The vinasse-based porous carbon is CO under normal pressure 2 Adsorption capacity 6.34 mmol/g -1 ，H 2 S adsorption capacity 6.68 mmol. Multidot.g -1 ，SO 2 Adsorption capacity 9.52 mmol/g -1 . At the same time, innovateProton type ionic liquid is used for modifying the porous carbon, so that the sauce-flavored wine vinasse-based porous carbon composite ionic liquid gas adsorbent with higher thermal stability is created, and the adsorption capacity and the separation selectivity of the vinasse-based porous carbon to low-concentration gas are further improved. The sauce-flavor wine vinasse-based porous carbon composite ionic liquid gas adsorbent prepared by the invention is prepared by adsorbing CO 2 Shows excellent adsorption separation performance in the selective adsorption separation application, and CO is adsorbed under normal pressure 2 The adsorption capacity is increased to 10.7 mmol-g -1 . Because the prepared porous carbon composite ionic liquid gas adsorbent has the advantages of ultrahigh specific surface area, abundant pore structure properties and abundant active sites, the preparation method is simple, the operation is easy, the cost is low (about 87% of the cost of the sawdust commercial active carbon), and the like, so that the porous carbon composite ionic liquid gas adsorbent has a good industrial application prospect in the gas adsorption and separation fields of natural gas, methane, low-concentration coal bed gas, coal-fired flue gas and the like.
Claims (8)
1. A preparation method of a sauce-flavor wine vinasse-based porous carbon composite ionic liquid gas adsorbent is characterized by comprising the following steps of:
(1) 0.1-0.5 mol/L of sauce-flavor wine vinasse is firstly used -1 Removing impurities with hydrofluoric acid for 0.5-2 h, washing with deionized water, filtering, drying, pulverizing to 50-200 meshes, and introducing nitrogen at 100-200 ml/min -1 Under the nitrogen atmosphere at 5-10 ℃ for min -1 Heating to 500 ℃ for pre-carbonization for 1-3 h to obtain a porous carbon precursor;
(2) The porous carbon precursor and the activating agent are mechanically ball-milled and mixed according to a specific mass ratio, and then the flow is 50-100 ml.min -1 Under the nitrogen atmosphere at 5-10 ℃ for min -1 The temperature is raised to 600 to 800 ℃ at the temperature raising speed, secondary carbonization treatment is carried out for 1 to 3 hours, and then the secondary carbonization treatment is carried out for 0.1 to 0.5 mol.L -1 Washing the mixture with hydrochloric acid and deionized water to be neutral, filtering and drying to obtain the sauce-flavor wine vinasse-based porous carbon;
(3) The sauce-flavored wine vinasse-based porous carbon is compounded with ionic liquid according to specific mass, and then the sauce-flavored wine vinasse-based porous carbon composite ionic liquid gas adsorbent is obtained.
2. The preparation method of the sauce-flavored wine lees-based porous carbon composite ionic liquid gas adsorbent according to claim 1, wherein the main components of the sauce-flavored wine lees include, but are not limited to, fermented sorghum, rice hulls, wheat and corn.
3. The preparation method of the ionic liquid gas adsorbent compounded by the sauce-flavored wine lees-based porous carbon as claimed in claim 1, wherein the mass ratio of the porous carbon precursor to the activating agent is 1.
4. The preparation method of the Maotai-flavor wine vinasse-based porous carbon composite ionic liquid gas adsorbent according to claim 1 or 3, wherein the activating agent comprises but is not limited to KOH and K 2 CO 3 、KHCO 3 、K 3 PO 4 、NaOH、H 3 PO 4 、ZnCl 2 And NaNH 2 。
5. The preparation method of the sauce-flavored wine lees-based porous carbon composite ionic liquid gas adsorbent according to claim 1, wherein the mass ratio of the sauce-flavored wine lees-based porous carbon to the ionic liquid is 1.
6. The preparation method of the ionic liquid gas adsorbent compounded from the Maotai-flavor wine lees-based porous carbon according to claim 1 or 5, wherein the ionic liquid is carboxylate proton type ionic liquid.
7. The preparation method of the Maotai-flavor wine lees-based porous carbon composite ionic liquid gas adsorbent according to claim 6, wherein the organic amine structure required by the synthesis of the carboxylate proton type ionic liquid comprises but is not limited to ethylenediamine, diethylenetriamine, tetraethylenepentamine, polyethyleneimine, N- [3- (trimethoxysilyl) propyl ] ethylenediamine, 3-aminopropyltrimethoxysilane, tris (2-dimethylaminoethyl) amine, triethanolamine, tris (3, 6-dioxaheptyl) amine.
8. The preparation method of the Maotai-flavor wine vinasse-based porous carbon composite ionic liquid gas adsorbent according to claim 6, wherein the polycarboxylic acid structure required by the synthesis of the carboxylate proton type ionic liquid comprises but is not limited to iminodiacetic acid, ethylenediamine-N, N' -diacetic acid, nitrilotriacetic acid, 1,2,3, 4-butanetetracarboxylic acid and benzimidazole-5-carboxylic acid.
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